Clay enhancement of methane, low molecular weight hydrocarbon and halocarbon conversion by methanotrophic bacteria

DOEpatents

Apel, William A.; Dugan, Patrick R.

1995-01-01

An apparatus and method for increasing the rate of oxidation of toxic vapors by methanotrophic bacteria. The toxic vapors of interest are methane and trichloroethylene. The apparatus includes a gas phase bioreactor within a closed loop pumping system or a single pass system. The methanotrophic bacteria include Methylomonas methanica, Methylosinus trichosporium, and uncharacterized environmental enrichments.

Clay enhancement of methane, low molecular weight hydrocarbon and halocarbon conversion by methanotrophic bacteria

DOEpatents

Apel, William A.; Dugan, Patrick R.

1995-04-04

An apparatus and method for increasing the rate of oxidation of toxic vapors by methanotrophic bacteria. The toxic vapors of interest are methane and trichloroethylene. The apparatus includes a gas phase bioreactor within a closed loop pumping system or a single pass system. The methanotrophic bacteria include Methylomonas methanica, Methylosinus trichosporium, and uncharacterized environmental enrichments.

A modeling approach to direct interspecies electron transfer process in anaerobic transformation of ethanol to methane.

PubMed

Liu, Yiwen; Zhang, Yaobin; Zhao, Zhiqiang; Ngo, Huu Hao; Guo, Wenshan; Zhou, Junliang; Peng, Lai; Ni, Bing-Jie

2017-01-01

Recent studies have shown that direct interspecies electron transfer (DIET) plays an important part in contributing to methane production from anaerobic digestion. However, so far anaerobic digestion models that have been proposed only consider two pathways for methane production, namely, acetoclastic methanogenesis and hydrogenotrophic methanogenesis, via indirect interspecies hydrogen transfer, which lacks an effective way for incorporating DIET into this paradigm. In this work, a new mathematical model is specifically developed to describe DIET process in anaerobic digestion through introducing extracellular electron transfer as a new pathway for methane production, taking anaerobic transformation of ethanol to methane as an example. The developed model was able to successfully predict experimental data on methane dynamics under different experimental conditions, supporting the validity of the developed model. Modeling predictions clearly demonstrated that DIET plays an important role in contributing to overall methane production (up to 33 %) and conductive material (i.e., carbon cloth) addition would significantly promote DIET through increasing ethanol conversion rate and methane production rate. The model developed in this work will potentially enhance our current understanding on syntrophic metabolism via DIET.

Anaerobic oxidation of methane coupled to thiosulfate reduction in a biotrickling filter.

PubMed

Cassarini, Chiara; Rene, Eldon R; Bhattarai, Susma; Esposito, Giovanni; Lens, Piet N L

2017-09-01

Microorganisms from an anaerobic methane oxidizing sediment were enriched with methane gas as the substrate in a biotrickling filter (BTF) using thiosulfate as electron acceptor for 213days. Thiosulfate disproportionation to sulfate and sulfide were the dominating sulfur conversion process in the BTF and the sulfide production rate was 0.5mmoll -1 day -1 . A specific group of sulfate reducing bacteria (SRB), belonging to the Desulforsarcina/Desulfococcus group, was enriched in the BTF. The BTF biomass showed maximum sulfate reduction rate (0.38mmoll -1 day -1 ) with methane as sole electron donor, measured in the absence of thiosulfate in the BTF. Therefore, a BTF fed with thiosulfate as electron acceptor can be used to enrich SRB of the DSS group and activate the inoculum for anaerobic oxidation of methane coupled to sulfate reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ammonia chemistry in a flameless jet

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zieba, Mariusz; Schuster, Anja; Scheffknecht, Guenter

2009-10-15

In this paper, the nitrogen chemistry in an ammonia (NH{sub 3}) doped flameless jet is investigated using a kinetic reactor network model. The reactor network model is used to explain the main differences in ammonia chemistry for methane (CH{sub 4})-containing fuels and methane-free fuels. The chemical pathways of nitrogen oxides (NO{sub x}) formation and destruction are identified using rate-of-production analysis. The results show that in the case of natural gas, ammonia reacts relatively late at fuel lean condition leading to high NO{sub x} emissions. In the pre-ignition zone, the ammonia chemistry is blocked due to the absence of free radicalsmore » which are consumed by methane-methyl radical (CH{sub 3}) conversion. In the case of methane-free gas, the ammonia reacted very rapidly and complete decomposition was reached in the fuel rich region of the jet. In this case the necessary radicals for the ammonia conversion are generated from hydrogen (H{sub 2}) oxidation. (author)« less

Photocatalytic conversion of methane to methanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taylor, C.E.; Noceti, R.P.; D`Este, J.R.

1995-12-31

A long-term goal of our research group is the exploration of novel pathways for the direct oxidation of methane to liquid fuels, chemicals, and intermediates. The use of three relatively abundant and inexpensive reactants, light, water, and methane, to produce methanol is attractive. The products of reaction, methanol and hydrogen, are both commercially desirable, methanol being used as is or converted to a variety of other chemicals, and the hydrogen could be utilized in petroleum and/or chemical manufacturing. Methane is produced as a by-product of coal gasification. Depending upon reactor design and operating conditions, up to 18% of total gasifiermore » product may be methane. In addition, there are vast proven reserves of geologic methane in the world. Unfortunately, a large fraction of these reserves are in regions where there is little local demand for methane and it is not economically feasible to transport it to a market. There is a global research effort under way in academia, industry, and government to find methods to convert methane to useful, more readily transportable and storable materials. Methanol, the initial product of methane oxidation, is a desirable product of conversion because it retains much of the original energy of the methane while satisfying transportation and storage requirements. Investigation of direct conversion of methane to transportation fuels has been an ongoing effort at PETC for over 10 years. One of the current areas of research is the conversion of methane to methanol, under mild conditions, using light, water, and a semiconductor photocatalyst. The use of three relatively abundant and inexpensive reactants, light, water, and methane, to produce methanol, is attractive. Research in the laboratory is directed toward applying the techniques developed for the photocatalytic splitting of the water and the photochemical conversion of methane.« less

Biogasification of Walt Disney World biomass waste blend. Final report, January 1982-December 1985

DOE Office of Scientific and Technical Information (OSTI.GOV)

Biljetina, R.; Chynoweth, D.P.; Srivastava, V.J.

1986-10-01

The objective of the research is to develop efficient processes for conversion of biomass-waste blends to methane and other resources. To evaluate the technical and economic feasibility, an experimental test unit (ETU) was designed and operated at the Reedy Creek Wastewater Treatment Plant at Walt Disney World in Lake Buena Vista, Florida. The facility integrates a biomethanogenic-conversion process with a wastewater-treatment process employing water hyacinth ponds for secondary and tertiary treatment of sewage. Harvested water hyacinth is subsequently combined with sludge from the primary wastewater clarifier and fed at 1-wet-ton per day to the ETU digester. This results in themore » production of methane and other useful products. The digester was operated as a non-mixed, solids concentrating digester to encourage higher solids and microorganism retention times. Data collected during six steady-state operating periods confirmed earlier laboratory observations that this digester consistently produces 15 to 25% higher methane yields and conversions when compared to conventional stirred-tank digester. Digester operation was evaluated at different loading rates, solids blend ratios and feed configurations. Results from the program have provided a data base for the design of larger conversion systems.« less

Methane - fuel for the future

DOE Office of Scientific and Technical Information (OSTI.GOV)

McGeer, P.; Durbin, E.

1982-01-01

The 20 invited papers presented at the world conference on alternative fuel entitled 'Methane - fuel for the future' form the basis of this book. Papers discuss: the availability of alternative fuels (natural gas, biomass conversion to methane, methane from coal conversion); technological adaptions for alternative fuels (e.g. natural gas fueled engines, methane and diesel engines); commercial experience with alternative fuel programs. (e.g. retailing of methane); and some national programs for alternative fuels. One paper has been abstracted separately.

Bio-conversion of water hyacinths into methane gas, part 1

NASA Technical Reports Server (NTRS)

Wolverton, B. C.; Mcdonald, R. C.; Gordon, J.

1974-01-01

Bio-gas and methane production from the microbial anaerobic decomposition of water hyacinths (Eichhornia crassipes) (Mart) Solms was investigated. These experiments demonstrated the ability of water hyacinths to produce an average of 13.9 ml of methane gas per gram of wet plant weight. This study revealed that sample preparation had no significant effect on bio-gas and/or methane production. Pollution of water hyacinths by two toxic heavy materials, nickel and cadmium, increased the rate of methane production from 51.8 ml/day for non-contaminated plants incubated at 36 C to 81.0 ml/day for Ni-Cd contaminated plants incubated at the same temperature. The methane content of bio-gas evolved from the anaerobic decomposition of Ni-Cd contaminated plants was 91.1 percent as compared to 69.2 percent methane content of bio-gas collected from the fermentation of non-contaminated plants.

Effects of sonication on co-precipitation synthesis and activity of copper manganese oxide catalyst to remove methane and sulphur dioxide gases.

PubMed

Yap, Yeow Hong; Lim, Mitchell S W; Lee, Zheng Yee; Lai, Kar Chiew; Jamaal, Muhamad Ashraf; Wong, Farng Hui; Ng, Hoon Kiat; Lim, Siew Shee; Tiong, T Joyce

2018-01-01

The utilisation of ultrasound in chemical preparation has been the focus of intense study in various fields, including materials science and engineering. This paper presents a novel method of synthesising the copper-manganese oxide (Hopcalite) catalyst that is used for the removal of volatile organic compounds and greenhouse gases like carbon monoxide. Several samples prepared under different conditions, with and without ultrasound, were subjected to a series of characterisation tests such as XRD, BET, FE-SEM, EDX, TPR-H 2 , TGA and FT-IR in order to establish their chemical and physical properties. A series of catalytic tests using a micro-reactor were subsequently performed on the samples in order to substantiate the aforementioned properties by analysing their ability to oxidise compressed natural gas (CNG), containing methane and sulphur dioxide. Results showed that ultrasonic irradiation of the catalyst led to observable alterations in its morphology: surfaces of the particles were noticeably smoothed and an increased in amorphicity was detected. Furthermore, ultrasonic irradiation has shown to enhance the catalytic activity of Hopcalite, achieving a higher conversion of methane relative to non-sonicated samples. Varying the ultrasonic intensity also produced appreciable effects, whereby an increase in intensity results in a higher conversion rate. The catalyst sonicated at the highest intensity of 29.7W/cm 2 has a methane conversion rate of 13.5% at 400°C, which was the highest among all the samples tested. Copyright © 2017 Elsevier B.V. All rights reserved.

Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature

PubMed Central

2016-01-01

The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C–H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483–498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions. PMID:27413787

Methane production by anaerobic digestion of Bermuda grass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klass, D.L.; Ghosh, S.

1979-01-01

Bermuda grass (Cynodon dactylon) is one of the high-yield warm-season grasses that has been suggested as a promising raw material for conversion to methane. Experimental work performed with laboratory digesters to study the anaerobic digestion of Coastal Bermuda grass harvested in Louisiana and having a C/N ratio of 24 is described. Methane yields of about 1.9 SCF/lb of volatile solids( VS) added were observed under conventional mesophilic high-rate conditions. When supplemental nitrogen additions were made, the yields increased up to 3.5 SCF/lb of VS added indicating that the nitrogen content of the grass examined was insufficient to sustain high-rate digestionmore » at the higher yield level. Thermophilic digestion with supplemental nitrogen additions afforded methane yields of about 2.7 SCF/lb VS added. Carbon and energy balances were calculated and the relative biodegradabilities of the organics were estimated.« less

Methane-Powered Vehicles

NASA Technical Reports Server (NTRS)

1982-01-01

Liquid methane is beginning to become an energy alternative to expensive oil as a power source for automotive vehicles. Methane is the principal component of natural gas, costs less than half as much as gasoline, and its emissions are a lot cleaner than from gasoline or diesel engines. Beech Aircraft Corporation's Boulder Division has designed and is producing a system for converting cars and trucks to liquid methane operation. Liquid methane (LM) is a cryogenic fuel which must be stored at a temperature of 260 degrees below zero Fahrenheit. The LM system includes an 18 gallon fuel tank in the trunk and simple "under the hood" carburetor conversion equipment. Optional twin-fuel system allows operator to use either LM or gasoline fuel. Boulder Division has started deliveries for 25 vehicle conversions and is furnishing a liquid methane refueling station. Beech is providing instruction for Northwest Natural Gas, for conversion of methane to liquid state.

Biogeochemistry: Hexadecane decay by methanogenesis

USGS Publications Warehouse

Anderson, Robert T.; Lovely, Derek R.

2000-01-01

The potential for the biological conversion of long-chain saturated hydrocarbons to methane under anaerobic conditions has been demonstrated by using an enrichment culture of bacteria to degrade pure-phase hexadecane1. The formation of methane in hydrocarbon-rich subsurface zones could be explained if a similar conversion of long-chain alkanes to methane were to take place in subsurface environments. If this process could be stimulated in the subsurface, it could be used to enhance hydrocarbon recovery from petroleum reserves1, 2. Parkes2, however, questions the environmental significance of the enrichment-culture results1 on the grounds that alkane conversion to methane is very slow and because sulphate-reducing and methanogenic bacteria might both be necessary for even this slow process to occur, restricting the conversion to specialized, unusual zones in sediments. Here we show that, on the contrary, subsurface bacteria can adapt to convert hexadecane to methane rapidly and in the absence of sulphate-reducing bacteria.

Effect of bio-column composed of aged refuse on methane abatement--a novel configuration of biological oxidation in refuse landfill.

PubMed

Han, Dan; Zhao, Youcai; Xue, Binjie; Chai, Xiaoli

2010-01-01

An experimental bio-column composed of aged refuse was installed around the exhaust pipe as a new way to mitigate methane in refuse landfill. One of the objectives of this work was to assess the effect of aged refuse thickness in bio-column on reducing CH4 emissions. Over the study period, methane oxidation was observed at various thicknesses, 5 cm (small size), 10 cm (middle size) and 15 cm (large size), representing one to three times of pipeline diameters. The middle and large size both showed over 90% methane conversion, and the highest methane conversion rate of above 95% occurred in the middle-size column cell. Michaelis-Menten equation addressed the methanotrophs diffusion in different layers of the bio-columns. Maximum methanotrophic activity (Vmax) measured at the three thicknesses ranged from 6.4 x 10(-3) to 15.6 x 10(-3) units, and the half-saturation value (K(M)) ranged from 0.85% to 1.67%. Both the highest Vmax and K(M) were observed at the middle-size of the bio-column, as well as the largest methanotrophs population, suggesting a significant efficiency of methane mitigation happened in the optimum zone with greatest affinity and methanotrophic bacteria activities. Therefore, bio-column is a potential style for methane abatement in landfill, and the aged refuse both naturally formed and artificially placed in the column plays a critical role in CH4 emission.

Conversion of (Meth)acrylic acids to methane granular sludge: Initiation by specific anerobic microflora

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shtarkman, N.B.; Obraztova, A.Y.; Laurinavichyus, K.S.

1995-03-01

The role of a specific anaerobic microflora in the initiation of degradation of (meth)acrylic acids to methane by granular sludge from a UASB reactor was investigated. Associations of anaerobic bacteria isolated from the anaerobic sludge, which was used for a long time for treatment of wastewater from (meth)acrylate production, were able to realize the initial stage of (meth)acrylic acid decomposition, i.e., a conversion of acrylic and methacrylic acids to propionic and isobutyric acids, respectively. When added to granules, these association played a role of an {open_quotes}initiator{close_quotes} of the degradation process, which was then continued by the granular sludge microflora utilizingmore » propionate and isobutyrate. Some characteristics of the granules adapted to propionate or isobutyrate are presented. The rates of propionate and isobutyrate consumption by adapted granules is, respectively, 21 and 53 times higher than the values obtained for nonadapted granules. A combined use of {open_quotes}initiating{close_quotes} bacteria and adapted granules provided degradation of (meth)acrylic acids with a maximum methane yield. The possibility is discussed of employing the granules, which are adapted to short-chain fatty acids, and the {open_quotes}initiating{close_quotes} bacteria, which accomplish the initial steps of the organic material decomposition to lower fatty acids, for the conversion of various chemical compounds to methane. 10 refs., 3 figs., 2 tabs.« less

New approach to control the methanogenic reactor of a two-phase anaerobic digestion system.

PubMed

von Sachs, Jürgen; Meyer, Ulrich; Rys, Paul; Feitkenhauer, Heiko

2003-03-01

A new control strategy for the methanogenic reactor of a two-phase anaerobic digestion system has been developed and successfully tested on the laboratory scale. The control strategy serves the purpose to detect inhibitory effects and to achieve good conversion. The concept is based on the idea that volatile fatty acids (VFA) can be measured in the influent of the methanogenic reactor by means of titration. Thus, information on the output (methane production) and input of the methanogenic reactor is available, and a (carbon) mass balance can be obtained. The control algorithm comprises a proportional/integral structure with the ratio of (a) the methane production rate measured online and (b) a maximum methane production rate expected (derived from the stoichiometry) as a control variable. The manipulated variable is the volumetric feed rate. Results are shown for an experiment with VFA (feed) concentration ramps and for experiments with sodium chloride as inhibitor.

Direct Conversion of Methane to Value-Added Chemicals over Heterogeneous Catalysts: Challenges and Prospects.

PubMed

Schwach, Pierre; Pan, Xiulian; Bao, Xinhe

2017-07-12

The quest for an efficient process to convert methane efficiently to fuels and high value-added chemicals such as olefins and aromatics is motivated by their increasing demands and recently discovered large reserves and resources of methane. Direct conversion to these chemicals can be realized either oxidatively via oxidative coupling of methane (OCM) or nonoxidatively via methane dehydroaromatization (MDA), which have been under intensive investigation for decades. While industrial applications are still limited by their low yield (selectivity) and stability issues, innovations in new catalysts and concepts are needed. The newly emerging strategy using iron single sites to catalyze methane conversion to olefins, aromatics, and hydrogen (MTOAH) attracted much attention when it was reported. Because the challenge lies in controlled dehydrogenation of the highly stable CH 4 and selective C-C coupling, we focus mainly on the fundamentals of C-H activation and analyze the reaction pathways toward selective routes of OCM, MDA, and MTOAH. With this, we intend to provide some insights into their reaction mechanisms and implications for future development of highly selective catalysts for direct conversion of methane to high value-added chemicals.

Treatment of corn ethanol distillery wastewater using two-stage anaerobic digestion.

PubMed

Ráduly, B; Gyenge, L; Szilveszter, Sz; Kedves, A; Crognale, S

In this study the mesophilic two-stage anaerobic digestion (AD) of corn bioethanol distillery wastewater is investigated in laboratory-scale reactors. Two-stage AD technology separates the different sub-processes of the AD in two distinct reactors, enabling the use of optimal conditions for the different microbial consortia involved in the different process phases, and thus allowing for higher applicable organic loading rates (OLRs), shorter hydraulic retention times (HRTs) and better conversion rates of the organic matter, as well as higher methane content of the produced biogas. In our experiments the reactors have been operated in semi-continuous phase-separated mode. A specific methane production of 1,092 mL/(L·d) has been reached at an OLR of 6.5 g TCOD/(L·d) (TCOD: total chemical oxygen demand) and a total HRT of 21 days (5.7 days in the first-stage, and 15.3 days in the second-stage reactor). Nonetheless the methane concentration in the second-stage reactor was very high (78.9%); the two-stage AD outperformed the reference single-stage AD (conducted at the same reactor loading rate and retention time) by only a small margin in terms of volumetric methane production rate. This makes questionable whether the higher methane content of the biogas counterbalances the added complexity of the two-stage digestion.

Bio-conversion of water hyacinths into methane gas. Part 1. [Effects of cadmium and nickel pollution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolverton, B.C.; Mcdonald, R.C.; Gordon, J.

1974-07-01

Bio-gas and methane production from the microbial anaerobic decomposition of water hyacinths (Eichhornia crassipes) (Mart) Solms was investigated. These experiments demonstrated the ability of water hyacinths to produce an average of 13.9 ml of methane gas per gram of wet plant weight. This study revealed that sample preparation had no significant effect on bio-gas and/or methane production. Pollution of water hyacinths by two toxic heavy materials, nickel and cadmium, increased the rate of methane production from 51.8 ml/day for non-contaminated plants incubated at 36 C to 81.0 ml/day for Ni-Cd contaminated plants incubated at the same temperature. The methane contentmore » of bio-gas evolved from the anaerobic decomposition of Ni-Cd contaminated plants was 91.1 percent as compared to 69.2 percent methane content of bio-gas collected from the fermentation of non-contaminated plants. (Author) (GRA)« less

Metabolic engineering of Methanosarcina acetivorans for lactate production from methane.

PubMed

McAnulty, Michael J; Poosarla, Venkata Giridhar; Li, Jine; Soo, Valerie W C; Zhu, Fayin; Wood, Thomas K

2017-04-01

We previously demonstrated anaerobic conversion of the greenhouse gas methane into acetate using an engineered archaeon that produces methyl-coenzyme M reductase (Mcr) from unculturable microorganisms from a microbial mat in the Black Sea to create the first culturable prokaryote that reverses methanogenesis and grows anaerobically on methane. In this work, we further engineered the same host with the goal of converting methane into butanol. Instead, we discovered a process for converting methane to a secreted valuable product, L-lactate, with sufficient optical purity for synthesizing the biodegradable plastic poly-lactic acid. We determined that the 3-hydroxybutyryl-CoA dehydrogenase (Hbd) from Clostridium acetobutylicum is responsible for lactate production. This work demonstrates the first metabolic engineering of a methanogen with a synthetic pathway; in effect, we produce a novel product (lactate) from a novel substrate (methane) by cloning the three genes for Mcr and one for Hbd. We further demonstrate the utility of anaerobic methane conversion with an increased lactate yield compared to aerobic methane conversion to lactate. Biotechnol. Bioeng. 2017;114: 852-861. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Dense ceramic membranes for converting methane to syngas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balachandran, U.; Dusek, J.T.; Picciolo, J.J.

1995-07-01

Dense mixed-oxide ceramics capable of conducting both electrons and oxygen ions are promising materials for partial oxygenation of methane to syngas. We are particularly interested in an oxide based on the Sr-Fe-Co-O system. Dense ceramic membrane tubes have been fabricated by a plastic extrusion technique. The sintered tubes were then used to selectively transport oxygen from air through the membrane to make syngas without the use of external electrodes. The sintered tubes have operated for >1000 h, and methane conversion efficiencies of >98% have been observed. Mechanical properties, structural integrity of the tubes during reactor operation, results of methane conversion,more » selectivity of methane conversion products, oxygen permeation, and fabrication of multichannel configurations for large-scale production of syngas will be presented.« less

Temperature dependence of bioelectrochemical CO2 conversion and methane production with a mixed-culture biocathode.

PubMed

Yang, Hou-Yun; Bao, Bai-Ling; Liu, Jing; Qin, Yuan; Wang, Yi-Ran; Su, Kui-Zu; Han, Jun-Cheng; Mu, Yang

2018-02-01

This study evaluated the effect of temperature on methane production by CO 2 reduction during microbial electrosynthesis (MES) with a mixed-culture biocathode. Reactor performance, in terms of the amount and rate of methane production, current density, and coulombic efficiency, was compared at different temperatures. The microbial properties of the biocathode at each temperature were also analyzed by 16S rRNA gene sequencing. The results showed that the optimum temperature for methane production from CO 2 reduction in MES with a mixed-culture cathode was 50°C, with the highest amount and rate of methane production of 2.06±0.13mmol and 0.094±0.01mmolh -1 , respectively. In the mixed-culture biocathode MES, the coulombic efficiency of methane formation was within a range of 19.15±2.31% to 73.94±2.18% due to by-product formation at the cathode, including volatile fatty acids and hydrogen. Microbial analysis demonstrated that temperature had an impact on the diversity of microbial communities in the biofilm that formed on the MES cathode. Specifically, the hydrogenotrophic methanogen Methanobacterium became the predominant archaea for methane production from CO 2 reduction, while the abundance of the aceticlastic methanogen Methanosaeta decreased with increased temperature. Copyright © 2017. Published by Elsevier B.V.

Biogas reforming over multi walled carbon nanotubes with Co-Mo/MgO nanoparticles

NASA Astrophysics Data System (ADS)

Khavarian, Mehrnoush; Mohamed, Abdul Rahman

2017-12-01

The utilization of biogas for the production of valuable chemicals is among the very important processes in the energy research field. The most suitable process for biogas reforming is dry reforming of methane. An obvious drawback is the variable composition of biogas rather than the stoichiometrically equimolar quantities of methane and carbon dioxide. Moreover, activating the methane and carbon dioxide molecules in the reforming reaction provides many challenges in exploring new concepts and opportunities for development of unique catalysts. In the present work, the catalytic activity behavior of Co-Mo-MgO/multi-walled carbon nanotubes (MWCNTs) nanocomposite in dry reforming was investigated with different CO2/CH4 feed ratio to evaluate the performance of this catalyst for biogas reforming reaction. It was found that conversions of methane and carbon dioxide were greatly influenced by the feed gas ratio. The CH4 and CO2 conversions are 83 % and 87 % at the reaction temperature of 825 °C, GHSV of 175 L/h.gcat and CO2/CH4 feed ratio of unity. The minimum carbon deposition rate is observed at the CO2/CH4 feed ratio of 0.6 which is 0.080 gc/gcat-h.

ELECTROCHEMISTRY AND ON-CELL REFORMATION MODELING FOR SOLID OXIDE FUEL CELL STACKS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Recknagle, Kurtis P.; Jarboe, Daniel T.; Johnson, Kenneth I.

2007-01-16

ABSTRACT Providing adequate and efficient cooling schemes for solid-oxide-fuel-cell (SOFC) stacks continues to be a challenge coincident with the development of larger, more powerful stacks. The endothermic steam-methane reformation reaction can provide cooling and improved system efficiency when performed directly on the electrochemically active anode. Rapid kinetics of the endothermic reaction typically causes a localized temperature depression on the anode near the fuel inlet. It is desirable to extend the endothermic effect over more of the cell area and mitigate the associated differences in temperature on the cell to alleviate subsequent thermal stresses. In this study, modeling tools validated formore » the prediction of fuel use, on-cell methane reforming, and the distribution of temperature within SOFC stacks, are employed to provide direction for modifying the catalytic activity of anode materials to control the methane conversion rate. Improvements in thermal management that can be achieved through on-cell reforming is predicted and discussed. Two operating scenarios are considered: one in which the methane fuel is fully pre-reformed, and another in which a substantial percentage of the methane is reformed on-cell. For the latter, a range of catalytic activity is considered and the predicted thermal effects on the cell are presented. Simulations of the cell electrochemical and thermal performance with and without on-cell reforming, including structural analyses, show a substantial decrease in thermal stresses for an on-cell reforming case with slowed methane conversion.« less

Comparison of methane production potential, biodegradability, and kinetics of different organic substrates.

PubMed

Li, Yeqing; Zhang, Ruihong; Liu, Guangqing; Chen, Chang; He, Yanfeng; Liu, Xiaoying

2013-12-01

The methane production potential, biodegradability, and kinetics of a wide range of organic substrates were determined using a unified and simple method. Results showed that feedstocks that contained high energy density and easily degradable substrates exhibited high methane production potential and biodegradability. Lignocellulosic biomass with high content of fibrous compositions had low methane yield and biodegradability. Feedstocks with high lignin content (≥ 15%, on a TS basis) had low first-order rate constant (0.05-0.06 1/d) compared to others. A negative linear correlation between lignin content and experimental methane yield (or biodegradability) was found for lignocellulosic and manure wastes. This could be used as a fast method to predict the methane production potential and biodegradability of fiber-rich substrates. The findings of this study provided a database for the conversion efficiency of different organic substrates and might be useful for applications of biomethane potential assay and anaerobic digestion in the future. Copyright © 2013 Elsevier Ltd. All rights reserved.

Partial oxidative conversion of methane to methanol through selective inhibition of methanol dehydrogenase in methanotrophic consortium from landfill cover soil.

PubMed

Han, Ji-Sun; Ahn, Chang-Min; Mahanty, Biswanath; Kim, Chang-Gyun

2013-11-01

Using a methanotrophic consortium (that includes Methylosinus sporium NCIMB 11126, Methylosinus trichosporium OB3b, and Methylococcus capsulatus Bath) isolated from a landfill site, the potential for partial oxidation of methane into methanol through selective inhibition of methanol dehydrogenase (MDH) over soluble methane monooxygenase (sMMO) with some selected MDH inhibitors at varied concentration range, was evaluated in batch serum bottle and bioreactor experiments. Our result suggests that MDH activity could effectively be inhibited either at 40 mM of phosphate, 100 mM of NaCl, 40 mM of NH4Cl or 50 μM of EDTA with conversion ratios (moles of CH3OH produced per mole CH4 consumed) of 58, 80, 80, and 43 %, respectively. The difference between extent of inhibition in MDH activity and sMMO activity was significantly correlated (n = 6, p < 0.05) with resultant methane to methanol conversion ratio. In bioreactor study with 100 mM of NaCl, a maximum specific methanol production rate of 9 μmol/mg h was detected. A further insight with qPCR analysis of MDH and sMMO coding genes revealed that the gene copy number continued to increase along with biomass during reactor operation irrespective of presence or absence of inhibitor, and differential inhibition among two enzymes was rather the key for methanol production.

Microwave-assisted direct synthesis of butene from high-selectivity methane

NASA Astrophysics Data System (ADS)

Lu, Yi-heng; Li, Kang; Lu, Yu-wei

2017-12-01

Methane was directly converted to butene liquid fuel by microwave-induced non-oxidative catalytic dehydrogenation under 0.1-0.2 MPa. The results show that, under microwave heating in a two-stage fixed-bed reactor, in which nickel powder and NiOx-MoOy/SiO2 are used as the catalyst, the methane-hydrogen mixture is used as the raw material, with no acetylene detected. The methane conversion is more than 73.2%, and the selectivity of methane to butene is 99.0%. Increasing the hydrogen/methane feed volume ratio increases methane conversion and selectivity. Gas chromatography/electron impact ionization/mass spectrometry chromatographic analysis showed that the liquid fuel produced by methane dehydrogenation oligomerization contained 89.44% of butene, and the rest was acetic acid, ethanol, butenol and butyric acid, and the content was 1.0-3.0 wt%.

Wood biodegradation in laboratory-scale landfills.

PubMed

Wang, Xiaoming; Padgett, Jennifer M; De la Cruz, Florentino B; Barlaz, Morton A

2011-08-15

The objective of this research was to characterize the anaerobic biodegradability of major wood products in municipal waste by measuring methane yields, decay rates, the extent of carbohydrate decomposition, carbon storage, and leachate toxicity. Tests were conducted in triplicate 8 L reactors operated to obtain maximum yields. Measured methane yields for red oak, eucalyptus, spruce, radiata pine, plywood (PW), oriented strand board (OSB) from hardwood (HW) and softwood (SW), particleboard (PB) and medium-density fiberboard (MDF) were 32.5, 0, 7.5, 0.5, 6.3, 84.5, 0, 5.6, and 4.6 mL CH(4) dry g(-1), respectively. The red oak, a HW, exhibited greater decomposition than either SW (spruce and radiata), a trend that was also measured for the OSB-HW relative to OSB-SW. However, the eucalyptus (HW) exhibited toxicity. Thus, wood species have unique methane yields that should be considered in the development of national inventories of methane production and carbon storage. The current assumption of uniform biodegradability is not appropriate. The ammonia release from urea formaldehyde as present in PB and MDF could contribute to ammonia in landfill leachate. Using the extent of carbon conversion measured in this research, 0-19.9%, predicted methane production from a wood mixture using the Intergovernmental Panel for Climate Change waste model is only 7.9% of that predicted using the 50% carbon conversion default.

Batch conversion of methane to methanol using Methylosinus trichosporium OB3b as biocatalyst.

PubMed

Hwang, In Yeub; Hur, Dong Hoon; Lee, Jae Hoon; Park, Chang-Ho; Chang, In Seop; Lee, Jin Won; Lee, Eun Yeol

2015-03-01

Recently, methane has attracted much attention as an alternative carbon feedstock since it is the major component of abundant shale and natural gas. In this work, we produced methanol from methane using whole cells of Methylosinus trichosporium OB3b as the biocatalyst. M. trichosporium OB3b was cultured on NMS medium with a supply of 7:3 air/methane ratio at 30°C. The optimal concentrations of various methanol dehydrogenase inhibitors such as potassium phosphate and EDTA were determined to be 100 and 0.5 mM, respectively, for an efficient production of methanol. Sodium formate (40 mM) as a reducing power source was added to enhance the conversion efficiency. A productivity of 49.0 mg/l·h, titer of 0.393 g methanol/l, and conversion of 73.8% (mol methanol/mol methane) were obtained under the optimized batch condition.

Determination of Chemical Kinetic Rate Constants of a Model for Carbothermal Processing of Lunar Regolith Simulant Using Methane

NASA Technical Reports Server (NTRS)

Balasubramaniam, R; Gokoglu, S.; Hegde, U.

2009-01-01

We have previously developed a chemical conversion model of the carbothermal processing of lunar regolith using methane to predict the rate of production of carbon monoxide. In this carbothermal process, gaseous methane is pyrolyzed as it flows over the hot surface of a molten zone of lunar regolith and is converted to carbon and hydrogen. Hydrogen is carried away by the exiting stream of gases and carbon is deposited on the melt surface. The deposited carbon mixes with the melt and reacts with the metal oxides in it to produce carbon monoxide that bubbles out of the melt. In our model, we assume that the flux of carbon deposited is equal to the product of the surface reaction rate constant gamma and the concentration of methane adjacent to the melt surface. Similarly, the rate of consumption of carbon per unit volume in the melt is equal to the product of the melt reaction rate constant k and the concentrations of carbon and metal oxide in the melt. In this paper, we describe our effort to determine gamma and k by comparison of the predictions from our model with test data obtained by ORBITEC (Orbital Technologies Corporation). The concentration of methane adjacent to the melt surface is a necessary input to the model. It is inferred from the test data by a mass balance of methane, adopting the usual assumptions of the continuously-stirred-tank-reactor model, whereby the average concentration of a given gaseous species equals its exit concentration. The reaction rates gamma and k have been determined by a non-linear least-squares fit to the test data for the production of carbon monoxide and the fraction of the incoming methane that is converted. The comparison of test data with our model predictions using the determined chemical kinetic rate constants provides a consistent interpretation of the process over the full range of temperatures, pressures, and methane flow rates used in the tests, thereby increasing our confidence to use the model for scale-up purposes.

High rates of anaerobic oxidation of methane, ethane and propane coupled to thiosulphate reduction.

PubMed

Suarez-Zuluaga, Diego A; Weijma, Jan; Timmers, Peer H A; Buisman, Cees J N

2015-03-01

Anaerobic methane oxidation coupled to sulphate reduction and the use of ethane and propane as electron donors by sulphate-reducing bacteria represent new opportunities for the treatment of streams contaminated with sulphur oxyanions. However, growth of microbial sulphate-reducing populations with methane, propane or butane is extremely slow, which hampers research and development of bioprocesses based on these conversions. Thermodynamic calculations indicate that the growth rate with possible alternative terminal electron acceptors such as thiosulphate and elemental sulphur may be higher, which would facilitate future research. Here, we investigate the use of these electron acceptors for oxidation of methane, ethane and propane, with marine sediment as inoculum. Mixed marine sediments originating from Aarhus Bay (Denmark) and Eckernförde Bay (Germany) were cultivated anaerobically at a pH between 7.2 and 7.8 and a temperature of 15 °C in the presence of methane, ethane and propane and various sulphur electron acceptors. The sulphide production rates in the conditions with methane, ethane and propane with sulphate were respectively 2.3, 2.2 and 1.8 μmol S L(-1) day(-1). For sulphur, no reduction was demonstrated. For thiosulphate, the sulphide production rates were up to 50 times higher compared to those of sulphate, with 86.2, 90.7 and 108.1 μmol S L(-1) day(-1) for methane, ethane and propane respectively. This sulphide production was partly due to disproportionation, 50 % for ethane but only 7 and 14 % for methane and propane respectively. The oxidation of the alkanes in the presence of thiosulphate was confirmed by carbon dioxide production. This is, to our knowledge, the first report of thiosulphate use as electron acceptor with ethane and propane as electron donors. Additionally, these results indicate that thiosulphate is a promising electron acceptor to increase start-up rates for sulphate-reducing bioprocesses coupled to short-chain alkane oxidation.

Diagnostic studies of H2 Ar N2 microwave plasmas containing methane or methanol using tunable infrared diode laser absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hempel, F.; Davies, P. B.; Loffhagen, D.; Mechold, L.; Röpcke, J.

2003-11-01

Tunable infrared diode laser absorption spectroscopy has been used to detect the methyl radical and nine stable molecules, CH4, CH3OH, C2H2, C2H4, C2H6, NH3, HCN, CH2O and C2N2, in H2-Ar-N2 microwave plasmas containing up to 7% of methane or methanol, under both flowing and static conditions. The degree of dissociation of the hydrocarbon precursor molecules varied between 20% and 97%. The methyl radical concentration was found to be in the range 1012-1013 molecules cm-3. By analysing the temporal development of the molecular concentrations under static conditions it was found that HCN and NH3 are the final products of plasma chemical conversion. The fragmentation rates of methane and methanol (RF(CH4) = (2-7) × 1015 molecules J-1, RF(CH3OH) = (6-9) × 1015 molecules J-1) and the respective conversion rates to methane, hydrogen cyanide and ammonia (RCmax(CH4) = 1.2 × 1015 molecules J-1, RCmax(HCN) = 1.3 × 1015 molecules J-1, RCmax(NH3) = 1 × 1014 molecules J-1) have been determined for different hydrogen to nitrogen concentration ratios. An extensive model of the chemical reactions involved in the H2-N2-Ar-CH4 plasma has been developed. Model calculations were performed by including 22 species, 145 chemical reactions and appropriate electron impact dissociation rate coefficients. The results of the model calculations showed satisfactory agreement between calculated and measured concentrations. The most likely main chemical pathways involved in these plasmas are discussed and an appropriate reaction scheme is proposed.

Potential use and the energy conversion efficiency analysis of fermentation effluents from photo and dark fermentative bio-hydrogen production.

PubMed

Zhang, Zhiping; Li, Yameng; Zhang, Huan; He, Chao; Zhang, Quanguo

2017-12-01

Effluent of bio-hydrogen production system also can be adopted to produce methane for further fermentation, cogeneration of hydrogen and methane will significantly improve the energy conversion efficiency. Platanus Orientalis leaves were taken as the raw material for photo- and dark-fermentation bio-hydrogen production. The resulting concentrations of acetic, butyric, and propionic acids and ethanol in the photo- and dark-fermentation effluents were 2966mg/L and 624mg/L, 422mg/L and 1624mg/L, 1365mg/L and 558mg/L, and 866mg/L and 1352mg/L, respectively. Subsequently, we calculated the energy conversion efficiency according to the organic contents of the effluents and their energy output when used as raw material for methane production. The overall energy conversion efficiencies increased by 15.17% and 22.28%, respectively, when using the effluents of photo and dark fermentation. This two-step bio-hydrogen and methane production system can significantly improve the energy conversion efficiency of anaerobic biological treatment plants. Copyright © 2017. Published by Elsevier Ltd.

Methane Conversion to Ethylene and Aromatics on PtSn Catalysts

DOE PAGES

Gerceker, Duygu; Motagamwala, Ali Hussain; Rivera-Dones, Keishla R.; ...

2017-02-03

Pt and PtSn catalysts supported on SiO 2 and H-ZSM-5 were studied for methane conversion under nonoxidative conditions. Addition of Sn to Pt/SiO 2 increased the turnover frequency for production of ethylene by a factor of 3, and pretreatment of the catalyst at 1123 K reduced the extent of coke formation. Pt and PtSn catalysts supported on H-ZSM-5 zeolite were prepared to improve the activity and selectivity to non-coke products. Ethylene formation rates were 20 times faster over a PtSn(1:3)/H-ZSM-5 catalyst with SiO 2:Al 2O 3 = 280 in comparison to those over PtSn(3:1)/SiO 2. H-ZSM-5-supported catalysts were also activemore » for the formation of aromatics, and the rates of benzene and naphthalene formation were increased by using more acidic H-ZSM-5 supports. These catalysts operate through a bifunctional mechanism, in which ethylene is first produced on highly dispersed PtSn nanoparticles and then is subsequently converted to benzene and naphthalene on Brønsted acid sites within the zeolite support. The most active and stable PtSn catalyst forms carbon products at a rate, 2.5 mmol of C/((mol of Pt) s), which is comparable to that of state-of-the-art Mo/H-ZSM-5 catalysts with same metal loading operated under similar conditions (1.8 mmol of C/((mol of Mo) s)). Scanning transmission electron microscopy measurements suggest the presence of smaller Pt nanoparticles on H-ZSM-5-supported catalysts, in comparison to SiO 2-supported catalysts, as a possible source of their high activity. As a result, a microkinetic model of methane conversion on Pt and PtSn surfaces, built using results from density functional theory calculations, predicts higher coupling rates on bimetallic and stepped surfaces, supporting the experimental observations that relate the high catalytic activity to small PtSn particles.« less

Methane Pyrolysis and Disposing Off Resulting Carbon

NASA Technical Reports Server (NTRS)

Sharma, P. K.; Rapp, D.; Rahotgi, N. K.

1999-01-01

Sabatier/Electrolysis (S/E) is a leading process for producing methane and oxygen for application to Mars ISPP. One significant problem with this process is that it produces an excess of methane for combustion with the amount of oxygen that is produced. Therefore, one must discard roughly half of the methane to obtain the proper stoichiometric methane/oxygen mixture for ascent from Mars. This is wasteful of hydrogen, which must be brought from Earth and is difficult to transport to Mars and store on Mars. To reduced the problem of transporting hydrogen to Mars, the S/E process can be augmented by another process which reduces overall hydrogen requirement. Three conceptual approaches for doing this are (1) recover hydrogen from the excess methane produced by the S/E process, (2) convert the methane to a higher hydrocarbon or other organic with a lower H/C ratio than methane, and (3) use a separate process (such as zirconia or reverse water gas shift reaction) to produce additional oxygen, thus utilizing all the methane produced by the Sabatier process. We report our results here on recovering hydrogen from the excess methane using pyrolysis of methane. Pyrolysis has the advantage that it produces almost pure hydrogen, and any unreacted methane can pass through the S/E process reactor. It has the disadvantage that disposing of the carbon produced by pyrolysis presents difficulties. Hydrogen may be obtained from methane by pyrolysis in the temperature range 10000-12000C. The main reaction products are hydrogen and carbon, though very small amounts of higher hydrocarbons, including aromatic hydrocarbons are formed. The conversion efficiency is about 95% at 12000C. One needs to distinguish between thermodynamic equilibrium conversion and conversion limited by kinetics in a finite reactor.

Oxidative coupling of methane using inorganic membrane reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Y.H.; Moser, W.R.; Dixon, A.G.

1995-12-31

The goal of this research is to improve the oxidative coupling of methane in a catalytic inorganic membrane reactor. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and relatively higher yields than in fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gasmore » phase reactions, which are believed to be a main route for formation of CO{sub x} products. Such gas phase reactions are a cause for decreased selectivity in oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Modeling work which aimed at predicting the observed experimental trends in porous membrane reactors was also undertaken in this research program.« less

CO2 Injection Into CH4 Hydrate Reservoirs: Quantifying Controls of Micro-Scale Processes

NASA Astrophysics Data System (ADS)

Bigalke, N. K.; Deusner, C.; Kossel, E.; Haeckel, M.

2014-12-01

The exchangeability of methane for carbon dioxide in gas hydrates opens the possibility of producing emission-neutral hydrocarbon energy. Recent field tests have shown that the production of natural gas from gas hydrates is feasible via injection of carbon dioxide into sandy, methane-hydrate-bearing sediment strata. Industrial-scale application of this method requires identification of thermo- and fluid-dynamic as well as kinetic controls on methane yield from and carbon dioxide retention within the reservoir. Extraction of gas via injection of carbon dioxide into the hydrate reservoir triggers a number of macroscopic effects, which are revealed for example by changes of the hydraulic conductivity and geomechanical stability. Thus far, due to analytical limitations, localized reactions and fluid-flow phenomena held responsible for these effects remain unresolved on the microscale (1 µm - 1 mm) and at near-natural reservoir conditions. We address this deficit by showing results from high-resolution, two-dimensional Raman spectroscopy mappings of an artificial hydrate reservoir during carbon dioxide injection under realistic reservoir conditions. The experiments allow us to resolve hydrate conversion rate and efficiency as well as activation of fluid pathways in space and time and their effect on methane yield, carbon-dioxide retention and hydraulic conductivity of the reservoir. We hypothesize that the conversion of single hydrate grains is a diffusion-controlled process which starts at the grain surface before continuing into the grain interior and show that the conversion can be modeled simply by using published permeation coefficients for CO2 and CH4 in hydrate and grain size as only input parameters.

Nanoceria Supported Single-Atom Platinum Catalysts for Direct Methane Conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Pengfei; Pu, Tiancheng; Nie, Anmin

Nanoceria-supported atomic Pt catalysts (denoted as Pt 1@CeO 2) have been synthesized and demonstrated with advanced catalytic performance for the non-oxidative, direct conversion of methane. These catalysts were synthesized by calcination of Pt-impregnated porous ceria nanoparticles at high temperature (ca. 1,000 °C), with the atomic dispersion of Pt characterized by combining aberra-tion-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectroscopy (XPS), X-ray absorption spec-troscopy (XAS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analyses. The Pt 1@CeO 2 catalysts exhibited much superior catalytic performance to its nanoparticulated counterpart, achieving 14.4% of methane conversion at 975 °C andmore » 74.6% selectivity toward C 2 products (ethane, ethylene and acetylene). Comparative studies of the Pt1@CeO 2 catalysts with different loadings as well as the nanoparticulated counterpart reveal the single-atom Pt to be the active sites for selective conversion of methane into C 2 hydrocarbons.« less

Nanoceria Supported Single-Atom Platinum Catalysts for Direct Methane Conversion

DOE PAGES

Xie, Pengfei; Pu, Tiancheng; Nie, Anmin; ...

2018-04-03

Nanoceria-supported atomic Pt catalysts (denoted as Pt 1@CeO 2) have been synthesized and demonstrated with advanced catalytic performance for the non-oxidative, direct conversion of methane. These catalysts were synthesized by calcination of Pt-impregnated porous ceria nanoparticles at high temperature (ca. 1,000 °C), with the atomic dispersion of Pt characterized by combining aberra-tion-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectroscopy (XPS), X-ray absorption spec-troscopy (XAS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analyses. The Pt 1@CeO 2 catalysts exhibited much superior catalytic performance to its nanoparticulated counterpart, achieving 14.4% of methane conversion at 975 °C andmore » 74.6% selectivity toward C 2 products (ethane, ethylene and acetylene). Comparative studies of the Pt1@CeO 2 catalysts with different loadings as well as the nanoparticulated counterpart reveal the single-atom Pt to be the active sites for selective conversion of methane into C 2 hydrocarbons.« less

High performance biological methanation in a thermophilic anaerobic trickle bed reactor.

PubMed

Strübing, Dietmar; Huber, Bettina; Lebuhn, Michael; Drewes, Jörg E; Koch, Konrad

2017-12-01

In order to enhance energy efficiency of biological methanation of CO 2 and H 2 , this study investigated the performance of a thermophilic (55°C) anaerobic trickle bed reactor (ATBR) (58.1L) at ambient pressure. With a methane production rate of up to 15.4m 3 CH4 /(m 3 trickle bed ·d) at methane concentrations above 98%, the ATBR can easily compete with the performance of other mixed culture methanation reactors. Control of pH and nutrient supply turned out to be crucial for stable operation and was affected significantly by dilution due to metabolic water production, especially during demand-orientated operation. Considering practical applications, inoculation with digested sludge, containing a diverse biocenosis, showed high adaptive capacity due to intrinsic biological diversity. However, no macroscopic biofilm formation was observed at thermophilic conditions even after 313days of operation. The applied approach illustrates the high potential of thermophilic ATBRs as a very efficient energy conversion and storage technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

2015-16 ENSO Drove Tropical Soil Moisture Dynamics and Methane Fluxes

NASA Astrophysics Data System (ADS)

Aronson, E. L.; Dierick, D.; Botthoff, J.; Swanson, A. C.; Johnson, R. F.; Allen, M. F.

2017-12-01

The El Niño/Southern Oscillation Event (ENSO) cycle drives large-scale climatic trends globally. Within the new world tropics, El Niño brings dryer weather than the counterpart La Niña. Atmospheric methane growth rates have shown extreme variability over the past three decades. One proposed driver is the proportion of tropical land surface saturated, affecting methane production or consumption. We measured methane flux bimonthly through the transition of 2015-16 ENSO. The date of measurement, across El Niño and La Niña within the typical "rainy" and "dry" seasons, to be the most significant driver of methane flux. Soil moisture varied across this time period, and regulated methane flux. During the strong El Niño, extreme dry soil conditions occurred in a typical "rainy" season month reducing soil moisture. Wetter than usual soil conditions appeared during the "rainy" season month of the moderate La Niña. The dry El Niño soils corresponded to greater methane consumption by tropical forest soils, and a reduced local atmospheric column methane concentration. Conversely, the wet La Niña soils had lower methane consumption and higher local atmospheric column methane concentrations. The ENSO cycle is a strong driver of tropical terrestrial and wetland soil moisture conditions, and can regulate global atmospheric methane dynamics.

Evaluating biochemical methane production from brewer's spent yeast.

PubMed

Sosa-Hernández, Ornella; Parameswaran, Prathap; Alemán-Nava, Gibrán Sidney; Torres, César I; Parra-Saldívar, Roberto

2016-09-01

Anaerobic digestion treatment of brewer's spent yeast (SY) is a viable option for bioenergy capture. The biochemical methane potential (BMP) assay was performed with three different samples (SY1, SY2, and SY3) and SY1 dilutions (75, 50, and 25 % on a v/v basis). Gompertz-equation parameters denoted slow degradability of SY1 with methane production rates of 14.59-4.63 mL/day and lag phases of 10.72-19.7 days. Performance and kinetic parameters were obtained with the Gompertz equation and the first-order hydrolysis model with SY2 and SY3 diluted 25 % and SY1 50 %. A SY2 25 % gave a 17 % of TCOD conversion to methane as well as shorter lag phase (<1 day). Average estimated hydrolysis constant for SY was 0.0141 (±0.003) day(-1), and SY2 25 % was more appropriate for faster methane production. Methane capture and biogas composition were dependent upon the SY source, and co-digestion (or dilution) can be advantageous.

Microwave-assisted direct synthesis of butene from high-selectivity methane

PubMed Central

Li, Kang; Lu, Yu-wei

2017-01-01

Methane was directly converted to butene liquid fuel by microwave-induced non-oxidative catalytic dehydrogenation under 0.1–0.2 MPa. The results show that, under microwave heating in a two-stage fixed-bed reactor, in which nickel powder and NiOx–MoOy/SiO2 are used as the catalyst, the methane–hydrogen mixture is used as the raw material, with no acetylene detected. The methane conversion is more than 73.2%, and the selectivity of methane to butene is 99.0%. Increasing the hydrogen/methane feed volume ratio increases methane conversion and selectivity. Gas chromatography/electron impact ionization/mass spectrometry chromatographic analysis showed that the liquid fuel produced by methane dehydrogenation oligomerization contained 89.44% of butene, and the rest was acetic acid, ethanol, butenol and butyric acid, and the content was 1.0–3.0 wt%. PMID:29308261

Enzyme-Embedded, Microstructural Reactors for Industrial Biocatalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker, Sarah E.; Knipe, J. M.; Oakdale, J.

In this project we explored enzyme-catalyzed methane conversion to methanol. Industrial biological approaches to methane conversion using whole organisms are predicted to be more energy efficient than chemical approaches, but are limited by mass transfer of the gas phase reactants, methane and oxygen, to the organisms. We demonstrated that 3D printing the enzyme particulate Methane Mono Oxygenase (pMMO) embedded in a polymer can improve the kinetics of methane to methanol conversion. This improvement was likely due to the ability to increase the surface area of the catalytic material using 3D printing. We also demonstrated the first continuous use of pMMOmore » in a flow-through reactor. In order to understand the fundamental kinetic properties of pMMO, we conducted an in-depth study of pMMO kinetics using analytical tools developed in our lab. Finally, we developed a new copolymer system that allowed tuning of the gas permeability of the biocatalytic material.« less

Catalytic conversion of methane to methanol using Cu-zeolites.

PubMed

Alayon, Evalyn Mae C; Nachtegaal, Maarten; Ranocchiari, Marco; van Bokhoven, Jeroen A

2012-01-01

The conversion of methane to value-added liquid chemicals is a promising answer to the imminent demand for fuels and chemical synthesis materials in the advent of a dwindling petroleum supply. Current technology requires high energy input for the synthesis gas production, and is characterized by low overall selectivity, which calls for alternative reaction routes. The limitation to achieve high selectivity is the high C-H bond strength of methane. High-temperature reaction systems favor gas-phase radical reactions and total oxidation. This suggests that the catalysts for methane activation should be active at low temperatures. The enzymatic-inspired metal-exchanged zeolite systems apparently fulfill this need, however, methanol yield is low and a catalytic process cannot yet be established. Homogeneous and heterogeneous catalytic systems have been described which stabilize the intermediate formed after the first C-H activation. The understanding of the reaction mechanism and the determination of the active metal sites are important for formulating strategies for the upgrade of methane conversion catalytic technologies.

40 CFR 98.366 - Data reporting requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... type). (11) Methane conversion factor used for each MMS component. (12) Average ambient temperature used to select each methane conversion factor. (13) N2O emissions (results of Equation JJ-13). (14) N... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Manure Management § 98.366 Data reporting requirements. (a) In...

40 CFR 98.366 - Data reporting requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... type). (11) Methane conversion factor used for each MMS component. (12) Average ambient temperature used to select each methane conversion factor. (13) N2O emissions (results of Equation JJ-13). (14) N... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Manure Management § 98.366 Data reporting requirements. (a) In...

40 CFR 98.366 - Data reporting requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... type). (11) Methane conversion factor used for each MMS component. (12) Average ambient temperature used to select each methane conversion factor. (13) N2O emissions (results of Equation JJ-13). (14) N... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Manure Management § 98.366 Data reporting requirements. (a) In...

40 CFR 98.366 - Data reporting requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... type). (11) Methane conversion factor used for each MMS component. (12) Average ambient temperature used to select each methane conversion factor. (13) N2O emissions (results of Equation JJ-13). (14) N... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Manure Management § 98.366 Data reporting requirements. (a) In...

Production of Renewable Natural Gas from Waste Biomass

NASA Astrophysics Data System (ADS)

Kumar, Sachin; Suresh, S.; Arisutha, S.

2013-03-01

Biomass energy is expected to make a major contribution to the replacement of fossil fuels. Methane produced from biomass is referred to as bio-methane, green gas, bio-substitute natural gas or renewable natural gas (RNG) when it is used as a transport fuel. Research on upgrading of the cleaned producer gas to RNG is still ongoing. The present study deals with the conversion of woody biomass into fuels, RNG using gasifier. The various effects of parameters like temperature, pressure, and tar formation on conversion were also studied. The complete carbon conversion was observed at 480 °C and tar yield was significantly less. When biomass was gasified with and without catalyst at about 28 s residence time, ~75 % (w/w) and 88 % (w/w) carbon conversion for without and with catalyst was observed. The interest in RNG is growing; several initiatives to demonstrate the thermal-chemical conversion of biomass into methane and/or RNG are under development.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Warren, B.K.; Campbell, K.D.

Methane oxidative coupling studies were carried out in an atmospheric quartz reactor at temperatures between 700 and 800/degree/C. New catalysts prepared and studied included doped alkaline earth catalysts, lanthanide oxides, and proprietary catalysts. Neodymium oxide, Nd/sub 2/O/sub 3/, was found to be as active and selective as samarium oxide, Sm/sub 2/O/sub 3/, in contrast to literature reports. Proprietary Union Carbide catalysts (UCC-S:1) showed initial methane conversions and C/sub 2/ selectivities comparable to literature catalysts. Atypically low carbon dioxide to carbon monoxide ratios (typically ten times lower than those seen in the literature or other catalysts tested) and high ethylene tomore » ethane ratios (3 to 6 compared to typical literature ratios below 1) were obtained. These results are interesting because ethylene is more valuable than ethane and carbon monoxide is more valuable than carbon dioxide. With these UCC-S:1 catalysts, rapid deactivation was coupled with an observed shift in product ratios toward those more typical in the literature. Initial cases for process conceptualization studies were selected. The Comparison Case will consist of the conversion sequence from methane to synthesis gas to methanol to olefins to liquid hydrocarbon fuels. Case 1 will consist of the conversion of methane to ethylene and ethane. Case 2 will be the direct conversion of methane to C/sub 2/'s followed by conversion to liquid hydrocarbon fuels. 7 figs., 18 tabs.« less

A novel process for volatile fatty acids production from syngas by integrating with mesophilic alkaline fermentation of waste activated sludge.

PubMed

Rao, Yue; Wan, Jingjing; Liu, Yafeng; Angelidaki, Irini; Zhang, Shicheng; Zhang, Yalei; Luo, Gang

2018-08-01

The present study proposed and demonstrated a novel process for the bioconversion of syngas (mainly CO and H 2 ) to valuable volatile fatty acids (VFA) by integrating with mesophilic alkaline fermentation of waste activated sludge (WAS). The results showed that although pH 9 was suitable for VFA production from WAS, 62.5% of the consumed CO was converted to methane due to the presence of hydrogenogenic pathway for CO conversion. The increase of pH from 9 to 9.5 inhibited the methane production from CO because of the possible presence of only acetogenic pathway for CO conversion. However, methane was still produced from H 2 contained in syngas through hydrogenotrophic methanogenesis, and around 32-34% of the consumed syngas was converted to methane. At both pH 9 and 9.5, methane was produced by hydrogenotrophic methanogens Methanobacteriales. Further increase of pH to 10 effectively inhibited methane production from syngas, and efficient VFA (mainly acetate with the concentration of around 135 mM) production by simultaneous conversion of syngas and WAS was achieved. High acetate concentrations (>150 mM) were shown to have serious negative effects on the conversion of syngas. The addition of syngas to the mesophilic alkaline fermentation of WAS at pH 10 not only resulted in the enrichment of some known bacteria related with syngas conversion, but also changed the microbial community compositions for the fermentation of WAS. Copyright © 2018 Elsevier Ltd. All rights reserved.

Process Parameters for Successful Synthesis of Carbon Nanotubes by Chemical Vapor Deposition: Implications for Chemical Mechanisms and Life-cycle Assessment

NASA Astrophysics Data System (ADS)

Xue, Ke

Manufacturing of carbon nanotubes (CNTs) via chemical vapor deposition (CVD) calls for thermal treatment associated with gas-phase rearrangement and catalyst deposition to achieve high cost efficiency and limited influence on environmental impact. Taking advantage of higher degree of structure control and economical efficiency, catalytic chemical vapor deposition (CCVD) has currently become the most prevailing synthesis approach for the synthesis of large-scale pure CNTs in past years. Because the synthesis process of CNTs dominates the potential ecotoxic impacts, materials consumption, energy consumption and greenhouse gas emissions should be further limited to efficiently reduce life cycle ecotoxicity of carbon naotubes. However, efforts to reduce energy and material requirements in synthesis of CNTs by CCVD are hindered by a lack of mechanistic understanding. In this thesis, the effect of operating parameters, especially the temperature, carbon source concentration, and residence time on the synthesis were studied to improve the production efficiency in a different angle. Thus, implications on the choice of operating parameters could be provided to help the synthesis of carbon nanotubes. Here, we investigated the typical operating parameters in conditions that have yielded successful CNT production in the published academic literature of over seventy articles. The data were filtered by quality of the resultant product and deemed either "successful" or "unsuccessful" according to the authors. Furthermore, growth rate data were tabulated and used as performance metric for the process whenever possible. The data provided us an opportunity to prompt possible and common methods for practioners in the synthesis of CNTs and motivate routes to achieve energy and material minimization. The statistical analysis revealed that methane and ethylene often rely on thermal conversion process to form direct carbon precursor; further, methane and ethylene could not be the direct CNT precursors by themselves. Acetylene does not show an additional energy demand or thermal conversion in the synthesis, and it could be the direct CNT precursors by itself; or at least, it would be most easily to get access to carbon nanotube growth while minimizing synthesis temperature. In detail, methane employs more energy demand (Tavg=883°C) than ethylene (Tavg=766°C), which in turn demands more energy than acetylene (Tavg=710°C) to successfully synthesize carbon nanotubes. The distinction in energy demand could be the result of kinetic energy requirements by the thermal conversion process of methane and ethylene to form direct CNT precursors, and methane employs the highest activation demand among three hydrocarbons. Thus, these results support the hypothesis that methane and ethylene could be thermally converted to form acetylene before CNT incorporation. In addition, methane and ethylene show the demand for hydrogen in thermal conversion process before CNT incorporation; whereas, hydrogen does not contribute to the synthesis via acetylene before CNT incorporation, except the reduction of catalyst. At relatively low hydrogen concentration, this work suggests that hydrogen prompts growth of carbon nanotubes via methane and ethylene, probably by reducing the catalysts or participating thermal reactions. In addition, "polymerization-like formation mechanism" could be supported by the higher growth rate of CNTs via ethylene than acetylene. There could be an optimum residence time to maintain a relatively higher growth rate. At too low residence time, carbon source could not be accumulated, causing a waste of material; while too high residence time may cause the limitation of carbon source supplement and accumulation of byproducts. At last, high concentration of carbon source and hydrogen could cause more energy consumption, while it helps to achieve a high growth rate, due to the more presence of direct carbon precursor.

Methane Production by Microbial Mats Under Low Sulfate Concentrations

NASA Technical Reports Server (NTRS)

Bebout, Brad M.; Hoehler, Tori M.; Thamdrup, Bo; Albert, Dan; Carpenter, Steven P.; Hogan, Mary; Turk, Kendra; DesMarais, David J.

2003-01-01

Cyanobacterial mats collected in hypersaline salterns were incubated in a greenhouse under low sulfate concentrations ([SO4]) and examined for their primary productivity and emissions of methane and other major carbon species. Atmospheric greenhouse warming by gases such as carbon dioxide and methane must have been greater during the Archean than today in order to account for a record of moderate to warm paleoclemates, despite a less luminous early sun. It has been suggested that decreased levels of oxygen and sulfate in Archean oceans could have significantly stimulated microbial methanogenesis relative to present marine rates, with a resultant increase in the relative importance of methane in maintaining the early greenhouse. We maintained modern microbial mats, models of ancient coastal marine communities, in artificial brine mixtures containing both modern [SO4=] (ca. 70 mM) and "Archean" [SO4] (less than 0.2 mM). At low [SO4], primary production in the mats was essentially unaffected, while rates of sulfate reduction decreased by a factor of three, and methane fluxes increased by up to ten-fold. However, remineralization by methanogenesis still amounted to less than 0.4 % of the total carbon released by the mats. The relatively low efficiency of conversion of photosynthate to methane is suggested to reflect the particular geometry and chemical microenvironment of hypersaline cyanobacterial mats. Therefore, such mats w-ere probably relatively weak net sources of methane throughout their 3.5 Ga history, even during periods of low- environmental levels oxygen and sulfate.

Transition metal sulfide loaded catalyst

DOEpatents

Maroni, Victor A.; Iton, Lennox E.; Pasterczyk, James W.; Winterer, Markus; Krause, Theodore R.

1994-01-01

A zeolite based catalyst for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C.sub.2 + hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

Granular Carbon-Based Electrodes as Cathodes in Methane-Producing Bioelectrochemical Systems

PubMed Central

Liu, Dandan; Roca-Puigros, Marta; Geppert, Florian; Caizán-Juanarena, Leire; Na Ayudthaya, Susakul P.; Buisman, Cees; ter Heijne, Annemiek

2018-01-01

Methane-producing bioelectrochemical systems generate methane by using microorganisms to reduce carbon dioxide at the cathode with external electricity supply. This technology provides an innovative approach for renewable electricity conversion and storage. Two key factors that need further attention are production of methane at high rate, and stable performance under intermittent electricity supply. To study these key factors, we have used two electrode materials: granular activated carbon (GAC) and graphite granules (GG). Under galvanostatic control, the biocathodes achieved methane production rates of around 65 L CH4/m2catproj/d at 35 A/m2catproj, which is 3.8 times higher than reported so far. We also operated all biocathodes with intermittent current supply (time-ON/time-OFF: 4–2′, 3–3′, 2–4′). Current-to-methane efficiencies of all biocathodes were stable around 60% at 10 A/m2catproj and slightly decreased with increasing OFF time at 35 A/m2catproj, but original performance of all biocathodes was recovered soon after intermittent operation. Interestingly, the GAC biocathodes had a lower overpotential than the GG biocathodes, with methane generation occurring at −0.52 V vs. Ag/AgCl for GAC and at −0.92 V for GG at a current density of 10 A/m2catproj. 16S rRNA gene analysis showed that Methanobacterium was the dominant methanogen and that the GAC biocathodes experienced a higher abundance of proteobacteria than the GG biocathodes. Both cathode materials show promise for the practical application of methane-producing BESs. PMID:29946543

Methane production by anaerobic digestion of Bermuda grass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klass, D.L.; Ghosh, S.

1981-01-01

Bermuda grass (Cynodon dactylon) is one of the high-yield warm-season grasses that has been suggested as a promising raw material for conversion to methane. Experimental work performed with laboratory digesters to study the anaerobic digestion of Coastal Bermuda grass harvested in Louisiana and having a C/N ratio of 24 is described. Methane yields of about 1.9 SCF/lb of volatile solids (VS) added were observed under conventional mesophilic high-rate conditions. When supplemental nitrogen additions were made, the methane yields increased. This observation along with the compositional data compiled on the grass used in this work indicated that the nitrogen content ofmore » the unsupplemented grass was insufficient to sustain high-rate digestion at the higher yield level. However, as the C/N ratio was reduced by addition of ammonium chloride, the methane yield continually increased up to 3.5 SCF/lb added at the lowest C/N ratio examined (6.3) even after relatively high concentrations of ammonium nitrogen were measured in the effluent. It appears that the added nutrient had a stimulatory effect on methane production above the point where nitrogen was not limiting. Thermophilic digestion with supplemental nitrogen additions afforded methane yields of about 2.7 SCF/lb VS added. Carbon and energy balances were calculated and the relative biodegradabilities of the organics were estimated. It was concluded from this work that Coastal Bermuda grass can be converted to high-methane gas under conventional anaerobic digestion conditions. The performance of the particular lot of grass studied was substantially improved by supplemental nitrogen additions. (Refs. 12).« less

Kinetics of (reversible) internal reforming of methane in solid oxide fuel cells under stationary and APU conditions

NASA Astrophysics Data System (ADS)

Timmermann, H.; Sawady, W.; Reimert, R.; Ivers-Tiffée, E.

The internal reforming of methane in a solid oxide fuel cell (SOFC) is investigated and modeled for flow conditions relevant to operation. To this end, measurements are performed on anode-supported cells (ASC), thereby varying gas composition (y CO = 4-15%, yH2 = 5 - 17 % , yCO2 = 6 - 18 % , yH2O = 2 - 30 % , yCH4 = 0.1 - 20 %) and temperature (600-850 °C). In this way, operating conditions for both stationary applications (methane-rich pre-reformate) as well as for auxiliary power unit (APU) applications (diesel-POX reformate) are represented. The reforming reaction is monitored in five different positions alongside the anodic gas channel by means of gas chromatography. It is shown that methane is converted in the flow field for methane-rich gas compositions, whereas under operation with diesel reformate the direction of the reaction is reversed for temperatures below 675 °C, i.e. (exothermic) methanation occurs along the anode. Using a reaction model, a rate equation for reforming could be derived which is also valid in the case of methanation. By introducing this equation into the reaction model the methane conversion along a catalytically active Ni-YSZ cermet SOFC anode can be simulated for the operating conditions specified above.

Simultaneous hydrogen utilization and in situ biogas upgrading in an anaerobic reactor.

PubMed

Luo, Gang; Johansson, Sara; Boe, Kanokwan; Xie, Li; Zhou, Qi; Angelidaki, Irini

2012-04-01

The possibility of converting hydrogen to methane and simultaneous upgrading of biogas was investigated in both batch tests and fully mixed biogas reactor, simultaneously fed with manure and hydrogen. Batch experiments showed that hydrogen could be converted to methane by hydrogenotrophic methanogenesis with conversion of more than 90% of the consumed hydrogen to methane. The hydrogen consumption rates were affected by both P(H₂) (hydrogen partial pressure) and mixing intensity. Inhibition of propionate and butyrate degradation by hydrogen (1 atm) was only observed under high mixing intensity (shaking speed 300 rpm). Continuous addition of hydrogen (flow rate of 28.6 mL/(L/h)) to an anaerobic reactor fed with manure, showed that more than 80% of the hydrogen was utilized. The propionate and butyrate level in the reactor was not significantly affected by the hydrogen addition. The methane production rate of the reactor with H₂ addition was 22% higher, compared to the control reactor only fed with manure. The CO₂ content in the produced biogas was only 15%, while it was 38% in the control reactor. However, the addition of hydrogen resulted in increase of pH (from 8.0 to 8.3) due to the consumption of bicarbonate, which subsequently caused slight inhibition of methanogenesis. Copyright © 2011 Wiley Periodicals, Inc.

Transition metal sulfide loaded catalyst

DOEpatents

Maroni, V.A.; Iton, L.E.; Pasterczyk, J.W.; Winterer, M.; Krause, T.R.

1994-04-26

A zeolite-based catalyst is described for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C[sub 2]+ hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

Magnesium carbide synthesis from methane and magnesium oxide - a potential methodology for natural gas conversion to premium fuels and chemicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Diaz, A.F.; Modestino, A.J.; Howard, J.B.

1995-12-31

Diversification of the raw materials base for manufacturing premium fuels and chemicals offers U.S. and international consumers economic and strategic benefits. Extensive reserves of natural gas in the world provide a valuable source of clean gaseous fuel and chemical feedstock. Assuming the availability of suitable conversion processes, natural gas offers the prospect of improving flexibility in liquid fuels and chemicals manufacture, and thus, the opportunity to complement, supplement, or displace petroleum-based production as economic and strategic considerations require. The composition of natural gas varies from reservoir to reservoir but the principal hydrocarbon constituent is always methane (CH{sub 4}). With itsmore » high hydrogen-to-carbon ratio, methane has the potential to produce hydrogen or hydrogen-rich products. However, methane is a very chemically stable molecule and, thus, is not readily transformed to other molecules or easily reformed to its elements (H{sub 2} and carbon). In many cases, further research is needed to augment selectivity to desired product(s), increase single-pass conversions, or improve economics (e.g. there have been estimates of $50/bbl or more for liquid products) before the full potential of these methodologies can be realized on a commercial scale. With the trade-off between gas conversion and product selectivity, a major challenge common to many of these technologies is to simultaneously achieve high methane single-pass conversions and high selectivity to desired products. Based on the results of the scoping runs, there appears to be strong indications that a breakthrough has finally been achieved in that synthesis of magnesium carbides from MgO and methane in the arc discharge reactor has been demonstrated.« less

Printable enzyme-embedded materials for methane to methanol conversion

DOE PAGES

Blanchette, Craig D.; Knipe, Jennifer M.; Stolaroff, Joshuah K.; ...

2016-06-15

An industrial process for the selective activation of methane under mild conditions would be highly valuable for controlling emissions to the environment and for utilizing vast new sources of natural gas. The only selective catalysts for methane activation and conversion to methanol under mild conditions are methane monooxygenases (MMOs) found in methanotrophic bacteria; however, these enzymes are not amenable to standard enzyme immobilization approaches. Using particulate methane monooxygenase (pMMO), we create a biocatalytic polymer material that converts methane to methanol. We demonstrate embedding the material within a silicone lattice to create mechanically robust, gas-permeable membranes, and direct printing of micron-scalemore » structures with controlled geometry. Remarkably, the enzymes retain up to 100% activity in the polymer construct. The printed enzyme-embedded polymer motif is highly flexible for future development and should be useful in a wide range of applications, especially those involving gas–liquid reactions.« less

NREL Advancements in Methane Conversion Lead to Cleaner Air, Useful Products

DOE Office of Scientific and Technical Information (OSTI.GOV)

2016-06-01

Researchers at NREL leveraged the recent on-site development of gas fermentation capabilities and novel genetic tools to directly convert methane to lactic acid using an engineered methanotrophic bacterium. The results provide proof-of-concept data for a gas-to-liquids bioprocess that concurrently produces fuels and chemicals from methane. NREL researchers developed genetic tools to express heterologous genes in methanotrophic organisms, which have historically been difficult to genetically engineer. Using these tools, researchers demonstrated microbial conversion of methane to lactate, a high-volume biochemical precursor predominantly utilized for the production of bioplastics. Methane biocatalysis offers a means to concurrently liquefy and upgrade natural gas andmore » renewable biogas, enabling their utilization in conventional transportation and industrial manufacturing infrastructure. Producing chemicals and fuels from methane expands the suite of products currently generated from biorefineries, municipalities, and agricultural operations, with the potential to increase revenue and significantly reduce greenhouse gas emissions.« less

Printable enzyme-embedded materials for methane to methanol conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blanchette, Craig D.; Knipe, Jennifer M.; Stolaroff, Joshuah K.

An industrial process for the selective activation of methane under mild conditions would be highly valuable for controlling emissions to the environment and for utilizing vast new sources of natural gas. The only selective catalysts for methane activation and conversion to methanol under mild conditions are methane monooxygenases (MMOs) found in methanotrophic bacteria; however, these enzymes are not amenable to standard enzyme immobilization approaches. Using particulate methane monooxygenase (pMMO), we create a biocatalytic polymer material that converts methane to methanol. We demonstrate embedding the material within a silicone lattice to create mechanically robust, gas-permeable membranes, and direct printing of micron-scalemore » structures with controlled geometry. Remarkably, the enzymes retain up to 100% activity in the polymer construct. The printed enzyme-embedded polymer motif is highly flexible for future development and should be useful in a wide range of applications, especially those involving gas–liquid reactions.« less

Printable enzyme-embedded materials for methane to methanol conversion

PubMed Central

Blanchette, Craig D.; Knipe, Jennifer M.; Stolaroff, Joshuah K.; DeOtte, Joshua R.; Oakdale, James S.; Maiti, Amitesh; Lenhardt, Jeremy M.; Sirajuddin, Sarah; Rosenzweig, Amy C.; Baker, Sarah E.

2016-01-01

An industrial process for the selective activation of methane under mild conditions would be highly valuable for controlling emissions to the environment and for utilizing vast new sources of natural gas. The only selective catalysts for methane activation and conversion to methanol under mild conditions are methane monooxygenases (MMOs) found in methanotrophic bacteria; however, these enzymes are not amenable to standard enzyme immobilization approaches. Using particulate methane monooxygenase (pMMO), we create a biocatalytic polymer material that converts methane to methanol. We demonstrate embedding the material within a silicone lattice to create mechanically robust, gas-permeable membranes, and direct printing of micron-scale structures with controlled geometry. Remarkably, the enzymes retain up to 100% activity in the polymer construct. The printed enzyme-embedded polymer motif is highly flexible for future development and should be useful in a wide range of applications, especially those involving gas–liquid reactions. PMID:27301270

Initial development and performance evaluation of a process for formation of dense carbon by pyrolysis of methane

NASA Technical Reports Server (NTRS)

Noyes, G. P.; Cusick, R. J.

1985-01-01

The three steps in pyrolytic carbon formation are: (1) gaseous hydrocarbon polymerization and aromatic formation; (2) gas-phase condensation and surface adsorption/impingement of polyaromatic hydrocarbon; and (3) final dehydration to carbon. The structure of the carbon in the various stages of formation is examined. The apparatuses and experimental procedures for the pyrolysis of methane in a 60 cm long quartz reactor tube at temperatures ranging from 1400-1600 K are described. The percentage of carbon converted and its density are calculated and tabularly presented. The results reveal that dense carbon formation is maximized and soot eliminated by this procedure. It is observed that conversion efficiency depends on the composition of the inlet gas and conversion increases with increasing temperature. Based on the experimental data a three-man carbon reactor subsystem (CRS) is developed; the functions of the Sabatier Methanation Reactor, two carbon formation reactors and fluid handling components of the CRS are analyzed. The CRS forms 16 kg of carbon at a rate of 0.8 kg/day for 20 days in a two percent volume density quartz wool packing at temperature of 1500-1600 K.

Hydrate kinetics study in the presence of nonaqueous liquid by nuclear magnetic resonance spectroscopy and imaging.

PubMed

Susilo, Robin; Moudrakovski, Igor L; Ripmeester, John A; Englezos, Peter

2006-12-28

The dynamics of methane hydrate growth and decomposition were studied by nuclear magnetic resonance (NMR) spectroscopy and imaging (MRI). Three well-known large molecule guest substances (LMGS) were used as structure H hydrate formers: 2,2-dimethylbutane (NH), methylcyclohexane (MCH), tert-butyl methyl ether (TBME). In addition, the impact of a non-hydrate former (n-heptane/nC7) was studied. The methane diffusion and hydrate growth were monitored by recording the 2H NMR spectra at 253 K and approximately 4.5 MPa for 20 h. The results revealed that methane diffuses faster in TBME and NH, slower in nC7, and slowest in MCH. The TBME system gives the fastest hydrate formation kinetics followed by NH, MCH, and nC7. The conversion of water into hydrate was also observed. The imaging study showed that TBME has a strong affinity toward ice, which is not the case for the NH and MCH systems. The degree of ice packing was also found to affect the LMGS distribution between ice particles. Highly packed ice increases the mass transfer resistance and hence limits the contact between LMGS and ice. It was also found that "temperature ramping" above the ice point improves the conversion significantly. Finally, hydrates were found to dissociate quickly within the first hour at atmospheric pressure and subsequently at a much slower rate. Methane dissolved in LMGS was also seen. The residual methane in hydrate phase and dissolved in LMGS phase explain the faster kinetics during hydrate re-formation.

Application of a rotating impeller anode in a bioelectrochemical anaerobic digestion reactor for methane production from high-strength food waste.

PubMed

Park, Jungyu; Lee, Beom; Shin, Wonbeom; Jo, Sangyeol; Jun, Hangbae

2018-07-01

In this study, a practical bioelectrochemical anaerobic digestion (BEAD) reactor equipped with a rotating STS304 impeller was tested to verify its methane production performance. Methane production in the BEAD reactor was possible without accumulation of volatile fatty acids (VFAs) and decreases in pH at high organic loading rates (OLRs) up to 6 kg-COD/m 3 ·d (COD: chemical oxygen demand). Methane production in a BEAD-O (open circuit) reactor was inhibited at OLRs above 4 kg-COD/m 3 ·d; however, the performance could be recovered bioelectrochemically by supplying voltage. The population density of hydrogenotrophic methanogens increased to 73.3% in the BEAD-C (closed circuit) reactor, even at high OLRs, through the removal of VFAs and conversion of hydrogen to methane. The energy efficiency in the BEAD-C reactor was 85.6%, indicating that the commercialization of BEAD reactors equipped with rotating STS304 impeller electrodes is possible. Copyright © 2018 Elsevier Ltd. All rights reserved.

