High temperature ceramic-tubed reformer

NASA Astrophysics Data System (ADS)

Williams, Joseph J.; Rosenberg, Robert A.; McDonough, Lane J.

1990-03-01

The overall objective of the HiPHES project is to develop an advanced high-pressure heat exchanger for a convective steam/methane reformer. The HiPHES steam/methane reformer is a convective, shell and tube type, catalytic reactor. The use of ceramic tubes will allow reaction temperature higher than the current state-of-the-art outlet temperatures of about 1600 F using metal tubes. Higher reaction temperatures increase feedstock conversion to synthesis gas and reduce energy requirements compared to currently available radiant-box type reformers using metal tubes. Reforming of natural gas is the principal method used to produce synthesis gas (primarily hydrogen and carbon monoxide, H2 and CO) which is used to produce hydrogen (for refinery upgrading), methanol, as well as several other important materials. The HiPHES reformer development is an extension of Stone and Webster's efforts to develop a metal-tubed convective reformer integrated with a gas turbine cycle.

FTIR study of methanol decomposition on gold catalyst for fuel cells

NASA Astrophysics Data System (ADS)

Boccuzzi, F.; Chiorino, A.; Manzoli, M.

The interaction of methanol (m), methanol-water (mw) and methanol-water-oxygen (mwo) on Au/TiO 2 catalyst has been investigated by in situ infrared spectroscopy (FTIR) and quadrupole mass spectrometry (QMS) at different temperatures. The aim of the work is to elucidate the nature and the abundance of the surface intermediates formed in different experimental conditions and to understand the mechanisms of methanol decomposition, of steam reforming and of combined reforming reactions. FTIR spectra run at room temperature in the different reaction mixtures show that differently coordinated methoxy species, that is on top species adsorbed on oxygen vacancy sites, on top species on uncoordinated Ti 4+ sites and bridged species on two Ti 4+ ions, are produced in all the mixtures. Quite strong formaldehyde and formate species adsorbed on gold are produced already at 403 K only in the combined reforming reaction mixture. At 473 K, on top species on uncoordinated Ti 4+ sites and methoxy species adsorbed on oxygen vacancy sites reduce their intensity and, at the same time, some formate species adsorbed on the support are produced in the steam reforming and combined reforming mixtures. At 523 K, on both methanol and methanol-water reaction mixtures, no more definite surface species are evidenced by FTIR on the catalysts, while in the methanol-water-oxygen mixture some residual methoxy and formate species are still present. Moreover, methanol is no more detected by QMS in the gas phase. A role of oxygen adsorbed on gold particles near oxygen vacancies of the support in the oxidative dehydrogenation of methanol is proposed.

Activation of catalysts for synthesizing methanol from synthesis gas

DOEpatents

Blum, David B.; Gelbein, Abraham P.

1985-01-01

A method for activating a methanol synthesis catalyst is disclosed. In this method, the catalyst is slurried in an inert liquid and is activated by a reducing gas stream. The activation step occurs in-situ. That is, it is conducted in the same reactor as is the subsequent step of synthesizing methanol from a methanol gas stream catalyzed by the activated catalyst still dispersed in a slurry.

Characteristics of hydrogen produced by partial oxidation and auto-thermal reforming in a small methanol reformer

NASA Astrophysics Data System (ADS)

Horng, Rong-Fang; Chou, Huann-Ming; Lee, Chiou-Hwang; Tsai, Hsien-Te

This paper investigates experimentally, the transient characteristics of a small methanol reformer using partial oxidation (POX) and auto-thermal reforming (ATR) for fuel cell applications. The parameters varied were heating temperature, methanol supply rate, steady mode shifting temperature, O 2/C (O 2/CH 3OH) and S/C (H 2O/CH 3OH) molar ratios with the main aim of promoting a rapid response and a high flow rate of hydrogen. The experiments showed that a high steady mode shifting temperature resulted in a faster temperature rise at the catalyst outlet and vice versa and that a low steady mode shifting temperature resulted in a lower final hydrogen concentration. However, when the mode shifting temperature was too high, the hydrogen production response was not necessarily improved. It was subsequently shown that the optimum steady mode shifting temperature for this experimental set-up was approximately 75 °C. Further, the hydrogen concentration produced by the auto-thermal process was as high as 49.12% and the volume flow rate up to 23.0 L min -1 compared to 40.0% and 20.5 L min -1 produced by partial oxidation.

In situ XPS study of methanol reforming on PdGa near-surface intermetallic phases

PubMed Central

Rameshan, Christoph; Stadlmayr, Werner; Penner, Simon; Lorenz, Harald; Mayr, Lukas; Hävecker, Michael; Blume, Raoul; Rocha, Tulio; Teschner, Detre; Knop-Gericke, Axel; Schlögl, Robert; Zemlyanov, Dmitry; Memmel, Norbert; Klötzer, Bernhard

2012-01-01

In situ X-ray photoelectron spectroscopy and low-energy ion scattering were used to study the preparation, (thermo)chemical and catalytic properties of 1:1 PdGa intermetallic near-surface phases. Deposition of several multilayers of Ga metal and subsequent annealing to 503–523 K led to the formation of a multi-layered 1:1 PdGa near-surface state without desorption of excess Ga to the gas phase. In general, the composition of the PdGa model system is much more variable than that of its PdZn counterpart, which results in gradual changes of the near-surface composition with increasing annealing or reaction temperature. In contrast to near-surface PdZn, in methanol steam reforming, no temperature region with pronounced CO2 selectivity was observed, which is due to the inability of purely intermetallic PdGa to efficiently activate water. This allows to pinpoint the water-activating role of the intermetallic/support interface and/or of the oxide support in the related supported PdxGa/Ga2O3 systems, which exhibit high CO2 selectivity in a broad temperature range. In contrast, corresponding experiments starting on the purely bimetallic model surface in oxidative methanol reforming yielded high CO2 selectivity already at low temperatures (∼460 K), which is due to efficient O2 activation on PdGa. In situ detected partial and reversible oxidative Ga segregation on intermetallic PdGa is associated with total oxidation of intermediate C1 oxygenates to CO2. PMID:22875996

Multi-fuel reformers for fuel cells used in transportation. Phase 1: Multi-fuel reformers

NASA Astrophysics Data System (ADS)

1994-05-01

DOE has established the goal, through the Fuel Cells in Transportation Program, of fostering the rapid development and commercialization of fuel cells as economic competitors for the internal combustion engine. Central to this goal is a safe feasible means of supplying hydrogen of the required purity to the vehicular fuel cell system. Two basic strategies are being considered: (1) on-board fuel processing whereby alternative fuels such as methanol, ethanol or natural gas stored on the vehicle undergo reformation and subsequent processing to produce hydrogen, and (2) on-board storage of pure hydrogen provided by stationary fuel processing plants. This report analyzes fuel processor technologies, types of fuel and fuel cell options for on-board reformation. As the Phase 1 of a multi-phased program to develop a prototype multi-fuel reformer system for a fuel cell powered vehicle, the objective of this program was to evaluate the feasibility of a multi-fuel reformer concept and to select a reforming technology for further development in the Phase 2 program, with the ultimate goal of integration with a DOE-designated fuel cell and vehicle configuration. The basic reformer processes examined in this study included catalytic steam reforming (SR), non-catalytic partial oxidation (POX) and catalytic partial oxidation (also known as Autothermal Reforming, or ATR). Fuels under consideration in this study included methanol, ethanol, and natural gas. A systematic evaluation of reforming technologies, fuels, and transportation fuel cell applications was conducted for the purpose of selecting a suitable multi-fuel processor for further development and demonstration in a transportation application.

Catalytic partial oxidation reforming of hydrocarbon fuels.

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

Ahmed, S.

1998-09-21

The polymer electrolyte fuel cell (PEFC) is the primary candidate as the power source for light-duty transportation systems. On-board conversion of fuels (reforming) to supply the required hydrogen has the potential to provide the driving range that is typical of today's automobiles. Petroleum-derived fuels, gasoline or some distillate similar to it, are attractive because of their existing production, distribution, and retailing infrastructure. The fuel may be either petroleum-derived or other alternative fuels such as methanol, ethanol, natural gas, etc. [1]. The ability to use a variety of fuels is also attractive for stationary distributed power generation [2], such as inmore » buildings, or for portable power in remote locations. Argonne National Laboratory has developed a catalytic reactor based on partial oxidation reforming that is suitable for use in light-duty vehicles powered by fuel cells. The reactor has shown the ability to convert a wide variety of fuels to a hydrogen-rich gas at less than 800 C, temperatures that are several hundreds of degrees lower than alternative noncatalytic processes. The fuel may be methanol, ethanol, natural gas, or petroleum-derived fuels that are blends of various hydrocarbons such as paraffins, olefins, aromatics, etc., as in gasoline. This paper will discuss the results obtained from a bench-scale (3-kWe) reactor., where the reforming of gasoline and natural gas generated a product gas that contained 38% and 42% hydrogen on a dry basis at the reformer exit, respectively.« less

Remarkable support effect on the reactivity of Pt/In2O3/MOx catalysts for methanol steam reforming

NASA Astrophysics Data System (ADS)

Liu, Xin; Men, Yong; Wang, Jinguo; He, Rong; Wang, Yuanqiang

2017-10-01

Effects of supports over Pt/In2O3/MOx catalysts with extremely low loading of Pt (1 wt%) and In2O3 loadings (3 wt%) are investigated for the hydrogen production of methanol steam reforming (MSR) in the temperature range of 250-400 °C. Under practical conditions without the pre-reduction, the 1Pt/3In2O3/CeO2 catalyst shows the highly efficient catalytic performance, achieving almost complete methanol conversion (98.7%) and very low CO selectivity of 2.6% at 325 °C. The supported Pt/In2O3 catalysts are characterized by means of Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), high-resolution transmission microscopy (HRTEM), temperature programmed reduction with hydrogen (H2-TPR), CO pulse chemisorption, temperature programmed desorption of methanol and water (CH3OH-TPD and H2O-TPD). These demonstrate that the nature of catalyst support of Pt/In2O3/MOx plays crucial roles in the Pt dispersion associated by the strong interaction among Pt, In2O3 and supporting materials and the surface redox properties at low temperature, and thus affects their capability to activate the reactants and determines the catalytic activity of methanol steam reforming. The superior 1Pt/3In2O3/CeO2 catalyst, exhibiting a remarkable reactivity and stability for 32 h on stream, demonstrates its potential for efficient hydrogen production of methanol steam reforming in mobile and de-centralized H2-fueled PEMFC systems.

Process assessment of small scale low temperature methanol synthesis

NASA Astrophysics Data System (ADS)

Hendriyana, Susanto, Herri; Subagjo

2015-12-01

Biomass is a renewable energy resource and has the potential to make a significant impact on domestic fuel supplies. Biomass can be converted to fuel like methanol via several step process. The process can be split into following main steps: biomass preparation, gasification, gas cooling and cleaning, gas shift and methanol synthesis. Untill now these configuration still has a problem like high production cost, catalyst deactivation, economy of scale and a huge energy requirements. These problems become the leading inhibition for biomass conversion to methanol, which should be resolved to move towards the economical. To address these issues, we developed various process and new configurations for methanol synthesis via methyl formate. This configuration combining two reactors: the one reactor for the carbonylation of methanol and CO to form methyl formate, and the second for the hydrogenolysis of methyl formate and H2 to form two molecule of methanol. Four plant process configurations were compared with the biomass basis is 300 ton/day. The first configuration (A) is equipped with a steam reforming process for converting methane to CO and H2 for increasing H2/CO ratio. CO2 removal is necessary to avoid poisoning the catalyst. COSORB process used for the purpose of increasing the partial pressure of CO in the feed gas. The steam reforming process in B configuration is not used with the aim of reducing the number of process equipment, so expect lower investment costs. For C configuration, the steam reforming process and COSORB are not used with the aim of reducing the number of process equipment, so expect lower investment costs. D configuration is almost similar to the configuration A. This configuration difference is in the synthesis of methanol which was held in a single reactor. Carbonylation and hydrogenolysis reactions carried out in the same reactor one. These processes were analyzed in term of technical process, material and energy balance and economic

Process assessment of small scale low temperature methanol synthesis

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

Hendriyana; Chemical Engineering Department, Faculty of Industrial Technology, InstitutTeknologi Bandung; Susanto, Herri, E-mail: herri@che.itb.ac.id

2015-12-29

Biomass is a renewable energy resource and has the potential to make a significant impact on domestic fuel supplies. Biomass can be converted to fuel like methanol via several step process. The process can be split into following main steps: biomass preparation, gasification, gas cooling and cleaning, gas shift and methanol synthesis. Untill now these configuration still has a problem like high production cost, catalyst deactivation, economy of scale and a huge energy requirements. These problems become the leading inhibition for biomass conversion to methanol, which should be resolved to move towards the economical. To address these issues, we developedmore » various process and new configurations for methanol synthesis via methyl formate. This configuration combining two reactors: the one reactor for the carbonylation of methanol and CO to form methyl formate, and the second for the hydrogenolysis of methyl formate and H{sub 2} to form two molecule of methanol. Four plant process configurations were compared with the biomass basis is 300 ton/day. The first configuration (A) is equipped with a steam reforming process for converting methane to CO and H{sub 2} for increasing H{sub 2}/CO ratio. CO{sub 2} removal is necessary to avoid poisoning the catalyst. COSORB process used for the purpose of increasing the partial pressure of CO in the feed gas. The steam reforming process in B configuration is not used with the aim of reducing the number of process equipment, so expect lower investment costs. For C configuration, the steam reforming process and COSORB are not used with the aim of reducing the number of process equipment, so expect lower investment costs. D configuration is almost similar to the configuration A. This configuration difference is in the synthesis of methanol which was held in a single reactor. Carbonylation and hydrogenolysis reactions carried out in the same reactor one. These processes were analyzed in term of technical process, material and

Metal membrane-type 25-kW methanol fuel processor for fuel-cell hybrid vehicle

NASA Astrophysics Data System (ADS)

Han, Jaesung; Lee, Seok-Min; Chang, Hyuksang

A 25-kW on-board methanol fuel processor has been developed. It consists of a methanol steam reformer, which converts methanol to hydrogen-rich gas mixture, and two metal membrane modules, which clean-up the gas mixture to high-purity hydrogen. It produces hydrogen at rates up to 25 N m 3/h and the purity of the product hydrogen is over 99.9995% with a CO content of less than 1 ppm. In this fuel processor, the operating condition of the reformer and the metal membrane modules is nearly the same, so that operation is simple and the overall system construction is compact by eliminating the extensive temperature control of the intermediate gas streams. The recovery of hydrogen in the metal membrane units is maintained at 70-75% by the control of the pressure in the system, and the remaining 25-30% hydrogen is recycled to a catalytic combustion zone to supply heat for the methanol steam-reforming reaction. The thermal efficiency of the fuel processor is about 75% and the inlet air pressure is as low as 4 psi. The fuel processor is currently being integrated with 25-kW polymer electrolyte membrane fuel-cell (PEMFC) stack developed by the Hyundai Motor Company. The stack exhibits the same performance as those with pure hydrogen, which proves that the maximum power output as well as the minimum stack degradation is possible with this fuel processor. This fuel-cell 'engine' is to be installed in a hybrid passenger vehicle for road testing.