Biocatalytic methanation of hydrogen and carbon dioxide in an anaerobic three-phase system.

PubMed

Burkhardt, M; Koschack, T; Busch, G

2015-02-01

A new type of anaerobic trickle-bed reactor was used for biocatalytic methanation of hydrogen and carbon dioxide under mesophilic temperatures and ambient pressure in a continuous process. The conversion of gaseous substrates through immobilized hydrogenotrophic methanogenic archaea in a biofilm is a unique feature of this type of reactor. Due to the formation of a three-phase system on the carrier surface and operation as a plug flow reactor without gas recirculation, a complete reaction could be observed. With a methane concentration higher than c(CH4) = 98%, the product gas exhibits a very high quality. A specific methane production of P(CH4) = 1.49 Nm(3)/(m(3)(SV) d) was achieved at a hydraulic loading rate of LR(H2) = 6.0 Nm(3)/(m(3)(SV) d). The relation between trickle flow through the reactor and productivity could be shown. An application for methane enrichment in combination with biogas facilities as a source of carbon dioxide has also been positively proven. Copyright © 2014 Elsevier Ltd. All rights reserved.

Impact of cell design and operating conditions on the performances of SOFC fuelled with methane

NASA Astrophysics Data System (ADS)

Laurencin, J.; Lefebvre-Joud, F.; Delette, G.

An in-house-model has been developed to study the thermal and electrochemical behaviour of a planar SOFC fed directly with methane and incorporated in a boiler. The usual Ni-YSZ cermet has been considered for the anode material. It has been found that methane reforming into hydrogen occurs only at the cell inlet in a limited depth within the anode. A sensitivity analysis has allowed establishing that anode thicknesses higher than ∼400-500 μm are required to achieve both the optimal methane conversion and electrochemical performances. The direct internal reforming (DIR) mechanisms and the impact of operating conditions on temperature gradients and SOFC electrical efficiencies have been investigated considering the anode supported cell configuration. It has been shown that the temperature gradient is minimised in the autothermal mode of cell operation. Thermal equilibrium in the stack has been found to be strongly dependent on radiative heat losses with the stack envelope. Electrochemical performance and cell temperature maps have been established as a function of methane flow rates and cell voltages.

Small Molecule Catalysts for Harvesting Methane Gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker, S. E.; Ceron-Hernandez, M.; Oakdale, J.

As the average temperature of the earth increases the impact of these changes are becoming apparent. One of the most dramatic changes to the environment is the melting of arctic permafrost. The disappearance of the permafrost has resulted in release of streams of methane that was trapped in remote areas as gas hydrates in ice. Additionally, the use of fracking has also increased emission of methane. Currently, the methane is either lost to the atmosphere or flared. If these streams of methane could be brought to market, this would be an abundant source of revenue. A cheap conversion of gaseousmore » methane to a more convenient form for transport would be necessary to economical. Conversion of methane is a difficult reaction since the C-H bond is very stable (104 kcal/mole). At the industrial scale, the Fischer-Tropsch reaction can be used to convert gaseous methane to liquid methanol but is this method is impractical for these streams that have low pressures and are located in remote areas. Additionally, the Fischer-Tropsch reaction results in over oxidation of the methane leading to many products that would need to be separated.« less

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

NASA Astrophysics Data System (ADS)

Shan, Junjun; Li, Mengwei; Allard, Lawrence F.; Lee, Sungsik; Flytzani-Stephanopoulos, Maria

2017-11-01

An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. We find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolite-supported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. We anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful chemicals.

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shan, Junjun; Li, Mengwei; Allard, Lawrence F.

An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media(5-8) that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid,more » which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. Here, we find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolitesupported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. Finally, we anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful chemicals.« less

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

DOE PAGES

Shan, Junjun; Li, Mengwei; Allard, Lawrence F.; ...

2017-11-30

An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media(5-8) that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid,more » which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. Here, we find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolitesupported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. Finally, we anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful chemicals.« less

Investigation of the characteristics of a compact steam reformer integrated with a water-gas shift reactor

NASA Astrophysics Data System (ADS)

Seo, Yong-Seog; Seo, Dong-Joo; Seo, Yu-Taek; Yoon, Wang-Lai

The objective of this study is to investigate numerically a compact steam methane reforming (SMR) system integrated with a water-gas shift (WGS) reactor. Separate numerical models are established for the combustion part, SMR and WGS reaction bed. The concentration of species at the exits of the SMR and WGS bed, and the temperatures in the WGS bed are in good agreement with the measured data. Heat transfer to the catalyst beds and the catalytic reactions in the SMR and WGS catalyst bed are investigated as a function of the operation parameters. The conversion of methane at the exit of the SMR catalyst bed is calculated to be 87%, and the carbon monoxide concentration at the outlet of the WGS bed is estimated to be 0.45%. The effects of the cooling heat flux at the outside wall of the system and steam-to-carbon (S/C) ratio are also examined. As the cooling heat flux increases, both the methane conversion and carbon monoxide content are reduced in the SMR bed, and the carbon monoxide conversion is improved in the WGS bed. Both methane conversion and carbon dioxide reduction increase with increasing steam-to-carbon ratio.

Bovine Host Genetic Variation Influences Rumen Microbial Methane Production with Best Selection Criterion for Low Methane Emitting and Efficiently Feed Converting Hosts Based on Metagenomic Gene Abundance

PubMed Central

Roehe, Rainer; Dewhurst, Richard J.; Duthie, Carol-Anne; Rooke, John A.; McKain, Nest; Ross, Dave W.; Hyslop, Jimmy J.; Waterhouse, Anthony; Freeman, Tom C.

2016-01-01

Methane produced by methanogenic archaea in ruminants contributes significantly to anthropogenic greenhouse gas emissions. The host genetic link controlling microbial methane production is unknown and appropriate genetic selection strategies are not developed. We used sire progeny group differences to estimate the host genetic influence on rumen microbial methane production in a factorial experiment consisting of crossbred breed types and diets. Rumen metagenomic profiling was undertaken to investigate links between microbial genes and methane emissions or feed conversion efficiency. Sire progeny groups differed significantly in their methane emissions measured in respiration chambers. Ranking of the sire progeny groups based on methane emissions or relative archaeal abundance was consistent overall and within diet, suggesting that archaeal abundance in ruminal digesta is under host genetic control and can be used to genetically select animals without measuring methane directly. In the metagenomic analysis of rumen contents, we identified 3970 microbial genes of which 20 and 49 genes were significantly associated with methane emissions and feed conversion efficiency respectively. These explained 81% and 86% of the respective variation and were clustered in distinct functional gene networks. Methanogenesis genes (e.g. mcrA and fmdB) were associated with methane emissions, whilst host-microbiome cross talk genes (e.g. TSTA3 and FucI) were associated with feed conversion efficiency. These results strengthen the idea that the host animal controls its own microbiota to a significant extent and open up the implementation of effective breeding strategies using rumen microbial gene abundance as a predictor for difficult-to-measure traits on a large number of hosts. Generally, the results provide a proof of principle to use the relative abundance of microbial genes in the gastrointestinal tract of different species to predict their influence on traits e.g. human metabolism, health and behaviour, as well as to understand the genetic link between host and microbiome. PMID:26891056

Bovine Host Genetic Variation Influences Rumen Microbial Methane Production with Best Selection Criterion for Low Methane Emitting and Efficiently Feed Converting Hosts Based on Metagenomic Gene Abundance.

PubMed

Roehe, Rainer; Dewhurst, Richard J; Duthie, Carol-Anne; Rooke, John A; McKain, Nest; Ross, Dave W; Hyslop, Jimmy J; Waterhouse, Anthony; Freeman, Tom C; Watson, Mick; Wallace, R John

2016-02-01

Methane produced by methanogenic archaea in ruminants contributes significantly to anthropogenic greenhouse gas emissions. The host genetic link controlling microbial methane production is unknown and appropriate genetic selection strategies are not developed. We used sire progeny group differences to estimate the host genetic influence on rumen microbial methane production in a factorial experiment consisting of crossbred breed types and diets. Rumen metagenomic profiling was undertaken to investigate links between microbial genes and methane emissions or feed conversion efficiency. Sire progeny groups differed significantly in their methane emissions measured in respiration chambers. Ranking of the sire progeny groups based on methane emissions or relative archaeal abundance was consistent overall and within diet, suggesting that archaeal abundance in ruminal digesta is under host genetic control and can be used to genetically select animals without measuring methane directly. In the metagenomic analysis of rumen contents, we identified 3970 microbial genes of which 20 and 49 genes were significantly associated with methane emissions and feed conversion efficiency respectively. These explained 81% and 86% of the respective variation and were clustered in distinct functional gene networks. Methanogenesis genes (e.g. mcrA and fmdB) were associated with methane emissions, whilst host-microbiome cross talk genes (e.g. TSTA3 and FucI) were associated with feed conversion efficiency. These results strengthen the idea that the host animal controls its own microbiota to a significant extent and open up the implementation of effective breeding strategies using rumen microbial gene abundance as a predictor for difficult-to-measure traits on a large number of hosts. Generally, the results provide a proof of principle to use the relative abundance of microbial genes in the gastrointestinal tract of different species to predict their influence on traits e.g. human metabolism, health and behaviour, as well as to understand the genetic link between host and microbiome.

Methane-Oxidizing Enzymes: An Upstream Problem in Biological Gas-to-Liquids Conversion

PubMed Central

Lawton, Thomas J.; Rosenzweig, Amy C.

2017-01-01

Biological conversion of natural gas to liquids (Bio-GTL) represents an immense economic opportunity. In nature, aerobic methanotrophic bacteria and anaerobic archaea are able to selectively oxidize methane using methane monooxygenase (MMO) and methyl coenzyme M reductase (MCR) enzymes. Although significant progress has been made toward genetically manipulating these organisms for biotechnological applications, the enzymes themselves are slow, complex, and not recombinantly tractable in traditional industrial hosts. With turnover numbers of 0.16–13 s−1, these enzymes pose a considerable upstream problem in the biological production of fuels or chemicals from methane. Methane oxidation enzymes will need to be engineered to be faster to enable high volumetric productivities; however, efforts to do so and to engineer simpler enzymes have been minimally successful. Moreover, known methane-oxidizing enzymes have different expression levels, carbon and energy efficiencies, require auxiliary systems for biosynthesis and function, and vary considerably in terms of complexity and reductant requirements. The pros and cons of using each methane-oxidizing enzyme for Bio-GTL are considered in detail. The future for these enzymes is bright, but a renewed focus on studying them will be critical to the successful development of biological processes that utilize methane as a feedstock. PMID:27366961

Methane-Oxidizing Enzymes: An Upstream Problem in Biological Gas-to-Liquids Conversion.

PubMed

Lawton, Thomas J; Rosenzweig, Amy C

2016-08-03

Biological conversion of natural gas to liquids (Bio-GTL) represents an immense economic opportunity. In nature, aerobic methanotrophic bacteria and anaerobic archaea are able to selectively oxidize methane using methane monooxygenase (MMO) and methyl coenzyme M reductase (MCR) enzymes. Although significant progress has been made toward genetically manipulating these organisms for biotechnological applications, the enzymes themselves are slow, complex, and not recombinantly tractable in traditional industrial hosts. With turnover numbers of 0.16-13 s(-1), these enzymes pose a considerable upstream problem in the biological production of fuels or chemicals from methane. Methane oxidation enzymes will need to be engineered to be faster to enable high volumetric productivities; however, efforts to do so and to engineer simpler enzymes have been minimally successful. Moreover, known methane-oxidizing enzymes have different expression levels, carbon and energy efficiencies, require auxiliary systems for biosynthesis and function, and vary considerably in terms of complexity and reductant requirements. The pros and cons of using each methane-oxidizing enzyme for Bio-GTL are considered in detail. The future for these enzymes is bright, but a renewed focus on studying them will be critical to the successful development of biological processes that utilize methane as a feedstock.

Method for the photocatalytic conversion of methane

DOEpatents

Noceti, R.P.; Taylor, C.E.; D`Este, J.R.

1998-02-24

A method for converting methane to methanol is provided comprising subjecting the methane to visible light in the presence of a catalyst and an electron transfer agent. Another embodiment of the invention provides for a method for reacting methane and water to produce methanol and hydrogen comprising preparing a fluid containing methane, an electron transfer agent and a photolysis catalyst, and subjecting said fluid to visible light for an effective period of time. 3 figs.

Method for the photocatalytic conversion of methane

DOEpatents

Noceti, Richard P.; Taylor, Charles E.; D'Este, Joseph R.

1998-01-01

A method for converting methane to methanol is provided comprising subjecting the methane to visible light in the presence of a catalyst and an electron transfer agent. Another embodiment of the invention provides for a method for reacting methane and water to produce methanol and hydrogen comprising preparing a fluid containing methane, an electron transfer agent and a photolysis catalyst, and subjecting said fluid to visible light for an effective period of time.

Emission quantification using the tracer gas dispersion method: The influence of instrument, tracer gas species and source simulation.

PubMed

Delre, Antonio; Mønster, Jacob; Samuelsson, Jerker; Fredenslund, Anders M; Scheutz, Charlotte

2018-09-01

The tracer gas dispersion method (TDM) is a remote sensing method used for quantifying fugitive emissions by relying on the controlled release of a tracer gas at the source, combined with concentration measurements of the tracer and target gas plumes. The TDM was tested at a wastewater treatment plant for plant-integrated methane emission quantification, using four analytical instruments simultaneously and four different tracer gases. Measurements performed using a combination of an analytical instrument and a tracer gas, with a high ratio between the tracer gas release rate and instrument precision (a high release-precision ratio), resulted in well-defined plumes with a high signal-to-noise ratio and a high methane-to-tracer gas correlation factor. Measured methane emission rates differed by up to 18% from the mean value when measurements were performed using seven different instrument and tracer gas combinations. Analytical instruments with a high detection frequency and good precision were established as the most suitable for successful TDM application. The application of an instrument with a poor precision could only to some extent be overcome by applying a higher tracer gas release rate. A sideward misplacement of the tracer gas release point of about 250m resulted in an emission rate comparable to those obtained using a tracer gas correctly simulating the methane emission. Conversely, an upwind misplacement of about 150m resulted in an emission rate overestimation of almost 50%, showing the importance of proper emission source simulation when applying the TDM. Copyright © 2018 Elsevier B.V. All rights reserved.

Current and temperature distributions in-situ acquired by electrode-segmentation along a microtubular solid oxide fuel cell operating with syngas

NASA Astrophysics Data System (ADS)

Aydın, Özgür; Nakajima, Hironori; Kitahara, Tatsumi

2015-10-01

Addressing the fuel distribution and endothermic cooling by the internal reforming, we have measured longitudinal current/temperature variations by ;Electrode-segmentation; in a microtubular solid oxide fuel cell operated with syngas (50% pre-reformed methane) and equivalent H2/N2 (100% conversion of syngas to H2) at three different flow rates. Regardless of the syngas flow rates, currents and temperatures show irregular fluctuations with varying amplitudes from upstream to downstream segment. Analysis of the fluctuations suggests that the methane steam reforming reaction is highly affected by the H2 partial pressure. Current-voltage curves plotted for the syngas and equivalent H2/N2 flow rates reveal that the fuel depletion is enhanced toward the downstream during the syngas operation, resulting in a larger performance degradation. All the segments exhibit temperature drops with the syngas flow compared with the equivalent H2/N2 flow due to the endothermic cooling by the methane steam reforming reaction. Despite the drops, the segment temperatures remain above the furnace temperature; besides, the maximum temperature difference along the cell diminishes. The MSR reaction rate does not consistently increase with the decreasing gas inlet velocity (increasing residence time on the catalyst); which we ascribe to the dominating impact of the local temperatures.

NOTE: Laboratory Studies of Catalysis of CO to Organics on Grain Analogs

NASA Astrophysics Data System (ADS)

Ferrante, R. F.; Moore, M. H.; Nuth, J. A.; Smith, T.

2000-05-01

Experiments simulating heterogeneous conversion of H 2 and CO into simple hydrocarbons in astrophysical environments have been performed, utilizing realistic cosmic grain analogs of Fe-doped silicates as Fischer-Tropsch-Type catalysts. Catalysis was studied for temperatures from 470-670 K and reactant gas mixtures of H 2/CO with a ratio of 2-100. The total gas pressure was near 0.5 bar. Maximum conversion rates of a few percentage points were achieved over a 3-h time period. Major products were methane, ethane, ethylene, carbon dioxide, and water. Products were identified by IR spectroscopy.

Effect of ferrihydrite biomineralization on methanogenesis in an anaerobic incubation from paddy soil

NASA Astrophysics Data System (ADS)

Zhuang, Li; Xu, Jielong; Tang, Jia; Zhou, Shungui

2015-05-01

Microbial reduction of Fe(III) can be one of the major factors controlling methane production from anaerobic sedimentary environments, such as paddy soils and wetlands. Although secondary iron mineralization following Fe(III) reduction is a process that occurs naturally over time, it has not yet been considered in methanogenic systems. This study performed a long-term anaerobic incubation of a paddy soil and ferrihydrite-supplemented soil cultures to investigate methanogenesis during ferrihydrite biomineralization. The results revealed that the long-term effect of ferrihydrite on methanogenesis may be enhancement rather than suppression documented in previous studies. During initial microbial ferrihydrite reduction, methanogenesis was suppressed; however, the secondary minerals of magnetite formation was simultaneous with facilitated methanogenesis in terms of average methane production rate and acetate utilization rate. In the phase of magnetite formation, microbial community analysis revealed a strong stimulation of the bacterial Geobacter, Bacillus, and Sedimentibacter and the archaeal Methanosarcina in the ferrihydrite-supplemented cultures. Direct electric syntrophy between Geobacter and Methanosarcina via conductive magnetite is the plausible mechanism for methanogenesis acceleration along with magnetite formation. Our data suggested that a change in iron mineralogy might affect the conversion of anaerobic organic matter to methane and might provide a fresh perspective on the mitigation of methane emissions from paddy soils by ferric iron fertilization.

Effect of Catalytic Cylinders on Autothermal Reforming of Methane for Hydrogen Production in a Microchamber Reactor

PubMed Central

Yan, Yunfei; Guo, Hongliang; Zhang, Li; Zhu, Junchen; Yang, Zhongqing; Tang, Qiang; Ji, Xin

2014-01-01

A new multicylinder microchamber reactor is designed on autothermal reforming of methane for hydrogen production, and its performance and thermal behavior, that is, based on the reaction mechanism, is numerically investigated by varying the cylinder radius, cylinder spacing, and cylinder layout. The results show that larger cylinder radius can promote reforming reaction; the mass fraction of methane decreased from 26% to 21% with cylinder radius from 0.25 mm to 0.75 mm; compact cylinder spacing corresponds to more catalytic surface and the time to steady state is decreased from 40 s to 20 s; alteration of staggered and aligned cylinder layout at constant inlet flow rates does not result in significant difference in reactor performance and it can be neglected. The results provide an indication and optimize performance of reactor; it achieves higher conversion compared with other reforming reactors. PMID:25097877

Samaria-doped Ceria Modified Ni/YSZ Anode for Direct Methane Fuel in Tubular Solid Oxide Fuel Cells by Impregnation Method

NASA Astrophysics Data System (ADS)

Zhang, Long-shan; Gao, Jian-feng; Tian, Rui-fen; Xia, Chang-rong

2009-08-01

A porous NiO/yttria-stabilized zirconia anode substrate for tubular solid oxide fuel cells was prepared by gel casting technique. Nano-scale samaria-doped ceria (SDC) particles were formed onto the anode substrate to modify the anode microstructure by the impregnation of solution of Sm(NO3)3 and Ce(NO3)3. Electrochemical impedance spectroscopy, current-voltage and current-powder curves of the cells were measured using an electrochemical workstation. Scanning electron microcopy was used to observe the microstructure. The results indicate that the stability of the performance of the cell operated on humidified methane can be significantly improved by incorporating the nano-structured SDC particles, compared with the unmodified cell. This verifies that the coated SDC electrodes are very effective in suppressing catalytic carbon formation by blocking methane from approaching the Ni, which is catalytically active towards methane pyrolysis. In addition, it was found that a small amount of deposited carbon is beneficial to the performance of the anode. The cell showed a peak power density of 225 mW/cm2 when it was fed with H2 fuel at 700 °C, but the power density increased to 400 mW/cm2 when the fuel was switched from hydrogen to methane at the same flow rate. Methane conversion achieved about 90%, measured by gas chromatogram with a 10.0 mL/min flow rate of fuel at 700 °C. Although the carbon deposition was not suppressed absolutely, some deposited carbon was beneficial for performance improvement.

Methane utilization in Methylomicrobium alcaliphilum 20ZR: a systems approach.

PubMed

Akberdin, Ilya R; Thompson, Merlin; Hamilton, Richard; Desai, Nalini; Alexander, Danny; Henard, Calvin A; Guarnieri, Michael T; Kalyuzhnaya, Marina G

2018-02-06

Biological methane utilization, one of the main sinks of the greenhouse gas in nature, represents an attractive platform for production of fuels and value-added chemicals. Despite the progress made in our understanding of the individual parts of methane utilization, our knowledge of how the whole-cell metabolic network is organized and coordinated is limited. Attractive growth and methane-conversion rates, a complete and expert-annotated genome sequence, as well as large enzymatic, 13 C-labeling, and transcriptomic datasets make Methylomicrobium alcaliphilum 20Z R an exceptional model system for investigating methane utilization networks. Here we present a comprehensive metabolic framework of methane and methanol utilization in M. alcaliphilum 20Z R . A set of novel metabolic reactions governing carbon distribution across central pathways in methanotrophic bacteria was predicted by in-silico simulations and confirmed by global non-targeted metabolomics and enzymatic evidences. Our data highlight the importance of substitution of ATP-linked steps with PPi-dependent reactions and support the presence of a carbon shunt from acetyl-CoA to the pentose-phosphate pathway and highly branched TCA cycle. The diverged TCA reactions promote balance between anabolic reactions and redox demands. The computational framework of C 1 -metabolism in methanotrophic bacteria can represent an efficient tool for metabolic engineering or ecosystem modeling.

Thermochemical Pretreatment for Anaerobic Digestion of Sorted Waste

NASA Astrophysics Data System (ADS)

Hao, W.; Hongtao, W.

2008-02-01

The effect of alkaline hydrothermal pre-treatment for anaerobic digestion of mechanically-sorted municipal solid waste (MSW) and source-sorted waste was studied. Waste was hydrothermally pre-treated in dilute alkali solution. Hydrolysis product was incubated in 500 ml saline bottle to determine methane potential (MP) under mesospheric anaerobic conditions. Optimum reaction condition obtained in the study is 170 °C at the dose of 4 g NaOH/100 g solid for one hour. Soluble COD was 13936 mg/L and methane yield was 164 ml/g VS for 6 days incubation at optimum conditions. More than 50% biogas increase was achieved over the control, and methane conversion ratio on carbon basis was enhanced to 30.6%. The digestion period was less than 6 days when pre-treatment temperature was above 130 °C. The organic part of sorted waste is mainly constituted of kitchen garbage and leaf. Model kitchen garbage was completely liquidized at 130 °C for one hour and the methane yield was 276 ml/g VS. Addition of alkali enhance hydroxylation rate and methane yield slightly. The biogas potential of leaf could be observed by pre-treatment above 150 °C under alkaline condition.

Insight into the role of facultative bacteria stimulated by micro-aeration in continuous bioreactors converting LCFA to methane.

PubMed

Duarte, Maria Salomé; Silva, Sérgio A; Salvador, Andreia F; Cavaleiro, Ana Júlia; Stams, Alfons J M; Alves, Maria Madalena; Pereira, Maria Alcina

2018-05-15

Conversion of unsaturated long chain fatty acids (LCFA) to methane in continuous bioreactors is not fully understood. Palmitate (C16:0) often accumulates during oleate (C18:1) biodegradation in methanogenic bioreactors, and the reason why this happens and which microorganisms catalyze this reaction remains unknown. Facultative anaerobic bacteria are frequently found in continuous reactors operated at high LCFA loads, but their function is unclear. To get more insight on the role of these bacteria, LCFA conversion was studied under microaerophilic conditions. For that, we compared bioreactors treating oleate-based wastewater (organic loading rates of 1 and 3 kg COD m-3 d-1), operated under different redox conditions (strictly anaerobic-AnR, -350 mV; microaerophilic-MaR, -250 mV). At the higher load, palmitate accumulated 7 times more in the MaR, where facultative anaerobes were more abundant, and only the biomass from this reactor could recover the methanogenic activity after a transient inhibition. In a second experiment, the abundance of facultative anaerobic bacteria, particularly Pseudomonas spp. (from which two strains were isolated), was strongly correlated (p<0.05) with palmitate-to-total LCFA percentage in the biofilm formed in a continuous plug flow reactor fed with very high loads of oleate. This work strongly suggests that micro-aeration stimulates the development of facultative bacteria that are critical for achieving LCFA conversion to methane in continuous bioreactors. Microbial networks and interactions of facultative and strict anaerobes in microbial communities should be considered in future studies.

High-rate two-phase process for the anaerobic degradation of cellulose, employing rumen microorganisms for an efficient acidogenesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gijzen, H.J.; Zwart, K.B.; Verhagen, F.J.M.

1988-04-05

A novel two-stage anaerobic process for the microbial conversion of cellulose into biogas has been developed. In the first phase, a mixed population of rumen bacteria and ciliates was used in the hydrolysis and fermentation of cellulose. The volatile fatty acids (VFA) produced in this acidogenic reactor were subsequently converted into biogas in a UASB-type methanogenic reactor. A stepwise increase of the loading rate from 11.9 to 25.8 g volatile solids/L reactor volume/day (g VS/L/day) did not affect the degradation efficiency in the acidogenic reactor, whereas the methanogenic reactor appeared to be overloaded at the highest loading rate. Cellulose digestionmore » was almost complete at all loading rates applied. The two-stage anaerobic process was also tested with a closed fluid circuit. In this instance total methane production was 0.438 L CH/sub 4//g VS added, which is equivalent to 98% of the theoretical value. The application of rumen microorganisms in combination with a high-rate methane reactor is proposed as a means of efficient anaerobic degradation of cellulosic residues to methane. Because this newly developed two-phase system is based on processes and microorganisms from the ruminant, it will be referred to as Rumen Derived Anaerobic Digestion (RUDAD)-process.« less

A comparison of methane emissions following rice paddies conversion to crab-fish farming wetlands in southeast China.

PubMed

Hu, Zhiqiang; Wu, Shuang; Ji, Cheng; Zou, Jianwen; Zhou, Quansuo; Liu, Shuwei

2016-01-01

Rice paddies and aquaculture wetlands are typical agricultural wetlands that constitute one of the important sources of atmospheric methane (CH4). Traditional transplanted rice paddies have been experiencing conversion to pond aquaculture wetlands for pursuing higher economic benefits over the past decades in southeast China. A parallel field experiment was carried out to compare CH4 emissions from a transplanted rice paddy and its converted crab-fish farming wetland in southeast China. Over the rice-growing season, CH4 fluxes averaged 1.86 mg m(-2) h(-1) from rice paddies, and 1.14 and 0.50 mg m(-2) h(-1) for the treatments with or without aquatic vegetation present in the crab-fish farming wetlands, respectively. When averaged across the treatments, seasonal CH4 emissions from crab-fish framing wetlands were 52% lower than those from rice paddies. The CH4 fluxes were negatively related to water dissolved oxygen (DO) concentration but positively related to soil/sediment dissolved organic carbon (DOC) content in crab-fish farming wetlands. Dependence of CH4 fluxes on DO or DOC was intensified by the aquatic vegetation presence. By extrapolating the present CH4 emission rate with the current rice paddy-converted aquaculture cultivation area, the seasonal CH4 emissions from inland aquaculture wetlands during the critical farming stage (20 June to 18 October) were estimated to be 33.6 Gg ha(-1) in southeast China in 2012. Rice paddies conversion to crab-fish farming wetlands might have reduced CH4 emissions by 22-54% in mainland China. Results of this study suggest that the conversion of transplanted rice paddies to crab-fish aquaculture wetlands for higher economic benefits would also lead to a lower ecosystem CH4 release rate.

Exposure to polystyrene nanoplastic leads to inhibition of anaerobic digestion system.

PubMed

Fu, Shan-Fei; Ding, Jian-Nan; Zhang, Yun; Li, Yi-Fei; Zhu, Rong; Yuan, Xian-Zheng; Zou, Hua

2018-06-01

In this study, impacts of nanoplastic on the pure and mixed anaerobic digestion systems were investigated. Results showed the growth and metabolism of Acetobacteroides hydrogenigenes were partly inhibited by nanoplastic existed in the pure anaerobic digestion system. The anaerobic digestion of sewage sludge was also obviously inhibited by nanoplastic existed in the mixed anaerobic digestion system. Both the methane yield and methane production rate of the mixed anaerobic digestion system showed negative correlation with the nanoplastic concentration. Compared with anaerobic digestion system without nanoplastic, methane yield and maximum daily methane yield at the nanoplastic concentration of 0.2g/L decreased for 14.4% and 40.7%, respectively. In addition, the start-up of mixed anaerobic digestion system was prolonged by addition of nanoplastic. Microbial community structure analysis indicated the microbial community structures were also affected by nanoplastic existed in the system. At the nanoplastic concentration of 0.2g/L, the relative abundances of family Cloacamonaceae, Porphyromonadaceae, Anaerolinaceae and Gracilibacteraceae decreased partly. Conversely, the relative abundances of family Anaerolinaceae, Clostridiaceae, Geobacteraceae, Dethiosulfovibrionaceae and Desulfobulbaceae improved partly. Copyright © 2017 Elsevier B.V. All rights reserved.

Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Okolie, Chukwuemeka; Belhseine, Yasmeen F.; Lyu, Yimeng

Direct conversion of methane into alcohols is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can selectively oxidize methane to methanol and ethanol in a single, steady-state process at 723 K using O2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to the synergy between the small Lewis acidicmore » NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.« less

Conversion of Methane to Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Okolie, Chukwuemeka; Belhseine, Yasmeen F.; Lyu, Yimeng

Here, the conversion of methane into alcohols under moderate reaction conditions is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can convert methane to methanol and ethanol in a single, steady-state process at 723 K using O 2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO 2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to themore » synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.« less

Conversion of Methane to Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

DOE PAGES

Okolie, Chukwuemeka; Belhseine, Yasmeen F.; Lyu, Yimeng; ...

2017-08-08

Here, the conversion of methane into alcohols under moderate reaction conditions is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can convert methane to methanol and ethanol in a single, steady-state process at 723 K using O 2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO 2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to themore » synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.« less

Sorghums for methane production. Final report, April 1983 to March 1986

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hiler, E.A.; Miller, F.R.; Dominy, R.E.

1986-06-01

The objective of the research is to develop an integrated system for methane production utilizing high-energy sorghum as the feedstock. The report provides specifics of research activities in the sorghums-for-methane production program sponsored by Gas Research Institute and co-funded by Texas Agricultural Experiment Station. Emphasis is placed on third-year results in the report since first- and second-year results are given in earlier reports. Researchers in the program include plant geneticists, sorghum physiologists, chemists, agronomists, ruminant physiologists, agricultural and systems engineers, and agricultural economists. Major research emphasis is on genetic manipulation, physiology and production systems, harvesting, storage, processing and conversion systems,more » inhibitors, and economic and systems analyses. During the third year, increasing emphasis continued on the storage, processing, and conversion aspects of the program because of the critical importance of high efficiency and conversion to the economic implementation of the system.« less

CH4 and N2O emissions from China's beef feedlots with ad libitum and restricted feeding in fall and spring seasons.

PubMed

Lin, Zhi; Liao, Wenhua; Yang, Yuanyuan; Gao, Zhiling; Ma, Wenqi; Wang, Dianwu; Cao, Yufeng; Li, Jianguo; Cai, Zhenjiang

2015-04-01

Accurately quantifying methane (CH4) and nitrous oxide (N2O) emissions from beef operations in China is necessary to evaluate the contribution of beef cattle to greenhouse gas budgets at the national and global level. Methane and N2O emissions from two intensive beef feedlots in the North China Plain, one with a restricted feeding strategy and high manure collection frequency and the other with an ad libitum feeding strategy and low manure collection frequency, were quantified in the fall and spring seasons using an inverse dispersion technique. The diel pattern of CH4 from the beef feedlot with an ad libitum feed strategy (single peak during a day) differed from that under a restricted feeding condition (multiple peaks during a day), but little difference in the diel pattern of N2O emissions between two feeding strategies was observed. The two-season average CH4 emission rates of the two intensive feedlots were 230 and 198gCH4animal(-1)d(-1) and accounted for 6.7% and 6.8% of the gross energy intake, respectively, indicating little impact of the feeding strategy and manure collection frequency on the CH4 conversion factor at the feedlot level. However, the average N2O emission rates (21.2g N2Oanimal(-1)d(-1)) and conversion factor (8.5%) of the feedlot with low manure collection frequency were approximately 131% and 174% greater, respectively, than the feedlot under high frequency conditions, which had a N2O emission rate and conversion factor of 9.2g N2Oanimal(-1)d(-1) and 3.1%, respectively, indicating that increasing manure collection frequency played an important role in reducing N2O emissions from beef feedlots. In addition, comparison indicated that China's beef and dairy cattle in feedlots appeared to have similar CH4 conversion factors. Copyright © 2015 Elsevier Inc. All rights reserved.

Anaerobic digestion of water hyacinth and sludge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Biljetina, R.; Srivastava, V.J.; Chynoweth, D.P.

1986-01-01

The Institute of Gas Technology (IGT) has been operating an experimental test unit (ETU) at the Walt Disney World (WDW) wastewater treatment plant to demonstrate the conversion of water hyacinth and sludge to methane in a solids concentrating (SOLCON) digester. Results from 2 years to operation have confirmed earlier laboratory observations that this digester achieves higher methane yields and solids conversion than those observed in continuous stirred tank reactors. Methane yields as high as 0.49 m/sup 3/ kg/sup -1/ (7.9 SCF/lb) volatile solids added have been obtained during steady-state operation on a blend of water hyacinth and sludge. 9 refs.,more » 5 figs., 5 tabs.« less

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands.

PubMed

Dalcin Martins, Paula; Hoyt, David W; Bansal, Sheel; Mills, Christopher T; Tfaily, Malak; Tangen, Brian A; Finocchiaro, Raymond G; Johnston, Michael D; McAdams, Brandon C; Solensky, Matthew J; Smith, Garrett J; Chin, Yu-Ping; Wilkins, Michael J

2017-08-01

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions. © 2017 John Wiley & Sons Ltd.

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dalcin Martins, Paula; Hoyt, David W.; Bansal, Sheel

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxesmore » to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR, and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations, or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield non-competitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.« less

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands

USGS Publications Warehouse

Martins, Paula; Hoyt, David W.; Bansal, Sheel; Mills, Christopher T.; Tfaily, Malak; Tangen, Brian; Finocchiaro, Raymond; Johnston, Michael D.; McAdams, Brandon C.; Solensky, Matthew J.; Smith, Garrett J.; Chin, Yu-Ping; Wilkins, Michael J.

2017-01-01

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.

Uncertainty propagation in modeling of plasma-assisted hydrogen production from biogas

NASA Astrophysics Data System (ADS)

Zaherisarabi, Shadi; Venkattraman, Ayyaswamy

2016-10-01

With the growing concern of global warming and the resulting emphasis on decreasing greenhouse gas emissions, there is an ever-increasing need to utilize energy-production strategies that can decrease the burning of fossil fuels. In this context, hydrogen remains an attractive clean-energy fuel that can be oxidized to produce water as a by-product. In spite of being an abundant species, hydrogen is seldom found in a form that is directly usable for energy-production. While steam reforming of methane is one popular technique for hydrogen production, plasma-assisted conversion of biogas (carbon dioxide + methane) to hydrogen is an attractive alternative. Apart from producing hydrogen, the other advantage of using biogas as raw material is the fact that two potent greenhouse gases are consumed. In this regard, modeling is an important tool to understand and optimize plasma-assisted conversion of biogas. The primary goal of this work is to perform a comprehensive statistical study that quantifies the influence of uncertain rate constants thereby determining the key reaction pathways. A 0-D chemical kinetics solver in the OpenFOAM suite is used to perform a series of simulations to propagate the uncertainty in rate constants and the resulting mean and standard deviation of outcomes.

Structured catalyst bed and method for conversion of feed materials to chemical products and liquid fuels

DOEpatents

Wang, Yong , Liu; Wei, [Richland, WA

2012-01-24

The present invention is a structured monolith reactor and method that provides for controlled Fischer-Tropsch (FT) synthesis. The invention controls mass transport limitations leading to higher CO conversion and lower methane selectivity. Over 95 wt % of the total product liquid hydrocarbons obtained from the monolithic catalyst are in the carbon range of C.sub.5-C.sub.18. The reactor controls readsorption of olefins leading to desired products with a preselected chain length distribution and enhanced overall reaction rate. And, liquid product analysis shows readsorption of olefins is reduced, achieving a narrower FT product distribution.

Carbon nanotubes accelerate methane production in pure cultures of methanogens and in a syntrophic coculture.

PubMed

Salvador, Andreia F; Martins, Gilberto; Melle-Franco, Manuel; Serpa, Ricardo; Stams, Alfons J M; Cavaleiro, Ana J; Pereira, M Alcina; Alves, M Madalena

2017-07-01

Carbon materials have been reported to facilitate direct interspecies electron transfer (DIET) between bacteria and methanogens improving methane production in anaerobic processes. In this work, the effect of increasing concentrations of carbon nanotubes (CNT) on the activity of pure cultures of methanogens and on typical fatty acid-degrading syntrophic methanogenic coculture was evaluated. CNT affected methane production by methanogenic cultures, although acceleration was higher for hydrogenotrophic methanogens than for acetoclastic methanogens or syntrophic coculture. Interestingly, the initial methane production rate (IMPR) by Methanobacterium formicicum cultures increased 17 times with 5 g·L -1 CNT. Butyrate conversion to methane by Syntrophomonas wolfei and Methanospirillum hungatei was enhanced (∼1.5 times) in the presence of CNT (5 g·L -1 ), but indications of DIET were not obtained. Increasing CNT concentrations resulted in more negative redox potentials in the anaerobic microcosms. Remarkably, without a reducing agent but in the presence of CNT, the IMPR was higher than in incubations with reducing agent. No growth was observed without reducing agent and without CNT. This finding is important to re-frame discussions and re-interpret data on the role of conductive materials as mediators of DIET in anaerobic communities. It also opens new challenges to improve methane production in engineered methanogenic processes. © 2017 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Assessment of anaerobic biodegradability of five different solid organic wastes

NASA Astrophysics Data System (ADS)

Kristanto, Gabriel Andari; Asaloei, Huinny

2017-03-01

The concept of waste to energy emerges as an alternative solution to increasing waste generation and energy crisis. In the waste to energy concept, waste will be used to produce renewable energy through thermochemical, biochemical, and physiochemical processes. In an anaerobic digester, organic matter brake-down due to anaerobic bacteria produces methane gas as energy source. The organic waste break-down is affected by various characteristics of waste components, such as organic matter content (C, N, O, H, P), solid contents (TS and VS), nutrients ratio (C/N), and pH. This research aims to analyze biodegradability and potential methane production (CH4) from organic waste largely available in Indonesia. Five solid wastes comprised of fecal sludge, cow rumen, goat farm waste, traditional market waste, and tofu dregs were analyzed which showed tofu dregs as waste with the highest rate of biodegradability compared to others since the tofu dregs do not contain any inhibitor which is lignin, have 2.7%VS, 14 C/N ratios and 97.3% organic matter. The highest cumulative methane production known as Biochemical Methane Potential was achieved by tofu dregs with volume of 77 ml during 30-day experiment which then followed by cow rumen, goat farm waste, and traditional market waste. Subsequently, methane productions were calculated through percentage of COD reduction, which showed the efficiency of 99.1% that indicates complete conversion of the high organic matter into methane.

Methane utilization in Methylomicrobium alcaliphilum 20Z R: a systems approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akberdin, Ilya R.; Thompson, Merlin; Hamilton, Richard

Biological methane utilization, one of the main sinks of the greenhouse gas in nature, represents an attractive platform for production of fuels and value-added chemicals. Despite the progress made in our understanding of the individual parts of methane utilization, our knowledge of how the whole-cell metabolic network is organized and coordinated is limited. Attractive growth and methane-conversion rates, a complete and expert-annotated genome sequence, as well as large enzymatic, 13C-labeling, and transcriptomic datasets make Methylomicrobium alcaliphilum 20Z R an exceptional model system for investigating methane utilization networks. Here we present a comprehensive metabolic framework of methane and methanol utilization inmore » M. alcaliphilum 20Z R. A set of novel metabolic reactions governing carbon distribution across central pathways in methanotrophic bacteria was predicted by in-silico simulations and confirmed by global non-targeted metabolomics and enzymatic evidences. Our data highlight the importance of substitution of ATP-linked steps with PPi-dependent reactions and support the presence of a carbon shunt from acetyl-CoA to the pentose-phosphate pathway and highly branched TCA cycle. The diverged TCA reactions promote balance between anabolic reactions and redox demands. As a result, the computational framework of C 1-metabolism in methanotrophic bacteria can represent an efficient tool for metabolic engineering or ecosystem modeling.« less

Methane utilization in Methylomicrobium alcaliphilum 20Z R: a systems approach

DOE PAGES

Akberdin, Ilya R.; Thompson, Merlin; Hamilton, Richard; ...

2018-02-06

Biological methane utilization, one of the main sinks of the greenhouse gas in nature, represents an attractive platform for production of fuels and value-added chemicals. Despite the progress made in our understanding of the individual parts of methane utilization, our knowledge of how the whole-cell metabolic network is organized and coordinated is limited. Attractive growth and methane-conversion rates, a complete and expert-annotated genome sequence, as well as large enzymatic, 13C-labeling, and transcriptomic datasets make Methylomicrobium alcaliphilum 20Z R an exceptional model system for investigating methane utilization networks. Here we present a comprehensive metabolic framework of methane and methanol utilization inmore » M. alcaliphilum 20Z R. A set of novel metabolic reactions governing carbon distribution across central pathways in methanotrophic bacteria was predicted by in-silico simulations and confirmed by global non-targeted metabolomics and enzymatic evidences. Our data highlight the importance of substitution of ATP-linked steps with PPi-dependent reactions and support the presence of a carbon shunt from acetyl-CoA to the pentose-phosphate pathway and highly branched TCA cycle. The diverged TCA reactions promote balance between anabolic reactions and redox demands. As a result, the computational framework of C 1-metabolism in methanotrophic bacteria can represent an efficient tool for metabolic engineering or ecosystem modeling.« less

Development of a carbon formation reactor for carbon dioxide reduction

NASA Technical Reports Server (NTRS)

Noyes, G.

1985-01-01

Applied research, engineering development, and performance evaluation were conducted on a process for formation of dense carbon by pyrolysis of methane. Experimental research showed that dense (0.7 to 1.6 g/cc bulk density and 1.6 to 2.2 g/cc solid density) carbon can be produced by methane pyrolysis in quartzwool-packed quartz tubes at temperatrues of 1100 to 1300 C. This result supports the condensation theory of pyrolytic carbon formation from gaseous hydrocarbons. A full-scale Breadboard Carbon Formation Reactor (CFR) was designed, fabricated, and tested at 1100 to 1200 C with 380 to 2280 sccm input flows of methane. Single-pass conversion of methane to carbon ranged from 60 to 100 percent, with 89 percent average conversion. Performance was projected for an Advanced Carbon Reactor Subsystem (ACRS) which indicated that the ACRS is a viable option for management of metabolic carbon on long-duration space missions.

Steam conversion of liquefied petroleum gas and methane in microchannel reactor

NASA Astrophysics Data System (ADS)

Dimov, S. V.; Gasenko, O. A.; Fokin, M. I.; Kuznetsov, V. V.

2018-03-01

This study presents experimental results of steam conversion of liquefied petroleum gas and methane in annular catalytic reactor - heat exchanger. The steam reforming was done on the Rh/Al2O3 nanocatalyst with the heat applied through the microchannel gap from the outer wall. Concentrations of the products of chemical reactions in the outlet gas mixture are measured at different temperatures of reactor. The range of channel wall temperatures at which the ratio of hydrogen and carbon oxide in the outlet mixture grows substantially is determined. Data on the composition of liquefied petroleum gas conversion products for the ratio S/C = 5 was received for different GHVS.

Modeling and Design Optimization of Multifunctional Membrane Reactors for Direct Methane Aromatization

PubMed Central

Fouty, Nicholas J.; Carrasco, Juan C.; Lima, Fernando V.

2017-01-01

Due to the recent increase of natural gas production in the U.S., utilizing natural gas for higher-value chemicals has become imperative. Direct methane aromatization (DMA) is a promising process used to convert methane to benzene, but it is limited by low conversion of methane and rapid catalyst deactivation by coking. Past work has shown that membrane separation of the hydrogen produced in the DMA reactions can dramatically increase the methane conversion by shifting the equilibrium toward the products, but it also increases coke production. Oxygen introduction into the system has been shown to inhibit this coke production while not inhibiting the benzene production. This paper introduces a novel mathematical model and design to employ both methods in a multifunctional membrane reactor to push the DMA process into further viability. Multifunctional membrane reactors, in this case, are reactors where two different separations occur using two differently selective membranes, on which no systems studies have been found. The proposed multifunctional membrane design incorporates a hydrogen-selective membrane on the outer wall of the reaction zone, and an inner tube filled with airflow surrounded by an oxygen-selective membrane in the middle of the reactor. The design is shown to increase conversion via hydrogen removal by around 100%, and decrease coke production via oxygen addition by 10% when compared to a tubular reactor without any membranes. Optimization studies are performed to determine the best reactor design based on methane conversion, along with coke and benzene production. The obtained optimal design considers a small reactor (length = 25 cm, diameter of reaction tube = 0.7 cm) to subvert coke production and consumption of the product benzene as well as a high permeance (0.01 mol/s·m2·atm1/4) through the hydrogen-permeable membrane. This modeling and design approach sets the stage for guiding further development of multifunctional membrane reactor models and designs for natural gas utilization and other chemical reaction systems. PMID:28850068

Efficient 1.6 Micron Laser Source for Methane DIAL

NASA Technical Reports Server (NTRS)

Shuman, Timothy; Burnham, Ralph; Nehrir, Amin R.; Ismail, Syed; Hair, Johnathan W.

2013-01-01

Methane is a potent greenhouse gas and on a per molecule basis has a warming influence 72 times that of carbon dioxide over a 20 year horizon. Therefore, it is important to look at near term radiative effects due to methane to develop mitigation strategies to counteract global warming trends via ground and airborne based measurements systems. These systems require the development of a time-resolved DIAL capability using a narrow-line laser source allowing observation of atmospheric methane on local, regional and global scales. In this work, a demonstrated and efficient nonlinear conversion scheme meeting the performance requirements of a deployable methane DIAL system is presented. By combining a single frequency 1064 nm pump source and a seeded KTP OPO more than 5 mJ of 1.6 µm pulse energy is generated with conversion efficiencies in excess of 20%. Even without active cavity control instrument limited linewidths (50 pm) were achieved with an estimated spectral purity of 95%. Tunable operation over 400 pm (limited by the tuning range of the seed laser) was also demonstrated. This source demonstrated the critical needs for a methane DIAL system motivating additional development of the technology.

Co-digestion of polylactide and kitchen garbage in hyperthermophilic and thermophilic continuous anaerobic process.

PubMed

Wang, Feng; Hidaka, Taira; Tsuno, Hiroshi; Tsubota, Jun

2012-05-01

Two series of two-phase anaerobic systems, consisting of a hyperthermophilic (80°C) reactor and a thermophilic (55°C) reactor, fed with a mixture of kitchen garbage (KG) and polylactide (PLA), was compared with a single-phase thermophilic reactor for the overall performance. The result indicated that ammonia addition under hyperthermophilic condition promoted the transformation of PLA particles to lactic acid. The systems with hyperthermophilic treatment had advantages on PLA transformation and methane conversion ratio to the control system. Under the organic loading rate (OLR) of 10.3 g COD/(L day), the PLA transformation ratios of the two-phase systems were 82.0% and 85.2%, respectively, higher than that of the control system (63.5%). The methane conversion ratios of the two-phase systems were 82.9% and 80.8%, respectively, higher than 70.1% of the control system. The microbial community analysis indicated that hyperthermophilic treatment is easily installed to traditional thermophilic anaerobic digestion plants without inoculation of special bacteria. Copyright © 2012 Elsevier Ltd. All rights reserved.

40 CFR Table A-7 to Subpart A of... - Data Elements That Are Inputs to Emission Equations and for Which the Reporting Deadline Is March...

Code of Federal Regulations, 2013 CFR

2013-07-01

... mass balance equation. K 98.116(b) Only annual production by product from each EAF (No CEMS). K 98.116... contributed by methane. Y 98.256(f)(7) Only molar volume conversion factor. Y 98.256(f)(10) Only coke burn-off... methane in coking gas. Y 98.256(l)(5) Only molar volume conversion factor. Y 98.256(m)(3) Only total...

Application of methane fermentation technology into organic wastes in closed agricultural system

NASA Astrophysics Data System (ADS)

Endo, Ryosuke; Kitaya, Yoshiaki

Sustainable and recycling-based systems are required in space agriculture which takes place in an enclosed environment. Methane fermentation is one of the most major biomass conversion technologies, because (1) it provides a renewable energy source as biogas including methane, suitable for energy production, (2) the nutrient-rich solids left after digestion can be used as compost for agriculture. In this study, the effect of the application of methane fermentation technology into space agriculture on the material and energy cycle was investigated.

Pilot plant operation of a nonadiabatic methanation reactor. [15 refs. ; Raney nickel catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schehl, R.R.; Pennline, H.W.; Strakey, J.P.

The design and operation of a pilot plant scale hybrid methanation reactor is discussed. The hybrid methanator, utilizing a finned, Raney nickel coated insert, consolidates features of the tube-wall and hot-gas-recycle methanation reactors. Data are presented from four tests lasting from 3/sup 1///sub 2/ weeks to three months. Topics discussed include conversion, product yields, catalyst properties, and reactor temperature profiles. A one-dimensional mathematical model capable of explaining reactor performance trends is employed.

Perovskite nanocomposites as effective CO2-splitting agents in a cyclic redox scheme

PubMed Central

Zhang, Junshe; Haribal, Vasudev; Li, Fanxing

2017-01-01

We report iron-containing mixed-oxide nanocomposites as highly effective redox materials for thermochemical CO2 splitting and methane partial oxidation in a cyclic redox scheme, where methane was introduced as an oxygen “sink” to promote the reduction of the redox materials followed by reoxidation through CO2 splitting. Up to 96% syngas selectivity in the methane partial oxidation step and close to complete conversion of CO2 to CO in the CO2-splitting step were achieved at 900° to 980°C with good redox stability. The productivity and production rate of CO in the CO2-splitting step were about seven times higher than those in state-of-the-art solar-thermal CO2-splitting processes, which are carried out at significantly higher temperatures. The proposed approach can potentially be applied for acetic acid synthesis with up to 84% reduction in CO2 emission when compared to state-of-the-art processes. PMID:28875171

Catalyst for the methanation of carbon monoxide in sour gas

DOEpatents

Kustes, William A.; Hausberger, Arthur L.

1985-01-01

The invention involves the synergistic effect of the specific catalytic constituents on a specific series of carriers for the methanation of carbon monoxide in the presence of sulfur at relatively high temperatures and at low steam to gas ratios in the range of 0.2:1 or less. This effect was obtained with catalysts comprising the mixed sulfides and oxides of nickel and chromium supported on carriers comprising magnesium aluminate and magnesium silicate. Conversion of carbon monoxide to methane was in the range of from 40 to 80%. Tests of this combination of metal oxides and sulfides on other carriers and tests of other metal oxides and sulfides on the same carrier produced a much lower level of conversion.

Effect of packing material on methane activation in a dielectric barrier discharge reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jo, Sungkwon; Hoon Lee, Dae; Seok Kang, Woo

2013-12-15

The conversion of methane is measured in a planar-type dielectric barrier discharge reactor using γ-Al{sub 2}O{sub 3} (sphere), α-Al{sub 2}O{sub 3} (sphere), and γ-Al{sub 2}O{sub 3} (16–20 mesh). Investigations on the surface properties and shape of the three packing materials clearly indicate that methane activation is considerably affected by the material used. Capacitances inside the discharge gap are estimated from charge–voltage plots, and a comparison of the generated and transferred charges for different packing conditions show that the difference in surface properties between γ- and α-phase Al{sub 2}O{sub 3} affects the discharge characteristics. Moreover, all packing conditions show different chargemore » characteristics that are related to the electron density. Finally, the packing material's shape affects the local electron temperature, which is strongly related to methane conversion. The combined results indicate that both microscale and macroscale variations in a packing material affect the discharge characteristics, and a packing material should be considered carefully for effective methane activation.« less

Anaerobic co-digestion of steam-treated Quercus serrata chips and sewage sludge under mesophilic and thermophilic conditions.

PubMed

Wang, Feng; Hidaka, Taira; Sakurai, Kensuke; Tsumori, Jun

2014-08-01

The biodegradation of Quercus serrata chips was evaluated by anaerobic digestion under various steam explosion conditions. In continuous experiments, untreated chips (W₀) and chips steam-treated at less than 1.0 MPa (W₁) and 2.0 MPa (W₄) were co-digested with sewage sludge (S₁ and S₂) taken from two different wastewater treatment plants. The apparent methane yield of W₁ and W₄ co-digested with S₁ (thermophilic) was 261 dm(3)/kgVS (volatile solids) and 248 dm(3)/kgVS, respectively. The apparent methane yield of W₄ co-digested with S₂ was 258 dm(3)/kgVS (mesophilic) and 271 dm(3)/kgVS (thermophilic). Methane production was inhibited by W₀ due to components released during hydrolysis. The methane conversion ratio of pretreated chips obtained in batch experiments varied from 40.5% to 53.8% (mesophilic) and from 49.0% to 63.7% (thermophilic). The methane conversion ratio increased with decreasing acid-soluble lignin content in the chips. Copyright © 2014 Elsevier Ltd. All rights reserved.

Microbial Physiology of the Conversion of Residual Oil to Methane: A Protein Prospective

NASA Astrophysics Data System (ADS)

Morris, Brandon E. L.; Bastida-Lopez, Felipe; von Bergen, Martin; Richnow, Hans-Hermann; Suflita, Joseph M.

2010-05-01

Traditional petroleum recovery techniques are unable to extract the majority of oil in most petroliferous deposits. The recovery of even a fraction of residual hydrocarbon in conventional reserves could represent a substantive energy supply. To this end, the microbial conversion of residual oil to methane has gained increasing relevance in recent years [1,2]. Worldwide demand for methane is expected to increase through 2030 [3], as it is a cleaner-burning alternative to traditional fuels [4]. To investigate the microbial physiology of hydrocarbon-decomposition and ultimate methanogenesis, we initiated a two-pronged approach. First, a model alkane-degrading sulfate-reducing bacterium, Desulfoglaeba alkanexedens, was used to interrogate the predominant metabolic pathway(s) differentially expressed during growth on either n-decane or butyrate. A total of 81 proteins were differentially expressed during bacterial growth on butyrate, while 100 proteins were unique to the alkane-grown condition. Proteins related to alkylsuccinate synthase, or the homologous 1-methyl alkylsuccinate synthase, were identified only in the presence of the hydrocarbon. Secondly, we used a newly developed stable isotope probing technique [5] targeted towards proteins to monitor the flux of carbon through a residual oil-degrading bacterial consortium enriched from a gas-condensate contaminated aquifer [1]. Combined carbon and hydrogen stable isotope fractionation identified acetoclastic methanogenesis as the dominant process in this system. Such findings agree with the previous clone library characterization of the consortium. Furthermore, hydrocarbon activation was determined to be the rate-limiting process during the net conversion of residual oil to methane. References 1. Gieg, L.M., K.E. Duncan, and J.M. Suflita, Bioenegy production via microbial conversion of residual oil to natural gas. Appl Environ Micro, 2008. 74(10): p. 3022-3029. 2. Jones, D.M., et al., Crude-oil biodegradation via methanogenesis in subsurface petroleum reserviors. Nature, 2008. 451: p. 176-180. 3. US-DOE, E.I.A., International Energy Outlook 2009. 2009, United States Department of Energy: Washington D.C. 4. DeLuchi, M.A., Emissions of greenhouse gases from the use of transportation fuels and electricity, US-DoE, Editor. 1991, Center for Transportation Research, Argonne National Laboratory: Chicago, Illinois. 5. Jehmlich, N., et al., Protein-based stable isotope probing (Protein-SIP) reveals active species within anoxic mixed cultures. ISME, 2008. 2: p. 1122-1133.

Clean fuels from biomass. [cellulose fermentation to methane

NASA Technical Reports Server (NTRS)

Hsu, Y. Y.

1974-01-01

The potential of growing crops as a source of fuels is examined, and it is shown that enough arable land is available in the U.S. so that, even with a modest rate of crop yield, the nation could be supplied by fuel crops. The technologies for fuel conversion are available; however, some R&D efforts are needed for scaling up design. Fuel crop economics are discussed and shown to be nonprohibitive.

Thermodynamic analysis on the CO2 conversion processes of methane dry reforming for hydrogen production and CO2 hydrogenation to dimethyl ether

NASA Astrophysics Data System (ADS)

He, Xinyi; Liu, Liping

2017-12-01

Based on the principle of Gibbs free energy minimization, the thermodynamic analysis on the CO2 conversion processes of dry reforming of methane for H2 and CO2 hydrogenation to dimethyl ether was carried out. The composition of the reaction system was determined on the basis of reaction mechanism. The effects of reaction temperature, pressure and raw material composition on the equilibrium conversion and the selectivity of products were analyzed. The results show that high temperature, low pressure, CO2/CH4 molar ratio of 1.0-1.5 and appropriate amount of oxygen are beneficial to the dry reforming of methane. For CO2 hydrogenation to dimethyl ether, low temperature, high pressure, the appropriate H2/CO2 and the proper CO addition in feed are favorable. The calculated results are compared with the relevant studies, indicating that industrial catalytic technology needs further improvement.

Low-temperature superacid catalysis: Reactions of n - butane and propane catalyzed by iron- and manganese-promoted sulfated zirconia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsz-Keung, Cheung; d`Itri, J.L.; Lange, F.C.

1995-12-31

The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments catalytic testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure, 225-450{degrees}C, and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, these reactions were accompanied by cracking; at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part frommore » coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup -8} mol/(g of catalyst {center_dot}s). The observation of butanes, pentanes, and methane as products is consistent with Olah superacid chemistry, whereby propane is first protonated by a very strong acid to form a carbonium ion. The carbonium ion then decomposes into methane and an ethyl cation which undergoes oligocondensation reactions with propane to form higher molecular weight alkanes. The results are consistent with the identification of iron- and manganese-promoted sulfated zirconia as a superacid.« less

Cu-ZSM-5 catalyzed low-temperature hydrogen peroxide-induced methane-to-methanol conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yang; Li, Zhenglong; Allard, Jr., Lawrence Frederick

2017-01-01

We report that Cu-ZSM-5 is an effective catalyst for methane oxidation with hydrogen peroxide. We find that synthesis via ion-exchage and reaction conditions are important factors for the observed efficiency of Cu-ZSM-5.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lebarbier Dagel, Vanessa M.; Li, J.; Taylor, Charles E.

This collaborative joint research project is in the area of advanced gasification and conversion, within the Chinese Academy of Sciences (CAS)-National Energy Technology Laboratory (NETL)-Pacific Northwest National Laboratory (PNNL) Memorandum of Understanding. The goal for this subtask is the development of advanced syngas conversion technologies. Two areas of investigation were evaluated: Sorption-Enhanced Synthetic Natural Gas Production from Syngas The conversion of synthetic gas (syngas) to synthetic natural gas (SNG) is typically catalyzed by nickel catalysts performed at moderate temperatures (275 to 325°C). The reaction is highly exothermic and substantial heat is liberated, which can lead to process thermal imbalance andmore » destruction of the catalyst. As a result, conversion per pass is typically limited, and substantial syngas recycle is employed. Commercial methanation catalysts and processes have been developed by Haldor Topsoe, and in some reports, they have indicated that there is a need and opportunity for thermally more robust methanation catalysts to allow for higher per-pass conversion in methanation units. SNG process requires the syngas feed with a higher H2/CO ratio than typically produced from gasification processes. Therefore, the water-gas shift reaction (WGS) will be required to tailor the H2/CO ratio. Integration with CO2 separation could potentially eliminate the need for a separate WGS unit, thereby integrating WGS, methanation, and CO2 capture into one single unit operation and, consequently, leading to improved process efficiency. The SNG process also has the benefit of producing a product stream with high CO2 concentrations, which makes CO2 separation more readily achievable. The use of either adsorbents or membranes that selectively separate the CO2 from the H2 and CO would shift the methanation reaction (by driving WGS for hydrogen production) and greatly improve the overall efficiency and economics of the process. The scope of this activity was to develop methods and enabling materials for syngas conversion to SNG with readily CO2 separation. Suitable methanation catalyst and CO2 sorbent materials were developed. Successful proof-of-concept for the combined reaction-sorption process was demonstrated, which culminated in a research publication. With successful demonstration, a decision was made to switch focus to an area of fuels research of more interest to all three research institutions (CAS-NETL-PNNL). Syngas-to-Hydrocarbon Fuels through Higher Alcohol Intermediates There are two types of processes in syngas conversion to fuels that are attracting R&D interest: 1) syngas conversion to mixed alcohols; and 2) syngas conversion to gasoline via the methanol-to-gasoline process developed by Exxon-Mobil in the 1970s. The focus of this task was to develop a one-step conversion technology by effectively incorporating both processes, which is expected to reduce the capital and operational cost associated with the conversion of coal-derived syngas to liquid fuels. It should be noted that this work did not further study the classic Fischer-Tropsch reaction pathway. Rather, we focused on the studies for unique catalyst pathways that involve the direct liquid fuel synthesis enabled by oxygenated intermediates. Recent advances made in the area of higher alcohol synthesis including the novel catalytic composite materials recently developed by CAS using base metal catalysts were used.« less

Carbon kinetic isotope effect in the reaction of CH4 with HO

NASA Technical Reports Server (NTRS)

Davidson, J. A.; Cantrell, C. A.; Tyler, S. C.; Shetter, R. E.; Cicerone, R. J.

1987-01-01

The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.

Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking

DOE PAGES

Lustemberg, Pablo G.; Palomino, Robert M.; Gutierrez, Ramon A.; ...

2018-05-28

The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is of great environmental interest and remains a challenge despite many efforts. Extended surfaces of metallic nickel are inactive for a direct CH 4 → CH 3OH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO 2(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts. On the basis of ambient pressure X-ray photoemission spectroscopy andmore » density functional theory calculations, we demonstrate that water plays a crucial role in blocking catalyst sites where methyl species could fully decompose, an essential factor for diminishing the production of CO and CO 2, and in generating sites on which methoxy species and ultimately methanol can form. In addition to water-site blocking, one needs the effects of metal-support interactions to bind and activate methane and water. Lastly, these findings should be considered when designing metal/oxide catalysts for converting methane to value-added chemicals and fuels.« less

Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lustemberg, Pablo G.; Palomino, Robert M.; Gutierrez, Ramon A.

The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is of great environmental interest and remains a challenge despite many efforts. Extended surfaces of metallic nickel are inactive for a direct CH 4 → CH 3OH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO 2(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts. On the basis of ambient pressure X-ray photoemission spectroscopy andmore » density functional theory calculations, we demonstrate that water plays a crucial role in blocking catalyst sites where methyl species could fully decompose, an essential factor for diminishing the production of CO and CO 2, and in generating sites on which methoxy species and ultimately methanol can form. In addition to water-site blocking, one needs the effects of metal-support interactions to bind and activate methane and water. Lastly, these findings should be considered when designing metal/oxide catalysts for converting methane to value-added chemicals and fuels.« less

Ammonium conversion and its feedback effect on methane oxidation of Methylosinus sporium.

PubMed

He, Ruo; Chen, Min; Ma, Ruo-Chan; Su, Yao; Zhang, Xuan

2017-04-01

Ammonium (NH 4 + ) is not only nitrogen source that can support methanotrophic growth, but also it can inhibit methane (CH 4 ) oxidation by competing with CH 4 for the active site of methane monooxygenase. NH 4 + conversion and its feedback effect on the growth and activity of methanotrophs were evaluated with Methylosinus sporium used as a model methanotroph. Nitrogen sources could affect the CH 4 -derived carbon distribution, which varied with incubation time and nitrogen concentrations. More CH 4 -derived carbon was incorporated into biomass in the media with NH 4 + -N, compared to nitrate-nitrogen (NO 3 - -N), as sole nitrogen source at the nitrogen concentrations of 10-18 mmol L -1 . Although ammonia (NH 3 ) oxidation activity of methanotrophs was considerably lower, only accounting for 0.01-0.06% of CH 4 oxidation activity in the experimental cultures, NH 4 + conversion could lead to the pH decrease and toxic intermediates accumulation in the their habits. Compared with NH 4 + , nitrite (NO 2 - ) accumulation in the NH 4 + conversion of methanotroph had stronger inhibition on its activity, especially the joint inhibition of NO 2 - accumulation and the pH decrease during the NH 4 + -N conversion. These results suggested that more attention should be paid to the feedback effects of NH 4 + conversion by methanotrophs to understand effects of NH 4 + on CH 4 oxidation in the environments. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Determination of biogas generation potential as a renewable energy source from supermarket wastes.

PubMed

Alkanok, Gizem; Demirel, Burak; Onay, Turgut T

2014-01-01

Fruit, vegetable, flower waste (FVFW), dairy products waste (DPW), meat waste (MW) and sugar waste (SW) obtained from a supermarket chain were anaerobically digested, in order to recover methane as a source of renewable energy. Batch mesophilic anaerobic reactors were run at total solids (TS) ratios of 5%, 8% and 10%. The highest methane yield of 0.44 L CH4/g VS(added) was obtained from anaerobic digestion of wastes (FVFW+DPW+MW+SW) at 10% TS, with 66.4% of methane (CH4) composition in biogas. Anaerobic digestion of mixed wastes at 5% and 8% TS provided slightly lower methane yields of 0.41 and 0.40 L CH4/g VS(added), respectively. When the wastes were digested alone without co-substrate addition, the highest methane yield of 0.40 L CH4/g VS(added) was obtained from FVFW at 5% TS. Generally, although the volatile solids (VS) conversion percentages seemed low during the experiments, higher methane yields could be obtained from anaerobic digestion of supermarket wastes. A suitable carbon/nitrogen (C/N) ratio, proper adjustment of the buffering capacity and the addition of essential trace nutrients (such as Ni) could improve VS conversion and biogas production yields significantly. Copyright © 2013 Elsevier Ltd. All rights reserved.

Electricity from methane by reversing methanogenesis

PubMed Central

McAnulty, Michael J.; G. Poosarla, Venkata; Kim, Kyoung-Yeol; Jasso-Chávez, Ricardo; Logan, Bruce E.; Wood, Thomas K.

2017-01-01

Given our vast methane reserves and the difficulty in transporting methane without substantial leaks, the conversion of methane directly into electricity would be beneficial. Microbial fuel cells harness electrical power from a wide variety of substrates through biological means; however, the greenhouse gas methane has not been used with much success previously as a substrate in microbial fuel cells to generate electrical current. Here we construct a synthetic consortium consisting of: (i) an engineered archaeal strain to produce methyl-coenzyme M reductase from unculturable anaerobic methanotrophs for capturing methane and secreting acetate; (ii) micro-organisms from methane-acclimated sludge (including Paracoccus denitrificans) to facilitate electron transfer by providing electron shuttles (confirmed by replacing the sludge with humic acids), and (iii) Geobacter sulfurreducens to produce electrons from acetate, to create a microbial fuel cell that converts methane directly into significant electrical current. Notably, this methane microbial fuel cell operates at high Coulombic efficiency. PMID:28513579

Electricity from methane by reversing methanogenesis

NASA Astrophysics Data System (ADS)

McAnulty, Michael J.; G. Poosarla, Venkata; Kim, Kyoung-Yeol; Jasso-Chávez, Ricardo; Logan, Bruce E.; Wood, Thomas K.

2017-05-01

Given our vast methane reserves and the difficulty in transporting methane without substantial leaks, the conversion of methane directly into electricity would be beneficial. Microbial fuel cells harness electrical power from a wide variety of substrates through biological means; however, the greenhouse gas methane has not been used with much success previously as a substrate in microbial fuel cells to generate electrical current. Here we construct a synthetic consortium consisting of: (i) an engineered archaeal strain to produce methyl-coenzyme M reductase from unculturable anaerobic methanotrophs for capturing methane and secreting acetate; (ii) micro-organisms from methane-acclimated sludge (including Paracoccus denitrificans) to facilitate electron transfer by providing electron shuttles (confirmed by replacing the sludge with humic acids), and (iii) Geobacter sulfurreducens to produce electrons from acetate, to create a microbial fuel cell that converts methane directly into significant electrical current. Notably, this methane microbial fuel cell operates at high Coulombic efficiency.

Assessing the greenhouse impact of natural gas

NASA Astrophysics Data System (ADS)

Cathles, L. M.

2012-06-01

The global warming impact of substituting natural gas for coal and oil is currently in debate. We address this question here by comparing the reduction of greenhouse warming that would result from substituting gas for coal and some oil to the reduction which could be achieved by instead substituting zero carbon energy sources. We show that substitution of natural gas reduces global warming by 40% of that which could be attained by the substitution of zero carbon energy sources. At methane leakage rates that are ˜1% of production, which is similar to today's probable leakage rate of ˜1.5% of production, the 40% benefit is realized as gas substitution occurs. For short transitions the leakage rate must be more than 10 to 15% of production for gas substitution not to reduce warming, and for longer transitions the leakage must be much greater. But even if the leakage was so high that the substitution was not of immediate benefit, the 40%-of-zero-carbon benefit would be realized shortly after methane emissions ceased because methane is removed quickly from the atmosphere whereas CO2 is not. The benefits of substitution are unaffected by heat exchange to the ocean. CO2 emissions are the key to anthropogenic climate change, and substituting gas reduces them by 40% of that possible by conversion to zero carbon energy sources. Gas substitution also reduces the rate at which zero carbon energy sources must eventually be introduced.

Method for in situ biological conversion of coal to methane

DOEpatents

Volkwein, Jon C.

1995-01-01

A method and apparatus are provided for the in situ biological conversion of coal to methane comprising culturing on a coal-containing substrate a consortium of microorganisms capable of degrading the coal into methane under suitable conditions. This consortium of microorganisms can be obtained from an underground cavity such as an abandoned mine which underwent a change from being supplied with sewage to where no sewage was present, since these conditions have favored the development of microorganisms capable of using coal as a carbon source and converting coal to methane. The consortium of microorganisms obtained from such abandoned coal mines can be isolated and introduced to hard-to-reach coal-containing substrates which lack such microorganisms and which would otherwise remain unrecoverable. The present invention comprises a significant advantage in that useable energy can be obtained from a number of abandoned mine sites or other areas wherein coal is no longer being recovered, and such energy can be obtained in a safe, efficient, and inexpensive manner.

Development of vanadium-phosphate catalysts for methanol production by selective oxidation of methane

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCormick, R.L.

1995-12-31

The United States has vast natural gas reserves which could contribute significantly to our energy security if economical technologies for conversion to liquid fuels and chemicals were developed. Many of these reserves are small scale or in remote locations and of little value unless they can be transported to consumers. Transportation is economically performed via pipeline, but this route is usually unavailable in remote locations. Another option is to convert the methane in the gas to liquid hydrocarbons, such as methanol, which can easily and economically be transported by truck. Therefore, the conversion of methane to liquid hydrocarbons has themore » potential to decrease our dependence upon oil imports by opening new markets for natural gas and increasing its use in the transportation and chemical sectors of the economy. In this project, we are attempting to develop, and explore new catalysts capable of direct oxidation of methane to methanol. The specific objectives of this work are discussed.« less

Anaerobic co-digestion of sugarcane press mud with vinasse on methane yield.

PubMed

López González, Lisbet Mailin; Pereda Reyes, Ileana; Romero Romero, Osvaldo

2017-10-01

The conversion efficiency of high solids waste digestion as sugarcane press mud (P) may be limited due to hydrolysis step. The option of co-digestion with vinasse, main liquid waste generated from ethanol production, was investigated under batch regime at mesophilic conditions (37.5±1°C) and the best mixture was evaluated under semicontinuous regime in stirred-tank reactors. The maximum values for methane yield in batch tests were for V 75 /P 25 and V 50 /P 50 mixtures (on basis of the chemical oxygen demand (COD) percentage added in the mixture), with an average value of 246NmL CH 4 g -1 COD fed , which was 13% higher than that of press mud alone. A highest methane production rate of 69.6NmL CH 4 g -1 COD fed -1 d -1 was obtained for the mixtureV 75 /P 25 . During the experiment carried out in CSTR reactors, the organic loading rate (OLR) was increased from 0.5 up to 2.2gVSL -1 d -1 . Methane yields of 365L CH 4 kg -1 VS and biogas productivities of 1.6LL -1 were obtained in co-digestion, which was 64% higher in comparison to mono-digestion. The performance of the process in mono-digestion was less stable than in co-digestion, with a significant fall of methane yield to 1.8kgVSm -3 d -1 , and a partial inhibition of the methanogenic archaeas when the OLR was increased up to 2.2kgVSm -3 d -1 . The co-digestion of vinasse with press mud is a good option for the treatment of streams at the alcohol-sugar industry. Copyright © 2017 Elsevier Ltd. All rights reserved.

Genome-Scale Metabolic Reconstructions and Theoretical Investigation of Methane Conversion in Methylomicrobium buryatense Strain 5G(B1)

DOE PAGES

de la Torre, Andrea; Metivier, Aisha; Chu, Frances; ...

2015-11-25

Methane-utilizing bacteria (methanotrophs) are capable of growth on methane and are attractive systems for bio-catalysis. However, the application of natural methanotrophic strains to large-scale production of value-added chemicals/biofuels requires a number of physiological and genetic alterations. An accurate metabolic model coupled with flux balance analysis can provide a solid interpretative framework for experimental data analyses and integration.

Characteristics of adapted hydrogenotrophic community during biomethanation.

PubMed

Rachbauer, Lydia; Beyer, Reinhard; Bochmann, Günther; Fuchs, Werner

2017-10-01

The results presented in this study were carried out as concomitant experiments during the start-up and operation of a biomethanation unit to evaluate the effect of process parameters on carbon conversion, product formation (methane and acetate) and community composition. For that, two different samples were withdrawn from a trickle-bed reactor with immobilized enrichment culture of hydrogenotrophic methanogens adapted from sewage sludge. One sample was taken from the recirculation liquid during start-up phase while the other was withdrawn directly from the carrier material in the reactor. Elevated acid levels especially during start-up were shown to affect the overall carbon conversion. This effect was also seen during the acid tolerance testing reported here. Final acid concentrations of 1.6±0.3g/L resulted in a reduced conversion ratio of only 46%. Without acid addition complete conversion of CO 2 in the headspace was achieved. However, maximum methane production of 0.55±0.02mmol after 4days of incubation was monitored at moderate initial acetate concentration of 0.4g/L. In both analyzed inoculation materials Methanobacterium species were by far the most dominant Archaea with 21.8% in the recirculation liquid during start-up and 84.8% in the enrichment culture immobilized on the carrier material. The microbial composition of the two analyzed samples is in accordance with the results obtained for the carbon conversion and product formation. With approximately 50% of Bacteroidetes and Firmicutes present during reactor start-up the acetic acid production significantly contributed to the overall carbon conversion. In contrast, methane was produced almost exclusively in trials representing continuous operation where acetogenic bacteria accounted only up to 17.5%. In summary, the acid accumulation monitored during reactor start-up of a biomethanation unit is most likely to result from the microbial composition present. Nevertheless, complete adaptation to hydrogenotrophic conditions was proven to alter the consortium and yield methane as main product alongside high carbon conversion of up to 70.5±1.8%. Copyright © 2017 Elsevier B.V. All rights reserved.

Assessment of hydrothermal pretreatment of various lignocellulosic biomass with CO2 catalyst for enhanced methane and hydrogen production.

PubMed

Eskicioglu, Cigdem; Monlau, Florian; Barakat, Abdellatif; Ferrer, Ivet; Kaparaju, Prasad; Trably, Eric; Carrère, Hélène

2017-09-01

Hydrothermal pretreatment of five lignocellulosic substrates (i.e. wheat straw, rice straw, biomass sorghum, corn stover and Douglas fir bark) were conducted in the presence of CO 2 as a catalyst. To maximize disintegration and conversion into bioenergy (methane and hydrogen), pretreatment temperatures and subsequent pressures varied with a range of 26-175 °C, and 25-102 bars, respectively. Among lignin, cellulose and hemicelluloses, hydrothermal pretreatment caused the highest reduction (23-42%) in hemicelluloses while delignification was limited to only 0-12%. These reductions in structural integrity resulted in 20-30% faster hydrolysis rates during anaerobic digestion for the pretreated substrates of straws, sorghum, and corn stover while Douglas fir bark yielded 172% faster hydrolysis/digestion due to its highly refractory nature in the control. Furans and phenolic compounds formed in the pretreated hydrolyzates were below the inhibitory levels for methane and hydrogen production which had a range of 98-340 ml CH 4 /g volatile solids (VS) and 5-26 ml H 2 /g VS, respectively. Results indicated that hydrothermal pretreatment is able to accelerate the rate of biodegradation without generating high levels of inhibitory compounds while showing no discernible effect on ultimate biodegradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

MnTiO3-driven low-temperature oxidative coupling of methane over TiO2-doped Mn2O3-Na2WO4/SiO2 catalyst

PubMed Central

Wang, Pengwei; Zhao, Guofeng; Wang, Yu; Lu, Yong

2017-01-01

Oxidative coupling of methane (OCM) is a promising method for the direct conversion of methane to ethene and ethane (C2 products). Among the catalysts reported previously, Mn2O3-Na2WO4/SiO2 showed the highest conversion and selectivity, but only at 800° to 900°C, which represents a substantial challenge for commercialization. We report a TiO2-doped Mn2O3-Na2WO4/SiO2 catalyst by using Ti-MWW zeolite as TiO2 dopant as well as SiO2 support, enabling OCM with 26% conversion and 76% C2-C3 selectivity at 720°C because of MnTiO3 formation. MnTiO3 triggers the low-temperature Mn2+↔Mn3+ cycle for O2 activation while working synergistically with Na2WO4 to selectively convert methane to C2-C3. We also prepared a practical Mn2O3-TiO2-Na2WO4/SiO2 catalyst in a ball mill. This catalyst can be transformed in situ into MnTiO3-Na2WO4/SiO2, yielding 22% conversion and 62% selectivity at 650°C. Our results will stimulate attempts to understand more fully the chemistry of MnTiO3-governed low-temperature activity, which might lead to commercial exploitation of a low-temperature OCM process. PMID:28630917

Hybrid bioinorganic approach to solar-to-chemical conversion.