Gas processing developments. Why not use methanol for hydrate control

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

Nielsen, R.B.; Bucklin, R.W.

1983-04-01

Hydrate formation in turboexpander plants can be avoided more economically by using methanol than by using solid bed dehydration. Although the first turboexpander plant used methanol, most expander installations now have used solid bed dehydration. The reasons are obscure, since methanol often grants greater ease of operation as well as lower capital and operating costs, especially when the water in the feed gas is low or when recompression is required. Natural gas generally contains water before processing. High pressure, low temperature, or both favor the combination of water with light gases to form hydrates. Free water always must be presentmore » for hydrates to form. Hydrates cause problems by plugging pipelines, valves, and other process equipment. Therefore, proper equipment design requires accurate prediction of the limiting conditions at which hydrates are formed anytime a gas stream containing hydrate formers and free water is cooled below 80 F. (16 refs.)« less

Design, fabrication and performance evaluation of an integrated reformed methanol fuel cell for portable use

NASA Astrophysics Data System (ADS)

Zhang, Shubin; Zhang, Yufeng; Chen, Junyu; Yin, Congwen; Liu, Xiaowei

2018-06-01

In this paper, an integrated reformed methanol fuel cell (RMFC) as a portable power source is designed, fabricated and tested. The RMFC consists of a methanol steam reformer (MSR), a high temperature proton exchange membrane fuel cell (HT-PEMFC) stack, a microcontroller unit (MCU) and other auxiliaries. First, a system model based on Matlab/Simulink is established to investigate the mass and energy transport characteristics within the whole system. The simulation results suggest a hydrogen flow rate of at least 670 sccm is needed for the system to output 30 W and simultaneously maintain thermal equilibrium. Second, a metallic MSR and an HT-PEMFC stack with 12 cells are fabricated and tested. The tests show that the RMFC system is able to function normally when the performances of all the components meet the minimum requirements. At last, in the experiment of successfully powering a laptop, the RMFC system exhibits a stable performance during the complete work flow of all the phases, namely start-up, output and shutdown. Moreover, with a conservative design of 20 W power rating, maximum energy conversion efficiency of the RMFC system can be achieved (36%), and good stability in long-term operation is shown.

Methanol Gas-Sensing Properties of SWCNT-MIP Composites

NASA Astrophysics Data System (ADS)

Zhang, Jin; Zhu, Qin; Zhang, Yumin; Zhu, Zhongqi; Liu, Qingju

2016-11-01

The single-walled carbon nanotube (SWCNT)-molecularly imprinted powder (MIP) composites in this paper were prepared by mixing SWCNTs with MIPs. The structure and micrograph of the as-prepared SWCNTs-MIPs samples were characterized by XRD and TEM. The gas-sensing properties were tested through indirect-heating sensors based on SWCNT-MIP composites fabricating on an alumina tube with Au electrodes and Pt wires. The results showed that the structure of SWCNTs-MIPs is of orthogonal perovskite and the average particle size of the SWCNTs-MIPs was in the range of 10-30 nm. SWCNTs-MIPs exhibit good methanol gas-sensitive properties. At 90 °C, the response to 1 ppm methanol is 19.7, and the response to the interferent is lower than 5 to the other interferent gases (ethanol, formaldehyde, toluene, acetone, ammonia, and gasoline). The response time and recovery time are 50 and 58 s, respectively.

Heat and fuel coupled operation of a high temperature polymer electrolyte fuel cell with a heat exchanger methanol steam reformer

NASA Astrophysics Data System (ADS)

Schuller, G.; Vázquez, F. Vidal; Waiblinger, W.; Auvinen, S.; Ribeirinha, P.

2017-04-01

In this work a methanol steam reforming (MSR) reactor has been operated thermally coupled to a high temperature polymer electrolyte fuel cell stack (HT-PEMFC) utilizing its waste heat. The operating temperature of the coupled system was 180 °C which is significantly lower than the conventional operating temperature of the MSR process which is around 250 °C. A newly designed heat exchanger reformer has been developed by VTT (Technical Research Center of Finland LTD) and was equipped with commercially available CuO/ZnO/Al2O3 (BASF RP-60) catalyst. The liquid cooled, 165 cm2, 12-cell stack used for the measurements was supplied by Serenergy A/S. The off-heat from the electrochemical fuel cell reaction was transferred to the reforming reactor using triethylene glycol (TEG) as heat transfer fluid. The system was operated up to 0.4 A cm-2 generating an electrical power output of 427 Wel. A total stack waste heat utilization of 86.4% was achieved. It has been shown that it is possible to transfer sufficient heat from the fuel cell stack to the liquid circuit in order to provide the needed amount for vaporizing and reforming of the methanol-water-mixture. Furthermore a set of recommendations is given for future system design considerations.

Methanol-Water Aqueous-Phase Reforming with the Assistance of Dehydrogenases at Near-Room Temperature.

PubMed

Shen, Yangbin; Zhan, Yulu; Li, Shuping; Ning, Fandi; Du, Ying; Huang, Yunjie; He, Ting; Zhou, Xiaochun

2018-03-09

As an excellent hydrogen-storage medium, methanol has many advantages, such as high hydrogen content (12.6 wt %), low cost, and availability from biomass or photocatalysis. However, conventional methanol-water reforming usually proceeds at high temperatures. In this research, we successfully designed a new effective strategy to generate hydrogen from methanol at near-room temperature. The strategy involved two main processes: CH 3 OH→HCOOH→H 2 and NADH→HCOOH→H 2 . The first process (CH 3 OH→HCOOH→H 2 ) was performed by an alcohol dehydrogenase (ADH), an aldehyde dehydrogenase (ALDH), and an Ir catalyst. The second procedure (NADH→HCOOH→H 2 ) was performed by formate dehydrogenase (FDH) and the Ir catalyst. The Ir catalyst used was a previously reported polymer complex catalyst [Cp*IrCl 2 (ppy); Cp*=pentamethylcyclopentadienyl, ppy=polypyrrole] with high catalytic activity for the decomposition of formic acid at room temperature and is compatible with enzymes, coenzymes, and poisoning chemicals. Our results revealed that the optimum hydrogen generation rate could reach up to 17.8 μmol h -1  g cat -1 under weak basic conditions at 30 °C. This will have high impact on hydrogen storage, production, and applications and should also provide new inspiration for hydrogen generation from methanol. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

METHANOL MEASUREMENT IN AUTO EXHAUST USING A GAS-FILTER CORRELATION SPECTROMETER

EPA Science Inventory

Spectroscopic methods offer an alternative to wet chemical methods for analysis of methanol emissions from automobiles. The gas filter correlation infrared optical analysis approach appears very promising. The report describes the gas correlation optical system constructed to ana...

Fuel Processing System for a 5kW Methanol Fuel Cell Power Unit.

DTIC Science & Technology

1985-11-27

report documents the development and design of a 5kW neat methanol reformer for phosphoric acid fuel cell power plants . The reformer design was based...VAPORIZATION OF METHANOL ........... 4.3 REFORMING/SHIFT CATALYST BED ......... 2 5.0 COMPONENT TESTING............... 5.1 COMBUSTION TUBE...69 36 Catalyst Bed Temperature Profile Before and After Transient ................. 70 37 Assembly -5kw Neat Methanol Reformer. ......... 72 Page No

Dry reforming of methane to syngas: a potential alternative process for value added chemicals-a techno-economic perspective.

PubMed

Mondal, Kartick; Sasmal, Sankar; Badgandi, Srikant; Chowdhury, Dipabali Roy; Nair, Vinod

2016-11-01

During the past decade, there has been increasing global concern over the rise of anthropogenic CO 2 emission into the Earth's atmosphere (J Air Waste Manage Assoc 53:645-715, 2003). The utilization of CO 2 to produce any valuable product is need of the hour. The production of syngas from CO 2 and CH 4 seems to be one of the promising alternatives in terms of industrial utilization, as it offers several advantages: (a) mitigation of CO 2 , (b) transformation of natural gas and CO 2 into valuable syngas, and (c) producing syngas with H 2 /CO ratio 1 which may further be used for the production of valuable petrochemicals (J Air Waste Manage Assoc 53:645-715, 2003). A conceptual design for the production of synthesis gas by dry reforming of methane is presented here. An economic assessment of this process with an integrated methanol production section as a case was conceptualized and compared with the conventional steam methane reforming route to produce methanol. The economic study indicated that dry reforming of natural gas/methane is a competitive process with lower operating and capital costs in comparison with steam reforming assuming negligible cost of CO 2 import.

The use of advanced steam reforming technology for hydrogen production

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

Abbishaw, J.B.; Cromarty, B.J.

1996-12-01

The demand for supplementary hydrogen production in refineries is growing significantly world-wide as environmental legislation concerning cleaner gasoline and diesel fuels is introduced. The main manufacturing method is by steam reforming. The process has been developed both to reduce the capital cost and increase efficiency, reliability and ease of operation. ICI Katalco`s Leading Concept Hydrogen or LCH process continues this process of improvement by replacing the conventional fired steam reformer with a type of heat exchange reformer known as the Gas Heated Reformer or GHR. The GHR was first used in the Leading Concept Ammonia process, LCA at ICI`s manufacturingmore » site at Severnside, England and commissioned in 1988 and later in the Leading Concept Methanol (LCM) process for methanol at Melbourne, Australia and commissioned in 1994. The development of the LCH process follows on from both LCA and LCM processes. This paper describes the development and use of the GHR in steam reforming, and shows how the GHR can be used in LCH. A comparison between the LCH process and a conventional hydrogen plant is given, showing the benefits of the LCH process in certain circumstances.« less

40 CFR 86.1320-90 - Gas meter or flow instrumentation calibration; particulate, methanol, and formaldehyde measurement.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 20 2012-07-01 2012-07-01 false Gas meter or flow instrumentation... instrumentation calibration; particulate, methanol, and formaldehyde measurement. (a) Sampling for particulate, methanol and formaldehyde emissions requires the use of gas meters or flow instrumentation to determine...

40 CFR 86.1320-90 - Gas meter or flow instrumentation calibration; particulate, methanol, and formaldehyde measurement.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 20 2013-07-01 2013-07-01 false Gas meter or flow instrumentation... instrumentation calibration; particulate, methanol, and formaldehyde measurement. (a) Sampling for particulate, methanol and formaldehyde emissions requires the use of gas meters or flow instrumentation to determine...

40 CFR 86.1320-90 - Gas meter or flow instrumentation calibration; particulate, methanol, and formaldehyde measurement.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 19 2010-07-01 2010-07-01 false Gas meter or flow instrumentation... instrumentation calibration; particulate, methanol, and formaldehyde measurement. (a) Sampling for particulate, methanol and formaldehyde emissions requires the use of gas meters or flow instrumentation to determine...

40 CFR 86.1320-90 - Gas meter or flow instrumentation calibration; particulate, methanol, and formaldehyde measurement.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 19 2011-07-01 2011-07-01 false Gas meter or flow instrumentation... instrumentation calibration; particulate, methanol, and formaldehyde measurement. (a) Sampling for particulate, methanol and formaldehyde emissions requires the use of gas meters or flow instrumentation to determine...

40 CFR 86.120-94 - Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 19 2012-07-01 2012-07-01 false Gas meter or flow instrumentation... Procedures § 86.120-94 Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde... or flow instrumentation to determine flow through the particulate filters, methanol impingers and...

40 CFR 86.120-94 - Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 18 2011-07-01 2011-07-01 false Gas meter or flow instrumentation... Procedures § 86.120-94 Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde... or flow instrumentation to determine flow through the particulate filters, methanol impingers and...

40 CFR 86.120-94 - Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 19 2014-07-01 2014-07-01 false Gas meter or flow instrumentation... Procedures § 86.120-94 Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde... or flow instrumentation to determine flow through the particulate filters, methanol impingers and...

40 CFR 86.120-94 - Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 19 2013-07-01 2013-07-01 false Gas meter or flow instrumentation... Procedures § 86.120-94 Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde... or flow instrumentation to determine flow through the particulate filters, methanol impingers and...

40 CFR 86.120-94 - Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 18 2010-07-01 2010-07-01 false Gas meter or flow instrumentation... Procedures § 86.120-94 Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde... or flow instrumentation to determine flow through the particulate filters, methanol impingers and...

Zircon Supported Copper Catalysts for the Steam Reforming of Methanol

NASA Astrophysics Data System (ADS)

Widiastri, M.; Fendy, Marsih, I. N.

2008-03-01

Steam reforming of methanol (SRM) is known as one of the most favorable catalytic processes for producing hydrogen. Current research on zirconia, ZrO2 supported copper catalyst revealed that CuO/ZrO2 as an active catalyst for the SRM. Zircon, ZrSiO4 is available from the by-product of tin mining. In the work presented here, the catalytic properties of CuO/ZrSiO4 with various copper oxide compositions ranging from 2.70% (catalyst I), 4.12% (catalyst II), and 7.12%-mass (catalyst III), synthesized by an incipient wetness impregnation technique, were investigated to methanol conversion, selectivity towards CO formation, and effect of ZnO addition (7.83%CuO/8.01%ZnO/ZrSiO4 = catalyst V). The catalytic activity was obtained using a fixed bed reactor and the zircon supported catalyst activity was compared to those of CuO/ZnO/Al2O3 catalyst (catalyst IV) and commercial Kujang LTSC catalyst. An X-ray powder diffraction (XRD) analysis was done to identify the abundant phases of the catalysts. The catalysts topography and particle diameter were measured with scanning electron microscopy (SEM) and composition of the catalysts was measured by SEM-EDX, scanning electron microscope-energy dispersive using X-ray analysis. The results of this research provide information on the possibility of using zircon (ZrSiO4) as solid support for SRM catalysts.

Predicted exhaust emissions from a methanol and jet fueled gas turbine combustor

NASA Technical Reports Server (NTRS)

Adelman, H. G.; Browning, L. H.; Pefley, R. K.

1975-01-01

A computer model of a gas turbine combustor has been used to predict the kinetic combustion and pollutant formation processes for methanol and simulated jet fuel. Use of the kinetic reaction mechanisms has also allowed a study of ignition delay and flammability limit of these two fuels. The NOX emissions for methanol were predicted to be from 69 to 92% lower than those for jet fuel at the same equivalence ratio which is in agreement with experimentally observed results. The high heat of vaporization of methanol lowers both the combustor inlet mixture temperatures and the final combustion temperatures. The lower combustion temperatures lead to low NOX emissions while the lower inlet mixture temperatures increase methanol's ignition delay. This increase in ignition delay dictates the lean flammability limit of methanol to be 0.8, while jet fuel is shown to combust at 0.4.