PubMed

Nichols, Eva M; Gallagher, Joseph J; Liu, Chong; Su, Yude; Resasco, Joaquin; Yu, Yi; Sun, Yujie; Yang, Peidong; Chang, Michelle C Y; Chang, Christopher J

2015-09-15

Natural photosynthesis harnesses solar energy to convert CO2 and water to value-added chemical products for sustaining life. We present a hybrid bioinorganic approach to solar-to-chemical conversion in which sustainable electrical and/or solar input drives production of hydrogen from water splitting using biocompatible inorganic catalysts. The hydrogen is then used by living cells as a source of reducing equivalents for conversion of CO2 to the value-added chemical product methane. Using platinum or an earth-abundant substitute, α-NiS, as biocompatible hydrogen evolution reaction (HER) electrocatalysts and Methanosarcina barkeri as a biocatalyst for CO2 fixation, we demonstrate robust and efficient electrochemical CO2 to CH4 conversion at up to 86% overall Faradaic efficiency for ≥ 7 d. Introduction of indium phosphide photocathodes and titanium dioxide photoanodes affords a fully solar-driven system for methane generation from water and CO2, establishing that compatible inorganic and biological components can synergistically couple light-harvesting and catalytic functions for solar-to-chemical conversion.

Hybrid bioinorganic approach to solar-to-chemical conversion

PubMed Central

Nichols, Eva M.; Gallagher, Joseph J.; Liu, Chong; Su, Yude; Resasco, Joaquin; Yu, Yi; Sun, Yujie; Yang, Peidong; Chang, Michelle C. Y.; Chang, Christopher J.

2015-01-01

Natural photosynthesis harnesses solar energy to convert CO2 and water to value-added chemical products for sustaining life. We present a hybrid bioinorganic approach to solar-to-chemical conversion in which sustainable electrical and/or solar input drives production of hydrogen from water splitting using biocompatible inorganic catalysts. The hydrogen is then used by living cells as a source of reducing equivalents for conversion of CO2 to the value-added chemical product methane. Using platinum or an earth-abundant substitute, α-NiS, as biocompatible hydrogen evolution reaction (HER) electrocatalysts and Methanosarcina barkeri as a biocatalyst for CO2 fixation, we demonstrate robust and efficient electrochemical CO2 to CH4 conversion at up to 86% overall Faradaic efficiency for ≥7 d. Introduction of indium phosphide photocathodes and titanium dioxide photoanodes affords a fully solar-driven system for methane generation from water and CO2, establishing that compatible inorganic and biological components can synergistically couple light-harvesting and catalytic functions for solar-to-chemical conversion. PMID:26305947

Microbial fuel cells: Running on gas

NASA Astrophysics Data System (ADS)

Ren, Zhiyong Jason

2017-06-01

Methane is an abundant energy source that is used for power generation in thermal power plants via combustion, but direct conversion to electricity in fuel cells remains challenging. Now, a microbial fuel cell is demonstrated to efficiently convert methane directly to current by careful selection of a consortium of microorganisms.

Evidence of sulfate-dependent anaerobic methane oxidation within an area impacted by coalbed methane-related gas migration

EPA Science Inventory

The rapid development of unconventional gas resources has been accompanied by an increase in public awareness regarding the potential effects of drilling operations on drinking water sources. Incidents have been reported involving blowouts (e.g., Converse County, WY; Lawrence Tow...

Feasibility of a peat biogasification process

NASA Astrophysics Data System (ADS)

Buivid, M. G.; Wise, D. L.; Rader, A. M.; McCarty, P. L.; Owen, W. F.

1980-07-01

The feasibility of a two-stage biogasification process for the conversion of peat reserves, the energy content of which in the United States is greater than that of uranium, shale oil or petroleum and natural gas combined, into pipeline-quality methane is investigated. Samples of wet-harvested reed-sedge peat were pretreated in alkaline and nonalkaline conditions in the presence and absence of oxidation in order to determine the most favorable conditions for the conversion of cellulosic and lignaceous fractions to water-soluble, fermentable compounds, and the resulting products were subjected to anaerobic fermentation to methane. Conversion efficiencies obtained reveal that up to 26% of the initial heat content of peat was converted to methane when alkaline heat pretreatment was employed. Analysis of the process parameters by a computer model to determine equipment sizes, mass and energy balances and costs indicates that for a 79,200 GJ/day plant the total capital requirement would be $323,000,000, annual operating costs would be $44,000,000 and average SNG cost would be $3.16/GJ, assuming a 90% stream factor with a delivered peat slurry costing $0.0033/kg.

Sludge accumulation and conversion to methane in a septic tank treating domestic wastewater or black water.

PubMed

Elmitwalli, Tarek

2013-01-01

Although the septic tank is the most applied on-site system for wastewater pre-treatment, limited research has been performed to determine sludge accumulation and biogas production in the tank. Therefore a dynamic mathematical model based on the Anaerobic Digestion Model No. 1 (ADM1) was developed for anaerobic digestion of the accumulated sludge in a septic tank treating domestic wastewater or black water. The results showed that influent chemical oxygen demand (COD) concentration and hydraulic retention time (HRT) of the tank mainly control the filling time with sludge, while operational temperature governs characteristics of the accumulated sludge and conversion to methane. For obtaining stable sludge and high conversion, the tank needs to be operated for a period more than a year without sludge wasting. Maximum conversion to methane in the tank is about 50 and 60% for domestic wastewater and black water, respectively. The required period for sludge wasting depends on the influent COD concentration and the HRT, while characteristics of the wasted sludge are affected by operational temperature followed by the influent COD concentration and the HRT. Sludge production from the tank ranges between 0.19 to 0.22 and 0.13 to 0.15 L/(person.d), for the domestic wastewater and black water, respectively.

Partial oxidation of methane by pulsed corona discharges

NASA Astrophysics Data System (ADS)

Hoeben, W. F. L. M.; Boekhoven, W.; Beckers, F. J. C. M.; van Heesch, E. J. M.; Pemen, A. J. M.

2014-09-01

Pulsed corona-induced partial oxidation of methane in humid oxygen or carbon dioxide atmospheres has been investigated for future fuel synthesis applications. The obtained product spectrum is wide, i.e. saturated, unsaturated and oxygen-functional hydrocarbons. The generally observed methane conversion levels are 6-20% at a conversion efficiency of about 100-250 nmol J-1. The main products are ethane, ethylene and acetylene. Higher saturated hydrocarbons up to C6 have been detected. The observed oxygen-functional hydrocarbons are methanol, ethanol and lower concentrations of aldehydes, ketones, dimethylether and methylformate. Methanol seems to be exclusively produced with CH4/O2 mixtures at a maximum production efficiency of 0.35 nmol J-1. CH4/CO2 mixtures appear to yield higher hydrocarbons. Carboxylic acids appear to be mainly present in the aqueous reactor phase, possibly together with higher molecular weight species.

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol.

PubMed

Grundner, Sebastian; Markovits, Monica A C; Li, Guanna; Tromp, Moniek; Pidko, Evgeny A; Hensen, Emiel J M; Jentys, Andreas; Sanchez-Sanchez, Maricruz; Lercher, Johannes A

2015-06-25

Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon-hydrogen bonds in methane and its subsequent transformation to methanol. The similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towards methanol, in both the enzyme system and copper-exchanged mordenite.

NiCo as catalyst for magnetically induced dry reforming of methane

NASA Astrophysics Data System (ADS)

Varsano, F.; Bellusci, M.; Provino, A.; Petrecca, M.

2018-03-01

In this paper we report the activation of the dry reforming reaction by induction heating of a NiCo alloy. The catalyst plays a double role, serving both as a promoter for the reforming reaction and producing the heat induced by dissipation of the electromagnetic energy. The elevated temperatures imposed by the reforming reaction suggest the choice of an alloy with a Curie temperature >800°C. In this respect Ni:Co ratio 60:40 was chosen. Alloy active sites for CH4and CO2activation are created by a mechanochemical treatment of the alloy that increases solid-state defects. The catalyst has been successfully tested in a continuous-flow reactor working under atmospheric pressure. Methane conversion and hydrogen production yields have been measured as a function of the applied magnetic field, reactant flow rate and time on stream.

Photodissociation of cyanoacetylene: Application to the atmospheric chemistry of Titan

NASA Technical Reports Server (NTRS)

Clarke, David W.; Ferris, James P.

1995-01-01

The quantum yield and reaction threshold for the photochemical dissociation of cyanoacetylene into a hydrogen atom and the cyanoethynyl radical have been determined. The quantum yield at 185 nm is approximately 0.09. The threshold is approximately 240 nm. Combination of this data with literature values shows that production of excited-state cyanoacetylene is the major primary process resulting from irradiation between 185 and 254 nm. Also determined are the relative rate constants for the abstraction of a hydrogen atom from hydrogen, methane, and ethane by the cyanoethynyl radical (k(H2):k(CH4):k(C2H6) = 1:9.3:63). Implications of these results for the proposal that hydrogen abstraction plays an important role in the conversion of methane to ethane and in the protection of unsaturated compounds from photoconsumption in the atmosphere of Titan are discussed.

Direct Measure of the Dense Methane Phase in Gas Shale Organic Porosity by Neutron Scattering

DOE PAGES

Eberle, Aaron P. R.; King, Hubert E.; Ravikovitch, Peter I.; ...

2016-08-30

Here, we report the first direct measurements of methane density in shale gas using small-angle neutron scattering. At a constant pressure, the density of methane in the inorganic pores is similar to the gas bulk density of the system conditions. Conversely, the methane density is 2.1 ± 0.2 times greater in the organic mesopores. Furthermore, classical density functional theory calculations show that this excess density in the organic pores persists to elevated temperatures, typical of shale gas reservoir conditions, providing new insight into the hydrocarbon storage mechanisms within these reservoirs.

Biogasification of water hyacinth and sludge for methane production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chynoweth, D.P.; Biljetina, R.; Srivastava, V.J.

1985-01-01

Research is in progress to determine the technical and economic feasibility of treatment of domestic sewage using primary settling and water hyacinth ponds and conversion of the organic products of this treatment (primary sludge and hyacinth) to substitute natural gas. This paper describes the status of the conversion component of this program which is centered on anaerobic digestion of hyacinth/sludge blends to methane. The results of several experiments conducted successfully in a large-scale experimental test unit located at the hyacinth treatment facility at Walt Disney are presented. 11 refs., 5 figs., 4 tabs.

Methane on Titan: Photochemical-Meteorological-Hydrogeochemical Cycle

NASA Astrophysics Data System (ADS)

Atreya, S. K.; Niemann, H. B.; Owen, T. C.; Adams, E. Y.; Demick, J. E.; GCMS Team

2005-08-01

Photochemically driven destruction of methane in Titan's stratosphere leads to irreversible conversion to heavier hydrocarbons (1). The latter would largely condense out of the atmosphere (2). In the absence of recycling, Titan's methane would thus be destroyed in 10-100 million years (1). However, methane is key to the maintenance of Titan's nitrogen atmosphere. Without warming provided by CH4-generated hydrocarbon hazes in the stratosphere and pressure induced opacity in the infrared, particularly by H2-N2 and CH4-N2 collisions in the troposphere, the atmosphere would gradually diminish to tens of millibar pressure (3). Thus, the source-sink cycle of methane is crucial to the evolutionary history of Titan and its atmosphere. The GCMS measurements show that a ``methalogical" cycle with surface evaporation, cloud formation, followed by precipitation (rain) of methane exists. However, this ``closed" cycle does not recycle methane lost to heavy hydrocarbons. A source is required. Unlike the deep, hot, H2-rich interiors of the giant planets, Titan's interior is ill suited for thermochemical conversion of hydrocarbons back to methane. Instead we propose that serpentinization is an effective process for producing methane in Titan's interior (4). Hydration of ultramafic silicates, followed by reaction between the released H2 gas and CO2 or carbon grains can produce large quantities of CH4 at relatively mild (40-90oC) temperatures. Such thermal conditions are believed to exist below the purported water-ammonia ocean (5). Storage of methane produced via serpentinization can occur in form of clathrates. Evidence of outgassing from Titan's interior is provided by GCMS (6) and VIMS (7) data. (1) Wilson, Atreya, JGR 109, E06002, doi:10.1029/2003JE002181, 2004. (2) Wilson, Atreya, PSS 51, 1017, 2003. (3) Lorenz etal. Science 275, 642, 1997. (4) Owen etal. Phys. Uspekhi, in press. (5) Grasset, Pargamin, PSS 53, 371, 2005. (6) Niemann etal., Submitted to Nature, 2005. (7) Sotin etal., Nature 435, 786, 2005.

Methane uptake in urban forests and lawns

Treesearch

Peter M. Groffman; Richard V. Pouyat

2009-01-01

The largest natural biological sink for the radiatively active trace gas methane (CH4) is bacteria in soils that consume CH4 as an energy and carbon source. This sink has been shown to be sensitive to nitrogen (N) inputs and alterations of soil physical conditions. Given this sensitivity, conversion of native ecosystems to...

Conversion of MSW (municipal solids waste) to methane in the SOLCON (solids-concentrating) digester

DOE Office of Scientific and Technical Information (OSTI.GOV)

Biljetina, R.; Srivastava, V.J.; Isaacson, H.R.

1988-01-01

The Institute of Gas Technology (IGT) has been operating a 1200- gallon, anaerobic solids-concentrating (SOLCON) digester at the Walt Disney World Resort Complex in Lake Buena Vista, Florida since January of 1984. This digester development work is part of a larger effort, sponsored by the Gas Research Institute (GRI) Southern California Edison, that provides effective community waste treatment and disposal options while recovering a valuable methane resource from these wastes. Excellent conversions to methane have been obtained in the SOLCON digester during 4 years of uninterrupted operation. Data were collected on: (1) Wastes from experimental municipal wastewater treatment applications. Watermore » hyacinths were harvested from secondary wastewater treatment channels and combined with sludge from primary clarifiers to maximize potential methane recoveries in the digester. (2) Wastes from agricultural operations. Sorghum was selected as a candidate because it represents both a potential energy crop, as well as, a waste resource if only portions of the plant are converted after grain production. (3) Wastes from municipal waste collection.« less

Potential for direct interspecies electron transfer in methanogenic wastewater digester aggregates.

PubMed

Morita, Masahiko; Malvankar, Nikhil S; Franks, Ashley E; Summers, Zarath M; Giloteaux, Ludovic; Rotaru, Amelia E; Rotaru, Camelia; Lovley, Derek R

2011-01-01

Mechanisms for electron transfer within microbial aggregates derived from an upflow anaerobic sludge blanket reactor converting brewery waste to methane were investigated in order to better understand the function of methanogenic consortia. The aggregates were electrically conductive, with conductivities 3-fold higher than the conductivities previously reported for dual-species aggregates of Geobacter species in which the two species appeared to exchange electrons via interspecies electron transfer. The temperature dependence response of the aggregate conductance was characteristic of the organic metallic-like conductance previously described for the conductive pili of Geobacter sulfurreducens and was inconsistent with electron conduction through minerals. Studies in which aggregates were incubated with high concentrations of potential electron donors demonstrated that the aggregates had no significant capacity for conversion of hydrogen to methane. The aggregates converted formate to methane but at rates too low to account for the rates at which that the aggregates syntrophically metabolized ethanol, an important component of the reactor influent. Geobacter species comprised 25% of 16S rRNA gene sequences recovered from the aggregates, suggesting that Geobacter species may have contributed to some but probably not all of the aggregate conductivity. Microorganisms most closely related to the acetate-utilizing Methanosaeta concilii accounted for more than 90% of the sequences that could be assigned to methane producers, consistent with the poor capacity for hydrogen and formate utilization. These results demonstrate for the first time that methanogenic wastewater aggregates can be electrically conductive and suggest that direct interspecies electron transfer could be an important mechanism for electron exchange in some methanogenic systems.

Transient studies of low temperature catalysts for methane conversion. Final report, [September 1992--March 1996

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolf, E.E.

1996-09-30

The objective of this project is to use transient techniques to study gas surface interactions during the oxidative conversion of methane. Two groups of catalysts were studied: a double oxide of vanadium and phosphate or VPO, and double oxides of Ni, Co and Rh and lanthana. The objective of the studies involving the VPO catalyst was to understand gas-surface interactions leading to the formation of formaldehyde. In the second group of catalysts, involving metallo-oxides, the main objective was to study the gas-surface interactions that determine the selectivity to C{sub 2} hydrocarbons or synthesis gas. Transient techniques were used to studymore » the methane-surface interactions and the role of lattice oxygen. The selection of the double oxides was made on the hypothesis that the metal oxide would provide an increase interaction with methane whereas the phosphate or lanthanide would provide the sites for oxygen adsorption. The hypothesis behind this selection of catalysts was that increasing the methane interaction with the catalysts would lower the reaction temperature and thus increase the selectivity to the desired products over the total oxidation reaction. In both groups of catalysts the role of Li as a modifier of the selectivity was also studied in detail.« less

Anaerobic microbial redox processes in a landfill leachate contaminated aquifer (Grindsted, Denmark)

NASA Astrophysics Data System (ADS)

Ludvigsen, L.; Albrechtsen, H.-J.; Heron, G.; Bjerg, P. L.; Christensen, T. H.

1998-10-01

The distribution of anaerobic microbial redox processes was investigated along a 305 m long transect of a shallow landfill-leachate polluted aquifer. By unamended bioassays containing sediment and groundwater, 37 samples were investigated with respect to methane production, sulfate, iron, and manganese reduction, and denitrification. Methane production was restricted to the most reduced part of the plume with rates of 0.003-0.055 nmol CH 4/g dry weight/day. Sulfate reduction was observed at rates of maximum 1.8 nmol SO 42-/g dry weight/day along with methane production in the plume, but sulfate reduction was also observed further downgradient of the landfill. Iron reduction at rates of 5-19 nmol Fe(II)/g dry weight/day was observed in only a few samples, but this may be related to a high detection limit for the iron reducing bioassay. Manganese reduction at rates of maximum 2.4 nmol Mn(II)/g dry weight/day and denitrification at rates of 0.2-37 nmol N 2O-N/g dry weight/day were observed in the less reduced part of the plume. All the redox processes were microbial processes. In many cases, several redox processes took place simultaneously, but in all samples one process dominated accounting for more than 70% of the equivalent carbon conversion. The bioassays showed that the redox zones in the plume identified from the groundwater composition (e.g. as methanogenic and sulfate reducing) locally hosted also other redox processes (e.g. iron reduction). This may have implications for the potential of the redox zone to degrade trace amounts of organic chemicals and suggests that unamended bioassays may be an important supplement to other approaches in characterizing the redox processes in an anaerobic plume.

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol

DOE PAGES

Grundner, Sebastian; Markovits, Monica A. C.; Li, Guanna; ...

2015-06-25

Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon–hydrogen bonds in methane and its subsequent transformation to methanol. In conclusion, the similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towardsmore » methanol, in both the enzyme system and copper-exchanged mordenite.« less

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol

PubMed Central

Grundner, Sebastian; Markovits, Monica A.C.; Li, Guanna; Tromp, Moniek; Pidko, Evgeny A.; Hensen, Emiel J.M.; Jentys, Andreas; Sanchez-Sanchez, Maricruz; Lercher, Johannes A.

2015-01-01

Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon–hydrogen bonds in methane and its subsequent transformation to methanol. The similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towards methanol, in both the enzyme system and copper-exchanged mordenite. PMID:26109507

Effect of influent COD/SO4(2-) ratios on UASB treatment of a synthetic sulfate-containing wastewater.

PubMed

Hu, Yong; Jing, Zhaoqian; Sudo, Yuta; Niu, Qigui; Du, Jingru; Wu, Jiang; Li, Yu-You

2015-07-01

The effect of the chemical oxygen demand/sulfate (COD/SO4(2-)) ratio on the anaerobic treatment of synthetic chemical wastewater containing acetate, ethanol, and sulfate, was investigated using a UASB reactor. The experimental results show that at a COD/SO4(2-) ratio of 20 and a COD loading rate of 25.2gCODL(-1)d(-1), a COD removal of as high as 87.8% was maintained. At a COD/SO4(2-) ratio of 0.5 (sulfate concentration 6000mgL(-1)), however, the COD removal was 79.2% and the methane yield was 0.20LCH4gCOD(-1). The conversion of influent COD to methane dropped from 80.5% to 54.4% as the COD/SO4(2-) ratio decreased from 20 to 0.5. At all the COD/SO4(2-) ratios applied, over 79.4% of the total electron flow was utilized by methane-producing archaea (MPA), indicating that methane fermentation was the predominant reaction. The majority of the methane was produced by acetoclastic MPA at high COD/SO4(2-) ratios and both acetoclastic and hydrogenthrophic MPA at low COD/SO4(2-) ratios. Only at low COD/SO4(2-) ratios were SRB species such as Desulfovibrio found to play a key role in ethanol degradation, whereas all the SRB species were found to be incomplete oxidizers at both high and low COD/SO4(2-) ratios. Copyright © 2015 Elsevier Ltd. All rights reserved.

Continuous hydrogen and methane production from Agave tequilana bagasse hydrolysate by sequential process to maximize energy recovery efficiency.

PubMed

Montiel Corona, Virginia; Razo-Flores, Elías

2018-02-01

Continuous H 2 and CH 4 production in a two-stage process to increase energy recovery from agave bagasse enzymatic-hydrolysate was studied. In the first stage, the effect of organic loading rate (OLR) and stirring speed on volumetric hydrogen production rate (VHPR) was evaluated in a continuous stirred tank reactor (CSTR); by controlling the homoacetogenesis with the agitation speed and maintaining an OLR of 44 g COD/L-d, it was possible to reach a VHPR of 6 L H 2 /L-d, equivalent to 1.34 kJ/g bagasse. In the second stage, the effluent from CSTR was used as substrate to feed a UASB reactor for CH 4 production. Volumetric methane production rate (VMPR) of 6.4 L CH 4 /L-d was achieved with a high OLR (20 g COD/L-d) and short hydraulic retention time (HRT, 14 h), producing 225 mL CH 4 /g-bagasse equivalent to 7.88 kJ/g bagasse. The two-stage continuous process significantly increased energy conversion efficiency (56%) compared to one-stage hydrogen production (8.2%). Copyright © 2017 Elsevier Ltd. All rights reserved.

Treatment of gas from an in situ conversion process

DOEpatents

Diaz, Zaida [Katy, TX; Del Paggio, Alan Anthony [Spring, TX; Nair, Vijay [Katy, TX; Roes, Augustinus Wilhelmus Maria [Houston, TX

2011-12-06

A method of producing methane is described. The method includes providing formation fluid from a subsurface in situ conversion process. The formation fluid is separated to produce a liquid stream and a first gas stream. The first gas stream includes olefins. At least the olefins in the first gas stream are contacted with a hydrogen source in the presence of one or more catalysts and steam to produce a second gas stream. The second gas stream is contacted with a hydrogen source in the presence of one or more additional catalysts to produce a third gas stream. The third gas stream includes methane.

SPaMOB eat atmospheric methane in Antarctica

NASA Astrophysics Data System (ADS)

Lau, C. Y. M.; Edwards, C. R.; Onstott, T. C.

2016-12-01

The diverse and endemic soil microorganisms that have adapted to the hostile environments in Antarctica are facing challenges due to climate change. The seasonally thawed active layer would exhibit greater daily and/or seasonal temperature variations and different soil moisture regimes, which would cause compositional shifts in these microbial communities. Our preliminary data reveal that Antarctic cryosols from the Taylor Dry Valley are capable of oxidizing methane at atmospheric concentration ( 2 ppmv) at significantly higher rates than the acidic mineral cryosols from the Canadian High Arctic (N 79°) [The ISME J (2015) 9: 1880-1891]. Understanding of this understudied behavior for these active layer cryosols is important for determining the potential methane feedback responses in the Antarctic region. We therefore investigate the biodiversity and genome-wide adaptation of the responsible Southern Polar atmospheric methane-oxidizing bacteria (SPaMOB) in these cryosols. Methane consumption at atmospheric concentration at 4 and 10°C was monitored over a period of four weeks. Two cryosol samples that oxidized methane at both temperatures were selected for molecular analyses. PCR-cloning and sequencing of pmoA (particulate methane monooxygenase beta subunit), the marker gene of methane oxidation, revealed that the SPaMOB in alkaline Antarctic cryosols are closely related to Upland Soil Cluster γ (USCγ), whereas the high Canadian Arctic cryosols contain predominantly USCa-like phylotypes. Four metagenomic libraries were prepared from total DNA and sequenced (2x100bp, Illumina). Quality-filtered reads (avg. 20 M reads per library) were de novo assembled and annotated. A 42.8 kb-long contig containing the pmoCBAcluster was successfully assembled. The pmoA gene is closely related to our USCγ clone sequences. In addition to pmo genes, the presence of genes for conversion of methanol to formaldehyde, production of formate and eventually CO2 indicates SPaMOB's ability of complete methane oxidation. Carbon assimilation pathway is suggested by the presence of genes involved in serine synthesis, serine cycle and tricarboxylic acid cycle. This study provides the first genetic basis for a possible role of Antarctica as a current and future methane sink.

Plasma catalytic reforming of methane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bromberg, L.; Cohn, D.R.; Rabinovich, A.

1998-08-01

Thermal plasma technology can be efficiently used in the production of hydrogen and hydrogen-rich gases from methane and a variety of fuels. This paper describes progress in plasma reforming experiments and calculations of high temperature conversion of methane using heterogeneous processes. The thermal plasma is a highly energetic state of matter that is characterized by extremely high temperatures (several thousand degrees Celsius) and high degree of dissociation and substantial degree of ionization. The high temperatures accelerate the reactions involved in the reforming process. Hydrogen-rich gas (50% H{sub 2}, 17% CO and 33% N{sub 2}, for partial oxidation/water shifting) can bemore » efficiently made in compact plasma reformers. Experiments have been carried out in a small device (2--3 kW) and without the use of efficient heat regeneration. For partial oxidation/water shifting, it was determined that the specific energy consumption in the plasma reforming processes is 16 MJ/kg H{sub 2} with high conversion efficiencies. Larger plasmatrons, better reactor thermal insulation, efficient heat regeneration and improved plasma catalysis could also play a major role in specific energy consumption reduction and increasing the methane conversion. A system has been demonstrated for hydrogen production with low CO content ({approximately} 1.5%) with power densities of {approximately} 30 kW (H{sub 2} HHV)/liter of reactor, or {approximately} 10 m{sup 3}/hr H{sub 2} per liter of reactor. Power density should further increase with increased power and improved design.« less

Seasonal Oxygen Dynamics in a Thermokarst Bog in Interior Alaska: Implications for Rates of Methane Oxidation

NASA Astrophysics Data System (ADS)

Neumann, R. B.; Moorberg, C.; Wong, A.; Waldrop, M. P.; Turetsky, M. R.

2015-12-01

Methane is a potent greenhouse gas, and wetlands represent the largest natural source of methane to the atmosphere. However, much of the methane generated in anoxic wetlands never gets emitted to the atmosphere; up to >90% of generated methane can get oxidized to carbon dioxide. Thus, oxidation is an important methane sink and changes in the rate of methane oxidation can affect wetland methane emissions. Most methane is aerobically oxidized at oxic-anoxic interfaces where rates of oxidation strongly depend on methane and oxygen concentrations. In wetlands, oxygen is often the limiting substrate. To improve understanding of belowground oxygen dynamics and its impact on methane oxidation, we deployed two planar optical oxygen sensors in a thermokarst bog in interior Alaska. Previous work at this site indicated that, similar to other sites, rates of methane oxidation decrease over the growing season. We used the sensors to track spatial and temporal patterns of oxygen concentrations over the growing season. We coupled these in-situ oxygen measurements with periodic oxygen injection experiments performed against the sensor to quantify belowground rates of oxygen consumption. We found that over the season, the thickness of the oxygenated water layer at the peatland surface decreased. Previous research has indicated that in sphagnum-dominated peatlands, like the one studied here, rates of methane oxidation are highest at or slightly below the water table. It is in these saturated but oxygenated locations that both methane and oxygen are available. Thus, a seasonal reduction in the thickness of the oxygenated water layer could restrict methane oxidation. The decrease in thickness of the oxygenated layer coincided with an increase in the rate of oxygen consumption during our oxygen injection experiments. The increase in oxygen consumption was not explained by temperature; we infer it was due to an increase in substrate availability for oxygen consuming reactions and/or abundance of key microbial populations. Together, the data provide an explanation for the seasonal decrease in methane oxidation: rates of oxygen consumption increase over the season, which decreases the amount of oxygen dissolved in porewater at the peatland surface and reduces rates of methane oxidation.

Mechanism of Methane Transport from the Rhizosphere to the Atmosphere through Rice Plants 1

PubMed Central

Nouchi, Isamu; Mariko, Shigeru; Aoki, Kazuyuki

1990-01-01

To clarify the mechanisms of methane transport from the rhizosphere into the atmosphere through rice plants (Oryza sativa L.), the methane emission rate was measured from a shoot whose roots had been kept in a culture solution with a high methane concentration or exposed to methane gas in the gas phase by using a cylindrical chamber. No clear correlation was observed between change in the transpiration rate and that in the methane emission rate. Methane was mostly released from the culm, which is an aggregation of leaf sheaths, but not from the leaf blade. Micropores which are different from stomata were newly found at the abaxial epidermis of the leaf sheath by scanning electron microscopy. The measured methane emission rate was much higher than the calculated methane emission rate that would result from transpiration and the methane concentration in the culture solution. Rice roots could absorb methane gas in the gas phase without water uptake. These results suggest that methane dissolved in the soil water surrounding the roots diffuses into the cell-wall water of the root cells, gasifies in the root cortex, and then is mostly released through the micropores in the leaf sheaths. Images Figure 7 PMID:16667719

Starvation and recovery in the deep-sea methanotroph Methyloprofundus sedimenti.

PubMed

Tavormina, Patricia L; Kellermann, Matthias Y; Antony, Chakkiath Paul; Tocheva, Elitza I; Dalleska, Nathan F; Jensen, Ashley J; Valentine, David L; Hinrichs, Kai-Uwe; Jensen, Grant J; Dubilier, Nicole; Orphan, Victoria J

2017-01-01

In the deep ocean, the conversion of methane into derived carbon and energy drives the establishment of diverse faunal communities. Yet specific biological mechanisms underlying the introduction of methane-derived carbon into the food web remain poorly described, due to a lack of cultured representative deep-sea methanotrophic prokaryotes. Here, the response of the deep-sea aerobic methanotroph Methyloprofundus sedimenti to methane starvation and recovery was characterized. By combining lipid analysis, RNA analysis, and electron cryotomography, it was shown that M. sedimenti undergoes discrete cellular shifts in response to methane starvation, including changes in headgroup-specific fatty acid saturation levels, and reductions in cytoplasmic storage granules. Methane starvation is associated with a significant increase in the abundance of gene transcripts pertinent to methane oxidation. Methane reintroduction to starved cells stimulates a rapid, transient extracellular accumulation of methanol, revealing a way in which methane-derived carbon may be routed to community members. This study provides new understanding of methanotrophic responses to methane starvation and recovery, and lays the initial groundwork to develop Methyloprofundus as a model chemosynthesizing bacterium from the deep sea. © 2016 John Wiley & Sons Ltd.

Catalyst and process development for synthesis gas conversion to isobutylene. Final report, September 1, 1990--January 31, 1994

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anthony, R.G.; Akgerman, A.

1994-05-06

Previous work on isosynthesis (conversion of synthesis gas to isobutane and isobutylene) was performed at very low conversions or extreme process conditions. The objectives of this research were (1) determine the optimum process conditions for isosynthesis; (2) determine the optimum catalyst preparation method and catalyst composition/properties for isosynthesis; (3) determine the kinetics for the best catalyst; (4) develop reactor models for trickle bed, slurry, and fixed bed reactors; and (5) simulate the performance of fixed bed trickle flow reactors, slurry flow reactors, and fixed bed gas phase reactors for isosynthesis. More improvement in catalyst activity and selectivity is needed beforemore » isosynthesis can become a commercially feasible (stand-alone) process. Catalysts prepared by the precipitation method show the most promise for future development as compared with those prepared hydrothermally, by calcining zirconyl nitrate, or by a modified sol-gel method. For current catalysts the high temperatures (>673 K) required for activity also cause the production of methane (because of thermodynamics). A catalyst with higher activity at lower temperatures would magnify the unique selectivity of zirconia for isobutylene. Perhaps with a more active catalyst and acidification, oxygenate production could be limited at lower temperatures. Pressures above 50 atm cause an undesirable shift in product distribution toward heavier hydrocarbons. A model was developed that can predict carbon monoxide conversion an product distribution. The rate equation for carbon monoxide conversion contains only a rate constant and an adsorption equilibrium constant. The product distribution was predicted using a simple ratio of the rate of CO conversion. This report is divided into Introduction, Experimental, and Results and Discussion sections.« less

Component and System Sensitivity Considerations for Design of a Lunar ISRU Oxygen Production Plant

NASA Technical Reports Server (NTRS)

Linne, Diane L.; Gokoglu, Suleyman; Hegde, Uday G.; Balasubramaniam, Ramaswamy; Santiago-Maldonado, Edgardo

2009-01-01

Component and system sensitivities of some design parameters of ISRU system components are analyzed. The differences between terrestrial and lunar excavation are discussed, and a qualitative comparison of large and small excavators is started. The effect of excavator size on the size of the ISRU plant's regolith hoppers is presented. Optimum operating conditions of both hydrogen and carbothermal reduction reactors are explored using recently developed analytical models. Design parameters such as batch size, conversion fraction, and maximum particle size are considered for a hydrogen reduction reactor while batch size, conversion fraction, number of melt zones, and methane flow rate are considered for a carbothermal reduction reactor. For both reactor types the effect of reactor operation on system energy and regolith delivery requirements is presented.

The Effect of Copper Addition on the Activity and Stability of Iron-Based CO₂ Hydrogenation Catalysts.

PubMed

Bradley, Matthew J; Ananth, Ramagopal; Willauer, Heather D; Baldwin, Jeffrey W; Hardy, Dennis R; Williams, Frederick W

2017-09-20

Iron-based CO₂ catalysts have shown promise as a viable route to the production of olefins from CO₂ and H₂ gas. However, these catalysts can suffer from low conversion and high methane selectivity, as well as being particularly vulnerable to water produced during the reaction. In an effort to improve both the activity and durability of iron-based catalysts on an alumina support, copper (10-30%) has been added to the catalyst matrix. In this paper, the effects of copper addition on the catalyst activity and morphology are examined. The addition of 10% copper significantly increases the CO₂ conversion, and decreases methane and carbon monoxide selectivity, without significantly altering the crystallinity and structure of the catalyst itself. The FeCu/K catalysts form an inverse spinel crystal phase that is independent of copper content and a metallic phase that increases in abundance with copper loading (>10% Cu). At higher loadings, copper separates from the iron oxide phase and produces metallic copper as shown by SEM-EDS. An addition of copper appears to increase the rate of the Fischer-Tropsch reaction step, as shown by modeling of the chemical kinetics and the inter- and intra-particle transport of mass and energy.

Gasification of land-based biomass. Final report July 78-December 82

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chynoweth, D.P.; Jerger, D.E.; Conrad, J.R.

1983-06-01

The objective of this research was to develop efficient processes for conversion of land-based biomass to methane and other resources. One task was to determine the relative suitability of selected species or feedstocks for biological and thermal gasification processes. The second task was to narrow options for design and operation of the experimental test unit (ETU) on water hyacinth and sludge at Walt Disney World (WDW) and to provide a scientific base for understanding rate- and yield-limiting reactions for biogasification of these feedstocks, (separately and as blends).

Formation of Acetylene in the Reaction of Methane with Iron Carbide Cluster Anions FeC3- under High-Temperature Conditions.

PubMed

Li, Hai-Fang; Jiang, Li-Xue; Zhao, Yan-Xia; Liu, Qing-Yu; Zhang, Ting; He, Sheng-Gui

2018-03-01

The underlying mechanism for non-oxidative methane aromatization remains controversial owing to the lack of experimental evidence for the formation of the first C-C bond. For the first time, the elementary reaction of methane with atomic clusters (FeC 3 - ) under high-temperature conditions to produce C-C coupling products has been characterized by mass spectrometry. With the elevation of temperature from 300 K to 610 K, the production of acetylene, the important intermediate proposed in a monofunctional mechanism of methane aromatization, was significantly enhanced, which can be well-rationalized by quantum chemistry calculations. This study narrows the gap between gas-phase and condensed-phase studies on methane conversion and suggests that the monofunctional mechanism probably operates in non-oxidative methane aromatization. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of biogas generation potential as a renewable energy source from supermarket wastes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alkanok, Gizem; Demirel, Burak, E-mail: burak.demirel@boun.edu.tr; Onay, Turgut T.

2014-01-15

Highlights: • Disposal of supermarket wastes in landfills may contribute to environmental pollution. • High methane yields can be obtained from supermarket wastes by anaerobic co-digestion. • Fruit and vegetable wastes or dairy products wastes could individually be handled by a two-stage anaerobic process. • Buffering capacity, trace metal and C/N ratio are essential for digestion of supermarket wastes. - Abstract: Fruit, vegetable, flower waste (FVFW), dairy products waste (DPW), meat waste (MW) and sugar waste (SW) obtained from a supermarket chain were anaerobically digested, in order to recover methane as a source of renewable energy. Batch mesophilic anaerobic reactorsmore » were run at total solids (TS) ratios of 5%, 8% and 10%. The highest methane yield of 0.44 L CH{sub 4}/g VS{sub added} was obtained from anaerobic digestion of wastes (FVFW + DPW + MW + SW) at 10% TS, with 66.4% of methane (CH{sub 4}) composition in biogas. Anaerobic digestion of mixed wastes at 5% and 8% TS provided slightly lower methane yields of 0.41 and 0.40 L CH{sub 4}/g VS{sub added}, respectively. When the wastes were digested alone without co-substrate addition, the highest methane yield of 0.40 L CH{sub 4}/g VS{sub added} was obtained from FVFW at 5% TS. Generally, although the volatile solids (VS) conversion percentages seemed low during the experiments, higher methane yields could be obtained from anaerobic digestion of supermarket wastes. A suitable carbon/nitrogen (C/N) ratio, proper adjustment of the buffering capacity and the addition of essential trace nutrients (such as Ni) could improve VS conversion and biogas production yields significantly.« less

Assessment of Methane Emissions – Impact of Using Natural Gas Engines in Unconventional Resource Development

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nix, Andrew; Johnson, Derek; Heltzel, Robert

Researchers at the Center for Alternative Fuels, Engines, and Emissions (CAFEE) completed a multi-year program under DE-FE0013689 entitled, “Assessing Fugitive Methane Emissions Impact Using Natural Gas Engines in Unconventional Resource Development.” When drilling activity was high and industry sought to lower operating costs and reduce emissions they began investing in dual fuel and dedicated natural gas engines to power unconventional well equipment. From a review of literature we determined that the prime-movers (or major fuel consumers) of unconventional well development were the service trucks (trucking), horizontal drilling rig (drilling) engines, and hydraulic stimulation pump (fracturing) engines. Based on early findingsmore » from on-road studies we assessed that conversion of prime movers to operate on natural gas could contribute to methane emissions associated with unconventional wells. As such, we collected significant in-use activity data from service trucks and in-use activity, fuel consumption, and gaseous emissions data from drilling and fracturing engines. Our findings confirmed that conversion of the prime movers to operate as dual fuel or dedicated natural gas – created an additional source of methane emissions. While some gaseous emissions were decreased from implementation of these technologies – methane and CO 2 equivalent emissions tended to increase, especially for non-road engines. The increases were highest for dual fuel engines due to methane slip from the exhaust and engine crankcase. Dedicated natural gas engines tended to have lower exhaust methane emissions but higher CO 2 emissions due to lower efficiency. Therefore, investing in currently available natural gas technologies for prime movers will increase the greenhouse gas footprint of the unconventional well development industry.« less

Commercialization of waste gob gas and methane produced in conjunction with coal mining operations. Final report, August 1992--December 1993

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1993-12-01

The primary objectives of the project were to identify and evaluate existing processes for (1) using gas as a feedstock for production of marketable, value-added commodities, and (2) enriching contaminated gas to pipeline quality. The following gas conversion technologies were evaluated: (1) transformation to liquid fuels, (2) manufacture of methanol, (3) synthesis of mixed alcohols, and (4) conversion to ammonia and urea. All of these involved synthesis gas production prior to conversion to the desired end products. Most of the conversion technologies evaluated were found to be mature processes operating at a large scale. A drawback in all of themore » processes was the need to have a relatively pure feedstock, thereby requiring gas clean-up prior to conversion. Despite this requirement, the conversion technologies were preliminarily found to be marginally economic. However, the prohibitively high investment for a combined gas clean-up/conversion facility required that REI refocus the project to investigation of gas enrichment alternatives. Enrichment of a gas stream with only one contaminant is a relatively straightforward process (depending on the contaminant) using available technology. However, gob gas has a unique nature, being typically composed of from constituents. These components are: methane, nitrogen, oxygen, carbon dioxide and water vapor. Each of the four contaminants may be separated from the methane using existing technologies that have varying degrees of complexity and compatibility. However, the operating and cost effectiveness of the combined system is dependent on careful integration of the clean-up processes. REI is pursuing Phase 2 of this project for demonstration of a waste gas enrichment facility using the approach described above. This is expected to result in the validation of the commercial and technical viability of the facility, and the refinement of design parameters.« less

Renewable Natural Gas Clean-up Challenges and Applications

DTIC Science & Technology

2011-01-13

produced from digesters ─ Animal manure (dairy cows, swine) ─ Waste water treatment facilities > Methane from Landfills > RNG produced from...AGR used in process • Two stage + trim methanation reactor • Dehydration to achieve gas pipeline specifications ~ 70% conversion efficiency 21... digestion of agricultural waste for on-site electricity generation ─Altamont Landfill—Landfill gas (LFG) cleanup for production of liquefied natural gas

Temporal variation of aerobic methane oxidation over a tidal cycle in a wetland of northern Taiwan.

NASA Astrophysics Data System (ADS)

Lee, T. Y.; Wang, P. L.; Lin, L. H.

2017-12-01

Aerobic methanotrophy plays an important role in controlling methane emitted from wetlands. However, the activity of aerobic methanotrophy regulated by temporal fluctuation of oxygen and methane supply in tidal wetlands is not well known. This study aims to examine the dynamics of methane fluxes and potential aerobic methane consumption rates in a tidal wetland of northern Taiwan, where the variation of environmental characteristics, such as sulfate and methane concentration in pore water has been demonstrated during a tidal cycle. Two field campaigns were carried out in December of 2016 and March of 2017. Fluxes of methane emission, methane concentrations in surface sediments and oxygen profiles were measured at different tidal phases. Besides, batch incubations were conducted on surface sediments in order to quantify potential microbial methane consumption rates and to derive the kinetic parameters for aerobic methanotrophy. Our results demonstrated temporal changes of the surface methane concentration and the methane emission flux during a tidal cycle, while the oxygen flux into the sediment was kept at a similar magnitude. The methane flux was low when the surface was exposed for both shortest and longest periods of time. The potential aerobic methane oxidation rate was high for sample collected from the surface sediments exposed the longest. No correlation could be found between the potential aerobic methane oxidation rate and either the oxygen downward flux or methane emission flux. The decoupled relationships between these observed rates and fluxes suggest that, rather than aerobic methanotrophy, heterotrophic respirations exert a profound control on oxygen flux, and the methane emission is not only been affected by methane consumption but also methane production at depths. The maximum potential rate and the half saturation concentration determined from the batch incubations were high for the surface sediments collected in low tide, suggesting that aerobic methanotrophy could be modulated to reach peak activity once the influence of saline water is reduced to a low level.

Hydrogen production from methane using oxygen-permeable ceramic membranes

NASA Astrophysics Data System (ADS)

Faraji, Sedigheh

Non-porous ceramic membranes with mixed ionic and electronic conductivity have received significant interest in membrane reactor systems for the conversion of methane and higher hydrocarbons to higher value products like hydrogen. However, hydrogen generation by this method has not yet been commercialized and suffers from low membrane stability, low membrane oxygen flux, high membrane fabrication costs, and high reaction temperature requirements. In this dissertation, hydrogen production from methane on two different types of ceramic membranes (dense SFC and BSCF) has been investigated. The focus of this research was on the effects of different parameters to improve hydrogen production in a membrane reactor. These parameters included operating temperature, type of catalyst, membrane material, membrane thickness, membrane preparation pH, and feed ratio. The role of the membrane in the conversion of methane and the interaction with a Pt/CeZrO2 catalyst has been studied. Pulse studies of reactants and products over physical mixtures of crushed membrane material and catalyst have clearly demonstrated that a synergy exists between the membrane and the catalyst under reaction conditions. The degree of catalyst/membrane interaction strongly impacts the conversion of methane and the catalyst performance. During thermogravimetric analysis, the onset temperature of oxygen release for BSCF was observed to be lower than that for SFC while the amount of oxygen release was significantly greater. Pulse injections of CO2 over crushed membranes at 800°C have shown more CO2 dissociation on the BSCF membrane than the SFC membrane, resulting in higher CO formation on the BSCF membrane. Similar to the CO2 pulses, when CO was injected on the samples at 800°C, CO2 production was higher on BSCF than SFC. It was found that hydrogen consumption on BSCF particles is 24 times higher than that on SFC particles. Furthermore, Raman spectroscopy and temperature programmed desorption studies of CO and CO2 showed a higher CO and CO2 adsorption (for temperatures ranging from room temperature to 600°C) on BSCF compared to the SFC membrane. CO2 reforming reactions on BSCF and SFC dense membranes in a membrane reactor showed higher methane conversion and H2/CO ratio on BSCF than SFC in the presence of the Pt/CeZrO2 catalyst. This high conversion and H2/CO ratio could be ascribed to higher CO, CO2, and H2 adsorption on BSCF than SFC, resulting in higher steam and CO2 reforming on the BSCF. The Pt-Ni/CeZrO2 catalyst exhibits promising performance for hydrogen production. Platinum enhances the reducibility of Ni/Al2O 3 and Ni/CeZrO2 catalysts resulting in improved catalysts for H2 production at moderate temperatures. TPR and Raman studies show an alloy formation in the Pt-Ni/Al2O3 catalyst. Further work is required to study the interaction between Pt and Ni in the bimetallic Pt-Ni/CeZrO2 and Pt-Ni/Al2O3 catalysts. Although the Pt-Ni/Al2O3 catalyst shows high methane conversion in the presence of the BSCF membrane at 800°C, the activity of this catalyst is low at 600°C. Pt-Ni/CeZrO2 bimetallic catalyst demonstrates superior performance compared to Pt-Ni/Al2O3 catalyst at 600°C. The thinner BSCF membrane (2.2 mm) demonstrates a higher methane conversion and H2:CO ratio than the thicker BSCF membrane (2.6 mm) because membrane oxygen flux is inversely proportional to thickness. Varying the pH of the precursor solution during membrane preparation has no significant effect on the oxygen flux or the reaction. The CH 4:CO2 feed ratio significantly affects the hydrogen production over the BSCF membrane. Altering the CH4:CO2 ratio has a direct impact on the oxygen flux, which in turn can influence the reaction pathway. These studies suggest that the Pt-Ni/CeZrO2 catalyst might be suitable for low-temperature hydrocarbon conversion reactions over thin BSCF ceramic membranes. Most importantly, the BSCF membrane can reduce the apparent activation energy of the CO2 reforming reaction by changing the reaction pathway to include more steam reforming.

Fiber Laser methane sensor with the function of self-diagnose

NASA Astrophysics Data System (ADS)

Li, Yan-fang; Wei, Yu-bin; Shang, Ying; Wang, Chang; Liu, Tong-yu

2012-02-01

Using the technology of tunable diode laser absorption spectroscopy and the technology of micro-electronics, a fiber laser methane sensor based on the microprocessor C8051F410 is given. In this paper, we use the DFB Laser as the light source of the sensor. By tuning temperature and driver current of the DFB laser, we can scan the laser over the methane absorption line, Based on the Beer-Lambert law, through detect the variation of the light power before and after the absorption we realize the methane detection. It makes the real-time and online detection of methane concentration to be true, and it has the advantages just as high accuracy, immunity to other gases , long calibration cycle and so on. The sensor has the function of adaptive gain and self-diagnose. By introducing digital potentiometers, the gain of the photoelectric conversion operational amplifier can be controlled by the microprocessor according to the light power. When the gain and the conversion voltage achieve the set value, then we can consider the sensor in a fault status, and then the software will alarm us to check the status of the probe. So we improved the dependence and the stability of the measured results. At last we give some analysis on the sensor according the field application and according the present working, we have a look of our next work in the distance.

Simultaneous Hydrogen and Methane Production Through Multi-Phase Anaerobic Digestion of Paperboard Mill Wastewater Under Different Operating Conditions.

PubMed

Farghaly, Ahmed; Tawfik, Ahmed

2017-01-01

Multi-phase anaerobic reactor for H 2 and CH 4 production from paperboard mill wastewater was studied. The reactor was operated at hydraulic retention times (HRTs) of 12, 18, 24, and 36 h, and organic loading rates (OLRs) of 2.2, 1.5, 1.1, and 0.75 kg chemical oxygen demand (COD)/m 3  day, respectively. HRT of 12 h and OLR of 2.2 kg COD/m 3  day provided maximum hydrogen yield of 42.76 ± 14.5 ml/g COD removed and volumetric substrate uptake rate (-rS) of 16.51 ± 4.43 mg COD/L h. This corresponded to the highest soluble COD/total COD (SCOD/TCOD) ratio of 56.25 ± 3.3 % and the maximum volatile fatty acid (VFA) yield (Y VFA ) of 0.21 ± 0.03 g VFA/g COD, confirming that H 2 was mainly produced through SCOD conversion. The highest methane yield (18.78 ± 3.8 ml/g COD removed ) and -rS of 21.74 ± 1.34 mgCOD/L h were achieved at an HRT of 36 h and OLR of 0.75 kg COD/m 3  day. The maximum hydrogen production rate (HPR) and methane production rate (MPR) were achieved at carbon to nitrogen (C/N) ratio of 47.9 and 14.3, respectively. This implies the important effect of C/N ratio on the distinction between the dominant microorganism bioactivities responsible for H 2 and CH 4 production.

Solar Spectrum Photocatalytic Conversion of CO2 and Water Vapor Into Hydrocarbons Using TiO2 Nanoparticle Membranes

NASA Astrophysics Data System (ADS)

Rani, Sanju; Bao, Ningzhong; Roy, Somnath C.

2014-01-01

A viable option for recycling carbon dioxide is through the sunlight-powered photocatalytic conversion of CO2 and water vapor into hydrocarbon fuels over highly active nanocatalysts. With photocatalytic CO2 reduction sunlight, a renewable energy source as durable as the sun, is used to drive the catalytic reaction with the resultant fuel products compatible with the current hydrocarbon-based energy infrastructure. The use of co-catalyst (Cu, Pt)-sensitized TiO2 nanoparticle wafers in the photocatalytic conversion of CO2 and water vapor to hydrocarbon fuels, with optimal humidity levels and exposure times established. We also attempted to increase product formation by sputtering both co-catalysts on the nanoparticle wafer's surface, with the resulting product rates significantly higher than that of either the Cu or Pt coated samples. When the TiO2 nanoparticle wafers are used in a flow-through membrane implementation we find a significant increase in product rates of formation, including methane, hydrogen, and carbon monoxide. We believe that nanocatalyst-based flow-through membranes are a viable route for achieving large-scale and low cost photocatalytic solar fuel production.

Interactions between nitrogen cycling and methane oxidation in the pelagic waters of the Gulf of Mexico.

NASA Astrophysics Data System (ADS)

Joye, S. B.; Weber, S.; Battles, J.; Montoya, J. P.

2014-12-01

Methane is an important greenhouse gas that plays a critical role in climate variation. Although a variety of marine methane sources and sinks have been identified, key aspects of the fate of methane in the ocean remain poorly constrained. At cold seeps in the Gulf of Mexico and elsewhere, methane is introduced into the overlying water column via fluid escape from the seabed. We quantified the fate of methane in the water column overlying seafloor cold seeps, in a brine basin, and at several control sites. Our goals were to determine the factors that regulated methane consumption and assimilation and to explore how these controlling factors varied among and between sites. In particular, we examined the impact of nitrogen availability on methane oxidation and studied the ability of methane oxidizing bacteria to fix molecular nitrogen. Methane oxidation rates were highest in the methane rich bottom waters of natural hydrocabron seeps. At these sites, inorganic nitrogen addition stimulated methane oxidation in laboratory experiments. In vitro shipboard experiments revealed that rates of methane oxidation and nitrogen fixation were correlated strongly, suggesting that nitrogen fixation may have been mediated by methanotrophic bacteria. The highest rates of methane oxidation and nitrogen fixation were observed in the deepwater above at natural hydrocarbon seeps. Rates of methane oxidation were substantial along the chemocline of a brine basin but in these ammonium-rich brines, addition of inorganic nitrogen had little impact on methane oxidation suggesting that methanotrophy in these waters were not nitrogen limited. Control sites exhibited the lowest methane concentrations and methane oxidation rates but even these waters exhibited substantial potential for methane oxidation when methane and inorganic nitrogen concentrations were increased. Together, these data suggest that the availability of inorganic nitrogen plays a critical role in regulating methane oxidation in pelagic ocean waters. Some methanotrophs may obtain a competitive advantage in nitrogen-limited oceanic environments by fixing molecular nitrogen. The importance of such "methano-diazotrophy" on a global scale warrants further investigation.

Seasonal Rates of Methane Oxidation in Anoxic Marine Sediments

PubMed Central

Iversen, Niels; Blackburn, T. Henry

1981-01-01

Methane concentrations and rates of methane oxidation were measured in intact sediment cores from an inshore marine sediment at Jutland, Denmark. The rates of methane oxidation, determined by the appearance of 14CO2 from injected 14CH4, varied with sediment depth and season. Most methane oxidation was anoxic, but oxygen may have contributed to methane oxidation at the sediment surface. Cumulative rates (0- to 12-cm depth) for methane oxidation at Kysing Fjord were 3.34, 3.48, 8.60, and 17.04 μmol m−2 day−1 for April (4°C), May (13°C), July (17°C), and August (21°C), respectively. If all of the methane was oxidized by sulfate, it would account for only 0.01 to 0.06% of the sulfate reduction. The data indicate that methane was produced, in addition to being oxidized, in the 0- to 18-cm sediment stratum. PMID:16345784

The Reduction of Lunar Regolith by Carbothermal Processing Using Methane

NASA Technical Reports Server (NTRS)

Balasubramaniam, R.; Hegde, U.; Gokoglu, S.

2010-01-01

The processing of lunar regolith for the production of oxygen is a key component of the In-Situ Resource Utilization plans Currently being developed by NASA. In the carbothermal process, a portion of the surface of the regolith in a container is heated by exposure to a heat source so that a small zone of molten regolith is established. A continuous flow of methane is maintained over the molten regolith zone. In this paper, we discuss the development of a chemical conversion model of the carbothermal process to predict the rate of production of carbon monoxide. Our model is based on a mechanism where methane pyrolyzes when it comes in contact with the surface of the hot molten regolith to form solid carbon and hydrogen gas. Carbon is deposited on the surface of the melt, and hydrogen is released into the gas stream above the melt surface. We assume that the deposited carbon mixes in the molten regolith and reacts with metal oxides in a reduction reaction by which gaseous carbon monoxide is liberated. Carbon monoxide bubbles through the melt and is released into the gas stream. It is further processed downstream to ultimately produce oxygen.

The Reduction of Lunar Regolith by Carbothermal Processing Using Methane

NASA Technical Reports Server (NTRS)

Balasubramaniam, R.; Gokoglu, S. A.; Hegde, U.

2010-01-01

The processing of lunar regolith for the production of oxygen is a key component of the In-Situ Resource Utilization plans currently being developed by NASA. In the carbothermal process, a portion of the surface of the regolith in a container is heated by exposure to a heat source so that a small zone of molten regolith is established. A continuous flow of methane is maintained over the molten regolith zone. In this paper, we discuss the development of a chemical conversion model of the carbothermal process to predict the rate of production of carbon monoxide. Our model is based on a mechanism where methane pyrolyzes when it comes in contact with the surface of the hot molten regolith to form solid carbon and hydrogen gas. Carbon is deposited on the surface of the melt, and hydrogen is released into the gas stream above the melt surface. We assume that the deposited carbon mixes in the molten regolith and reacts with metal oxides in a reduction reaction by which gaseous carbon monoxide is liberated. Carbon monoxide bubbles through the melt and is released into the gas stream. It is further processed downstream to ultimately produce oxygen.

Treatment of natural rubber processing wastewater using a combination system of a two-stage up-flow anaerobic sludge blanket and down-flow hanging sponge system.

PubMed

Tanikawa, D; Syutsubo, K; Hatamoto, M; Fukuda, M; Takahashi, M; Choeisai, P K; Yamaguchi, T

2016-01-01

A pilot-scale experiment of natural rubber processing wastewater treatment was conducted using a combination system consisting of a two-stage up-flow anaerobic sludge blanket (UASB) and a down-flow hanging sponge (DHS) reactor for more than 10 months. The system achieved a chemical oxygen demand (COD) removal efficiency of 95.7% ± 1.3% at an organic loading rate of 0.8 kg COD/(m(3).d). Bacterial activity measurement of retained sludge from the UASB showed that sulfate-reducing bacteria (SRB), especially hydrogen-utilizing SRB, possessed high activity compared with methane-producing bacteria (MPB). Conversely, the acetate-utilizing activity of MPB was superior to SRB in the second stage of the reactor. The two-stage UASB-DHS system can reduce power consumption by 95% and excess sludge by 98%. In addition, it is possible to prevent emissions of greenhouse gases (GHG), such as methane, using this system. Furthermore, recovered methane from the two-stage UASB can completely cover the electricity needs for the operation of the two-stage UASB-DHS system, accounting for approximately 15% of the electricity used in the natural rubber manufacturing process.

Comparative evaluation of anaerobic digestion for sewage sludge and various organic wastes with simple modeling.

PubMed

Hidaka, Taira; Wang, Feng; Tsumori, Jun

2015-09-01

Anaerobic co-digestion of sewage sludge and other organic wastes, such as kitchen garbage, food waste, and agricultural waste, at a wastewater treatment plant (WWTP) is a promising method for both energy and material recovery. Substrate characteristics and the anaerobic digestion performance of sewage sludge and various organic wastes were compared using experiments and modeling. Co-digestion improved the value of digested sewage sludge as a fertilizer. The relationship between total and soluble elemental concentrations was correlated with the periodic table: most Na and K (alkali metals) were soluble, and around 20-40% of Mg and around 10-20% of Ca (alkaline earth metals) were soluble. The ratio of biodegradable chemical oxygen demand of organic wastes was 65-90%. The methane conversion ratio and methane production rate under mesophilic conditions were evaluated using a simplified mathematical model. There was reasonably close agreement between the model simulations and the experimental results in terms of methane production and nitrogen concentration. These results provide valuable information and indicate that the model can be used as a pre-evaluation tool to facilitate the introduction of co-digestion at WWTPs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Genome-scale metabolic reconstructions and theoretical investigation of methane conversion in Methylomicrobium buryatense strain 5G(B1).

PubMed

de la Torre, Andrea; Metivier, Aisha; Chu, Frances; Laurens, Lieve M L; Beck, David A C; Pienkos, Philip T; Lidstrom, Mary E; Kalyuzhnaya, Marina G

2015-11-25

Methane-utilizing bacteria (methanotrophs) are capable of growth on methane and are attractive systems for bio-catalysis. However, the application of natural methanotrophic strains to large-scale production of value-added chemicals/biofuels requires a number of physiological and genetic alterations. An accurate metabolic model coupled with flux balance analysis can provide a solid interpretative framework for experimental data analyses and integration. A stoichiometric flux balance model of Methylomicrobium buryatense strain 5G(B1) was constructed and used for evaluating metabolic engineering strategies for biofuels and chemical production with a methanotrophic bacterium as the catalytic platform. The initial metabolic reconstruction was based on whole-genome predictions. Each metabolic step was manually verified, gapfilled, and modified in accordance with genome-wide expression data. The final model incorporates a total of 841 reactions (in 167 metabolic pathways). Of these, up to 400 reactions were recruited to produce 118 intracellular metabolites. The flux balance simulations suggest that only the transfer of electrons from methanol oxidation to methane oxidation steps can support measured growth and methane/oxygen consumption parameters, while the scenario employing NADH as a possible source of electrons for particulate methane monooxygenase cannot. Direct coupling between methane oxidation and methanol oxidation accounts for most of the membrane-associated methane monooxygenase activity. However the best fit to experimental results is achieved only after assuming that the efficiency of direct coupling depends on growth conditions and additional NADH input (about 0.1-0.2 mol of incremental NADH per one mol of methane oxidized). The additional input is proposed to cover loss of electrons through inefficiency and to sustain methane oxidation at perturbations or support uphill electron transfer. Finally, the model was used for testing the carbon conversion efficiency of different pathways for C1-utilization, including different variants of the ribulose monophosphate pathway and the serine cycle. We demonstrate that the metabolic model can provide an effective tool for predicting metabolic parameters for different nutrients and genetic perturbations, and as such, should be valuable for metabolic engineering of the central metabolism of M. buryatense strains.

Photoenhanced anaerobic digestion of organic acids

DOEpatents

Weaver, Paul F.

1990-01-01

A process is described for rapid conversion of organic acids and alcohols anaerobic digesters into hydrogen and carbon dioxide, the optimal precursor substrates for production of methane. The process includes addition of photosynthetic bacteria to the digester and exposure of the bacteria to radiant energy (e.g., solar energy). The process also increases the pH stability of the digester to prevent failure of the digester. Preferred substrates for photosynthetic bacteria are the organic acid and alcohol waste products of fermentative bacteria. In mixed culture with methanogenic bacteria or in defined co-culture with non-aceticlastic methanogenic bacteria, photosynthetic bacteria are capable of facilitating the conversion or organic acids and alcohols into methane with low levels of light energy input.

Analysis of Percent On-Cell Reformation of Methane in SOFC Stacks: Thermal, Electrical and Stress Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Recknagle, Kurtis P.; Yokuda, Satoru T.; Jarboe, Daniel T.

2006-04-07

This report summarizes a parametric analysis performed to determine the effect of varying the percent on-cell reformation (OCR) of methane on the thermal and electrical performance for a generic, planar solid oxide fuel cell (SOFC) stack design. OCR of methane can be beneficial to an SOFC stack because the reaction (steam-methane reformation) is endothermic and can remove excess heat generated by the electrochemical reactions directly from the cell. The heat removed is proportional to the amount of methane reformed on the cell. Methane can be partially pre-reformed externally, then supplied to the stack, where rapid reaction kinetics on the anodemore » ensures complete conversion. Thus, the thermal load varies with methane concentration entering the stack, as does the coupled scalar distributions, including the temperature and electrical current density. The endotherm due to the reformation reaction can cause a temperature depression on the anode near the fuel inlet, resulting in large thermal gradients. This effect depends on factors that include methane concentration, local temperature, and stack geometry.« less

Ethane's 12C/13C Ratio in Titan: Implications for Methane Replenishment

NASA Technical Reports Server (NTRS)

Jennings, Donald E.; Nixon, C. A.; Romani, P. N.; Bjoraker, G. L.; Sada, P. V.; Lunsford, A. W.; Boyle, R. J.; Hesman, B. E.; McCabe, G. H.

2009-01-01

As the .main destination of carbon in the destruction of methane in the atmosphere of Titan, ethane provides information about the carbon isotopic composition of the reservoir from which methane is replenished. If the amount of methane entering the atmosphere is presently equal to the amount converted to ethane, the 12C/13C ratio in ethane should be close to the ratio in the reservoir. We have measured the 12C/13C ratio in ethane both with Cassini CIRS(exp 1) and from the ground and find that it is very close to the telluric standard and outer planet values (89), consistent with a primordial origin for the methane reservoir. The lower 12C/13C ratio measured for methane by Huygens GCMS (82.3) can be explained if the conversion of CH4 to CH3 (and C2H6) favors 12C over 13C with a carbon kinetic isotope effect of 1.08. The time required for the atmospheric methane to reach equilibrium, i.e., for replenishment to equal destruction, is approximately 5 methane atmospheric lifetimes.

A New Energy-Saving Catalytic System: Carbon Dioxide Activation by a Metal/Carbon Catalyst.

PubMed

Yun, Danim; Park, Dae Sung; Lee, Kyung Rok; Yun, Yang Sik; Kim, Tae Yong; Park, Hongseok; Lee, Hyunjoo; Yi, Jongheop

2017-09-22

The conversion of CO 2 into useful chemicals is an attractive method to reduce greenhouse gas emissions and to produce sustainable chemicals. However, the thermodynamic stability of CO 2 means that a lot of energy is required for its conversion into chemicals. Here, we suggest a new catalytic system with an alternative heating system that allows minimal energy consumption during CO 2 conversion. In this system, electrical energy is transferred as heat energy to the carbon-supported metal catalyst. Fast ramping rates allow high operating temperatures (T app =250 °C) to be reached within 5 min, which leads to an 80-fold decrease of energy consumption in methane reforming using CO 2 (DRM). In addition, the consumed energy normalized by time during the DRM reaction in this current-assisted catalysis is sixfold lower (11.0 kJ min -1 ) than that in conventional heating systems (68.4 kJ min -1 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance of a passively vented field-scale biofilter for the microbial oxidation of landfill methane.

PubMed

Gebert, J; Gröngröft, A

2006-01-01

An upflow biofilter system was operated on a passively vented landfill for the treatment of residual landfill methane. Biofilter methane emissions as a basis for determining methane removal rates were assessed by manual and automated chamber measurements, by measuring methane concentrations in the top layer gaseous phase in combination with gas flow rates, and by evaluating the methane load in the reverse gas flow following the change of landfill gas flux direction as governed by the course of barometric pressure. Methane removal rates were very high with maximum values of 80 g h(-1) m(-3). For the observed cases, the limit of biofilter methane oxidation capacity was not reached and absolute removal rates were thus linearly correlated to the amount of methane entering the filter. The analysis of methane loads flowing back from the biofilter following phases of longer, continuous and non-oscillating landfill gas emission, however, revealed that in these situations biofilter performance is restricted by deficient oxygen supply. At the oxygen-restricted capacity limit, removal rates are influenced by temperature (positively), methane influx (negatively) and flow rate (negatively) as a measure for the displacement of oxygen. These situations, however, account for only 12% of all emission phases. The investigated biofilter capacity, as derived from laboratory analyses of methanotrophic activities, is sufficient to oxidise 62% of the methane load emitted annually. Field and laboratory data provide a stable basis for the dimensioning of filters in future applications.

A method for the calculation of anaerobic oxidation of methane rates across regional scales: an example from the Belt Seas and The Sound (North Sea-Baltic Sea transition)

NASA Astrophysics Data System (ADS)

Mogollón, José M.; Dale, Andrew W.; Jensen, Jørn B.; Schlüter, Michael; Regnier, Pierre

2013-08-01

Estimating the amount of methane in the seafloor globally as well as the flux of methane from sediments toward the ocean-atmosphere system are important considerations in both geological and climate sciences. Nevertheless, global estimates of methane inventories and rates of methane production and consumption through anaerobic oxidation in marine sediments are very poorly constrained. Tools for regionally assessing methane formation and consumption rates would greatly increase our understanding of the spatial heterogeneity of the methane cycle as well as help constrain the global methane budget. In this article, an algorithm for calculating methane consumption rates in the inner shelf is applied to the gas-rich sediments of the Belt Seas and The Sound (North Sea-Baltic Sea transition). It is based on the depth of free gas determined by hydroacoustic techniques and the local methane solubility concentration. Due to the continuous nature of shipboard hydroacoustic measurements, this algorithm captures spatial heterogeneities in methane fluxes better than geochemical analyses of point sources such as observational/sampling stations. The sensibility of the algorithm with respect to the resolution of the free gas depth measurements (2 m vs. 50 cm) is proven of minor importance (a discrepancy of <10%) for a small part of the study area. The algorithm-derived anaerobic methane oxidation rates compare well with previous measured and modeling studies. Finally, regional results reveal that contemporary anaerobic methane oxidation in worldwide inner-shelf sediments may be an order of magnitude lower (ca. 0.24 Tmol year-1) than previous estimates (4.6 Tmol year-1). These algorithms ultimately help improve regional estimates of anaerobic oxidation of methane rates.

Ecosystem and physiological controls over methane production in northern wetlands

NASA Technical Reports Server (NTRS)

Valentine, David W.; Holland, Elisabeth A.; Schimel, David S.

1994-01-01

Peat chemistry appears to exert primary control over methane production rates in the Canadian Northern Wetlands Study (NOWES) area. We determined laboratory methane production rate potentials in anaerobic slurries of samples collected from a transect of sites through the NOWES study area. We related methane production rates to indicators of resistance to microbial decay (peat C: N and lignin: N ratios) and experimentally manipulated substrate availability for methanogenesis using ethanol (EtOH) and plant litter. We also determined responses of methane production to pH and temperature. Methane production potentials declined along the gradient of sites from high rates in the coastal fens to low rates in the interior bogs and were generally highest in surface layers. Strong relationships between CH4 production potentials and peat chemistry suggested that methanogenesis was limited by fermentation rates. Methane production at ambient pH responded strongly to substrate additions in the circumneutral fens with narrow lignin: N and C: N ratios (delta CH4/delta EtOH = 0.9-2.3 mg/g) and weakly in the acidic bogs with wide C: N and lignin: N ratios (delta CH4/delta EtOH = -0.04-0.02 mg/g). Observed Q(sub 10) values ranged from 1.7 to 4.7 and generally increased with increasing substrate availability, suggesting that fermentation rates were limiting. Titration experiments generally demonstrated inhibition of methanogenesis by low pH. Our results suggest that the low rates of methane emission observed in interior bogs during NOWES likely resulted from pH and substrate quality limitation of the fermentation step in methane production and thus reflect intrinsically low methane production potentials. Low methane emission rates observed during NOWES will likely be observed in other northern wetland regions with similar vegetation chemistry.

Enhanced coproduction of hydrogen and methane from cornstalks by a three-stage anaerobic fermentation process integrated with alkaline hydrolysis.

PubMed

Cheng, Xi-Yu; Liu, Chun-Zhao

2012-01-01

A three-stage anaerobic fermentation process including H(2) fermentation I, H(2) fermentation II, methane fermentation was developed for the coproduction of hydrogen and methane from cornstalks. Hydrogen production from cornstalks using direct microbial conversion by Clostridium thermocellum 7072 was markedly enhanced in the two-stage thermophilic hydrogen fermentation process integrated with alkaline treatment. The highest total hydrogen yield from cornstalks in the two-stage fermentation process reached 74.4 mL/g-cornstalk. The hydrogen fermentation effluents and alkaline hydrolyzate were further used for methane fermentation by anaerobic granular sludge, and the total methane yield reached 205.8 mL/g-cornstalk. The total energy recovery in the three-stage anaerobic fermentation process integrated with alkaline hydrolysis reached 70.0%. Copyright © 2011 Elsevier Ltd. All rights reserved.

Agriculture's impact on microbial diversity and associated fluxes of carbon dioxide and methane

PubMed Central

Levine, Uri Y; Teal, Tracy K; Robertson, G Philip; Schmidt, Thomas M

2011-01-01

Agriculture has marked impacts on the production of carbon dioxide (CO2) and consumption of methane (CH4) by microbial communities in upland soils—Earth's largest biological sink for atmospheric CH4. To determine whether the diversity of microbes that catalyze the flux of these greenhouse gases is related to the magnitude and stability of these ecosystem-level processes, we conducted molecular surveys of CH4-oxidizing bacteria (methanotrophs) and total bacterial diversity across a range of land uses and measured the in situ flux of CH4 and CO2 at a site in the upper United States Midwest. Conversion of native lands to row-crop agriculture led to a sevenfold reduction in CH4 consumption and a proportionate decrease in methanotroph diversity. Sites with the greatest stability in CH4 consumption harbored the most methanotroph diversity. In fields abandoned from agriculture, the rate of CH4 consumption increased with time along with the diversity of methanotrophs. Conversely, estimates of total bacterial diversity in soil were not related to the rate or stability of CO2 emission. These combined results are consistent with the expectation that microbial diversity is a better predictor of the magnitude and stability of processes catalyzed by organisms with highly specialized metabolisms, like CH4 oxidation, as compared with processes driven by widely distributed metabolic processes, like CO2 production in heterotrophs. The data also suggest that managing lands to conserve or restore methanotroph diversity could mitigate the atmospheric concentrations of this potent greenhouse gas. PMID:21490688

Microbial Ecology of Thermophilic Anaerobic Digestion. Final Report

DOE R&D Accomplishments Database

Zinder, Stephen H.

2000-04-15

This grant supported research on methanogenic archaea. The two major areas that were supported were conversion of acetic acid to methane and nitrogen fixation by Methanosarcina. Among the achievements of this research were the isolation of novel methanogenic cultures, elucidation of the pathways from acetate to methane, description of a specific DNA-binding complex in nitrogen fixing methanogens, and demonstration of an alternative nitrogenase in Methanosarcina.

Microwave Hydrogen Production from Methane

DTIC Science & Technology

2012-04-01

combustion NOx control of reciprocating engine exhaust and fuel cell application of biogas . Our target is to obtain the methane conversion efficiency...demonstration of MW technology removing and destroying hydrogen sulfide (H2S) and siloxanes from biogas produced by Sacramento Regional Wastewater...running on biogas and is currently conducting the field demonstration of the unit at Tollenaar Dairy in Elk Grove, CA. SMUD, California Air Resources

7 CFR 1940.311 - Environmental assessments for Class I actions.

Code of Federal Regulations, 2013 CFR

2013-01-01

... designed for on-farm needs such as methane digestors and fuel alcohol production facilities; (5) Financial assistance for the conversion of more than 160 acres of pasture to agricultural production, but no more than 320 acres, provided that in a conversion to agricultural production no wetlands are affected, in which...

7 CFR 1940.311 - Environmental assessments for Class I actions.

Code of Federal Regulations, 2014 CFR

2014-01-01

... designed for on-farm needs such as methane digestors and fuel alcohol production facilities; (5) Financial assistance for the conversion of more than 160 acres of pasture to agricultural production, but no more than 320 acres, provided that in a conversion to agricultural production no wetlands are affected, in which...

7 CFR 1940.311 - Environmental assessments for Class I actions.

Code of Federal Regulations, 2012 CFR

2012-01-01

... designed for on-farm needs such as methane digestors and fuel alcohol production facilities; (5) Financial assistance for the conversion of more than 160 acres of pasture to agricultural production, but no more than 320 acres, provided that in a conversion to agricultural production no wetlands are affected, in which...

7 CFR 1940.311 - Environmental assessments for Class I actions.

Code of Federal Regulations, 2011 CFR

2011-01-01

... designed for on-farm needs such as methane digestors and fuel alcohol production facilities; (5) Financial assistance for the conversion of more than 160 acres of pasture to agricultural production, but no more than 320 acres, provided that in a conversion to agricultural production no wetlands are affected, in which...

Estimating Landfill Methane Oxidation Using the Information of CO2/CH4 Fluxes Measured By the Eddy Covariance Method

NASA Astrophysics Data System (ADS)

Xu, L.; McDermitt, D. K.; Li, J.; Green, R. B.

2016-12-01

Methane plays a critical role in the radiation balance and chemistry of the atmosphere. Globally, landfill methane emission contributes about 10-19% of the anthropogenic methane burden into the atmosphere. In the United States, 18% of annual anthropogenic methane emissions come from landfills, which represent the third largest source of anthropogenic methane emissions, behind enteric fermentation and natural gas and oil production. One uncertainty in estimating landfill methane emissions is the fraction of methane oxidized when methane produced under anaerobic conditions passes through the cover soil. We developed a simple stoichiometric model to estimate the landfill methane oxidation fraction when the anaerobic CO2/CH4 production ratio is known. The model predicts a linear relationship between CO2 emission rates and CH4 emission rates, where the slope depends on anaerobic CO2/CH4 production ratio and the fraction of methane oxidized, and the intercept depends on non-methane-dependent oxidation processes. The model was tested with eddy covariance CO2 and CH4 emission rates at Bluff Road Landfill in Lincoln Nebraska. It predicted zero oxidation rate in the northern portion of this landfill where a membrane and vents were present. The zero oxidation rate was expected because there would be little opportunity for methane to encounter oxidizing conditions before leaving the vents. We also applied the model at the Turkey Run Landfill in Georgia to estimate the CH4 oxidation rate over a one year period. In contrast to Bluff Road Landfill, the Turkey Run Landfill did not have a membrane or vents. Instead, methane produced in the landfill had to diffuse through a 0.5 m soil cap before release to the atmosphere. We observed evidence for methane oxidation ranging from about 18% to above 60% depending upon the age of deposited waste material. The model will be briefly described, and results from the two contrasting landfills will be discussed in this presentation.

Methane-bearing fluids in subduction zones: an experimental study of abiotic methanogenesis during serpentinization at 12 kbar and 300°C

NASA Astrophysics Data System (ADS)

Lazar, C.; Manning, C. E.

2009-12-01

Serpentinization within subduction zones may generate reduced fluids that contain higher concentrations of abiotic methane than near-surface ultramafic environments. We present preliminary experimental data suggesting that the kinetics of abiotic methanogenesis are enhanced at high pressures. Thermodynamic calculations of C-O-H fluid speciations at the low oxygen fugacities attained during early serpentinization suggest complete conversion of oxidized carbon to methane, yet previous field and experimental investigations have reported fluid compositions with CH4/CO2 far below equilibrium (McCollom and Seewald, 2007). Much experimental work, therefore, has focused on CH4 production rates and the kinetic effects of temperature and mineral catalysis (Horita and Berdt, 1999; Foustoukos and Seyfried, 2004). Methane has been shown experimentally to form at very high pressures (Scott et al, 2004), but the quantitative effect of pressure on methanogenesis kinetics is unknown. We present preliminary results of a comparison of methane production rates at 0.35 and 12 kbar, 300°C, using experiments performed in piston cylinder and cold seal hydrothermal apparatus. Carbon was introduced as a roughly 70 mmol solution of isotopically-labeled formic acid, H13COOH, known to decompose to 13CO2 and H2 at run conditions. Roughly 15 mL of this solution, along with 1.9 mg of natural awaruite (Ni3Fe), was loaded into a gold capsule and then sealed via DC spot welding. Awaruite, a known methane catalyst (Horita and Berndt, 1999), was added to increase the overall rates of all experiments in order to boost the concentration for analysis and as an fO2 buffer appropriate for serpentinization. The experiments were held at T and P for approximately 160 hours. After each run, the capsule was placed in a gas vial and punctured with a needle. The contents of the vial were extracted via gas syringe and injected into gas chromatograph mass spectrometer (GC-MS). CH4 concentration in the 12 kbar run was approximately twice that of the low pressure experiment. In addition to this kinetic enhancement, high pressure strongly favors calcite dissolution (Caciagli and Manning, 2003), thus providing fluids rich in CO2, a reactant in the canonical hydrothermal abiotic methanogenesis reaction, CO2 + 4H2 = CH4 + 2H2O. Hydrogen should also be common within subduction zones, given the significant potential for serpentinization of ultramafic rocks in the forearc mantle and the oceanic lithospheric mantle. Metasomatism of the forearc mantle by CO2-H2O fluids, for example, should generate methane-rich fluids. The details of high pressure methane are complicated by graphite saturation, fluid flow, carbonate stability, fluid-rock ratio, and other geochemical parameters, to be addressed in the future. Nevertheless, given the likely widespread distribution of high pressure serpentinization environments throughout the Solar System, high pressure methane may play a role in atmospheric methane on Mars, the Faint Young Sun problem on the early Earth, the potential for life on Europa, and the synthesis of prebiotic chemicals on any geologically active planet.

Methane-Stimulated Benthic Marine Nitrogen Fixation at Deep-Sea Methane Seeps

NASA Astrophysics Data System (ADS)

Dekas, A. E.; Orphan, V.

2011-12-01

Biological nitrogen fixation (the conversion of N2 to NH3) is a critical process in the oceans, counteracting the production of N2 gas by dissimilatory bacterial metabolisms and providing a source of bioavailable nitrogen to many nitrogen-limited ecosystems. Although current measurements of N2 production and consumption in the oceans indicate that the nitrogen cycle is not balanced, recent findings on the limits of nitrogen fixation suggest that the perceived imbalance is an artifact of an incomplete assessment of marine diazotrophy. One currently poorly studied and potentially underappreciated habitat for diazotrophic organisms is the sediments of the deep-sea. In the present study we investigate the distribution and magnitude of benthic marine diazotrophy at several active deep-sea methane seeps (Mound 12, Costa Rica; Eel River Basin, CA, USA; Hydrate Ridge, OR, USA; and Monterey Canyon, CA, USA). Using 15N2 and 15NH4 sediment incubation experiments followed by single-cell (FISH-NanoSIMS) and bulk isotopic analysis (EA-IRMS), we observed total protein synthesis (15N uptake from 15NH4) and nitrogen fixation (15N update from 15N2). The highest rates of nitrogen fixation observed in the methane seep sediment incubation experiments were over an order of magnitude greater than those previously published from non-seep deep-sea sediments (Hartwig and Stanley, Deep-Sea Research, 1978, 25:411-417). However, methane seep diazotrophy appears to be highly spatially variable, with sediments exhibiting no nitrogen fixation originating only centimeters away from sediments actively incorporating 15N from 15N2. The greatest spatial variability in diazotrophy was observed with depth in the sediment, and corresponded to steep gradients in sulfate and methane. The maximum rates of nitrogen fixation were observed within the methane-sulfate transition zone, where organisms mediating the anaerobic oxidation of methane are typically in high abundance. Additionally, incubation experiments without added methane were observed to have little to no nitrogen fixation activity. In previous work, we demonstrated the capability of uncultured methanotrophic archaea (ANME-2) to fix nitrogen when associated with sulfate reducing bacterial symbionts. These new results suggest that these microbes may be the dominant nitrogen-fixing organisms in methane seep sediment. Intriguingly, characterization of the diversity of nifH genes from our sediment incubations as well as published nifH sequences reported from other seep habitats suggest the potential for other diazotrophic microorganisms in addition to the ANME-2 archaea. To further explore this possibility, FISH-NanoSIMS analyses were conducted on two dominant free-living sulfate-reducing lineages from seep incubations demonstrating nitrogen fixation activity. Preliminary results from this analysis suggest that single cells belonging to the Desulfobulbaceae may also be involved in nitrogen fixation in methane seeps. Despite this demonstrated potential, the extent of methane-independent diazotrophy by non-ANME diazotrophs appears to be low within the methane seep environment. Further studies are necessary to assess the greater diversity and activity of diazotrophs in other deep-sea sedimentary habitats.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gerceker, Duygu; Motagamwala, Ali Hussain; Rivera-Dones, Keishla R.

Pt and PtSn catalysts supported on SiO 2 and H-ZSM-5 were studied for methane conversion under nonoxidative conditions. Addition of Sn to Pt/SiO 2 increased the turnover frequency for production of ethylene by a factor of 3, and pretreatment of the catalyst at 1123 K reduced the extent of coke formation. Pt and PtSn catalysts supported on H-ZSM-5 zeolite were prepared to improve the activity and selectivity to non-coke products. Ethylene formation rates were 20 times faster over a PtSn(1:3)/H-ZSM-5 catalyst with SiO 2:Al 2O 3 = 280 in comparison to those over PtSn(3:1)/SiO 2. H-ZSM-5-supported catalysts were also activemore » for the formation of aromatics, and the rates of benzene and naphthalene formation were increased by using more acidic H-ZSM-5 supports. These catalysts operate through a bifunctional mechanism, in which ethylene is first produced on highly dispersed PtSn nanoparticles and then is subsequently converted to benzene and naphthalene on Brønsted acid sites within the zeolite support. The most active and stable PtSn catalyst forms carbon products at a rate, 2.5 mmol of C/((mol of Pt) s), which is comparable to that of state-of-the-art Mo/H-ZSM-5 catalysts with same metal loading operated under similar conditions (1.8 mmol of C/((mol of Mo) s)). Scanning transmission electron microscopy measurements suggest the presence of smaller Pt nanoparticles on H-ZSM-5-supported catalysts, in comparison to SiO 2-supported catalysts, as a possible source of their high activity. As a result, a microkinetic model of methane conversion on Pt and PtSn surfaces, built using results from density functional theory calculations, predicts higher coupling rates on bimetallic and stepped surfaces, supporting the experimental observations that relate the high catalytic activity to small PtSn particles.« less

Biomethanation of Syngas Using Anaerobic Sludge: Shift in the Catabolic Routes with the CO Partial Pressure Increase.

PubMed

Sancho Navarro, Silvia; Cimpoia, Ruxandra; Bruant, Guillaume; Guiot, Serge R

2016-01-01

Syngas generated by thermal gasification of biomass or coal can be steam reformed and purified into methane, which could be used locally for energy needs, or re-injected in the natural gas grid. As an alternative to chemical catalysis, the main components of the syngas (CO, CO2, and H2) can be used as substrates by a wide range of microorganisms, to be converted into gas biofuels, including methane. This study evaluates the carboxydotrophic (CO-consuming) methanogenic potential present in an anaerobic sludge from an upflow anaerobic sludge bed (UASB) reactor treating waste water, and elucidates the CO conversion routes to methane at 35 ± 3°C. Kinetic activity tests under CO at partial pressures (pCO) varying from 0.1 to 1.5 atm (0.09-1.31 mmol/L in the liquid phase) showed a significant carboxydotrophic activity potential for growing conditions on CO alone. A maximum methanogenic activity of 1 mmol CH4 per g of volatile suspended solid and per day was achieved at 0.2 atm of CO (0.17 mmol/L), and then the rate decreased with the amount of CO supplied. The intermediary metabolites such as acetate, H2, and propionate started to accumulate at higher CO concentrations. Inhibition experiments with 2-bromoethanesulfonic acid (BES), fluoroacetate, and vancomycin showed that in a mixed culture CO was converted mainly to acetate by acetogenic bacteria, which was further transformed to methane by acetoclastic methanogens, while direct methanogenic CO conversion was negligible. Methanogenesis was totally blocked at high pCO in the bottles (≥1 atm). However it was possible to achieve higher methanogenic potential under a 100% CO atmosphere after acclimation of the sludge to CO. This adaptation to high CO concentrations led to a shift in the archaeal population, then dominated by hydrogen-utilizing methanogens, which were able to take over acetoclastic methanogens, while syntrophic acetate oxidizing (SAO) bacteria oxidized acetate into CO2 and H2. The disaggregation of the granular sludge showed a negative impact on their methanogenic activity, confirming that the acetoclastic methanogens were the most sensitive to CO, and a contrario, the advantage of using granular sludge for further development toward large-scale methane production from CO-rich syngas.

Biomethanation of Syngas Using Anaerobic Sludge: Shift in the Catabolic Routes with the CO Partial Pressure Increase

PubMed Central

Sancho Navarro, Silvia; Cimpoia, Ruxandra; Bruant, Guillaume; Guiot, Serge R.

2016-01-01

Syngas generated by thermal gasification of biomass or coal can be steam reformed and purified into methane, which could be used locally for energy needs, or re-injected in the natural gas grid. As an alternative to chemical catalysis, the main components of the syngas (CO, CO2, and H2) can be used as substrates by a wide range of microorganisms, to be converted into gas biofuels, including methane. This study evaluates the carboxydotrophic (CO-consuming) methanogenic potential present in an anaerobic sludge from an upflow anaerobic sludge bed (UASB) reactor treating waste water, and elucidates the CO conversion routes to methane at 35 ± 3°C. Kinetic activity tests under CO at partial pressures (pCO) varying from 0.1 to 1.5 atm (0.09–1.31 mmol/L in the liquid phase) showed a significant carboxydotrophic activity potential for growing conditions on CO alone. A maximum methanogenic activity of 1 mmol CH4 per g of volatile suspended solid and per day was achieved at 0.2 atm of CO (0.17 mmol/L), and then the rate decreased with the amount of CO supplied. The intermediary metabolites such as acetate, H2, and propionate started to accumulate at higher CO concentrations. Inhibition experiments with 2-bromoethanesulfonic acid (BES), fluoroacetate, and vancomycin showed that in a mixed culture CO was converted mainly to acetate by acetogenic bacteria, which was further transformed to methane by acetoclastic methanogens, while direct methanogenic CO conversion was negligible. Methanogenesis was totally blocked at high pCO in the bottles (≥1 atm). However it was possible to achieve higher methanogenic potential under a 100% CO atmosphere after acclimation of the sludge to CO. This adaptation to high CO concentrations led to a shift in the archaeal population, then dominated by hydrogen-utilizing methanogens, which were able to take over acetoclastic methanogens, while syntrophic acetate oxidizing (SAO) bacteria oxidized acetate into CO2 and H2. The disaggregation of the granular sludge showed a negative impact on their methanogenic activity, confirming that the acetoclastic methanogens were the most sensitive to CO, and a contrario, the advantage of using granular sludge for further development toward large-scale methane production from CO-rich syngas. PMID:27536280

Temperature regulates methane production through the function centralization of microbial community in anaerobic digestion.

PubMed

Lin, Qiang; De Vrieze, Jo; He, Guihua; Li, Xiangzhen; Li, Jiabao

2016-09-01

Temperature is crucial for the performance of anaerobic digestion process. In this study of anaerobic digestion of swine manure, the relationship between the microbial gene expression and methane production at different temperatures (25-55°C) was revealed through metatranscriptomic analysis. Daily methane production and total biogas production increased with temperature up to 50°C, but decreased at 55°C. The functional gene expression showed great variation at different temperatures. The function centralization (opposite to alpha-diversity), assessed by the least proportions of functional pathways contributing for at least 50% of total reads positively correlated to methane production. Temperature regulated methane production probably through reducing the diversity of functional pathways, but enhancing central functional pathways, so that most of cellular activities and resource were invested in methanogenesis and related pathways, enhancing the efficiency of conversion of substrates to methane. This research demonstrated the importance of function centralization for efficient system functioning. Copyright © 2016 Elsevier Ltd. All rights reserved.

Template-Assisted Wet-Combustion Synthesis of Fibrous Nickel-Based Catalyst for Carbon Dioxide Methanation and Methane Steam Reforming.

PubMed

Aghayan, M; Potemkin, D I; Rubio-Marcos, F; Uskov, S I; Snytnikov, P V; Hussainova, I

2017-12-20

Efficient capture and recycling of CO 2 enable not only prevention of global warming but also the supply of useful low-carbon fuels. The catalytic conversion of CO 2 into an organic compound is a promising recycling approach which opens new concepts and opportunities for catalytic and industrial development. Here we report about template-assisted wet-combustion synthesis of a one-dimensional nickel-based catalyst for carbon dioxide methanation and methane steam reforming. Because of a high temperature achieved in a short time during reaction and a large amount of evolved gases, the wet-combustion synthesis yields homogeneously precipitated nanoparticles of NiO with average particle size of 4 nm on alumina nanofibers covered with a NiAl 2 O 4 nanolayer. The as-synthesized core-shell structured fibers exhibit outstanding activity in steam reforming of methane and sufficient activity in carbon dioxide methanation with 100% selectivity toward methane formation. The as-synthesized catalyst shows stable operation under the reaction conditions for at least 50 h.

Methane, carbon dioxide, and nitrous oxide emissions from septic tank systems.

PubMed

Diaz-Valbuena, Libia R; Leverenz, Harold L; Cappa, Christopher D; Tchobanoglous, George; Horwath, William R; Darby, Jeannie L

2011-04-01

Emissions of CH4, CO2, and N2O from conventional septic tank systems are known to occur, but there is a dearth of information as to the extent. Mass emission rates of CH4, CO2, and N2O, as measured with a modified flux chamber approach in eight septic tank systems, were determined to be 11, 33.3, and 0.005 g capita(-1) day(-1), respectively, in this research. Existing greenhouse gas (GHG) emission models based on BOD (biochemical oxygen demand) loading have estimated methane emissions to be as high as 27.1 g CH4 capita(-1) day(-1), more than twice the value measured in our study, and concluded that septic tanks are potentially significant sources of GHGs due to the large number of systems currently in use. Based on the measured CH4 emission value, a revised CH4 conversion factor of 0.22 (compared to 0.5) for use in the emissions models is suggested. Emission rates of CH4, CO2, and N2O were also determined from measurements of gas concentrations and flow rates in the septic vent system and were found to be 10.7, 335, and 0.2 g capita(-1)day(-1), respectively. The excellent agreement in the CH4 emission rates between the flux chamber and the vent values indicates the dominant CH4 source is the septic tank.

Quantification of methane fluxes from industrial sites using a combination of a tracer release method and a Gaussian model

NASA Astrophysics Data System (ADS)

Ars, S.; Broquet, G.; Yver-Kwok, C.; Wu, L.; Bousquet, P.; Roustan, Y.

2015-12-01

Greenhouse gas (GHG) concentrations keep on increasing in the atmosphere since industrial revolution. Methane (CH4) is the second most important anthropogenic GHG after carbon dioxide (CO2). Its sources and sinks are nowadays well identified however their relative contributions remain uncertain. The industries and the waste treatment emit an important part of the anthropogenic methane that is difficult to quantify because the sources are fugitive and discontinuous. A better estimation of methane emissions could help industries to adapt their mitigation's politic and encourage them to install methane recovery systems in order to reduce their emissions while saving money. Different methods exist to quantify methane emissions. Among them is the tracer release method consisting in releasing a tracer gas near the methane source at a well-known rate and measuring both their concentrations in the emission plume. The methane rate is calculated using the ratio of methane and tracer concentrations and the emission rate of the tracer. A good estimation of the methane emissions requires a good differentiation between the methane actually emitted by the site and the methane from the background concentration level, but also a good knowledge of the sources distribution over the site. For this purpose, a Gaussian plume model is used in addition to the tracer release method to assess the emission rates calculated. In a first step, the data obtained for the tracer during a field campaign are used to tune the model. Different model's parameterizations have been tested to find the best representation of the atmospheric dispersion conditions. Once these parameters are set, methane emissions are estimated thanks to the methane concentrations measured and a Bayesian inversion. This enables to adjust the position and the emission rate of the different methane sources of the site and remove the methane background concentration.

In-Situ Quantification of Microbial Processes Controlling Methane Emissions From Rice Plants

NASA Astrophysics Data System (ADS)

Schroth, M. H.; Cho, R.; Zeyer, J. A.

2011-12-01

Methane is an important greenhouse gas contributing to global warming. Among other sources, rice (paddy) soils represent a major nonpoint source of biogenic methane. In flooded paddy soils methane is produced under anaerobic conditions. Conversely, methanotrophic microorganisms oxidize methane to carbon dioxide in the root zone of rice plants, thus reducing overall methane emissions to the atmosphere. We present a novel combination of methods to quantify methanogenesis and methane oxidation in paddy soils and to link methane turnover to net emissions of rice plants. To quantify methane turnover in the presence of high methane background concentrations, small-scale push-pull tests (PPTs) were conducted in paddy soils using stable isotope-labeled substrates. Deuterated acetate and 13-C bicarbonate were employed to discern and quantify acetoclastic and hydrogenotrophic methanogenesis, while 13-C methane was employed to quantify methane oxidation. During 2.5 hr-long PPTs, 140 mL of a test solution containing labeled substrates and nonreactive tracers (Ar, Br-) was injected into paddy soils of potted rice plants. After a short rest period, 480 mL of test solution/pore water mixture was extracted from the same location. Methane turnover was then computed from extraction-phase breakthrough curves of substrates and/or products, and nonreactive tracers. To link methane turnover to net emissions, methane emissions from paddy soils and rice plants were individually determined immediately preceding PPTs using static flux chambers. We will present results of a series of experiments conducted in four different potted rice plants. Preliminary results indicate substantial variability in methane turnover and net emission between different rice plants. The employed combination of methods appears to provide a robust means to quantitatively link methane turnover in paddy soils to net emissions from rice plants.

A novel atmospheric tritium sampling system

NASA Astrophysics Data System (ADS)

Qin, Lailai; Xia, Zhenghai; Gu, Shaozhong; Zhang, Dongxun; Bao, Guangliang; Han, Xingbo; Ma, Yuhua; Deng, Ke; Liu, Jiayu; Zhang, Qin; Ma, Zhaowei; Yang, Guo; Liu, Wei; Liu, Guimin

2018-06-01

The health hazard of tritium is related to its chemical form. Sampling different chemical forms of tritium simultaneously becomes significant. Here a novel atmospheric tritium sampling system (TS-212) was developed to collect the tritiated water (HTO), tritiated hydrogen (HT) and tritiated methane (CH3T) simultaneously. It consisted of an air inlet system, three parallel connected sampling channels, a hydrogen supply module, a methane supply module and a remote control system. It worked at air flow rate of 1 L/min to 5 L/min, with temperature of catalyst furnace at 200 °C for HT sampling and 400 °C for CH3T sampling. Conversion rates of both HT and CH3T to HTO were larger than 99%. The collecting efficiency of the two-stage trap sets for HTO was larger than 96% in 12 h working-time without being blocked. Therefore, the collected efficiencies of TS-212 are larger than 95% for tritium with different chemical forms in environment. Besides, the remote control system made sampling more intelligent, reducing the operator's work intensity. Based on the performance parameters described above, the TS-212 can be used to sample atmospheric tritium in different chemical forms.

Carbon-13 Isotopic Abundance and Concentration of Atmospheric Methane for Background Air in the Southern and Northern Hemispheres from 1978 to 1989 (NDP-049)

DOE Data Explorer

Stevens, C. M. [Chemical Technology Division, Argonne National Laboratory, Argonne, Illinois (USA)

2012-01-01

This data package presents atmospheric CH4 concentration and 13C isotopic abundance data derived from air samples collected over the period 1978-1989 at globally distributed clean-air sites. The data set comprises 201 records, 166 from the Northern Hemisphere and 35 from the Southern Hemisphere. The air samples were collected mostly in rural or marine locations remote from large sources of CH4 and are considered representative of tropospheric background conditions. The air samples were processed by isolation of CH4 from air and conversion to CO2 for isotopic analysis by isotope ratio mass spectrometry. These data represent one of the earliest records of 13C isotopic yy!measurements for atmospheric methane and have been used to refine estimates of CH4 emissions, calculate annual growth rates of emissions from changing sources, and provide evidence for changes in the rate of atmospheric removal of CH4. The data records consist of sample collection date; number of samples combined for analysis; sampling location; analysis date; CH4 concentration; 13C isotopic abundance; and flag codes to indicate outliers, repeated analyses, and other information.

Gas hydrate formation rates from dissolved-phase methane in porous laboratory specimens

USGS Publications Warehouse

Waite, William F.; Spangenberg, E.K.

2013-01-01

Marine sands highly saturated with gas hydrates are potential energy resources, likely forming from methane dissolved in pore water. Laboratory fabrication of gas hydrate-bearing sands formed from dissolved-phase methane usually requires 1–2 months to attain the high hydrate saturations characteristic of naturally occurring energy resource targets. A series of gas hydrate formation tests, in which methane-supersaturated water circulates through 100, 240, and 200,000 cm3 vessels containing glass beads or unconsolidated sand, show that the rate-limiting step is dissolving gaseous-phase methane into the circulating water to form methane-supersaturated fluid. This implies that laboratory and natural hydrate formation rates are primarily limited by methane availability. Developing effective techniques for dissolving gaseous methane into water will increase formation rates above our observed (1 ± 0.5) × 10−7 mol of methane consumed for hydrate formation per minute per cubic centimeter of pore space, which corresponds to a hydrate saturation increase of 2 ± 1% per day, regardless of specimen size.

Big Soda Lake (Nevada). 3. Pelagic methanogenesis and anaerobic methane oxidation

USGS Publications Warehouse

Iversen, Niels; Oremland, Ronald S.; Klug, Michael J.

1987-01-01

In situ rates of methanogenesis and methane oxidation were measured in meromictic Big Soda Lake. Methane production was measured by the accumulation of methane in the headspaces of anaerobically sealed water samples; radiotracer was used to follow methane oxidation. Nearly all the methane oxidation occurred in the anoxic zones of the lake. Rates of anaerobic oxidation exceeded production at all depths studied in both the mixolimnion (2–6 vs. 0.1–1 nmol liter−1 d−1) and monimolimnion (49–85 vs. 1.6–12 nmol liter−1 d−1) of the lake. Thus, a net consumption of methane equivalent to 1.36 mmol m−2 d−1 occurred in the anoxic water column. Anaerobic methane oxidation had a first-order rate constant of 8.1±0.5 × 10−4 d−1, and activity was eliminated by filter sterilization. However, in situ methane oxidation was of insufficient magnitude to cause a noticeable decrease of ambient dissolved methane levels over an incubation period of 97 h.

Aerated biofilters with multiple-level air injection configurations to enhance biological treatment of methane emissions.

PubMed

Farrokhzadeh, Hasti; Hettiaratchi, J Patrick A; Jayasinghe, Poornima; Kumar, Sunil

2017-09-01

Aiming to improve conventional methane biofilter performance, a multiple-level aeration biofilter design is proposed. Laboratory flow-through column experiments were conducted to evaluate three actively-aerated methane biofilter configurations. Columns were aerated at one, two, and three levels of the bed depth, with air introduced at flow rates calculated from methane oxidation reaction stoichiometry. Inlet methane loading rates were increased in five stages between 6 and 18mL/min. The effects of methane feeding rate, levels of aeration, and residence time on methane oxidation rates were determined. Samples collected after completion of flow-through experiments were used to determine methane oxidation kinetic parameters, V max , K m , and methanotrophic community distribution across biofilter columns. Results obtained from mixed variances analysis and response surfaces, as well as methanotrophic activity data, suggested that, biofilter column with two aeration levels has the most even performance over time, maintaining 85.1% average oxidation efficiency over 95days of experiments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Theoretical Investigation of Methane Hydroxylation over Isoelectronic [FeO]2+- and [MnO]+-Exchanged Zeolites Activated by N2O.

PubMed

Mahyuddin, M Haris; Shiota, Yoshihito; Staykov, Aleksandar; Yoshizawa, Kazunari

2017-09-05

While the most likely structure of the active site in iron-containing zeolites has been recently identified as [FeO] 2+ (Snyder et al. Nature 2016, 536, 317-321), the mechanism for the direct conversion of methane to methanol over this active species is still debatable between the direct-radical-rebound or nonradical (concerted) mechanism. Using density functional theory on periodic systems, we calculated the two reaction mechanisms over two d 4 isoelectronic systems, [FeO] 2+ and [MnO] + zeolites. We found that [FeO] 2+ zeolites favor the direct-radical-rebound mechanism with low CH 4 activation energies, while [MnO] + zeolites prefer the nonradical mechanism with higher CH 4 activation energies. These contrasts, despite their isoelectronic structures, are mainly due to the differences in the metal coordination number and O α (oxo) spin density. Moreover, molecular orbital analyses suggest that the zeolite steric hindrance further degrades the reactivity of [MnO] + zeolites toward methane. Two types of zeolite frameworks, i.e., medium-pore ZSM-5 (MFI framework) and small-pore SSZ-39 (AEI framework) zeolites, were evaluated, but no significant differences in the reactivity were found. The rate-determining reaction step is found to be methanol desorption instead of methane activation. Careful examination of the most stable sites hosting the active species and calculation for N 2 O decomposition over [Fe] 2+ -MFI and -AEI zeolites were also performed.

Co-digestion of agricultural and municipal waste to produce energy and soil amendment.

PubMed

Macias-Corral, Maritza A; Samani, Zohrab A; Hanson, Adrian T; Funk, Paul A

2017-09-01

In agriculture, manure and cotton gin waste are major environmental liabilities. Likewise, grass is an important organic component of municipal waste. These wastes were combined and used as substrates in a two-phase, pilot-scale anaerobic digester to evaluate the potential for biogas (methane) production, waste minimisation, and the digestate value as soil amendment. The anaerobic digestion process did not show signs of inhibition. Biogas production increased during the first 2 weeks of operation, when chemical oxygen demand and volatile fatty acid concentrations and the organic loading rate to the system were high. Chemical oxygen demand from the anaerobic columns remained relatively steady after the first week of operation, even at high organic loading rates. The experiment lasted about 1 month and produced 96.5 m 3 of biogas (68 m 3 of CH 4 ) per tonne of waste. In terms of chemical oxygen demand to methane conversion efficiency, the system generated 62% of the theoretical methane production; the chemical oxygen demand/volatile solids degradation rate was 62%, compared with the theoretical 66%. The results showed that co-digestion and subsequent digestate composting resulted in about 60% and 75% mass and volume reductions, respectively. Digestate analysis showed that it can be used as a high nutrient content soil amendment. The digestate met Class A faecal coliform standards (highest quality) established in the United States for biosolids. Digestion and subsequent composting concentrated the digestate nitrogen, phosphorus, and potassium content by 37%, 24%, and 317%, respectively. Multi-substrate co-digestion is a practical alternative for agricultural waste management, minimisation of landfill disposal, and it also results in the production of valuable products.

Direct Internal Reformation and Mass Transport in the Solid Oxide Fuel Cell Anode: A Pore-Scale Lattice Boltzmann Study with Detailed Reaction Kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grew, Kyle N.; Joshi, Abhijit S.; Chiu, W. K. S.

2010-11-30

The solid oxide fuel cell (SOFC) allows the conversion of chemical energy that is stored in a given fuel, including light hydrocarbons, to electrical power. Hydrocarbon fuels, such as methane, are logistically favourable and provide high energy densities. However, the use of these fuels often results in a decreased efficiency and life. An improved understanding of the reactive flow in the SOFC anode can help address these issues. In this study, the transport and heterogeneous internal reformation of a methane based fuel is addressed. The effect of the SOFC anode's complex structure on transport and reactions is shown to exhibitmore » a complicated interplay between the local molar concentrations and the anode structure. Strong coupling between the phenomenological microstructures and local reformation reaction rates are recognised in this study, suggesting the extension to actual microstructures may provide new insights into the reformation processes.« less

Internal reforming of methane in solid oxide fuel cell systems

NASA Astrophysics Data System (ADS)

Peters, R.; Dahl, R.; Klüttgen, U.; Palm, C.; Stolten, D.

Internal reforming is an attractive option offering a significant cost reduction, higher efficiencies and faster load response of a solid oxide fuel cell (SOFC) power plant. However, complete internal reforming may lead to several problems which can be avoided with partial pre-reforming of natural gas. In order to achieve high total plant efficiency associated with low energy consumption and low investment costs, a process concept has been developed based on all the components of the SOFC system. In the case of anode gas recycling an internal steam circuit exists. This has the advantage that there is no need for an external steam generator and the steam concentration in the anode gas is reduced. However, anode gas recycling has to be proven by experiments in a pre-reformer and for internal reforming. The addition of carbon dioxide clearly shows a decrease in catalyst activity, while for temperatures higher than 1000 K hydrogen leads to an increase of the measured methane conversion rates.

Optimisation of substrate blends in anaerobic co-digestion using adaptive linear programming.

PubMed

García-Gen, Santiago; Rodríguez, Jorge; Lema, Juan M

2014-12-01

Anaerobic co-digestion of multiple substrates has the potential to enhance biogas productivity by making use of the complementary characteristics of different substrates. A blending strategy based on a linear programming optimisation method is proposed aiming at maximising COD conversion into methane, but simultaneously maintaining a digestate and biogas quality. The method incorporates experimental and heuristic information to define the objective function and the linear restrictions. The active constraints are continuously adapted (by relaxing the restriction boundaries) such that further optimisations in terms of methane productivity can be achieved. The feasibility of the blends calculated with this methodology was previously tested and accurately predicted with an ADM1-based co-digestion model. This was validated in a continuously operated pilot plant, treating for several months different mixtures of glycerine, gelatine and pig manure at organic loading rates from 1.50 to 4.93 gCOD/Ld and hydraulic retention times between 32 and 40 days at mesophilic conditions. Copyright © 2014 Elsevier Ltd. All rights reserved.

The conversion of CO 2 to methanol on orthorhombic β-Mo 2C and Cu/β-Mo 2C catalysts: Mechanism for admetal induced change in the selectivity and activity

DOE PAGES

Posada-Pérez, Sergio; Ramírez, Pedro J.; Gutiérrez, Ramón A.; ...

2016-02-01

Here, the conversion of CO 2 into methanol catalyzed by β-Mo 2C and Cu/β-Mo 2C surfaces has been investigated by means of a combined experimental and theoretical study. Experiments have shown the direct activation and dissociation of the CO 2 molecule on bare β-Mo 2C, whereas on Cu/β-Mo 2C, CO 2 must be assisted by hydrogen for its conversion. Methane and CO are the main products on the clean surface and methanol production is lower. However, the deposition of Cu clusters avoids methane formation and increases methanol production even above that corresponding to a model of the technical catalyst. DFTmore » calculations on surface models of both possible C- and Mo-terminations corroborate the experimental observations. Calculations for the clean Mo-terminated surface reveal the existence of two possible routes for methane production (C + 4H → CH 4; CH 3O + 3H → CH 4 + H 2O) which are competitive with methanol synthesis, displaying slightly lower energy barriers. On the other hand, a model for Cu deposited clusters on the Mo-terminated surface points towards a new route for methanol and CO production avoiding methane formation. The new route is a direct consequence of the generation of a Mo 2C–Cu interface. The present experimental and theoretical results entail the interesting catalytic properties of Mo 2C as an active support of metallic nanoparticles, and also illustrate how the deposition of a metal can drastically change the activity and selectivity of a carbide substrate for CO 2 hydrogenation.« less

Monodeuterated Methane, an Isotopic Tool To Assess Biological Methane Metabolism Rates

PubMed Central

Steele, Joshua A.; Ziebis, Wiebke; Scheller, Silvan; Case, David; Reynard, Linda M.; Orphan, Victoria J.

2017-01-01

ABSTRACT Biological methane oxidation is a globally relevant process that mediates the flux of an important greenhouse gas through both aerobic and anaerobic metabolic pathways. However, measuring these metabolic rates presents many obstacles, from logistical barriers to regulatory hurdles and poor precision. Here we present a new approach for investigating microbial methane metabolism based on hydrogen atom dynamics, which is complementary to carbon-focused assessments of methanotrophy. The method uses monodeuterated methane (CH3D) as a metabolic substrate, quantifying the aqueous D/H ratio over time using off-axis integrated cavity output spectroscopy. This approach represents a nontoxic, comparatively rapid, and straightforward approach that supplements existing radiotopic and stable carbon isotopic methods; by probing hydrogen atoms, it offers an additional dimension for examining rates and pathways of methane metabolism. We provide direct comparisons between the CH3D procedure and the well-established 14CH4 radiotracer method for several methanotrophic systems, including type I and II aerobic methanotroph cultures and methane-seep sediment slurries and carbonate rocks under anoxic and oxic incubation conditions. In all applications tested, methane consumption values calculated via the CH3D method were directly and consistently proportional to 14C radiolabel-derived methane oxidation rates. We also employed this method in a nontraditional experimental setup, using flexible, gas-impermeable bags to investigate the role of pressure on seep sediment methane oxidation rates. Results revealed an 80% increase over atmospheric pressure in methanotrophic rates the equivalent of ~900-m water depth, highlighting the importance of this parameter on methane metabolism and exhibiting the flexibility of the newly described method. IMPORTANCE Microbial methane consumption is a critical component of the global carbon cycle, with wide-ranging implications for climate regulation and hydrocarbon exploitation. Nonetheless, quantifying methane metabolism typically involves logistically challenging methods and/or specialized equipment; these impediments have limited our understanding of methane fluxes and reservoirs in natural systems, making effective management difficult. Here, we offer an easily implementable, precise method using monodeuterated methane (CH3D) that advances three specific aims. First, it allows users to directly compare methane consumption rates between different experimental treatments of the same inoculum. Second, by empirically linking the CH3D procedure with the well-established 14C radiocarbon approach, we determine absolute scaling factors that facilitate rate measurements for several aerobic and anaerobic systems of interest. Third, CH3D represents a helpful tool in evaluating the relationship between methane activation and full oxidation in methanotrophic metabolisms. The procedural advantages, consistency, and novel research questions enabled by the CH3D method should prove useful in a wide range of culture-based and environmental microbial systems to further elucidate methane metabolism dynamics. PMID:28861523

Monodeuterated Methane, an Isotopic Tool To Assess Biological Methane Metabolism Rates.

PubMed

Marlow, Jeffrey J; Steele, Joshua A; Ziebis, Wiebke; Scheller, Silvan; Case, David; Reynard, Linda M; Orphan, Victoria J

2017-01-01

Biological methane oxidation is a globally relevant process that mediates the flux of an important greenhouse gas through both aerobic and anaerobic metabolic pathways. However, measuring these metabolic rates presents many obstacles, from logistical barriers to regulatory hurdles and poor precision. Here we present a new approach for investigating microbial methane metabolism based on hydrogen atom dynamics, which is complementary to carbon-focused assessments of methanotrophy. The method uses monodeuterated methane (CH 3 D) as a metabolic substrate, quantifying the aqueous D/H ratio over time using off-axis integrated cavity output spectroscopy. This approach represents a nontoxic, comparatively rapid, and straightforward approach that supplements existing radiotopic and stable carbon isotopic methods; by probing hydrogen atoms, it offers an additional dimension for examining rates and pathways of methane metabolism. We provide direct comparisons between the CH 3 D procedure and the well-established 14 CH 4 radiotracer method for several methanotrophic systems, including type I and II aerobic methanotroph cultures and methane-seep sediment slurries and carbonate rocks under anoxic and oxic incubation conditions. In all applications tested, methane consumption values calculated via the CH 3 D method were directly and consistently proportional to 14 C radiolabel-derived methane oxidation rates. We also employed this method in a nontraditional experimental setup, using flexible, gas-impermeable bags to investigate the role of pressure on seep sediment methane oxidation rates. Results revealed an 80% increase over atmospheric pressure in methanotrophic rates the equivalent of ~900-m water depth, highlighting the importance of this parameter on methane metabolism and exhibiting the flexibility of the newly described method. IMPORTANCE Microbial methane consumption is a critical component of the global carbon cycle, with wide-ranging implications for climate regulation and hydrocarbon exploitation. Nonetheless, quantifying methane metabolism typically involves logistically challenging methods and/or specialized equipment; these impediments have limited our understanding of methane fluxes and reservoirs in natural systems, making effective management difficult. Here, we offer an easily implementable, precise method using monodeuterated methane (CH 3 D) that advances three specific aims. First, it allows users to directly compare methane consumption rates between different experimental treatments of the same inoculum. Second, by empirically linking the CH 3 D procedure with the well-established 14 C radiocarbon approach, we determine absolute scaling factors that facilitate rate measurements for several aerobic and anaerobic systems of interest. Third, CH 3 D represents a helpful tool in evaluating the relationship between methane activation and full oxidation in methanotrophic metabolisms. The procedural advantages, consistency, and novel research questions enabled by the CH 3 D method should prove useful in a wide range of culture-based and environmental microbial systems to further elucidate methane metabolism dynamics.

Titan's surface-atmosphere system before and after Huygens

NASA Astrophysics Data System (ADS)

Lunine, Jonathan I.

2015-04-01

Speculation about the nature of Titan's surface-atmosphere interactions goes back to the discovery of methane in its atmosphere in 1943 but beginning in the early 1970's surface models began to grapple more quantitatively with the source of methane and its instability in the atmosphere. The role of molecular nitrogen in the atmosphere was first quantitatively considered at that time as well. The Voyager 1 flyby put a thick atmosphere of molecular nitrogen and methane on an observational footing, and made an atmospheric descent probe quite feasible. The measured high methane humidity made seas of methane and possibly other constituents an attractive possible source of methane and sink of its photolytic products, influencing the choice of instruments for a descent probe. At the time of Huygens' actual descent to the surface, global seas had been ruled out, and the Cassini Orbiter was just beginning to gather imaging and radar data of the surface. The fluvial nature of the Huygens landing site and presence of volatiles just below the surface were important discoveries of Huygens itself. Together with Cassini, Huygens painted a picture of a cryogenic desert with occasional violent methane rainstorms feeding streams that tumble pebbles of ice and organics downhill, the whole surrounded by dunes whose organic-rich particles are harvested from the chemical conversion of methane to more refractory compounds high in the atmosphere. And yet many mysteries remain. The large bodies of liquid methane are restricted to high latitudes. Most of the river valleys seen in Cassini radar data seem to run down to nowhere. And the ultimate source and replenishment of methane, although seemingly more strongly tied to the interior than before Cassini-Huygens, remain unresolved. Huygens gave us the only imaging of Titan's surface with a resolution good enough to follow fluvial processes all the way from the contextual geology, to channels, to the stream debris washed out into the plains. What would we see if we could image even just 10% of Titan at Huygens resolution? Conversely, what might we have concluded about Titan were only the Cassini Orbiter data available, without Huygens? It is clear that Huygens gave us one tantalizing look through the keyhole at a mysterious room, but to truly understand what was glimpsed will require a future mission to open wide the door.

Direct measurements of methane emissions from abandoned oil and gas wells in Pennsylvania

PubMed Central

Kang, Mary; Kanno, Cynthia M.; Reid, Matthew C.; Zhang, Xin; Mauzerall, Denise L.; Celia, Michael A.; Chen, Yuheng; Onstott, Tullis C.

2014-01-01

Abandoned oil and gas wells provide a potential pathway for subsurface migration and emissions of methane and other fluids to the atmosphere. Little is known about methane fluxes from the millions of abandoned wells that exist in the United States. Here, we report direct measurements of methane fluxes from abandoned oil and gas wells in Pennsylvania, using static flux chambers. A total of 42 and 52 direct measurements were made at wells and at locations near the wells (“controls”) in forested, wetland, grassland, and river areas in July, August, October 2013 and January 2014, respectively. The mean methane flow rates at these well locations were 0.27 kg/d/well, and the mean methane flow rate at the control locations was 4.5 × 10−6 kg/d/location. Three out of the 19 measured wells were high emitters that had methane flow rates that were three orders of magnitude larger than the median flow rate of 1.3 × 10−3 kg/d/well. Assuming the mean flow rate found here is representative of all abandoned wells in Pennsylvania, we scaled the methane emissions to be 4–7% of estimated total anthropogenic methane emissions in Pennsylvania. The presence of ethane, propane, and n-butane, along with the methane isotopic composition, indicate that the emitted methane is predominantly of thermogenic origin. These measurements show that methane emissions from abandoned oil and gas wells can be significant. The research required to quantify these emissions nationally should be undertaken so they can be accurately described and included in greenhouse gas emissions inventories. PMID:25489074

Direct measurements of methane emissions from abandoned oil and gas wells in Pennsylvania.

PubMed

Kang, Mary; Kanno, Cynthia M; Reid, Matthew C; Zhang, Xin; Mauzerall, Denise L; Celia, Michael A; Chen, Yuheng; Onstott, Tullis C

2014-12-23

Abandoned oil and gas wells provide a potential pathway for subsurface migration and emissions of methane and other fluids to the atmosphere. Little is known about methane fluxes from the millions of abandoned wells that exist in the United States. Here, we report direct measurements of methane fluxes from abandoned oil and gas wells in Pennsylvania, using static flux chambers. A total of 42 and 52 direct measurements were made at wells and at locations near the wells ("controls") in forested, wetland, grassland, and river areas in July, August, October 2013 and January 2014, respectively. The mean methane flow rates at these well locations were 0.27 kg/d/well, and the mean methane flow rate at the control locations was 4.5 × 10(-6) kg/d/location. Three out of the 19 measured wells were high emitters that had methane flow rates that were three orders of magnitude larger than the median flow rate of 1.3 × 10(-3) kg/d/well. Assuming the mean flow rate found here is representative of all abandoned wells in Pennsylvania, we scaled the methane emissions to be 4-7% of estimated total anthropogenic methane emissions in Pennsylvania. The presence of ethane, propane, and n-butane, along with the methane isotopic composition, indicate that the emitted methane is predominantly of thermogenic origin. These measurements show that methane emissions from abandoned oil and gas wells can be significant. The research required to quantify these emissions nationally should be undertaken so they can be accurately described and included in greenhouse gas emissions inventories.

Iron-mediated anaerobic oxidation of methane in brackish coastal sediments.

PubMed

Egger, Matthias; Rasigraf, Olivia; Sapart, Célia J; Jilbert, Tom; Jetten, Mike S M; Röckmann, Thomas; van der Veen, Carina; Bândă, Narcisa; Kartal, Boran; Ettwig, Katharina F; Slomp, Caroline P

2015-01-06

Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

Low-temperature conversion of methane to methanol on CeO x/Cu 2O catalysts: Water controlled activation of the C–H Bond

DOE PAGES

Zuo, Zhijun; Ramírez, Pedro J.; Senanayake, Sanjaya D.; ...

2016-10-10

Here, an inverse CeO 2/Cu 2O/Cu(111) catalyst is able to activate methane at room temperature producing C, CH x fragments and CO x species on the oxide surface. The addition of water to the system leads to a drastic change in the selectivity of methane activation yielding only adsorbed CH x fragments. At a temperature of 450 K, in the presence of water, a CH 4 → CH 3OH catalytic transformation occurs with a high selectivity. OH groups formed by the dissociation of water saturate the catalyst surface, removing sites that could decompose CH x fragments, and generating centers onmore » which methane can directly interact to yield methanol.« less

Process simulation and comparison of biological conversion of syngas and hydrogen in biogas plants

NASA Astrophysics Data System (ADS)

Awais Salman, Chaudhary; Schwede, Sebastian; Thorin, Eva; Yan, Jinyue

2017-11-01

Organic waste is a good source of clean energy. However, different fractions of waste have to be utilized efficiently. One way is to find pathways to convert waste into useful products via various available processes (gasification, pyrolysis anaerobic digestion, etc.) and integrate them to increase the combined efficiency of the process. The syngas and hydrogen produced from the thermal conversion of biomass can be upgraded to biomethane via biological methanation. The current study presents the simulation model to predict the amount of biomethane produced by injecting the hydrogen and syngas. Hydrogen injection is modelled both in-situ and ex-situ while for syngas solely the ex-situ case has been studied. The results showed that 85% of the hydrogen conversion was achieved for the ex-situ reactor while 81% conversion rate was achieved for the in-situ reactor. The syngas could be converted completely in the bio-reactor. However, the addition of syngas resulted in an increase of carbon dioxide. Simulation of biomethanation of gas addition showed a biomethane concentration of 87% while for hydrogen addition an increase of 74% and 80% for in-situ and ex-situ addition respectively.

Development of eye-safe lidar for aerosol measurements

NASA Technical Reports Server (NTRS)

Singh, Upendra N.; Wilderson, Thomas D.

1990-01-01

Research is summarized on the development of an eye safe Raman conversion system to carry out lidar measurements of aerosol and clouds from an airborne platform. Radiation is produced at the first Stokes wavelength of 1.54 micron in the eye safe infrared, when methane is used as the Raman-active medium, the pump source being a Nd:YAG laser at 1.064 micron. Results are presented for an experimental study of the dependence of the 1.54 micron first Stokes radiation on the focusing geometry, methane gas pressure, and pump energy. The specific new technique developed for optimizing the first Stokes generation involves retroreflecting the backward-generated first Stokes light back into the Raman cell as a seed Stokes beam which is then amplified in the temporal tail of the pump beam. Almost 20 percent conversion to 1.54 micron is obtained. Complete, assembled hardware for the Raman conversion system was delivered to the Goddard Space Flight Center for a successful GLOBE flight (1989) to measure aerosol backscatter around the Pacific basin.

High-strength fermentable wastewater reclamation through a sequential process of anaerobic fermentation followed by microalgae cultivation.

PubMed

Qi, Wenqiang; Chen, Taojing; Wang, Liang; Wu, Minghong; Zhao, Quanyu; Wei, Wei

2017-03-01

In this study, the sequential process of anaerobic fermentation followed by microalgae cultivation was evaluated from both nutrient and energy recovery standpoints. The effects of different fermentation type on the biogas generation, broth metabolites' composition, algal growth and nutrients' utilization, and energy conversion efficiencies for the whole processes were discussed. When the fermentation was designed to produce hydrogen-dominating biogas, the total energy conversion efficiency (TECE) of the sequential process was higher than that of the methane fermentation one. With the production of hydrogen in anaerobic fermentation, more organic carbon metabolites were left in the broth to support better algal growth with more efficient incorporation of ammonia nitrogen. By applying the sequential process, the heat value conversion efficiency (HVCE) for the wastewater could reach 41.2%, if methane was avoided in the fermentation biogas. The removal efficiencies of organic metabolites and NH 4 + -N in the better case were 100% and 98.3%, respectively. Copyright © 2016 Elsevier Ltd. All rights reserved.

Intrinsic selectivity and structure sensitivity of Rhodium catalysts for C 2+ oxygenate production [On the intrinsic selectivity and structure sensitivity of Rhodium catalysts for C 2+ oxygenate production

DOE PAGES

Yang, Nuoya; Medford, Andrew J.; Liu, Xinyan; ...

2016-01-31

Synthesis gas (CO + H 2) conversion is a promising route to converting coal, natural gas, or biomass into synthetic liquid fuels. Rhodium has long been studied as it is the only elemental catalyst that has demonstrated selectivity to ethanol and other C 2+ oxygenates. However, the fundamentals of syngas conversion over rhodium are still debated. In this work a microkinetic model is developed for conversion of CO and H 2 into methane, ethanol, and acetaldehyde on the Rh (211) and (111) surfaces, chosen to describe steps and close-packed facets on catalyst particles. The model is based on DFT calculationsmore » using the BEEF-vdW functional. The mean-field kinetic model includes lateral adsorbate–adsorbate interactions, and the BEEF-vdW error estimation ensemble is used to propagate error from the DFT calculations to the predicted rates. The model shows the Rh(211) surface to be ~6 orders of magnitude more active than the Rh(111) surface, but highly selective toward methane, while the Rh(111) surface is intrinsically selective toward acetaldehyde. A variety of Rh/SiO 2 catalysts are synthesized, tested for catalytic oxygenate production, and characterized using TEM. The experimental results indicate that the Rh(111) surface is intrinsically selective toward acetaldehyde, and a strong inverse correlation between catalytic activity and oxygenate selectivity is observed. Furthermore, iron impurities are shown to play a key role in modulating the selectivity of Rh/SiO 2 catalysts toward ethanol. The experimental observations are consistent with the structure-sensitivity predicted from theory. As a result, this work provides an improved atomic-scale understanding and new insight into the mechanism, active site, and intrinsic selectivity of syngas conversion over rhodium catalysts and may also guide rational design of alloy catalysts made from more abundant elements.« less

Intrinsic selectivity and structure sensitivity of Rhodium catalysts for C 2+ oxygenate production [On the intrinsic selectivity and structure sensitivity of Rhodium catalysts for C 2+ oxygenate production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Nuoya; Medford, Andrew J.; Liu, Xinyan

Synthesis gas (CO + H 2) conversion is a promising route to converting coal, natural gas, or biomass into synthetic liquid fuels. Rhodium has long been studied as it is the only elemental catalyst that has demonstrated selectivity to ethanol and other C 2+ oxygenates. However, the fundamentals of syngas conversion over rhodium are still debated. In this work a microkinetic model is developed for conversion of CO and H 2 into methane, ethanol, and acetaldehyde on the Rh (211) and (111) surfaces, chosen to describe steps and close-packed facets on catalyst particles. The model is based on DFT calculationsmore » using the BEEF-vdW functional. The mean-field kinetic model includes lateral adsorbate–adsorbate interactions, and the BEEF-vdW error estimation ensemble is used to propagate error from the DFT calculations to the predicted rates. The model shows the Rh(211) surface to be ~6 orders of magnitude more active than the Rh(111) surface, but highly selective toward methane, while the Rh(111) surface is intrinsically selective toward acetaldehyde. A variety of Rh/SiO 2 catalysts are synthesized, tested for catalytic oxygenate production, and characterized using TEM. The experimental results indicate that the Rh(111) surface is intrinsically selective toward acetaldehyde, and a strong inverse correlation between catalytic activity and oxygenate selectivity is observed. Furthermore, iron impurities are shown to play a key role in modulating the selectivity of Rh/SiO 2 catalysts toward ethanol. The experimental observations are consistent with the structure-sensitivity predicted from theory. As a result, this work provides an improved atomic-scale understanding and new insight into the mechanism, active site, and intrinsic selectivity of syngas conversion over rhodium catalysts and may also guide rational design of alloy catalysts made from more abundant elements.« less

Comparison of facility-level methane emission rates from natural gas production well pads in the Marcellus, Denver-Julesburg, and Uintah Basins

NASA Astrophysics Data System (ADS)

Omara, M.; Li, X.; Sullivan, M.; Subramanian, R.; Robinson, A. L.; Presto, A. A.

2015-12-01

The boom in shale natural gas (NG) production, brought about by advances in horizontal drilling and hydraulic fracturing, has yielded both economic benefits and concerns about environmental and climate impacts. In particular, leakages of methane from the NG supply chain could substantially increase the carbon footprint of NG, diminishing its potential role as a transition fuel between carbon intensive fossil fuels and renewable energy systems. Recent research has demonstrated significant variability in measured methane emission rates from NG production facilities within a given shale gas basin. This variability often reflect facility-specific differences in NG production capacity, facility age, utilization of emissions capture and control, and/or the level of facility inspection and maintenance. Across NG production basins, these differences in facility-level methane emission rates are likely amplified, especially if significant variability in NG composition and state emissions regulations are present. In this study, we measured methane emission rates from the NG production sector in the Marcellus Shale Basin (Pennsylvania and West Virginia), currently the largest NG production basin in the U.S., and contrast these results with those of the Denver-Julesburg (Colorado) and Uintah (Utah) shale basins. Facility-level methane emission rates were measured at 106 NG production facilities using the dual tracer flux (nitrous oxide and acetylene), Gaussian dispersion simulations, and the OTM 33A techniques. The distribution of facility-level average methane emission rate for each NG basin will be discussed, with emphasis on how variability in NG composition (i.e., ethane-to-methane ratios) and state emissions regulations impact measured methane leak rates. While the focus of this presentation will be on the comparison of methane leak rates among NG basins, the use of three complimentary top-down methane measurement techniques provides a unique opportunity to explore the effectiveness of each approach, which will also be discussed.

Methane Leak Rates from Natural Gas Wells in Norther California

NASA Astrophysics Data System (ADS)

Cui, Y.; Yoon, S.; Chen, Y.; Falk, M.; Kuwayama, T.; Croes, B. E.; Herner, J.; Vijayan, A.

2017-12-01

Methane is a potent greenhouse gas (GHG) and is the second most prevalent GHG emitted in California from human activities. As part of a comprehensive effort to reduce GHG emissions and meet the statewide climate goals, California has proposed a Short Lived Climate Pollutant (SLCP) Strategy that includes a 40% reduction of methane emissions from 2013 levels by 2030, with goals to reduce oil and gas related emissions and capture methane emissions from dairy operations and organic waste. There is growing evidence in the recent scientific literature suggesting that methane emissions can come from every stage of the oil and gas supply chain. During oil and gas production operations, studies reported that a small number of oil and gas wells made up a large fraction of total methane emissions from the wells. In such a fat-tail distribution, the mean methane leak rate from wells is orders of magnitude larger than the median, which indicates the presence of super emitter sources. However, since the super emitters are often positioned as outliers in a fat-tail distribution and do not always behave consistently, measuring their leak rates is challenging, but critical to quantify their impacts and identify potential mitigation opportunities. This presentation will discuss of methane leak rates measured from natural gas wells in Northern California for different well operations: active, idle, and plugged. The leak rates demonstrated fat-tail distributions, and the mean leak rates for each well operation status were an order of magnitude higher than the median leak rates. It was also observed that roughly 20% of wells contributed more than 80% of methane emissions. Further data collection is needed with a larger number of samples to better understand the relationship between the leak rates and well operation status. Such measurements could help improve the estimate of methane emissions from natural gas wells and inform methane reduction policies and programs in California.

Annual variability and regulation of methane and sulfate fluxes in Baltic Sea estuarine sediments

NASA Astrophysics Data System (ADS)

Sawicka, Joanna E.; Brüchert, Volker

2017-01-01

Marine methane emissions originate largely from near-shore coastal systems, but emission estimates are often not based on temporally well-resolved data or sufficient understanding of the variability of methane consumption and production processes in the underlying sediment. The objectives of our investigation were to explore the effects of seasonal temperature, changes in benthic oxygen concentration, and historical eutrophication on sediment methane concentrations and benthic fluxes at two type localities for open-water coastal versus eutrophic, estuarine sediment in the Baltic Sea. Benthic fluxes of methane and oxygen and sediment pore-water concentrations of dissolved sulfate, methane, and 35S-sulfate reduction rates were obtained over a 12-month period from April 2012 to April 2013. Benthic methane fluxes varied by factors of 5 and 12 at the offshore coastal site and the eutrophic estuarine station, respectively, ranging from 0.1 mmol m-2 d-1 in winter at an open coastal site to 2.6 mmol m-2 d-1 in late summer in the inner eutrophic estuary. Total oxygen uptake (TOU) and 35S-sulfate reduction rates (SRRs) correlated with methane fluxes showing low rates in the winter and high rates in the summer. The highest pore-water methane concentrations also varied by factors of 6 and 10 over the sampling period with the lowest values in the winter and highest values in late summer-early autumn. The highest pore-water methane concentrations were 5.7 mM a few centimeters below the sediment surface, but they never exceeded the in situ saturation concentration. Of the total sulfate reduction, 21-24 % was coupled to anaerobic methane oxidation, lowering methane concentrations below the sediment surface far below the saturation concentration. The data imply that bubble emission likely plays no or only a minor role in methane emissions in these sediments. The changes in pore-water methane concentrations over the observation period were too large to be explained by temporal changes in methane formation and methane oxidation rates due to temperature alone. Additional factors such as regional and local hydrostatic pressure changes and coastal submarine groundwater flow may also affect the vertical and lateral transport of methane.

Distribution and Rate of Methane Oxidation in Sediments of the Florida Everglades †

PubMed Central

King, Gary M.; Roslev, Peter; Skovgaard, Henrik

1990-01-01

Rates of methane emission from intact cores were measured during anoxic dark and oxic light and dark incubations. Rates of methane oxidation were calculated on the basis of oxic incubations by using the anoxic emissions as an estimate of the maximum potential flux. This technique indicated that methane oxidation consumed up to 91% of the maximum potential flux in peat sediments but that oxidation was negligible in marl sediments. Oxygen microprofiles determined for intact cores were comparable to profiles measured in situ. Thus, the laboratory incubations appeared to provide a reasonable approximation of in situ activities. This was further supported by the agreement between measured methane fluxes and fluxes predicted on the basis of methane profiles determined by in situ sampling of pore water. Methane emissions from peat sediments, oxygen concentrations and penetration depths, and methane concentration profiles were all sensitive to light-dark shifts as determined by a combination of field and laboratory analyses. Methane emissions were lower and oxygen concentrations and penetration depths were higher under illuminated than under dark conditions; the profiles of methane concentration changed in correspondence to the changes in oxygen profiles, but the estimated flux of methane into the oxic zone changed negligibly. Sediment-free, root-associated methane oxidation showed a pattern similar to that for methane oxidation in the core analyses: no oxidation was detected for roots growing in marl sediment, even for roots of Cladium jamaicense, which had the highest activity for samples from peat sediments. The magnitude of the root-associated oxidation rates indicated that belowground plant surfaces may not markedly increase the total capacity for methane consumption. However, the data collectively support the notion that the distribution and activity of methane oxidation have a major impact on the magnitude of atmospheric fluxes from the Everglades. PMID:16348299

Comparison of Landfill Methane Oxidation Measured Using Stable Isotope Analysis and CO2/CH4 Fluxes Measured by the Eddy Covariance Method

NASA Astrophysics Data System (ADS)

Xu, L.; Chanton, J.; McDermitt, D. K.; Li, J.; Green, R. B.

2015-12-01

Methane plays a critical role in the radiation balance and chemistry of the atmosphere. Globally, landfill methane emission contributes about 10-19% of the anthropogenic methane burden into the atmosphere. In the United States, 18% of annual anthropogenic methane emissions come from landfills, which represent the third largest source of anthropogenic methane emissions, behind enteric fermentation and natural gas and oil production. One uncertainty in estimating landfill methane emissions is the fraction of methane oxidized when methane produced under anaerobic conditions passes through the cover soil. We developed a simple stoichiometric model to estimate methane oxidation fraction when the anaerobic CO2 / CH4 production ratio is known, or can be estimated. The model predicts a linear relationship between CO2 emission rates and CH4 emission rates, where the slope depends on anaerobic CO2 / CH4 production ratio and the fraction of methane oxidized, and the intercept depends on non-methane-dependent oxidation processes. The model was tested using carbon dioxide emission rates (fluxes) and methane emission rates (fluxes) measured using the eddy covariance method over a one year period at the Turkey Run landfill in Georgia, USA. The CO2 / CH4 production ratio was estimated by measuring CO2 and CH4 concentrations in air sampled under anaerobic conditions deep inside the landfill. We also used a mass balance approach to independently estimate fractional oxidation based on stable isotope measurements (δ13C of methane) of gas samples taken from deep inside the landfill and just above the landfill surface. Results from the two independent methods agree well. The model will be described and methane oxidation will be discussed in relation to wind direction, location at the landfill, and age of the deposited refuse.

Bioconversion of methane to lactate by an obligate methanotrophic bacterium

DOE PAGES

Henard, Calvin A.; Smith, Holly; Dowe, Nancy; ...

2016-02-23

Methane is the second most abundant greenhouse gas (GHG), with nearly 60% of emissions derived from anthropogenic sources. Microbial conversion of methane to fuels and value-added chemicals offers a means to reduce GHG emissions, while also valorizing this otherwise squandered high-volume, high-energy gas. However, to date, advances in methane biocatalysis have been constrained by the low-productivity and limited genetic tractability of natural methane-consuming microbes. Here, leveraging recent identification of a novel, tractable methanotrophic bacterium, Methylomicrobium buryatense, we demonstrate microbial biocatalysis of methane to lactate, an industrial platform chemical. Heterologous overexpression of a Lactobacillus helveticus L-lactate dehydrogenase in M. buryatense resultedmore » in an initial titer of 0.06 g lactate/L from methane. Cultivation in a 5 L continuously stirred tank bioreactor enabled production of 0.8 g lactate/L, representing a 13-fold improvement compared to the initial titer. The yields (0.05 g lactate/g methane) and productivity (0.008 g lactate/L/h) indicate the need and opportunity for future strain improvement. Additionally, real-time analysis of methane utilization implicated gas-to-liquid transfer and/or microbial methane consumption as process limitations. This work opens the door to develop an array of methanotrophic bacterial strain-engineering strategies currently employed for biocatalytic sugar upgrading to “green” chemicals and fuels.« less

Bioconversion of methane to lactate by an obligate methanotrophic bacterium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henard, Calvin A.; Smith, Holly; Dowe, Nancy

Methane is the second most abundant greenhouse gas (GHG), with nearly 60% of emissions derived from anthropogenic sources. Microbial conversion of methane to fuels and value-added chemicals offers a means to reduce GHG emissions, while also valorizing this otherwise squandered high-volume, high-energy gas. However, to date, advances in methane biocatalysis have been constrained by the low-productivity and limited genetic tractability of natural methane-consuming microbes. Here, leveraging recent identification of a novel, tractable methanotrophic bacterium, Methylomicrobium buryatense, we demonstrate microbial biocatalysis of methane to lactate, an industrial platform chemical. Heterologous overexpression of a Lactobacillus helveticus L-lactate dehydrogenase in M. buryatense resultedmore » in an initial titer of 0.06 g lactate/L from methane. Cultivation in a 5 L continuously stirred tank bioreactor enabled production of 0.8 g lactate/L, representing a 13-fold improvement compared to the initial titer. The yields (0.05 g lactate/g methane) and productivity (0.008 g lactate/L/h) indicate the need and opportunity for future strain improvement. Additionally, real-time analysis of methane utilization implicated gas-to-liquid transfer and/or microbial methane consumption as process limitations. This work opens the door to develop an array of methanotrophic bacterial strain-engineering strategies currently employed for biocatalytic sugar upgrading to “green” chemicals and fuels.« less

Bioconversion of methane to lactate by an obligate methanotrophic bacterium

PubMed Central

Henard, Calvin A.; Smith, Holly; Dowe, Nancy; Kalyuzhnaya, Marina G.; Pienkos, Philip T.; Guarnieri, Michael T.

2016-01-01

Methane is the second most abundant greenhouse gas (GHG), with nearly 60% of emissions derived from anthropogenic sources. Microbial conversion of methane to fuels and value-added chemicals offers a means to reduce GHG emissions, while also valorizing this otherwise squandered high-volume, high-energy gas. However, to date, advances in methane biocatalysis have been constrained by the low-productivity and limited genetic tractability of natural methane-consuming microbes. Here, leveraging recent identification of a novel, tractable methanotrophic bacterium, Methylomicrobium buryatense, we demonstrate microbial biocatalysis of methane to lactate, an industrial platform chemical. Heterologous overexpression of a Lactobacillus helveticus L-lactate dehydrogenase in M. buryatense resulted in an initial titer of 0.06 g lactate/L from methane. Cultivation in a 5 L continuously stirred tank bioreactor enabled production of 0.8 g lactate/L, representing a 13-fold improvement compared to the initial titer. The yields (0.05 g lactate/g methane) and productivity (0.008 g lactate/L/h) indicate the need and opportunity for future strain improvement. Additionally, real-time analysis of methane utilization implicated gas-to-liquid transfer and/or microbial methane consumption as process limitations. This work opens the door to develop an array of methanotrophic bacterial strain-engineering strategies currently employed for biocatalytic sugar upgrading to “green” chemicals and fuels. PMID:26902345

Fractionation of carbon and hydrogen isotopes by methane-oxidizing bacteria

USGS Publications Warehouse

Coleman, D.D.; Risatti, J.B.; Schoell, M.

1981-01-01

Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas and can sometimes be used for gas-source rock correlations. Methane-oxidizing bacteria, however, can significantly change the carbon isotopic composition of methane; the origin of gas that has been partially oxidized by these bacteria could therefore be misinterpreted. We cultured methane-oxidizing bacteria at two different temperatures and monitored the carbon and hydrogen isotopic compositions of the residual methane. The residual methane was enriched in both 13C and D. For both isotopic species, the enrichment at equivalent levels of conversion was greater at 26??C than at 11.5??C. The change in ??D relative to the change in ??13C was independent of temperature within the range studied. One culture exhibited a change in the fractionation pattern for carbon (but not for hydrogen) midway through the experiment, suggesting that bacterial oxidation of methane may occur via more than one pathway. The change in the ??D value for the residual methane was from 8 to 14 times greater than the change in the ??13C value, indicating that combined carbon and hydrogen isotopic analysis may be an effective way of identifying methane which has been subjected to partial oxidation by bacteria. ?? 1981.

A full scale worm reactor for efficient sludge reduction by predation in a wastewater treatment plant.

PubMed

Tamis, J; van Schouwenburg, G; Kleerebezem, R; van Loosdrecht, M C M

2011-11-15

Sludge predation can be an effective solution to reduce sludge production at a wastewater treatment plant. Oligochaete worms are the natural consumers of biomass in benthic layers in ecosystems. In this study the results of secondary sludge degradation by the aquatic Oligochaete worm Aulophorus furcatus in a 125 m(3) reactor and further sludge conversion in an anaerobic tank are presented. The system was operated over a period of 4 years at WWTP Wolvega, the Netherlands and was fed with secondary sludge from a low loaded activated sludge process. It was possible to maintain a stable and active population of the aquatic worm species A. furcatus during the full period. Under optimal conditions a sludge conversion of 150-200 kg TSS/d or 1.2-1.6 kg TSS/m(3)/d was established in the worm reactor. The worms grew as a biofilm on carrier material in the reactor. The surface specific conversion rate reached 140-180 g TSS/m(2)d and the worm biomass specific conversion rate was 0.5-1 g TSS sludge/g dry weight worms per day. The sludge reduction under optimal conditions in the worm reactor was 30-40%. The degradation by worms was an order of magnitude larger than the endogenous conversion rate of the secondary sludge. Effluent sludge from the worm reactor was stored in an anaerobic tank where methanogenic processes became apparent. It appeared that besides reducing the sludge amount, the worms' activity increased anaerobic digestibility, allowing for future optimisation of the total system by maximising sludge reduction and methane formation. In the whole system it was possible to reduce the amount of sludge by at least 65% on TSS basis. This is a much better total conversion than reported for anaerobic biodegradability of secondary sludge of 20-30% efficiency in terms of TSS reduction. Copyright © 2011 Elsevier Ltd. All rights reserved.

Extraction of soluble substances from organic solid municipal waste to increase methane production.

PubMed

Campuzano, Rosalinda; González-Martínez, Simón

2015-02-01

This work deals with the analysis of the methane production from Mexico City's urban organic wastes after separating soluble from suspended substances. Water was used to extract soluble substances under three different water to waste ratios and after three extraction procedures. Methane production was measured at 35 °C during 21 days using a commercial methane potential testing device. Results indicate that volatile solids extraction increases with dilution rate to a maximum of 40% at 20 °C and to 43% at 93 °C. The extracts methane production increases with the dilution rate as a result of enhanced dissolved solids extraction. The combined (extract and bagasse) methane production reached, in 6 days, 66% of the total methane produced in 21 days. The highest methane production rates were measured during the first six days. Copyright © 2014 Elsevier Ltd. All rights reserved.

Lignocellulose-derived thin stillage composition and efficient biological treatment with a high-rate hybrid anaerobic bioreactor system.

PubMed

Oosterkamp, Margreet J; Méndez-García, Celia; Kim, Chang-H; Bauer, Stefan; Ibáñez, Ana B; Zimmerman, Sabrina; Hong, Pei-Ying; Cann, Isaac K; Mackie, Roderick I

2016-01-01

This study aims to chemically characterize thin stillage derived from lignocellulosic biomass distillation residues in terms of organic strength, nutrient, and mineral content. The feasibility of performing anaerobic digestion on these stillages at mesophilic (40 °C) and thermophilic (55 °C) temperatures to produce methane was demonstrated. The microbial communities involved were further characterized. Energy and sugar cane stillage have a high chemical oxygen demand (COD of 43 and 30 g/L, respectively) and low pH (pH 4.3). Furthermore, the acetate concentration in sugar cane stillage was high (45 mM) but was not detected in energy cane stillage. There was also a high amount of lactate in both types of stillage (35-37 mM). The amount of sugars was 200 times higher in energy cane stillage compared to sugar cane stillage. Although there was a high concentration of sulfate (18 and 23 mM in sugar and energy cane stillage, respectively), both thin stillages were efficiently digested anaerobically with high COD removal under mesophilic and thermophilic temperature conditions and with an organic loading rate of 15-21 g COD/L/d. The methane production rate was 0.2 L/g COD, with a methane percentage of 60 and 64, and 92 and 94 % soluble COD removed, respectively, by the mesophilic and thermophilic reactors. Although both treatment processes were equally efficient, there were different microbial communities involved possibly arising from the differences in the composition of energy cane and sugar cane stillage. There was more acetic acid in sugar cane stillage which may have promoted the occurrence of aceticlastic methanogens to perform a direct conversion of acetate to methane in reactors treating sugar cane stillage. Results showed that thin stillage contains easily degradable compounds suitable for anaerobic digestion and that hybrid reactors can efficiently convert thin stillage to methane under mesophilic and thermophilic conditions. Furthermore, we found that optimal conditions for biological treatment of thin stillage were similar for both mesophilic and thermophilic reactors. Bar-coded pyrosequencing of the 16S rRNA gene identified different microbial communities in mesophilic and thermophilic reactors and these differences in the microbial communities could be linked to the composition of the thin stillage.

Light-Dependent Aerobic Methane Oxidation Reduces Methane Emissions from Seasonally Stratified Lakes

PubMed Central

Oswald, Kirsten; Milucka, Jana; Brand, Andreas; Littmann, Sten; Wehrli, Bernhard; Kuypers, Marcel M. M.; Schubert, Carsten J.

2015-01-01

Lakes are a natural source of methane to the atmosphere and contribute significantly to total emissions compared to the oceans. Controls on methane emissions from lake surfaces, particularly biotic processes within anoxic hypolimnia, are only partially understood. Here we investigated biological methane oxidation in the water column of the seasonally stratified Lake Rotsee. A zone of methane oxidation extending from the oxic/anoxic interface into anoxic waters was identified by chemical profiling of oxygen, methane and δ13C of methane. Incubation experiments with 13C-methane yielded highest oxidation rates within the oxycline, and comparable rates were measured in anoxic waters. Despite predominantly anoxic conditions within the zone of methane oxidation, known groups of anaerobic methanotrophic archaea were conspicuously absent. Instead, aerobic gammaproteobacterial methanotrophs were identified as the active methane oxidizers. In addition, continuous oxidation and maximum rates always occurred under light conditions. These findings, along with the detection of chlorophyll a, suggest that aerobic methane oxidation is tightly coupled to light-dependent photosynthetic oxygen production both at the oxycline and in the anoxic bottom layer. It is likely that this interaction between oxygenic phototrophs and aerobic methanotrophs represents a widespread mechanism by which methane is oxidized in lake water, thus diminishing its release into the atmosphere. PMID:26193458

Conversion of crude oil to methane by a microbial consortium enriched from oil reservoir production waters

PubMed Central

Berdugo-Clavijo, Carolina; Gieg, Lisa M.

2014-01-01

The methanogenic biodegradation of crude oil is an important process occurring in petroleum reservoirs and other oil-containing environments such as contaminated aquifers. In this process, syntrophic bacteria degrade hydrocarbon substrates to products such as acetate, and/or H2 and CO2 that are then used by methanogens to produce methane in a thermodynamically dependent manner. We enriched a methanogenic crude oil-degrading consortium from production waters sampled from a low temperature heavy oil reservoir. Alkylsuccinates indicative of fumarate addition to C5 and C6 n-alkanes were identified in the culture (above levels found in controls), corresponding to the detection of an alkyl succinate synthase encoding gene (assA/masA) in the culture. In addition, the enrichment culture was tested for its ability to produce methane from residual oil in a sandstone-packed column system simulating a mature field. Methane production rates of up to 5.8 μmol CH4/g of oil/day were measured in the column system. Amounts of produced methane were in relatively good agreement with hydrocarbon loss showing depletion of more than 50% of saturate and aromatic hydrocarbons. Microbial community analysis revealed that the enrichment culture was dominated by members of the genus Smithella, Methanosaeta, and Methanoculleus. However, a shift in microbial community occurred following incubation of the enrichment in the sandstone columns. Here, Methanobacterium sp. were most abundant, as were bacterial members of the genus Pseudomonas and other known biofilm forming organisms. Our findings show that microorganisms enriched from petroleum reservoir waters can bioconvert crude oil components to methane both planktonically and in sandstone-packed columns as test systems. Further, the results suggest that different organisms may contribute to oil biodegradation within different phases (e.g., planktonic vs. sessile) within a subsurface crude oil reservoir. PMID:24829563

Methane production by anaerobic digestion of water hyacinth (Eichhornia crassipes)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klass, D.L.; Ghosh, S.

1980-01-01

Water hyacinth under conventional high-rate digestion conditions exhibited higher methane yields and energy recovery efficiencies when grown in sewage-fed lagoons as compared to the corresponding values obtained with water hyacinth grown in a fresh-water pond. Mesophilic digestion provided the highest feed energy recovered in the product gas as methane while thermophilic digestion, when operated at sufficiently high loading rates and reduced detention times, gave the highest specific methane production rates. Methane yields, volatile solids reduction, and energy recovery as methane for the sewage-grown water hyacinth were in the same range as those observed for other biomass substrates when digested undermore » similar conditions.« less

Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Aiguo; Austin, Danielle; Karmakar, Abhoy

The technical feasibility of coaromatization of acetic acid derived from biomass and methane was investigated under mild reaction conditions (400 °C and 30 bar) over silver-, zinc-, and/or gallium-modified zeolite catalysts. On the basis of GC-MS, Micro-GC, and TGA analysis, more light aromatic hydrocarbons, less phenol formation, lower coke production, and higher methane conversion are observed over 5%Zn-1%Ga/ZSM-5 catalyst in comparison with catalytic performance over the other catalysts. Direct evidence of methane incorporation into aromatics over 5%Zn-1%Ga/ZSM-5 catalyst is witnessed in 1H, 2H, and 13C NMR spectra, revealing that the carbon from methane prefers to occupy the phenyl carbon sitesmore » and the benzylic carbon sites, and the hydrogen of methane favors the aromatic and benzylic substitutions of product molecules. In combination with the 13C NMR results for isotopically labeled acetic acid ( 13CH 3COOH and CH 3 13COOH), it can be seen that the methyl and carbonyl carbons of acetic acid are equally involved in the formation of ortho, meta and para carbons of the aromatics, whereas the phenyl carbons directly bonded with alkyl substituent groups and benzylic carbons are derived mainly from the carboxyl carbon of acetic acid. After various catalyst characterizations by using TEM, XRD, DRIFT, NH 3-TPD, and XPS, the excellent catalytic performance might be closely related to the highly dispersed zinc and gallium species on the zeolite support, moderate surface acidity, and an appropriate ratio of weak acidic sites to strong acidic sites as well as the fairly stable oxidation state during acetic acid conversion under a methane environment. Two mechanisms of the coaromatization of acetic acid and methane have also been proposed after consulting all the collected data in this study. In conclusion, the results reported in this paper could potentially lead to more cost-effective utilization of abundant natural gas and biomass.« less

Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst

DOE PAGES

Wang, Aiguo; Austin, Danielle; Karmakar, Abhoy; ...

2017-04-19

The technical feasibility of coaromatization of acetic acid derived from biomass and methane was investigated under mild reaction conditions (400 °C and 30 bar) over silver-, zinc-, and/or gallium-modified zeolite catalysts. On the basis of GC-MS, Micro-GC, and TGA analysis, more light aromatic hydrocarbons, less phenol formation, lower coke production, and higher methane conversion are observed over 5%Zn-1%Ga/ZSM-5 catalyst in comparison with catalytic performance over the other catalysts. Direct evidence of methane incorporation into aromatics over 5%Zn-1%Ga/ZSM-5 catalyst is witnessed in 1H, 2H, and 13C NMR spectra, revealing that the carbon from methane prefers to occupy the phenyl carbon sitesmore » and the benzylic carbon sites, and the hydrogen of methane favors the aromatic and benzylic substitutions of product molecules. In combination with the 13C NMR results for isotopically labeled acetic acid ( 13CH 3COOH and CH 3 13COOH), it can be seen that the methyl and carbonyl carbons of acetic acid are equally involved in the formation of ortho, meta and para carbons of the aromatics, whereas the phenyl carbons directly bonded with alkyl substituent groups and benzylic carbons are derived mainly from the carboxyl carbon of acetic acid. After various catalyst characterizations by using TEM, XRD, DRIFT, NH 3-TPD, and XPS, the excellent catalytic performance might be closely related to the highly dispersed zinc and gallium species on the zeolite support, moderate surface acidity, and an appropriate ratio of weak acidic sites to strong acidic sites as well as the fairly stable oxidation state during acetic acid conversion under a methane environment. Two mechanisms of the coaromatization of acetic acid and methane have also been proposed after consulting all the collected data in this study. In conclusion, the results reported in this paper could potentially lead to more cost-effective utilization of abundant natural gas and biomass.« less

Alternative Fuels Data Center

Science.gov Websites

vehicles altered to operate on propane, natural gas, methane gas, ethanol, or electricity are classified as information about vehicle conversion certification requirements, see the Alternative Fuels Data Center's

Biogasification of Walt Disney World biomass waste blend. Annual report Jan-Dec 82

DOE Office of Scientific and Technical Information (OSTI.GOV)

Biljetina, R.; Chynoweth, D.P.; Janulis, J.

1983-05-01

The objective of this research is to develop efficient processes for conversion of biomass-waste blends to methane and other resources. To evaluate the technical and economic feasibility, an experimental test facility (ETU) is being designed and installed at the Reedy Creek Wastewater Treatment Plant at Walt Disney World, Orlando, Florida. The facility will integrate a biomethanogenic conversion process with a waste-water treatment process employing water hyacinth ponds for secondary and tertiary treatment of sewage produced at Walt Disney World. The ETU will be capable of feeding 1-wet ton per day of water hyacinth-sludge blends to the digestion system for productionmore » of methane and other byproducts. The detailed design of the facility has been completed and procurement of equipment is in progress.« less

An introduction of CO₂ conversion by dry reforming with methane and new route of low-temperature methanol synthesis.

PubMed

Shi, Lei; Yang, Guohui; Tao, Kai; Yoneyama, Yoshiharu; Tan, Yisheng; Tsubaki, Noritatsu

2013-08-20

Carbon dioxide is one of the highest contributors to the greenhouse effect, as well as a cheap and nontoxic building block for single carbon source chemistry. As such, CO₂ conversion is one of most important research areas in energy and environment sciences, as well as in catalysis technology. For chemical conversion of CO₂, natural gas (mainly CH₄) is a promising counterpart molecule to the CO₂-related reaction, due to its high availability and low price. More importantly, being able to convert CH₄ to useful fuels and molecules is advantageous, because it is also a kind of "greenhouse effect" gas, and can be an energy alternative to petroleum oil. In this Account, we discuss our development of efficient catalysts with precisely designed nanostructure for CO₂ reforming of CH₄ to produce syngas (mixture of CO and H₂), which can then be converted to many chemicals and energy products. This new production flow can establish a GTL (gas-to-liquid) industry, being currently pushed by the shale gas revolution. From the viewpoint of GTL industry, developing a catalyst for CO₂ reforming of CH₄ is a challenge, because they need a very high production rate to make the huge GTL methane reformer as small as possible. In addition, since both CO₂ and CH₄ give off carbon deposits that deactivate non-precious metallic catalysts very quickly, the total design of catalyst support and supported metallic nanoparticles is necessary. We present a simple but useful method to prepare bimodal catalyst support, where small pores are formed inside large ones during the self-organization of nanoparticles from solution. Large pores enhance the mass transfer rate, while small pores provide large surface areas to disperse active metallic nanoparticles. More importantly, building materials for small pores can also be used as promoters or cocatalysts to further enhance the total activity and stability. Produced syngas from methane reforming is generally catalytically converted in situ via one of two main routes. The first is to use Fischer-Tropsch synthesis (FTS), a process that catalytically converts syngas to hydrocarbons of varying molecular weights. The second is methanol synthesis. The latter has better atomic economy, since the oxygen atom in CO is included in the product and CO₂ can be blended into syngas as a reactant. However, production of methanol is very inefficient in this reaction: only 10-15% one-pass conversion typically at 5.0-10.0 MPa and 523-573 K, due to the severe thermodynamic limitations of this exothermal reaction (CO + 2H₂ = CH₃OH). In this Account, we propose and develop a new route of low-temperature methanol synthesis from CO₂-containing syngas only by adding alcohols, including methanol itself. These alcohols act as homogeneous cocatalysts and the solvent, realizing 70-100% one-pass conversion at only 5.0 MPa and 443 K. The key step is the reaction of the adsorbed formate species with alcohols to yield ester species at low temperatures, followed by the hydrogenation of ester by hydrogen atoms on metallic Cu. This changes the normal reaction path of conventional, high-temperature methanol synthesis from formate via methoxy to methanol.