Viewpoint: methanol poisoning outbreak in Libya: a need for policy reforms.

PubMed

Taleb, Ziyad Ben; Bahelah, Raed

2014-11-01

We address the controversies surrounding a 2013 outbreak of methanol poisoning in Tripoli, Libya. We critically examine and systematically analyze the outbreak to highlight the lessons learned from this disaster and how to act properly to prevent similar outbreaks in future. Many health problems have been directly attributed to drinking alcohol; the type and quality of alcohol determines the detrimental effects. An unregulated and flourishing black market in alcohol is among the factors behind the Libyan tragedy, where approximately 90 deaths and about 1000 hospital admissions were reported. We reviewed gaps in local and regional alcohol policy, and highlighted the issue of illegally produced and home-made alcohol. Collaboration between countries in the region plus critical health and policy reforms in Libya, with emphasis on public health preparedness, can dramatically decrease morbidity and mortality associated with such outbreaks.

Fuel cell integrated with steam reformer

DOEpatents

Beshty, Bahjat S.; Whelan, James A.

1987-01-01

A H.sub.2 -air fuel cell integrated with a steam reformer is disclosed wherein a superheated water/methanol mixture is fed to a catalytic reformer to provide a continuous supply of hydrogen to the fuel cell, the gases exhausted from the anode of the fuel cell providing the thermal energy, via combustion, for superheating the water/methanol mixture.

Adsorptive removal of catalyst poisons from coal gas for methanol synthesis

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

Bhatt, B.L.; Golden, T.C.; Hsiung, T.H.

1991-12-01

As an integral part of the liquid-phase methanol (LPMEOH) process development program, the present study evaluated adsorptive schemes to remove traces of catalyst poisons such as iron carbonyl, carbonyl sulfide, and hydrogen sulfide from coal gas on a pilot scale. Tests were conducted with coal gas from the Cool Water gasification plant at Daggett, California. Iron carbonyl, carbonyl sulfide, and hydrogen sulfide were effectively removed from the coal gas. The adsorption capacities of Linde H-Y zeolite and Calgon BPL carbon for Fe(CO){sub 5} compared well with previous bench-scale results at similar CO{sub 2} partial pressure. Adsorption of COS by Calgonmore » FCA carbon appeared to be chemical and nonregenerable by thermal treatment in nitrogen. A Cu/Zn catalyst removed H{sub 2}S very effectively. With the adsorption system on-line, a methanol catalyst showed stable activity during 120 h operation, demonstrating the feasibility of adsorptive removal of trace catalyst poisons from the synthesis gas. Mass transfer coefficients were estimated for Fe(CO){sub 5} and COS removal which can be directly used for design and scale up.« less

Hydrogen production by reforming of liquid hydrocarbons in a membrane reactor for portable power generation-Experimental studies

NASA Astrophysics Data System (ADS)

Damle, Ashok S.

One of the most promising technologies for lightweight, compact, portable power generation is proton exchange membrane (PEM) fuel cells. PEM fuel cells, however, require a source of pure hydrogen. Steam reforming of hydrocarbons in an integrated membrane reactor has potential to provide pure hydrogen in a compact system. Continuous separation of product hydrogen from the reforming gas mixture is expected to increase the yield of hydrogen significantly as predicted by model simulations. In the laboratory-scale experimental studies reported here steam reforming of liquid hydrocarbon fuels, butane, methanol and Clearlite ® was conducted to produce pure hydrogen in a single step membrane reformer using commercially available Pd-Ag foil membranes and reforming/WGS catalysts. All of the experimental results demonstrated increase in hydrocarbon conversion due to hydrogen separation when compared with the hydrocarbon conversion without any hydrogen separation. Increase in hydrogen recovery was also shown to result in corresponding increase in hydrocarbon conversion in these studies demonstrating the basic concept. The experiments also provided insight into the effect of individual variables such as pressure, temperature, gas space velocity, and steam to carbon ratio. Steam reforming of butane was found to be limited by reaction kinetics for the experimental conditions used: catalysts used, average gas space velocity, and the reactor characteristics of surface area to volume ratio. Steam reforming of methanol in the presence of only WGS catalyst on the other hand indicated that the membrane reactor performance was limited by membrane permeation, especially at lower temperatures and lower feed pressures due to slower reconstitution of CO and H 2 into methane thus maintaining high hydrogen partial pressures in the reacting gas mixture. The limited amount of data collected with steam reforming of Clearlite ® indicated very good match between theoretical predictions and

Systematic Search for Chemical Reactions in Gas Phase Contributing to Methanol Formation in Interstellar Space.

PubMed

Gamez-Garcia, Victoria G; Galano, Annia

2017-10-05

A massive search for chemical routes leading to methanol formation in gas phase has been conducted using computational chemistry, at the CBS-QB3 level of theory. The calculations were performed at five different temperatures (100, 80, 50, 20, and 10 K) and at three pressures (0.1, 0.01, and 0.001 atm) for each temperature. The search was focused on identifying reactions with the necessary features to be viable in the interstellar medium (ISM). A searching strategy was applied to that purpose, which allowed to reduce an initial set of 678 possible reactions to a subset of 11 chemical routes that are recommended, for the first time, as potential candidates for contributing to methanol formation in the gas phase of the ISM. They are all barrier-less, and thus they are expected to take place at collision rates. Hopefully, including these reactions in the currently available models, for the gas-phase methanol formation in the ISM, would help improving the predicted fractional abundance of this molecule in dark clouds. Further investigations, especially those dealing with grain chemistry and electronic excited states, would be crucial to get a complete picture of the methanol formation in the ISM.

Thinking on Sichuan-Chongqing gas pipeline transportation system reform under market-oriented conditions

NASA Astrophysics Data System (ADS)

Duan, Yanzhi

2017-01-01

The gas pipeline networks in Sichuan and Chongqing (Sichuan-Chongqing) region have formed a fully-fledged gas pipeline transportation system in China, which supports and promotes the rapid development of gas market in Sichuan-Chongqing region. In the circumstances of further developed market-oriented economy, it is necessary to carry out further the pipeline system reform in the areas of investment/financing system, operation system and pricing system to lay a solid foundation for improving future gas production and marketing capability and adapting itself to the national gas system reform, and to achieve the objectives of multiparty participated pipeline construction, improved pipeline transportation efficiency and fair and rational pipeline transportation prices. In this article, main thinking on reform in the three areas and major deployment are addressed, and corresponding measures on developing shared pipeline economy, providing financial support to pipeline construction, setting up independent regulatory agency to enhance the industrial supervision for gas pipeline transportation, and promoting the construction of regional gas trade market are recommended.

Stabilization of Hydrogen Production via Methanol Steam Reforming in Microreactor by Al2O3 Nano-Film Enhanced Catalyst Adhesion.

PubMed

Jeong, Heondo; Na, Jeong-Geol; Jang, Min Su; Ko, Chang Hyun

2016-05-01

In hydrogen production by methanol steam reforming reaction with microchannel reactor, Al2O3 thin film formed by atomic layer deposition (ALD) was introduced on the surface of microchannel reactor prior to the coating of catalyst particles. Methanol conversion rate and hydrogen production rate, increased in the presence of Al2O3 thin film. Over-view and cross-sectional scanning electron microscopy study showed that the adhesion between catalyst particles and the surface of microchannel reactor enhanced due to the presence of Al2O3 thin film. The improvement of hydrogen production rate inside the channels of microreactor mainly came from the stable fixation of catalyst particles on the surface of microchannels.

Direct methanol fuel cell and system

DOEpatents

Wilson, Mahlon S.

2004-10-26

A fuel cell having an anode and a cathode and a polymer electrolyte membrane located between anode and cathode gas diffusion backings uses a methanol vapor fuel supply. A permeable polymer electrolyte membrane having a permeability effective to sustain a carbon dioxide flux equivalent to at least 10 mA/cm.sup.2 provides for removal of carbon dioxide produced at the anode by reaction of methanol with water. Another aspect of the present invention includes a superabsorpent polymer material placed in proximity to the anode gas diffusion backing to hold liquid methanol or liquid methanol solution without wetting the anode gas diffusion backing so that methanol vapor from the liquid methanol or liquid methanol-water solution is supplied to the membrane.

Water co-catalyzed selective dehydrogenation of methanol to formaldehyde and hydrogen

NASA Astrophysics Data System (ADS)

Shan, Junjun; Lucci, Felicia R.; Liu, Jilei; El-Soda, Mostafa; Marcinkowski, Matthew D.; Allard, Lawrence F.; Sykes, E. Charles H.; Flytzani-Stephanopoulos, Maria

2016-08-01

The non-oxidative dehydrogenation of methanol to formaldehyde is considered a promising method to produce formaldehyde and clean hydrogen gas. Although Cu-based catalysts have an excellent catalytic activity in the oxidative dehydrogenation of methanol, metallic Cu is commonly believed to be unreactive for the dehydrogenation of methanol in the absence of oxygen adatoms or oxidized copper. Herein we show that metallic Cu can catalyze the dehydrogenation of methanol in the absence of oxygen adatoms by using water as a co-catalyst both under realistic reaction conditions using silica-supported PtCu nanoparticles in a flow reactor system at temperatures below 250 °C, and in ultra-high vacuum using model PtCu(111) catalysts. Adding small amounts of isolated Pt atoms into the Cu surface to form PtCu single atom alloys (SAAs) greatly enhances the dehydrogenation activity of Cu. Under the same reaction conditions, the yields of formaldehyde from PtCu SAA nanoparticles are more than one order of magnitude higher than on the Cu nanoparticles, indicating a significant promotional effect of individual, isolated Pt atoms. Moreover, this study also shows the unexpected role of water in the activation of methanol. Water, a catalyst for methanol dehydrogenation at low temperatures, becomes a reactant in the methanol steam reforming reactions only at higher temperatures over the same metal catalyst.

Hydrogen production from alcohol reforming in a microwave ‘tornado’-type plasma

NASA Astrophysics Data System (ADS)

Tatarova, E.; Bundaleska, N.; Dias, F. M.; Tsyganov, D.; Saavedra, R.; Ferreira, C. M.

2013-12-01

In this work, an experimental investigation of microwave plasma-assisted reforming of different alcohols is presented. A microwave (2.45 GHz) ‘tornado’-type plasma with a high-speed tangential gas injection (swirl) at atmospheric pressure is applied to decompose alcohol molecules, namely methanol, ethanol and propanol, and to produce hydrogen-rich gas. The reforming efficiency is investigated both in Ar and Ar+ water vapor plasma environments. The hydrogen yield dependence on the partial alcohol flux is analyzed. Mass spectrometry and Fourier transform infrared spectroscopy are used to detect the outlet gas products from the decomposition process. Hydrogen, carbon monoxide, carbon dioxide and solid carbon are the main decomposition by-products. A significant increase in the hydrogen production rate is observed with the addition of a small amount of water. Furthermore, optical emission spectroscopy is applied to detect the radiation emitted by the plasma and to estimate the gas temperature and electron density.

Method for making methanol

DOEpatents

Mednick, R. Lawrence; Blum, David B.

1987-01-01

Methanol is made in a liquid-phase methanol reactor by entraining a methanol-forming catalyst in an inert liquid and contacting said entrained catalyst with a synthesis gas comprising hydrogen and carbon monoxide.

A Novel Study of Methane-Rich Gas Reforming to Syngas and Its Kinetics over Semicoke Catalyst

PubMed Central

Zhang, Guojie; Su, Aiting; Qu, Jiangwen; Du, Yannian

2014-01-01

A small-size gasification unit is improved through process optimization to simulate industrial United Gas Improvement Company gasification. It finds that the reaction temperature has important impacts on semicoke catalyzed methane gas mixture. The addition of water vapor can enhance the catalytic activity of reforming, which is due to the fact that addition of water vapor not only removes carbon deposit produced in the reforming and gasification reaction processes, but also participates in gasification reaction with semicoke to generate some active oxygen-containing functional groups. The active oxygen-containing functional groups provide active sites for carbon dioxide reforming of methane, promoting the reforming reaction. It also finds that the addition of different proportions of methane-rich gas can yield synthesis gas with different H2/CO ratio. The kinetics study shows that the semicoke can reduce the activation energy of the reforming reaction and promote the occurrence of the reforming reaction. The kinetics model of methane reforming under the conditions of steam gasification over semicoke is as follows: k-=5.02×103·pCH40.71·pH20.26·exp(−74200/RT). PMID:24959620

Hydrogen Production by Steam Reforming of Natural Gas Over Vanadium-Nickel-Alumina Catalysts.

PubMed

Yoo, Jaekyeong; Park, Seungwon; Song, Ji Hwan; Song, In Kyu

2018-09-01

A series of vanadium-nickel-alumina (xVNA) catalysts were prepared by a single-step sol-gel method with a variation of vanadium content (x, wt%) for use in the hydrogen production by steam reforming of natural gas. The effect of vanadium content on the physicochemical properties and catalytic activities of xVNA catalysts in the steam reforming of natural gas was investigated. It was found that natural gas conversion and hydrogen yield showed volcano-shaped trends with respect to vanadium content. It was also revealed that natural gas conversion and hydrogen yield increased with decreasing nickel crystallite size.

Oxo-exchange of gas-phase uranyl, neptunyl, and plutonyl with water and methanol.

PubMed

Lucena, Ana F; Odoh, Samuel O; Zhao, Jing; Marçalo, Joaquim; Schreckenbach, Georg; Gibson, John K

2014-02-17

A challenge in actinide chemistry is activation of the strong bonds in the actinyl ions, AnO2(+) and AnO2(2+), where An = U, Np, or Pu. Actinyl activation in oxo-exchange with water in solution is well established, but the exchange mechanisms are unknown. Gas-phase actinyl oxo-exchange is a means to probe these processes in detail for simple systems, which are amenable to computational modeling. Gas-phase exchange reactions of UO2(+), NpO2(+), PuO2(+), and UO2(2+) with water and methanol were studied by experiment and density functional theory (DFT); reported for the first time are experimental results for UO2(2+) and for methanol exchange, as well as exchange rate constants. Key findings are faster exchange of UO2(2+) versus UO2(+) and faster exchange with methanol versus water; faster exchange of UO2(+) versus PuO2(+) was quantified. Computed potential energy profiles (PEPs) are in accord with the observed kinetics, validating the utility of DFT to model these exchange processes. The seemingly enigmatic result of faster exchange for uranyl, which has the strongest oxo-bonds, may reflect reduced covalency in uranyl as compared with plutonyl.

Method for forming synthesis gas using a plasma-catalyzed fuel reformer

DOEpatents

Hartvigsen, Joseph J; Elangovan, S; Czernichowski, Piotr; Hollist, Michele

2015-04-28

A method of forming a synthesis gas utilizing a reformer is disclosed. The method utilizes a reformer that includes a plasma zone to receive a pre-heated mixture of reactants and ionize the reactants by applying an electrical potential thereto. A first thermally conductive surface surrounds the plasma zone and is configured to transfer heat from an external heat source into the plasma zone. The reformer further includes a reaction zone to chemically transform the ionized reactants into synthesis gas comprising hydrogen and carbon monoxide. A second thermally conductive surface surrounds the reaction zone and is configured to transfer heat from the external heat source into the reaction zone. The first thermally conductive surface and second thermally conductive surface are both directly exposed to the external heat source. A corresponding apparatus and system are also disclosed herein.