Assessment of methane generation, oxidation, and emission in a subtropical landfill test cell.

PubMed

Moreira, João M L; Candiani, Giovano

2016-08-01

This paper presents results of a methane balance assessment in a test cell built in a region with a subtropical climate near São Paulo, Brazil. Measurements and calculations were carried out to obtain the total methane emission to the atmosphere, the methane oxidation rate in the cover, and the total methane generation rate in the test cell. The oxidation rate was obtained through a calculation scheme based on a vertical one-dimensional methane transport in the cover region. The measured maximum and mean methane fluxes to the atmosphere were 124.4 and 15.87 g m(-2) d(-1), respectively. The total methane generation rate obtained for the test cell was 0.0380 ± 0.0075 mol s(-1). The results yielded that 69 % of the emitted methane occurred through the central well and 31 % through the cover interface with the atmosphere. The evaluations of the methane oxidation fraction for localized conditions in the lateral embankment of the test cell yielded 0.36 ± 0.11, while for the whole test cell yielded 0.15 ± 0.10. These results conciliate localized and overall evaluations reported in the literature. The specific methane generation rate obtained for the municipal solid waste with an age of 410 days was 317 ± 62 mol year(-1) ton(-1). This result from the subtropical São Paulo region is lower than reported figures for tropical climates and higher than reported figures for temperate climates.

Microbially-Enhanced Coal Bed Methane: Strategies for Increased Biogenic Production

NASA Astrophysics Data System (ADS)

Davis, K.; Barhart, E. P.; Schweitzer, H. D.; Cunningham, A. B.; Gerlach, R.; Hiebert, R.; Fields, M. W.

2014-12-01

Coal is the largest fossil fuel resource in the United States. Most of this coal is deep in the subsurface making it costly and potentially dangerous to extract. However, in many of these deep coal seams, methane, the main component of natural gas, has been discovered and successfully harvested. Coal bed methane (CBM) currently accounts for approximately 7.5% of the natural gas produced in the U.S. Combustion of natural gas produces substantially less CO2 and toxic emissions (e.g. heavy metals) than combustion of coal or oil thereby making it a cleaner energy source. In the large coal seams of the Powder River Basin (PRB) in southeast Montana and northeast Wyoming, CBM is produced almost entirely by biogenic processes. The in situ conversion of coal to CBM by the native microbial community is of particular interest for present and future natural gas sources as it provides the potential to harvest energy from coal seams with lesser environmental impacts than mining and burning coal. Research at Montana State University has shown the potential for enhancing the subsurface microbial processes that produce CBM. Long-term batch enrichments have investigated the methane enhancement potential of yeast extract as well as algal and cyanobacterial biomass additions with increased methane production observed with all three additions when compared to no addition. Future work includes quantification of CBM enhancement and normalization of additions. This presentation addresses the options thus far investigated for increasing CBM production and the next steps for developing the enhanced in situ conversion of coal to CBM.

Enzymes involved in the anaerobic oxidation of n-alkanes: from methane to long-chain paraffins

PubMed Central

Callaghan, Amy V.

2013-01-01

Anaerobic microorganisms play key roles in the biogeochemical cycling of methane and non-methane alkanes. To date, there appear to be at least three proposed mechanisms of anaerobic methane oxidation (AOM). The first pathway is mediated by consortia of archaeal anaerobic methane oxidizers and sulfate-reducing bacteria (SRB) via “reverse methanogenesis” and is catalyzed by a homolog of methyl-coenzyme M reductase. The second pathway is also mediated by anaerobic methane oxidizers and SRB, wherein the archaeal members catalyze both methane oxidation and sulfate reduction and zero-valent sulfur is a key intermediate. The third AOM mechanism is a nitrite-dependent, “intra-aerobic” pathway described for the denitrifying bacterium, ‘Candidatus Methylomirabilis oxyfera.’ It is hypothesized that AOM proceeds via reduction of nitrite to nitric oxide, followed by the conversion of two nitric oxide molecules to dinitrogen and molecular oxygen. The latter can be used to functionalize the methane via a particulate methane monooxygenase. With respect to non-methane alkanes, there also appear to be novel mechanisms of activation. The most well-described pathway is the addition of non-methane alkanes across the double bond of fumarate to form alkyl-substituted succinates via the putative glycyl radical enzyme, alkylsuccinate synthase (also known as methylalkylsuccinate synthase). Other proposed mechanisms include anaerobic hydroxylation via ethylbenzene dehydrogenase-like enzymes and an “intra-aerobic” denitrification pathway similar to that described for ‘Methylomirabilis oxyfera.’ PMID:23717304

CH{sub 4} and N{sub 2}O emissions from China’s beef feedlots with ad libitum and restricted feeding in fall and spring seasons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Zhi; Liao, Wenhua; Yang, Yuanyuan

Accurately quantifying methane (CH{sub 4}) and nitrous oxide (N{sub 2}O) emissions from beef operations in China is necessary to evaluate the contribution of beef cattle to greenhouse gas budgets at the national and global level. Methane and N{sub 2}O emissions from two intensive beef feedlots in the North China Plain, one with a restricted feeding strategy and high manure collection frequency and the other with an ad libitum feeding strategy and low manure collection frequency, were quantified in the fall and spring seasons using an inverse dispersion technique. The diel pattern of CH{sub 4} from the beef feedlot with anmore » ad libitum feed strategy (single peak during a day) differed from that under a restricted feeding condition (multiple peaks during a day), but little difference in the diel pattern of N{sub 2}O emissions between two feeding strategies was observed. The two-season average CH{sub 4} emission rates of the two intensive feedlots were 230 and 198 g CH{sub 4} animal{sup −1} d{sup −1} and accounted for 6.7% and 6.8% of the gross energy intake, respectively, indicating little impact of the feeding strategy and manure collection frequency on the CH{sub 4} conversion factor at the feedlot level. However, the average N{sub 2}O emission rates (21.2 g N{sub 2}O animal{sup −1} d{sup −1}) and conversion factor (8.5%) of the feedlot with low manure collection frequency were approximately 131% and 174% greater, respectively, than the feedlot under high frequency conditions, which had a N{sub 2}O emission rate and conversion factor of 9.2 g N{sub 2}O animal{sup −1} d{sup −1} and 3.1%, respectively, indicating that increasing manure collection frequency played an important role in reducing N{sub 2}O emissions from beef feedlots. In addition, comparison indicated that China’s beef and dairy cattle in feedlots appeared to have similar CH{sub 4} conversion factors. - Highlights: • CH{sub 4} and N{sub 2}O emissions from China’s beef feedlots were provided in the first time. • Feeding strategies determined the diurnal pattern of feedlot CH{sub 4} emission. • Frequency of manure collection played an important role in N{sub 2}O from feedlots.« less

Statistical atmospheric inversion of local gas emissions by coupling the tracer release technique and local-scale transport modelling: a test case with controlled methane emissions

NASA Astrophysics Data System (ADS)

Ars, Sébastien; Broquet, Grégoire; Yver Kwok, Camille; Roustan, Yelva; Wu, Lin; Arzoumanian, Emmanuel; Bousquet, Philippe

2017-12-01

This study presents a new concept for estimating the pollutant emission rates of a site and its main facilities using a series of atmospheric measurements across the pollutant plumes. This concept combines the tracer release method, local-scale atmospheric transport modelling and a statistical atmospheric inversion approach. The conversion between the controlled emission and the measured atmospheric concentrations of the released tracer across the plume places valuable constraints on the atmospheric transport. This is used to optimise the configuration of the transport model parameters and the model uncertainty statistics in the inversion system. The emission rates of all sources are then inverted to optimise the match between the concentrations simulated with the transport model and the pollutants' measured atmospheric concentrations, accounting for the transport model uncertainty. In principle, by using atmospheric transport modelling, this concept does not strongly rely on the good colocation between the tracer and pollutant sources and can be used to monitor multiple sources within a single site, unlike the classical tracer release technique. The statistical inversion framework and the use of the tracer data for the configuration of the transport and inversion modelling systems should ensure that the transport modelling errors are correctly handled in the source estimation. The potential of this new concept is evaluated with a relatively simple practical implementation based on a Gaussian plume model and a series of inversions of controlled methane point sources using acetylene as a tracer gas. The experimental conditions are chosen so that they are suitable for the use of a Gaussian plume model to simulate the atmospheric transport. In these experiments, different configurations of methane and acetylene point source locations are tested to assess the efficiency of the method in comparison to the classic tracer release technique in coping with the distances between the different methane and acetylene sources. The results from these controlled experiments demonstrate that, when the targeted and tracer gases are not well collocated, this new approach provides a better estimate of the emission rates than the tracer release technique. As an example, the relative error between the estimated and actual emission rates is reduced from 32 % with the tracer release technique to 16 % with the combined approach in the case of a tracer located 60 m upwind of a single methane source. Further studies and more complex implementations with more advanced transport models and more advanced optimisations of their configuration will be required to generalise the applicability of the approach and strengthen its robustness.

Alkane Oxidation: Methane Monooxygenases, Related Enzymes, and Their Biomimetics.

PubMed

Wang, Vincent C-C; Maji, Suman; Chen, Peter P-Y; Lee, Hung Kay; Yu, Steve S-F; Chan, Sunney I

2017-07-12

Methane monooxygenases (MMOs) mediate the facile conversion of methane into methanol in methanotrophic bacteria with high efficiency under ambient conditions. Because the selective oxidation of methane is extremely challenging, there is considerable interest in understanding how these enzymes carry out this difficult chemistry. The impetus of these efforts is to learn from the microbes to develop a biomimetic catalyst to accomplish the same chemical transformation. Here, we review the progress made over the past two to three decades toward delineating the structures and functions of the catalytic sites in two MMOs: soluble methane monooxygenase (sMMO) and particulate methane monooxygenase (pMMO). sMMO is a water-soluble three-component protein complex consisting of a hydroxylase with a nonheme diiron catalytic site; pMMO is a membrane-bound metalloenzyme with a unique tricopper cluster as the site of hydroxylation. The metal cluster in each of these MMOs harnesses O 2 to functionalize the C-H bond using different chemistry. We highlight some of the common basic principles that they share. Finally, the development of functional models of the catalytic sites of MMOs is described. These efforts have culminated in the first successful biomimetic catalyst capable of efficient methane oxidation without overoxidation at room temperature.

Hydrogen generator, via catalytic partial oxidation of methane for fuel cells

NASA Astrophysics Data System (ADS)

Recupero, Vincenzo; Pino, Lidia; Di Leonardo, Raffaele; Lagana', Massimo; Maggio, Gaetano

It is well known that the most acknowledged process for generation of hydrogen for fuel cells is based upon the steam reforming of methane or natural gas. A valid alternative could be a process based on partial oxidation of methane, since the process is mildly exothermic and therefore not energy intensive. Consequently, great interest is expected from conversion of methane into syngas, if an autothermal, low energy intensive, compact and reliable process could be developed. This paper covers the activities, performed by the CNR Institute of Transformation and Storage of Energy (CNR-TAE), on theoretical and experimental studies for a compact hydrogen generator, via catalytic selective partial oxidation of methane, integrated with second generation fuel cells (EC-JOU2 contract). In particular, the project focuses the attention on methane partial oxidation via heterogeneous selective catalysts, in order to: demonstrate the basic catalytic selective partial oxidation of methane (CSPOM) technology in a subscale prototype, equivalent to a nominal output of 5 kWe; develop the CSPOM technology for its application in electric energy production by means of fuel cells; assess, by a balance of plant analysis, and a techno-economic evaluation, the potential benefits of the CSPOM for different categories of fuel cells.

Electron string ion sources for carbon ion cancer therapy accelerators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boytsov, A. Yu.; Donets, D. E.; Donets, E. D.

2015-08-15

The type of the Electron String Ion Sources (ESIS) is considered to be the appropriate one to produce pulsed C{sup 4+} and C{sup 6+} ion beams for cancer therapy accelerators. In fact, the new test ESIS Krion-6T already now provides more than 10{sup 10} C{sup 4+} ions per pulse and about 5 × 10{sup 9} C{sup 6+} ions per pulse. Such ion sources could be suitable to apply at synchrotrons. It has also been found that Krion-6T can provide more than 10{sup 11} C{sup 6+} ions per second at the 100 Hz repetition rate, and the repetition rate can bemore » increased at the same or larger ion output per second. This makes ESIS applicable at cyclotrons as well. ESIS can be also a suitable type of ion source to produce the {sup 11}C radioactive ion beams. A specialized cryogenic cell was experimentally tested at the Krion-2M ESIS for pulse injection of gaseous species into the electron string. It has been shown in experiments with stable methane that the total conversion efficiency of methane molecules to C{sup 4+} ions reached 5%÷10%. For cancer therapy with simultaneous irradiation and precise dose control (positron emission tomography) by means of {sup 11}C, transporting to the tumor with the primary accelerated {sup 11}C{sup 4+} beam, this efficiency is preliminarily considered to be large enough to produce the {sup 11}C{sup 4+} beam from radioactive methane and to inject this beam into synchrotrons.« less

Methanosarcinaceae and Acetate-Oxidizing Pathways Dominate in High-Rate Thermophilic Anaerobic Digestion of Waste-Activated Sludge

PubMed Central

Ho, Dang P.; Jensen, Paul D.

2013-01-01

This study investigated the process of high-rate, high-temperature methanogenesis to enable very-high-volume loading during anaerobic digestion of waste-activated sludge. Reducing the hydraulic retention time (HRT) from 15 to 20 days in mesophilic digestion down to 3 days was achievable at a thermophilic temperature (55°C) with stable digester performance and methanogenic activity. A volatile solids (VS) destruction efficiency of 33 to 35% was achieved on waste-activated sludge, comparable to that obtained via mesophilic processes with low organic acid levels (<200 mg/liter chemical oxygen demand [COD]). Methane yield (VS basis) was 150 to 180 liters of CH4/kg of VSadded. According to 16S rRNA pyrotag sequencing and fluorescence in situ hybridization (FISH), the methanogenic community was dominated by members of the Methanosarcinaceae, which have a high level of metabolic capability, including acetoclastic and hydrogenotrophic methanogenesis. Loss of function at an HRT of 2 days was accompanied by a loss of the methanogens, according to pyrotag sequencing. The two acetate conversion pathways, namely, acetoclastic methanogenesis and syntrophic acetate oxidation, were quantified by stable carbon isotope ratio mass spectrometry. The results showed that the majority of methane was generated by nonacetoclastic pathways, both in the reactors and in off-line batch tests, confirming that syntrophic acetate oxidation is a key pathway at elevated temperatures. The proportion of methane due to acetate cleavage increased later in the batch, and it is likely that stable oxidation in the continuous reactor was maintained by application of the consistently low retention time. PMID:23956388

Evidence of sulfate-dependent anaerobic methane oxidation ...

EPA Pesticide Factsheets

The rapid development of unconventional gas resources has been accompanied by an increase in public awareness regarding the potential effects of drilling operations on drinking water sources. Incidents have been reported involving blowouts (e.g., Converse County, WY; Lawrence Township, PA; Aliso Canyon, CA) and home/property explosions (e.g., Bainbridge Township, OH; Dimock, PA; Huerfano County, CO) caused by methane migration in the subsurface within areas of natural gas development. We evaluated water quality characteristics in the northern Raton Basin of Colorado and documented the response of the Poison Canyon aquifer system several years after upward migration of methane gas occurred from the deeper Vermejo Formation coalbed production zone. Results show persistent secondary water quality impacts related to the biodegradation of methane. We identify four distinct characteristics of groundwater methane attenuation in the Poison Canyon aquifer: (i) consumption of methane and sulfate and production of sulfide and bicarbonate, (ii) methane loss coupled to production of higher-molecular-weight (C2+) gaseous hydrocarbons, (iii) patterns of 13C enrichment and depletion in methane and dissolved inorganic carbon, and (iv) a systematic shift in sulfur and oxygen isotope ratios of sulfate, indicative of microbial sulfate reduction. We also show that the biogeochemical response of the aquifer system has not mobilized naturally occurring trace metals, including arsenic,

Biogeochemical Carbon Cycling in Ultrabasic Reducing Springs in Sonoma County, CA

NASA Astrophysics Data System (ADS)

Cotton, J. M.; Morrill, P.; Johnson, O.; Nealson, K. H.; Sherwood Lollar, B.; Eigenbrode, J.; Fogel, M.

2006-12-01

Dissolved gases in the ultrabasic spring waters from The Cedars in Sonoma County, CA were analyzed for concentrations and carbon and hydrogen isotopic ratios in order to determine the geobiological processes occurring in this extreme environment of unknown biological activity. The ultrabasic, highly reducing conditions unique to these springs result from local serpentinization. Gases bubbling from the springs are mainly composed of methane, hydrogen, and nitrogen. Serpentinization is a process characteristic of early Earth, Mars and Titan that is thought to produce abiogenic hydrocarbons as well as provide geochemical energy for chemolithotrophic life. Methane, CO2, hydrogen and nitrogen were detected in the aqueous phases. Earlier work indicated that the primary source of the methane in the free gases bubbling from the springs was associated with microbial fermentation a suspected source of the dissolved methane. Here we report, a negative, linear correlation between concentrations of CO2 and methane that is an indicator of microbial anaerobic methane oxidation taking place in the ultrabasic waters. Furthermore, as the concentrations of methane decrease, the concentration of CO2 increases and both reactant and product become 13C-enriched. These observations are consistent with microbial oxidation of methane, suggesting a biogeochemical carbon cycle exists in these springs. We hypothesize that one group of microbes is breaking down organic matter by a process of fermentation to produce methane and CO2. The CO2 dissolves in the basic springs, while most of the methane escapes solution. The residual dissolved methane undergoes a conversion to CO2 by anaerobic methane oxidation.

Rapid rates of aerobic methane oxidation at the feather edge of gas hydrate stability in the waters of Hudson Canyon, US Atlantic Margin

NASA Astrophysics Data System (ADS)

Leonte, Mihai; Kessler, John D.; Kellermann, Matthias Y.; Arrington, Eleanor C.; Valentine, David L.; Sylva, Sean P.

2017-05-01

Aerobic oxidation is an important methane sink in seawater overlying gas seeps. Recent surveys have identified active methane seeps in the waters of Hudson Canyon, US Atlantic Margin near the updip limit of methane clathrate hydrate stability. The close proximity of these seeps to the upper stability limit of methane hydrates suggests that changing bottom water temperatures may influence the release rate of methane into the overlying water column. In order to assess the significance of aerobic methane oxidation in limiting the atmospheric expression of methane released from Hudson Canyon, the total extent of methane oxidized along with integrated oxidation rates were quantified. These calculations were performed by combining the measurements of the natural levels of methane concentrations, stable carbon isotopes, and water current velocities into kinetic isotope models yielding rates ranging from 22.8 ± 17 to 116 ± 76 nM/day with an average of 62.7 ± 37 nM/day. Furthermore, an average of 63% of methane released into the water column from an average depth of 515 m was oxidized before leaving this relatively small study area (6.5 km2). Results from the kinetic isotope model were compared to previously-published but concurrently-sampled ex situ measurements of oxidation potential performed using 13C-labeled methane. Ex situ rates were substantially lower, ranging from 0.1 to 22.5 nM/day with an average of 5.6 ± 2.3 nM/day, the discrepancy likely due to the inherent differences between these two techniques. Collectively, the results reveal exceptionally-rapid methane oxidation, with turnover times for methane as low as 0.3-3.7 days, indicating that methane released to the water column is removed quantitatively within the greater extent of Hudson Canyon. The red line represents the original Rayleigh model output, Eq. (1), detailed in the text. The red line represents the original Rayleigh model output, Eq. (1), detailed in the text.

Temperature and hydrology affect methane emissions from Prairie Pothole Wetlands

USGS Publications Warehouse

Bansal, Sheel; Tangen, Brian; Finocchiaro, Raymond

2016-01-01

The Prairie Pothole Region (PPR) in central North America consists of millions of depressional wetlands that each have considerable potential to emit methane (CH4). Changes in temperature and hydrology in the PPR from climate change may affect methane fluxes from these wetlands. To assess the potential effects of changes in climate on methane emissions, we examined the relationships between flux rates and temperature or water depth using six years of bi-weekly flux measurements during the snow-free period from six temporarily ponded and six permanently ponded wetlands in North Dakota, USA. Methane flux rates were among the highest reported for freshwater wetlands, and had considerable spatial and temporal variation. Methane flux rates increased with increasing temperature and water depth, and were especially high when conditions were warmer and wetter than average (163 ± 28 mg CH4 m−2 h−1) compared to warmer and drier (37 ± 7 mg CH4 m−2 h−1). Methane emission rates from permanent wetlands were less sensitive to changes in temperature and water depth compared to temporary wetlands, likely due to higher sulfate concentrations in permanent wetlands. While the predicted increase in temperature with climate change will likely increase methane emission rates from PPR wetlands, drier conditions could moderate these increases.

Evaluating the influences of mixing strategies on the Biochemical Methane Potential test.

PubMed

Wang, Bing; Björn, Annika; Strömberg, Sten; Nges, Ivo Achu; Nistor, Mihaela; Liu, Jing

2017-01-01

Mixing plays an important role in the Biochemical Methane Potential (BMP) test, but only limited efforts have been put into it. In this study, various mixing strategies were applied to evaluate the influences on the BMP test, i.e., no mixing, shaking in water bath, shake manually once per day (SKM), automated unidirectional and bidirectional mixing. The results show that the effects of mixing are prominent for the most viscous substrate investigated, as both the highest methane production and highest maximal daily methane production were obtained at the highest mixing intensity. However, the organic removal efficiencies were not affected, which might offer evidence that mixing helps the release of gases trapped in digester liquid. Moreover, mixing is required for improved methane production when the digester content is viscous, conversely, mixing is unnecessary or SKM might be sufficient for the BMP test if the digester content is quite dilute or the substrate is easily degraded. Copyright © 2016 Elsevier Ltd. All rights reserved.

A new method of two-phase anaerobic digestion for fruit and vegetable waste treatment.

PubMed

Wu, Yuanyuan; Wang, Cuiping; Liu, Xiaoji; Ma, Hailing; Wu, Jing; Zuo, Jiane; Wang, Kaijun

2016-07-01

A novel method of two-phase anaerobic digestion where the acid reactor is operated at low pH 4.0 was proposed and investigated. A completely stirred tank acid reactor and an up-flow anaerobic sludge bed methane reactor were operated to examine the possibility of efficient degradation of lactate and to identify their optimal operating conditions. Lactate with an average concentration of 14.8g/L was the dominant fermentative product and Lactobacillus was the predominant microorganism in the acid reactor. The effluent from the acid reactor was efficiently degraded in the methane reactor and the average methane yield was 261.4ml/gCOD removed. Organisms of Methanosaeta were the predominant methanogen in granular sludge of methane reactor, however, after acclimation hydrogenotrophic methanogens enriched, which benefited for the conversion of lactate to acetate. The two-phase AD system exhibited a low hydraulic retention time of 3.56days and high methane yield of 348.5ml/g VS removed. Copyright © 2016 Elsevier Ltd. All rights reserved.

Determination of the isotopic composition of atmospheric methane and its application in the Antarctic

NASA Technical Reports Server (NTRS)

Lowe, David C.; Brenninkmeijer, Carl A. M.; Tyler, Stanley C.; Dlugkencky, Edward J.

1991-01-01

A procedure for establishing the C-13/C-12 ratio and the C-14 abundance in the atmospheric methane is discussed. The method involves air sample collection, measurement of the methane mixing ratio by gas chromotography followed by quantitative conversion of the methane in the air samples to CO2 and H2O, and analysis of the resulting CO2 for the C-13/C-12 ratio by stable isotope ratio mass spectrometry and measurement of C-14 content by accelerator mass spectrometry. The carbon isotropic composition of methane in air collected at Baring Head, New Zealand, and in air collected on aircraft flights between New Zealand and Antarctica is determined by the method, and no gradient in the composition between Baring Head and the South Pole station is found. As the technique is refined, and more data is gathered, small seasonal and long-term variations in C-13 are expected to be resolved.

A quantitative assessment of methane cycling in Hikurangi Margin sediments (New Zealand) using geophysical imaging and biogeochemical modeling

NASA Astrophysics Data System (ADS)

Luo, Min; Dale, Andrew W.; Haffert, Laura; Haeckel, Matthias; Koch, Stephanie; Crutchley, Gareth; De Stigter, Henko; Chen, Duofu; Greinert, Jens

2016-12-01

Takahe seep, located on the Opouawe Bank, Hikurangi Margin, is characterized by a well-defined subsurface seismic chimney structure ˜80,500 m2 in area. Subseafloor geophysical data based on acoustic anomaly layers indicated the presence of gas hydrate and free gas layers within the chimney structure. Reaction-transport modeling was applied to porewater data from 11 gravity cores to constrain methane turnover rates and benthic methane fluxes in the upper 10 m. Model results show that methane dynamics were highly variable due to transport and dissolution of ascending gas. The dissolution of gas (up to 3761 mmol m-2 yr-1) dwarfed the rate of methanogenesis within the simulated sediment column (2.6 mmol m-2 yr-1). Dissolved methane is mainly consumed by anaerobic oxidation of methane (AOM) at the base of the sulfate reduction zone and trapped by methane hydrate formation below it, with maximum rates in the central part of the chimney (946 and 2420 mmol m-2 yr-1, respectively). A seep-wide methane budget was constrained by combining the biogeochemical model results with geophysical data and led to estimates of AOM rates, gas hydrate formation, and benthic dissolved methane fluxes of 3.68 × 104 mol yr-1, 73.85 × 104 mol yr-1, and 1.19 × 104 mol yr-1, respectively. A much larger flux of methane probably escapes in gaseous form through focused bubble vents. The approach of linking geochemical model results with spatial geophysical data put forward here can be applied elsewhere to improve benthic methane turnover rates from limited single spot measurements to larger spatial scales.

Emissions of Methane and Other Hydrocarbons Due to Wellbore Leaks

NASA Astrophysics Data System (ADS)

Lyman, S. N.; Mansfield, M. L.

2013-12-01

The explosive growth of oil and gas production in the United States has focused public and regulatory attention on environmental impacts of hydrocarbon extraction, including air quality and climate impacts. However, EPA and others have acknowledged that current air emissions factors and inventories for many oil and gas-related source categories are inadequate or lacking entirely. One potentially important emissions source is leakage of natural gas from wellbores. This phenomenon has long been recognized to occur, but no attempt has been made to quantify emission rates of gas leaked from wellbores to the atmosphere. Soil gas measurements carried out by USGS over the last several years in Utah's oil and gas fields have shown that, while concentrations of methane in soils near many wells are low, soil gas near some wells can contain more than 10% methane, indicating that underground leakage is occurring. In summer 2013 we carried out a campaign to measure the emission rate of methane and other hydrocarbons from soils near wells in two oil and gas fields in Utah. We measured emissions from several locations on some well pads to determine the change in emission rate with distance from well heads, and we measured at non-well sites in the same fields to determine background emission rates. Methane emission rates at some wells exceeded 3 g m-2 h-1, while emission rates at other wells were similar to background levels, and a correlation was observed between soil gas methane concentrations and methane emission rates from the soil. We used these data to estimate total methane and hydrocarbon emission rates from these two fields.

Catalysts for conversion of methane to higher hydrocarbons

DOEpatents

Siriwardane, Ranjani V.

1993-01-01

Catalysts for converting methane to higher hydrocarbons such as ethane and ethylene in the presence of oxygen at temperatures in the range of about 700.degree. to 900.degree. C. are described. These catalysts comprise calcium oxide or gadolinium oxide respectively promoted with about 0.025-0.4 mole and about 0.1-0.7 mole sodium pyrophosphate. A preferred reaction temperature in a range of about 800.degree. to 850.degree. C. with a preferred oxygen-to-methane ratio of about 2:1 provides an essentially constant C.sub.2 hydrocarbon yield in the range of about 12 to 19 percent over a period of time greater than about 20 hours.

Biogasification of Walt Disney World biomass waste blend. Annual report, January-December 1983

DOE Office of Scientific and Technical Information (OSTI.GOV)

Biljetina, R.; Chynoweth, D.P.; Janulis, J.

1984-09-01

The objective of this research is to develop efficient processes for conversion of biomass-waste blends to methane and other resources. To evaluate the technical and economic feasibility, an experimental test unit (ETU) was designed and installed at the Reedy Creek Wastewater Treatment Plant at Walt Disney World in Lake Buena Vista, Florida. The facility integrates a biomethanogenic conversion process with a wastewater treatment process employing water hyacinth ponds for secondary and tertiary treatment of sewage. Harvested water hyacinth is subsequently combined with sludge from the primary wastewater clarifier and fed at 1-wet-ton per day to the ETU digester. This resultsmore » in the production of methane and other useful byproducts. Design, procurement of equipment, and installation has been completed. Start-up of the ETU is in progress.« less

Bio-energy conversion performance, biodegradability, and kinetic analysis of different fruit residues during discontinuous anaerobic digestion.

PubMed

Zhao, Chen; Yan, Hu; Liu, Yan; Huang, Yan; Zhang, Ruihong; Chen, Chang; Liu, Guangqing

2016-06-01

Huge amounts of fruit residues are produced and abandoned annually. The high moisture and organic contents of these residues makes them a big problem to the environment. Conversely, they are a potential resource to the world. Anaerobic digestion is a good way to utilize these organic wastes. In this study, the biomethane conversion performances of a large number of fruit residues were determined and compared using batch anaerobic digestion, a reliable and easily accessible method. The results showed that some fruit residues containing high contents of lipids and carbohydrates, such as loquat peels and rambutan seeds, were well fit for anaerobic digestion. Contrarily, residues with high lignin content were strongly recommended not to be used as a single substrate for methane production. Multiple linear regression model was adopted to simulate the correlation between the organic component of these fruit residues and their experimental methane yield, through which the experimental methane yield could probably be predicted for any other fruit residues. Four kinetic models were used to predict the batch anaerobic digestion process of different fruit residues. It was shown that the modified Gompertz and Cone models were better fit for the fruit residues compared to the first-order and Fitzhugh models. The first findings of this study could provide useful reference and guidance for future studies regarding the applications and potential utilization of fruit residues. Copyright © 2016 Elsevier Ltd. All rights reserved.

40 CFR Table A-7 to Subpart A of... - Data Elements That Are Inputs to Emission Equations and for Which the Reporting Deadline Is March...

Code of Federal Regulations, 2014 CFR

2014-07-01

....116(b) Only annual production by product from each EAF (No CEMS). K 98.116(e)(4) All. K 98.116(e)(5... factor if using Eq. Y-3. Y 98.256(e)(10) Only fraction of carbon in the flare gas contributed by methane... methane in coking gas. Y 98.256(l)(5) Only molar volume conversion factor. Y 98.256(m)(3) Only total...

Modeling of simultaneous anaerobic methane and ammonium oxidation in a membrane biofilm reactor.

PubMed

Chen, Xueming; Guo, Jianhua; Shi, Ying; Hu, Shihu; Yuan, Zhiguo; Ni, Bing-Jie

2014-08-19

Nitrogen removal by using the synergy of denitrifying anaerobic methane oxidation (DAMO) and anaerobic ammonium oxidation (Anammox) microorganisms in a membrane biofilm reactor (MBfR) has previously been demonstrated experimentally. In this work, a mathematical model is developed to describe the simultaneous anaerobic methane and ammonium oxidation by DAMO and Anammox microorganisms in an MBfR for the first time. In this model, DAMO archaea convert nitrate, both externally fed and/or produced by Anammox, to nitrite, with methane as the electron donor. Anammox and DAMO bacteria jointly remove the nitrite fed/produced, with ammonium and methane as the electron donor, respectively. The model is successfully calibrated and validated using the long-term (over 400 days) dynamic experimental data from the MBfR, as well as two independent batch tests at different operational stages of the MBfR. The model satisfactorily describes the methane oxidation and nitrogen conversion data from the system. Modeling results show the concentration gradients of methane and nitrogen would cause stratification of the biofilm, where Anammox bacteria mainly grow in the biofilm layer close to the bulk liquid and DAMO organisms attach close to the membrane surface. The low surface methane loadings result in a low fraction of DAMO microorganisms, but the high surface methane loadings would lead to overgrowth of DAMO bacteria, which would compete with Anammox for nitrite and decrease the fraction of Anammox bacteria. The results suggest an optimal methane supply under the given condition should be applied not only to benefit the nitrogen removal but also to avoid potential methane emissions.

[The processes of methane formation and oxidation in the soils of the Russian arctic tundra].

PubMed

Berestovskaia, Iu Iu; Rusanov, I I; Vasil'eva, L V; Pimenov, N V

2005-01-01

Methane emission from the following types of tundra soils was studied: coarse humic gleyey loamy cryo soil, peaty gley soil, and peaty gleyey midloamy cryo soil of the arctic tundra. All the soils studied were found to be potential sources of atmospheric methane. The highest values of methane emission were recorded in August at a soil temperature of 8-10 degrees C. Flooded parcels were the sources of atmospheric methane throughout the observation period. The rates of methane production and oxidation in tundra soils of various types at 5 and 15 degrees C were studied by the radioisotope method. Methane oxidation was found to occur in bog water, in the green part of peat moss, and in all the soil horizons studied. Methane formation was recorded in the horizons of peat, in clay with plant roots, and in peaty moss dust of the bogey parcels. At both temperatures, the methane oxidation rate exceeded the rate of methane formation in all the horizons of the mossy-lichen tundra and of the bumpy sinkhole complex. Methanogenesis prevailed only in a sedge-peat moss bog at 15 degrees C. Enrichment bacterial cultures oxidizing methane at 5 and 15 degrees C were obtained. Different types of methanotrophic bacteria were shown to be responsible for methane oxidation under these conditions. A representative of type I methylotrophs oxidized methane at 5 degrees C, and Methylocella tundrae, a psychroactive representative of an acidophilic methanotrophic genus Methylocella, at 15 degrees C.

Valorization of CH4 emissions into high-added-value products: Assessing the production of ectoine coupled with CH4 abatement.

PubMed

Cantera, Sara; Lebrero, Raquel; Sadornil, Lidia; García-Encina, Pedro A; Muñoz, Raúl

2016-11-01

This study assessed an innovative strategy for the valorization of dilute methane emissions based on the bio-conversion of CH4 (the second most important greenhouse gas (GHG)) into ectoine by the methanotrophic ectoine-producing strain Methylomicrobium alcaliphilum 20 Z. The influence of CH4 (2-20%), Cu(2+) (0.05-50 μM) and NaCl (0-9%) concentration as well as temperature (25-35 °C) on ectoine synthesis and specific CH4 biodegradation rate was evaluated for the first time. Concentrations of 20% CH4 (at 3% NaCl, 0.05 μM Cu(2+), 25 °C) and 6% NaCl (at 4% CH4, 0.05 μM Cu(2+), 25 °C) supported the maximum intra-cellular ectoine production yield (31.0 ±1.7 and 66.9 ±4.2 mg g biomass(-1), respectively). On the other hand, extra-cellular ectoine concentrations of up to 4.7 ± 0.1 mg L(-1) were detected at high Cu(2+)concentrations (50 μM), despite this methanotroph has not been previously classified as an ectoine-excreting strain. This research demonstrated the feasibility of the bio-conversion of dilute emissions of methane into high-added value products in an attempt to develop a sustainable GHG bioeconomy. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of methane partial pressure on the performance of a membrane biofilm reactor coupling methane-dependent denitrification and anammox.

PubMed

Cai, Chen; Hu, Shihu; Chen, Xueming; Ni, Bing-Jie; Pu, Jiaoyang; Yuan, Zhiguo

2018-10-15

Complete nitrogen removal has recently been demonstrated by integrating anaerobic ammonium oxidation (anammox) and denitrifying anaerobic methane oxidation (DAMO) processes. In this work, the effect of methane partial pressure on the performance of a membrane biofilm reactor (MBfR) consisting of DAMO and anammox microorganisms was evaluated. The activities of DAMO archaea and DAMO bacteria in the biofilm increased significantly with increased methane partial pressure, from 367 ± 9 and 58 ± 22 mg-N L -1 d -1 to 580 ± 12 and 222 ± 22 mg-N L -1 d -1 , respectively, while the activity of anammox bacteria only increased slightly, when the methane partial pressure was elevated from 0.24 to 1.39 atm in the short-term batch tests. The results were supported by a long-term (seven weeks) continuous test, when the methane partial pressure was dropped from 1.39 to 0.78 atm. The methane utilization efficiency was always above 96% during both short-term and long-term tests. Taken together, nitrogen removal rate (especially the nitrate reduction rate by DAMO archaea) and methane utilization efficiency could be maintained at high levels in a broad range of methane partial pressure (0.24-1.39 atm in this study). In addition, a previously established DAMO/anammox biofilm model was used to analyze the experimental data. The observed impacts of methane partial pressure on biofilm activity were well explained by the modeling results. These results suggest that methane partial pressure can potentially be used as a manipulated variable to control reaction rates, ultimately to maintain high nitrogen removal efficiency, according to nitrogen loading rate. Copyright © 2018 Elsevier B.V. All rights reserved.

Phosphoketolase overexpression increases biomass and lipid yield from methane in an obligate methanotrophic biocatalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henard, Calvin A.; Smith, Holly K.; Guarnieri, Michael T.

Microbial conversion of methane to high-value bio-based chemicals and materials offers a path to mitigate GHG emissions and valorize this abundant-yet -underutilized carbon source. In addition to fermentation optimization strategies, rational methanotrophic bacterial strain engineering offers a means to reach industrially relevant titers, carbon yields, and productivities of target products. The phosphoketolase pathway functions in heterofermentative bacteria where carbon flux through two sugar catabolic pathways to mixed acids (lactic acid and acetic acid) increases cellular ATP production. Importantly, this pathway also serves as an alternative route to produce acetyl-CoA that bypasses the CO 2 lost through pyruvate decarboxylation in themore » Embden-Meyerhof-Parnas pathway. Thus, the phosphoketolase pathway can be leveraged for carbon efficient biocatalysis to acetyl-CoA-derived intermediates and products. Here, we show that the industrially promising methane biocatalyst, Methylomicrobium buryatense, encodes two phosphoketolase isoforms that are expressed in methanol- and methane-grown cells. Overexpression of the PktB isoform led to a 2-fold increase in intracellular acetyl-CoA concentration, and a 2.6-fold yield enhancement from methane to microbial biomass and lipids compared to wild-type, increasing the potential for methanotroph lipid-based fuel production. Off-gas analysis and metabolite profiling indicated that global metabolic rearrangements, including significant increases in post-translational protein acetylation and gene expression of the tetrahydromethanopterin-linked pathway, along with decreases in several excreted products, coincided with the superior biomass and lipid yield observed in the engineered strain. Further, these data suggest that phosphoketolase may play a key regulatory role in methanotrophic bacterial metabolism. As a result, given that acetyl-CoA is a key intermediate in several biosynthetic pathways, phosphoketolase overexpression offers a viable strategy to enhance the economics of an array of biological methane conversion processes.« less

Phosphoketolase overexpression increases biomass and lipid yield from methane in an obligate methanotrophic biocatalyst.

PubMed

Henard, Calvin A; Smith, Holly K; Guarnieri, Michael T

2017-05-01

Microbial conversion of methane to high-value bio-based fuels, chemicals, and materials offers a path to mitigate GHG emissions and valorize this abundant-yet -underutilized carbon source. In addition to fermentation optimization strategies, rational methanotrophic bacterial strain engineering offers a means to reach industrially relevant titers, carbon yields, and productivities of target products. The phosphoketolase pathway functions in heterofermentative bacteria where carbon flux through two sugar catabolic pathways to mixed acids (lactic acid and acetic acid) increases cellular ATP production. Importantly, this pathway also serves as an alternative route to produce acetyl-CoA that bypasses the CO 2 lost through pyruvate decarboxylation in the Embden-Meyerhof-Parnas pathway. Thus, the phosphoketolase pathway can be leveraged for carbon efficient biocatalysis to acetyl-CoA-derived intermediates and products. Here, we show that the industrially promising methane biocatalyst, Methylomicrobium buryatense, encodes two phosphoketolase isoforms that are expressed in methanol- and methane-grown cells. Overexpression of the PktB isoform led to a 2-fold increase in intracellular acetyl-CoA concentration, and a 2.6-fold yield enhancement from methane to microbial biomass and lipids compared to wild-type, increasing the potential for methanotroph lipid-based fuel production. Off-gas analysis and metabolite profiling indicated that global metabolic rearrangements, including significant increases in post-translational protein acetylation and gene expression of the tetrahydromethanopterin-linked pathway, along with decreases in several excreted products, coincided with the superior biomass and lipid yield observed in the engineered strain. Further, these data suggest that phosphoketolase may play a key regulatory role in methanotrophic bacterial metabolism. Given that acetyl-CoA is a key intermediate in several biosynthetic pathways, phosphoketolase overexpression offers a viable strategy to enhance the economics of an array of biological methane conversion processes. Copyright © 2017. Published by Elsevier Inc.

Phosphoketolase overexpression increases biomass and lipid yield from methane in an obligate methanotrophic biocatalyst

DOE PAGES

Henard, Calvin A.; Smith, Holly K.; Guarnieri, Michael T.

2017-04-02

Microbial conversion of methane to high-value bio-based chemicals and materials offers a path to mitigate GHG emissions and valorize this abundant-yet -underutilized carbon source. In addition to fermentation optimization strategies, rational methanotrophic bacterial strain engineering offers a means to reach industrially relevant titers, carbon yields, and productivities of target products. The phosphoketolase pathway functions in heterofermentative bacteria where carbon flux through two sugar catabolic pathways to mixed acids (lactic acid and acetic acid) increases cellular ATP production. Importantly, this pathway also serves as an alternative route to produce acetyl-CoA that bypasses the CO 2 lost through pyruvate decarboxylation in themore » Embden-Meyerhof-Parnas pathway. Thus, the phosphoketolase pathway can be leveraged for carbon efficient biocatalysis to acetyl-CoA-derived intermediates and products. Here, we show that the industrially promising methane biocatalyst, Methylomicrobium buryatense, encodes two phosphoketolase isoforms that are expressed in methanol- and methane-grown cells. Overexpression of the PktB isoform led to a 2-fold increase in intracellular acetyl-CoA concentration, and a 2.6-fold yield enhancement from methane to microbial biomass and lipids compared to wild-type, increasing the potential for methanotroph lipid-based fuel production. Off-gas analysis and metabolite profiling indicated that global metabolic rearrangements, including significant increases in post-translational protein acetylation and gene expression of the tetrahydromethanopterin-linked pathway, along with decreases in several excreted products, coincided with the superior biomass and lipid yield observed in the engineered strain. Further, these data suggest that phosphoketolase may play a key regulatory role in methanotrophic bacterial metabolism. As a result, given that acetyl-CoA is a key intermediate in several biosynthetic pathways, phosphoketolase overexpression offers a viable strategy to enhance the economics of an array of biological methane conversion processes.« less

Freshwater wetland sediments support substantial rates of anaerobic oxidation of methane (AOM)

NASA Astrophysics Data System (ADS)

Segarra, K. E.; Samarkin, V.; Schubotz, F.; Yoshinaga, M. Y.; Hinrichs, K.; Joye, S. B.

2012-12-01

Freshwater wetlands are characterized by high rates of methanogenesis and are the single largest source of atmospheric methane. Anaerobic oxidation of methane (AOM), a previously underappreciated process in these systems, may be an important component in freshwater methane budgets. Here we report some of the first direct measurements of AOM in wetland sediments. We examined seasonal methane cycling within three freshwater wetlands (two peat wetlands and one tidal, freshwater creekbank) along the eastern coast of the US. Rates of AOM were high (up to 286 nmol per cubic cm per day) and varied on a seasonal basis. Despite low sulfate concentrations, rates of sulfate reduction were sufficient to support all the observed AOM activity, though rates of these two processes were not correlated. This study highlights the importance of AOM in freshwater sediments, where this process, in conjunction with sulfate reduction, may control emissions of methane to the atmosphere through competitive interactions with methanogens and the consumption of large fractions of the methane produced from acetate and hydrogen. The zone of maximum AOM activity was marked by enriched stable carbon isotopic signatures (δ13C) of methane and depleted signatures of DIC. However, the δ13C of archaeal and bacterial lipids were not indicative of methanotrophy. Studies that evaluate the role of AOM in wetlands using lipid and isotope-based approaches may therefore underestimate its importance.

Methane production in the sulfate-depleted sediments of two marine basins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuivila, K.M.; Murray, J.W.; Devol, A.H.

1990-02-01

Rates of methane production via both acetate fermentation and CO{sub 2} reduction were directly measured with radiotracer techniques in the sulfate-depleted sediments of Saanich and Princess Louisa Inlets. Comparison of measured and modeled rates suggests that these two pathways account for the majority of methane produced below the sulfate reduction zone in the sediments of both basins. Methane production via CO{sub 2} reduction was slightly more important than acetate fermentation with 57-58% of the methane in Saanich Inlet and 52-57% in Princess Louisa Inlet being produced from bicarbonate. The results from Saanich Inlet, a seasonally anoxic basin, are compared withmore » Princess Louisa Inlet, with a permanently oxic hypolimnion. Although the two basins have comparable organic-carbon rain rates, the rates of methanogenesis are much lower in Princess Louisa Inlet. This decrease in methane production can be attributed to the consumption of organic carbon via aerobic respiration occurring in the surface sediments of Princess Louisa Inlet, thereby decreasing the actual input of organic carbon to the zone of methane production. The relative importance of CO{sub 2} reduction and acetate fermentation in the production of methane was the same in both basins, suggesting that prior aerobic degradation of the organic matter has little influence on the pathways of methane production. The results from this study in the two marine systems (high sulfate) are also compared to published studies in freshwater environments (low sulfate) where acetate fermentation is the predominant pathway of methane production.« less

Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal–Organic Framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei

The catalyzed conversion of shale gas-derived light hydrocarbons, e.g. methane to methanol, for further application as automotive fuels and/or bulk chemicals is especially attractive in light of improved methods of hydrocarbon extraction. MOF based catalysts have previously been demonstrated to be active for a range of catalytic reactions. In this work we used Cu-NU1000 as a methane-to-methanol oxidation catalyst. In addition to product studies, in-situ X-ray Absorption Spectroscopic (XAS) experiments are performed under catalytic conditions in order to follow the modification of the Cu-species and directly probe the structure/activity properties of the Cu-NU1000 system. The insights reported herein serve asmore » a first look at metal-organic framework materials as catalysts for methane oxidation and be the basis for development of the subsequent generations of materials.« less

Carbon Dioxide-Free Hydrogen Production with Integrated Hydrogen Separation and Storage.

PubMed

Dürr, Stefan; Müller, Michael; Jorschick, Holger; Helmin, Marta; Bösmann, Andreas; Palkovits, Regina; Wasserscheid, Peter

2017-01-10

An integration of CO 2 -free hydrogen generation through methane decomposition coupled with hydrogen/methane separation and chemical hydrogen storage through liquid organic hydrogen carrier (LOHC) systems is demonstrated. A potential, very interesting application is the upgrading of stranded gas, for example, gas from a remote gas field or associated gas from off-shore oil drilling. Stranded gas can be effectively converted in a catalytic process by methane decomposition into solid carbon and a hydrogen/methane mixture that can be directly fed to a hydrogenation unit to load a LOHC with hydrogen. This allows for a straight-forward separation of hydrogen from CH 4 and conversion of hydrogen to a hydrogen-rich LOHC material. Both, the hydrogen-rich LOHC material and the generated carbon on metal can easily be transported to destinations of further industrial use by established transport systems, like ships or trucks. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mars Atmospheric Conversion to Methane and Water: An Engineering Model of the Sabatier Reactor with Characterization of Ru/Al2O3 for Long Duration Use on Mars

NASA Technical Reports Server (NTRS)

Meier, Anne J.; Shah, Malay; Petersen, Elspeth; Hintze, Paul; Muscatello, Tony

2017-01-01

The Atmospheric Processing Module (APM) is a Mars In-Situ Resource Utilization (ISRU) technology designed to demonstrate conversion of the Martian atmosphere into methane and water. The Martian atmosphere consists of approximately 95 carbon dioxide (CO2) and residual argon and nitrogen. APM utilizes cryocoolers for CO2 acquisition from a simulated Martian atmosphere and pressure. The captured CO2 is sublimated and pressurized as a feedstock into the Sabatier reactor, which converts CO2 and hydrogen to methane and water. The Sabatier reaction occurs over a packed bed reactor filled with Ru/Al2O3 pellets. The long duration use of the APM system and catalyst was investigated for future scaling and failure limits. Failure of the catalyst was detected by gas chromatography and temperature sensors on the system. Following this, characterization and experimentation with the catalyst was carried out with analysis including x-ray photoelectron spectroscopy and scanning electron microscopy with elemental dispersive spectroscopy. This paper will discuss results of the catalyst performance, the overall APM Sabatier approach, as well as intrinsic catalyst considerations of the Sabatier reactor performance incorporated into a chemical model.

Determining the flux of methane into Hudson Canyon at the edge of methane clathrate hydrate stability

USGS Publications Warehouse

Weinsten, A.; Navarrete, L; Ruppel, Carolyn D.; Weber, T.C.; Leonte, M.; Kellermann, M.; Arrington, E.; Valentine, D.L.; Scranton, M.L; Kessler, John D.

2016-01-01

Methane seeps were investigated in Hudson Canyon, the largest shelf-break canyon on the northern US Atlantic Margin. The seeps investigated are located at or updip of the nominal limit of methane clathrate hydrate stability. The acoustic identification of bubble streams was used to guide water column sampling in a 32 km2 region within the canyon's thalweg. By incorporating measurements of dissolved methane concentration with methane oxidation rates and current velocity into a steady-state box model, the total emission of methane to the water column in this region was estimated to be 12 kmol methane per day (range: 6 – 24 kmol methane per day). These analyses suggest this methane is largely retained inside the canyon walls below 300 m water depth, and that it is aerobically oxidized to near completion within the larger extent of Hudson Canyon. Based on estimated methane emissions and measured oxidation rates, the oxidation of this methane to dissolved CO2 is expected to have minimal influences on seawater pH. This article is protected by copyright. All rights reserved.

Determining the flux of methane into Hudson Canyon at the edge of methane clathrate hydrate stability

NASA Astrophysics Data System (ADS)

Weinstein, Alexander; Navarrete, Luis; Ruppel, Carolyn; Weber, Thomas C.; Leonte, Mihai; Kellermann, Matthias Y.; Arrington, Eleanor C.; Valentine, David L.; Scranton, Mary I.; Kessler, John D.

2016-10-01

Methane seeps were investigated in Hudson Canyon, the largest shelf-break canyon on the northern U.S. Atlantic Margin. The seeps investigated are located at or updip of the nominal limit of methane clathrate hydrate stability. The acoustic identification of bubble streams was used to guide water column sampling in a 32 km2 region within the canyon's thalweg. By incorporating measurements of dissolved methane concentration with methane oxidation rates and current velocity into a steady state box model, the total emission of methane to the water column in this region was estimated to be 12 kmol methane per day (range: 6-24 kmol methane per day). These analyses suggest that the emitted methane is largely retained inside the canyon walls below 300 m water depth, and that it is aerobically oxidized to near completion within the larger extent of Hudson Canyon. Based on estimated methane emissions and measured oxidation rates, the oxidation of this methane to dissolved CO2 is expected to have minimal influences on seawater pH.

Methane drainage with horizontal boreholes in advance of longwall mining: an analysis. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gabello, D.P.; Felts, L.L.; Hayoz, F.P.

1981-05-01

The US Department of Energy (DOE) Morgantown Energy Technology Center has implemented a comprehensive program to demonstrate the technical and economic viability of coalbed methane as an energy resource. The program is directed toward solution of technical and institutional problems impeding the recovery and use of large quantities of methane contained in the nation's minable and unminable coalbeds. Conducted in direct support of the DOE Methane Recovery from Coalbeds Project, this study analyzes the economic aspects of a horizontal borehole methane recovery system integrated as part of a longwall mine operation. It establishes relationships between methane selling price and annualmore » mine production, methane production rate, and the methane drainage system capital investment. Results are encouraging, indicating that an annual coal production increase of approximately eight percent would offset all associated drainage costs over the range of methane production rates and capital investments considered.« less

Anaerobic digestion of municipal solid waste: Utility of process residues as a soil amendment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rivard, C.J.; Nagle, N.J.; Kay, B.D.

1995-12-31

Tuna processing wastes (sludges high in fat, oil, and grease [FOG]) and municipal solid waste (MSW) generated on Tutuila Island, American Samoa, represent an ongoing disposal challenge. The biological conversion of the organic fraction of these wastes to useful products, including methane and fertilizer-grade residue, through anaerobic high-solids digestion is currently in scale-up development. The suitability of the anaerobic digestion residues as a soil amendment was evaluated through extensive chemical analysis and greenhouse studies using corn as an indicator crop. Additionally, native Samoan soil was used to evaluate the specific application rates for the compost. Experiments established that anaerobic residuesmore » increase crop yields in direct proportion to increases in the application rate. Additionally, nutrient saturation was not demonstrated within the range of application rates evaluated for the Samoan soil. Beyond nutrient supplementation, organic residue amendment to Samoan soil imparts enhanced water and nutrient-binding capacities.« less

Effects of soil structure destruction on methane production and carbon partitioning between methanogenic pathways in tropical rain forest soils

NASA Astrophysics Data System (ADS)

Teh, Yit Arn; Silver, Whendee L.

2006-03-01

Controls on methanogenesis are often determined from laboratory incubations of soils converted to slurries. Destruction of soil structure during slurry conversion may disrupt syntrophic associations, kill methanogens, and/or alter the microsite distribution of methanogenic activity, suppressing CH4 production. The effects of slurry conversion on methanogenesis were investigated to determine if disruption of aggregate structure impacted methanogenesis, substrate utilization, and C partitioning between methanogenic pathways. Soils were collected from the tropical rain forest life zone of the Luquillo Experimental Forest, Puerto Rico, and exposed to different physical disturbances, including flooding and physical homogenization. Slurry conversion negatively impacted methanogenesis. Rates of CH4 production declined by a factor of 17 after well-aggregated soils were converted to slurries. Significantly more 13C-acetate was recovered in CO2 compared to CH4 after slurry conversion, suggesting that methanogens consumed less acetate after slurry conversion and may have competed less effectively with other anaerobes for acetate. Isotopic data indicate that the relative partitioning of C between aceticlastic and hydrogenotrophic pathways was unchanged after slurry conversion. These data suggest that experiments which destroy soil structure may significantly underestimate methanogenesis and overestimate the potential for other microorganisms to compete with methanogens for organic substrates. Current knowledge of the factors that regulate methanogenesis in soil may be biased by the findings of slurry-based experiments, that do not accurately represent the complex, spatially heterogeneous conditions found in well-aggregated soils.

Constraining the Methane Budget Variations after the Pinatubo Eruption using a Combined Forward and Inverse Modeling Approach

NASA Astrophysics Data System (ADS)

Banda, N.; Krol, M. C.; van Weele, M.; van Noije, T.; Dlugokencky, E. J.; Röckmann, T.

2015-12-01

The eruption of Pinatubo in 1991 caused global scale changes in climate and radiation. Large perturbations in the methane growth rate were observed after the eruption, caused by variations in either methane sources or methane sinks. Natural methane emissions from wetlands are influenced by changes in temperature and precipitation, having a significant contribution to methane variability. The main removal of methane from the atmosphere is the reaction with the hydroxyl radical (OH). OH concentrations are in turn sensitive to temperature, humidity and the amount of UV radiation. In Bândă et al. (2015), we quantified the variability in methane sources and sinks in the 5 years following the eruption, using the 3D chemistry and transport model TM5. We derived an OH inter-annual variability of 1.6% during this period. A 4.5% increase in OH levels from 1992 to 1993, caused by enhanced stratospheric ozone depletion, a recovery of stratospheric aerosols and decreased NMVOC emissions, was found to contribute to the observed drop in methane growth rate. However, using bottom-up inventories of methane emissions, the exact timing and magnitude of the observed methane growth rate variations could not be matched by our simulations. The variability in natural wetland emissions and in biomass burning emissions is quite uncertain in this period. Emission reductions in the Former Soviet Union were also proposed as a reason for the observed decrease in methane growth rate. Based on the OH variability from our previous chemistry forward model simulations, we infer methane emissions after the Pinatubo eruption using a linearized inverse modeling setup. We can therefore quantify the variability in the methane emissions needed to match the methane variations observed in weekly air samples collected in NOAA's Cooperative Global Air Sampling Network and to identify the emission categories that contributed to these variations. Reference: Bândă, N., Krol, M., van Weele, M., van Noije, T., Le Sager, P., and Röckmann, T.: Can we explain the observed methane variability after the Mount Pinatubo eruption?, Atmos. Chem. Phys. Discuss., 15, 19111-19160, doi:10.5194/acpd-15-19111-2015, 2015.

Polyhydroxyalkanoates in waste activated sludge enhances anaerobic methane production through improving biochemical methane potential instead of hydrolysis rate.

PubMed

Wang, Qilin; Sun, Jing; Zhang, Chang; Xie, Guo-Jun; Zhou, Xu; Qian, Jin; Yang, Guojing; Zeng, Guangming; Liu, Yiqi; Wang, Dongbo

2016-01-21

Anaerobic sludge digestion is the main technology for sludge reduction and stabilization prior to sludge disposal. Nevertheless, methane production from anaerobic digestion of waste activated sludge (WAS) is often restricted by the poor biochemical methane potential and slow hydrolysis rate of WAS. This work systematically investigated the effect of PHA levels of WAS on anaerobic methane production, using both experimental and mathematical modeling approaches. Biochemical methane potential tests showed that methane production increased with increased PHA levels in WAS. Model-based analysis suggested that the PHA-based method enhanced methane production by improving biochemical methane potential of WAS, with the highest enhancement being around 40% (from 192 to 274 L CH4/kg VS added; VS: volatile solid) when the PHA levels increased from 21 to 143 mg/g VS. In contrast, the hydrolysis rate (approximately 0.10 d(-1)) was not significantly affected by the PHA levels. Economic analysis suggested that the PHA-based method could save $1.2/PE/y (PE: population equivalent) in a typical wastewater treatment plant (WWTP). The PHA-based method can be easily integrated into the current WWTP to enhance methane production, thereby providing a strong support to the on-going paradigm shift in wastewater management from pollutant removal to resource recovery.

Zero valent iron significantly enhances methane production from waste activated sludge by improving biochemical methane potential rather than hydrolysis rate.

PubMed

Liu, Yiwen; Wang, Qilin; Zhang, Yaobin; Ni, Bing-Jie

2015-02-05

Anaerobic digestion has been widely applied for waste activated sludge (WAS) treatment. However, methane production from anaerobic digestion of WAS is usually limited by the slow hydrolysis rate and/or poor biochemical methane potential of WAS. This work systematically studied the effects of three different types of zero valent iron (i.e., iron powder, clean scrap and rusty scrap) on methane production from WAS in anaerobic digestion, by using both experimental and mathematical approaches. The results demonstrated that both the clean and the rusty iron scrap were more effective than the iron powder for improving methane production from WAS. Model-based analysis showed that ZVI addition significantly enhanced methane production from WAS through improving the biochemical methane potential of WAS rather than its hydrolysis rate. Economic analysis indicated that the ZVI-based technology for enhancing methane production from WAS is economically attractive, particularly considering that iron scrap can be freely acquired from industrial waste. Based on these results, the ZVI-based anaerobic digestion process of this work could be easily integrated with the conventional chemical phosphorus removal process in wastewater treatment plant to form a cost-effective and environment-friendly approach, enabling maximum resource recovery/reuse while achieving enhanced methane production in wastewater treatment system.

Zero Valent Iron Significantly Enhances Methane Production from Waste Activated Sludge by Improving Biochemical Methane Potential Rather Than Hydrolysis Rate

PubMed Central

Liu, Yiwen; Wang, Qilin; Zhang, Yaobin; Ni, Bing-Jie

2015-01-01

Anaerobic digestion has been widely applied for waste activated sludge (WAS) treatment. However, methane production from anaerobic digestion of WAS is usually limited by the slow hydrolysis rate and/or poor biochemical methane potential of WAS. This work systematically studied the effects of three different types of zero valent iron (i.e., iron powder, clean scrap and rusty scrap) on methane production from WAS in anaerobic digestion, by using both experimental and mathematical approaches. The results demonstrated that both the clean and the rusty iron scrap were more effective than the iron powder for improving methane production from WAS. Model-based analysis showed that ZVI addition significantly enhanced methane production from WAS through improving the biochemical methane potential of WAS rather than its hydrolysis rate. Economic analysis indicated that the ZVI-based technology for enhancing methane production from WAS is economically attractive, particularly considering that iron scrap can be freely acquired from industrial waste. Based on these results, the ZVI-based anaerobic digestion process of this work could be easily integrated with the conventional chemical phosphorus removal process in wastewater treatment plant to form a cost-effective and environment-friendly approach, enabling maximum resource recovery/reuse while achieving enhanced methane production in wastewater treatment system. PMID:25652244

Polyhydroxyalkanoates in waste activated sludge enhances anaerobic methane production through improving biochemical methane potential instead of hydrolysis rate

PubMed Central

Wang, Qilin; Sun, Jing; Zhang, Chang; Xie, Guo-Jun; Zhou, Xu; Qian, Jin; Yang, Guojing; Zeng, Guangming; Liu, Yiqi; Wang, Dongbo

2016-01-01

Anaerobic sludge digestion is the main technology for sludge reduction and stabilization prior to sludge disposal. Nevertheless, methane production from anaerobic digestion of waste activated sludge (WAS) is often restricted by the poor biochemical methane potential and slow hydrolysis rate of WAS. This work systematically investigated the effect of PHA levels of WAS on anaerobic methane production, using both experimental and mathematical modeling approaches. Biochemical methane potential tests showed that methane production increased with increased PHA levels in WAS. Model-based analysis suggested that the PHA-based method enhanced methane production by improving biochemical methane potential of WAS, with the highest enhancement being around 40% (from 192 to 274 L CH4/kg VS added; VS: volatile solid) when the PHA levels increased from 21 to 143 mg/g VS. In contrast, the hydrolysis rate (approximately 0.10 d−1) was not significantly affected by the PHA levels. Economic analysis suggested that the PHA-based method could save $1.2/PE/y (PE: population equivalent) in a typical wastewater treatment plant (WWTP). The PHA-based method can be easily integrated into the current WWTP to enhance methane production, thereby providing a strong support to the on-going paradigm shift in wastewater management from pollutant removal to resource recovery. PMID:26791952

Zero Valent Iron Significantly Enhances Methane Production from Waste Activated Sludge by Improving Biochemical Methane Potential Rather Than Hydrolysis Rate

NASA Astrophysics Data System (ADS)

Liu, Yiwen; Wang, Qilin; Zhang, Yaobin; Ni, Bing-Jie

2015-02-01

Anaerobic digestion has been widely applied for waste activated sludge (WAS) treatment. However, methane production from anaerobic digestion of WAS is usually limited by the slow hydrolysis rate and/or poor biochemical methane potential of WAS. This work systematically studied the effects of three different types of zero valent iron (i.e., iron powder, clean scrap and rusty scrap) on methane production from WAS in anaerobic digestion, by using both experimental and mathematical approaches. The results demonstrated that both the clean and the rusty iron scrap were more effective than the iron powder for improving methane production from WAS. Model-based analysis showed that ZVI addition significantly enhanced methane production from WAS through improving the biochemical methane potential of WAS rather than its hydrolysis rate. Economic analysis indicated that the ZVI-based technology for enhancing methane production from WAS is economically attractive, particularly considering that iron scrap can be freely acquired from industrial waste. Based on these results, the ZVI-based anaerobic digestion process of this work could be easily integrated with the conventional chemical phosphorus removal process in wastewater treatment plant to form a cost-effective and environment-friendly approach, enabling maximum resource recovery/reuse while achieving enhanced methane production in wastewater treatment system.

Polyhydroxyalkanoates in waste activated sludge enhances anaerobic methane production through improving biochemical methane potential instead of hydrolysis rate

NASA Astrophysics Data System (ADS)

Wang, Qilin; Sun, Jing; Zhang, Chang; Xie, Guo-Jun; Zhou, Xu; Qian, Jin; Yang, Guojing; Zeng, Guangming; Liu, Yiqi; Wang, Dongbo

2016-01-01

Anaerobic sludge digestion is the main technology for sludge reduction and stabilization prior to sludge disposal. Nevertheless, methane production from anaerobic digestion of waste activated sludge (WAS) is often restricted by the poor biochemical methane potential and slow hydrolysis rate of WAS. This work systematically investigated the effect of PHA levels of WAS on anaerobic methane production, using both experimental and mathematical modeling approaches. Biochemical methane potential tests showed that methane production increased with increased PHA levels in WAS. Model-based analysis suggested that the PHA-based method enhanced methane production by improving biochemical methane potential of WAS, with the highest enhancement being around 40% (from 192 to 274 L CH4/kg VS added; VS: volatile solid) when the PHA levels increased from 21 to 143 mg/g VS. In contrast, the hydrolysis rate (approximately 0.10 d-1) was not significantly affected by the PHA levels. Economic analysis suggested that the PHA-based method could save $1.2/PE/y (PE: population equivalent) in a typical wastewater treatment plant (WWTP). The PHA-based method can be easily integrated into the current WWTP to enhance methane production, thereby providing a strong support to the on-going paradigm shift in wastewater management from pollutant removal to resource recovery.

Subsurface characterization of methane production and oxidation from a New Hampshire wetland.

PubMed

Shoemaker, J K; Schrag, D P

2010-06-01

We measured the carbon isotopic composition of pore water carbon dioxide from Sallie's Fen, a New Hampshire poor fen. The isotope profiles are used in combination with a one-dimensional diffusion-reaction model to calculate rates of methane production, oxidation and transport over an annual cycle. We show how the rates vary with depth over a seasonal cycle, with methane produced deeper during the winter months and at progressively shallower depths into the summer season. The rates of methane production, constrained by the measured delta(13)C(dic) profiles, cannot explain high methane emission during the summer. We suggest that much of the methane produced during this time comes either from the unsaturated peat, or from the top 1-3 cm of saturated peat where episodic exchange with the atmosphere makes it invisible to our method.

Aerobic methane production in surface waters of the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Finke, N.; Crespo-Medina, M.; Schweers, J.; Joye, S. B.

2011-12-01

Near surface water of the global oceans often show elevated methane concentrations compared to the water column below with concentrations in supersaturation in regard to the atmosphere (Lamontagne et al. 1973), resulting in a source of this potent greenhouse gas to the atmosphere. The mechanisms leading to methane supersaturation in surface waters remains unclear. Incubations with Trichodesmium-containing Pacific surface water suggested methylphosphonate as potential methane precursor under phosphate limiting conditions (Karl et al. 2008), whereas in phosphate rich Arctic surface waters, DMSP addition stimulated methane production (Damm et al. 2010). Surface waters of the Gulf of Mexico typically exhibit a methane maximum that is conincident with the deep chlorophyll maximum, below the depths where Trichodesmium is abundant. Addition of methylphosphonate, dimethylsulfoniopropionate (DMSP) or methane thiol (MeSH), the proposed methane precursor in DMSP conversion to methane, to oxic sea water did not affect methane production within the chlorophyll maximum at most stations, whereas methyl phosphonate addition stimulated methane production in the surface water and proposed deep Trichodesmium horizon. Pre-filtration of the water through a 10 μm sieve, which eliminated Trichodesmium, or through a 1.2 μm filter, which eliminated additional cyanobacteria such as Synechococcus, did not reduce methane production. Under dark oxic and dark anoxic conditions, however, methane production was reduced 5 and 7-20 fold, respectively, indicating that anerobic methane production in anoxic microniches is not responsible for the methane production. The reduction of methane production under dark conditions suggests that methane production is, in some yet unrecognized way, linked to phototrophic metabolism. Cyanobacteria are likely not responsible for the observed aerobic methane production in the surface waters of the Gulf of Mexico and while methylphosphonate is a potential precursor in the surface waters, the precursor and methanism of methane production within the coincident deep chlorophyll/methane maximum remains unknown. Lamontagne R, Swinnert J, Linnenbo V, Smith WD (1973) Methane concentrations in various marine environments. Journal of Geophysical Research 78, 5317-5324 Karl DM et al. (2008) Aerobic production of methane in the sea. Nature Geosciences 1, 473-478 Damm E et al. (2010) Methane production in aerobic oligotrophic surface water in the central Arctic Ocean. Biogeosciences 7, 1099-1108

Enhanced activity and stability of La-doped CeO2 monolithic catalysts for lean-oxygen methane combustion.

PubMed

Zhu, Wenjun; Jin, Jianhui; Chen, Xiao; Li, Chuang; Wang, Tonghua; Tsang, Chi-Wing; Liang, Changhai

2018-02-01

Effective utilization of coal bed methane is very significant for energy utilization and environment protection. Catalytic combustion of methane is a promising way to eliminate trace amounts of oxygen in the coal bed methane and the key to this technology is the development of high-efficiency catalysts. Herein, we report a series of Ce 1-x La x O 2-δ (x = 0-0.8) monolithic catalysts for the catalytic combustion of methane, which are prepared by citric acid method. The structural characterization shows that the substitution of La enhance the oxygen vacancy concentration and reducibility of the supports and promote the migration of the surface oxygen, as a result improve the catalytic activity of CeO 2 . M-Ce 0.8 La 0.2 O 2-δ (monolithic catalyst, Ce 0.8 La 0.2 O 2-δ coated on cordierite honeycomb) exhibits outstanding activity for methane combustion, and the temperature for 10 and 90% methane conversion are 495 and 580 °C, respectively. Additionally, Ce 0.8 La 0.2 O 2-δ monolithic catalyst presents excellent stability at high temperature. These Ce 1-x La x O 2-δ monolithic materials with a small amount of La incorporation therefore show promises as highly efficient solid solution catalysts for lean-oxygen methane combustion. Graphical abstract ᅟ.

Reducing the environmental impact of methane emissions from dairy farms by anaerobic digestion of cattle waste.

PubMed

Marañón, E; Salter, A M; Castrillón, L; Heaven, S; Fernández-Nava, Y

2011-08-01

Four dairy cattle farms considered representative of Northern Spain milk production were studied. Cattle waste was characterised and energy consumption in the farms was inventoried. Methane emissions due to slurry/manure management and fuel consumption on the farms were calculated. The possibility of applying anaerobic digestion to the slurry to minimise emissions and of using the biogas produced to replace fossil fuels on the farm was considered. Methane emissions due to slurry management (storage and use as fertiliser) ranged from 34 to 66kg CH(4)cow(-1)year(-1) for dairy cows and from 13 to 25kg CH(4)cow(-1)year(-1) for suckler calves. Cattle on these farms are housed for most of the year, and the contribution from emissions from manure dropped in pastures is insignificant due to the very low methane conversion factors. If anaerobic digestion were implemented on the farms, the potential GHG emissions savings per livestock unit would range from 978 to 1776kg CO(2)eq year(-1), with the main savings due to avoided methane emissions during slurry management. The methane produced would be sufficient to supply digester heating needs (35-55% of the total methane produced) and on-farm fuel energy requirements. Copyright © 2011 Elsevier Ltd. All rights reserved.

Microbial minorities modulate methane consumption through niche partitioning

PubMed Central

Bodelier, Paul LE; Meima-Franke, Marion; Hordijk, Cornelis A; Steenbergh, Anne K; Hefting, Mariet M; Bodrossy, Levente; von Bergen, Martin; Seifert, Jana

2013-01-01

Microbes catalyze all major geochemical cycles on earth. However, the role of microbial traits and community composition in biogeochemical cycles is still poorly understood mainly due to the inability to assess the community members that are actually performing biogeochemical conversions in complex environmental samples. Here we applied a polyphasic approach to assess the role of microbial community composition in modulating methane emission from a riparian floodplain. We show that the dynamics and intensity of methane consumption in riparian wetlands coincide with relative abundance and activity of specific subgroups of methane-oxidizing bacteria (MOB), which can be considered as a minor component of the microbial community in this ecosystem. Microarray-based community composition analyses demonstrated linear relationships of MOB diversity parameters and in vitro methane consumption. Incubations using intact cores in combination with stable isotope labeling of lipids and proteins corroborated the correlative evidence from in vitro incubations demonstrating γ-proteobacterial MOB subgroups to be responsible for methane oxidation. The results obtained within the riparian flooding gradient collectively demonstrate that niche partitioning of MOB within a community comprised of a very limited amount of active species modulates methane consumption and emission from this wetland. The implications of the results obtained for biodiversity–ecosystem functioning are discussed with special reference to the role of spatial and temporal heterogeneity and functional redundancy. PMID:23788331

Microbial minorities modulate methane consumption through niche partitioning.

PubMed

Bodelier, Paul L E; Meima-Franke, Marion; Hordijk, Cornelis A; Steenbergh, Anne K; Hefting, Mariet M; Bodrossy, Levente; von Bergen, Martin; Seifert, Jana

2013-11-01

Microbes catalyze all major geochemical cycles on earth. However, the role of microbial traits and community composition in biogeochemical cycles is still poorly understood mainly due to the inability to assess the community members that are actually performing biogeochemical conversions in complex environmental samples. Here we applied a polyphasic approach to assess the role of microbial community composition in modulating methane emission from a riparian floodplain. We show that the dynamics and intensity of methane consumption in riparian wetlands coincide with relative abundance and activity of specific subgroups of methane-oxidizing bacteria (MOB), which can be considered as a minor component of the microbial community in this ecosystem. Microarray-based community composition analyses demonstrated linear relationships of MOB diversity parameters and in vitro methane consumption. Incubations using intact cores in combination with stable isotope labeling of lipids and proteins corroborated the correlative evidence from in vitro incubations demonstrating γ-proteobacterial MOB subgroups to be responsible for methane oxidation. The results obtained within the riparian flooding gradient collectively demonstrate that niche partitioning of MOB within a community comprised of a very limited amount of active species modulates methane consumption and emission from this wetland. The implications of the results obtained for biodiversity-ecosystem functioning are discussed with special reference to the role of spatial and temporal heterogeneity and functional redundancy.

Methane production from bicarbonate and acetate in an anoxic marine sediment

NASA Technical Reports Server (NTRS)

Crill, P. M.; Martens, C. S.

1986-01-01

Methane production from C-14 labeled bicarbonate and acetate was measured over the top 28 cm of anoxic Cape Lookout Bight sediments during the summer of 1983. The depth distribution and magnitude of summed radioisotopically determined rates compare well with previous measurements of total methane production and the sediment-water methane flux. Methane production from CO2 reduction and acetate fermentation accounts for greater than 80 percent of the total production rate and sediment-water flux. Methane production from bicarbonate was found to occur in all depth intervals sampled except those in the top 2 cm, whereas significant methane production from acetate only occurred at depths below 10 cm where sulfate was exhausted. Acetate provided 20 to 29 percent of the measured methane production integrated over the top 30 cm of the sediments.

Could Methane Oxidation in Lakes Be Enhanced by Eutrophication?

NASA Astrophysics Data System (ADS)

Van Grinsven, S.; Villanueva, L.; Harrison, J.; S Sinninghe Damsté, J.

2017-12-01

Climate change and eutrophication both affect aquatic ecosystems. Eutrophication is caused by high nutrient inputs, leading to algal blooms, oxygen depletion and disturbances of the natural balances in aquatic systems. Methane, a potent greenhouse gas produced biologically by anaerobic degradation of organic matter, is often released from the sediments of lakes and marine systems to overlying water and the atmosphere. Methane oxidation, a microbial methane consumption process, can limit methane emission from lakes and reservoirs by 50-80%. Here, we studied methane oxidation in a seasonally stratified reservoir: Lacamas Lake in Washington, USA. We found this lake has a large summer storage capacity of methane in its deep water layer, with a very active microbial community capable of oxidizing exceptionally high amounts of methane. The natural presence of terminal electron acceptors is, however, too low to support these high potential rates. Addition of eutrophication-related nutrients such as nitrate and sulfate increased the methane removal rates by 4 to 7-fold. The microbial community was studied using 16S rRNA gene amplicon sequencing and preliminary results indicate the presence of a relatively unknown facultative anaerobic methane oxidizer of the genus Methylomonas, capable of using nitrate as an electron donor. Experiments in which anoxic and oxic conditions were rapidly interchanged showed this facultative anaerobic methane oxidizer has an impressive flexibility towards large, rapid changes in environmental conditions and this feature might be key to the unexpectedly high methane removal rates in eutrophied and anoxic watersheds.

Mechanistic insights into heterogeneous methane activation

DOE PAGES

Latimer, Allegra A.; Aljama, Hassan; Kakekhani, Arvin; ...

2017-01-11

While natural gas is an abundant chemical fuel, its low volumetric energy density has prompted a search for catalysts able to transform methane into more useful chemicals. This search has often been aided through the use of transition state (TS) scaling relationships, which estimate methane activation TS energies as a linear function of a more easily calculated descriptor, such as final state energy, thus avoiding tedious TS energy calculations. It has been shown that methane can be activated via a radical or surface-stabilized pathway, both of which possess a unique TS scaling relationship. Herein, we present a simple model tomore » aid in the prediction of methane activation barriers on heterogeneous catalysts. Analogous to the universal radical TS scaling relationship introduced in a previous publication, we show that a universal TS scaling relationship that transcends catalysts classes also seems to exist for surface-stabilized methane activation if the relevant final state energy is used. We demonstrate that this scaling relationship holds for several reducible and irreducible oxides, promoted metals, and sulfides. By combining the universal scaling relationships for both radical and surface-stabilized methane activation pathways, we show that catalyst reactivity must be considered in addition to catalyst geometry to obtain an accurate estimation for the TS energy. Here, this model can yield fast and accurate predictions of methane activation barriers on a wide range of catalysts, thus accelerating the discovery of more active catalysts for methane conversion.« less

Mechanistic insights into heterogeneous methane activation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Latimer, Allegra A.; Aljama, Hassan; Kakekhani, Arvin

While natural gas is an abundant chemical fuel, its low volumetric energy density has prompted a search for catalysts able to transform methane into more useful chemicals. This search has often been aided through the use of transition state (TS) scaling relationships, which estimate methane activation TS energies as a linear function of a more easily calculated descriptor, such as final state energy, thus avoiding tedious TS energy calculations. It has been shown that methane can be activated via a radical or surface-stabilized pathway, both of which possess a unique TS scaling relationship. Herein, we present a simple model tomore » aid in the prediction of methane activation barriers on heterogeneous catalysts. Analogous to the universal radical TS scaling relationship introduced in a previous publication, we show that a universal TS scaling relationship that transcends catalysts classes also seems to exist for surface-stabilized methane activation if the relevant final state energy is used. We demonstrate that this scaling relationship holds for several reducible and irreducible oxides, promoted metals, and sulfides. By combining the universal scaling relationships for both radical and surface-stabilized methane activation pathways, we show that catalyst reactivity must be considered in addition to catalyst geometry to obtain an accurate estimation for the TS energy. Here, this model can yield fast and accurate predictions of methane activation barriers on a wide range of catalysts, thus accelerating the discovery of more active catalysts for methane conversion.« less

Plasma conversion of methane into higher hydrocarbons at surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sackinger, W.M.; Kamath, V.A.

1995-12-31

Natural gas is widely abundant, is easily withdrawn from reservoirs, is commonly produced as an associated gas along with crude oil production, and is found in many geologic settings as a resource separate from oil. A much larger fraction of the natural gas may be produced from a gas reservoir, as compared with a crude oil reservoir. However, natural gas is normally transported by pipeline, and the energy throughput of such a pipeline is perhaps only 20% to 30% of the throughput of an oil pipeline of the same size and cost. Gas is difficult to transport in moderate quantitiesmore » at low cost, as it must either have a special pipeline or must be liquified into LNG, shipped in cryogenic LNG tankers, and regasified chemical stability of methane has made it difficult to convert it directly into conventional hydrocarbon fuel mixtures, and has also impeded its use as a feedstock for petrochemical production. Experiments are described in which a methane plasma is created, and the resulting methyl and hydrogen ions have been accelerated within a microchannel array so that they interact with neutral methane molecules on the inside surfaces of the microchannels. No catalysts are used, and the device operates at room temperature. Impact energies of the ions are in the range of 15 ev to greater than 100 ev, and the energy delivered in the interaction at the surfaces has caused the production of larger hydrocarbon molecules, such as C{sub 2}H{sub 2}, C{sub 2}H{sub 4}, and C{sub 2}H{sub 6}, along with C{sub 3}, C{sub 4}, C{sub 5}, C{sub 6}, C{sub 7}, and C{sub 8} molecules. Conversion effectiveness is greater at higher pressure, due to the increased ionic activity. The costs of production of the plasma conversion devices are projected to be quite low, and the technology appears to be commercially and economically feasible.« less

Building a better methane generation model: Validating models with methane recovery rates from 35 Canadian landfills.

PubMed

Thompson, Shirley; Sawyer, Jennifer; Bonam, Rathan; Valdivia, J E

2009-07-01

The German EPER, TNO, Belgium, LandGEM, and Scholl Canyon models for estimating methane production were compared to methane recovery rates for 35 Canadian landfills, assuming that 20% of emissions were not recovered. Two different fractions of degradable organic carbon (DOC(f)) were applied in all models. Most models performed better when the DOC(f) was 0.5 compared to 0.77. The Belgium, Scholl Canyon, and LandGEM version 2.01 models produced the best results of the existing models with respective mean absolute errors compared to methane generation rates (recovery rates + 20%) of 91%, 71%, and 89% at 0.50 DOC(f) and 171%, 115%, and 81% at 0.77 DOC(f). The Scholl Canyon model typically overestimated methane recovery rates and the LandGEM version 2.01 model, which modifies the Scholl Canyon model by dividing waste by 10, consistently underestimated methane recovery rates; this comparison suggested that modifying the divisor for waste in the Scholl Canyon model between one and ten could improve its accuracy. At 0.50 DOC(f) and 0.77 DOC(f) the modified model had the lowest absolute mean error when divided by 1.5 yielding 63 +/- 45% and 2.3 yielding 57 +/- 47%, respectively. These modified models reduced error and variability substantially and both have a strong correlation of r = 0.92.

Methanogenic degradation of toilet-paper cellulose upon sewage treatment in an anaerobic membrane bioreactor at room temperature.

PubMed

Chen, Rong; Nie, Yulun; Kato, Hiroyuki; Wu, Jiang; Utashiro, Tetsuya; Lu, Jianbo; Yue, Shangchao; Jiang, Hongyu; Zhang, Lu; Li, Yu-You

2017-03-01

Toilet-paper cellulose with rich but refractory carbon sources, are the main insoluble COD fractions in sewage. An anaerobic membrane bioreactor (AnMBR) was configured for sewage treatment at room temperature and its performance on methanogenic degradation of toilet paper was highlighted. The results showed, high organic removal (95%), high methane conversion (90%) and low sludge yield (0.08gVSS/gCOD) were achieved in the AnMBR. Toilet-paper cellulose was fully biodegraded without accumulation in the mixed liquor and membrane cake layer. Bioconversion efficiency of toilet paper approached 100% under a high organic loading rate (OLR) of 2.02gCOD/L/d and it could provide around 26% of total methane generation at most of OLRs. Long sludge retention time and co-digestion of insoluble/soluble COD fractions achieving mutualism of functional microorganisms, contributed to biodegradation of toilet-paper cellulose. Therefore the AnMBR successfully implemented simultaneously methanogenic bioconversion of toilet-paper cellulose and soluble COD in sewage at room temperature. Copyright © 2016 Elsevier Ltd. All rights reserved.

Waste-to-Energy Cogeneration Project, Centennial Park

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Clay; Mandon, Jim; DeGiulio, Thomas

The Waste-to-Energy Cogeneration Project at Centennial Park has allowed methane from the closed Centennial landfill to export excess power into the the local utility’s electric grid for resale. This project is part of a greater brownfield reclamation project to the benefit of the residents of Munster and the general public. Installation of a gas-to-electric generator and waste-heat conversion unit take methane byproduct and convert it into electricity at the rate of about 103,500 Mwh/year for resale to the local utility. The sale of the electricity will be used to reduce operating budgets by covering the expenses for streetlights and utilitymore » bills. The benefits of such a project are not simply financial. Munster’s Waste-to Energy Cogeneration Project at Centennial Park will reduce the community’s carbon footprint in an amount equivalent to removing 1,100 cars from our roads, conserving enough electricity to power 720 homes, planting 1,200 acres of trees, or recycling 2,000 tons of waste instead of sending it to a landfill.« less

Microbial Methane Oxidation Rates in Guandu Wetland of northern Taiwan

NASA Astrophysics Data System (ADS)

Yu, Zih-Huei; Wang, Pei-Ling; Lin, Li-Hung

2016-04-01

Wetland is one of the major sources of atmospheric methane. The exact magnitude of methane emission is essentially controlled by microbial processes. Besides of methanogenesis, methanotrophy oxidizes methane with the reduction of various electron acceptors under oxic or anoxic conditions. The interplay of these microbial activities determines the final methane flux under different circumstances. In a tidal wetland, the cyclic flooding and recession of tide render oxygen and sulfate the dominant electron acceptors for methane oxidation. However, the details have not been fully examined, especially for the linkage between potential methane oxidation rates and in situ condition. In this study, a sub-tropical wetland in northern Taiwan, Guandu, was chosen to examine the tidal effect on microbial methane regulation. Several sediment cores were retrieved during high tide and low tide period and their geochemical profiles were characterized to demonstrate in situ microbial activities. Incubation experiments were conducted to estimate potential aerobic and anaerobic methane oxidation rates in surface and core sediments. Sediment cores collected in high tide and low tide period showed different geochemical characteristics, owning to tidal inundation. Chloride and sulfate concentration were lower during low tide period. A spike of enhanced sulfate at middle depth intervals was sandwiched by two sulfate depleted zones above and underneath. Methane was accumulated significantly with two methane depletion zones nearly mirroring the sulfate spike zone identified. During the high tide period, sulfate decreased slightly with depth with methane production inhibited at shallow depths. However, a methane consumption zone still occurred near the surface. Potential aerobic methane oxidation rates were estimated between 0.7 to 1.1 μmole/g/d, showing no difference between the samples collected at high tide or low tide period. However, a lag phase was widely observed and the lag phase lasted over a longer period of time for the samples collected in high tide period. It seems that aerobic methanotrophs needed a longer period of time to recovery and/or had low activities, since they had been suppressed by low oxygen concentration during high tide period. The rates of anaerobic methane oxidation ranged between 1.5 and 4.0 nmole/g/d for samples collected at high tide period, whereas lower rates ranging from 0.2 to 2.0 nmole/g/d were observed for samples at low tide period. The addition of basal salt solution apparently stimulated methane consumption significantly. Based on the field observation and laboratory incubations, our results indicated a dynamic shift of metabolic zonation in tidally influenced wetlands. Aerobic methanotrophy appears to outpace anaerobic methanotrophy by orders of magnitude regardless of tidal inundation. This together with methanogenesis regulated by the availability of sulfate and organic degradation plays a major role in controlling methane emission. While anaerobic methanotrophy is relatively minor in methane cycling, its linkage with the sulfate availability modulates the coupling of carbon and sulfur turnover under anoxic conditions.

Methodology to Collect Natural Gas from Methane Hydrate Deposits Using Sunlight: Design of Direct Sunlight Exposure System

NASA Astrophysics Data System (ADS)

Shimada, M.; Shimada, J.; Tsunashima, K.; Aoyama, C.

2017-12-01

Methane hydrate is anticipated to be the unconventional natural gas energy resource. Two types of methane hydrates are known to exist, based on the settings: "shallow" type and "sand layer" type. In comparison, shallow type is considered an advantage due to its high purity and the more simple exploration. However, not much development methods have been made in the area of extraction techniques. Currently, heating and depressurization are used as methods to collect sand layer methane hydrate, but these methods are still under examination and not yet to be implemented. This is probably because fossil fuel is used for the extraction process instead of natural energy. It is necessary to utilize natural energy instead of relying on fossil fuel. This is why sunlight is believed to be the most significant alternative. Solar power generation is commonly used to extract sunlight, but it is said that this process causes extreme energy loss since solar energy converted to electricity requires conversion to heat energy. A new method is contrived to accelerate the decomposition of methane hydrate with direct sunlight utilizing optical fibers. Authors will present details of this new method to collect methane hydrate with direct sunlight exposure.

Methane hydrate synthesis from ice: Influence of pressurization and ethanol on optimizing formation rates and hydrate yield

USGS Publications Warehouse

Chen, Po-Chun.; Huang, Wuu-Liang; Stern, Laura A.

2010-01-01

Polycrystalline methane gas hydrate (MGH) was synthesized using an ice-seeding method to investigate the influence of pressurization and ethanol on the hydrate formation rate and gas yield of the resulting samples. When the reactor is pressurized with CH4 gas without external heating, methane hydrate can be formed from ice grains with yields up to 25% under otherwise static conditions. The rapid temperature rise caused by pressurization partially melts the granular ice, which reacts with methane to form hydrate rinds around the ice grains. The heat generated by the exothermic reaction of methane hydrate formation buffers the sample temperature near the melting point of ice for enough time to allow for continuous hydrate growth at high rates. Surprisingly, faster rates and higher yields of methane hydrate were found in runs with lower initial temperatures, slower rates of pressurization, higher porosity of the granular ice samples, or mixtures with sediments. The addition of ethanol also dramatically enhanced the formation of polycrystalline MGH. This study demonstrates that polycrystalline MGH with varied physical properties suitable for different laboratory tests can be manufactured by controlling synthesis procedures or parameters. Subsequent dissociation experiments using a gas collection apparatus and flowmeter confirmed high methane saturation (CH 4·2O, with n = 5.82 ± 0.03) in the MGH. Dissociation rates of the various samples synthesized at diverse conditions may be fitted to different rate laws, including zero and first order.

Chemical Aspects of Astrophysically Observed Extraterrestrial Methanol, Hydrocarbon Derivatives, and Ions.

PubMed

Olah, George A; Mathew, Thomas; Prakash, G K Surya; Rasul, Golam

2016-02-10

Astrophysically observed extraterrestrial molecular matter contains, besides hydrogen and water, methane and methanol as the most abundant species. Feasible pathways and chemical aspects of their formation as well as of derived hydrocarbon homologues and their ions (carbocations and carbanions) are discussed on the basis of observed similarities with our studied terrestrial chemistry. The preferred pathway for converting extraterrestrial methane according to Ali et al. is based on CH5(+) and Olah's related nonclassical carbonium ion chemistry. On the basis of the observed higher reactivity of methanol compared with methane in various chemical reactions, a feasible new pathway is proposed for the conversion of extraterrestrial methanol to hydrocarbons, their derivatives, and carbocations together with a possible connection with methonium ion-based chemistry.

Development of a Hydrogasification Process for Co-Production of Substitute Natural Gas (SNG) and Electric Power from Western Coals-Phase I

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raymond Hobbs

2007-05-31

The Advanced Hydrogasification Process (AHP)--conversion of coal to methane--is being developed through NETL with a DOE Grant and has successfully completed its first phase of development. The results so far are encouraging and have led to commitment by DOE/NETL to begin a second phase--bench scale reactor vessel testing, expanded engineering analysis and economic perspective review. During the next decade new means of generating electricity, and other forms of energy, will be introduced. The members of the AHP Team envision a need for expanded sources of natural gas or substitutes for natural gas, to fuel power generating plants. The initial workmore » the team has completed on a process to use hydrogen to convert coal to methane (pipeline ready gas) shows promising potential. The Team has intentionally slanted its efforts toward the needs of US electric utilities, particularly on fuels that can be used near urban centers where the greatest need for new electric generation is found. The process, as it has evolved, would produce methane from coal by adding hydrogen. The process appears to be efficient using western coals for conversion to a highly sought after fuel with significantly reduced CO{sub 2} emissions. Utilities have a natural interest in the preservation of their industry, which will require a dramatic reduction in stack emissions and an increase in sustainable technologies. Utilities tend to rank long-term stable supplies of fuel higher than most industries and are willing to trade some ratio of cost for stability. The need for sustainability, stability and environmentally compatible production are key drivers in the formation and progression of the AHP development. In Phase II, the team will add a focus on water conservation to determine how the basic gasification process can be best integrated with all the plant components to minimize water consumption during SNG production. The process allows for several CO{sub 2} reduction options including consumption of the CO{sub 2} in the original process as converted to methane. The process could under another option avoid emissions following the conversion to SNG through an adjunct algae conversion process. The algae would then be converted to fuels or other products. An additional application of the algae process at the end use natural gas fired plant could further reduce emissions. The APS team fully recognizes the competition facing the process from natural gas and imported liquid natural gas. While we expect those resources to set the price for methane in the near-term, the team's work to date indicates that the AHP process can be commercially competitive, with the added benefit of assuring long-term energy supplies from North American resources. Conversion of coal to a more readily transportable fuel that can be employed near load centers with an overall reduction of greenhouses gases is edging closer to reality.« less

Characterization of methane emissions from five cold heavy oil production with sands (CHOPS) facilities.

PubMed

Roscioli, Joseph R; Herndon, Scott C; Yacovitch, Tara I; Knighton, W Berk; Zavala-Araiza, Daniel; Johnson, Matthew R; Tyner, David R

2018-03-07

Cold heavy oil production with sands (CHOPS) is a common oil extraction method in the Canadian provinces of Alberta and Saskatchewan that can result in significant methane emissions due to annular venting. Little is known about the magnitude of these emissions, nor their contributions to the regional methane budget. Here the authors present the results of field measurements of methane emissions from CHOPS wells and compare them with self-reported venting rates. The tracer ratio method was used not only to analyze total site emissions but at one site it was also used to locate primary emission sources and quantify their contributions to the facility-wide emission rate, revealing the annular vent to be a dominant source. Emissions measured from five different CHOPS sites in Alberta showed large discrepancies between the measured and reported rates, with emissions being mainly underreported. These methane emission rates are placed in the context of current reporting procedures and the role that gas-oil ratio (GOR) measurements play in vented volume estimates. In addition to methane, emissions of higher hydrocarbons were also measured; a chemical "fingerprint" associated with CHOPS wells in this region reveals very low emission ratios of ethane, propane, and aromatics versus methane. The results of this study may inform future studies of CHOPS sites and aid in developing policy to mitigate regional methane emissions. Methane measurements from cold heavy oil production with sand (CHOPS) sites identify annular venting to be a potentially major source of emissions at these facilities. The measured emission rates are generally larger than reported by operators, with uncertainty in the gas-oil ratio (GOR) possibly playing a large role in this discrepancy. These results have potential policy implications for reducing methane emissions in Alberta in order to achieve the Canadian government's goal of reducing methane emissions by 40-45% below 2012 levels within 8 yr.

Associations among methane emission traits measured in the feedlot and in respiration chambers in Angus cattle bred to vary in feed efficiency.

PubMed

Herd, R M; Velazco, J I; Arthur, P F; Hegarty, R F

2016-11-01

The objective of the study was to evaluate associations among animal performance and methane emission traits under feedlot conditions and in respiration chambers in Angus cattle bred to vary in residual feed intake (RFI), which is a measure of feed efficiency. Fifty-nine cattle were tested for feedlot RFI, of which 41 had methane production recorded on an ad libitum grain-based ration in the feedlot, 59 on a restricted grain-based ration in respiration chambers, and 57 on a restricted roughage ration in respiration chambers. The cattle became older and heavier as they went through the different phases of the experiment, but their feed intake (expressed as DMI) and daily emission of enteric methane (methane production rate; MPR) did not increase proportionally, as feed offered was restricted in the respiration chamber tests. Methane emissions by individual animals relative to their DMI were calculated as methane yield (MY; MPR/DMI) and as 2 measures of residual methane production (RMP and RMP), which were calculated as the difference between measured MPR and that predicted from feed intake by 2 different equations. Within each test regime, MPR was positively correlated ( = 0.28 to 0.61) with DMI. Phenotypic correlations for MY, RMP, and RMP between the feedlot test and the restricted grain test ( = 0.40 to 0.43) and between the restricted grain test and the restricted roughage test were moderate ( = 0.36 to 0.41) and moderate to strong between the feedlot test and the restricted roughage test ( = 0.54 to 0.58). These results indicate that the rankings of animals for methane production relative to feed consumed are relatively stable over the 3 test phases. Feedlot feed conversion ratio and RFI were not correlated with MPR in the feedlot test and grain-based chamber test but were negatively correlated with MPR in the chamber roughage test ( = -0.31 and -0.37). Both were negatively correlated with MY and RMP in the feedlot test ( = -0.42 to -0.54) and subsequent chamber roughage test ( = -0.27 to -0.49). Midparent estimated breeding values for RFI tended to be negatively correlated with MY and RMP in the feedlot test ( = -0.27 and -0.27) and were negatively correlated with MY, RMP, and RMP in the chamber roughage test ( = -0.33 to -0.36). These results showed that in young growing cattle, lower RFI was associated with higher MY, RMP, and RMP but had no significant association with MPR.

The combined effects of supplementing monensin and 3-nitrooxypropanol on methane emissions, growth rate, and feed conversion efficiency in beef cattle fed high forage and high grain diets.

PubMed

Vyas, Diwakar; Alemu, Aklilu W; McGinn, Sean M; Duval, Stephane M; Kindermann, Maik; Beauchemin, Karen A

2018-05-05

The study objective was to evaluate the combined effects of supplementing monensin (MON) and the methane (CH4) inhibitor 3-nitrooxypropanol (NOP) on enteric CH4 emissions, growth rate and feed conversion efficiency of backgrounding and finishing beef cattle. Two hundred and forty crossbred steers were used in a 238-d feeding study and fed a backgrounding diet for the first 105-d (backgrounding phase), transition diets for 28 d, followed by a finishing diet for 105-d (finishing phase). Treatments were: 1) Control (no additive); 2) MON (monensin supplemented at 33 mg/kg DM; 3) NOP (3-nitrooxypropanol supplemented at 200 mg/kg DM for backgrounding or 125 mg/kg DM for finishing phase); 4) MONOP (33 mg/kg DM MON supplemented with either 200 mg/kg DM or 125 mg/kg DM NOP). The experiment was a randomized complete block (weight: heavy and light) design with 2 (NOP) × 2 (MON) factorial arrangement of treatments using 24 pens (8 cattle/pen; 6 pens/treatment) at the main feedlot and 8 pens (6 cattle/pen; 2 pens/treatment) at the controlled environment building (CEB) feedlot. Five animals per treatment were moved to chambers for methane measurements during both phases. Data were analyzed using a Mixed procedure of SAS with pen as experimental unit (except CH4). Location (Main vs CEB) had no significant effect and was thus omitted from the final model. Overall, there were few interactions between MON and NOP indicating that the effects of the 2 compounds were independent. When cattle were fed the backgrounding diet, pen DMI was decreased by 7% while gain-to-feed ratio (G:F) was improved by 5% with NOP supplementation (P < 0.01). Similarly, MON improved G:F ratio by 4% (P < 0.01), but without affecting DMI. During the finishing phase, DMI tended (P = 0.06) to decrease by 5% with both MON (5%) and NOP (5%), while average daily gain tended (P = 0.08) to decrease by 3% with MON. Gain-to-feed ratio for finishing cattle was improved with NOP by 3% (P < 0.01); however, no effects were observed with MON. 3-Nitrooxypropanol decreased CH4 yield (g/kg DMI) by 42% and 37% with backgrounding and finishing diets (P ≤ 0.01), respectively, while MON did not lower CH4 yield. Overall, these results demonstrate efficacy of NOP in reducing enteric CH4 emissions and subsequently improving feed conversion efficiency in cattle fed high forage and high grain diets. Furthermore, effects of NOP did not depend upon whether MON was included in the diet.

Intense methane ebullition from open water area of a shallow peatland lake on the eastern Tibetan Plateau.

PubMed

Zhu, Dan; Wu, Yan; Chen, Huai; He, Yixin; Wu, Ning

2016-01-15

Methane fluxes from a shallow peatland lake (3450 m a.s.l., 1.6 km(2) in area, maximum depth <1m) on eastern Tibetan Plateau were measured with floating chamber method during May to August, 2009. The overall average of methane emission rate during the study period was 34.71±29.15 mg CH4 m(-2) h(-1). The occurrence of ebullition among the overall methane flux from Lake Medo was about 74%. The average rate of ebullition was 32.45±28.31 mg CH4 m(-2) h(-1), which accounted for 93% of the overall average of methane emission. Significant seasonal variation was found for occurrence (P<0.05) and rate (P<0.01) of ebullition, both peaking synchronously in mid-summer. Both the occurrence and rate of ebullition were found positively related to sediment temperature but negatively related to lake water depth. The high methane production in the lake sediment was likely fueled by organic carbon loaded from surrounding peatlands to the lake. The shallowness of the water column could be another important favorable factor for methane-containing bubble formation in the sediment and their transportation to the atmosphere. The methane ebullition must have been enhanced by the low atmospheric pressure (ca. 672 hPa) in the high-altitude environment. For a better understanding on the mechanism of methane emission from alpine lakes, more lakes on the Tibetan Plateau should be studied in the future for their methane ebullition. Copyright © 2015 Elsevier B.V. All rights reserved.

Methane and carbon dioxide emissions from Shan-Chu-Ku landfill site in northern Taiwan.

PubMed

Hegde, Ullas; Chang, Tsan-Chang; Yang, Shang-Shyng

2003-09-01

To investigate the methane and carbon dioxide emissions from landfill, samples were taken of material up to 5 years old from Shan-Chu-Ku landfill located in the northern part of Taiwan. Atmospheric concentrations of carbon dioxide, methane and nitrous oxide ranged from 310 to 530, 2.64 to 20.16 and 0.358 to 1.516 ppmv with the measurement of gas-type open-path Fourier transform infra-red (FTIR) spectroscopy during February 1998 to March 2000, respectively. Average methane emission rate was 13.17, 65.27 and 0.99 mgm(-2)h(-1) measured by the gas chromatography chamber method in 1-2, 2-3 and 5 year-old landfill, respectively. Similarly, average carbon dioxide emission rate was 93.70, 314.60 and 48.46 mgm(-2)h(-1), respectively. About 2-3 year-old landfill had the highest methane and carbon dioxide emission rates among the tested areas, while 5 year-old landfill was the least. Methane emission rate at night in most tested locations was higher than that in the daytime. Total amount of methane and carbon dioxide emission from this landfill was around 171 and 828 ton in 1999, respectively.

Co-aromatization of olefin and methane over Ag-Ga/ZSM-5 catalyst at low temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Peng; Gatip, Richard; Yung, Matthew

The massive exploitation of shale gas in the past decade has boosted the production of natural gas and reduced its price dramatically. The methane activation and following conversion into more valuable fuels and chemicals have thus become more and more attractive, while the introduction of hydrocarbons to enhance the methane activation at mild conditions represents a promising approach. In the present work, the co-aromatization of methane with propylene has been studied at 400 °C. The presence of methane would increase the toluene to benzene ratio as well as the average carbon number of the formed liquid aromatic products compared tomore » its propylene alone counterpart. Among the gas products, the formations of C 3H 8, C 4H 8 and C 4H 10 also get promoted when methane is present. The incorporation of methane into the product molecules is also directly evidenced by the 1H, 2D and 13C NMR spectroscopy of the liquid products obtained from the reaction between propylene (or styrene) and isotope labelled methane. Hydrogen from methane would contribute a large portion of the hydrogen in the product molecules, while the benzylic and aromatic hydrogen sites are favored compared with those on the alkyl side chains. The activation of methane is also observed in the DRIFT spectra when deuterium enriched methane is engaged as the methane source and evidenced by the escalated exothermic feature when olefin aromatization takes place under methane environment. The excellent catalytic performance of Ag-Ga/ZSM-5 might be because of the better dispersion of Ag and Ga on the ZSM-5 surface and moderate amount of strong Brosted and Lewis surface acid sites. All the observations suggest that methane might be activated nonoxidatively and converted into aromatics if suitable catalyst is charged under the assistance of co-existing olefin. In conclusion, the reported synergetic effect could potentially lead to the more economic utilization of abundant natural gas and petrochemical intermediates.« less

Bioassay for estimating the biogenic methane-generating potential of coal samples

USGS Publications Warehouse

Jones, Elizabeth J.P.; Voytek, Mary A.; Warwick, Peter D.; Corum, Margo D.; Cohn, Alexander G.; Bunnell, Joseph E.; Clark, Arthur C.; Orem, William H.

2008-01-01

Generation of secondary biogenic methane in coal beds is likely controlled by a combination of factors such as the bioavailability of coal carbon, the presence of a microbial community to convert coal carbon to methane, and an environment supporting microbial growth and methanogenesis. A set of treatments and controls was developed to bioassay the bioavailability of coal for conversion to methane under defined laboratory conditions. Treatments included adding a well-characterized consortium of bacteria and methanogens (enriched from modern wetland sediments) and providing conditions to support endemic microbial activity. The contribution of desorbed methane in the bioassays was determined in treatments with bromoethane sulfonic acid, an inhibitor of microbial methanogenesis. The bioassay compared 16 subbituminous coal samples collected from beds in Texas (TX), Wyoming (WY), and Alaska (AK), and two bituminous coal samples from Pennsylvania (PA). New biogenic methane was observed in several samples of subbituminous coal with the microbial consortium added, but endemic activity was less commonly observed. The highest methane generation [80 µmol methane/g coal (56 scf/ton or 1.75 cm3/g)] was from a south TX coal sample that was collected from a non-gas-producing well. Subbituminous coals from the Powder River Basin, WY and North Slope Borough, AK contained more sorbed (original) methane than the TX coal sample and generated 0–23 µmol/g (up to 16 scf/ton or 0.5 cm3/g) new biogenic methane in the bioassay. Standard indicators of thermal maturity such as burial depth, nitrogen content, and calorific value did not explain differences in biogenic methane among subbituminous coal samples. No original methane was observed in two bituminous samples from PA, nor was any new methane generated in bioassays of these samples. The bioassay offers a new tool for assessing the potential of coal for biogenic methane generation, and provides a platform for studying the mechanisms involved in this economically important activity.

Co-aromatization of olefin and methane over Ag-Ga/ZSM-5 catalyst at low temperature

DOE PAGES

He, Peng; Gatip, Richard; Yung, Matthew; ...

2017-04-22

The massive exploitation of shale gas in the past decade has boosted the production of natural gas and reduced its price dramatically. The methane activation and following conversion into more valuable fuels and chemicals have thus become more and more attractive, while the introduction of hydrocarbons to enhance the methane activation at mild conditions represents a promising approach. In the present work, the co-aromatization of methane with propylene has been studied at 400 °C. The presence of methane would increase the toluene to benzene ratio as well as the average carbon number of the formed liquid aromatic products compared tomore » its propylene alone counterpart. Among the gas products, the formations of C 3H 8, C 4H 8 and C 4H 10 also get promoted when methane is present. The incorporation of methane into the product molecules is also directly evidenced by the 1H, 2D and 13C NMR spectroscopy of the liquid products obtained from the reaction between propylene (or styrene) and isotope labelled methane. Hydrogen from methane would contribute a large portion of the hydrogen in the product molecules, while the benzylic and aromatic hydrogen sites are favored compared with those on the alkyl side chains. The activation of methane is also observed in the DRIFT spectra when deuterium enriched methane is engaged as the methane source and evidenced by the escalated exothermic feature when olefin aromatization takes place under methane environment. The excellent catalytic performance of Ag-Ga/ZSM-5 might be because of the better dispersion of Ag and Ga on the ZSM-5 surface and moderate amount of strong Brosted and Lewis surface acid sites. All the observations suggest that methane might be activated nonoxidatively and converted into aromatics if suitable catalyst is charged under the assistance of co-existing olefin. In conclusion, the reported synergetic effect could potentially lead to the more economic utilization of abundant natural gas and petrochemical intermediates.« less

Vertical gradients in carbon flow and methane production in a sulfate-rich oil sands tailings pond.

PubMed

Stasik, Sebastian; Wendt-Potthoff, Katrin

2016-12-01

Oil sands tailings ponds are primary storage basins for tailings produced during oil sands processing in Alberta (Canada). Due to microbial metabolism, methane production contributes to greenhouse gas emissions, but positively affects tailings densification, which is relevant for operational water re-use. Depending on the age and depth of tailings, the activity of sulfate-reducing bacteria (SRB) may control methanogenesis due to the competition for substrates. To assess the depth-related impact of sulfate reduction on CH 4 emissions, original tailings of two vicinal pond profiles were incubated in anoxic microcosms with/without molybdate as selective inhibitor of microbial sulfate reduction. Integrating methane production rates, considerable volumes of CH 4 emissions (∼5.37 million L d -1 ) may be effectively prevented by the activity of SRB in sulfidic tailings between 3.5 and 7.5 m. To infer metabolic potentials controlling methanogenic pathways, a set of relevant organic acids (acetate, formate, propionate, butyrate, lactate) was added to part of the microcosms. Generally, organic acid transformation shifted with depth, with highest rates (305-446 μmol L -1  d -1 ) measured in fresh tailings at 5.5-7.5 m. In all depths, a transient accumulation of acetate revealed its importance as key intermediate during organic matter decomposition. SRB dominated the transformation of acetate, butyrate and propionate, but were not essential for lactate and formate turnover. Acetate as methanogenic substrate was important only at 13.5 m. At 1-7.5 m, methanogenesis significantly increased in presence of organic acids, most likely due to the syntrophic oxidation of acetate to CO 2 by SRB and subsequent conversion to CH 4 . Copyright © 2016 Elsevier Ltd. All rights reserved.

REGIONAL ASSESSMENT OF METHANE EMISSION RATES FROM RESERVOIRS IN THE MIDWESTERN UNITED STATES

EPA Science Inventory

Reservoirs are a globally significant source of methane (CH4) to the atmosphere, but regional and global emission estimates are poorly constrained due to high variability in emission rates among reservoirs and a lack of measurements in some areas geographic areas. Methane emissi...

First records of a field experiment on fertilizer effects on methane emission from rice fields in Hunan-Province (PR China)

NASA Astrophysics Data System (ADS)

Wassmann, R.; Wang, M. X.; Shangguan, X. J.; Xie, X. L.; Shen, R. X.; Wang, Y. S.; Papen, H.; Rennenberg, H.; Seiler, W.

Fertilizer effects on methane emission from Chinese rice fields were investigated by a praxis-oriented approach applying balanced amendments of N, P and K. The data set obtained covered the emission rates of app. one month in early rice and one month in late rice 1991. An intercomparison between the 4 treatments showed pronounced differences in the magnitudes of methane emission rates. The combined organic/mineral fertilizer application, commonly used as local farming practice, resulted in relatively high seasonal averages of methane emission rates (26.5 mg CH4 m-2 h-1 in early rice and 50.1 mg CH4 m-2 h-1 in late rice). The lowest emission rates were observed in the plot with pure mineral fertilization (6.5 mg CH4 m-2 h-1 in early rice and 14.3 mg CH4 m-2 h-1 in late rice). Pure organic fertilizers by unfermented substances yielded the highest methane emission rates of all field trials (38.6 mg CH4 m-2 h-1 in early rice and 56.2 CH4 m-2 h-1 in late rice). The fertilization with fermented material derived from biogas generators resulted in substantially lower emission rates than the other trials with organic amendments, the seasonal averages corresponded to 15.9 mg CH4 m-2 h-1 (early rice) and 22.5 mg CH4 m-2 h-1 (late rice). Interpretation of the results can be obtained from the different potentials of these fertilizers for methane production. Based on this concept the different methane emission rates observed with organic/mineral, pure mineral and pure unfermented-organic fertilizers could directly be attributed to the different quantities of organic matter incorporated into the soil. The low methane emission from the plot treated with fermented material could be explained by a depletion of potential methane precursors resulting from the preceding fermentation. The results of this investigation provide evidence that the extensive use of specific chemical fertilizers and the application of sludge from the operation of biogas generators could lead to a net reduction of the methane emission from rice fields.

IR Studies of the Spin-Nuclear Conversion in the Vicinity of alpha α - beta β - Transition in Cryodeposited Methane Films

NASA Astrophysics Data System (ADS)

Drobyshev, A.; Aldiyarov, A.; Sokolov, D.; Shinbayeva, A.

2017-06-01

Solid methane belongs to a group of crystals containing hydrogen atoms, whose macroscopic properties are greatly influenced by the spin interaction of hydrogen nuclei. In particular, the methane molecule, which has four protons with spin I=1/2, has three total spin modifications: para-, ortho- and meta-states with three values of the total spin moments of 0, 1 and 2, respectively. Equilibrium concentrations of these modifications and relaxation times are dependent on the temperature, affecting the observed thermal properties of solid methane, such as thermal conductivity, specific heat, thermal expansion. In this paper, we attempt to explain the peculiarities of thin film growth of methane at cryogenic temperatures from the viewpoint of spin-nuclear transformations. Our observations of absorption intensity at a frequency corresponding to 1/2 of the absorption band amplitude of deformation vibrations record a step-like change in the position of the absorption band during the sample deposition process. The observed phenomenon, in our opinion, is the demonstration of spin transformations during deposition.

The effect of elevated methane pressure on methane hydrate dissociation

USGS Publications Warehouse

Circone, S.; Stern, L.A.; Kirby, S.H.

2004-01-01

Methane hydrate, equilibrated at P, T conditions within the hydrate stability field, was rapidly depressurized to 1.0 or 2.0 MPa and maintained at isobaric conditions outside its stability field, while the extent and rate of hydrate dissociation was measured at fixed, externally maintained temperatures between 250 and 288 K. The dissociation rate decreases with increasing pressure at a given temperature. Dissociation rates at 1.0 MPa parallel the complex, reproducible T-dependence previously observed between 250 and 272 K at 0.1 MPa. The lowest rates were observed near 268 K, such that >50% of the sample can persist for more than two weeks at 0.1 MPa to more than a month at 1 and 2 MPa. Varying the pressure stepwise in a single experiment increased or decreased the dissociation rate in proportion to the rates observed in the isobaric experiments, similar to the rate reversibility previously observed with stepwise changes in temperature at 0.1 MPa. At fixed P, T conditions, the rate of methane hydrate dissociation decreases monotonically with time, never achieving a steady rate. The relationship between time (t) and the extent of hydrate dissociation is empirically described by: Evolved gas (%) = A??tB where the pre-exponential term A ranges from 0 to 16% s-B and the exponent B is generally <1. Based on fits of the dissociation results to Equation 1 for the full range of temperatures (204 to 289 K) and pressures (0.1 to 2.0 MPa) investigated, the derived parameters can be used to predict the methane evolution curves for pure, porous methane hydrate to within ??5%. The effects of sample porosity and the presence of quartz sand and seawater on methane hydrate dissociation are also described using Equation 1.

Ecosystem level methane fluxes from tidal freshwater and brackish marshes of the Mississippi River Delta: Implications for coastal wetland carbon projects

USGS Publications Warehouse

Holm, Guerry O.; Perez, Brian C.; McWhorter, David E.; Krauss, Ken W.; Johnson, Darren J.; Raynie, Richard C.; Killebrew, Charles J.

2016-01-01

Sulfate from seawater inhibits methane production in tidal wetlands, and by extension, salinity has been used as a general predictor of methane emissions. With the need to reduce methane flux uncertainties from tidal wetlands, eddy covariance (EC) techniques provide an integrated methane budget. The goals of this study were to: 1) establish methane emissions from natural, freshwater and brackish wetlands in Louisiana based on EC; and 2) determine if EC estimates conform to a methane-salinity relationship derived from temperate tidal wetlands with chamber sampling. Annual estimates of methane emissions from this study were 62.3 g CH4/m2/yr and 13.8 g CH4/m2/yr for the freshwater and brackish (8–10 psu) sites, respectively. If it is assumed that long-term, annual soil carbon sequestration rates of natural marshes are ~200 g C/m2/yr (7.3 tCO2e/ha/yr), healthy brackish marshes could be expected to act as a net radiative sink, equivalent to less than one-half the soil carbon accumulation rate after subtracting methane emissions (4.1 tCO2e/ha/yr). Carbon sequestration rates would need case-by-case assessment, but the EC methane emissions estimates in this study conformed well to an existing salinity-methane model that should serve as a basis for establishing emission factors for wetland carbon offset projects.

Constraining the relationships between anaerobic oxidation of methane and sulfate reduction under in situ methane concentrations

NASA Astrophysics Data System (ADS)

Zhuang, G.; Wegener, G.; Joye, S. B.

2017-12-01

The anaerobic oxidation of methane (AOM) is an important microbial metabolism in the global carbon cycle. In marine methane seeps sediment, this process is mediated by syntrophic consortium that includes anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). Stoichiometrically in AOM methane oxidation should be coupled to sulfate reduction (SR) in a 1:1 ratio. However, weak coupling of AOM and SR in seep sediments was frequently observed from the ex situ rate measurements, and the metabolic dynamics of AOM and SR under in situ conditions remain poorly understood. Here we investigated the metabolic activity of AOM and SR with radiotracers by restoring in situ methane concentrations under pressure to constrain the in situ relationships between AOM and SR in the cold seep sediments of Gulf of Mexico as well as the sediment-free AOM enrichments cultivated from cold seep of Italian Island Elba or hydrothermal vent of Guaymas Basin5. Surprisingly, we found that AOM rates strongly exceeded those of SR when high pressures and methane concentrations were applied at seep sites of GC600 and GC767 in Gulf of Mexico. With the addition of molybdate, SR was inhibited but AOM was not affected, suggesting the potential coupling of AOM with other terminal processes. Amendments of nitrate, iron, manganese and AQDS to the SR-inhibited slurries did not stimulate or inhibit the AOM activity, indicating either those electron acceptors were not limiting for AOM in the sediments or AOM was coupled to other process (e.g., organic matter). In the ANME enrichments, higher AOM rates were also observed with the addition of high concentrations of methane (10mM and 50 mM). The tracer transfer of CO2 to methane, i.e., the back reaction of AOM, increased with increasing methane concentrations and accounted for 1%-5% of the AOM rates. AOM rates at 10 mM and 50 mM methane concentration were much higher than the SR rates, suggesting those two processes were not tightly coupled. Collectively, our results provided evidence for the possible decoupling of AOM and SR under in situconditions. This decoupling appears to be widespread in methane-rich marine sediment, motivating a wide variety of future research endeavors.

Coal-Packed Methane Biofilter for Mitigation of Green House Gas Emissions from Coal Mine Ventilation Air

PubMed Central

Limbri, Hendy; Gunawan, Cindy; Thomas, Torsten; Smith, Andrew; Scott, Jason; Rosche, Bettina

2014-01-01

Methane emitted by coal mine ventilation air (MVA) is a significant greenhouse gas. A mitigation strategy is the oxidation of methane to carbon dioxide, which is approximately twenty-one times less effective at global warming than methane on a mass-basis. The low non-combustible methane concentrations at high MVA flow rates call for a catalytic strategy of oxidation. A laboratory-scale coal-packed biofilter was designed and partially removed methane from humidified air at flow rates between 0.2 and 2.4 L min−1 at 30°C with nutrient solution added every three days. Methane oxidation was catalysed by a complex community of naturally-occurring microorganisms, with the most abundant member being identified by 16S rRNA gene sequence as belonging to the methanotrophic genus Methylocystis. Additional inoculation with a laboratory-grown culture of Methylosinus sporium, as investigated in a parallel run, only enhanced methane consumption during the initial 12 weeks. The greatest level of methane removal of 27.2±0.66 g methane m−3 empty bed h−1 was attained for the non-inoculated system, which was equivalent to removing 19.7±2.9% methane from an inlet concentration of 1% v/v at an inlet gas flow rate of 1.6 L min−1 (2.4 min empty bed residence time). These results show that low-cost coal packing holds promising potential as a suitable growth surface and contains methanotrophic microorganisms for the catalytic oxidative removal of methane. PMID:24743729

Anaerobic Co-digestion for Enhanced Renewable Energy and Green House Gas Emission Reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Navaratnam, Navaneethan; Zitomer, Daniel

2012-05-01

The need to develop renewable energy is important for replacing fossil fuel, which is limited in quantity and also tends to increase in price over time. The addition of high strength organic wastes in municipal anaerobic digesters is growing and tends to increase renewable energy production. In addition, conversion of wastes to energy significantly reduces uncontrolled greenhouse gas emissions. Co-digestion of municipal sludge with any combination of wastes can result in synergistic, antagonistic or neutral outcomes. The objectives of this study were to identify potential co-digestates, determine synergistic, antagonistic and neutral effects, determine economic benefits, quantify performance of bench scalemore » co-digesters, identify influence of co-digestion on microbial communities and implement appropriate co-digestion, if warranted, after full-scale testing. A market study was used to identify promising co-digestates. Most promising wastes were determined by biochemical methane potential (BMP) and other testing followed by a simple economic analysis. Performance was investigated using bench-scale digesters receiving synthetic primary sludge with and without co-digestates. Denaturing gradient gel electrophoresis (DGGE) and quantitative polymerase chain reaction (qPCR) analyses were performed on the gene encoding the α subunit of methyl coenzyme M reductase (mcrA) to compare methanogen communities among the digesters. One significant band contributing to the greatest difference in banding patterns was excised, cloned, amplified and sequenced. Full- scale co-digestion was conducted using the most promising co-digestate at South Shore Wastewater Reclamation Facility (Oak Creek, WI). Over 80 wastes were identified from 54 facilities within 160 km of an existing municipal digester. A simple economic comparison identified the greatest benefits for seven co-digestates. Methane production rates of two co- digester systems increased by 105% and 66% in comparison to a control system. These increases were great than anticipated based on theoretical methane production from the additional chemical oxygen demand (COD) of the co-digestates. Co-digestion of the most promising wastes with primary sludge was estimated to generate enough electricity to power more than 2500 houses. Synergistic outcomes of co-digestion may be caused by chances in microbial community resulting in more rapid methane production rate and higher specific methanogenic activities of the biomass against acetate, propionate and H2 as substrates. The presence of Methanospirillum hungatei correlated to higher SMAs in the Co-Digester 1 system. In subsequent full-scale testing, acid whey in addition to primary sludge increased methane production by 16 %, biogas methane content by 5%, methane yield per VS destroyed by 9% ( from 650 to 710 L CH4 / kg VSdestroyed ) and volatile solids removal by 20%. Co-digestion is a promising technology to increase renewable energy production and convert municipal digesters into regional renewable energy facilities.« less

Anaerobic digestion of cattail by rumen cultures.

PubMed

Hu, Zhen-Hu; Yu, Han-Qing

2006-01-01

The anaerobic digestion of aquatic plants could serve the dual roles for producing renewable energy and reducing waste. In this study, the anaerobic digestion of cattail (Typha latifolia linn), a lignocellulosic aquatic plant, by rumen microorganisms in batch cultures was investigated. At a substrate level of 12.4 g/l volatile solids (VS) and pH 6.7, maximum VS conversion of 66% was achieved within an incubation time of 125 h. However, a decrease in pH from 6.7 to 5.8 resulted in a marked reduction in VS conversion. The total volatile fatty acids (VFAs) yield was about 0.56 g/g VS digested. Acetate and propionate were the major aqueous fermentation products, while butyrate, i-butyrate and valerate were also formed in smaller quantities. Biogas that was produced was composed of carbon dioxide, methane and hydrogen. A modified Gompertz equation was developed to describe substrate consumption and product formation. The hydrolysis of insoluble components was the rate-limiting step in the anaerobic digestion of cattail.

Secondary fermentation in the runen of a sheep given a diet based on molasses.

PubMed

Rowe, J B; Loughnan, M L; Nolan, J V; Leng, R A

1979-03-01

1. The extent of conversion of acetate-carbon to carbon dioxide in the rumen of a 40 kg wether consuming 1 kg molasses/d was estimated using isotope-tracer-dilution techniques. 2. There was a high rate of conversion of acetate to CO2 (6.0 g C/d) in the rumen. There were high concentrations in the rumen of Methanosarcina approximately 6 x 10(9)/ml which represents a significant proportion of the rumen bacterial biomass. These organisms are usually found in mud and sludge and are capable of oxidizing acetate. 3. The most likely explanation of these results was that there was an extensive secondary or sludge-type fermentation occurring in the rumen which results in volatile fatty acids being converted to CO2 and methane. In similar studies with sheep given lucerne (Medicago sativa) diets, conversion of acetate-C to CO2 within the rumen was not evident. 4. It is suggested that a major effect of the presence of secondary fermentation processes in the rumen may be to reduce availability of energy nutrients to the animal, and to alter the ratio protein:energy in the absorbed nutrients.

Physical and Biological Carbon Isotope Fractionation in Methane During Gas-Push-Pull-Tests

NASA Astrophysics Data System (ADS)

Gonzalez-Gil, G.; Schroth, M. H.; Gomez, K.; Zeyer, J.

2005-12-01

Stable isotope analyses have become a common tool to assess microbially-mediated processes in subsurface environments. We investigated if stable carbon isotope analysis can be used as a tool to complement gas push-pull tests (GPPTs), a novel technique that was recently developed and tested for the in-situ quantification of CH4 oxidation in soils. During a GPPT a gas mixture containing CH4, O2 and nonreactive tracer gases is injected into the soil, where CH4 is oxidized by indigenous microorganisms. Thereafter, a blend of injected gas mixture and soil air is extracted from the same location, and CH4 oxidation is quantified from an analysis of extracted CH4 and tracer gases. To assess the magnitude of physical isotope fractionation due to molecular diffusion during GPPTs, we conducted laboratory experiments in the absence of microbial activity in a 1m-high, 1m-diameter tank filled with dry sand. During the GPPTs' extraction phase, the isotopic composition of methane was analyzed. Results indicated strong carbon isotope fractionation (>20 per mil) during GPPTs. To assess the combined effect of physical and biological isotope fractionation, numerical simulations of GPPTs were conducted in which microbial CH4 isotope fractionation was simulated using first-order rate constants and microbial kinetic isotope fractionation factors previously reported for methane oxidation in landfill environments. Results of these simulations indicated that for small CH4 oxidation rates, overall isotope fractionation in CH4 is dominated by physical fractionation. Conversely, for high CH4 oxidation rates, overall fractionation is dominated by biological fractionation. Thus, CH4 isotope fractionation data alone from a single GPPT cannot be used to assess microbial CH4 oxidation. However, biological fractionation may be quantified if physical fractionation due to diffusion is known. This can be achieved by conducting two sequential GPPTs, with microbial activity being inhibited in the second test.

Analysis of fixed bed data for the extraction of a rate mechanism for the reaction of hematite with methane

DOE PAGES

Breault, Ronald W.; Monazam, Esmail R.

2015-04-01

In this study, chemical looping combustion is a promising technology for the capture of CO 2 involving redox materials as oxygen carriers. The effects of reduction conditions, namely, temperature and fuel partial pressure on the conversion products are investigated. The experiments were conducted in a laboratory fixed-bed reactor that was operated cyclically with alternating reduction and oxidation periods. Reactions are assumed to occur in the shell surrounding the particle grains with diffusion of oxygen to the surface from the grain core. Activation energies for the shell and core reactions range from 9 to 209 kJ/mol depending on the reaction step.

Preparation and characterization of ligand types intermediate in the metal catalyzed conversion of coal to methane, methanol, and higher alkanes and alcohols. Second technical progress report, September 1, 1979-February 28, 1981

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gladysz, J. A.

1980-11-10

Mechanistic studies of anionic formyl complexes were made. The rate of decomposition of the formyl (CO)/sub 4/Mn(COC/sub 6/H/sub 5/)(CHO)/sup -/ anion as a function of counter-ion and trialkylborane present was examined. The deuterated formyl (CO)/sub 4/Mn(COC/sub 6/H/sub 5/)(CDO)/sup -/ was prepared and its decomposition was monitored by H/sup 2/ NMR. The data obtained indicate that the formyl decomposes by a disproportionative pathway not by initial CO loss, as commonly noted for formyl complexes.

Physical Conditions Associated with Widespread Seafloor Methane Discharge on the Northern US Atlantic Margin

NASA Astrophysics Data System (ADS)

Skarke, A. D.; Ruppel, C. D.; Brothers, D. S.

2014-12-01

Recent analysis of water column backscatter data and remotely operated vehicle (ROV) video imagery collected by NOAA Ship Okeanos Explorer between 2011 and 2013 revealed methane discharge from the seafloor at over 570 gas seep locations along the northern US Atlantic margin. To the best of our knowledge, such large-scale seepage has not previously been observed on a passive margin outside the Arctic or not spatially associated with a petroleum basin. This seepage has implications for the global carbon cycle, ocean chemistry (e.g., acidification), and in some cases, the climate system. Using data collected by Okeanos Explorer and NOAA's Deep Discoverer ROV, we combine water column backscatter data with video imagery and seafloor backscatter data to estimate gas flux and constrain the geoacoustic properties of the seabed at methane discharge sites. The total methane flux from the northern US Atlantic margin seeps is conservatively estimated at ~15-90 Mg y-1, based on observations of gas bubble volume, discharge rates, and discharge points per site. However, fewer than 1% of the identified seep sites have been inspected with a ROV, and this estimate is likely to be revised upward as the characteristics of the seeps are further constrained. Another important observation to emerge from our analysis is the lack of spatial correlation between seep sites and the ~5000 pockmarks mapped on the northern part of the US Atlantic margin. In this region, pockmarks, which are often easily identified by geophysical imaging of the seafloor, should not be considered potential target sites for finding undiscovered areas of seepage. Conversely, discrete patches of elevated relative seafloor acoustic backscatter amplitude do appear to be correlated with the spatial distribution of methane seeps, implying anomalous seafloor characteristic at seep loci. This finding is consistent with ROV video observations of authigenic carbonate outcrops and extensive chemosynthetic bivalve communities at seep sites, which create a seafloor substrate with higher acoustic impedance. This result suggests that seafloor acoustic reflectivity data, which are far more commonly collected and archived than water column backscatter data, might be used diagnostically to identify and constrain the distribution of seafloor locations of methane discharge.

Depth distribution of microbial production and oxidation of methane in northern boreal peatlands.

PubMed

Sundh, I; Nilsson, M; Granberg, G; Svensson, B H

1994-05-01

The depth distributions of anaerobic microbial methane production and potential aerobic microbial methane oxidation were assessed at several sites in both Sphagnum- and sedge-dominated boreal peatlands in Sweden, and compared with net methane emissions from the same sites. Production and oxidation of methane were measured in peat slurries, and emissions were measured with the closed-chamber technique. Over all eleven sites sampled, production was, on average, highest 12 cm below the depth of the average water table. On the other hand, highest potential oxidation of methane coincided with the depth of the average water table. The integrated production rate in the 0-60 cm interval ranged between 0.05 and 1.7 g CH4 m (-2) day(-) and was negatively correlated with the depth of the average water table (linear regression: r (2) = 0.50, P = 0.015). The depth-integrated potential CH4-oxidation rate ranged between 3.0 and 22.1 g CH4 m(-2) day(-1) and was unrelated to the depth of the average water table. A larger fraction of the methane was oxidized at sites with low average water tables; hence, our results show that low net emission rates in these environments are caused not only by lower methane production rates, but also by conditions more favorable for the development of CH4-oxidizing bacteria in these environments.

Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition

NASA Astrophysics Data System (ADS)

Alavi, Saman; Ripmeester, J. A.

2010-04-01

Nonequilibrium, constant energy, constant volume (NVE) molecular dynamics simulations are used to study the decomposition of methane clathrate hydrate in contact with water. Under adiabatic conditions, the rate of methane clathrate decomposition is affected by heat and mass transfer arising from the breakup of the clathrate hydrate framework and release of the methane gas at the solid-liquid interface and diffusion of methane through water. We observe that temperature gradients are established between the clathrate and solution phases as a result of the endothermic clathrate decomposition process and this factor must be considered when modeling the decomposition process. Additionally we observe that clathrate decomposition does not occur gradually with breakup of individual cages, but rather in a concerted fashion with rows of structure I cages parallel to the interface decomposing simultaneously. Due to the concerted breakup of layers of the hydrate, large amounts of methane gas are released near the surface which can form bubbles that will greatly affect the rate of mass transfer near the surface of the clathrate phase. The effects of these phenomena on the rate of methane hydrate decomposition are determined and implications on hydrate dissociation in natural methane hydrate reservoirs are discussed.

Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition.

PubMed

Alavi, Saman; Ripmeester, J A

2010-04-14

Nonequilibrium, constant energy, constant volume (NVE) molecular dynamics simulations are used to study the decomposition of methane clathrate hydrate in contact with water. Under adiabatic conditions, the rate of methane clathrate decomposition is affected by heat and mass transfer arising from the breakup of the clathrate hydrate framework and release of the methane gas at the solid-liquid interface and diffusion of methane through water. We observe that temperature gradients are established between the clathrate and solution phases as a result of the endothermic clathrate decomposition process and this factor must be considered when modeling the decomposition process. Additionally we observe that clathrate decomposition does not occur gradually with breakup of individual cages, but rather in a concerted fashion with rows of structure I cages parallel to the interface decomposing simultaneously. Due to the concerted breakup of layers of the hydrate, large amounts of methane gas are released near the surface which can form bubbles that will greatly affect the rate of mass transfer near the surface of the clathrate phase. The effects of these phenomena on the rate of methane hydrate decomposition are determined and implications on hydrate dissociation in natural methane hydrate reservoirs are discussed.

Experimental and modeling study on decomposition kinetics of methane hydrates in different media.

PubMed

Liang, Minyan; Chen, Guangjin; Sun, Changyu; Yan, Lijun; Liu, Jiang; Ma, Qinglan

2005-10-13

The decomposition kinetic behaviors of methane hydrates formed in 5 cm3 porous wet activated carbon were studied experimentally in a closed system in the temperature range of 275.8-264.4 K. The decomposition rates of methane hydrates formed from 5 cm3 of pure free water and an aqueous solution of 650 g x m(-3) sodium dodecyl sulfate (SDS) were also measured for comparison. The decomposition rates of methane hydrates in seven different cases were compared. The results showed that the methane hydrates dissociate more rapidly in porous activated carbon than in free systems. A mathematical model was developed for describing the decomposition kinetic behavior of methane hydrates below ice point based on an ice-shielding mechanism in which a porous ice layer was assumed to be formed during the decomposition of hydrate, and the diffusion of methane molecules through it was assumed to be one of the control steps. The parameters of the model were determined by correlating the decomposition rate data, and the activation energies were further determined with respect to three different media. The model was found to well describe the decomposition kinetic behavior of methane hydrate in different media.

Selective methane chlorination to methyl chloride by zeolite Y-based catalysts

NASA Astrophysics Data System (ADS)

Joo, Hyeonho; Kim, Daeho; Lim, Kwang Soo; Choi, Yong Nam; Na, Kyungsu

2018-03-01

The CH4 chlorination over Y zeolites was investigated to produce CH3Cl in a high yield. Three different catalytic systems based on Y zeolite were tested for enhancement of CH4 conversion and CH3Cl selectivity: (i) HY zeolites in H+-form having various Si/Al ratios, (ii) Pt/HY zeolites supporting Pt metal nanoparticles, (iii) Pt/NaY zeolites in Na+-form supporting Pt metal nanoparticles. The reaction was carried out using the gas mixture of CH4 and Cl2 with the respective flow rates of 15 and 10 mL min-1 at 300-350 °C using a fixed-bed reactor under a continuous gas flow condition (gas hourly space velocity = 3000 mL g-1 h-1). Above the reaction temperature of 300 °C, the CH4 chlorination is spontaneous even in the absence of catalyst, achieving 23.6% of CH4 conversion with 73.4% of CH3Cl selectivity. Under sufficient supplement of thermal energy, Cl2 molecules can be dissociated to two chlorine radicals, which triggered the C-H bond activation of CH4 molecule and thereby various chlorinated methane products (i.e., CH3Cl, CH2Cl2, CHCl3, CCl4) could be produced. When the catalysts were used under the same reaction condition, enhancement in the CH4 conversion was observed. The Pt-free HY zeolite series with varied Si/Al ratios gave around 27% of CH4 conversion, but there was a slight decrease in CH3Cl selectivity with about 64%. Despite the difference in acidity of HY zeolites having different Si/Al ratios, no prominent effect of the Si/Al ratios on the catalytic performance was observed. This suggests that the catalytic contribution of HY zeolites under the present reaction condition is not strong enough to overcome the spontaneous CH4 chlorination. When the Pt/HY zeolite catalysts were used, the CH4 conversion reached further up to 30% but the CH3Cl selectivity decreased to 60%. Such an enhancement of CH4 conversion could be attributed to the strong catalytic activity of HY and Pt/HY zeolite catalysts. However, both catalysts induced the radical cleavage of Cl2 more favorably, which ultimately decreased the CH3Cl selectivity. Such trade-off relationship between CH4 conversion and CH3Cl selectivity can be slightly broken by using Pt/NaY zeolite catalyst that is known to possess Frustrated Lewis Pairs (FLP) that are very useful for ionic cleavage of H2 to H+ and H-. Similarly, in the present work, Pt/NaY(FLP) catalysts enhanced the CH4 conversion while keeping the CH3Cl selectivity as compared to the Pt/HY zeolite catalysts.

Methane production and consumption in an active volcanic environment of Southern Italy.

PubMed

Castaldi, Simona; Tedesco, Dario

2005-01-01

Methane fluxes were measured, using closed chambers, in the Crater of Solfatara volcano, Campi Flegrei (Southern Italy), along eight transects covering areas of the crater presenting different landscape physiognomies. These included open bare areas, presenting high geothermal fluxes, and areas covered by vegetation, which developed along a gradient from the central open area outwards, in the form of maquis, grassland and woodland. Methane fluxes decreased logarithmically (from 150 to -4.5 mg CH4 m(-2)day(-1)) going from the central part of the crater (fangaia) to the forested edges, similarly to the CO2 fluxes (from 1500 g CO2 m(-2)day(-1) in the centre of the crater to almost zero flux in the woodlands). In areas characterized by high emissions, soil presented elevated temperature (up to 70 degrees C at 0-10 cm depth) and extremely low pH (down to 1.8). Conversely, in woodland areas pH was higher (between 3.7 and 5.1) and soil temperature close to air values. Soil (0-10 cm) was sampled, in two different occasions, along the eight transects, and was tested for methane oxidation capacity in laboratory. Areas covered by vegetation mostly consumed CH4 in the following order woodland>macchia>grassland. Methanotrophic activity was also measured in soil from the open bare area. Oxidation rates were comparable to those measured in the plant covered areas and were significantly correlated with field CH4 emissions. The biological mechanism of uptake was demonstrated by the absence of activity in autoclaved replicates. Thus results suggest the existence of a population of micro-organisms adapted to this extreme environment, which are able to oxidize CH4 and whose activity could be stimulated and supported by elevated concentrations of CH4.

Methane oxidation in Saanich Inlet during summer stratification

NASA Technical Reports Server (NTRS)

Ward, B. B.; Kilpatrick, K. A.; Wopat, A. E.; Minnich, E. C.; Lidstrom, M. E.

1989-01-01

Saanich Inlet, British Columbia, an fjord on the southeast coast of Vancouver Island, typically stratifies in summer, leading to the formation of an oxic-anoxic interface in the water column and accumulation of methane in the deep water. The results of methane concentration measurements in the water column of the inlet at various times throughout the summer months in 1983 are presented. Methane gradients and calculated diffusive fluxes across the oxic-anoxic interface increased as the summer progressed. Methane distribution and consumption in Saanich Inlet were studied in more detail during August 1986. At this time, a typical summer stratification with an oxic-anoxic interface around 140 m was present. At the interface, steep gradients in nutrient concentrations, bacterial abundance and methane concentration were observed. Methane oxidation was detected in the aerobic surface waters and in the anaerobic deep layer, but highest rates occurred in a narrow layer at the oxic-anoxic interface. Estimated methane oxidation rates were suffcient to consume 100 percent of the methane provided by diffusive flux from the anoxic layer. Methane oxidation is thus a mechanism whereby atmospheric flux from anoxic waters is minimized.

High-Frequency Measurements of Tree Methane Fluxes Indicate a Primary Souce Inside Tree Tissue

NASA Astrophysics Data System (ADS)

Brewer, P.; Megonigal, P.

2017-12-01

Methane emissions from the boles and shoots of living upland trees is a recent discovery with significant implications for methane budgets. Forest soil methane uptake is the greatest terrestrial methane sink, but studies have shown this may be partially for fully offset by tree methane sources. However, our ability to quantify the tree source has been hampered because the ultimate biological source(s) of methane is unclear. We measured methane fluxes from two species of living tree boles in an Eastern North American deciduous forest over 100 consecutive days. Our two hour sampling intervals allowed us to characterize diurnal patterns and seasonal dynamics. We observed wide intraspecific differences in average flux rates and diurnal dynamics, even between adjacent individuals. This and other properties of the fluxes indicates the primary methane source is likely within the tree tissues, not in soil or groundwater. Emissions of methane from trees offset approximately 10% of soil uptake on average, but at times tree fluxes were much higher. Preliminary analyses indicate the highest rates are related to tree life history, tree growth, temperature, ground-water depth, and soil moisture.

Towards Understanding the Impact of Production Techniques and Regulations on Widely Varying Methane Emission Rates in Western Basins

NASA Astrophysics Data System (ADS)

Robertson, A.; Edie, R.; Soltis, J.; Field, R. A.; Murphy, S. M.

2017-12-01

Recent airborne and mobile lab-based studies by our group and others have demonstrated that production-normalized emission rates of methane can vary dramatically between different Western basins. Three oil and gas basins that are geographically near one another and have relatively similar production characteristics (all three basins produce a mix of natural gas and condensate) have starkly different production-normalized methane emission rates at both the facility and basin-wide levels. This presentation will review previously published data on methane emissions from these basins (Denver Julesburg, Uintah, and Upper Green River) and present new measurement work supporting and expanding upon previous estimates. Beyond this, we use facility level data emissions data combined with information about the date of last upgrade to determine what impact regulations have had on methane emission rates from facilities within the basins. We also investigate what impact different approaches to production may have, in particular the role of having many individual wells processed at a central facility with high throughput is analyzed in terms of its impact on methane emissions.

Towards Understanding the Impact of Production Techniques and Regulations on Widely Varying Methane Emission Rates in Western Basins

NASA Astrophysics Data System (ADS)

Regayre, L. A.; Johnson, J. S.; Yoshioka, M.; Pringle, K.; Sexton, D.; Booth, B.; Mann, G.; Lee, L.; Bellouin, N.; Lister, G. M. S.; Johnson, C.; Johnson, B. T.; Mollard, J.; Carslaw, K. S.

2016-12-01

Recent airborne and mobile lab-based studies by our group and others have demonstrated that production-normalized emission rates of methane can vary dramatically between different Western basins. Three oil and gas basins that are geographically near one another and have relatively similar production characteristics (all three basins produce a mix of natural gas and condensate) have starkly different production-normalized methane emission rates at both the facility and basin-wide levels. This presentation will review previously published data on methane emissions from these basins (Denver Julesburg, Uintah, and Upper Green River) and present new measurement work supporting and expanding upon previous estimates. Beyond this, we use facility level data emissions data combined with information about the date of last upgrade to determine what impact regulations have had on methane emission rates from facilities within the basins. We also investigate what impact different approaches to production may have, in particular the role of having many individual wells processed at a central facility with high throughput is analyzed in terms of its impact on methane emissions.

Asparagus stem as a new lignocellulosic biomass feedstock for anaerobic digestion: increasing hydrolysis rate, methane production and biodegradability by alkaline pretreatment.

PubMed

Chen, Xiaohua; Gu, Yu; Zhou, Xuefei; Zhang, Yalei

2014-07-01

Recently, anaerobic digestion of lignocellulosic biomass for methane production has attracted considerable attention. However, there is little information regarding methane production from asparagus stem, a typical lignocellulosic biomass, by anaerobic digestion. In this study, alkaline pretreatment of asparagus stem was investigated for its ability to increase hydrolysis rate and methane production and to improve biodegradability (BD). The hydrolysis rate increased with increasing NaOH dose, due to higher removal rates of lignin and hemicelluloses. However, the optimal NaOH dose was 6% (w/w) according to the specific methane production (SMP). Under this condition, the SMP and the technical digestion time of the NaOH-treated asparagus stem were 242.3 mL/g VS and 18 days, which were 38.4% higher and 51.4% shorter than those of the untreated sample, respectively. The BD was improved from 40.1% to 55.4%. These results indicate that alkaline pretreatment could be an efficient method for increasing methane production from asparagus stem. Copyright © 2014 Elsevier Ltd. All rights reserved.

Anaerobic co-digestion of commercial food waste and dairy manure: Characterizing biochemical parameters and synergistic effects.

PubMed

Ebner, Jacqueline H; Labatut, Rodrigo A; Lodge, Jeffrey S; Williamson, Anahita A; Trabold, Thomas A

2016-06-01

Anaerobic digestion of commercial food waste is a promising alternative to landfilling commercial food waste. This study characterized 11 types of commercial food wastes and 12 co-digestion blends. Bio-methane potential, biodegradable fraction, and apparent first-order hydrolysis rate coefficients were reported based upon biochemical methane potential (BMP) assays. Food waste bio-methane potentials ranged from 165 to 496 mL CH4/g VS. Substrates high in lipids or readily degradable carbohydrates showed the highest methane production. Average bio-methane potential observed for co-digested substrates was -5% to +20% that of the bio-methane potential of the individual substrates weighted by VS content. Apparent hydrolysis rate coefficients ranged from 0.19d(-1) to 0.65d(-1). Co-digested substrates showed an accelerated apparent hydrolysis rate relative to the weighted average of individual substrate rates. These results provide a database of key bio-digestion parameters to advance modeling and utilization of commercial food waste in anaerobic digestion. Copyright © 2016 Elsevier Ltd. All rights reserved.

Partitioning Effects during Terminal Carbon and Electron Flow in Sediments of a Low-Salinity Meltwater Pond near Bratina Island, McMurdo Ice Shelf, Antarctica

PubMed Central

Mountfort, Douglas O.; Kaspar, Heinrich F.; Downes, Malcolm; Asher, Rodney A.

1999-01-01

A study of anaerobic sediments below cyanobacterial mats of a low-salinity meltwater pond called Orange Pond on the McMurdo Ice Shelf at temperatures simulating those in the summer season (<5°C) revealed that both sulfate reduction and methane production were important terminal anaerobic processes. Addition of [2-14C]acetate to sediment samples resulted in the passage of label mainly to CO2. Acetate addition (0 to 27 mM) had little effect on methanogenesis (a 1.1-fold increase), and while the rate of acetate dissimilation was greater than the rate of methane production (6.4 nmol cm−3 h−1 compared to 2.5 to 6 nmol cm−3 h−1), the portion of methane production attributed to acetate cleavage was <2%. Substantial increases in the methane production rate were observed with H2 (2.4-fold), and H2 uptake was totally accounted for by methane production under physiological conditions. Formate also stimulated methane production (twofold), presumably through H2 release mediated through hydrogen lyase. Addition of sulfate up to 50-fold the natural levels in the sediment (interstitial concentration, ∼0.3 mM) did not substantially inhibit methanogenesis, but the process was inhibited by 50-fold chloride (36 mM). No net rate of methane oxidation was observed when sediments were incubated anaerobically, and denitrification rates were substantially lower than rates for sulfate reduction and methanogenesis. The results indicate that carbon flow from acetate is coupled mainly to sulfate reduction and that methane is largely generated from H2 and CO2 where chloride, but not sulfate, has a modulating role. Rates of methanogenesis at in situ temperatures were four- to fivefold less than maximal rates found at 20°C. PMID:10584008

A model for methane production in anaerobic digestion of swine wastewater.

PubMed

Yang, Hongnan; Deng, Liangwei; Liu, Gangjin; Yang, Di; Liu, Yi; Chen, Ziai

2016-10-01

A study was conducted using a laboratory-scale anaerobic sequencing batch digester to investigate the quantitative influence of organic loading rates (OLRs) on the methane production rate during digestion of swine wastewater at temperatures between 15 °C and 35 °C. The volumetric production rate of methane (Rp) at different OLRs and temperatures was obtained. The maximum volumetric methane production rates (Rpmax) were 0.136, 0.796, 1.294, 1.527 and 1.952 LCH4 L(-1) d(-1) at corresponding organic loading rates of 1.2, 3.6, 5.6, 5.6 and 7.2 g volatile solids L(-1) d(-1), respectively, which occurred at 15, 20, 25, 30 and 35 °C, respectively. A new model was developed to describe the quantitative relationship between Rp and OLR. In addition to the maximum volumetric methane production rate (Rpmax) and the half-saturation constant (KLR) commonly used in previous models such as the modified Stover-Kincannon model and Deng model, the new model introduced a new index (KD) that denoted the speed of volumetric methane production rate approaching the maximum as a function of temperature. The new model more satisfactorily described the influence of OLR on the rate of methane production than other models as confirmed by higher determination coefficients (R(2)) (0.9717-0.9900) and lower bias between the experimental and predicted data in terms of the root mean square error and the Akaike Information Criterion. Data from other published research also validated the applicability and generality of the new kinetic model to different types of wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Enzymes and microorganisms in food industry waste processing and conversion to useful products: a review of the literature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carroad, P.A.; Wilke, C.R.

1976-12-01

Bioconversion of food processing wastes is receiving increased attention with the realization that waste components represent an available and utilizable resource for conversion to useful products. Liquid wastes are characterized as dilute streams containing sugars, starches, proteins, and fats. Solid wastes are generally cellulosic, but may contain other biopolymers. The greatest potential for economic bioconversion is represented by processes to convert cellulose to glucose, glucose to alcohol and protein, starch to invert sugar, and dilute waste streams to methane by anaerobic digestion. Microbial or enzymatic processes to accomplish these conversions are described.

Structures of microbial communities found in anaerobic batch runs that produce methane from propionic acid--Seeded from full-scale anaerobic digesters above a certain threshold.

PubMed

Kim, Woong; Shin, Seung Gu; Han, Gyuseong; Cho, Kyungjin; Hwang, Seokhwan

2015-11-20

The volatile fatty acid propionate inhibits anaerobic digestion during organic waste treatments. To examine potential microbial interactions that accelerate propionate oxidation, anaerobic digestion systems seeded with various types of anaerobic sludge were analyzed. Seed samples were collected from 10 different full-scale anaerobic reactors in South Korea. Propionate oxidation was estimated as the methane production rate per gram of propionate used per day. Two domestic sewage sludge showed the highest methane production rate values, 109.1 ± 4.2 and 74.5 ± 8.6 mL CH4/(g propionate ∙ d). A food waste recycling wastewater source exhibited the lowest methane production rate, 33.2 ± 2.6 mL CH4/(g propionate ∙ d). To investigate how the microbial community structure affected propionate oxidation, qualitative molecular analyses were carried out using denaturing gradient gel electrophoresis. Methanosaeta concilii, an aceticlastic methanogen, was detected in most batch runs. Smithella propionica, a unique propionate oxidizer and simultaneous producer of acetate, was found in domestic sewage sludge sources showing the highest methane production rate; in contrast, Desulfobulbus rhabdoformis, a sulfate reducer coupled with the consumption of acetate to be used as a precursor of methane, was observed in food waste recycling wastewater sludge source showing the lowest methane production rate. Thus, we propose that S. propionica, a syntrophic acetate producer using propionate, might cooperate with aceticlastic methanogens for high methane production during anaerobic digestion that included propionate. Copyright © 2015 Elsevier B.V. All rights reserved.

Utilization of coal mine methane for methanol and SCP production. Topical report, May 5, 1995--March 4, 1996

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1998-12-31

The feasibility of utilizing a biological process to reduce methane emissions from coal mines and to produce valuable single cell protein (SCP) and/or methanol as a product has been demonstrated. The quantities of coal mine methane from vent gas, gob wells, premining wells and abandoned mines have been determined in order to define the potential for utilizing mine gases as a resource. It is estimated that 300 MMCFD of methane is produced in the United States at a typical concentration of 0.2-0.6 percent in ventilation air. Of this total, almost 20 percent is produced from the four Jim Walter Resourcesmore » (JWR) mines, which are located in very gassy coal seams. Worldwide vent gas production is estimated at 1 BCFD. Gob gas methane production in the U.S. is estimated to be 38 MMCFD. Very little gob gas is produced outside the U.S. In addition, it is estimated that abandoned mines may generate as much as 90 MMCFD of methane. In order to make a significant impact on coal mine methane emissions, technology which is able to utilize dilute vent gases as a resource must be developed. Purification of the methane from the vent gases would be very expensive and impractical. Therefore, the process application must be able to use a dilute methane stream. Biological conversion of this dilute methane (as well as the more concentrated gob gases) to produce single cell protein (SCP) and/or methanol has been demonstrated in the Bioengineering Resources, Inc. (BRI) laboratories. SCP is used as an animal feed supplement, which commands a high price, about $0.11 per pound.« less

Refining Field Measurements of Methane Flux Rates from Abandoned Oil and Gas Wells

NASA Astrophysics Data System (ADS)

Lagron, C. S.; Kang, M.; Riqueros, N. S.; Jackson, R. B.

2015-12-01

Recent studies in Pennsylvania demonstrate the potential for significant methane emissions from abandoned oil and gas wells. A subset of tested wells was high emitting, with methane flux rates up to seven orders of magnitude greater than natural fluxes (up to 105 mg CH4/hour, or about 2.5LPM). These wells contribute disproportionately to the total methane emissions from abandoned oil and gas wells. The principles guiding the chamber design have been developed for lower flux rates, typically found in natural environments, and chamber design modifications may reduce uncertainty in flux rates associated with high-emitting wells. Kang et al. estimate errors of a factor of two in measured values based on previous studies. We conduct controlled releases of methane to refine error estimates and improve chamber design with a focus on high-emitters. Controlled releases of methane are conducted at 0.05 LPM, 0.50 LPM, 1.0 LPM, 2.0 LPM, 3.0 LPM, and 5.0 LPM, and at two chamber dimensions typically used in field measurements studies of abandoned wells. As most sources of error tabulated by Kang et al. tend to bias the results toward underreporting of methane emissions, a flux-targeted chamber design modification can reduce error margins and/or provide grounds for a potential upward revision of emission estimates.

Methane Recovery from Animal Manures The Current Opportunities Casebook

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lusk, P.

1998-09-22

Growth and concentration of the livestock industry create opportunities for the proper disposal of the large quantities of manures generated at dairy, swine, and poultry farms. Pollutants from unmanaged livestock wastes can degrade the environment, and methane emitted from decomposing manure may contribute to global climate change. One management system not only helps prevent pollution but can also convert a manure problem into a new profit center. Economic evaluations and case studies of operating systems indicate that the anaerobic digestion of livestock manures is a commercially viable conversion technology with considerable potential for providing profitable coproducts, including a cost-effective renewablemore » fuel for livestock production operations. This casebook examines some of the current opportunities for recovering methane from anaerobic digestion animal manures.« less

Effect of Sodium Dodecyl Sulfate Surfactant on Methane Hydrate Formation: A Molecular Dynamics Study.

PubMed

Choudhary, Nilesh; Hande, Vrushali R; Roy, Sudip; Chakrabarty, Suman; Kumar, Rajnish

2018-06-28

In experimental studies, it has been observed that the presence of sodium dodecyl sulfate (SDS) significantly increases the kinetics of hydrate formation and the final water-to-hydrate conversion ratio. In this study, we intend to understand the molecular mechanism behind the effect of SDS on the formation of methane hydrate through molecular dynamics simulation. Hydrate formation conditions similar to that of laboratory experiments were chosen to study hydrate growth kinetics in 1 wt % SDS solution. We also investigate the effect of interactions with isolated SDS molecules on methane hydrate growth. It was observed that the hydrophobic tail part of the SDS molecule favorably interacts with the growing hydrate surface and may occupy the partial hydrate cages while the head groups remain exposed to water.

Experimental Study on Properties of Methane Diffusion of Coal Block under Triaxial Compressive Stress

PubMed Central

Zhao, Hong-Bao

2014-01-01

Taking the standard size coal block samples defined by ISRM as research objects, both properties of methane diffusion of coal block under triaxial compressive stress and characteristic influences caused by methane pressure were systematically studied with thermo-fluid-solid coupling with triaxial servocontrolled seepage equipment of methane-containing coal. The result shows the methane diffusion property of coal block under triaxial compressive stress was shown in four-stage as follow, first is sharply reduce stage, second is hyperbolic reduce stage, third is close to a fixed value stage, fourth stage is 0. There is a special point making the reduced rate of characteristic curve of methane diffusion speed become sharply small; the influences of shape of methane diffusion speed characteristic curve caused by methane pressure are not obvious, which only is shown in numerical size of methane diffusion speed. Test time was extended required by appear of the special point makes the reduce rate of methane diffusion speed become sharply small. The fitting four-phase relation of methane diffusion of coal block under triaxial compressive stress was obtained, and the idea is proposed that influences of the fitting four-phase relation caused by methane pressure were only shown in value of fitting parameters. PMID:25531000

Methane emissions associated with the conversion of marshland to cropland and climate change on the Sanjiang Plain of Northeast China from 1950 to 2100

NASA Astrophysics Data System (ADS)

Li, T.; Huang, Y.; Zhang, W.; Yu, Y. Q.