Improvement in methanol production by regulating the composition of synthetic gas mixture and raw biogas.

PubMed

Patel, Sanjay K S; Mardina, Primata; Kim, Dongwook; Kim, Sang-Yong; Kalia, Vipin C; Kim, In-Won; Lee, Jung-Kul

2016-10-01

Raw biogas can be an alternative feedstock to pure methane (CH4) for methanol production. In this investigation, we evaluated the methanol production potential of Methylosinus sporium from raw biogas originated from an anaerobic digester. Furthermore, the roles of different gases in methanol production were investigated using synthetic gas mixtures of CH4, carbon dioxide (CO2), and hydrogen (H2). Maximum methanol production was 5.13, 4.35, 6.28, 7.16, 0.38, and 0.36mM from raw biogas, CH4:CO2, CH4:H2, CH4:CO2:H2, CO2, and CO2:H2, respectively. Supplementation of H2 into raw biogas increased methanol production up to 3.5-fold. Additionally, covalent immobilization of M. sporium on chitosan resulted in higher methanol production from raw biogas. This study provides a suitable approach to improve methanol production using low cost raw biogas as a feed containing high concentrations of H2S (0.13%). To our knowledge, this is the first report on methanol production from raw biogas, using immobilized cells of methanotrophs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rapid starting methanol reactor system

DOEpatents

Chludzinski, Paul J.; Dantowitz, Philip; McElroy, James F.

1984-01-01

The invention relates to a methanol-to-hydrogen cracking reactor for use with a fuel cell vehicular power plant. The system is particularly designed for rapid start-up of the catalytic methanol cracking reactor after an extended shut-down period, i.e., after the vehicular fuel cell power plant has been inoperative overnight. Rapid system start-up is accomplished by a combination of direct and indirect heating of the cracking catalyst. Initially, liquid methanol is burned with a stoichiometric or slightly lean air mixture in the combustion chamber of the reactor assembly. The hot combustion gas travels down a flue gas chamber in heat exchange relationship with the catalytic cracking chamber transferring heat across the catalyst chamber wall to heat the catalyst indirectly. The combustion gas is then diverted back through the catalyst bed to heat the catalyst pellets directly. When the cracking reactor temperature reaches operating temperature, methanol combustion is stopped and a hot gas valve is switched to route the flue gas overboard, with methanol being fed directly to the catalytic cracking reactor. Thereafter, the burner operates on excess hydrogen from the fuel cells.

Tri-reforming and combined reforming of methane for producing syngas with desired hydrogen/carbon monoxide ratios

NASA Astrophysics Data System (ADS)

Pan, Wei

This dissertation is an exploratory study of a new process concept for direct production of synthesis gas (CO + H2) with desired H 2/CO ratios (1.5--2.0) for methanol synthesis and F-T synthesis, using CO2 together with steam and unconverted O2 in flue gas from fossil fuel-fired electric power plants to react with methane or natural gas. This new process is called tri-reforming, referring to simultaneous CO2-steam-O2 reforming of methane or natural gas. This study included (1) The investigation of carbon formation in the tri-reforming process. For comparison, carbon formation in the combined reforming and CO2 reforming reaction was studied as well. (2) The effect of reaction conditions and feed compositions on equilibrium composition (e.g. H2/CO ratio) and equilibrium conversions in the tri-reforming process. (3) The role of catalysts in the tri-reforming process, especially the effect of catalysts on CO2 conversion in the presence of H 2O and O2. It was clearly evidenced from this study that CO in the product stream is probably the major source of carbon over Ni/Al2O3 in the equimolar CO2-CH4 reforming at 650°C and 1 atm. Addition of either O2 or H2O into the CO 2 reforming reaction system can suppress carbon formation. It was demonstrated that carbon-free operation can be achieved in the tri-reforming process. A thermodynamic comparison of tri-reforming with feed compositions of (H2O+CO2+0.5O2)/CH4 (mol ratio) = 1 showed that O2 improves equilibrium CH4 conversion, yet greatly decreases equilibrium CO2 conversion. H2O in tri-reforming has a significant effect on the H2/CO ratio in the products, while O2 has a minor effect. A kinetic study and catalytic performance tests indicated that the support in a supported catalyst has a significant role in enhancing CO2 conversion to CO in the presence of H2O and O2 in tri-reforming. The Ni/MgO catalyst showed superior performance with close to equilibrium CH4 and CO2 conversions at 850°C, 1 atm, and 32,000 ml

Simultaneous determination of methanol, acetaldehyde, acetone, and ethanol in human blood by gas chromatography with flame ionization detection.

PubMed

Schlatter, J; Chiadmi, F; Gandon, V; Chariot, P

2014-01-01

Methanol, acetaldehyde, acetone, and ethanol, which are commonly used as biomarkers of several diseases, in acute intoxications, and forensic settings, can be detected and quantified in biological fluids. Gas chromatography (GC)-mass spectrometry techniques are complex, require highly trained personnel and expensive materials. Gas chromatographic determinations of ethanol, methanol, and acetone have been reported in one study with suboptimal accuracy. Our objective was to improve the assessment of these compounds in human blood using GC with flame ionization detection. An amount of 50 µl of blood was diluted with 300 µl of sterile water, 40 µl of 10% sodium tungstate, and 20 µl of 1% sulphuric acid. After centrifugation, 1 µl of the supernatant was injected into the gas chromatograph. We used a dimethylpolysiloxane capillary column of 30 m × 0.25 mm × 0.25 µm. We observed linear correlations from 7.5 to 240 mg/l for methanol, acetaldehyde, and acetone and from 75 to 2400 mg/l for ethanol. Precision at concentrations 15, 60, and 120 mg/l for methanol, acetaldehyde, and acetone and 150, 600, and 1200 mg/ml for ethanol were 0.8-6.9%. Ranges of accuracy were 94.7-98.9% for methanol, 91.2-97.4% for acetaldehyde, 96.1-98.7% for acetone, and 105.5-111.6% for ethanol. Limits of detection were 0.80 mg/l for methanol, 0.61 mg/l for acetaldehyde, 0.58 mg/l for acetone, and 0.53 mg/l for ethanol. This method is suitable for routine clinical and forensic practices.

Methanol steam reforming promoted by molten salt-modified platinum on alumina catalysts.

PubMed

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-09-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the "solid catalyst with ionic liquid layer" (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methanol Steam Reforming Promoted by Molten Salt-Modified Platinum on Alumina Catalysts

PubMed Central

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-01-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the “solid catalyst with ionic liquid layer” (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass %. PMID:25124120

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

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

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

Methanol steam reforming over Ni-CeO 2 model and powder catalysts: Pathways to high stability and selectivity for H 2/CO 2 production

DOE PAGES

Liu, Zongyuan; Yao, Siyu; Johnston-Peck, Aaron; ...

2017-08-25

Here, nickel-ceria has been reported as a very good catalysts for the reforming of methane. Here, the methanol steam reforming reaction on both powder (Ni-CeO 2) and model (Ni-CeO 2-x(111)) catalysts was investigated. The active phase evolution and surface species transformation on powder catalysts were studied via in situ X-ray diffraction (XRD) and diffuse reflectance infrared transform spectroscopy (DRIFTS). Phase transitions of NiO → NiC → Ni and CeO 2 → CeO 2-x were observed during the reaction. The simultaneous production of H 2/CO 2 demonstrates that the active phase of the catalysts contains metallic Ni supported over partially reducedmore » ceria. The DRIFTS experiments indicate that a methoxy to formate transition is associated with the reduction of ceria whereas the formation of carbonate species results from the presence of metallic Ni. A study of the reaction of methanol with Ni-CeO 2-x(111) by X-ray photoelectron spectroscopy (XPS) points to the essential role of metal-support interactions in an oxygen transfer from ceria to Ni that contributes to the high selectivity of the catalysts.« less

Methanol steam reforming over Ni-CeO 2 model and powder catalysts: Pathways to high stability and selectivity for H 2/CO 2 production

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

Liu, Zongyuan; Yao, Siyu; Johnston-Peck, Aaron

Here, nickel-ceria has been reported as a very good catalysts for the reforming of methane. Here, the methanol steam reforming reaction on both powder (Ni-CeO 2) and model (Ni-CeO 2-x(111)) catalysts was investigated. The active phase evolution and surface species transformation on powder catalysts were studied via in situ X-ray diffraction (XRD) and diffuse reflectance infrared transform spectroscopy (DRIFTS). Phase transitions of NiO → NiC → Ni and CeO 2 → CeO 2-x were observed during the reaction. The simultaneous production of H 2/CO 2 demonstrates that the active phase of the catalysts contains metallic Ni supported over partially reducedmore » ceria. The DRIFTS experiments indicate that a methoxy to formate transition is associated with the reduction of ceria whereas the formation of carbonate species results from the presence of metallic Ni. A study of the reaction of methanol with Ni-CeO 2-x(111) by X-ray photoelectron spectroscopy (XPS) points to the essential role of metal-support interactions in an oxygen transfer from ceria to Ni that contributes to the high selectivity of the catalysts.« less

Non-catalytic recuperative reformer

DOEpatents

Khinkis, Mark J.; Kozlov, Aleksandr P.; Kurek, Harry

2015-12-22

A non-catalytic recuperative reformer has a flue gas flow path for conducting hot flue gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is embedded in the flue gas flow path to permit heat transfer from the hot flue gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorific fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, extended surfaces of metal material such as stainless steel or metal alloy that are high in nickel content are included within at least a portion of the reforming mixture flow path.

Analytical methods for measuring the parameters of interstellar gas using methanol observations

NASA Astrophysics Data System (ADS)

Kalenskii, S. V.; Kurtz, S.

2016-08-01

The excitation of methanol in the absence of external radiation is analyzed, and LTE methods for probing interstellar gas considered. It is shown that rotation diagrams correctly estimate the gas kinetic temperature only if they are constructed using lines whose upper levels are located in the same K-ladders, such as the J 0- J -1 E lines at 157 GHz, the J 1- J 0 E lines at 165 GHz, and the J 2- J 1 E lines at 25 GHz. The gas density must be no less than 107 cm-3. Rotation diagrams constructed from lines with different K values for their upper levels (e.g., 2 K -1 K at 96 GHz, 3 K -2 K at 145 GHz, 5 K -4 K at 241 GHz) significantly underestimate the temperature, but enable estimation of the density. In addition, diagrams based on the 2 K -1 K lines can be used to estimate the methanol column density within a factor of about two to five. It is suggested that rotation diagrams should be used in the following manner. First, two rotation diagrams should be constructed, one from the lines at 96, 145, or 241 GHz, and another from the lines at 157, 165, or 25 GHz. The former diagram is used to estimate the gas density. If the density is about 107 cm-3 or higher, the latter diagram reproduces the temperature fairly well. If the density is around 106 cm-3, the temperature obtained from the latter diagram should be multiplied by a factor of 1.5-2. If the density is about 105 cm-3 or lower, then the latter diagram yields a temperature that is lower than the kinetic temperature by a factor of three or more, and should be used only as a lower limit for the kinetic temperature. The errors in the methanol column density determined from the integrated intensity of a single line can be more than an order of magnitude, even when the gas temperature is well known. However, if the J 0-( J - 1)0 E lines, as well as the J 1-( J - 1)1 A + or A - lines are used, the relative error in the column density is no more than a factor of a few.

Heterogeneous Chemistry Involving Methanol in Tropospheric Clouds

NASA Technical Reports Server (NTRS)

Tabazadeh, A.; Yokelson, R. J.; Singh, H. B.; Hobbs, P. V.; Crawford, J. H.; Iraci, L. T.

2004-01-01

In this report we analyze airborne measurements to suggest that methanol in biomass burning smoke is lost heterogeneously in clouds. When a smoke plume intersected a cumulus cloud during the SAFARI 2000 field project, the observed methanol gas phase concentration rapidly declined. Current understanding of gas and aqueous phase chemistry cannot explain the loss of methanol documented by these measurements. Two plausible heterogeneous reactions are proposed to explain the observed simultaneous loss and production of methanol and formaldehyde, respectively. If the rapid heterogeneous processing of methanol, seen in a cloud impacted by smoke, occurs in more pristine clouds, it could affect the oxidizing capacity of the troposphere on a global scale.

Liquid phase low temperature method for production of methanol from synthesis gas and catalyst formulations therefor

DOEpatents

Mahajan, Devinder

2005-07-26

The invention provides a homogenous catalyst for the production of methanol from purified synthesis gas at low temperature and low pressure which includes a transition metal capable of forming transition metal complexes with coordinating ligands and an alkoxide, the catalyst dissolved in a methanol solvent system, provided the transition metal complex is not transition metal carbonyl. The coordinating ligands can be selected from the group consisting of N-donor ligands, P-donor ligands, O-donor ligands, C-donor ligands, halogens and mixtures thereof.

Design and Operation of the Synthesis Gas Generator System for Reformed Propane and Glycerin Combustion

NASA Astrophysics Data System (ADS)

Pickett, Derek Kyle

Due to an increased interest in sustainable energy, biodiesel has become much more widely used in the last several years. Glycerin, one major waste component in biodiesel production, can be converted into a hydrogen rich synthesis gas to be used in an engine generator to recover energy from the biodiesel production process. This thesis contains information detailing the production, testing, and analysis of a unique synthesis generator rig at the University of Kansas. Chapter 2 gives a complete background of all major components, as well as how they are operated. In addition to component descriptions, methods for operating the system on pure propane, reformed propane, reformed glycerin along with the methodology of data acquisition is described. This chapter will serve as a complete operating manual for future students to continue research on the project. Chapter 3 details the literature review that was completed to better understand fuel reforming of propane and glycerin. This chapter also describes the numerical model produced to estimate the species produced during reformation activities. The model was applied to propane reformation in a proof of concept and calibration test before moving to glycerin reformation and its subsequent combustion. Chapter 4 first describes the efforts to apply the numerical model to glycerin using the calibration tools from propane reformation. It then discusses catalytic material preparation and glycerin reformation tests. Gas chromatography analysis of the reformer effluent was completed to compare to theoretical values from the numerical model. Finally, combustion of reformed glycerin was completed for power generation. Tests were completed to compare emissions from syngas combustion and propane combustion.