2012-05-01

Wetland loss and climate change are known to alter regional and global methane (CH4) budgets. Over the last six decades, an extensive area of marshland has been converted to cropland on the Sanjiang Plain in Northeast China, and a significant increase in air temperature has also been observed there, while the impacts on regional CH4 budgets remain uncertain. Through model simulation, we estimated the changes in CH4 emissions associated with the conversion of marshland to cropland and climate change in this area. Model simulations indicated a significant reduction of 1.1 Tg yr-1 from the 1950s to the 2000s in regional CH4 emissions. The cumulative reduction of CH4 from 1960 to 2009 was estimated to be ~36 Tg relative to the 1950s, and marshland conversion and the climate contributed 86 % and 14 % of this change, respectively. Interannual variation in precipitation (linear trend with P > 0.2) contributed to yearly fluctuations in CH4 emissions, but the relatively lower amount of precipitation over the period 1960-2009 (47 mm yr-1 lower on average than in the 1950s) contributed ~91 % of the reduction in the area-weighted CH4 flux. Global warming at a rate of 0.3 °C per decade (P < 0.001) has increased CH4 emissions significantly since the 1990s. Relative to the mean of the 1950s, the warming-induced increase in the CH4 flux has averaged 19 kg ha-1 yr-1 over the last two decades. For the RCP 2.6, RCP 4.5, RCP 6.0 and RCP 8.5 scenarios of the fifth IPCC assessment report (AR5), the CH4 flux is predicted to increase by 36 %, 52 %, 78 % and 95 %, respectively, by the 2080s compared to 1961-1990 in response to climate warming and wetting.

Spatial Variability in Biodegradation Rates as Evidenced by Methane Production from an Aquifer

PubMed Central

Adrian, Neal R.; Robinson, Joseph A.; Suflita, Joseph M.

1994-01-01

Accurate predictions of carbon and energy cycling rates in the environment depend on sampling frequencies and on the spatial variability associated with biological activities. We examined the variability associated with anaerobic biodegradation rates at two sites in an alluvial sand aquifer polluted by municipal landfill leachate. In situ rates of methane production were measured for almost a year, using anaerobic wells installed at two sites. Methane production ranged from 0 to 560 μmol · m-2 · day-1 at one site (A), while a range of 0 to 120,000 μmol · m-2 · day-1 was measured at site B. The mean and standard deviations associated with methane production at site A were 17 and 57 μmol · m-2 · day-1, respectively. The comparable summary statistics for site B were 2,000 and 9,900 μmol · m-2 · day-1. The coefficients of variation at sites A and B were 340 and 490%, respectively. Despite these differences, the two sites had similar seasonal trends, with the maximal rate of methane production occurring in summer. However, the relative variability associated with the seasonal rates changed very little. Our results suggest that (i) two spatially distinct sites exist in the aquifer, (ii) methanogenesis is a highly variable process, (iii) the coefficient of variation varied little with the rate of methane production, and (iv) in situ anaerobic biodegradation rates are lognormally distributed. PMID:16349410

Cation-exchanged zeolites for the selective oxidation of methane to methanol

DOE PAGES

Kulkarni, Ambarish R.; Zhao, Zhi-Jian; Siahrostami, Samira; ...

2017-10-19

Motivated by the increasing availability of cheap natural gas resources, considerable experimental and computational research efforts have focused on identifying selective catalysts for the direct conversion of methane to methanol. One promising class of catalysts are cation-exchanged zeolites, which have steadily increased in popularity over the past decade. Here, in this article, we first present a broad overview of this field from a conceptual perspective, and highlight the role of theory in developing a molecular-level understanding of the reaction. Next, by performing and analyzing a large database of density functional theory (DFT) calculations for a wide range of transition metalmore » cations, zeolite topologies and active site motifs, we present a unifying picture of the methane activation process in terms of active site stability, C–H bond activation and methanol extraction. Based on the trade-offs of active site stability and reactivity, we propose a framework for identifying new, promising active site motifs in these systems. Further, we show that the high methanol selectivity arises due to the strong binding nature of the C–H activation products. Lastly, using the atomistic and mechanistic insight obtained from these analyses, we summarize the key challenges and future strategies for improving the performance of cation-exchanged zeolites for this industrially relevant conversion.« less

Cation-exchanged zeolites for the selective oxidation of methane to methanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kulkarni, Ambarish R.; Zhao, Zhi-Jian; Siahrostami, Samira

Motivated by the increasing availability of cheap natural gas resources, considerable experimental and computational research efforts have focused on identifying selective catalysts for the direct conversion of methane to methanol. One promising class of catalysts are cation-exchanged zeolites, which have steadily increased in popularity over the past decade. Here, in this article, we first present a broad overview of this field from a conceptual perspective, and highlight the role of theory in developing a molecular-level understanding of the reaction. Next, by performing and analyzing a large database of density functional theory (DFT) calculations for a wide range of transition metalmore » cations, zeolite topologies and active site motifs, we present a unifying picture of the methane activation process in terms of active site stability, C–H bond activation and methanol extraction. Based on the trade-offs of active site stability and reactivity, we propose a framework for identifying new, promising active site motifs in these systems. Further, we show that the high methanol selectivity arises due to the strong binding nature of the C–H activation products. Lastly, using the atomistic and mechanistic insight obtained from these analyses, we summarize the key challenges and future strategies for improving the performance of cation-exchanged zeolites for this industrially relevant conversion.« less

Reducing Open Cell Landfill Methane Emissions with a Bioactive Alternative Daily

DOE Office of Scientific and Technical Information (OSTI.GOV)

Helene Hilger; James Oliver; Jean Bogner

2009-03-31

Methane and carbon dioxide are formed in landfills as wastes degrade. Molecule-for-molecule, methane is about 20 times more potent than carbon dioxide at trapping heat in the earth's atmosphere, and thus, it is the methane emissions from landfills that are scrutinized. For example, if emissions composed of 60% methane and 40% carbon dioxide were changed to a mix that was 40% methane and 60% carbon dioxide, a 30% reduction in the landfill's global warming potential would result. A 10% methane, 90% carbon dioxide ratio will result in a 75% reduction in global warming potential compared to the baseline. Gas collectionmore » from a closed landfill can reduce emissions, and it is sometimes combined with a biocover, an engineered system where methane oxidizing bacteria living in a medium such as compost, convert landfill methane to carbon dioxide and water. Although methane oxidizing bacteria merely convert one greenhouse gas (methane) to another (carbon dioxide), this conversion can offer significant reductions in the overall greenhouse gas contribution, or global warming potential, associated with the landfill. What has not been addressed to date is the fact that methane can also escape from a landfill when the active cell is being filled with waste. Federal regulations require that newly deposited solid waste to be covered daily with a 6 in layer of soil or an alternative daily cover (ADC), such as a canvas tarp. The aim of this study was to assess the feasibility of immobilizing methane oxidizing bacteria into a tarp-like matrix that could be used for alternative daily cover at open landfill cells to prevent methane emissions. A unique method of isolating methanotrophs from landfill cover soil was used to create a liquid culture of mixed methanotrophs. A variety of prospective immobilization techniques were used to affix the bacteria in a tarp-like matrix. Both gel encapsulation of methanotrophs and gels with liquid cores containing methanotrophs were readily made but prone to rapid desiccation. Bacterial adsorption onto foam padding, natural sponge, and geotextile was successful. The most important factor for success appeared to be water holding capacity. Prototype biotarps made with geotextiles plus adsorbed methane oxidizing bacteria were tested for their responses to temperature, intermittent starvation, and washing (to simulate rainfall). The prototypes were mesophilic, and methane oxidation activity remained strong after one cycle of starvation but then declined with repeated cycles. Many of the cells detached with vigorous washing, but at least 30% appeared resistant to sloughing. While laboratory landfill simulations showed that four-layer composite biotarps made with two different types of geotextile could remove up to 50% of influent methane introduced at a flux rate of 22 g m{sup -2} d{sup -1}, field experiments did not yield high activity levels. Tests revealed that there were high hour-to-hour flux variations in the field, which, together with frequent rainfall events, confounded the field testing. Overall, the findings suggest that a methanotroph embedded biotarp appears to be a feasible strategy to mitigate methane emission from landfill cells, although the performance of field-tested biotarps was not robust here. Tarps will likely be best suited for spring and summer use, although the methane oxidizer population may be able to shift and adapt to lower temperatures. The starvation cycling of the tarp may require the capacity for intermittent reinoculation of the cells, although it is also possible that a subpopulation will adapt to the cycling and become dominant. Rainfall is not expected to be a major factor, because a baseline biofilm will be present to repopulate the tarp. If strong performance can be achieved and documented, the biotarp concept could be extended to include interception of other compounds beyond methane, such as volatile aromatic hydrocarbons and chlorinated solvents.« less

The use of renewable energy in the form of methane via electrolytic hydrogen generation using carbon dioxide as the feedstock

NASA Astrophysics Data System (ADS)

Hashimoto, Koji; Kumagai, Naokazu; Izumiya, Koichi; Takano, Hiroyuki; Shinomiya, Hiroyuki; Sasaki, Yusuke; Yoshida, Tetsuya; Kato, Zenta

2016-12-01

The history reveals the continuous increase in world energy consumption and carbon emissions. For prevention of intolerable global warming and complete exhaustion of fossil fuels we need complete conversion from fossil fuel consumption to renewable energy. We have been performing the research and development of global carbon dioxide recycling for more than 25 years to supply renewable energy to the world in the form of methane produced by the reaction of carbon dioxide captured from chimney with hydrogen generated electrolytically using electricity generated by renewable energy. We created the cathode and anode for electrolytic hydrogen generation and the catalyst for carbon dioxide methanation by the reaction with hydrogen. The methane formation from renewable energy will be the most convenient and efficient key technology for the use of renewable energy by storage of intermittent and fluctuating electricity generated from renewable energy and by regeneration of stable electricity. Domestic and international cooperation of companies for industrialization is in progress.

Enhancing ethanol production from thermophilic and mesophilic solid digestate using ozone combined with aqueous ammonia pretreatment.

PubMed

Wang, Dianlong; Xi, Jiang; Ai, Ping; Yu, Liang; Zhai, Hong; Yan, Shuiping; Zhang, Yanlin

2016-05-01

Pretreatment with ozone combined with aqueous ammonia was used to recover residual organic carbon from recalcitrant solid digestate for ethanol production after anaerobic digestion (AD) of rice straw. Methane yield of AD at mesophilic and thermophilic conditions, and ethanol production of solid digestate were investigated. The results showed that the methane yield at thermophilic temperature was 72.2% higher than that at mesophilic temperature under the same conditions of 24days and 17% solid concentration. And also the ethanol production efficiency of solid digestate after thermophilic process was 24.3% higher than that of solid digestate after mesophilic process. In this study, the optimal conditions for integrated methane and ethanol processes were determined as 55°C, 17% solid concentration and 24days. 58.6% of glucose conversion, 142.8g/kg of methane yield and 65.2g/kg of ethanol yield were achieved, and the highest net energy balance was calculated as 6416kJ/kg. Copyright © 2016 Elsevier Ltd. All rights reserved.

Enhanced methane yield by co-digestion of sewage sludge with micro-algae and catering waste leachate.

PubMed

2018-04-04

The co-digestion of different wastes is a promising concept to improve methane generation during anaerobic process. However, the anaerobic co-digestion of catering waste leachate with algal biomass and sewage sludge has not been studied to date. This work investigated the methane generation by the anaerobic co-digestion of different mixtures of catering waste leachate, micro-algal biomass, and sewage sludge. Co-digestion of waste mixture containing equal ratios of three substrates had 39.31% higher methane yield than anaerobic digestion of raw sludge. This was possibly due to a proliferation of methanogens during the co-digestion period induced by multi-phase digestion of different wastes with different degrees of digestibility. Therefore, co-digestion of catering waste leachate, micro-algal biomass, and sewage sludge appears to be an efficient technology for energy conversion from waste resources. The scientific application of this co-digestion technology with these three substrates may play a role in solving important environmental issues of waste management.

Bioelectrochemical enhancement of methane production from highly concentrated food waste in a combined anaerobic digester and microbial electrolysis cell.

PubMed

Park, Jungyu; Lee, Beom; Tian, Donjie; Jun, Hangbae

2018-01-01

A microbial electrolysis cell (MEC) is a promising technology for enhancing biogas production from an anaerobic digestion (AD) reactor. In this study, the effects of the MEC on the rate of methane production from food waste were examined by comparing an AD reactor with an AD reactor combined with a MEC (AD+MEC). The use of the MEC accelerated methane production and stabilization via rapid organic oxidation and rapid methanogenesis. Over the total experimental period, the methane production rate and stabilization time of the AD+MEC reactor were approximately 1.7 and 4.0 times faster than those of the AD reactor. Interestingly however, at the final steady state, the methane yields of both the reactors were similar to the theoretical maximum methane yield. Based on these results, the MEC did not increase the methane yield over the theoretical value, but accelerated methane production and stabilization by bioelectrochemical reactions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Activity and Diversity of Methanotrophic Bacteria at Methane Seeps in Eastern Lake Constance Sediments ▿

PubMed Central

Deutzmann, Jörg S.; Wörner, Susanne; Schink, Bernhard

2011-01-01

The activity and community structure of aerobic methanotrophic communities were investigated at methane seeps (pockmarks) in the littoral and profundal zones of an oligotrophic freshwater lake (Lake Constance, Germany). Measurements of potential methane oxidation rates showed that sediments inside littoral pockmarks are hot spots of methane oxidation. Potential methane oxidation rates at littoral pockmark sites exceeded the rates of the surrounding sediment by 2 orders of magnitude. Terminal restriction fragment length polymorphism (T-RFLP) analysis of the pmoA gene revealed major differences in the methanotrophic community composition between littoral pockmarks and the surrounding sediments. Clone library analysis confirmed that one distinct Methylobacter-related group dominates the community at littoral pockmarks. In profundal sediments, the differences between pockmarks and surrounding sediments were found to be less pronounced. PMID:21335392

Stable isotope tracing of anaerobic methane oxidation in the gassy sediments of Eckernfoerde Bay, German Baltic Sea

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martens, C.S.; Albert, D.B.; Alperin, M.J.

Methane concentrations in the pore waters of Eckernfoerde Bay in the German Baltic Sea generally reach gas bubble saturation values within the upper meter of the sediment column. The depth at which saturation occurs is controlled by a balance between rates of methane production, consumption (oxidation), and transport. The relative importance of anaerobic methane oxidation (AMO) in controlling dissolved and gas bubble methane distributions in the bay's sediments is indirectly revealed through methane concentration versus depth profiles, depth variations in the stable C and H isotope composition of methane, and the C isotope composition of total dissolved inorganic carbon ({Sigma}CO{submore » 2}). Direct radiotracer measurements indicate that AMO rates of over 15 mM/yr are focused at the base of the sulfate reduction zone. Diagenetic equations that describe the depth destructions of the {delta}{sup 13}C and {delta}D values of methane reproduce isotopic shifts observed throughout the methane oxidation zone and are best fit with kinetic isotope fractionation factors of 1.012 {+-} 0.001 and 1.120 {plus{underscore}minus} 0.020 respectively.« less

Influence of Different Plant Species on Methane Emissions from Soil in a Restored Swiss Wetland

PubMed Central

Bhullar, Gurbir S.; Edwards, Peter J.; Olde Venterink, Harry

2014-01-01

Plants are a major factor influencing methane emissions from wetlands, along with environmental parameters such as water table, temperature, pH, nutrients and soil carbon substrate. We conducted a field experiment to study how different plant species influence methane emissions from a wetland in Switzerland. The top 0.5 m of soil at this site had been removed five years earlier, leaving a substrate with very low methanogenic activity. We found a sixfold difference among plant species in their effect on methane emission rates: Molinia caerulea and Lysimachia vulgaris caused low emission rates, whereas Senecio paludosus, Carex flava, Juncus effusus and Typha latifolia caused relatively high rates. Centaurea jacea, Iris sibirica, and Carex davalliana caused intermediate rates. However, we found no effect of either plant biomass or plant functional groups – based on life form or productivity of the habitat – upon methane emission. Emissions were much lower than those usually reported in temperate wetlands, which we attribute to reduced concentrations of labile carbon following topsoil removal. Thus, unlike most wetland sites, methane production in this site was probably fuelled chiefly by root exudation from living plants and from root decay. We conclude that in most wetlands, where concentrations of labile carbon are much higher, these sources account for only a small proportion of the methane emitted. Our study confirms that plant species composition does influence methane emission from wetlands, and should be considered when developing measures to mitigate the greenhouse gas emissions. PMID:24586894

Determining Methane Leak Locations and Rates with a Wireless Network Composed of Low-Cost, Printed Sensors

NASA Astrophysics Data System (ADS)

Smith, C. J.; Kim, B.; Zhang, Y.; Ng, T. N.; Beck, V.; Ganguli, A.; Saha, B.; Daniel, G.; Lee, J.; Whiting, G.; Meyyappan, M.; Schwartz, D. E.

2015-12-01

We will present our progress on the development of a wireless sensor network that will determine the source and rate of detected methane leaks. The targeted leak detection threshold is 2 g/min with a rate estimation error of 20% and localization error of 1 m within an outdoor area of 100 m2. The network itself is composed of low-cost, high-performance sensor nodes based on printed nanomaterials with expected sensitivity below 1 ppmv methane. High sensitivity to methane is achieved by modifying high surface-area-to-volume-ratio single-walled carbon nanotubes (SWNTs) with materials that adsorb methane molecules. Because the modified SWNTs are not perfectly selective to methane, the sensor nodes contain arrays of variously-modified SWNTs to build diversity of response towards gases with adsorption affinity. Methane selectivity is achieved through advanced pattern-matching algorithms of the array's ensemble response. The system is low power and designed to operate for a year on a single small battery. The SWNT sensing elements consume only microwatts. The largest power consumer is the wireless communication, which provides robust, real-time measurement data. Methane leak localization and rate estimation will be performed by machine-learning algorithms built with the aid of computational fluid dynamics simulations of gas plume formation. This sensor system can be broadly applied at gas wells, distribution systems, refineries, and other downstream facilities. It also can be utilized for industrial and residential safety applications, and adapted to other gases and gas combinations.

Effects of Land-Use Conversion from Double Rice Cropping to Vegetables on Methane and Nitrous Oxide Fluxes in Southern China

PubMed Central

Yuan, Ye; Dai, Xiaoqin; Wang, Huimin; Xu, Ming; Fu, Xiaoli; Yang, Fengting

2016-01-01

Compared with CO2, methane (CH4) and nitrous oxide (N2O) are potent greenhouse gases in terms of their global warming potentials. Previous studies have indicated that land-use conversion has a significant impact on greenhouse gas emissions. However, little is known regarding the impact of converting rice (Oryza sativa L.) to vegetable fields, an increasing trend in land-use change in southern China, on CH4 and N2O fluxes. The effects of converting double rice cropping to vegetables on CH4 and N2O fluxes were examined using a static chamber method in southern China from July 2012 to July 2013. The results indicate that CH4 fluxes could reach 31.6 mg C m−2 h−1 under rice before land conversion. The cumulative CH4 emissions for fertilized and unfertilized rice were 348.9 and 321.0 kg C ha−1 yr−1, respectively. After the land conversion, the cumulative CH4 emissions were −0.4 and 1.4 kg C ha−1 yr−1 for the fertilized and unfertilized vegetable fields, respectively. Similarly, the cumulative N2O fluxes under rice were 1.27 and 0.56 kg N ha−1 yr−1 for the fertilized and unfertilized treatments before the land conversion and 19.2 and 8.5 kg N ha−1 yr−1, respectively, after the land conversion. By combining the global warming potentials (GWPs) of both gases, the overall land-use conversion effect was minor (P = 0.36) with fertilization, but the conversion reduced GWP by 63% when rice and vegetables were not fertilized. Increase in CH4 emissions increased GWP under rice compared with vegetables with non-fertilization, but increased N2O emissions compensated for similar GWPs with fertilization under rice and vegetables. PMID:27195497

Effects of Land-Use Conversion from Double Rice Cropping to Vegetables on Methane and Nitrous Oxide Fluxes in Southern China.

PubMed

Yuan, Ye; Dai, Xiaoqin; Wang, Huimin; Xu, Ming; Fu, Xiaoli; Yang, Fengting

2016-01-01

Compared with CO2, methane (CH4) and nitrous oxide (N2O) are potent greenhouse gases in terms of their global warming potentials. Previous studies have indicated that land-use conversion has a significant impact on greenhouse gas emissions. However, little is known regarding the impact of converting rice (Oryza sativa L.) to vegetable fields, an increasing trend in land-use change in southern China, on CH4 and N2O fluxes. The effects of converting double rice cropping to vegetables on CH4 and N2O fluxes were examined using a static chamber method in southern China from July 2012 to July 2013. The results indicate that CH4 fluxes could reach 31.6 mg C m-2 h-1 under rice before land conversion. The cumulative CH4 emissions for fertilized and unfertilized rice were 348.9 and 321.0 kg C ha-1 yr-1, respectively. After the land conversion, the cumulative CH4 emissions were -0.4 and 1.4 kg C ha-1 yr-1 for the fertilized and unfertilized vegetable fields, respectively. Similarly, the cumulative N2O fluxes under rice were 1.27 and 0.56 kg N ha-1 yr-1 for the fertilized and unfertilized treatments before the land conversion and 19.2 and 8.5 kg N ha-1 yr-1, respectively, after the land conversion. By combining the global warming potentials (GWPs) of both gases, the overall land-use conversion effect was minor (P = 0.36) with fertilization, but the conversion reduced GWP by 63% when rice and vegetables were not fertilized. Increase in CH4 emissions increased GWP under rice compared with vegetables with non-fertilization, but increased N2O emissions compensated for similar GWPs with fertilization under rice and vegetables.

Accelerated methanogenesis from aliphatic and aromatic hydrocarbons under iron- and sulfate-reducing conditions.

PubMed

Siegert, Michael; Cichocka, Danuta; Herrmann, Steffi; Gründger, Friederike; Feisthauer, Stefan; Richnow, Hans-Hermann; Springael, Dirk; Krüger, Martin

2011-02-01

The impact of four electron acceptors on hydrocarbon-induced methanogenesis was studied. Methanogenesis from residual hydrocarbons may enhance the exploitation of oil reservoirs and may improve bioremediation. The conditions to drive the rate-limiting first hydrocarbon-oxidizing steps for the conversion of hydrocarbons into methanogenic substrates are crucial. Thus, the electron acceptors ferrihydrite, manganese dioxide, nitrate or sulfate were added to sediment microcosms acquired from two brackish water locations. Hexadecane, ethylbenzene or 1-(13)C-naphthalene were used as model hydrocarbons. Methane was released most rapidly from incubations amended with ferrihydrite and hexadecane. Ferrihydrite enhanced only hexadecane-dependent methanogenesis. The rates of methanogenesis were negatively affected by sulfate and nitrate at concentrations of more than 5 and 1 mM, respectively. Metal-reducing Geobacteraceae and potential sulfate reducers as well as Methanosarcina were present in situ and in vitro. Ferrihydrite addition triggered the growth of Methanosarcina-related methanogens. Additionally, methane was removed concomitantly by anaerobic methanotrophy. ANME-1 and -2 methyl coenzyme M reductase genes were detected, indicating anaerobic methanotrophy as an accompanying process [Correction added 16 December after online publication: 'methyl coenzyme A' changed to 'methyl coenzyme M' in this sentence]. The experiments presented here demonstrate the feasibility of enhancing methanogenic alkane degradation by ferrihydrite or sulfate addition in different geological settings. © 2010 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Formulation of steam-methane reforming rate in Ni-YSZ porous anode of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Sugihara, Shinichi; Kawamura, Yusuke; Iwai, Hiroshi

2018-02-01

The steam-methane reforming reaction on a Ni-YSZ (yttria-stabilized zirconia) cermet was experimentally investigated under atmospheric pressure and in the temperature range from 650 to 750 °C. We examined the effects of the partial pressures of methane and steam in the supply gas on the reaction rate. The experiments were conducted with a low Ni contained Ni-YSZ cermet sheet of thickness 0.1 mm. Its porous microstructure and accompanied parameters were quantified using the FIB-SEM (focused ion beam scanning electron microscopy) technique. A power-law-type rate equation incorporating the reaction-rate-limiting conditions was obtained on the basis of the unit surface area of the Ni-pore contact surface in the cermet. The kinetics indicated a strong positive dependence on the methane partial pressure and a negative dependence on the steam partial pressure. The obtained rate equation successfully reproduced the experimental results for Ni-YSZ samples having different microstructures in the case of low methane consumption. The equation also reproduced the limiting-reaction behaviours at different temperatures.

Carbothermal Processing of Lunar Regolith Using Methane

NASA Technical Reports Server (NTRS)

Balasubramaniam, R.; Hegde, U.; Gokoglu, S.

2009-01-01

The processing of lunar regolith for the production of oxygen is a key component of the In-Situ Resource Utilization plans currently being developed by NASA. Among various candidate processes, the modeling of oxygen production by hydrogen reduction, molten salt electrolysis, and carbothermal processing are presently being pursued. In the carbothermal process, a portion of the surface of the regolith in a container is heated by exposure to a heat source such as a laser beam or a concentrated solar heat flux, so that a small zone of molten regolith is established. The molten zone is surrounded by solid regolith particles that are poor conductors of heat. A continuous flow of methane is maintained over the molten regolith zone. Our model is based on a mechanism where methane pyrolyzes when it comes in contact with the surface of the hot molten regolith to form solid carbon and hydrogen gas. Carbon is deposited on the surface of the melt, and hydrogen is released into the gas stream above the melt surface. We assume that the deposited carbon mixes in the molten regolith and reacts with metal oxides in a reduction reaction by which gaseous carbon monoxide is liberated. Carbon monoxide bubbles through the melt and is released into the gas stream. Oxygen is produced subsequently by (catalytically) processing the carbon monoxide downstream. In this paper, we discuss the development of a chemical conversion model of the carbothermal process to predict the rate of production of carbon monoxide.

Carbothermal Processing of Lunar Regolith Using Methane

NASA Technical Reports Server (NTRS)

Balasubramaniam, R.; Hegde, U.; Gokoglu, S.

2008-01-01

The processing of lunar regolith for the production of oxygen is a key component of the In-Situ Resource Utilization plans currently being developed by NASA. Among various candidate processes, the modeling of oxygen production by hydrogen reduction, molten salt electrolysis, and carbothermal processing are presently being pursued. In the carbothermal process, a portion of the surface of the regolith in a container is heated by exposure to a heat source such as a laser beam or a concentrated solar heat flux, so that a small zone of molten regolith is established. The molten zone is surrounded by solid regolith particles that are poor conductors of heat. A continuous flow of methane is maintained over the molten regolith zone. Our model is based on a mechanism where methane pyrolyzes when it comes in contact with the surface of the hot molten regolith to form solid carbon and hydrogen gas. Carbon is deposited on the surface of the melt, and hydrogen is released into the gas stream above the melt surface. We assume that the deposited carbon mixes in the molten regolith and reacts with metal oxides in a reduction reaction by which gaseous carbon monoxide is liberated. Carbon monoxide bubbles through the melt and is released into the gas stream. Oxygen is produced subsequently by (catalytically) processing the carbon monoxide downstream. In this paper, we discuss the development of a chemical conversion model of the carbothermal process to predict the rate of production of carbon monoxide.

Controls on subsurface methane fluxes and shallow gas formation in Baltic Sea sediment (Aarhus Bay, Denmark)

NASA Astrophysics Data System (ADS)

Flury, Sabine; Røy, Hans; Dale, Andrew W.; Fossing, Henrik; Tóth, Zsuzsanna; Spiess, Volkhard; Jensen, Jørn Bo; Jørgensen, Bo Barker

2016-09-01

Shallow gas accumulates in coastal marine sediments when the burial rate of reactive organic matter beneath the sulfate zone is sufficiently high and the methanogenic zone is sufficiently deep. We investigated the controls on methane production and free methane gas accumulation along a 400 m seismo-acoustic transect across a sharp transition from gas-free into gas-bearing sediment in Aarhus Bay (Denmark). Twelve gravity cores were taken, in which the pore water was analyzed for inorganic solutes while rates of organic carbon mineralization were measured experimentally by 35SO42- radiotracer method. The thickness of organic-rich Holocene mud increased from 5 to 10 m along the transect concomitant with a shallowing of the depth of the sulfate-methane transition from >4 m to 2.5 m. In spite of drastic differences in the distribution of methane and sulfate in the sediment along the transect, there were only small differences in total mineralization, and methanogenesis was only equivalent to about 1% of sulfate reduction. Shallow gas appeared where the mud thickness exceeded 8-9 m. Rates of methanogenesis increased along the transect as did the upward diffusive flux of methane. Interestingly, the increase in the sedimentation rate and Holocene mud thickness had only a modest direct effect on methanogenesis rates in deep sediments. This increase in methane flux, however, triggered a shallowing of the sulfate-methane transition which resulted in a large increase in methanogenesis at the top of the methanogenic zone. Thus, our results demonstrate a positive feedback mechanism that causes a strong enhancement of methanogenesis and explains the apparently abrupt appearance of gas when a threshold thickness of organic-rich mud is exceeded.

Estimation of waste component-specific landfill decay rates using laboratory-scale decomposition data.

PubMed

De la Cruz, Florentino B; Barlaz, Morton A

2010-06-15

The current methane generation model used by the U.S. EPA (Landfill Gas Emissions Model) treats municipal solid waste (MSW) as a homogeneous waste with one decay rate. However, component-specific decay rates are required to evaluate the effects of changes in waste composition on methane generation. Laboratory-scale rate constants, k(lab), for the major biodegradable MSW components were used to derive field-scale decay rates (k(field)) for each waste component using the assumption that the average of the field-scale decay rates for each waste component, weighted by its composition, is equal to the bulk MSW decay rate. For an assumed bulk MSW decay rate of 0.04 yr(-1), k(field) was estimated to be 0.298, 0.171, 0.015, 0.144, 0.033, 0.02, 0.122, and 0.029 yr(-1), for grass, leaves, branches, food waste, newsprint, corrugated containers, coated paper, and office paper, respectively. The effect of landfill waste diversion programs on methane production was explored to illustrate the use of component-specific decay rates. One hundred percent diversion of yard waste and food waste reduced the year 20 methane production rate by 45%. When a landfill gas collection schedule was introduced, collectable methane was most influenced by food waste diversion at years 10 and 20 and paper diversion at year 40.

40 CFR 98.356 - Data reporting requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

...) Maximum CH4 production potential (B0) used as an input to Equation II-1 or II-2 of this subpart, from Table II-1 to this subpart. (4) Methane conversion factor (MCF) used as an input to Equation II-1 or II...

40 CFR 98.356 - Data reporting requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

...) Maximum CH4 production potential (B0) used as an input to Equation II-1 or II-2 of this subpart. (4) Methane conversion factor (MCF) used as an input to Equation II-1 or II-2 of this subpart. (5) Annual mass...

40 CFR 98.356 - Data reporting requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

...) Maximum CH4 production potential (B0) used as an input to Equation II-1 or II-2 of this subpart, from Table II-1 to this subpart. (4) Methane conversion factor (MCF) used as an input to Equation II-1 or II...

40 CFR 98.356 - Data reporting requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

...) Maximum CH4 production potential (B0) used as an input to Equation II-1 or II-2 of this subpart, from Table II-1 to this subpart. (4) Methane conversion factor (MCF) used as an input to Equation II-1 or II...

Rerouting Cellular Electron Flux To Increase the Rate of Biological Methane Production

PubMed Central

Catlett, Jennie L.; Ortiz, Alicia M.

2015-01-01

Methanogens are anaerobic archaea that grow by producing methane, a gas that is both an efficient renewable fuel and a potent greenhouse gas. We observed that overexpression of the cytoplasmic heterodisulfide reductase enzyme HdrABC increased the rate of methane production from methanol by 30% without affecting the growth rate relative to the parent strain. Hdr enzymes are essential in all known methane-producing archaea. They function as the terminal oxidases in the methanogen electron transport system by reducing the coenzyme M (2-mercaptoethane sulfonate) and coenzyme B (7-mercaptoheptanoylthreonine sulfonate) heterodisulfide, CoM-S-S-CoB, to regenerate the thiol-coenzymes for reuse. In Methanosarcina acetivorans, HdrABC expression caused an increased rate of methanogenesis and a decrease in metabolic efficiency on methylotrophic substrates. When acetate was the sole carbon and energy source, neither deletion nor overexpression of HdrABC had an effect on growth or methane production rates. These results suggest that in cells grown on methylated substrates, the cell compensates for energy losses due to expression of HdrABC with an increased rate of substrate turnover and that HdrABC lacks the appropriate electron donor in acetate-grown cells. PMID:26162885

Anaerobic co-digestion of food waste and dairy manure: effects of food waste particle size and organic loading rate.

PubMed

Agyeman, Fred O; Tao, Wendong

2014-01-15

This study was to comprehensively evaluate the effects of food waste particle size on co-digestion of food waste and dairy manure at organic loading rates increased stepwise from 0.67 to 3 g/L/d of volatile solids (VS). Three anaerobic digesters were fed semi-continuously with equal VS amounts of food waste and dairy manure. Food waste was ground to 2.5 mm (fine), 4 mm (medium), and 8 mm (coarse) for the three digesters, respectively. Methane production rate and specific methane yield were significantly higher in the digester with fine food waste. Digestate dewaterability was improved significantly by reducing food waste particle size. Specific methane yield was highest at the organic loading rate of 2g VS/L/d, being 0.63, 0.56, and 0.47 L CH4/g VS with fine, medium, and coarse food waste, respectively. Methane production rate was highest (1.40-1.53 L CH4/L/d) at the organic loading rate of 3 g VS/L/d. The energy used to grind food waste was minor compared with the heating value of the methane produced. Copyright © 2013 Elsevier Ltd. All rights reserved.

Three-dimensional numerical simulations of methane gas migration from decommissioned hydrocarbon production wells into shallow aquifers

NASA Astrophysics Data System (ADS)

Roy, N.; Molson, J.; Lemieux, J.-M.; Van Stempvoort, D.; Nowamooz, A.

2016-07-01

Three-dimensional numerical simulations are used to provide insight into the behavior of methane as it migrates from a leaky decommissioned hydrocarbon well into a shallow aquifer. The conceptual model includes gas-phase migration from a leaky well, dissolution into groundwater, advective-dispersive transport and biodegradation of the dissolved methane plume. Gas-phase migration is simulated using the DuMux multiphase simulator, while transport and fate of the dissolved phase is simulated using the BIONAPL/3D reactive transport model. Methane behavior is simulated for two conceptual models: first in a shallow confined aquifer containing a decommissioned leaky well based on a monitored field site near Lindbergh, Alberta, Canada, and secondly on a representative unconfined aquifer based loosely on the Borden, Ontario, field site. The simulations show that the Lindbergh site confined aquifer data are generally consistent with a 2 year methane leak of 2-20 m3/d, assuming anaerobic (sulfate-reducing) methane oxidation and with maximum oxidation rates of 1 × 10-5 to 1 × 10-3 kg/m3/d. Under the highest oxidation rate, dissolved methane decreased from solubility (110 mg/L) to the threshold concentration of 10 mg/L within 5 years. In the unconfined case with the same leakage rate, including both aerobic and anaerobic methane oxidation, the methane plume was less extensive compared to the confined aquifer scenarios. Unconfined aquifers may therefore be less vulnerable to impacts from methane leaks along decommissioned wells. At other potential leakage sites, site-specific data on the natural background geochemistry would be necessary to make reliable predictions on the fate of methane in groundwater.

Tropical small streams are a consistent source of methane

NASA Astrophysics Data System (ADS)

Vihermaa, Leena; Waldron, Susan

2013-04-01

To date only a few studies have quantified diffusive methane emissions from headwater streams therefore the magnitude and seasonal variation of these emissions remain poorly understood. Here we present results from two Western Amazonian small streams (first and second order) in Tambopata National Reserve, Peru. Towards the end of wet season, April-May 2012, the streams were sampled using a static floating chamber to accumulate methane. Samples were drawn from the headspace twice daily over period of four days on three separate occasions. The methane concentrations were analysed using a gas chromatograph and the linear part of concentration increase used to calculate the flux rates. The streams were consistently outgassing methane. The seasonally active first order stream outgassed 6 ±2.4 nmol CH4-C m-2 s-1 and the second order stream 20 ±4.0 nmol CH4-C m-2 s-1. The latter flux rate is comparable to fluxes measured from seasonally flooded Amazonian forest in previous studies. The range measured in our streams is comparable to previous results in temperate streams and the lower end of fluxes observed in some peatland streams. The only other study on Amazonian small streams detected methane fluxes that were 100 times greater than those measured here. Depending on the density of small streams in Amazonian basin and the prevalent flux rate, the fluvial methane fluxes may constitute a significant global warming potential. Upscaling to the Amazon basin, assuming small stream density of 0.2 %, as was found at our field site, and the flux rates detected, yields an annual global warming potential equal to approximately 1.5 Mt of CO2 which is of minor importance compared to aquatic CO2-C flux of 500 Mt yr-1 from the basin. However, if the higher fluxes detected in the previous study were prevalent, the basin wide methane flux could become significant. Further studies are needed to establish the stream density in the Amazon basin and typical methane flux rates.

Review on dry reforming of methane, a potentially more environmentally-friendly approach to the increasing natural gas exploitation

PubMed Central

Lavoie, Jean-Michel

2014-01-01

With the actual growth of the natural gas industry in the US as well as the potential and availability of this non-renewable carbon source worldwide, reforming of methane gas is getting increasing attention. Methane can be used for the production of heat or electricity, as well, it can be converted to syngas, a building block that could lead to the production of liquid fuels and chemicals, a very promising pathway in light of the increasing price of oil. Amongst the different reforming techniques, dry reforming could represent a very interesting approach both to valorize a cheap source or carbon (CO2) as well as to reduce the overall carbon footprint of the increasing worldwide fossil-based methane consumption. In this short review, attention will be given to the thermodynamics of dry reforming followed by an investigation on dry reforming using heterogeneous catalyst by focusing on the most popular elements used in literature for dry reforming. Attention will as well be given to other emerging techniques that may allow countering at one point the high thermodynamic penalties that accompanies conversion of methane using carbon dioxide. PMID:25426488

Factors that control the stable carbon isotopic composition of methane produced in an anoxic marine sediment

NASA Technical Reports Server (NTRS)

Alperin, M. J.; Blair, Neal E.; Albert, D. B.; Hoehler, T. M.; Martens, C. S.

1993-01-01

The carbon isotopic composition of methane produced in anoxic marine sediment is controlled by four factors: (1) the pathway of methane formation, (2) the isotopic composition of the methanogenic precursors, (3) the isotope fractionation factors for methane production, and (4) the isotope fractionation associated with methane oxidation. The importance of each factor was evaluated by monitoring stable carbon isotope ratios in methane produced by a sediment microcosm. Methane did not accumulate during the initial 42-day period when sediment contained sulfate, indicating little methane production from 'noncompetitive' substrates. Following sulfate depletion, methane accumulation proceeded in three distinct phases. First, CO2 reduction was the dominant methanogenic pathway and the isotopic composition of the methane produced ranged from -80 to -94 per thousand. The acetate concentration increased during this phase, suggesting that acetoclastic methanogenic bacteria were unable to keep pace with acetate production. Second, acetate fermentation became the dominant methanogenic pathway as bacteria responded to elevated acetate concentrations. The methane produced during this phase was progressively enriched in C-13, reaching a maximum delta(C-13) value of -42 per thousand. Third, the acetate pool experienced a precipitous decline from greater than 5 mM to less than 20 micro-M and methane production was again dominated by CO2 reduction. The delta(C-13) of methane produced during this final phase ranged from -46 to -58 per thousand. Methane oxidation concurrent with methane production was detected throughout the period of methane accumulation, at rates equivalent to 1 to 8 percent of the gross methane production rate. Thus methane oxidation was too slow to have significantly modified the isotopic signature of methane. A comparison of microcosm and field data suggests that similar microbial interactions may control seasonal variability in the isotopic composition of methane emitted from undisturbed Cape Lookout Bight sediment.

Dry Reforming of Methane in a Gliding Arc Plasmatron: Towards a Better Understanding of the Plasma Chemistry.

PubMed

Cleiren, Emelie; Heijkers, Stijn; Ramakers, Marleen; Bogaerts, Annemie

2017-10-23

Dry reforming of methane (DRM) in a gliding arc plasmatron is studied for different CH 4 fractions in the mixture. The CO 2 and CH 4 conversions reach their highest values of approximately 18 and 10 %, respectively, at 25 % CH 4 in the gas mixture, corresponding to an overall energy cost of 10 kJ L -1 (or 2.5 eV per molecule) and an energy efficiency of 66 %. CO and H 2 are the major products, with the formation of smaller fractions of C 2 H x (x=2, 4, or 6) compounds and H 2 O. A chemical kinetics model is used to investigate the underlying chemical processes. The calculated CO 2 and CH 4 conversion and the energy efficiency are in good agreement with the experimental data. The model calculations reveal that the reaction of CO 2 (mainly at vibrationally excited levels) with H radicals is mainly responsible for the CO 2 conversion, especially at higher CH 4 fractions in the mixture, which explains why the CO 2 conversion increases with increasing CH 4 fraction. The main process responsible for CH 4 conversion is the reaction with OH radicals. The excellent energy efficiency can be explained by the non-equilibrium character of the plasma, in which the electrons mainly activate the gas molecules, and by the important role of the vibrational kinetics of CO 2 . The results demonstrate that a gliding arc plasmatron is very promising for DRM. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dry reforming of methane via plasma-catalysis: influence of the catalyst nature supported on alumina in a packed-bed DBD configuration

NASA Astrophysics Data System (ADS)

Brune, L.; Ozkan, A.; Genty, E.; Visart de Bocarmé, T.; Reniers, F.

2018-06-01

These days, the consideration of CO2 as a feedstock has become the subject of more interest. The reutilization of CO2 is already possible via cold plasma techniques operating at atmospheric pressure. A promising technology is the dielectric barrier discharge (DBD). In most cases DBDs exhibit a low energy efficiency for CO2 conversion. However, several routes can be used to increase this efficiency and hence, the product formation. One of these routes is the packed-bed DBD configuration with porous beads inside the gap of the DBD, which also allows the coupling of plasma with catalysis. Catalysts can be introduced in such a configuration to exploit the synergistic effect between plasma and catalytically active surfaces, leading to a more efficient process. In this article, the dry reforming of methane (DRM) is studied, which aims to convert both CO2 and CH4, another greenhouse gas, at the same time. The conversions and energy costs of the DRM process are investigated and compared in both the packed-bed DBD configurations containing catalysts (Co, Cu or Ni) and the classical DBD. The change in filamentary behavior is studied in detail and correlated with the obtained conversions using gas chromatography, mass spectrometry and using an oscilloscope. A characterization of the catalysts on the beads is also carried out. Both the CO2 and CH4 conversions are clearly increased with the plasma-catalysis. Moreover, CH4 conversions as high as 90% can be obtained in certain conditions with copper catalysts.

Porous Silica Sol-Gel Glasses Containing Reactive V2O5 Groups

NASA Technical Reports Server (NTRS)

Stiegman, Albert E.

1995-01-01

Porous silica sol-gel glasses into which reactive vanadium oxide functional groups incorporated exhibit number of unique characteristics. Because they bind molecules of some species both reversibly and selectively, useful as chemical sensors or indicators or as scrubbers to remove toxic or hazardous contaminants. Materials also oxidize methane gas photochemically: suggests they're useful as catalysts for conversion of methane to alcohol and for oxidation of hydrocarbons in general. By incorporating various amounts of other metals into silica sol-gel glasses, possible to synthesize new materials with broad range of new characteristics.

Study on potency of municipal solid waste conversion into renewable energy by thermal incineration and bioconversion: case study of Medan city

NASA Astrophysics Data System (ADS)

Sarah, Maya; Misran, Erni

2018-03-01

Municipal solid waste (MSW) in Medan City is facing problems either with the quantity and management of MSW. Local authority only dumped approximately 73.9% MSW in the landfill over the years. Spontaneous phenomena of methane formation in dumping site indicates the potency of MSW conversion into energy by biochemical conversion. On the contrary, the presence of plastics, woods, papers, etc. in the MSW show the potency of MSW to be treated by thermal conversion. Both thermal incineration and anaerobic digestion may convert MSW Medan City into energy. This study evaluates potency of MSW conversion into renewable energy using proximate and ultimate analysis. Overall, MSW of Medan City has the opportunities to be converted into energy by both thermal and biochemical conversion with a special requirement such as pre-dry the MSW prior incineration process and degrade organic MSW in a bioreactor.

Clean fuels from biomass

NASA Technical Reports Server (NTRS)

Hsu, Y.-Y.

1976-01-01

The paper discusses the U.S. resources to provide fuels from agricultural products, the present status of conversion technology of clean fuels from biomass, and a system study directed to determine the energy budget, and environmental and socioeconomic impacts. Conversion processes are discussed relative to pyrolysis and anaerobic fermentation. Pyrolysis breaks the cellulose molecules to smaller molecules under high temperature in the absence of oxygen, wheras anaerobic fermentation is used to convert biomass to methane by means of bacteria. Cost optimization and energy utilization are also discussed.

Biodegradation of trichloroethylene by Methylosinus trichosporium OB3b.

PubMed Central

Tsien, H C; Brusseau, G A; Hanson, R S; Waclett, L P

1989-01-01

The methanotroph Methylosinus trichosporium OB3b, a type II methanotroph, degraded trichloroethylene at rates exceeding 1.2 mmol/h per g (dry weight) following the appearance of soluble methane monooxygenase in continuous and batch cultures. Cells capable oxidizing trichloroethylene contained components of soluble methane monooxygenase as demonstrated by Western blot (immunoblot) analysis with antibodies prepared against the purified enzyme. Growth of cultures in a medium containing 0.25 microM or less copper sulfate caused derepression of the synthesis of soluble methane monooxygenase. In these cultures, the specific rates of methane and methanol oxidation did not change during growth, while trichloroethylene oxidation increased with the appearance of soluble methane monooxygenase. M. trichosporium OB3b cells that contained soluble methane monooxygenase also degraded vinyl chloride, 1,1-dichloroethylene, cis-1,2-dichloroethylene, and trans-1,2-dichloroethylene. Images PMID:2515801

Fast start-up reactor for partial oxidation of methane with electrically-heated metallic monolith catalyst

NASA Astrophysics Data System (ADS)

Jung, Heon; Yoon, Wang Lai; Lee, Hotae; Park, Jong Soo; Shin, Jang Sik; La, Howon; Lee, Jong Dae

A palladium-washcoated metallic monolith catalyst is applied to the partial oxidation of methane to syngas. This catalyst is highly active at a gas hourly space velocity (GHSV) of 100,000 h -1. The compact partial oxidation (POX) reactor equipped with both 96 cc of the metallic monolith catalyst and an electrically-heated catalyst (EHC) has a start-up time of less than 1.5 min and a syngas generation capacity of 9.5 Nm 3 h -1. The POX reaction is sustained without the need for an external heater. With the stand-alone POX reactor, the methane conversion can be increased either by preheating the reactant mixture heat-exchanged with the product gas, or by supplying a larger amount of oxygen than is necessary for the reaction stoichiometry.

The effects of leachate recirculation with supplemental water addition on methane production and waste decomposition in a simulated tropical landfill.

PubMed

Sanphoti, N; Towprayoon, S; Chaiprasert, P; Nopharatana, A

2006-10-01

In order to increase methane production efficiency, leachate recirculation is applied in landfills to increase moisture content and circulate organic matter back into the landfill cell. In the case of tropical landfills, where high temperature and evaporation occurs, leachate recirculation may not be enough to maintain the moisture content, therefore supplemental water addition into the cell is an option that could help stabilize moisture levels as well as stimulate biological activity. The objectives of this study were to determine the effects of leachate recirculation and supplemental water addition on municipal solid waste decomposition and methane production in three anaerobic digestion reactors. Anaerobic digestion with leachate recirculation and supplemental water addition showed the highest performance in terms of cumulative methane production and the stabilization period time required. It produced an accumulated methane production of 54.87 l/kg dry weight of MSW at an average rate of 0.58 l/kg dry weight/d and reached the stabilization phase on day 180. The leachate recirculation reactor provided 17.04 l/kg dry weight at a rate of 0.14l/kg dry weight/d and reached the stabilization phase on day 290. The control reactor provided 9.02 l/kg dry weight at a rate of 0.10 l/kg dry weight/d, and reached the stabilization phase on day 270. Increasing the organic loading rate (OLR) after the waste had reached the stabilization phase made it possible to increase the methane content of the gas, the methane production rate, and the COD removal. Comparison of the reactors' efficiencies at maximum OLR (5 kgCOD/m(3)/d) in terms of the methane production rate showed that the reactor using leachate recirculation with supplemental water addition still gave the highest performance (1.56 l/kg dry weight/d), whereas the leachate recirculation reactor and the control reactor provided 0.69 l/kg dry weight/d and 0.43 l/kg dry weight/d, respectively. However, when considering methane composition (average 63.09%) and COD removal (average 90.60%), slight differences were found among these three reactors.

Extreme nitrogen deposition can change methane oxidation rate in moist acidic tundra soil in Arctic regions

NASA Astrophysics Data System (ADS)

Lee, J.; Kim, J.; Kang, H.

2017-12-01

Recently, extreme nitrogen(N) deposition events are observed in Arctic regions where over 90% of the annual N deposition occurred in just a few days. Since Arctic ecosystems are typically N-limited, input of extremely high amount of N could substantially affect ecosystem processes. CH4 is a potent greenhouse gas that has 25 times greater global warming potential than CO2 over a 100-year time frame. Ammonium is known as an inhibitor of methane oxidation and nitrate also shows inhibitory effect on it in temperate ecosystems. However, effects of N addition on Arctic ecosystems are still elusive. We conducted a lab-scale incubation experiment with moist acidic tundra (MAT) soil from Council, Alaska to investigate the effect of extreme N deposition events on methane oxidation. Zero point five % methane was added to the head space to determine the potential methane oxidation rate of MAT soil. Three treatments (NH4NO3-AN, (NH4)2SO4-AS, KNO3-PN) were used to compare effects of ammonium, nitrate and salts. All treatments were added in 3 levels: 10μg N gd.w-1(10), 50μg N gd.w-1(50) and 100μg N gd.w-1(100). AN10 and AN50 increased methane oxidation rate 1.7, 6% respectively. However, AN100 shows -8.5% of inhibitory effect. In AS added samples, all 3 concentrations (AN10, AN50, AN100) stimulated methane oxidation rate with 4.7, 8.9, 4%, respectively. On the contrary, PN50 (-9%) and PN100 (-59.5%) exhibited a significant inhibitory effect. We also analyzed the microbial gene abundance and community structures of methane oxidizing bacteria using a DNA-based fingerprinting method (T-RFLP) Our study results suggest that NH4+ can stimulate methane oxidation in Arctic MAT soil, while NO3- can inhibit methane oxidation significantly.

Sulfate addition as an effective method to improve methane fermentation performance and propionate degradation in thermophilic anaerobic co-digestion of coffee grounds, milk and waste activated sludge with AnMBR.

PubMed

Li, Qian; Li, Yu-You; Qiao, Wei; Wang, Xiaochang; Takayanagi, Kazuyuki

2015-06-01

This study was conducted to investigate the effects of sulfate on propionate degradation and higher organic loading rate (OLR) achievement in a thermophilic AnMBR for 373days using coffee grounds, milk and waste activated sludge (WAS) as the co-substrate. Without the addition of sulfate, the anaerobic system failed at an OLR of 14.6g-COD/L/d, with propionate accumulating to above 2.23g-COD/L, and recovery by an alkalinity supplement was not successful. After sulfate was added into substrates at a COD/SO4(2-) ratio of 200:1 to 350:1, biogas production increased proportionally with OLR increasing from 4.06 to 15.2g-COD/L/d. Propionic acid was maintained at less than 100mg-COD/L due to the effective conversion of propionic acid to methane after the sulfate supplement was added. The long-term stable performance of the AnMBR indicated that adding sulfate was beneficial for the degradation of propionate and achieving a higher OLR under the thermophilic condition. Copyright © 2015 Elsevier Ltd. All rights reserved.

Experimental comparison of MCFC performance using three different biogas types and methane

NASA Astrophysics Data System (ADS)

Bove, Roberto; Lunghi, Piero

Biogas recovery is an environmentally friendly and cost-effective practice that is getting consensus in both the scientific and industrial community, as the growing number of projects demonstrate. The use of fuel cells as energy conversion systems increases the conversion efficiency, as well as the environmental benefits. Molten carbonate fuel cells (MCFC) operate at a temperature of about 650 °C, thus presenting a high fuel flexibility, compared to low temperature fuel cells. Aim of the present study is to compare the performance of an MCFC single cell, fuelled with different biogas types as well as methane. The biogases considered are derived from the following processes: (1) steam gasification in an entrained flow gasifier; (2) steam gasification in a duel interconnect fluidized bed gasifier; (3) biogas from an anaerobic digestion process. The performances are evaluated for different fuel utilization and current densities. The results are an essential starting point for a complete system design and demonstration.

Combined Ceria Reduction and Methane Reforming in a Solar-Driven Particle-Transport Reactor.

PubMed

Welte, Michael; Warren, Kent; Scheffe, Jonathan R; Steinfeld, Aldo

2017-09-20

We report on the experimental performance of a solar aerosol reactor for carrying out the combined thermochemical reduction of CeO 2 and reforming of CH 4 using concentrated radiation as the source of process heat. The 2 kW th solar reactor prototype utilizes a cavity receiver enclosing a vertical Al 2 O 3 tube which contains a downward gravity-driven particle flow of ceria particles, either co-current or counter-current to a CH 4 flow. Experimentation under a peak radiative flux of 2264 suns yielded methane conversions up to 89% at 1300 °C for residence times under 1 s. The maximum extent of ceria reduction, given by the nonstoichiometry δ (CeO 2-δ ), was 0.25. The solar-to-fuel energy conversion efficiency reached 12%. The syngas produced had a H 2 :CO molar ratio of 2, and its calorific value was solar-upgraded by 24% over that of the CH 4 reformed.

Combined Ceria Reduction and Methane Reforming in a Solar-Driven Particle-Transport Reactor

PubMed Central

2017-01-01

We report on the experimental performance of a solar aerosol reactor for carrying out the combined thermochemical reduction of CeO2 and reforming of CH4 using concentrated radiation as the source of process heat. The 2 kWth solar reactor prototype utilizes a cavity receiver enclosing a vertical Al2O3 tube which contains a downward gravity-driven particle flow of ceria particles, either co-current or counter-current to a CH4 flow. Experimentation under a peak radiative flux of 2264 suns yielded methane conversions up to 89% at 1300 °C for residence times under 1 s. The maximum extent of ceria reduction, given by the nonstoichiometry δ (CeO2−δ), was 0.25. The solar-to-fuel energy conversion efficiency reached 12%. The syngas produced had a H2:CO molar ratio of 2, and its calorific value was solar-upgraded by 24% over that of the CH4 reformed. PMID:28966440

Catalytic conversion of light alkanes, Phase 3. Topical report, January 1990--December 1992

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

The mission of this work is to devise a new catalyst which can be used in the first simple, economic process to convert the light alkanes in natural gas to an alcohol-rich oxygenated product which can either be used as an environmentally friendly, high-performance liquid fuel, or a precursor to a liquid hydrocarbon transportation fuel. The authors have entered the proof-of-concept stage for converting isobutane to tert butyl alcohol in a practical process and are preparing to enter proof-of-concept of a propane to isopropyl alcohol process in the near future. Methane and ethane are more refractory and thus more difficultmore » to oxidize than the C{sub 3} and C{sub 4} hydrocarbons. Nonetheless, advances made in this area indicate that further research progress could achieve the goal of their direct conversion to alcohols. Progress in Phase 3 catalytic vapor phase methane and ethane oxidation over metals in regular oxidic lattices are the subject of this topical report.« less

Long-term decline of global atmospheric ethane concentrations and implications for methane.

PubMed

Simpson, Isobel J; Sulbaek Andersen, Mads P; Meinardi, Simone; Bruhwiler, Lori; Blake, Nicola J; Helmig, Detlev; Rowland, F Sherwood; Blake, Donald R

2012-08-23

After methane, ethane is the most abundant hydrocarbon in the remote atmosphere. It is a precursor to tropospheric ozone and it influences the atmosphere's oxidative capacity through its reaction with the hydroxyl radical, ethane's primary atmospheric sink. Here we present the longest continuous record of global atmospheric ethane levels. We show that global ethane emission rates decreased from 14.3 to 11.3 teragrams per year, or by 21 per cent, from 1984 to 2010. We attribute this to decreasing fugitive emissions from ethane's fossil fuel source--most probably decreased venting and flaring of natural gas in oil fields--rather than a decline in its other major sources, biofuel use and biomass burning. Ethane's major emission sources are shared with methane, and recent studies have disagreed on whether reduced fossil fuel or microbial emissions have caused methane's atmospheric growth rate to slow. Our findings suggest that reduced fugitive fossil fuel emissions account for at least 10-21 teragrams per year (30-70 per cent) of the decrease in methane's global emissions, significantly contributing to methane's slowing atmospheric growth rate since the mid-1980s.

Effect of biochar addition on hydrogen and methane production in two-phase anaerobic digestion of aqueous carbohydrates food waste.

PubMed

Sunyoto, Nimas M S; Zhu, Mingming; Zhang, Zhezi; Zhang, Dongke

2016-11-01

Effect of biochar addition on hydrogen and methane production in two-phase anaerobic digestion of aqueous carbohydrates was studied using bench-scale bioreactors. The cultures with biochar additions were placed in 100ml reactors and incubated at 35°C and pH 5 for hydrogen production. The residual cultures were then used for methane production, incubated at 35°C and pH 7. Daily yields of hydrogen and methane and weekly yield of volatile fatty acids (VFA) were measured. The hydrogen and methane production potentials, rate and lag phases of the two phases were analysed using the Gompertz model. The results showed that biochar addition increased the maximum production rates of hydrogen by 32.5% and methane 41.6%, improved hydrogen yield by 31.0% and methane 10.0%, and shortened the lag phases in the two phases by 36.0% and 41.0%, respectively. Biochar addition also enhanced VFA generation during hydrogen production and VFA degradation in methane production. Copyright © 2016 Elsevier Ltd. All rights reserved.

Methane turnover and methanotrophic communities in arctic aquatic ecosystems of the Lena Delta, Northeast Siberia.

PubMed

Osudar, Roman; Liebner, Susanne; Alawi, Mashal; Yang, Sizhong; Bussmann, Ingeborg; Wagner, Dirk

2016-08-01

Large amounts of organic carbon are stored in Arctic permafrost environments, and microbial activity can potentially mineralize this carbon into methane, a potent greenhouse gas. In this study, we assessed the methane budget, the bacterial methane oxidation (MOX) and the underlying environmental controls of arctic lake systems, which represent substantial sources of methane. Five lake systems located on Samoylov Island (Lena Delta, Siberia) and the connected river sites were analyzed using radiotracers to estimate the MOX rates, and molecular biology methods to characterize the abundance and the community composition of methane-oxidizing bacteria (MOB). In contrast to the river, the lake systems had high variation in the methane concentrations, the abundance and composition of the MOB communities, and consequently, the MOX rates. The highest methane concentrations and the highest MOX rates were detected in the lake outlets and in a lake complex in a flood plain area. Though, in all aquatic systems, we detected both, Type I and II MOB, in lake systems, we observed a higher diversity including MOB, typical of the soil environments. The inoculation of soil MOB into the aquatic systems, resulting from permafrost thawing, might be an additional factor controlling the MOB community composition and potentially methanotrophic capacity. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

A GIS approach to conducting biogeochemical research in wetlands

NASA Technical Reports Server (NTRS)

Brannon, David P.; Irish, Gary J.

1985-01-01

A project was initiated to develop an environmental data base to address spatial aspects of both biogeochemical cycling and resource management in wetlands. Specific goals are to make regional methane flux estimates and site specific water level predictions based on man controlled water releases within a wetland study area. The project will contribute to the understanding of the Earth's biosphere through its examination of the spatial variability of methane emissions. Although wetlands are thought to be one of the primary sources for release of methane to the atmosphere, little is known about the spatial variability of methane flux. Only through a spatial analysis of methane flux rates and the environmental factors which influence such rates can reliable regional and global methane emissions be calculated. Data will be correlated and studied from Landsat 4 instruments, from a ground survey of water level recorders, precipitation recorders, evaporation pans, and supplemental gauges, and from flood gate water release; and regional methane flux estimates will be made.

Physiology, biochemistry, and specific inhibitors of CH4, NH4+, and CO oxidation by methanotrophs and nitrifiers.

PubMed Central

Bédard, C; Knowles, R

1989-01-01

Ammonia oxidizers (family Nitrobacteraceae) and methanotrophs (family Methylococcaceae) oxidize CO and CH4 to CO2 and NH4+ to NO2-. However, the relative contributions of the two groups of organisms to the metabolism of CO, CH4, and NH4+ in various environments are not known. In the ammonia oxidizers, ammonia monooxygenase, the enzyme responsible for the conversion of NH4+ to NH2OH, also catalyzes the oxidation of CH4 to CH3OH. Ammonia monooxygenase also mediates the transformation of CH3OH to CO2 and cell carbon, but the pathway by which this is done is not known. At least one species of ammonia oxidizer, Nitrosococcus oceanus, exhibits a Km for CH4 oxidation similar to that of methanotrophs. However, the highest rate of CH4 oxidation recorded in an ammonia oxidizer is still five times lower than rates in methanotrophs, and ammonia oxidizers are apparently unable to grow on CH4. Methanotrophs oxidize NH4+ to NH2OH via methane monooxygenase and NH4+ to NH2OH via methane monooxygenase and NH2OH to NO2- via an NH2OH oxidase which may resemble the enzyme found in ammonia oxidizers. Maximum rates of NH4+ oxidation are considerably lower than in ammonia oxidizers, and the affinity for NH4+ is generally lower than in ammonia oxidizers. NH4+ does not apparently support growth in methanotrophs. Both ammonia monooxygenase and methane monooxygenase oxidize CO to CO2, but CO cannot support growth in either ammonia oxidizers or methanotrophs. These organisms have affinities for CO which are comparable to those for their growth substrates and often higher than those in carboxydobacteria. The methane monooxygenases of methanotrophs exist in two forms: a soluble form and a particulate form. The soluble form is well characterized and appears unrelated to the particulate. Ammonia monooxygenase and the particulate methane monooxygenase share a number of similarities. Both enzymes contain copper and are membrane bound. They oxidize a variety of inorganic and organic compounds, and their inhibitor profiles are similar. Inhibitors thought to be specific to ammonia oxidizers have been used in environmental studies of nitrification. However, almost all of the numerous compounds found to inhibit ammonia oxidizers also inhibit methanotrophs, and most of the inhibitors act upon the monooxygenases. Many probably exert their effect by chelating copper, which is essential to the proper functioning of some monooxygenases. The lack of inhibitors specific for one or the other of the two groups of bacteria hampers the determination of their relative roles in nature. PMID:2496288

Renewable energy: energy from agricultural products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1984-06-01

This study discusses major issues concerning fuels derived from agricultural products. Agricultural products, particularly sugarcane and corn, are currently meeting major energy needs in Florida. Recent figures indicate that about 10% of the gasoline sold in Florida is ethanol enriched. This gasohol contains a 10% mix of ethanol, which is generally produced from corn or sugarcane molasses. Sugarcane residues (bagasse) also supply most of the fuel to power Florida's large sugar processing industry. These products have the potential to play an expanded role in Florida's energy future. Principle areas of interest are: Growing crops such as napier grass or harvestingmore » water hyacinths to produce methane that can be substituted for natural gas; expanded use of sugar, starch, and industrial and agricultural wastes as raw materials for ethanol production; improved efficiency in conversion processes such as anaerobic digestion and fermentation. The Institute of Food and Agricultural Sciences at the University of Florida plays a leading national role in energy crops research, while Walt Disney World is using a demonstration project to convert water hyacinths into methane. Increased use of fuels produced from agricultural products depends largely on their costs compared to other fuels. Ethanol is currently attractive because of federal and state tax incentives. The growth potential of ethanol and methane is enhanced by the ease with which they can be blended with fossil fuels and thereby utilize the current energy distribution system. Neither ethanol nor methane appear able to compete in the free market for mass distribution at present, although studies indicate that genetic engineering and more efficient conversion processes may lower prices to cost effective levels. These fuels will be most cost effective in cases where waste products are utilized and the fuel is used close to the site of production.« less

Renewable energy: energy from agricultural products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1984-06-01

This report discusses the major issues concerning fuels derived from agricultural products. Agricultural products, particularly sugarcane and corn, are currently meeting major energy needs in Florida. Recent figures indicate that about 10 percent of the gasoline sold in Florida is ethanol enriched. This gasohol contains a 10 percent mix of ethanol, which is generally produced from corn or sugarcane molasses. Sugarcane residues (bagasse) also supply most of the fuel to power Florida's large sugar processing industry. These products have the potential to play an expanded role in Florida's energy future. Principle areas of interest are: growing crops such as napiermore » grass or harvesting water hyacinths to produce methane that can be substituted for natural gas; expanded use of sugar, starch, and industrial and agricultural wastes as raw materials for ethanol production; and improved efficiency in conversion processes such as anaerobic digestion and fermentation. The Institute of Food and Agricultural Sciences at the University of Florida plays a leading national role in energy crops research, while Walt Disney World is using a demonstration project to convert water hyacinths into methane. Increased use of fuels produced from agricultural products depends largely on their costs compared to other fuels. Ethanol is currently attractive because of federal and state tax incentives. The growth potential of ethanol and methane is enhanced by the ease with which they can be blended with fossil fuels and thereby utilize the current energy distribution system. Neither ethanol nor methane appear able to compete in the free market for mass distribution at present, although studies indicate that genetic engineering and more efficient conversion processes may lower prices to cost effective levels. These fuels will be most cost effective in cases where waste products are utilized and the fuel is used close to the site of production.« less

Monocopper active site for partial methane oxidation in Cu-exchanged 8MR zeolites

DOE PAGES

Kulkarni, Ambarish R.; Zhao, Zhi -Jian; Siahrostami, Samira; ...

2016-08-17

Direct conversion of methane to methanol using oxygen is experiencing renewed interest owing to the availability of new natural gas resources. Copper-exchanged zeolites such as mordenite and ZSM-5 have shown encouraging results, and di- and tri-copper species have been suggested as active sites. Recently, small eight-membered ring (8MR) zeolites including SSZ-13, -16, and -39 have been shown to be active for methane oxidation, but the active sites and reaction mechanisms in these 8MR zeolites are not known. In this work, we use density functional theory (DFT) calculations to systematically evaluate monocopper species as active sites for the partial methane oxidationmore » reaction in Cu-exchanged SSZ-13. On the basis of kinetic and thermodynamic arguments, we suggest that [Cu IIOH] + species in the 8MR are responsible for the experimentally observed activity. Furthermore, our results successfully explain the available spectroscopic data and experimental observations including (i) the necessity of water for methanol extraction and (ii) the effect of Si/Al ratio on the catalyst activity. Monocopper species have not yet been suggested as an active site for the partial methane oxidation reaction, and our results suggest that [Cu IIOH] + active site may provide complementary routes for methane activation in zeolites in addition to the known [Cu–O–Cu] 2+ and Cu 3O 3 motifs.« less

An experimental study of perovskite-structured mixed ionic- electronic conducting oxides and membranes

NASA Astrophysics Data System (ADS)

Zeng, Pingying

In recent decades, ceramic membranes based on mixed ionic and electronic conducting (MIEC) perovskite-structured oxides have received many attentions for their applications for air separation, or as a membrane reactor for methane oxidation. While numerous perovskite oxide materials have been explored over the past two decades; there are hardly any materials with sufficient practical economic value and performance for large scale applications, which justifies continuing the search for new materials. The main purposes of this thesis study are: (1) develop several novel SrCoO3-delta based MIEC oxides, SrCoCo1-xMxO3-delta, based on which membranes exhibit excellent oxygen permeability; (2) investigate the significant effects of the species and concentration of the dopants M (metal ions with fixed valences) on the various properties of these membranes; (3) investigate the significant effects of sintering temperature on the microstructures and performance of oxygen permeation membranes; and (4) study the performance of oxygen permeation membranes as a membrane reactor for methane combustion. To stabilize the cubic phase structure of the SrCoO3-delta oxide, various amounts of scandium was doped into the B-site of SrCoO 3-delta to form a series of new perovskite oxides, SrScxCoCo 1-xO3-delta (SSCx, x = 0-0.7). The significant effects of scandium-doping concentration on the phase structure, electrical conductivity, sintering performance, thermal and structural stability, cathode performance, and oxygen permeation performance of the SSCx membranes, were systematically studied. Also for a more in-depth understanding, the rate determination steps for the oxygen transport process through the membranes were clarified by theoretical and experimental investigation. It was found that only a minor amount of scandium (5 mol%) doping into the B-site of SrCoO3-delta can effectively stabilize the cubic phase structure, and thus significantly improve the electrical conductivity and oxygen permeability of the SrCoO3-delta membrane. Among all the disk-shaped SSCx (x = 0-0.7) membranes with a thickness of 0.91 mm, both SSC0.05 and SSC0.1 exhibit the highest oxygen permeation rate of about 3.2 mL.cm-2.min-1 (STP) at 900 °C, SSC0.1 also shows excellent cathode performance for a solid oxide fuel cell. Therefore SSC0.1 is of special interest, and thus investigated regarding the performance as a membrane reactor for methane combustion. The performance was evaluated based on the results of methane conversion rates and CO 2 selectivity. Inspired by the above findings, a series of mixed-conducting perovskite oxides SrCo0.95M0.05O3-delta (SCM, M = Bi5+, Zr4+, Ce4+, Sc3+ , La3+, Y3+, Al3+, Zn 2+) were prepared to study the effects of different dopants M on the performance of SrCo0.95M0.05O3-delta. It was found that the M cations significantly affect the crystal phase structure, grain growth, membrane porosity, electrical conductivity, and the oxygen permeability of the SCM membranes. Specifically, it is postulated in this study that the formation of the cubic perovskite structure is dependent on the electron configuration in the outer orbits of M cations, which may provide theoretical guidance for future development of high oxygen permeation ceramic membranes based on the perovskite materials. To study the significant effects of grain sizes on the oxygen permeation behaviors of La0.6Sr0.4Co0.2Fe0.8O3-delta (LSCF) and SrSc0.1Co0.9O 3-delta (SSC0.1) membranes, the LSCF and SSC0.1 membranes were sintered at various temperatures to form different microstructures. Properties of these membranes with varied grain sizes were compared. Results showed that the oxygen permeation rate of the LSCF membrane increases with increasing the grain size, however, it is interesting that the oxygen permeation rate of the SSC0.1 membrane decreases with increasing the grain size. This implies that oxygen transport occurs more, however, less rapidly along grain boundaries than through the bulks in the LSCF and SSC0.1 membranes, respectively. A LSCF hollow fiber membrane and a SSC0.1 planar membrane were applied as membrane reactors for methane combustion. To improve their performances, LSCF powder and SSC0.1 powder were dip-coated and spray-coated on the permeation sides of LSCF hollow fiber membranes and SSC0.1 planar membranes, respectively. The exhaust gas components were analyzed by Gas Chromatography (GC). The performance was evaluated based on the results of methane conversion rates and CO 2 selectivity. The highest CO2 selectivity of the LSCF hollow fiber membrane and the SSC0.1 planar membrane is about 88 and 85 %, respectively. This indicates that the application of an oxygen permeation membrane as methane combustion reactor is feasible.

Investigation of Redox Metal Oxides for Carbonaceous Fuel Conversion and CO2 Capture

NASA Astrophysics Data System (ADS)

Galinsky, Nathan Lee

The chemical looping combustion (CLC) process uses metal oxides, also referred to as oxygen carriers, in a redox scheme for conversion of carbonaceous fuels into a concentrated stream of CO2 and steam while also producing heat and electricity. The unique redox scheme of CLC allows CO2 capture with minimal energy penalty. The CLC process performance greatly depends on the oxygen carrier that is chosen. To date, more than 1000 oxygen carriers have been developed for chemical-looping processes using metal oxides containing first-row transition metals. Oxygen carriers are typically mixed with an inert ceramic support to improve their overall mechanical stability and recyclability. This study focuses on design of (i) iron oxide oxygen carriers for conversion of gaseous carbonaceous fuels and (ii) development of perovskite CaMnO 3-d with improved stability and redox properties for conversion of solid fuels. Iron oxide is cheap and environmentally benign. However, it suffers from low activity with carbonaceous fuels due partially to the low ionic conductivity of iron oxides. In order to address the low activity of iron-oxide-based oxygen carriers, support addition has been shown to lower the energy barrier of oxygen anion transport within the oxygen carrier. This work adds a mixed-ionic-and-electronic-conductor (MIEC) support to iron oxide to help facilitate O2- transport inside the lattice of iron oxide. The MIEC-supported iron oxide is compared to commonly used supports including TiO2 and Al2O 3 and the pure ionic conductor support yttria-stabilized zirconia (YSZ) for conversion of different carbonaceous fuels and hydrogen. Results show that the MIEC-supported iron oxide exhibits up to 70 times higher activity than non-MIEC-supported iron oxides for methane conversion. The MIEC supported iron oxide also shows good recyclability with only minor agglomeration and carbon formation observed. The effect of support-iron oxide synergies is further investigated to understand other physical and chemical properties that lead to highly active and recyclable oxygen carriers. Perovskite and fluorite-structured MIEC supports are tested for conversion of methane. The perovskite supported iron oxides exhibit higher activity and stability resulting from the high mixed conductivity of the support. Fluorite-structured CeO2 oxygen carriers deactivated by 75% after 10 redox cycles. This deactivation was attributed to agglomeration of iron oxide. The agglomeration was determined to occur due to Fe x+ transport during the oxidation step leading to high content of Fe on the surface of the oxygen carrier. Besides the MIEC supports, inert MgAl2O4 supported iron oxide is observed to activate in methane. The activation is attributed to carbon formation causing physical degradation of the oxygen carrier and leading to higher surface area and porosity. To achieve high activity with solid fuels, chemical looping with oxygen uncoupling (CLOU) is commonly used. This process uses oxygen carriers with high PO2 that allows the oxygen carrier to release a portion of their lattice oxygen as gaseous oxygen. In turn, the gaseous oxygen can react with solid fuel particles at a higher rate than the lattice oxygen. CaMnO 3 perovskite oxygen carriers offer high potential for CLOU. However, pure CaMnO3 suffers from long-term recyclability and sulfur poisoning. Addition of A-site (Ba and Sr) and B-site (Fe, Ni, Co, Al, and V) dopants are used to improve the performance of the base CaMnO3 oxygen carrier. Sr (A-site) and Fe (B-site) exhibit high compatibility with the base perovskite structure. Both dopants observe oxygen uncoupling properties up to 200°C below that of pure CaMnO3. Additionally, the doped structures also exhibit higher stability at high temperatures (>1000°C) and during redox cycles. The doped oxygen carriers also demonstrate significantly improved activity for coal char conversion.

Performance of Ni/dolomite pellet catalyst on gas distribution from cassava rhizome gasification with a modular fixed-bed gasifier.

PubMed

Sricharoenchaikul, V; Atong, D; Sornkade, P; Nisamaneenate, J

2017-05-01

Thermal conversion of cassava rhizome was performed using a modular downdraft gasifier with the addition of Ni-based catalysts as promising tar eliminating and produced gas upgrading techniques. The activities of a synthesized 5% Ni/dolomite pellet catalyst prepared by impregnation method were investigated in a secondary reactor downstream of the gasifier. High reforming activity of the Ni/dolomite pellet catalyst on tar reduction was achieved. The conversion to H 2 and CO was improved via steam reforming of methane and char reaction with CO 2 . Moreover, the formation of CH 4 and C x H y was diminished through the tar or condensable hydrocarbon reformed on the catalyst surface. The carbon and hydrogen conversions of cassava rhizome with prepared catalyst were 83.79% and 61.78%, respectively, at an air flow rate of 1.98 m 3 /hr. At this condition, tar formation was low, while the lower heating value was 4.39 MJ/m 3 and H 2 to CO molar ratio was 1.22. Generally, the addition of a catalyst not only enhanced gas production, but also reduced tar and particulate matter generation; thus, its implementation should help lessen the pollution control requirement and cost of operation, while allowing higher quality fuel gas production.

Methane distribution and oxidation around the Lena Delta in summer 2013

NASA Astrophysics Data System (ADS)

Bussmann, Ingeborg; Hackbusch, Steffen; Schaal, Patrick; Wichels, Antje

2017-11-01

The Lena River is one of the largest Russian rivers draining into the Laptev Sea. The predicted increases in global temperatures are expected to cause the permafrost areas surrounding the Lena Delta to melt at increasing rates. This melting will result in high amounts of methane reaching the waters of the Lena and the adjacent Laptev Sea. The only biological sink that can lower methane concentrations within this system is methane oxidation by methanotrophic bacteria. However, the polar estuary of the Lena River, due to its strong fluctuations in salinity and temperature, is a challenging environment for bacteria. We determined the activity and abundance of aerobic methanotrophic bacteria by a tracer method and by the quantitative polymerase chain reaction. We described the methanotrophic population with a molecular fingerprinting method (monooxygenase intergenic spacer analysis), as well as the methane distribution (via a headspace method) and other abiotic parameters, in the Lena Delta in September 2013. The median methane concentrations were 22 nmol L-1 for riverine water (salinity (S) < 5), 19 nmol L-1 for mixed water (5 < S < 20) and 28 nmol L-1 for polar water (S > 20). The Lena River was not the source of methane in surface water, and the methane concentrations of the bottom water were mainly influenced by the methane concentration in surface sediments. However, the bacterial populations of the riverine and polar waters showed similar methane oxidation rates (0.419 and 0.400 nmol L-1 d-1), despite a higher relative abundance of methanotrophs and a higher estimated diversity in the riverine water than in the polar water. The methane turnover times ranged from 167 days in mixed water and 91 days in riverine water to only 36 days in polar water. The environmental parameters influencing the methane oxidation rate and the methanotrophic population also differed between the water masses. We postulate the presence of a riverine methanotrophic population that is limited by sub-optimal temperatures and substrate concentrations and a polar methanotrophic population that is well adapted to the cold and methane-poor polar environment but limited by a lack of nitrogen. The diffusive methane flux into the atmosphere ranged from 4 to 163 µmol m2 d-1 (median 24). The diffusive methane flux accounted for a loss of 8 % of the total methane inventory of the investigated area, whereas the methanotrophic bacteria consumed only 1 % of this methane inventory. Our results underscore the importance of measuring the methane oxidation activities in polar estuaries, and they indicate a population-level differentiation between riverine and polar water methanotrophs.

Postextraction Separation, On-Board Storage, and Catalytic Conversion of Methane in Natural Gas: A Review.

PubMed

Saha, Dipendu; Grappe, Hippolyte A; Chakraborty, Amlan; Orkoulas, Gerassimos

2016-10-12

In today's perspective, natural gas has gained considerable attention, due to its low emission, indigenous availability, and improvement in the extraction technology. Upon extraction, it undergoes several purification protocols including dehydration, sweetening, and inert rejection. Although purification is a commercially established technology, several drawbacks of the current process provide an essential impetus for developing newer separation protocols, most importantly, adsorption and membrane separation. This Review summarizes the needs of natural gas separation, gives an overview of the current technology, and provides a detailed discussion of the progress in research on separation and purification of natural gas including the benefits and drawbacks of each of the processes. The transportation sector is another growing sector of natural gas utilization, and it requires an efficient and safe on-board storage system. Compressed natural gas (CNG) and liquefied natural gas (LNG) are the most common forms in which natural gas can be stored. Adsorbed natural gas (ANG) is an alternate storage system of natural gas, which is advantageous as compared to CNG and LNG in terms of safety and also in terms of temperature and pressure requirements. This Review provides a detailed discussion on ANG along with computation predictions. The catalytic conversion of methane to different useful chemicals including syngas, methanol, formaldehyde, dimethyl ether, heavier hydrocarbons, aromatics, and hydrogen is also reviewed. Finally, direct utilization of methane onto fuel cells is also discussed.