Steam Reforming of Methyl Fuel - Phase I

DTIC Science & Technology

1977-06-30

best catalyst . 2.0 TEST DESCRIPTION 2.1 Technical Background The basic reactions occurring in steam reforming of methanol are CH3OH + H20 CO2 + 3H 2...chamber contains the test catalyst . The fuel feed tank was filled with premixed methanol /gasoline mixture. Fuel flow as well as water flow were measured...carbon-oxygen bond formation and therefore follows a different mechanism than the methanol reaction . Different catalysts promote these types of

High-Temperature Desulfurization of Heavy Fuel-Derived Reformate Gas Streams for SOFC Applications

NASA Technical Reports Server (NTRS)

Flytzani-Stephanopoulos, Maria; Surgenor, Angela D.

2007-01-01

Desulfurization of the hot reformate gas produced by catalytic partial oxidation or autothermal reforming of heavy fuels, such as JP-8 and jet fuels, is required prior to using the gas in a solid oxide fuel cell (SOFC). Development of suitable sorbent materials involves the identification of sorbents with favorable sulfidation equilibria, good kinetics, and high structural stability and regenerability at the SOFC operating temperatures (650 to 800 C). Over the last two decades, a major barrier to the development of regenerable desulfurization sorbents has been the gradual loss of sorbent performance in cyclic sulfidation and regeneration at such high temperatures. Mixed oxide compositions based on ceria were examined in this work as regenerable sorbents in simulated reformate gas mixtures and temperatures greater than 650 C. Regeneration was carried out with dilute oxygen streams. We have shown that under oxidative regeneration conditions, high regeneration space velocities (greater than 80,000 h(sup -1)) can be used to suppress sulfate formation and shorten the total time required for sorbent regeneration. A major finding of this work is that the surface of ceria and lanthanan sorbents can be sulfided and regenerated completely, independent of the underlying bulk sorbent. This is due to reversible adsorption of H2S on the surface of these sorbents even at temperatures as high as 800 C. La-rich cerium oxide formulations are excellent for application to regenerative H2S removal from reformate gas streams at 650 to 800 C. These results create new opportunities for compact sorber/regenerator reactor designs to meet the requirements of solid oxide fuel cell systems at any scale.

Gas-Phase Hydrodesulfurization of JP-8 Light Fraction Using Steam Reformate

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

Huang, Xiwen; King, David L.

2006-10-11

Gas phase hydrodesulfurization of JP-8 light fraction was investigated over CoMo/Al2O3 and NiMo/Al2O3 catalysts. Use of a light fraction provides a fuel that is more easily desulfurized, and allows the process to operate in the vapor phase. This study investigated the utilization of reformate (syngas) from a steam reformer rather than pure H2 as gas feed to HDS unit. This is consistent with what might be available to the military during operation in the field. Dry syngas functions almost as well as pure H2 in the HDS reaction, and sulfur levels below 5ppmw are readily obtained from a feed initiallymore » containing 320ppmw sulfur. Addition of steam at 40 vol% to the gas feed has a significant negative impact on HDS performance with CoMo/Al2O3, but only a small effect with NiMo/Al2O3. The impacts of various process conditions on S removal efficiency were examined and will be described.« less

A comparison of hydrogen, methanol and gasoline as fuels for fuel cell vehicles: implications for vehicle design and infrastructure development

NASA Astrophysics Data System (ADS)

Ogden, Joan M.; Steinbugler, Margaret M.; Kreutz, Thomas G.

All fuel cells currently being developed for near term use in electric vehicles require hydrogen as a fuel. Hydrogen can be stored directly or produced onboard the vehicle by reforming methanol, or hydrocarbon fuels derived from crude oil (e.g., gasoline, diesel, or middle distillates). The vehicle design is simpler with direct hydrogen storage, but requires developing a more complex refueling infrastructure. In this paper, we present modeling results comparing three leading options for fuel storage onboard fuel cell vehicles: (a) compressed gas hydrogen storage, (b) onboard steam reforming of methanol, (c) onboard partial oxidation (POX) of hydrocarbon fuels derived from crude oil. We have developed a fuel cell vehicle model, including detailed models of onboard fuel processors. This allows us to compare the vehicle performance, fuel economy, weight, and cost for various vehicle parameters, fuel storage choices and driving cycles. The infrastructure requirements are also compared for gaseous hydrogen, methanol and gasoline, including the added costs of fuel production, storage, distribution and refueling stations. The delivered fuel cost, total lifecycle cost of transportation, and capital cost of infrastructure development are estimated for each alternative. Considering both vehicle and infrastructure issues, possible fuel strategies leading to the commercialization of fuel cell vehicles are discussed.

Regulatory reform for natural gas pipelines: The effect on pipeline and distribution company share prices

NASA Astrophysics Data System (ADS)

Jurman, Elisabeth Antonie

1997-08-01

The natural gas shortages in the 1970s focused considerable attention on the federal government's role in altering energy consumption. For the natural gas industry these shortages eventually led to the passage of the Natural Gas Policy Act (NGPA) in 1978 as part of the National Energy Plan. A series of events in the decade of the 1980s has brought about the restructuring of interstate natural gas pipelines which have been transformed by regulators and the courts from monopolies into competitive entities. This transformation also changed their relationship with their downstream customers, the LDCs, who no longer had to deal with pipelines as the only merchants of gas. Regulatory reform made it possible for LDCs to buy directly from producers using the pipelines only for delivery of their purchases. This study tests for the existence of monopoly rents by analyzing the daily returns of natural gas pipeline and utility industry stock price data from 1982 to 1990, a period of regulatory reform for the natural gas industry. The study's main objective is to investigate the degree of empirical support for claims that regulatory reforms increase profits in the affected industry, as the normative theory of regulation expects, or decrease profits, as advocates of the positive theory of regulation believe. I also test Norton's theory of risk which predicts that systematic risk will increase for firms undergoing deregulation. Based on a sample of twelve natural gas pipelines, and 25 utilities an event study concept was employed to measure the impact of regulatory event announcements on daily natural gas pipeline or utility industry stock price data using a market model regression equation. The results of this study provide some evidence that regulatory reforms did not increase the profits of pipeline firms, confirming the expectations of those who claim that excess profits result from regulation and will disappear, once that protection is removed and the firms are operating in

Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water

NASA Astrophysics Data System (ADS)

Cortright, R. D.; Davda, R. R.; Dumesic, J. A.

2002-08-01

Concerns about the depletion of fossil fuel reserves and the pollution caused by continuously increasing energy demands make hydrogen an attractive alternative energy source. Hydrogen is currently derived from nonrenewable natural gas and petroleum, but could in principle be generated from renewable resources such as biomass or water. However, efficient hydrogen production from water remains difficult and technologies for generating hydrogen from biomass, such as enzymatic decomposition of sugars, steam-reforming of bio-oils and gasification, suffer from low hydrogen production rates and/or complex processing requirements. Here we demonstrate that hydrogen can be produced from sugars and alcohols at temperatures near 500K in a single-reactor aqueous-phase reforming process using a platinum-based catalyst. We are able to convert glucose-which makes up the major energy reserves in plants and animals-to hydrogen and gaseous alkanes, with hydrogen constituting 50% of the products. We find that the selectivity for hydrogen production increases when we use molecules that are more reduced than sugars, with ethylene glycol and methanol being almost completely converted into hydrogen and carbon dioxide. These findings suggest that catalytic aqueous-phase reforming might prove useful for the generation of hydrogen-rich fuel gas from carbohydrates extracted from renewable biomass and biomass waste streams.

Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water.

PubMed

Cortright, R D; Davda, R R; Dumesic, J A

2002-08-29

Concerns about the depletion of fossil fuel reserves and the pollution caused by continuously increasing energy demands make hydrogen an attractive alternative energy source. Hydrogen is currently derived from nonrenewable natural gas and petroleum, but could in principle be generated from renewable resources such as biomass or water. However, efficient hydrogen production from water remains difficult and technologies for generating hydrogen from biomass, such as enzymatic decomposition of sugars, steam-reforming of bio-oils and gasification, suffer from low hydrogen production rates and/or complex processing requirements. Here we demonstrate that hydrogen can be produced from sugars and alcohols at temperatures near 500 K in a single-reactor aqueous-phase reforming process using a platinum-based catalyst. We are able to convert glucose -- which makes up the major energy reserves in plants and animals -- to hydrogen and gaseous alkanes, with hydrogen constituting 50% of the products. We find that the selectivity for hydrogen production increases when we use molecules that are more reduced than sugars, with ethylene glycol and methanol being almost completely converted into hydrogen and carbon dioxide. These findings suggest that catalytic aqueous-phase reforming might prove useful for the generation of hydrogen-rich fuel gas from carbohydrates extracted from renewable biomass and biomass waste streams.

Investigation of the In-Situ Oxidation of Methanol in Fuel Cells.

DTIC Science & Technology

1981-09-01

ability of the catalyst to tolerate carbon monoxide. Finally, a performance curve was obtained for the anodic oxidation of methanol : CH3OH ... CH3OH + H20 •» C02 + 3H2 In present methanol -air fuel cell power plants , the steam reforming process is usually carried out in a unit which is...KCY YIO"(CS (Continue on reverse ride it neeessnry and identity ay block number) Fuel Cell Platinum Catalysts Methanol Direct Oxidation Internal

The Methanol Economy Project

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

Olah, George; Prakash, G. K.

2014-02-01

The Methanol Economy Project is based on the concept of replacing fossil fuels with methanol generated either from renewable resources or abundant natural (shale) gas. The full methanol cycle was investigated in this project, from production of methanol through bromination of methane, bireforming of methane to syngas, CO 2 capture using supported amines, co-electrolysis of CO 2 and water to formate and syngas, decomposition of formate to CO 2 and H 2, and use of formic acid in a direct formic acid fuel cell. Each of these projects achieved milestones and provided new insights into their respective fields.

Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts

NASA Astrophysics Data System (ADS)

Lin, Lili; Zhou, Wu; Gao, Rui; Yao, Siyu; Zhang, Xiao; Xu, Wenqian; Zheng, Shijian; Jiang, Zheng; Yu, Qiaolin; Li, Yong-Wang; Shi, Chuan; Wen, Xiao-Dong; Ma, Ding

2017-03-01

Polymer electrolyte membrane fuel cells (PEMFCs) running on hydrogen are attractive alternative power supplies for a range of applications, with in situ release of the required hydrogen from a stable liquid offering one way of ensuring its safe storage and transportation before use. The use of methanol is particularly interesting in this regard, because it is inexpensive and can reform itself with water to release hydrogen with a high gravimetric density of 18.8 per cent by weight. But traditional reforming of methanol steam operates at relatively high temperatures (200-350 degrees Celsius), so the focus for vehicle and portable PEMFC applications has been on aqueous-phase reforming of methanol (APRM). This method requires less energy, and the simpler and more compact device design allows direct integration into PEMFC stacks. There remains, however, the need for an efficient APRM catalyst. Here we report that platinum (Pt) atomically dispersed on α-molybdenum carbide (α-MoC) enables low-temperature (150-190 degrees Celsius), base-free hydrogen production through APRM, with an average turnover frequency reaching 18,046 moles of hydrogen per mole of platinum per hour. We attribute this exceptional hydrogen production—which far exceeds that of previously reported low-temperature APRM catalysts—to the outstanding ability of α-MoC to induce water dissociation, and to the fact that platinum and α-MoC act in synergy to activate methanol and then to reform it.

Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts.

PubMed

Lin, Lili; Zhou, Wu; Gao, Rui; Yao, Siyu; Zhang, Xiao; Xu, Wenqian; Zheng, Shijian; Jiang, Zheng; Yu, Qiaolin; Li, Yong-Wang; Shi, Chuan; Wen, Xiao-Dong; Ma, Ding

2017-04-06

Polymer electrolyte membrane fuel cells (PEMFCs) running on hydrogen are attractive alternative power supplies for a range of applications, with in situ release of the required hydrogen from a stable liquid offering one way of ensuring its safe storage and transportation before use. The use of methanol is particularly interesting in this regard, because it is inexpensive and can reform itself with water to release hydrogen with a high gravimetric density of 18.8 per cent by weight. But traditional reforming of methanol steam operates at relatively high temperatures (200-350 degrees Celsius), so the focus for vehicle and portable PEMFC applications has been on aqueous-phase reforming of methanol (APRM). This method requires less energy, and the simpler and more compact device design allows direct integration into PEMFC stacks. There remains, however, the need for an efficient APRM catalyst. Here we report that platinum (Pt) atomically dispersed on α-molybdenum carbide (α-MoC) enables low-temperature (150-190 degrees Celsius), base-free hydrogen production through APRM, with an average turnover frequency reaching 18,046 moles of hydrogen per mole of platinum per hour. We attribute this exceptional hydrogen production-which far exceeds that of previously reported low-temperature APRM catalysts-to the outstanding ability of α-MoC to induce water dissociation, and to the fact that platinum and α-MoC act in synergy to activate methanol and then to reform it.

Efficacy of different methanolic plant extracts on anti-methanogenesis, rumen fermentation and gas production kinetics in vitro

PubMed Central

Sirohi, S.K.; Goel, N.; Pandey, P.

2012-01-01

The present study was carried out to evaluate the effect of methanolic extracts of three plants, mehandi (Lawsonia inermis), jaiphal (Myristica fragrans) and green chili (Capsicum annuum) on methanogenesis, rumen fermentation and fermentation kinetic parameters by in vitro gas production techniques. Single dose of each plant extract (1 ml / 30 ml buffered rumen fluid) and two sorghum fodder containing diets (high and low fiber diets) were used for evaluating the effect on methanogenesis and rumen fermentation pattern, while sequential incubations (0, 1, 2, 3, 6 9, 12, 24, 36, 48, 60, 72 and 96 h) were carried out for gas production kinetics. Results showed that methane production was reduced, ammonia nitrogen was increased significantly, while no significant effect was found on pH and protozoal population following addition of different plant extracts in both diets except mehandi. Green chili significantly reduced digestibility of dry matter, total fatty acid and acetate concentration at incubation with sorghum based high and low fiber diets. Among all treatments, green chili increased potential gas production, while jaiphal decreased the gas production rate constant significantly. The present results demonstrate that methanolic extracts of different plants are promising rumen modifying agents. They have the potential to modulate the methane production, potential gas production, gas production rate constant, dry matter digestibility and microbial biomass synthesis. PMID:26623296

Efficacy of different methanolic plant extracts on anti-methanogenesis, rumen fermentation and gas production kinetics in vitro.

PubMed

Sirohi, S K; Goel, N; Pandey, P

2012-01-01

The present study was carried out to evaluate the effect of methanolic extracts of three plants, mehandi (Lawsonia inermis), jaiphal (Myristica fragrans) and green chili (Capsicum annuum) on methanogenesis, rumen fermentation and fermentation kinetic parameters by in vitro gas production techniques. Single dose of each plant extract (1 ml / 30 ml buffered rumen fluid) and two sorghum fodder containing diets (high and low fiber diets) were used for evaluating the effect on methanogenesis and rumen fermentation pattern, while sequential incubations (0, 1, 2, 3, 6 9, 12, 24, 36, 48, 60, 72 and 96 h) were carried out for gas production kinetics. Results showed that methane production was reduced, ammonia nitrogen was increased significantly, while no significant effect was found on pH and protozoal population following addition of different plant extracts in both diets except mehandi. Green chili significantly reduced digestibility of dry matter, total fatty acid and acetate concentration at incubation with sorghum based high and low fiber diets. Among all treatments, green chili increased potential gas production, while jaiphal decreased the gas production rate constant significantly. The present results demonstrate that methanolic extracts of different plants are promising rumen modifying agents. They have the potential to modulate the methane production, potential gas production, gas production rate constant, dry matter digestibility and microbial biomass synthesis.

Waste-to-methanol: Process and economics assessment.

PubMed

Iaquaniello, Gaetano; Centi, Gabriele; Salladini, Annarita; Palo, Emma; Perathoner, Siglinda; Spadaccini, Luca

2017-11-01

The waste-to-methanol (WtM) process and related economics are assessed to evidence that WtM is a valuable solution both from economic, strategic and environmental perspectives. Bio-methanol from Refuse-derived-fuels (RdF) has an estimated cost of production of about 110€/t for a new WtM 300t/d plant. With respect to waste-to-energy (WtE) approach, this solution allows various advantages. In considering the average market cost of methanol and the premium as biofuel, the WtM approach results in a ROI (Return of Investment) of about 29%, e.g. a payback time of about 4years. In a hybrid scheme of integration with an existing methanol plant from natural gas, the cost of production becomes a profit even without considering the cap for bio-methanol production. The WtM process allows to produce methanol with about 40% and 30-35% reduction in greenhouse gas emissions with respect to methanol production from fossil fuels and bio-resources, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Methanol incorporation in clathrate hydrates and the implications for oil and gas pipeline flow assurance and icy planetary bodies

PubMed Central

Shin, Kyuchul; Udachin, Konstantin A.; Moudrakovski, Igor L.; Leek, Donald M.; Alavi, Saman; Ratcliffe, Christopher I.; Ripmeester, John A.

2013-01-01

One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.g., Titan) a liquid subsurface ocean and/or an atmosphere containing significant quantities of methane. In this work, we reveal a previously unverified role for methanol as a guest in clathrate hydrate cages. X-ray diffraction (XRD) and NMR experiments showed that at temperatures near 273 K, methanol is incorporated in the hydrate lattice along with other guest molecules. The amount of included methanol depends on the preparative method used. For instance, single-crystal XRD shows that at low temperatures, the methanol molecules are hydrogen-bonded in 4.4% of the small cages of tetrahydrofuran cubic structure II hydrate. At higher temperatures, NMR spectroscopy reveals a number of methanol species incorporated in hydrocarbon hydrate lattices. At temperatures characteristic of icy planetary bodies, vapor deposits of methanol, water, and methane or xenon show that the presence of methanol accelerates hydrate formation on annealing and that there is unusually complex phase behavior as revealed by powder XRD and NMR spectroscopy. The presence of cubic structure I hydrate was confirmed and a unique hydrate phase was postulated to account for the data. Molecular dynamics calculations confirmed the possibility of methanol incorporation into the hydrate lattice and show that methanol can favorably replace a number of methane guests. PMID:23661058

Methanol incorporation in clathrate hydrates and the implications for oil and gas pipeline flow assurance and icy planetary bodies.

PubMed

Shin, Kyuchul; Udachin, Konstantin A; Moudrakovski, Igor L; Leek, Donald M; Alavi, Saman; Ratcliffe, Christopher I; Ripmeester, John A

2013-05-21

One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.g., Titan) a liquid subsurface ocean and/or an atmosphere containing significant quantities of methane. In this work, we reveal a previously unverified role for methanol as a guest in clathrate hydrate cages. X-ray diffraction (XRD) and NMR experiments showed that at temperatures near 273 K, methanol is incorporated in the hydrate lattice along with other guest molecules. The amount of included methanol depends on the preparative method used. For instance, single-crystal XRD shows that at low temperatures, the methanol molecules are hydrogen-bonded in 4.4% of the small cages of tetrahydrofuran cubic structure II hydrate. At higher temperatures, NMR spectroscopy reveals a number of methanol species incorporated in hydrocarbon hydrate lattices. At temperatures characteristic of icy planetary bodies, vapor deposits of methanol, water, and methane or xenon show that the presence of methanol accelerates hydrate formation on annealing and that there is unusually complex phase behavior as revealed by powder XRD and NMR spectroscopy. The presence of cubic structure I hydrate was confirmed and a unique hydrate phase was postulated to account for the data. Molecular dynamics calculations confirmed the possibility of methanol incorporation into the hydrate lattice and show that methanol can favorably replace a number of methane guests.

Neat methanol fuel cell power plant

NASA Astrophysics Data System (ADS)

Abens, S.; Farooque, M.

1985-12-01

Attention is given to a fuel cell development effort which has been directed, by ease-of-supply, low weight, and low volume criteria toward the use of undiluted methanol. Partial oxidation and internal water recovery concepts are incorporated, allowing the onboard dilution of methanol fuel through mixing with exhaust-recovered water. This scheme is successfully demonstrated for the case of a 3 kW unit employing commercial cross flow heat exchangers, as well as for a 5 kW reformer flue exhaust water recovery design with U.S. Air force baseload stationary applications. The USAF powerplant has an overall thermal efficiency of 32 percent at rated load.

Atmospheric deposition of methanol over the Atlantic Ocean

PubMed Central

Yang, Mingxi; Nightingale, Philip D.; Beale, Rachael; Liss, Peter S.; Blomquist, Byron; Fairall, Christopher

2013-01-01

In the troposphere, methanol (CH3OH) is present ubiquitously and second in abundance among organic gases after methane. In the surface ocean, methanol represents a supply of energy and carbon for marine microbes. Here we report direct measurements of air–sea methanol transfer along a ∼10,000-km north–south transect of the Atlantic. The flux of methanol was consistently from the atmosphere to the ocean. Constrained by the aerodynamic limit and measured rate of air–sea sensible heat exchange, methanol transfer resembles a one-way depositional process, which suggests dissolved methanol concentrations near the water surface that are lower than what were measured at ∼5 m depth, for reasons currently unknown. We estimate the global oceanic uptake of methanol and examine the lifetimes of this compound in the lower atmosphere and upper ocean with respect to gas exchange. We also constrain the molecular diffusional resistance above the ocean surface—an important term for improving air–sea gas exchange models. PMID:24277830

Atmospheric deposition of methanol over the Atlantic Ocean.

PubMed

Yang, Mingxi; Nightingale, Philip D; Beale, Rachael; Liss, Peter S; Blomquist, Byron; Fairall, Christopher

2013-12-10

In the troposphere, methanol (CH3OH) is present ubiquitously and second in abundance among organic gases after methane. In the surface ocean, methanol represents a supply of energy and carbon for marine microbes. Here we report direct measurements of air-sea methanol transfer along a ∼10,000-km north-south transect of the Atlantic. The flux of methanol was consistently from the atmosphere to the ocean. Constrained by the aerodynamic limit and measured rate of air-sea sensible heat exchange, methanol transfer resembles a one-way depositional process, which suggests dissolved methanol concentrations near the water surface that are lower than what were measured at ∼5 m depth, for reasons currently unknown. We estimate the global oceanic uptake of methanol and examine the lifetimes of this compound in the lower atmosphere and upper ocean with respect to gas exchange. We also constrain the molecular diffusional resistance above the ocean surface-an important term for improving air-sea gas exchange models.

Homogeneous catalyst formulations for methanol production

DOEpatents

Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

1991-02-12

There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.-), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

Homogeneous catalyst formulations for methanol production

DOEpatents

Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

1990-01-01

There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.13 ), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

Improving the fuel economy of stoichiometrically fueled S.I. engines by means of EGR and enhanced ignition -- A comparison of gasoline, methanol and natural gas

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

Neame, G.R.; Gardiner, D.P.; Mallory, R.W.

1995-12-31

This paper describes an experimental study in which the potential for fuel economy improvements with EGR was investigated using an automotive V6 engine. Steady state engine dynamometer tests were run at 2,000 rpm and 200 kPa Brake Mean Effective Pressure (BMEP). The engine was fueled with gasoline, methanol or natural gas. Plasma jet ignition was evaluated as a means of improving EGR tolerance. EGR tolerance with methanol was found to be better than with gasoline, while natural gas showed the poorest EGR tolerance. Plasma jet ignition extended EGR limits for all three fuels. Fuel economy benefits were realized with naturalmore » gas and gasoline at low EGR rates and without EGR but plasma jet ignition provided no improvements with methanol until over 10% EGR was used. Plasma jet ignition made stable operation possible with methanol at 40% EGR, where fuel economy improvements were ultimately limited by the slow burning associated with the high EGR rate. Both slow burning and high cyclic variation affected gasoline at high EGR rates, while stability limits to spark advance with natural gas caused fuel economy to degrade at relatively low EGR rates.« less

Swarm intelligence for multi-objective optimization of synthesis gas production

NASA Astrophysics Data System (ADS)

Ganesan, T.; Vasant, P.; Elamvazuthi, I.; Ku Shaari, Ku Zilati

2012-11-01

In the chemical industry, the production of methanol, ammonia, hydrogen and higher hydrocarbons require synthesis gas (or syn gas). The main three syn gas production methods are carbon dioxide reforming (CRM), steam reforming (SRM) and partial-oxidation of methane (POM). In this work, multi-objective (MO) optimization of the combined CRM and POM was carried out. The empirical model and the MO problem formulation for this combined process were obtained from previous works. The central objectives considered in this problem are methane conversion, carbon monoxide selectivity and the hydrogen to carbon monoxide ratio. The MO nature of the problem was tackled using the Normal Boundary Intersection (NBI) method. Two techniques (Gravitational Search Algorithm (GSA) and Particle Swarm Optimization (PSO)) were then applied in conjunction with the NBI method. The performance of the two algorithms and the quality of the solutions were gauged by using two performance metrics. Comparative studies and results analysis were then carried out on the optimization results.

Optimizing the deposition of hydrogen evolution sites on suspended semiconductor particles using on-line photocatalytic reforming of aqueous methanol solutions.

PubMed

Busser, G Wilma; Mei, Bastian; Muhler, Martin

2012-11-01

The deposition of hydrogen evolution sites on photocatalysts is a crucial step in the multistep process of synthesizing a catalyst that is active for overall photocatalytic water splitting. An alternative approach to conventional photodeposition was developed, applying the photocatalytic reforming of aqueous methanol solutions to deposit metal particles on semiconductor materials such as Ga₂O₃ and (Ga₀.₆ Zn₀.₄)(N₀.₆O₀.₄). The method allows optimizing the loading of the co-catalysts based on the stepwise addition of their precursors and the continuous online monitoring of the evolved hydrogen. Moreover, a synergetic effect between different co-catalysts can be directly established. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Multi-fuel reformers for fuel cells used in transportation: Assessment of hydrogen storage technologies

NASA Astrophysics Data System (ADS)

1994-03-01

This report documents a portion of the work performed on Multi-fuel Reformers for Fuel Cells Used in Transportation. One objective of this program is to develop advanced fuel processing systems to reform methanol, ethanol, natural gas, and other hydrocarbons into hydrogen for use in transportation fuel cell systems, while a second objective is to develop better systems for on-board hydrogen storage. This report examines techniques and technology available for storage of pure hydrogen on board a vehicle as pure hydrogen of hydrides. The report focuses separately on near and far-term technologies, with particular emphasis on the former. Development of lighter, more compact near-term storage systems is recommended to enhance competitiveness and simplify fuel cell design. The far-term storage technologies require substantial applied research in order to become serious contenders.

Plasma reforming and partial oxidation of hydrocarbon fuel vapor to produce synthesis gas and/or hydrogen gas

DOEpatents

Kong, Peter C.; Detering, Brent A.

2003-08-19

Methods and systems for treating vapors from fuels such as gasoline or diesel fuel in an internal combustion engine, to form hydrogen gas or synthesis gas, which can then be burned in the engine to produce more power. Fuel vapor, or a mixture of fuel vapor and exhaust gas and/or air, is contacted with a plasma, to promote reforming reactions between the fuel vapor and exhaust gas to produce carbon monoxide and hydrogen gas, partial oxidation reactions between the fuel vapor and air to produce carbon monoxide and hydrogen gas, or direct hydrogen and carbon particle production from the fuel vapor. The plasma can be a thermal plasma or a non-thermal plasma. The plasma can be produced in a plasma generating device which can be preheated by contact with at least a portion of the hot exhaust gas stream, thereby decreasing the power requirements of the plasma generating device.

Acidities of Water and Methanol in Aqueous Solution and DMSO

ERIC Educational Resources Information Center

Gao, Daqing

2009-01-01

The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…

Highly selective and sensitive methanol gas sensor based on molecular imprinted silver-doped LaFeO3 core-shell and cage structures

NASA Astrophysics Data System (ADS)

Rong, Qian; Zhang, Yumin; Lv, Tianping; Shen, Kaiyuan; Zi, Baoye; Zhu, Zhongqi; Zhang, Jin; Liu, Qingju

2018-04-01

Silver-doped LaFeO3 molecularly imprinted polymers (SLMIPs) were synthesized by a sol-gel method combined with molecularly imprinted technology as precursors. The precursors were then used to prepare SLMIPs cage (SLM-cage) and SLMIPs core-shell (SLM-core-shell) structures by using a carbon sphere as the template and hydrothermal synthesis, respectively. The structures, morphologies, and surface areas of these materials were determined, as well as their gas-sensing properties and related mechanisms. The SLM-cage and SLM-core-shell samples exhibited good responses to methanol gas, with excellent selectivity. The response and optimum working temperature were 16.98 °C and 215 °C, 33.7 °C and 195 °C, respectively, with corresponding response and recovery times of 45 and 50 s (SLM-cage) and 42 and 57 s (SLM-core-shell) for 5 ppm methanol gas. Notably, the SLM-cage and SLM-core-shell samples exhibited lower responses (≤5 and ≤7, respectively) to other gases, including ethanol, ammonia, benzene, acetone, and toluene. Thus, these materials show potential as practical methanol detectors.

Highly selective and sensitive methanol gas sensor based on molecular imprinted silver-doped LaFeO3 core-shell and cage structures.

PubMed

Rong, Qian; Zhang, Yumin; Lv, Tianping; Shen, Kaiyuan; Zi, Baoye; Zhu, Zhongqi; Zhang, Jin; Liu, Qingju

2018-04-06

Silver-doped LaFeO 3 molecularly imprinted polymers (SLMIPs) were synthesized by a sol-gel method combined with molecularly imprinted technology as precursors. The precursors were then used to prepare SLMIPs cage (SLM-cage) and SLMIPs core-shell (SLM-core-shell) structures by using a carbon sphere as the template and hydrothermal synthesis, respectively. The structures, morphologies, and surface areas of these materials were determined, as well as their gas-sensing properties and related mechanisms. The SLM-cage and SLM-core-shell samples exhibited good responses to methanol gas, with excellent selectivity. The response and optimum working temperature were 16.98 °C and 215 °C, 33.7 °C and 195 °C, respectively, with corresponding response and recovery times of 45 and 50 s (SLM-cage) and 42 and 57 s (SLM-core-shell) for 5 ppm methanol gas. Notably, the SLM-cage and SLM-core-shell samples exhibited lower responses (≤5 and ≤7, respectively) to other gases, including ethanol, ammonia, benzene, acetone, and toluene. Thus, these materials show potential as practical methanol detectors.