Microbial electricity generation in rice paddy fields: recent advances and perspectives in rhizosphere microbial fuel cells.

PubMed

Kouzuma, Atsushi; Kaku, Nobuo; Watanabe, Kazuya

2014-12-01

Microbial fuel cells (MFCs) are devices that use living microbes for the conversion of organic matter into electricity. MFC systems can be applied to the generation of electricity at water/sediment interfaces in the environment, such as bay areas, wetlands, and rice paddy fields. Using these systems, electricity generation in paddy fields as high as ∼80 mW m(-2) (based on the projected anode area) has been demonstrated, and evidence suggests that rhizosphere microbes preferentially utilize organic exudates from rice roots for generating electricity. Phylogenetic and metagenomic analyses have been conducted to identify the microbial species and catabolic pathways that are involved in the conversion of root exudates into electricity, suggesting the importance of syntrophic interactions. In parallel, pot cultures of rice and other aquatic plants have been used for rhizosphere MFC experiments under controlled laboratory conditions. The findings from these studies have demonstrated the potential of electricity generation for mitigating methane emission from the rhizosphere. Notably, however, the presence of large amounts of organics in the rhizosphere drastically reduces the effect of electricity generation on methane production. Further studies are necessary to evaluate the potential of these systems for mitigating methane emission from rice paddy fields. We suggest that paddy-field MFCs represent a promising approach for harvesting latent energy of the natural world.

Optimization of pyrochlore catalysts for the dry reforming of methane

NASA Astrophysics Data System (ADS)

Polo Garzon, Felipe

The conversion of methane into syngas (a mixture of CO and H2), which can be further converted into a variety of chemicals and particularly liquid fuels, is of growing importance given recent increases in methane production world-wide. Furthermore, since using CO2 as the co-feed offers many environmental advantages, dry reforming of methane (DRM, CH4 + CO2 [special character omitted] 2CO + 2H 2) has received renewed attention. In recent years, experimentalists have shown that the Rh-substituted lanthanum zirconate pyrochlore (LRhZ) material is catalytically active for DRM, exhibits long-term thermal stability and resists deactivation; however, previous to this doctoral work, a detailed understanding of the reaction mechanism on pyrochlore catalyst surfaces was still scarce, making it difficult to optimize this material. In this work, initial computational efforts employing density functional theory (DFT) showed the plane (111) of the LRhZ crystal structure as the one catalytically active for DRM. In addition, the primary reaction pathway was identified, along with two rate determining steps (RDSs), the CH2 oxygenation step and the CHO dehydrogenation step, which lie on the CH 4 dehydrogenation/oxygenation path. The mechanistic understanding of DRM over LRhZ was further developed using steady-state isotopic transient kinetic analysis (SSITKA). Reversible adsorption of CO2 on the surface was observed, along with short surface residence times (< 0.6 s) at 650 and 800 °C, and increasing turnover frequencies with temperature. Comparisons between isotopic responses supported the DFT-derived reaction mechanism. Furthermore, isotopic transient kinetics confirmed that all metal atoms (Rh, Zr and La) on the surface are involved in the reaction mechanism, as previously pointed by DFT calculations. A DFT-based microkinetic model that predicts the reaction performance at different conditions was built. The model was validated against experimental data, showing remarkable agreement, which further confirmed the reliability of the DFT data. Computational analysis of one of the RDSs (the CHO dehydrogenation step) suggested Pd as an effective co-dopant to reduce the activation barrier of this step. This bimetallic Rh-Pd-substituted lanthanum zirconate pyrochlore (Rh-Pd-LZ) was synthesized, characterized and tested. The Rh-Pd-LZ catalyst successfully increased conversions at high temperatures while providing H 2 to CO ratios close to unity; thus fostering DRM and inhibiting the competing reaction, the reverse water gas shift reaction (RWGS, CO2 + H2 [special character omitted] CO + H2O). The Rh-Pd-LZ catalyst outperformed the initial catalyst, the LRhZ, at high temperatures.

Synthesis and characterization of Cu-Zn/TiO2 for the photocatalytic conversion of CO2 to methane.

PubMed

Rana, Adeem Ghaffar; Ahmad, Waqar; Al-Matar, Ali; Shawabkeh, Reyad; Aslam, Zaheer

2017-05-01

Different Cu-Zn/TiO 2 catalysts were synthesized by using the wet impregnation method. The prepared catalysts were used for the conversion of CO 2 into methane by photocatalysis. Various characterization techniques were used to observe the surface morphology, crystalline phase, Brunauer-Emmett-Teller (BET) surface area, presence of impregnated Cu and Zn, and functional group. Scanning electron microscope analysis showed spherical morphology, and slight agglomeration of catalyst particles was observed. BET analysis revealed that the surface area of the catalyst was decreased from 10 to 8.5 m 2 /g after impregnation of Cu and Zn over TiO 2 support. Synergetic effect of Cu and Zn over TiO 2 support (Cu 2.6 /TiO 2 , Zn 0.5 /TiO 2 and Cu 2.6 -Zn 0.5 /TiO 2 ) and the effects of Cu loading (0, 1.8, 2.1, 2.6 and 2.9 wt%) were also investigated at different feed molar ratios of H 2 /CO 2 (2:1 and 4:1). The Cu 2.6 -Zn 0.5 /TiO 2 catalyst showed a maximum conversion of 14.3% at a feed molar ratio of 4. The addition of Zn over the catalyst surface increased the conversion of CO 2 from 10% to 14.3% which might be due to synergy of Cu and Zn over TiO 2 support.

Chemical Processing in High-Pressure Aqueous Environments. 9. Process Development for Catalytic Gasification of Algae Feedstocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elliott, Douglas C.; Hart, Todd R.; Neuenschwander, Gary G.

Through the use of a metal catalyst, gasification of wet algae slurries can be accomplished with high levels of carbon conversion to gas at relatively low temperature (350 C). In a pressurized-water environment (20 MPa), near-total conversion of the organic structure of the algae to gases has been achieved in the presence of a supported ruthenium metal catalyst. The process is essentially steam reforming, as there is no added oxidizer or reagent other than water. In addition, the gas produced is a medium-heating value gas due to the synthesis of high levels of methane, as dictated by thermodynamic equilibrium. Asmore » opposed to earlier work, biomass trace components were removed by processing steps so that they did not cause processing difficulties in the fixed catalyst bed tubular reactor system. As a result, the algae feedstocks, even those with high ash contents, were much more reliably processed. High conversions were obtained even with high slurry concentrations. Consistent catalyst operation in these short-term tests suggested good stability and minimal poisoning effects. High methane content in the product gas was noted with significant carbon dioxide captured in the aqueous byproduct in combination with alkali constituents and the ammonia byproduct derived from proteins in the algae. High conversion of algae to gas products was found with low levels of byproduct water contamination and low to moderate loss of carbon in the mineral separation step.« less

Conversion of Cn-Unsaturated into Cn-2-Saturated LCFA Can Occur Uncoupled from Methanogenesis in Anaerobic Bioreactors.

PubMed

Cavaleiro, Ana J; Pereira, Maria Alcina; Guedes, Ana P; Stams, Alfons J M; Alves, M Madalena; Sousa, Diana Z

2016-03-15

Fat, oils, and grease present in complex wastewater can be readily converted to methane, but the energy potential of these compounds is not always recyclable, due to incomplete degradation of long chain fatty acids (LCFA) released during lipids hydrolysis. Oleate (C18:1) is generally the dominant LCFA in lipid-containing wastewater, and its conversion in anaerobic bioreactors results in palmitate (C16:0) accumulation. The reason why oleate is continuously converted to palmitate without further degradation via β-oxidation is still unknown. In this work, the influence of methanogenic activity in the initial conversion steps of unsaturated LCFA was studied in 10 bioreactors continuously operated with saturated or unsaturated C16- and C18-LCFA, in the presence or absence of the methanogenic inhibitor bromoethanesulfonate (BrES). Saturated Cn-2-LCFA accumulated both in the presence and absence of BrES during the degradation of unsaturated Cn-LCFA, and represented more than 50% of total LCFA. In the presence of BrES further conversion of saturated intermediates did not proceed, not even when prolonged batch incubation was applied. As the initial steps of unsaturated LCFA degradation proceed uncoupled from methanogenesis, accumulation of saturated LCFA can be expected. Analysis of the active microbial communities suggests a role for facultative anaerobic bacteria in the initial steps of unsaturated LCFA biodegradation. Understanding this role is now imperative to optimize methane production from LCFA.

Scaling methane oxidation: From laboratory incubation experiments to landfill cover field conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abichou, Tarek, E-mail: abichou@eng.fsu.edu; Mahieu, Koenraad; Chanton, Jeff

2011-05-15

Evaluating field-scale methane oxidation in landfill cover soils using numerical models is gaining interest in the solid waste industry as research has made it clear that methane oxidation in the field is a complex function of climatic conditions, soil type, cover design, and incoming flux of landfill gas from the waste mass. Numerical models can account for these parameters as they change with time and space under field conditions. In this study, we developed temperature, and water content correction factors for methane oxidation parameters. We also introduced a possible correction to account for the different soil structure under field conditions.more » These parameters were defined in laboratory incubation experiments performed on homogenized soil specimens and were used to predict the actual methane oxidation rates to be expected under field conditions. Water content and temperature corrections factors were obtained for the methane oxidation rate parameter to be used when modeling methane oxidation in the field. To predict in situ measured rates of methane with the model it was necessary to set the half saturation constant of methane and oxygen, K{sub m}, to 5%, approximately five times larger than laboratory measured values. We hypothesize that this discrepancy reflects differences in soil structure between homogenized soil conditions in the lab and actual aggregated soil structure in the field. When all of these correction factors were re-introduced into the oxidation module of our model, it was able to reproduce surface emissions (as measured by static flux chambers) and percent oxidation (as measured by stable isotope techniques) within the range measured in the field.« less

The complex relationships between methane emissions and water table at an ombrotrophic bog

NASA Astrophysics Data System (ADS)

Humphreys, Elyn; Roulet, Nigel; Moore, Tim

2017-04-01

Broad spatial and temporal variations in methane emissions from peatlands have been related to many variables including water table position, temperature and vegetation characteristics and functioning. In general, wetter peatlands tend to have greater methane emissions. However, over shorter periods of time and space, the relationship between water table and methane emissions can reverse, show hysteresis or be absent entirely. These relationships are investigated at the Mer Bleue Bog, a temperate ombrotrophic bog near Ottawa, Canada. Six years of concurrent growing season eddy covariance and automated chamber fluxes reveal the expected broad patterns. During the wettest growing season, the water table remained within 40 cm of the bog's hummock surfaces. Methane emissions were upwards of 20 to 45 mg C m-2 d-1 and exceeded the emission rates from two drier growing seasons which saw periods where the water table dropped to nearly 80 cm below the hummock surface. In those periods, methane emission rates declined to about 5 mg C m-2 d-1 or less. Lawn plots with aerenchymatous Eriophorum vegetation and high water tables had greatest emissions (exceeding 200 mg C m-2 d-1) compared to hummock plots vegetated by ericaceous shrubs, which had emissions rates similar to those measured by eddy covariance. However, within a growing season, hysteresis and inverse relationships between water table and methane emissions were observed at both ecosystem and chamber plot scales. These included periods between rainfall events where methane emissions increased while the water table deepened. The potential roles of methane production, consumption, storage and transport processes on these patterns will be discussed.

Catalytic Conversion of Cellulosic Biomass or Algal Biomass plus Methane to Drop in Hydrocarbon Fuels and Chemicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marker, Terry; Roberts, Michael; Linck, Martin

The goal of this Bioincubator Project was to improve the pyrolysis of biomass through the use of methane. Our initial concept was to use methane as a fluidizing gas with a hydrogen transfer catalyst. The results of the experiments did show that methane as a fluidizing gas, with a hydrogen transfer catalyst, does enhance catalytic pyrolysis over that which is achieved with an inert fluidizing gas. Using methane as a fluidizing gas, with a hydrogen transfer catalyst, consistently produced better products with lower oxygen content than the products produced when an inert gas was used. These improvements were also consistentmore » with the results obtained through pure component testing as well. However, the improvement was too small to justify any significant expense. The addition of hydrogen with a hydrogen transfer catalyst consistently showed a much greater, more significant effect than methane. This indicates that hydropyrolysis is a more effective approach to improved catalytic pyrolysis than methane addition. During the course of this project, another way to significantly increase biogenic liquid yields from pyrolysis through the use of methane was discovered. We discovered a remarkably stable CO2/steam reforming catalyst which directly makes a 2:1 H2/CO synthesis gas from the CO, CO2, methane, ethane and propane product gas from integrated hydropyrolysis and hydroconversion (IH2®). The biogenic synthesis gas can then be converted to liquid hydrocarbons using Fischer Tropsch. The hydrogen for the IH2 unit would then be provided through the use of added methane. By utilizing the biogenic gas to make liquids, 40% more biogenic liquid hydrocarbons can be made from wood, thereby increasing liquid yields from IH2 from 86GPT to 126GPT. It also simplifies the hydrogen plant since no CO or CO2 removal is required.« less

Soil methane and CO2 fluxes in rainforest and rubber plantations

NASA Astrophysics Data System (ADS)

Lang, Rong; Blagodatsky, Sergey; Goldberg, Stefanie; Xu, Jianchu

2017-04-01

Expansion of rubber plantations in South-East Asia has been a land use transformation trend leading to losses of natural forest cover in the region. Besides impact on ecosystem carbon stocks, this conversion influences the dynamics of greenhouse gas fluxes from soil driven by microbial activity, which has been insufficiently studied. Aimed to understand how land use change affects the soil CO2 and CH4 fluxes, we measured surface gas fluxes, gas concentration gradient, and 13C signature in CH4 and soil organic matter in profiles in a transect in Xishuangbanna, including a rainforest site and three rubber plantation sites with age gradient. Gas fluxes were measured by static chamber method and open chamber respiration system. Soil gases were sampled from installed gas samplers at 5, 10, 30, and 75cm depth at representative time in dry and rainy season. The soil CO2 flux was comparable in rainforest and old rubber plantations, while young rubber plantation had the lowest rate. Total carbon content in the surface soil well explained the difference of soil CO2 flux between sites. All sites were CH4 sinks in dry season and uptake decreased in the order of rainforest, old rubber plantations and young rubber plantation. From dry season to rainy season, CH4 consumption decreased with increasing CH4 concentration in the soil profile at all depths. The enrichment of methane by 13CH4 shifted towards to lowerδ13C, being the evidence of enhanced CH4 production process while net surface methane flux reflected the consumption in wet condition. Increment of CH4 concentration in the profile from dry to rainy season was higher in old rubber plantation compared to rainforest, while the shifting of δ13CH4 was larger in rainforest than rubber sites. Turnover rates of soil CO2 and CH4 suggested that the 0-5 cm surface soil was the most active layer for gaseous carbon exchange. δ13C in soil organic matter and soil moisture increased from rainforest, young rubber plantation to old rubber plantations. Conversion the forest into rubber plantation decreased soil respiration in young plantation and it recovered during rubber development. However, the CH4consumption by tropical upland forest soil decreased in converted rubber plantations of all ages, with more decrement in old plantation. Change forest into rubber plantations weakened the soil function as CH4 sink.

Theoretical Insights into Direct Methane to Methanol Conversion over Supported Dicopper Oxo Nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doan, Hieu A.; Li, Zhanyong; Farha, Omar K.

In this study, the prospect of using copper oxide nanoclusters grown by atomic layer deposition on a porphyrin support for selective oxidation of methane to methanol was examined by means of density functional theory (DFT) calculations. Ab initio thermodynamic analysis indicates that an active site in the form of Cu(μ-O)Cu can be stabilized by activation in O2 at 465K. Furthermore, a moderate methane activation energy barrier (Ea=54kJ/mol) is predicted, and the hydrogen abstraction activity of the active site could be attributed to the radical character of the bridging oxygen. Methanol extraction in this system is limited by a thermodynamic barriermore » to desorption of ΔG=57kJ/mol at 473K; however, desorption can be facilitated by the addition of water in a “stepped conversion” process. Overall, our results indicate similar activity between porphyrin-supported copper oxide nanoclusters and existing Cu-exchanged zeolites and provide a computational proof-of-concept for utilizing functionalized organic linkers in metal-organic frameworks (MOFs) for selective oxidation of methane to methanol.« less

Characterisation of water hyacinth with microwave-heated alkali pretreatment for enhanced enzymatic digestibility and hydrogen/methane fermentation.

PubMed

Lin, Richen; Cheng, Jun; Song, Wenlu; Ding, Lingkan; Xie, Binfei; Zhou, Junhu; Cen, Kefa

2015-04-01

Microwave-heated alkali pretreatment (MAP) was investigated to improve enzymatic digestibility and H2/CH4 production from water hyacinth. SEM revealed that MAP deconstructed the lignocellulose matrix and swelled the surfaces of water hyacinth. XRD indicated that MAP decreased the crystallinity index from 16.0 to 13.0 because of cellulose amorphisation. FTIR indicated that MAP effectively destroyed the lignin structure and disrupted the crystalline cellulose to reduce crystallinity. The reducing sugar yield of 0.296 g/gTVS was achieved at optimal hydrolysis conditions (microwave temperature = 190°C, time = 10 min, and cellulase dosage = 5 wt%). The sequentially fermentative hydrogen and methane yields from water hyacinth with MAP and enzymatic hydrolysis were increased to 63.9 and 172.5 mL/gTVS, respectively. The energy conversion efficiency (40.0%) in the two-stage hydrogen and methane cogeneration was lower than that (49.5%) in the one-stage methane production (237.4 mL/gTVS) from water hyacinth with MAP and enzymatic hydrolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.

Theoretical Insights into Direct Methane to Methanol Conversion over Supported Dicopper Oxo Nanoclusters

DOE PAGES

Doan, Hieu A.; Li, Zhanyong; Farha, Omar K.; ...

2018-04-08

In this study, the prospect of using copper oxide nanoclusters grown by atomic layer deposition on a porphyrin support for selective oxidation of methane to methanol was examined by means of density functional theory (DFT) calculations. Ab initio thermodynamic analysis indicates that an active site in the form of Cu(μ-O)Cu can be stabilized by activation in O2 at 465K. Furthermore, a moderate methane activation energy barrier (Ea=54kJ/mol) is predicted, and the hydrogen abstraction activity of the active site could be attributed to the radical character of the bridging oxygen. Methanol extraction in this system is limited by a thermodynamic barriermore » to desorption of ΔG=57kJ/mol at 473K; however, desorption can be facilitated by the addition of water in a “stepped conversion” process. Overall, our results indicate similar activity between porphyrin-supported copper oxide nanoclusters and existing Cu-exchanged zeolites and provide a computational proof-of-concept for utilizing functionalized organic linkers in metal-organic frameworks (MOFs) for selective oxidation of methane to methanol.« less

A laboratory study of anaerobic oxidation of methane in the presence of methane hydrate

NASA Astrophysics Data System (ADS)

Solem, R.; Bartlett, D.; Kastner, M.; Valentine, D.

2003-12-01

In order to mimic and study the process of anaerobic methane oxidation in methane hydrate regions we developed four high-pressure anaerobic bioreactors, designed to incubate environmental sediment samples, and enrich for populations of microbes associated with anaerobic methane oxidation (AMO). We obtained sediment inocula from a bacterial mat at the southern Hydrate Ridge, Cascadia, having cell counts approaching 1010 cells/cc. Ultimately, our goal is to produce an enriched culture of these microbes for characterization of the biochemical processes and chemical fluxes involved, as well as the unique adaptations required for, AMO. Molecular phylogenetic information along with results from fluorescent in situ hybridization indicate that consortia of Archaea and Bacteria are present which are related to those previously described for marine sediment AMO environments. Using a medium of enriched seawater and sediment in a 3:1 ratio, the system was incubated at 4° C under 43 atm of methane pressure; the temperature and pressure were kept constant. We have followed the reactions for seven months, particularly the vigorous consumption rates of dissolved sulfate and alkalinity production, as well as increases in HS-, and decreases in Ca concentrations. We also monitored the dissolved inorganic C (DIC) δ 13C values. The data were reproduced, and indicated that the process is extremely sensitive to changes in methane pressure. The rates of decrease in sulfate and increase in alkalinity concentrations were complimentary and showed considerable linearity with time. When the pressure in the reactor was decreased below the methane hydrate stability field, following the methane hydrate dissociation, sulfate reduction abruptly decreased. When the pressure was restored all the reactions returned to their previous rates. Much of the methane oxidation activity in the reactor is believed to occur in association with the methane hydrate. Upon the completion of one of the experiments, the chamber methane hydrate, liquid phase, and sediment were separated. FISH analyses of the dissociated hydrate fluid indicate a significant presence of Archaea in or on the hydrate. The cell densities in the bioreactor medium liquid phase were 7.2 x 107 cells/cc, and with the methane hydrate, 2.8 x 108 cells/cc.

Attribution of changes in global wetland methane emissions from pre-industrial to present using CLM4.5-BGC

DOE PAGES

Paudel, Rajendra; Mahowald, Natalie M.; Hess, Peter G. M.; ...

2016-03-10

An understanding of potential factors controlling methane emissions from natural wetlands is important to accurately project future atmospheric methane concentrations. Here, we examine the relative contributions of climatic and environmental factors, such as precipitation, temperature, atmospheric CO 2 concentration, nitrogen deposition, wetland inundation extent, and land-use and land-cover change, on changes in wetland methane emissions from preindustrial to present day (i.e., 1850-2005). We apply a mechanistic methane biogeochemical model integrated in the Community Land Model version 4.5 (CLM4.5), the land component of the Community Earth System Model. The methane model explicitly simulates methane production, oxidation, ebullition, transport through aerenchyma ofmore » plants, and aqueous and gaseous diffusion. We conduct a suite of model simulations from 1850 to 2005, with all changes in environmental factors included, and sensitivity studies isolating each factor. Globally, we estimate that preindustrial methane emissions were higher by 10% than present-day emissions from natural wetlands, with emissions changes from preindustrial to the present of +15%, -41%, and -11% for the high latitudes, temperate regions, and tropics, respectively. The most important change is due to the estimated change in wetland extent, due to the conversion of wetland areas to drylands by humans. This effect alone leads to higher preindustrial global methane fluxes by 33% relative to the present, with the largest change in temperate regions (+80%). These increases were partially offset by lower preindustrial emissions due to lower CO 2 levels (10%), shifts in precipitation (7%), lower nitrogen deposition (3%), and changes in land-use and land-cover (2%). Cooler temperatures in the preindustrial regions resulted in our simulations in an increase in global methane emissions of 6% relative to present day. Much of the sensitivity to these perturbations is mediated in the model by changes in methane substrate production and the areal extent of wetlands. The detrended interannual variability of high-latitude methane emissions is explained by the variation in substrate production and wetland inundation extent, whereas the tropical emission variability is explained by both of those variables and precipitation.« less

Attribution of changes in global wetland methane emissions from pre-industrial to present using CLM4.5-BGC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paudel, Rajendra; Mahowald, Natalie M.; Hess, Peter G. M.

An understanding of potential factors controlling methane emissions from natural wetlands is important to accurately project future atmospheric methane concentrations. Here, we examine the relative contributions of climatic and environmental factors, such as precipitation, temperature, atmospheric CO 2 concentration, nitrogen deposition, wetland inundation extent, and land-use and land-cover change, on changes in wetland methane emissions from preindustrial to present day (i.e., 1850-2005). We apply a mechanistic methane biogeochemical model integrated in the Community Land Model version 4.5 (CLM4.5), the land component of the Community Earth System Model. The methane model explicitly simulates methane production, oxidation, ebullition, transport through aerenchyma ofmore » plants, and aqueous and gaseous diffusion. We conduct a suite of model simulations from 1850 to 2005, with all changes in environmental factors included, and sensitivity studies isolating each factor. Globally, we estimate that preindustrial methane emissions were higher by 10% than present-day emissions from natural wetlands, with emissions changes from preindustrial to the present of +15%, -41%, and -11% for the high latitudes, temperate regions, and tropics, respectively. The most important change is due to the estimated change in wetland extent, due to the conversion of wetland areas to drylands by humans. This effect alone leads to higher preindustrial global methane fluxes by 33% relative to the present, with the largest change in temperate regions (+80%). These increases were partially offset by lower preindustrial emissions due to lower CO 2 levels (10%), shifts in precipitation (7%), lower nitrogen deposition (3%), and changes in land-use and land-cover (2%). Cooler temperatures in the preindustrial regions resulted in our simulations in an increase in global methane emissions of 6% relative to present day. Much of the sensitivity to these perturbations is mediated in the model by changes in methane substrate production and the areal extent of wetlands. The detrended interannual variability of high-latitude methane emissions is explained by the variation in substrate production and wetland inundation extent, whereas the tropical emission variability is explained by both of those variables and precipitation.« less

Non-Faradaic electrochemical promotion of catalytic methane reforming for methanol production

DOEpatents

Fan, Qinbai

2016-11-22

A method of converting methane to methanol at low temperatures utilizes a reactor including an anode, a cathode, a membrane separator between the anode and cathode, a metal oxide catalyst at the anode and a hydrogen recovery catalyst at the cathode. The method can convert methane to methanol at as rate exceeding the theoretical Faradaic rate due to the contribution of an electrochemical reaction occurring in tandem with a Faradaic reaction.

Molecular dynamics simulations of methane hydrate decomposition.

PubMed

Myshakin, Evgeniy M; Jiang, Hao; Warzinski, Robert P; Jordan, Kenneth D

2009-03-12

Molecular dynamics simulations have been carried out to study decomposition of methane hydrate at different cage occupancies. The decomposition rate is found to depend sensitively on the hydration number. The rate of the destruction of the cages displays Arrhenius behavior, consistent with an activated mechanism. During the simulations, reversible formation of partial water cages around methane molecules in the liquid was observed at the interface at temperatures above the computed hydrate decomposition temperature.

Estimating methane emissions from landfills based on rainfall, ambient temperature, and waste composition: The CLEEN model.

PubMed

Karanjekar, Richa V; Bhatt, Arpita; Altouqui, Said; Jangikhatoonabad, Neda; Durai, Vennila; Sattler, Melanie L; Hossain, M D Sahadat; Chen, Victoria

2015-12-01

Accurately estimating landfill methane emissions is important for quantifying a landfill's greenhouse gas emissions and power generation potential. Current models, including LandGEM and IPCC, often greatly simplify treatment of factors like rainfall and ambient temperature, which can substantially impact gas production. The newly developed Capturing Landfill Emissions for Energy Needs (CLEEN) model aims to improve landfill methane generation estimates, but still require inputs that are fairly easy to obtain: waste composition, annual rainfall, and ambient temperature. To develop the model, methane generation was measured from 27 laboratory scale landfill reactors, with varying waste compositions (ranging from 0% to 100%); average rainfall rates of 2, 6, and 12 mm/day; and temperatures of 20, 30, and 37°C, according to a statistical experimental design. Refuse components considered were the major biodegradable wastes, food, paper, yard/wood, and textile, as well as inert inorganic waste. Based on the data collected, a multiple linear regression equation (R(2)=0.75) was developed to predict first-order methane generation rate constant values k as functions of waste composition, annual rainfall, and temperature. Because, laboratory methane generation rates exceed field rates, a second scale-up regression equation for k was developed using actual gas-recovery data from 11 landfills in high-income countries with conventional operation. The Capturing Landfill Emissions for Energy Needs (CLEEN) model was developed by incorporating both regression equations into the first-order decay based model for estimating methane generation rates from landfills. CLEEN model values were compared to actual field data from 6 US landfills, and to estimates from LandGEM and IPCC. For 4 of the 6 cases, CLEEN model estimates were the closest to actual. Copyright © 2015 Elsevier Ltd. All rights reserved.

Using Optical Oxygen Sensors and Injection Experiments to Determine in situ Microbial Rate Constants for Methane Oxidation and Heterotrophic Respiration in a Boreal Bog and Fen

NASA Astrophysics Data System (ADS)

Waldo, N.; Moorberg, C.; Waldrop, M. P.; Turetsky, M. R.; Neumann, R. B.

2015-12-01

Wetlands are the largest natural source of methane to the atmosphere, and play a key role in feedback cycles to climate change. In recognition of this, many researchers are developing process-based models of wetland methane emissions at various scales. In these models, the three key biogeochemical reactions are methane production, methane oxidation, and heterotrophic respiration, and they are modeled using Michaelis-Menten kinetics. The majority of Michaelis-Menten rate constants used in models are based on experiments involving slurries of peat incubated in vials. While these slurries provide a highly controlled setting, they are different from in situ conditions in multiple ways; notably they lack live plants and the centimeter-scale heterogeneities that exist in the field. To determine rate constants in a system more representative of in situ conditions, we extracted peat cores intact from a bog and fen located in the Bonanza Creek Experimental Forest near Fairbanks, Alaska and part of the Alaska Peatland Experiment (APEX) research program. Into those cores we injected water with varying concentrations of methane and oxygen at multiple depths. We used planar oxygen sensors installed on the peat cores to collect high resolution, two dimensional oxygen concentration data during the injections and used oxygen consumption rates under various conditions to calculate rate constants. Results were compared to a similar but smaller set of injection experiments conducted against planar oxygen sensors installed in the bog. Results will inform parametrization of microbial processes in wetland models, improving estimates of methane emissions both under current climate conditions and in the future.

Development of optimal enzymatic and microbial conversion systems for biofuel production

NASA Astrophysics Data System (ADS)

Aramrueang, Natthiporn

The increase in demand for fuels, along with the concerns over the depletion of fossil fuels and the environmental problems associated with the use of the petroleum-based fuels, has driven the exploitation of clean and renewable energy. Through a collaboration project with Mendota Bioenergy LLC to produce advanced biofuel from sugar beet and other locally grown crops in the Central Valley of California through demonstration and commercial-scale biorefineries, the present study focused on the investigation of selected potential biomass as biofuel feedstock and development of bioconversion systems for sustainable biofuel production. For an efficient biomass-to-biofuel conversion process, three important steps, which are central to this research, must be considered: feedstock characterization, enzymatic hydrolysis of the feedstock, and the bioconversion process. The first part of the research focused on the characterization of various lignocellulosic biomass as feedstocks and investigated their potential ethanol yields. Physical characteristics and chemical composition were analyzed for four sugar beet varieties, three melon varieties, tomato, Jose tall wheatgrass, wheat hay, and wheat straw. Melons and tomato are those products discarded by the growers or processors due to poor quality. The mass-based ethanol potential of each feedstock was determined based on the composition. The high sugar-containing feedstocks are sugar beet roots, melons, and tomato, containing 72%, 63%, and 42% average soluble sugars on a dry basis, respectively. Thus, for these crops, the soluble sugars are the main substrate for ethanol production. The potential ethanol yields, on average, for sugar beet roots, melons, and tomato are 591, 526, and 448 L ethanol/metric ton dry basis (d.b.), respectively. Lignocellulosic biomass, including Jose Tall wheatgrass and wheat straw, are composed primarily of cellulose (27-39% d.b.) and hemicellulose (26-30% d.b.). The ethanol yields from these materials can range from 470 to 533 L ethanol/metric ton (d.b.) Sugar beet leaves contain nearly equal amounts of cellulose (13%), hemicellulose (16%), and pectin (17%). The potential ethanol yield of sugar beet leaves is 340 L ethanol/metric ton (d.b.). As remaining unused in great quantities during the production of sugar beet as a sugar and energy crop, sugar beet leaves was studied as a potential feedstock for the production of biofuel and valuable products. The enzymatic hydrolysis of sugar beet leaves was optimized for fermentable sugar production. Optimization of enzyme usage was performed to make the biorefinery process more cost- and energy-effective. In this research, response surface methodology was used to study the effects of enzyme loadings during the hydrolysis of sugar beet leaves at 10% total solids content, using a mix of cellulases, hemicellulases, and pectinases. The effects of enzyme loadings were studied with a five-level rotatable central composite design for maximum conversion of sugar beet leaves to fermentable sugars. The last part of this study investigated biogas production through the anaerobic digestion of microalgae as they have received much attention as another potential biofuel feedstock. Anaerobic digestion of Spirulina ( Arthrospira platensis) was conducted in batch reactors for the study of the kinetics and, in continuous stirred tank reactors (CSTR), for the study of the two important operating parameters: hydraulic retention time (HRT) and organic loading rate (OLR). The kinetics study on methane production from batch experiments shows first order kinetics and a reaction rate constant of 0.382 d-1. The maximum biogas and methane yields for Spirulina are 0.514 L/gVS and 0.360 L CH4/gVS, respectively. The methane content of the biogas is 68%. During the continuous anaerobic digestion in CSTR for OLR in the range of 1.0-4.0 gVS/L/d, biogas and methane yields are in the ranges of 0.276-0.502 L/ gVS and 0.163-0.342 L CH4/gVS, respectively. Methane content is 59-70% of the biogas. Methane yield decreases with an increase in OLR and a decrease in HRT. The maximum methane production is 0.342 L CH4/gVS at OLR of 1.0 gVS/L d and 25d-HRT, achieving 94% of the maximum yield produced by batch digestion. Ammonia inhibition and the accumulation of volatile fatty acids (VFA) were observed at high OLR. According to the results from the continuous digestion of Spirulina, the recommended HRT should be sufficient at least 15d, with the OLRmax of 2.0 gVS/L to prevent ammonia inhibition at higher feed concentrations. The OLR can be increased when the digester is operated at longer HRT since a long HRT provides a more stable operation. A mathematical model, based on the kinetics study from the batch process, was developed for the prediction of methane production during a continuous digestion process, in relation to HRT. Further improvement of the model may have to include the effects of ammonia inhibition and low solids retention time (SRT) to overcome these limitations. (Abstract shortened by UMI.).

Pretreatment of food waste with high voltage pulse discharge towards methane production enhancement.

PubMed

Zou, Lianpei; Ma, Chaonan; Liu, Jianyong; Li, Mingfei; Ye, Min; Qian, Guangren

2016-12-01

Anaerobic batch tests were performed to investigate the methane production enhancement and solid transformation rates from food waste (FW) by high voltage pulse discharge (HVPD) pretreatment. The total cumulative methane production with HVPD pretreatment was 134% higher than that of the control. The final volatile solids transformation rates of FW with and without HVPD pretreatment were 54.3% and 32.3%, respectively. Comparison study on HVPD pretreatment with acid, alkali and ultrasonic pretreatments showed that the methane production and COD removal rates of FW pretreated with HVPD were more than 100% higher than the control, but only about 50% higher can be obtained with other pretreatments. HVPD pretreatment could be a promising pretreatment method in the application of energy recovery from FW. Copyright © 2016 Elsevier Ltd. All rights reserved.

Anaerobic co-digestion of spent coffee grounds with different waste feedstocks for biogas production.

PubMed

Kim, Jaai; Kim, Hakchan; Baek, Gahyun; Lee, Changsoo

2017-02-01

Proper management of spent coffee grounds has become a challenging problem as the production of this waste residue has increased rapidly worldwide. This study investigated the feasibility of the anaerobic co-digestion of spent coffee ground with various organic wastes, i.e., food waste, Ulva, waste activated sludge, and whey, for biomethanation. The effect of co-digestion was evaluated for each tested co-substrate in batch biochemical methane potential tests by varying the substrate mixing ratio. Co-digestion with waste activated sludge had an apparent negative effect on both the yield and production rate of methane. Meanwhile, the other co-substrates enhanced the reaction rate while maintaining methane production at a comparable or higher level to that of the mono-digestion of spent coffee ground. The reaction rate increased with the proportion of co-substrates without a significant loss in methanation potential. These results suggest the potential to reduce the reaction time and thus the reactor capacity without compromising methane production. Copyright © 2016 Elsevier Ltd. All rights reserved.

On-site manufacture of propellant oxygen from lunar resources

NASA Technical Reports Server (NTRS)

Rosenberg, Sanders D.

1992-01-01

The Aerojet Carbothermal Process for the manufacture of oxygen from lunar resources has three essential steps: the reduction of silicate with methane to form carbon monoxide and hydrogen; the reduction of carbon monoxide with hydrogen to form methane and water; and the electrolysis of water to form oxygen and hydrogen. This cyclic process does not depend upon the presence of water or water precursors in the lunar materials; it will produce oxygen from silicates regardless of their precise composition and fine structure. Research on the first step of the process was initiated by determining some of the operating conditions required to reduce igneous rock with carbon and silicon carbide. The initial phase of research on the second step is completed; quantitative conversion of carbon monoxide and hydrogen to methane and water was achieved with a nickel-on-kieselguhr catalyst. The equipment used in and the results obtained from these process studies are reported in detail.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Detering, B.A.; Kong, P.C.; Thomas, C.P.

This paper describes the experimental demonstration of a process for direct conversion of methane to acetylene in a thermal plasma. The process utilizes a thermal plasma to dissociate methane and form an equilibrium mixture of acetylene followed by a supersonic expansion of the hot gas to preserve the produced acetylene in high yield. The high translational velocities and rapid cooling result in an overpopulation of atomic hydrogen which persists throughout the expansion process. The presence of atomic hydrogen shifts the equilibrium composition by inhibiting complete pyrolysis of methane and acetylene to solid carbon. This process has the potential to reducemore » the cost of producing acetylene from natural gas. Acetylene and hydrogen produced by this process could be used directly as industrial gases, building blocks for synthesis of industrial chemicals, or oligomerized to long chain liquid hydrocarbons for use as fuels. This process produces hydrogen and ultrafine carbon black in addition to acetylene.« less

A trimodal porous carbon as an effective catalyst for hydrogen production by methane decomposition.

PubMed

Shen, Yi; Lua, Aik Chong

2016-01-15

A new type of porous carbon with an interconnected trimodal pore system is synthesized by a nanocasting method using nanoparticulated bimodal micro-mesoporous silica particles as the template. The synthesized template and carbon material are characterized using transmission electron microscopy (TEM), field emission electron scanning microscopy (FESEM) and nitrogen adsorption-desorption test. The synthesized carbon material has an extremely high surface area, a large pore volume and an interconnected pore structure, which could provide abundant active sites and space for chemical reactions and minimize the diffusion resistance of the reactants. The resulting carbon is used as the catalyst for hydrogen production by the thermal decomposition of methane. The catalytic results show that the as-synthesized carbon in this study produces much higher methane conversion and hydrogen yield than the commercial carbon materials. Copyright © 2015 Elsevier Inc. All rights reserved.

Methane production, oxidation and emission in United Kingdom peatlands and the effect of anions from acid rain

NASA Astrophysics Data System (ADS)

Watson, Andrea

The production, oxidation and emission of methane in UK peatlands was investigated. The main field study site was Ellergower Moss, Dumfriesshire where the peat was characterised by hollows (water-filled depressions) and hummocks (raised vegetative areas). The pathways of carbon flow in peat under hummocks and hollows were determined and compared on a seasonal basis. Methane emissions were significantly greater from hollows than hummocks (0.88 mols and 0.07 mols CH4 m-2 y-1 respectively). Methane emission rates varied seasonally e.g. for hollows were 0.04 mmols CH4 m-2 d-1 for January and 2.3 mmols CH4 m-2 d-1 for June. Methane emissions were modulated by biological methane oxidation by 0% of methane produced in the winter months, increasing during spring until 97% of methane produced was oxidised in the summer months. Both methane oxidation and methanogenesis were strongly temperature dependant with Q10 values of 2.2 and 16, respectively. Rates of methane oxidation potential (MOP) were greatest between 4-8 cm depths below the level of the water table, and were located above the most active zone of methanogenesis (8-16 cm depths below the water table levels). This enabled vertically diffusing methane to be utilised by methanotrophic bacteria, providing a very efficient filter for methane. Methanogenesis was limited by hydrogen availability in the peat, but not by acetate, suggesting that methane was produced by hydrogenophilic methanogenic bacteria (MB), rather than acetate utilising MB. Acid rain pollutants were found to significantly affect carbon flow, with sulphate deposition causing a seasonal inhibition in methanogenesis. Carbon flow predominated through sulphate reduction in the winter and spring months (sulphate reduction to methane production ratio was 1008 and 189, for hummocks and hollows respectively) when sulphate was freely available and when temperatures were low. During the summer when temperatures increased and sulphate became limited carbon flow through methanogenesis predominated (sulphate reduction to methane production ratio 0.39 and 0.07, for hummocks and hollows respectively). The examination of two other peatlands-Great Dun Fell and Caithness which received higher and lower sulphate loadings than Ellergower respectively, did not show a consistent effect of sulphate inhibition on methanogenesis. The methane oxidation kinetics were used in a mathematical model to examine the effect of plant roots on increasing the vertical transport rate of methane out, and oxygen into the peat, by gas phase transport through the roots. (Abstract shortened by UMI.)

Fermentation Enhancement of Methanogenic Archaea Consortia from an Illinois Basin Coalbed via DOL Emulsion Nutrition

PubMed Central

Xiao, Dong; Peng, Su-Ping; Wang, En-Yuan

2015-01-01

Microbially enhanced coalbed methane technology must be used to increase the methane content in mining and generate secondary biogenic gas. In this technology, the metabolic processes of methanogenic consortia are the basis for the production of biomethane from some of the organic compounds in coal. Thus, culture nutrition plays an important role in remediating the nutritional deficiency of a coal seam. To enhance the methane production rates for microorganism consortia, different types of nutrition solutions were examined in this study. Emulsion nutrition solutions containing a novel nutritional supplement, called dystrophy optional modification latex, increased the methane yield for methanogenic consortia. This new nutritional supplement can help methanogenic consortia form an enhanced anaerobic environment, optimize the microbial balance in the consortia, and improve the methane biosynthesis rate. PMID:25884952

NMR study of methane + ethane structure I hydrate decomposition.

PubMed

Dec, Steven F; Bowler, Kristen E; Stadterman, Laura L; Koh, Carolyn A; Sloan, E Dendy

2007-05-24

The thermally activated decomposition of methane + ethane structure I hydrate was studied with use of 13C magic-angle spinning (MAS) NMR as a function of composition and temperature. The observed higher decomposition rate of large sI cages initially filled with ethane gas can be described in terms of a model where a distribution of sI unit cells exists such that a particular unit cell contains zero, one, or two methane molecules in the unit cell; this distribution of unit cells is combined to form the observed equilibrium composition. In this model, unit cells with zero methane molecules are the least stable and decompose more rapidly than those populated with one or two methane molecules leading to the observed overall faster decomposition rate of the large cages containing ethane molecules.

Microbial diversity in methanogenic hydrocarbon-degrading enrichment cultures isolated from a water-flooded oil reservoir (Dagang oil field, China)

NASA Astrophysics Data System (ADS)

Jiménez, Núria; Cai, Minmin; Straaten, Nontje; Yao, Jun; Richnow, Hans H.; Krüger, Martin

2015-04-01

Microbial transformation of oil to methane is one of the main degradation processes taking place in oil reservoirs, and it has important consequences as it negatively affects the quality and economic value of the oil. Nevertheless, methane could constitute a recovery method of carbon from exhausted reservoirs. Previous studies combining geochemical and isotopic analysis with molecular methods showed evidence for in situ methanogenic oil degradation in the Dagang oil field, China (Jiménez et al., 2012). However, the main key microbial players and the underlying mechanisms are still relatively unknown. In order to better characterize these processes and identify the main microorganisms involved, laboratory biodegradation experiments under methanogenic conditions were performed. Microcosms were inoculated with production and injection waters from the reservoir, and oil or 13C-labelled single hydrocarbons (e.g. n-hexadecane or 2-methylnaphthalene) were added as sole substrates. Indigenous microbiota were able to extensively degrade oil within months, depleting most of the n-alkanes in 200 days, and producing methane at a rate of 76 ± 6 µmol day-1 g-1 oil added. They could also produce heavy methane from 13C-labeled 2-methylnaphthalene, suggesting that further methanogenesis may occur from the aromatic and polyaromatic fractions of Dagang reservoir fluids. Microbial communities from oil and 2-methyl-naphthalene enrichment cultures were slightly different. Although, in both cases Deltaproteobacteria, mainly belonging to Syntrophobacterales (e.g. Syntrophobacter, Smithella or Syntrophus) and Clostridia, mostly Clostridiales, were among the most represented taxa, Gammaproteobacteria could be only identified in oil-degrading cultures. The proportion of Chloroflexi, exclusively belonging to Anaerolineales (e.g. Leptolinea, Bellilinea) was considerably higher in 2-methyl-naphthalene degrading cultures. Archaeal communities consisted almost exclusively of representatives of Methanomicrobia (mainly belonging to genera Methanosaeta and Methanoculleus). As both syntrophic Bacteria and methanogenic Archaea are abundant in Dagang, the studied areas of this oil field may have a significant potential to test the in situ conversion of oil into methane as a possible way to increase total hydrocarbon recovery.

Toxic effects of butyl elastomers on aerobic methane oxidation

NASA Astrophysics Data System (ADS)

Niemann, Helge; Steinle, Lea I.; Blees, Jan H.; Krause, Stefan; Bussmann, Ingeborg; Lehmann, Moritz F.; Treude, Tina

2013-04-01

Large quantities of the potent greenhouse gas methane are liberated into the water column of marine and lacustrine environments where it may be consumed by aerobic methane oxidising bacteria before reaching the atmosphere.The reliable quantification of aerobic methane oxidation (MOx) rates is consequently of paramount importance for estimating methane budgets and to understand the controls on water column methane cycling. A widely used set of methods for measuring MOx rates is based on the incubation of water samples during which the consumption of methane is monitored, for instance with radio-tracer assays. Typically, incubation vessels are sealed with butyl rubber stoppers because these elastomers are essentially impermeable for gases at the relevant time scales. We tested the effect of different stopper materials (unmodified- and halogenated butyl rubber) on MOx activity in environmental samples and in cultures of methane oxidising bacteria. MOx rates in samples sealed with unmodified butyl rubber were > 75% lower compared to parallel incubations with halogenated butyl rubber seals, suggesting inhibiting/toxic effects associated with the use of unmodified butyl elastomers. To further explore the cause of these effects, we analysed aqueous extracts of the different stoppers. Halogenated butyl rubber stoppers appeared to bleed off comparably little amounts of organics. In stark contrast, extracts of unmodified butyl rubber were contaminated with various organic compounds including potential bactericides such as benzyltoluenes, phenylalkanes and benzuothiazoles. We also found tetramethylthiourea, a scavenger of active oxygen species, which may inhibit the MOx pathway.

News from the "blowout", a man-made methane pockmark in the North Sea: chemosynthetic communities and microbial methane oxidation

NASA Astrophysics Data System (ADS)

Steinle, Lea I.; Wilfert, Philipp; Schmidt, Mark; Bryant, Lee; Haeckel, Matthias; Lehmann, Moritz F.; Linke, Peter; Sommer, Stefan; Treude, Tina; Niemann, Helge

2013-04-01

The accidental penetration of a base-Quaternary shallow gas pocket by a drilling rig in 1990 caused a "blowout" in the British sector of the North Sea (57°55.29' N, 01°37.86' E). Large quantities of methane have been seeping out of this man-made pockmark ever since. As the onset of gas seepage is well constrained, this site can be used as a natural laboratory to gain information on the development of methane oxidizing microbial communities at cold seeps. During an expedition with the R/V Celtic Explorer in July and August 2012, we collected sediments by video-guided push-coring with an ROV (Kiel 6000) along a gradient from inside the crater (close to where a jet of methane bubbles enters the water column) outwards. We also sampled the water column in a grid above the blowout at three different depths. In this presentation, we provide evidence for the establishment of methanotrophic communities in the sediment (AOM communities) on a time scale of decades. Furthermore, we will report data on methane concentrations and anaerobic methane oxidation rates in the sediment. Finally, we will also discuss the spatial distribution of methane and aerobic methane oxidation rates in the water column.

Combining tracer flux ratio methodology with low-flying aircraft measurements to estimate dairy farm CH4 emissions

NASA Astrophysics Data System (ADS)

Daube, C.; Conley, S.; Faloona, I. C.; Yacovitch, T. I.; Roscioli, J. R.; Morris, M.; Curry, J.; Arndt, C.; Herndon, S. C.

2017-12-01

Livestock activity, enteric fermentation of feed and anaerobic digestion of waste, contributes significantly to the methane budget of the United States (EPA, 2016). Studies question the reported magnitude of these methane sources (Miller et. al., 2013), calling for more detailed research of agricultural animals (Hristov, 2014). Tracer flux ratio is an attractive experimental method to bring to this problem because it does not rely on estimates of atmospheric dispersion. Collection of data occurred during one week at two dairy farms in central California (June, 2016). Each farm varied in size, layout, head count, and general operation. The tracer flux ratio method involves releasing ethane on-site with a known flow rate to serve as a tracer gas. Downwind mixed enhancements in ethane (from the tracer) and methane (from the dairy) were measured, and their ratio used to infer the unknown methane emission rate from the farm. An instrumented van drove transects downwind of each farm on public roads while tracer gases were released on-site, employing the tracer flux ratio methodology to assess simultaneous methane and tracer gas plumes. Flying circles around each farm, a small instrumented aircraft made measurements to perform a mass balance evaluation of methane gas. In the course of these two different methane quantification techniques, we were able to validate yet a third method: tracer flux ratio measured via aircraft. Ground-based tracer release rates were applied to the aircraft-observed methane-to-ethane ratios, yielding whole-site methane emission rates. Never before has the tracer flux ratio method been executed with aircraft measurements. Estimates from this new application closely resemble results from the standard ground-based technique to within their respective uncertainties. Incorporating this new dimension to the tracer flux ratio methodology provides additional context for local plume dynamics and validation of both ground and flight-based data.

Flash crystallization kinetics of methane (sI) hydrate in a thermoelectrically-cooled microreactor.

PubMed

Chen, Weiqi; Pinho, Bruno; Hartman, Ryan L

2017-09-12

The crystallization kinetics of methane (sI) hydrate were investigated in a thermoelectrically-cooled microreactor with in situ Raman spectroscopy. Step-wise and precise control of the temperature allowed acquisition of reproducible data within minutes, while the nucleation of methane hydrates can take up to 24 h in traditional batch reactors. The propagation rates of methane hydrate (from 3.1-196.3 μm s -1 ) at the gas-liquid interface were measured for different Reynolds' numbers (0.7-68.9), pressures (30.0-80.9 bar), and sub-cooling temperatures (1.0-4.0 K). The precise measurement of the propagation rates and their subsequent analyses revealed a transition from mixed heat-transfer-crystallization-rate-limited to mixed heat-transfer-mass-transfer-crystallization-rate-limited kinetics. A theoretical model, based on heat transfer, mass transfer, and intrinsic crystallization kinetics, was derived for the first time to understand the non-linear relationship between the propagation rate and sub-cooling temperature. The molecular diffusivity of methane within a stagnant film (ahead of the propagation front) was discovered to follow Stokes-Einstein, while calculated Hatta (0.50-0.68), Lewis (128-207), and beta (0.79-116) numbers also confirmed that the diffusive flux influences crystal growth. Understanding methane hydrate crystal growth is important to the atmospheric, oceanic, and planetary sciences and to energy production, storage, and transportation. Our discoveries could someday advance the science of other multiphase, high-pressure, and sub-cooled crystallizations.

Modeling of breath methane concentration profiles during exercise on an ergometer*

PubMed Central

Szabó, Anna; Unterkofler, Karl; Mochalski, Pawel; Jandacka, Martin; Ruzsanyi, Vera; Szabó, Gábor; Mohácsi, Árpád; Teschl, Susanne; Teschl, Gerald; King, Julian

2016-01-01

We develop a simple three compartment model based on mass balance equations which quantitatively describes the dynamics of breath methane concentration profiles during exercise on an ergometer. With the help of this model it is possible to estimate the endogenous production rate of methane in the large intestine by measuring breath gas concentrations of methane. PMID:26828421

Thermodynamic equilibrium calculations of dimethyl ether steam reforming and dimethyl ether hydrolysis

NASA Astrophysics Data System (ADS)

Semelsberger, Troy A.; Borup, Rodney L.

The production of a hydrogen-rich fuel-cell feed by dimethyl ether (DME) steam reforming was investigated using calculations of thermodynamic equilibrium as a function of steam-to-carbon ratio (0.00-4.00), temperature (100-600 °C), pressure (1-5 atm), and product species. Species considered were acetone, acetylene, carbon dioxide, carbon monoxide, dimethyl ether, ethane, ethanol, ethylene, formaldehyde, formic acid, hydrogen, isopropanol, methane, methanol, methyl-ethyl ether, n-propanol and water. Thermodynamic equilibrium calculations of DME steam reforming indicate complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide at temperatures greater than 200 °C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure ( P = 1 atm). Increasing the operating pressure shifts the equilibrium toward the reactants; increasing the pressure from 1 to 5 atm decreases the conversion of dimethyl ether from 99.5 to 76.2%. The trend of thermodynamically stable products in decreasing mole fraction is methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol-formaldehyde, formic acid, and acetylene were not observed. Based on the equilibrium calculations, the optimal processing conditions for dimethyl ether steam reforming occur at a steam-to-carbon ratio of 1.50, a pressure of 1 atm, and a temperature of 200 °C. These thermodynamic equilibrium calculations show dimethyl ether processed with steam will produce hydrogen-rich fuel-cell feeds—with hydrogen concentrations exceeding 70%. The conversion of dimethyl ether via hydrolysis (considering methanol as the only product) is limited by thermodynamic equilibrium. Equilibrium conversion increases with temperature and steam-to-carbon ratio. A maximum dimethyl ether conversion of 62% is achieved at a steam-to-carbon ratio of 5.00 and a processing temperature of 600 °C.

Mobile sensing of point-source fugitive methane emissions using Bayesian inference: the determination of the likelihood function

NASA Astrophysics Data System (ADS)

Zhou, X.; Albertson, J. D.

2016-12-01

Natural gas is considered as a bridge fuel towards clean energy due to its potential lower greenhouse gas emission comparing with other fossil fuels. Despite numerous efforts, an efficient and cost-effective approach to monitor fugitive methane emissions along the natural gas production-supply chain has not been developed yet. Recently, mobile methane measurement has been introduced which applies a Bayesian approach to probabilistically infer methane emission rates and update estimates recursively when new measurements become available. However, the likelihood function, especially the error term which determines the shape of the estimate uncertainty, is not rigorously defined and evaluated with field data. To address this issue, we performed a series of near-source (< 30 m) controlled methane release experiments using a specialized vehicle mounted with fast response methane analyzers and a GPS unit. Methane concentrations were measured at two different heights along mobile traversals downwind of the sources, and concurrent wind and temperature data are recorded by nearby 3-D sonic anemometers. With known methane release rates, the measurements were used to determine the functional form and the parameterization of the likelihood function in the Bayesian inference scheme under different meteorological conditions.

Carbon monoxide and methane adsorption of crude oil refinery using activated carbon from palm shells as biosorbent

NASA Astrophysics Data System (ADS)

Yuliusman; Afdhol, M. K.; Sanal, Alristo

2018-03-01

Carbon monoxide and methane gas are widely present in oil refineries. Off-potential gas is used as raw material for the petrochemical industry. In order for this off-gas to be utilized, carbon monoxide and methane must be removed from off-gas. This study aims to adsorb carbon monoxide and methane using activated carbon of palm shells and commercial activated carbon simultaneously. This research was conducted in 2 stages: 1) Preparation and characterization of activated carbon, 2) Carbon monoxide and methane adsorption test. The activation experiments using carbon dioxide at a flow rate of 150 ml/min yielded a surface area of 978.29 m2/g, Nitrogen at flow rate 150 ml/min yielded surface area 1241.48 m2/g, and carbon dioxide and nitrogen at a flow rate 200 ml/min yielded a surface area 300.37 m2/g. Adsorption of carbon monoxide and methane on activated carbon of palm shell systems yielded results in the amount of 0.5485 mg/g and 0.0649 mg/g and using commercial activated carbon yielded results in the amount of 0.5480 mg/g and 0.0650 mg/g

Confinement Effects on Carbon Dioxide Methanation: A Novel Mechanism for Abiotic Methane Formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Le, Thu; Striolo, Alberto; Turner, C. Heath

An important scientific debate focuses on the possibility of abiotic synthesis of hydrocarbons during oceanic crust-seawater interactions. While on-site measurements near hydrothermal vents support this possibility, laboratory studies have provided data that are in some cases contradictory. At conditions relevant for sub-surface environments it has been shown that classic thermodynamics favour the production of CO 2 from CH 4, while abiotic methane synthesis would require the opposite. However, confinement effects are known to alter reaction equilibria. This report shows that indeed thermodynamic equilibrium can be shifted towards methane production, suggesting that thermal hydrocarbon synthesis near hydrothermal vents and deeper inmore » the magma-hydrothermal system is possible. We report reactive ensemble Monte Carlo simulations for the CO 2 methanation reaction. We compare the predicted equilibrium composition in the bulk gaseous phase to that expected in the presence of confinement. In the bulk phase we obtain excellent agreement with classic thermodynamic expectations. When the reactants can exchange between bulk and a confined phase our results show strong dependency of the reaction equilibrium conversions, X CO2, on nanopore size, nanopore chemistry, and nanopore morphology. Some physical conditions that could shift significantly the equilibrium composition of the reactive system with respect to bulk observations are discussed.« less

Confinement Effects on Carbon Dioxide Methanation: A Novel Mechanism for Abiotic Methane Formation

DOE PAGES

Le, Thu; Striolo, Alberto; Turner, C. Heath; ...

2017-08-21

An important scientific debate focuses on the possibility of abiotic synthesis of hydrocarbons during oceanic crust-seawater interactions. While on-site measurements near hydrothermal vents support this possibility, laboratory studies have provided data that are in some cases contradictory. At conditions relevant for sub-surface environments it has been shown that classic thermodynamics favour the production of CO 2 from CH 4, while abiotic methane synthesis would require the opposite. However, confinement effects are known to alter reaction equilibria. This report shows that indeed thermodynamic equilibrium can be shifted towards methane production, suggesting that thermal hydrocarbon synthesis near hydrothermal vents and deeper inmore » the magma-hydrothermal system is possible. We report reactive ensemble Monte Carlo simulations for the CO 2 methanation reaction. We compare the predicted equilibrium composition in the bulk gaseous phase to that expected in the presence of confinement. In the bulk phase we obtain excellent agreement with classic thermodynamic expectations. When the reactants can exchange between bulk and a confined phase our results show strong dependency of the reaction equilibrium conversions, X CO2, on nanopore size, nanopore chemistry, and nanopore morphology. Some physical conditions that could shift significantly the equilibrium composition of the reactive system with respect to bulk observations are discussed.« less

Theoretical insights into the selective oxidation of methane to methanol in copper-exchanged mordenite

DOE PAGES

Zhao, Zhi -Jian; Kulkarni, Ambarish; Vilella, Laia; ...

2016-05-02

Selective oxidation of methane to methanol is one of the most difficult chemical processes to perform. A potential group of catalysts to achieve CH 4 partial oxidation are Cu-exchanged zeolites mimicking the active structure of the enzyme methane monooxygenase. However, the details of this conversion, including the structure of the active site, are still under debate. In this contribution, periodic density functional theory (DFT) methods were employed to explore the molecular features of the selective oxidation of methane to methanol catalyzed by Cu-exchanged mordenite (Cu-MOR). We focused on two types of previously suggested active species, CuOCu and CuOOCu. Our calculationsmore » indicate that the formation of CuOCu is more feasible than that of CuOOCu. In addition, a much lower C–H dissociation barrier is located on the former active site, indicating that C–H bond activation is easily achieved with CuOCu. We calculated the energy barriers of all elementary steps for the entire process, including catalyst activation, CH 4 activation, and CH 3OH desorption. Finally, our calculations are in agreement with experimental observations and present the first theoretical study examining the entire process of selective oxidation of methane to methanol.« less

The hunt for the most-wanted chemolithoautotrophic spookmicrobes

PubMed Central

2018-01-01

ABSTRACT Microorganisms are the drivers of biogeochemical methane and nitrogen cycles. Essential roles of chemolithoautotrophic microorganisms in these cycles were predicted long before their identification. Dedicated enrichment procedures, metagenomics surveys and single-cell technologies have enabled the identification of several new groups of most-wanted spookmicrobes, including novel methoxydotrophic methanogens that produce methane from methylated coal compounds and acetoclastic ‘Candidatus Methanothrix paradoxum’, which is active in oxic soils. The resultant energy-rich methane can be oxidized via a suite of electron acceptors. Recently, ‘Candidatus Methanoperedens nitroreducens’ ANME-2d archaea and ‘Candidatus Methylomirabilis oxyfera’ bacteria were enriched on nitrate and nitrite under anoxic conditions with methane as an electron donor. Although ‘Candidatus Methanoperedens nitroreducens’ and other ANME archaea can use iron citrate as an electron acceptor in batch experiments, the quest for anaerobic methane oxidizers that grow via iron reduction continues. In recent years, the nitrogen cycle has been expanded by the discovery of various ammonium-oxidizing prokaryotes, including ammonium-oxidizing archaea, versatile anaerobic ammonium-oxidizing (anammox) bacteria and complete ammonium-oxidizing (comammox) Nitrospira bacteria. Several biogeochemical studies have indicated that ammonium conversion occurs under iron-reducing conditions, but thus far no microorganism has been identified. Ultimately, iron-reducing and sulfate-dependent ammonium-oxidizing microorganisms await discovery. PMID:29873717

Comparison between acetate and hydrogen as electron donors and implications for the reductive dehalogenation of PCE and TCE.

PubMed

Lee, Il-Su; Bae, Jae-Ho; McCarty, Perry L

2007-10-30

Bioremediation by reductive dehalogenation of groundwater contaminated with tetrachloroethene (PCE) or trichloroethene (TCE) is generally carried out through the addition of a fermentable electron donor such as lactate, benzoate, carbohydrates or vegetable oil. These fermentable donors are converted by fermenting organisms into acetate and hydrogen, either of which might be used by dehalogenating microorganisms. Comparisons were made between H2 and acetate on the rate and extent of reductive dehalogenation of PCE. PCE dehalogenation with H2 alone was complete to ethene, but with acetate alone it generally proceeded only about half as fast and only to cis-1,2-dichloroethene (cDCE). Additionally, acetate was not used as an electron donor in the presence of H2. These findings suggest the fermentable electron donor requirement for PCE dehalogenation to ethene can be reduced up to 50% by separating PCE dehalogenation into two stages, the first of which uses acetate for the conversion of PCE to cDCE, and the second uses H2 for the conversion of cDCE to ethene. This can be implemented with a recycle system in which the fermentable substrate is added down-gradient, where the hydrogen being produced by fermentation effects cDCE conversion into ethene. The acetate produced is recycled up-gradient to achieve PCE conversion into cDCE. With the lower electron donor usage required, potential problems of aquifer clogging, excess methane production, and high groundwater chemical oxygen demand (COD) can be greatly reduced.

Comparison between acetate and hydrogen as electron donors and implications for the reductive dehalogenation of PCE and TCE

NASA Astrophysics Data System (ADS)

Lee, Il-Su; Bae, Jae-Ho; McCarty, Perry L.

2007-10-01

Bioremediation by reductive dehalogenation of groundwater contaminated with tetrachloroethene (PCE) or trichloroethene (TCE) is generally carried out through the addition of a fermentable electron donor such as lactate, benzoate, carbohydrates or vegetable oil. These fermentable donors are converted by fermenting organisms into acetate and hydrogen, either of which might be used by dehalogenating microorganisms. Comparisons were made between H 2 and acetate on the rate and extent of reductive dehalogenation of PCE. PCE dehalogenation with H 2 alone was complete to ethene, but with acetate alone it generally proceeded only about half as fast and only to cis-1,2-dichloroethene (cDCE). Additionally, acetate was not used as an electron donor in the presence of H 2. These findings suggest the fermentable electron donor requirement for PCE dehalogenation to ethene can be reduced up to 50% by separating PCE dehalogenation into two stages, the first of which uses acetate for the conversion of PCE to cDCE, and the second uses H 2 for the conversion of cDCE to ethene. This can be implemented with a recycle system in which the fermentable substrate is added down-gradient, where the hydrogen being produced by fermentation effects cDCE conversion into ethene. The acetate produced is recycled up-gradient to achieve PCE conversion into cDCE. With the lower electron donor usage required, potential problems of aquifer clogging, excess methane production, and high groundwater chemical oxygen demand (COD) can be greatly reduced.

Anaerobic Oxidation of Methane at a Marine Methane Seep in a Forearc Sediment Basin off Sumatra, Indian Ocean

PubMed Central

Siegert, Michael; Krüger, Martin; Teichert, Barbara; Wiedicke, Michael; Schippers, Axel

2011-01-01

A cold methane seep was discovered in a forearc sediment basin off the island Sumatra, exhibiting a methane-seep adapted microbial community. A defined seep center of activity, like in mud volcanoes, was not discovered. The seep area was rather characterized by a patchy distribution of active spots. The relevance of anaerobic oxidation of methane (AOM) was reflected by 13C-depleted isotopic signatures of dissolved inorganic carbon. The anaerobic conversion of methane to CO2 was confirmed in a 13C-labeling experiment. Methane fueled a vital microbial community with cell numbers of up to 4 × 109 cells cm−3 sediment. The microbial community was analyzed by total cell counting, catalyzed reporter deposition–fluorescence in situ hybridization (CARD–FISH), quantitative real-time PCR (qPCR), and denaturing gradient gel electrophoresis (DGGE). CARD–FISH cell counts and qPCR measurements showed the presence of Bacteria and Archaea, but only small numbers of Eukarya. The archaeal community comprised largely members of ANME-1 and ANME-2. Furthermore, members of the Crenarchaeota were frequently detected in the DGGE analysis. Three major bacterial phylogenetic groups (δ-Proteobacteria, candidate division OP9, and Anaerolineaceae) were abundant across the study area. Several of these sequences were closely related to the genus Desulfococcus of the family Desulfobacteraceae, which is in good agreement with previously described AOM sites. In conclusion, the majority of the microbial community at the seep consisted of AOM-related microorganisms, while the relevance of higher hydrocarbons as microbial substrates was negligible. PMID:22207865

Iron oxides alter methanogenic pathways of acetate in production water of high-temperature petroleum reservoir.

PubMed

Pan, Pan; Hong, Bo; Mbadinga, Serge Maurice; Wang, Li-Ying; Liu, Jin-Feng; Yang, Shi-Zhong; Gu, Ji-Dong; Mu, Bo-Zhong

2017-09-01

Acetate is a key intermediate in anaerobic crude oil biodegradation and also a precursor for methanogenesis in petroleum reservoirs. The impact of iron oxides, viz. β-FeOOH (akaganéite) and magnetite (Fe 3 O 4 ), on the methanogenic acetate metabolism in production water of a high-temperature petroleum reservoir was investigated. Methane production was observed in all the treatments amended with acetate. In the microcosms amended with acetate solely about 30% of the acetate utilized was converted to methane, whereas methane production was stimulated in the presence of magnetite (Fe 3 O 4 ) resulting in a 48.34% conversion to methane. Methane production in acetate-amended, β-FeOOH (akaganéite)-supplemented microcosms was much faster and acetate consumption was greatly improved compared to the other conditions in which the stoichiometric expected amounts of methane were not produced. Microbial community analysis showed that Thermacetogenium spp. (known syntrophic acetate oxidizers) and hydrogenotrophic methanogens closely related to Methanothermobacter spp. were enriched in acetate and acetate/magnetite (Fe 3 O 4 ) microcosms suggesting that methanogenic acetate metabolism was through hydrogenotrophic methanogenesis fueled by syntrophic acetate oxidizers. The acetate/β-FeOOH (akaganéite) microcosms, however, differed by the dominance of archaea closely related to the acetoclastic Methanosaeta thermophila. These observations suggest that supplementation of β-FeOOH (akaganéite) accelerated the production of methane further, driven the alteration of the methanogenic community, and changed the pathway of acetate methanogenesis from hydrogenotrophic methanogenesis fueled by syntrophic acetate oxidizers to acetoclastic.

Anaerobic Oxidation of Methane at a Marine Methane Seep in a Forearc Sediment Basin off Sumatra, Indian Ocean.

PubMed

Siegert, Michael; Krüger, Martin; Teichert, Barbara; Wiedicke, Michael; Schippers, Axel

2011-01-01

A cold methane seep was discovered in a forearc sediment basin off the island Sumatra, exhibiting a methane-seep adapted microbial community. A defined seep center of activity, like in mud volcanoes, was not discovered. The seep area was rather characterized by a patchy distribution of active spots. The relevance of anaerobic oxidation of methane (AOM) was reflected by (13)C-depleted isotopic signatures of dissolved inorganic carbon. The anaerobic conversion of methane to CO(2) was confirmed in a (13)C-labeling experiment. Methane fueled a vital microbial community with cell numbers of up to 4 × 10(9) cells cm(-3) sediment. The microbial community was analyzed by total cell counting, catalyzed reporter deposition-fluorescence in situ hybridization (CARD-FISH), quantitative real-time PCR (qPCR), and denaturing gradient gel electrophoresis (DGGE). CARD-FISH cell counts and qPCR measurements showed the presence of Bacteria and Archaea, but only small numbers of Eukarya. The archaeal community comprised largely members of ANME-1 and ANME-2. Furthermore, members of the Crenarchaeota were frequently detected in the DGGE analysis. Three major bacterial phylogenetic groups (δ-Proteobacteria, candidate division OP9, and Anaerolineaceae) were abundant across the study area. Several of these sequences were closely related to the genus Desulfococcus of the family Desulfobacteraceae, which is in good agreement with previously described AOM sites. In conclusion, the majority of the microbial community at the seep consisted of AOM-related microorganisms, while the relevance of higher hydrocarbons as microbial substrates was negligible.

Enhancing methane production from waste activated sludge using a novel indigenous iron activated peroxidation pre-treatment process.

PubMed

Zhou, Xu; Wang, Qilin; Jiang, Guangming

2015-04-01

Methane production from anaerobic digestion of waste activated sludge (WAS) is limited by the slow hydrolysis rate and/or poor methane potential of WAS. This study presents a novel pre-treatment strategy based on indigenous iron (in WAS) activated peroxidation to enhance methane production from WAS. Pre-treatment of WAS for 30 min at 50mg H2O2/g total solids (dry weight) and pH 2.0 (iron concentration in WAS was 7 mg/g TS) substantially enhanced WAS solubilization. Biochemical methane potential tests demonstrated that methane production was improved by 10% at a digestion time of 16d after incorporating the indigenous iron activated peroxidation pre-treatment. Model-based analysis indicated that indigenous iron activated peroxidation pre-treatment improved the methane potential by 13%, whereas the hydrolysis rate was not significantly affected. The economic analysis showed that the proposed pre-treatment method can save the cost by $112,000 per year in a treatment plant with a population equivalent of 300,000. Copyright © 2015 Elsevier Ltd. All rights reserved.

Titan through Time: Evolution of Titan's Atmosphere and its Hydrocarbon Cycle on the Surface

NASA Astrophysics Data System (ADS)

Gilliam, Ashley E.

The Introduction and Appendix i-A outline briefly the history of Titan exploration since its discovery by Christiaan Huygens in 1675 through the recent International Mission of Cassini-Huygens.. Chapter 1: This chapter discusses two possible pathways of loss of the two main gases from Titan's post-accretional atmosphere, methane (CH 4) and ammonia (NH3), by the mechanisms of thermal escape and emission from the interior coupled with thermal escape. Chapter 2: In this chapter, a simple photolysis model is created, where the second most abundant component of the present-day Titan atmosphere, methane (CH4), can either escape the atmosphere or undergo photolytic conversion to ethane (C2H6). Chapter 3: This chapter examines different fluvial features on Titan, identified by the Cassini spacecraft, and evaluates the possibilities of channel formation by two mechanisms: dissolution of ice by a concentrated solution of ammonium sulfate, and by mechanical erosion by flow of liquid ammonia and liquid ethane. Chapter 4: This chapter presents: (1) new explicit mathematical solutions of mixed 1st and 2nd order chemical reactions, represented by ordinary differential first-degree and Riccati equations; (2) the computed present-day concentrations of the three gases in Titan's scale atmosphere, treated as at near-steady state; and (3) an analysis of the reported and computed atmospheric concentrations of CH4, CH 3, and C2H6 on Titan, based on the reaction rate parameters of the species, the rate parameters taken as constants representative of their mean values. Chapter 5: This chapter examines the possible reactions of methane formation in terms of the thermodynamic relationships of the reactions that include pure carbon as graphite, the gases H2, CO2, H2 O, and serpentinization and magnetite formation from olivine fayalite. (Abstract shortened by ProQuest.).

Dynamics of protozoa in the rumen of cattle.

PubMed

Ffoulkes, D; Leng, R A

1988-05-01

1. The dynamics of protozoa were studied in two groups of rumen-fistulated cattle fed on a basal diet of molasses ad lib., with oaten chaff given at 6 or 18 g/kg live weight. This diet resulted in different mixtures of protozoal species in the populations in the rumen. 2. The rumen protozoa were studied by intrarumen injections of protozoa labelled in vitro with [14CH3]choline. An indication of protozoal death and fermentation of protozoal cell residues was obtained by measuring 14C loss via the methane pool. 3. After a single injection of labelled protozoa, the decline in the specific radioactivity (microCi/g nitrogen) of the protozoal pool in the rumen indicated that first-order kinetic processes applied. Conversely the specific radioactivity of protozoa, incubated in rumen fluid, remained constant indicating no growth in vitro, presumably owing to a rapid exhaustion of essential nutrients. 4. The protozoal populations in the rumen of cattle fed on the diet with the low level of oaten chaff were mainly small ciliates; but on the higher level of chaff in the diet, the large ciliates were a higher proportion of the total protozoal population present. 5. The mean pool size of protozoa in the rumen was significantly larger and the protozoal half-life tended to be longer for cattle fed on the higher level of chaff in the diet. The apparent production rate of protozoa in cattle fed on each diet was not significantly different and there were no differences in the production rate of methane. The percentage losses of label from protozoa in the rumen via the methane pool were not significantly different on the two diets and indicated that 74% of the protozoa that were apparently irreversibly lost from the rumen could be accounted for by death and lysis in the rumen and therefore only 26% of protozoa apparently entered the lower digestive tract.

Optical-cell evidence for superheated ice under gas-hydrate-forming conditions

USGS Publications Warehouse

Stern, L.A.; Hogenboom, D.L.; Durham, W.B.; Kirby, S.H.; Chou, I.-Ming

1998-01-01

We previously reported indirect but compelling evidence that fine-grained H2O ice under elevated CH4 gas pressure can persist to temperatures well above its ordinary melting point while slowly reacting to form methane clathrate hydrate. This phenomenon has now been visually verified by duplicating these experiments in an optical cell while observing the very slow hydrate-forming process as the reactants were warmed from 250 to 290 K at methane pressures of 23 to 30 MPa. Limited hydrate growth occurred rapidly after initial exposure of the methane gas to the ice grains at temperatures well within the ice subsolidus region. No evidence for continued growth of the hydrate phase was observed until samples were warmed above the equilibrium H2O melting curve. With continued heating, no bulk melting of the ice grains or free liquid water was detected anywhere within the optical cell until hydrate dissociation conditions were reached (292 K at 30 MPa), even though full conversion of the ice grains to hydrate requires 6-8 h at temperatures approaching 290 K. In a separate experimental sequence, unreacted portions of H2O ice grains that had persisted to temperatures above their ordinary melting point were successfully induced to melt, without dissociating the coexisting hydrate in the sample tube, by reducing the pressure overstep of the equilibrium phase boundary and thereby reducing the rate of hydrate growth at the ice-hydrate interface. Results from similar tests using CO2 as the hydrate-forming species demonstrated that this superheating effect is not unique to the CH4-H2O system.

Titan's missing ethane: From the atmosphere to the subsurface

NASA Astrophysics Data System (ADS)

Gilliam, Ashley E.; Lerman, Abraham

2016-09-01

The second most abundant component of the present-day Titan atmosphere, methane (CH4), is known to undergo photolytic conversion to ethane (C2H6) that accumulates as a liquid on Titan's surface. Condensation temperature of ethane is higher than that of methane, so that ethane "rain" may be expected to occur before the liquefaction of methane. At present, the partial pressure of ethane in the atmosphere is 1E-5 bar, much lower than 1E-1 bar of CH4. Estimated 8.46E17 kg or 1.37E6 km3 of C2H6 have been produced on Titan since accretion. The Titan surface reservoirs of ethane are lakes and craters, of estimated volume of 50,000 km3 and 61,000 km3, respectively. As these are smaller than the total volume of liquid ethane produced in the course of Titan's history, the excess may be stored in the subsurface of the crust, made primarily of water ice. The minimum porosity of the crust needed to accommodate all the liquid ethane would be only 0.9% of the uppermost 2 km of the crust. The occurrence of CH4 and liquid C2H6 on Titan has led to much speculation on the possibility of life on that satellite. The aggregation of organic molecules in a "primordial soup or bullion" depends in part on the viscosity of the medium, diffusivity of organic molecules in it, and rates of polymerization reactions. The temperatures on Titan, much lower than on primordial Earth, are less favorable to the "Second Coming of life" on Titan.

Investigating physical controls on methane and carbon ...

EPA Pesticide Factsheets

Reservoirs are a globally important source of carbon to the atmosphere. Several recent studies have found that both carbon dioxide (CO2) and methane (CH4) emissions from reservoirs are currently being underestimated by up to 50%. This underestimation is due to inadequate characterization of both spatial variability (e.g. ebullition and CO2 surface water concentration hot spots) and temporal variability (e.g. diurnal patterns, seasonal differences, and pulses driven by weather events or other disturbances). Use of the eddy covariance technique to measure CO2 and CH4 fluxes over reservoirs can help address the issues of spatial and temporal coverage. Here we present results from two eddy covariance measurement campaigns monitoring CO2 and CH4 fluxes over reservoirs in southwestern Ohio, US. The first campaign was part of a study looking at the effects of water level drawdown on reservoir methane ebullition. The eddy covariance results showed a clear response of CH4 emissions to the change in water level, increasing from a baseline of 3440 mg CH4 m-2 d-1 to a maximum of 6740 mg CH4 m-2 d-1 during the drawdown. These results agreed well with the emission rates measured via bubble samplers deployed in the same area as the tower. Conversely, the CO2 fluxes did not show a strong response to the drawdown. In the second campaign the eddy covariance system was deployed longer term at a mid-sized (2.4 km2) lake. Analyses of diurnal patterns in CO2 and CH4 emissions as well

Reactions of C1 Building Blocks

NASA Astrophysics Data System (ADS)

Stöcker, Michael

The chapter “Reactions of C1 Building Blocks” covers the direct conversion of methane to aromatics, the methanol-to-hydrocarbons (MTHC) conversion with respect to gasoline (methanol to gasoline) and olefins (methanol to olefins, methanol-to-propene) as well as some combinations like the TIGAS and Mobil's olefin-to-gasoline and distillate processes. The main focus within this chapter will be on the industrial processes, especially concerning the MTHC reactions - including catalytic systems, reaction conditions, process - and to a minor extent related to the mechanistic aspects and kinetic considerations.