Plasma Reforming And Partial Oxidation Of Hydrocarbon Fuel Vapor To Produce Synthesis Gas And/Or Hydrogen Gas

DOEpatents

Kong, Peter C.; Detering, Brent A.

2004-10-19

Methods and systems are disclosed for treating vapors from fuels such as gasoline or diesel fuel in an internal combustion engine, to form hydrogen gas or synthesis gas, which can then be burned in the engine to produce more power. Fuel vapor, or a mixture of fuel vapor and exhaust gas and/or air, is contacted with a plasma, to promote reforming reactions between the fuel vapor and exhaust gas to produce carbon monoxide and hydrogen gas, partial oxidation reactions between the fuel vapor and air to produce carbon monoxide and hydrogen gas, or direct hydrogen and carbon particle production from the fuel vapor. The plasma can be a thermal plasma or a non-thermal plasma. The plasma can be produced in a plasma generating device which can be preheated by contact with at least a portion of the hot exhaust gas stream, thereby decreasing the power requirements of the plasma generating device.

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

Environmental life cycle assessment of methanol and electricity co-production system based on coal gasification technology.

PubMed

Śliwińska, Anna; Burchart-Korol, Dorota; Smoliński, Adam

2017-01-01

This paper presents a life cycle assessment (LCA) of greenhouse gas emissions generated through methanol and electricity co-production system based on coal gasification technology. The analysis focuses on polygeneration technologies from which two products are produced, and thus, issues related to an allocation procedure for LCA are addressed in this paper. In the LCA, two methods were used: a 'system expansion' method based on two approaches, the 'avoided burdens approach' and 'direct system enlargement' methods and an 'allocation' method involving proportional partitioning based on physical relationships in a technological process. Cause-effect relationships in the analysed production process were identified, allowing for the identification of allocation factors. The 'system expansion' method involved expanding the analysis to include five additional variants of electricity production technologies in Poland (alternative technologies). This method revealed environmental consequences of implementation for the analysed technologies. It was found that the LCA of polygeneration technologies based on the 'system expansion' method generated a more complete source of information on environmental consequences than the 'allocation' method. The analysis shows that alternative technologies chosen for generating LCA results are crucial. Life cycle assessment was performed for the analysed, reference and variant alternative technologies. Comparative analysis was performed between the analysed technologies of methanol and electricity co-production from coal gasification as well as a reference technology of methanol production from the natural gas reforming process. Copyright © 2016 Elsevier B.V. All rights reserved.

In-situ study of the gas-phase composition and temperature of an intermediate-temperature solid oxide fuel cell anode surface fed by reformate natural gas

NASA Astrophysics Data System (ADS)

Santoni, F.; Silva Mosqueda, D. M.; Pumiglia, D.; Viceconti, E.; Conti, B.; Boigues Muñoz, C.; Bosio, B.; Ulgiati, S.; McPhail, S. J.

2017-12-01

An innovative experimental setup is used for in-depth and in-operando characterization of solid oxide fuel cell anodic processes. This work focuses on the heterogeneous reactions taking place on a 121 cm2 anode-supported cell (ASC) running with a H2, CH4, CO2, CO and steam gas mixture as a fuel, using an operating temperature of 923 K. The results have been obtained by analyzing the gas composition and temperature profiles along the anode surface in different conditions: open circuit voltage (OCV) and under two different current densities, 165 mA cm-2 and 330 mA cm-2, corresponding to 27% and 54% of fuel utilization, respectively. The gas composition and temperature analysis results are consistent, allowing to monitor the evolution of the principal chemical and electrochemical reactions along the anode surface. A possible competition between CO2 and H2O in methane internal reforming is shown under OCV condition and low current density values, leading to two different types of methane reforming: Steam Reforming and Dry Reforming. Under a current load of 40 A, the dominance of exothermic reactions leads to a more marked increase of temperature in the portion of the cell close to the inlet revealing that current density is not uniform along the anode surface.

Study of the influence of surfactants on the activity coefficients and mass transfer coefficients of methanol in aqueous mixtures by reversed-flow gas chromatography.

PubMed

Kotsalos, Efthimios; Brezovska, Boryana; Sevastos, Dimitrios; Vagena, Artemis; Koliadima, Athanasia; Kapolos, John; Karaiskakis, George

2017-11-17

This work focuses on the influences of surfactants on the activity coefficients, γ, of methanol in binary mixtures with water, as well as on the mass transfer coefficients, k c , for the evaporation of methanol, which is a ubiquitous component in the troposphere, from mixtures of methanol with water at various surfactant's and methanol's concentrations. The technique used is the Reversed-Flow Gas Chromatography (R.F.G.C.), a version of Inverse Gas Chromatography, which allows determining both parameters by performing only one experiment for the k c parameter and two experiments for the γ parameter. The k c and γ values decrease in the presence of the three surfactants used (CTAB, SDS, TRITON X-100) at all methanol's and surfactant's concentrations. The decrease in the methanol's molar fraction, at constant number of surfactant films leads to a decrease in the k c and γ values, while the decrease in the surfactant's concentration, at constant methanol's molar fraction leads to an increase in both the k c and γ parameters. Mass transfer coefficients for the evaporation of methanol at the surfactant films, are also calculated which are approximately between 4 and 5 orders of magnitude larger than the corresponding mass transfer coefficients at the liquid films. Finally, thicknesses of the boundary layer of methanol in the mixtures of methanol with water were determined. The quantities found are compared with those given in the literature or calculated theoretically using various empirical equations. The precision of the R.F.G.C. method for measuring γ and k c parameters is approximately high (94.3-98.0%), showing that R.F.G.C. can be used with success not only for the thermodynamic study of solutions, but also for the interphase transport. Copyright © 2017 Elsevier B.V. All rights reserved.

Biological Methanol Production by a Type II Methanotroph Methylocystis bryophila.

PubMed

Patel, Sanjay K S; Mardina, Primata; Kim, Sang-Yong; Lee, Jung-Kul; Kim, In-Won

2016-04-28

Methane (CH₄) is the most abundant component in natural gas. To reduce its harmful environmental effect as a greenhouse gas, CH₄ can be utilized as a low-cost feed for the synthesis of methanol by methanotrophs. In this study, several methanotrophs were examined for their ability to produce methanol from CH₄; including Methylocella silvestris, Methylocystis bryophila, Methyloferula stellata, and Methylomonas methanica. Among these methanotrophs, M. bryophila exhibited the highest methanol production. The optimum process parameters aided in significant enhancement of methanol production up to 4.63 mM. Maximum methanol production was observed at pH 6.8, 30°C, 175 rpm, 100 mM phosphate buffer, 50 mM MgCl₂ as a methanol dehydrogenase inhibitor, 50% CH₄ concentration, 24 h of incubation, and 9 mg of dry cell mass ml(-1) inoculum load, respectively. Optimization of the process parameters, screening of methanol dehydrogenase inhibitors, and supplementation with formate resulted in significant improvements in methanol production using M. bryophila. This report suggests, for the first time, the potential of using M. bryophila for industrial methanol production from CH₄.

Coal-to-methanol: an engineering evaluation of Texaco gasification and ICI methanol-synthesis route. Final report

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

Buckingham, P.A.; Cobb, D.D.; Leavitt, A.A.

1981-08-01

This report presents the results of a technical and economic evaluation of producing methanol from bituminous coal using Texaco coal gasification and ICI methanol synthesis. The scope of work included the development of an overall configuration for a large plant comprising coal preparation, air separation, coal gasification, shift conversion, COS hydrolysis, acid gas removal, methanol synthesis, methanol refining, and all required utility systems and off-site facilities. Design data were received from both Texaco and ICI while a design and cost estimate were received from Lotepro covering the Rectisol acid gas removal unit. The plant processes 14,448 tons per day (drymore » basis) of Illinois No. 6 bituminous coal and produces 10,927 tons per day of fuel-grade methanol. An overall thermal efficiency of 57.86 percent was calculated on an HHV basis and 52.64 percent based on LHV. Total plant investment at an Illinois plant site was estimated to be $1159 million dollars in terms of 1979 investment. Using EPRI's economic premises, the first-year product costs were calculated to $4.74 per million Btu (HHV) which is equivalent to $30.3 cents per gallon and $5.37 per million Btu (LHV).« less

Building carbon–carbon bonds using a biocatalytic methanol condensation cycle

PubMed Central

Bogorad, Igor W.; Chen, Chang-Ting; Theisen, Matthew K.; Wu, Tung-Yun; Schlenz, Alicia R.; Lam, Albert T.; Liao, James C.

2014-01-01

Methanol is an important intermediate in the utilization of natural gas for synthesizing other feedstock chemicals. Typically, chemical approaches for building C–C bonds from methanol require high temperature and pressure. Biological conversion of methanol to longer carbon chain compounds is feasible; however, the natural biological pathways for methanol utilization involve carbon dioxide loss or ATP expenditure. Here we demonstrated a biocatalytic pathway, termed the methanol condensation cycle (MCC), by combining the nonoxidative glycolysis with the ribulose monophosphate pathway to convert methanol to higher-chain alcohols or other acetyl-CoA derivatives using enzymatic reactions in a carbon-conserved and ATP-independent system. We investigated the robustness of MCC and identified operational regions. We confirmed that the pathway forms a catalytic cycle through 13C-carbon labeling. With a cell-free system, we demonstrated the conversion of methanol to ethanol or n-butanol. The high carbon efficiency and low operating temperature are attractive for transforming natural gas-derived methanol to longer-chain liquid fuels and other chemical derivatives. PMID:25355907

Stepwise Internal Energy Control for Protonated Methanol Clusters by Using the Inert Gas Tagging

NASA Astrophysics Data System (ADS)

Shimamori, Takuto; Kuo, Jer-Lai; Fujii, Asuka

2016-06-01

Preferred isomer structures of hydrogen-bonded clusters should depend on their temperature because of the entropy term in the free energy. To observe such temperature dependence, we propose a new approach to control the internal energy (vibrational temperature) of protonated clusters in the gas phase. We performed IR spectroscopy of protonated methanol clusters, H+ (CH{_3}OH) {_n}, n= 5 and 7, with the tagging by various inert gas species (Ar, CO{_2}, CO, CS{_2}, C{_2}H{_2}, and C{_6}H{_6}). We found that vibrational temperature of the tagged clusters raises with increase of the interaction energy with the tag species, and the observed cluster structures follow the theoretical prediction of the temperature dependence of the isomer population.

Two-stage gas-phase bioreactor for the combined removal of hydrogen sulphide, methanol and alpha-pinene.

PubMed

Rene, Eldon R; Jin, Yaomin; Veiga, María C; Kennes, Christian

2009-11-01

Biological treatment systems have emerged as cost-effective and eco-friendly techniques for treating waste gases from process industries at moderately high gas flow rates and low pollutant concentrations. In this study, we have assessed the performance of a two-stage bioreactor, namely a biotrickling filter packed with pall rings (BTF, 1st stage) and a perlite + pall ring mixed biofilter (BF, 2nd stage) operated in series, for handling a complex mixture of hydrogen sulphide (H2S), methanol (CH3OH) and alpha-pinene (C10H16). It has been reported that the presence of H2S can reduce the biofiltration efficiency of volatile organic compounds (VOCs) when both are present in the gas mixture. Hydrogen sulphide and methanol were removed in the first stage BTF, previously inoculated with H2S-adapted populations and a culture containing Candida boidinii, an acid-tolerant yeast, whereas, in the second stage, alpha-pinene was removed predominantly by the fungus Ophiostoma stenoceras. Experiments were conducted in five different phases, corresponding to inlet loading rates varying between 2.1 and 93.5 g m(-3) h(-1) for H2S, 55.3 and 1260.2 g m(-3) h(-1) for methanol, and 2.8 and 161.1 g m(-3) h(-1) for alpha-pinene. Empty bed residence times were varied between 83.4 and 10 s in the first stage and 146.4 and 17.6 s in the second stage. The BTF, working at a pH as low as 2.7 as a result of H2S degradation, removed most of the H2S and methanol but only very little alpha-pinene. On the other hand, the BF, at a pH around 6.0, removed the rest of the H2S, the non-degraded methanol and most of the alpha-pinene vapours. Attempts were originally made to remove the three pollutants in a single acidophilic bioreactor, but the Ophiostoma strain was hardly active at pH <4. The maximum elimination capacities (ECs) reached by the two-stage bioreactor for individual pollutants were 894.4 g m(-3) h(-1) for methanol, 45.1 g m(-3) h(-1) for H2S and 138.1 g m(-3) h(-1) for alpha-pinene. The

Selective catalytic oxidation: a new catalytic approach to the desulfurization of natural gas and liquid petroleum gas for fuel cell reformer applications

NASA Astrophysics Data System (ADS)

Lampert, J.

In both natural gas and liquid petroleum gas (LPG), sulfur degrades the performance of the catalysts used in fuel reformers and fuel cells. In order to improve system performance, the sulfur must be removed to concentrations of less than 200 ppbv (in many applications to less than 20 ppbv) before the fuel reforming operation. Engelhard Corporation presents a unique approach to the desulfurization of natural gas and LPG. This new method catalytically converts the organic and inorganic sulfur species to sulfur oxides. The sulfur oxides are then adsorbed on a high capacity adsorbent. The sulfur compounds in the fuel are converted to sulfur oxides by combining the fuel with a small amount of air. The mixture is then heated from 250 to 270 °C, and contacted with a monolith supported sulfur tolerant catalyst at atmospheric pressure. When Engelhard Corporation demonstrated this catalytic approach in the laboratory, the result showed sulfur breakthrough to be less than 10 ppbv in the case of natural gas, and less than 150 ppbv for LPG. We used a simulated natural gas and LPG mixture, doped with a 50-170 ppmv sulfur compound containing equal concentrations of COS, ethylmercaptan, dimethylsulfide, methylethylsulfide and tetrahydrothiophene. There is no need for recycled H 2 as in the case for hydrodesulfurization.

Use of natural gas, methanol, and ethanol fuel emulsions as environmentally friendly energy carriers for mobile heat power plants

NASA Astrophysics Data System (ADS)

Likhanov, V. A.; Lopatin, O. P.

2017-12-01

The need for using environmentally friendly energy carriers for mobile heat power plants (HPPs) is grounded. Ecologically friendly sources of energy, such as natural gas as well as renewable methyl and ethyl alcohols, are investigated. In order to develop, determine, and optimize the composition of environmentally friendly energy carriers for an HPP, the latter has been tested when working on diesel fuel (DF), compressed natural gas (CNG), and methanol and ethanol fuel emulsions (MFE, EFE). It has been experimentally established that, for the application of environmentally friendly energy carriers for a 4Ch 11.0/12.5 diesel engine of a mobile fuel and power plant, it is necessary to maintain the following ratio of components when working on CNG: 80% gas and 20% DF primer portion. When working on an alcohol mixture, emulsions of the following composition were used: 25% alcohol (methanol or ethanol), 0.5% detergent-dispersant additive succinimide C-5A, 7% water, and 67.5% DF. When this diesel passed from oil DF to environmentally friendly energy sources, it allowed for the reduction of the content of exhaust gases (EG) (1) when working on CNG with recirculation of exhaust gases (EGR) (recirculation was used to eliminate the increased amount of nitric oxides by using CNG): carbon black by 5.8 times, carbon dioxide by 45.9%, and carbon monoxide by 23.8%; (2) when working on MFE: carbon black by 6.4 times, nitrogen oxides by 29.6%, carbon dioxide by 10.1%, and carbon oxide by 47.6%; (3) when working on EFE: carbon black by 4.8 times; nitrogen oxides by 40.3%, carbon dioxide by 26.6%, and carbon monoxide by 28.6%. The prospects of use of environmentally friendly energy carriers in diesels of mobile HPPs, such as natural gas, ethanol, and methanol, has been determined.

Indonesia to build methanol plant

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

Alperowicz, N.

1992-08-05

P.T. Kaltim Methanol Industri (Jakarta), a company set up to build a new methanol plant in Indonesia, expects to award contracts for the construction of a new plant, Indonesia's second methanol unit, by the end of this year. P.T. Kaltim Methanol is a private company owned by P.T. Humpuss, an industrial group active in transport, airlines, and shipping of LNG and methanol. The 2,000-m.t./day plant will be built at Bontang, Kalimantan Island, close to the fertilizer producer P.T. Pupuk Kaltim and near the country's largest natural gas reserves. The site is also a deepsea port, handy for transportation of readymore » product. Three groups are in discussions with the investor on plant supply as well as methanol offtake deals. They are H G/Kockner; John Brown/Davy/Lucky Goldstar, offering the ICI process independently; and Lurgi/Metallgesellschaft (MG), proposing the Lurgi process. At least 60% of the output is expected to be exported, and both ICI and MG are understood to be interested in selling product from the future plant. Japan, Southeast Asia, and the US are targeted.« less

Gas Selectivity Control in Co3O4 Sensor via Concurrent Tuning of Gas Reforming and Gas Filtering using Nanoscale Hetero-Overlayer of Catalytic Oxides.

PubMed

Jeong, Hyun-Mook; Jeong, Seong-Yong; Kim, Jae-Hyeok; Kim, Bo-Young; Kim, Jun-Sik; Abdel-Hady, Faissal; Wazzan, Abdulaziz A; Al-Turaif, Hamad Ali; Jang, Ho Won; Lee, Jong-Heun

2017-11-29

Co 3 O 4 sensors with a nanoscale TiO 2 or SnO 2 catalytic overlayer were prepared by screen-printing of Co 3 O 4 yolk-shell spheres and subsequent e-beam evaporation of TiO 2 and SnO 2 . The Co 3 O 4 sensors with 5 nm thick TiO 2 and SnO 2 overlayers showed high responses (resistance ratios) to 5 ppm xylene (14.5 and 28.8) and toluene (11.7 and 16.2) at 250 °C with negligible responses to interference gases such as ethanol, HCHO, CO, and benzene. In contrast, the pure Co 3 O 4 sensor did not show remarkable selectivity toward any specific gas. The response and selectivity to methylbenzenes and ethanol could be systematically controlled by selecting the catalytic overlayer material, varying the overlayer thickness, and tuning the sensing temperature. The significant enhancement of the selectivity for xylene and toluene was attributed to the reforming of less reactive methylbenzenes into more reactive and smaller species and oxidative filtering of other interference gases, including ubiquitous ethanol. The concurrent control of the gas reforming and oxidative filtering processes using a nanoscale overlayer of catalytic oxides provides a new, general, and powerful tool for designing highly selective and sensitive oxide semiconductor gas sensors.

Internal reforming characteristics of cermet supported solid oxide fuel cell using yttria stabilized zirconia fed with partially reformed methane

NASA Astrophysics Data System (ADS)

Momma, Akihiko; Takano, Kiyonami; Tanaka, Yohei; Negishi, Akira; Kato, Ken; Nozaki, Ken; Kato, Tohru; Ichigi, Takenori; Matsuda, Kazuyuki; Ryu, Takashi

In order to investigate the internal reforming characteristics in a cermet supported solid oxide fuel cell (SOFC) using YSZ as the electrolyte, the concentration profiles of the gaseous species along the gas flow direction in the anode were measured. Partially reformed methane using a pre-reformer kept at a constant temperature is supplied to the center of the cell which is operated with a seal-less structure at the gas outlet. The anode gas is sucked in via silica capillaries to the initially evacuated gas tanks. The process is simultaneously carried out using five sampling ports. The sampled gas is analyzed by a gas chromatograph. Most of the measurements are made at the cell temperature (T cell) of 750 °C and at various temperatures of the pre-reformer (T ref) with various fuel utilizations (U f) of the cell. The composition of the fuel at the inlet of the anode was confirmed to be almost the same as that theoretically calculated assuming equilibrium at the temperature of the pre-reformer. The effect of internal reforming in the anode is clearly observed as a steady decrease in the methane concentration along the flow axis. The effect of the water-gas shift reaction is also observed as a decrease in the CO 2 concentration and an increase of CO concentration around the gas inlet region, as the water-gas shift reaction inversely proceeds when T cell is higher than T ref. The diffusion of nitrogen from the seal-less outermost edge is observed, and the diffusion is confirmed to be more significant as U f decreases. The observations are compared with the results obtained by the SOFC supported by lanthanum gallate electrolyte. With respect to the internal reforming performance, the cell investigated here is found to be more effective when compared to the previously reported electrolyte supported cell.

Thermal analysis of cylindrical natural-gas steam reformer for 5 kW PEMFC

NASA Astrophysics Data System (ADS)

Jo, Taehyun; Han, Junhee; Koo, Bonchan; Lee, Dohyung

2016-11-01

The thermal characteristics of a natural-gas based cylindrical steam reformer coupled with a combustor are investigated for the use with a 5 kW polymer electrolyte membrane fuel cell. A reactor unit equipped with nickel-based catalysts was designed to activate the steam reforming reaction without the inclusion of high-temperature shift and low-temperature shift processes. Reactor temperature distribution and its overall thermal efficiency depend on various inlet conditions such as the equivalence ratio, the steam to carbon ratio (SCR), and the fuel distribution ratio (FDR) into the reactor and the combustor components. These experiments attempted to analyze the reformer's thermal and chemical properties through quantitative evaluation of product composition and heat exchange between the combustor and the reactor. FDR is critical factor in determining the overall performance as unbalanced fuel injection into the reactor and the combustor deteriorates overall thermal efficiency. Local temperature distribution also influences greatly on the fuel conversion rate and thermal efficiency. For the experiments, the operation conditions were set as SCR was in range of 2.5-4.0 and FDR was in 0.4-0.7 along with equivalence ratio of 0.9-1.1; optimum results were observed for FDR of 0.63 and SCR of 3.0 in the cylindrical steam reformer.

The α-effect in gas-phase SN2 reactions of microsolvated anions: methanol as a solvent.

PubMed

Thomsen, Ditte L; Reece, Jennifer N; Nichols, Charles M; Hammerum, Steen; Bierbaum, Veronica M

2014-09-18

The α-effect, an enhanced reactivity of nucleophiles with a lone-pair adjacent to the reaction center, has been studied in solution for several decades. The gas-phase α-effect has recently been documented in studies of SN2 reactions as well as in competing reactions for both bare and microhydrated anions. In the present work we extend our studies of the significance of microsolvation on the α-effect, employing methanol as the solvent, in the expectation that the greater stability of the methanol cluster relative to the water cluster will lower the reactivity and thereby allow studies over a wider efficiency range. We compare the gas-phase reactivity of the microsolvated α-nucleophile HOO(-)(CH3OH) to that of microsolvated normal alkoxy nucleophiles, RO(-)(CH3OH) in reactions with CH3Cl and CH3Br. The results reveal enhanced reactivity of HOO(-)(CH3OH) toward both methyl halides relative to the normal nucleophiles, and clearly demonstrate the presence of an α-effect for the microsolvated α-nucleophile. The highly exothermic reactions with methyl bromide result in a smaller Brønsted βnuc value than observed for methyl chloride, and the α-effect in turn influences the reactions with methyl chloride more than with methyl bromide. Computational investigations reveal that reactions with methyl bromide proceed through earlier transition states with less advanced bond formation compared to the related reactions of methyl chloride. In addition, solvent interactions for HOO(-) are quite different from those with the normal nucleophiles at the transition state, indicating that differential solvation may well contribute to the α-effect. The greater thermodynamic and kinetic stability of the anion-methanol clusters relative to the anion-water clusters accounts well for the differences in the influence of solvation with the two protic polar solvents.

Effects of Fuel Cell Anode Recycle on Catalytic Fuel Reforming

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

Shekhawat, Dushyant; Berry, D.A.; Gardner, T.H.

2007-06-01

The presence of steam in the reactant gas of a catalytic fuel reformer decreases the formation of carbon, minimizing catalyst deactivation. However, the operation of the reformer without supplemental water reduces the size, weight, cost, and overall complexity of the system. The work presented here examines experimentally two options for adding steam to the reformer inlet: (I) recycle of a simulated fuel cell anode exit gas (comprised of mainly CO2, H2O, and N2 and some H2 and CO) and (II) recycle of the reformate from the reformer exit back to the reformer inlet (mainly comprised of H2, CO, and N2more » and some H2O and CO2). As expected, anode gas recycle reduced the carbon formation and increased the hydrogen concentration in the reformate. However, reformer recycle was not as effective due principally to the lower water content in the reformate compared to the anode gas. In fact, reformate recycle showed slightly increased carbon formation compared to no recycle. In an attempt to understand the effects of individual gases in these recycle streams (H2, CO, CO2, N2, and H2O), individual gas species were independently introduced to the reformer feed.« less

Effects of fuel cell anode recycle on catalytic fuel reforming

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

shekhawat, D.; Berry, D.; Gardner, T.

2007-01-01

The presence of steam in the reactant gas of a catalytic fuel reformer decreases the formation of carbon, minimizing catalyst deactivation. However, the operation of the reformer without supplemental water reduces the size, weight, cost, and overall complexity of the system. The work presented here examines experimentally two options for adding steam to the reformer inlet: (I) recycle of a simulated fuel cell anode exit gas (comprised of mainly CO2, H2O, and N2 and some H2 and CO) and (II) recycle of the reformate from the reformer exit back to the reformer inlet (mainly comprised of H2, CO, and N2more » and some H2O and CO2). As expected, anode gas recycle reduced the carbon formation and increased the hydrogen concentration in the reformate. However, reformer recycle was not as effective due principally to the lower water content in the reformate compared to the anode gas. In fact, reformate recycle showed slightly increased carbon formation compared to no recycle. In an attempt to understand the effects of individual gases in these recycle streams (H2, CO, CO2, N2, and H2O), individual gas species were independently introduced to the reformer feed. Published by Elsevier B.V.« less

Thermally efficient melting and fuel reforming for glass making

DOEpatents

Chen, Michael S.; Painter, Corning F.; Pastore, Steven P.; Roth, Gary S.; Winchester, David C.

1991-01-01

An integrated process for utilizing waste heat from a glass making furnace. The hot off-gas from the furnace is initially partially cooled, then fed to a reformer. In the reformer, the partially cooled off-gas is further cooled against a hydrocarbon which is thus reformed into a synthesis gas, which is then fed into the glass making furnace as a fuel. The further cooled off-gas is then recycled back to absorb the heat from the hot off-gas to perform the initial cooling.

Thermodynamic evaluation of hydrogen production for fuel cells by using bio-ethanol steam reforming: Effect of carrier gas addition

NASA Astrophysics Data System (ADS)

Hernández, Liliana; Kafarov, Viatcheslav

Omitting the influence of the addition of carrier gas to the reaction system for hydrogen production by bio-ethanol steam reforming can lead to wrong conclusions, especially when it is going to be made to scale. The effect of carrier gas addition to produce hydrogen using bio-ethanol steam reforming to feed fuel cells was evaluated. Thermodynamic calculations in equilibrium conditions were made, however the analysis derived from them can also be applied to kinetic conditions. These calculations were made by using the Aspen-HYSYS software at atmospheric pressure and different values of temperature, water/ethanol molar ratios, and inert (argon)/(water/ethanol) molar ratios. The addition of inert carrier gas modifies the concentrations of the reaction products in comparison to those obtained without its presence. This behavior occurs because most of the reactions which take place in bio-ethanol steam reforming have a positive difference of moles. This fact enhances the system sensitivity to inert concentration at low and moderated temperatures (<700 °C). At high values of temperature, the inert addition does not influence the composition of the reaction products because of the predominant effect of inverse WGS reaction.

A detailed kinetic mechanism including methanol and nitrogen pollutants relevant to the gas-phase combustion and pyrolysis of biomass-derived fuels

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

Coda Zabetta, Edgardo; Hupa, Mikko

2008-01-15

A detailed chemical kinetic mechanism for the simulation of the gas-phase combustion and pyrolysis of biomass-derived fuels was compiled by assembling selected reaction subsets from existing mechanisms (parents). The mechanism, here referred to as ''AaA,'' includes reaction subsets for the oxidation of hydrogen (H{sub 2}), carbon monoxide (CO), light hydrocarbons (C{sub 1} and C{sub 2}), and methanol (CH{sub 3}OH). The mechanism also takes into account reaction subsets of nitrogen pollutants, including the reactions relevant to staged combustion, reburning, and selective noncatalytic reduction (SNCR). The AaA mechanism was validated against suitable experimental data from the literature. Overall, the AaA mechanism gavemore » more accurate predictions than three other mechanisms of reference, although the reference mechanisms performed better occasionally. The predictions from AaA were also found to be consistent with the predictions of its parent mechanisms within most of their range of validity, thus transferring the validity of the parents to the inheriting mechanism (AaA). In parametric studies the AaA mechanism predicted that the effect of methanol on combustion and pollutants is often similar to that of light hydrocarbons, but it also showed that there are important exceptions, thus suggesting that methanol should be taken into account when simulating biomass combustion. To our knowledge, the AaA mechanism is currently the only mechanism that accounts for the chemistry of methanol and nitrogen relevant to the gas-phase combustion and pyrolysis of biomass-derived fuels. (author)« less

A miniature fuel reformer system for portable power sources

NASA Astrophysics Data System (ADS)

Dolanc, Gregor; Belavič, Darko; Hrovat, Marko; Hočevar, Stanko; Pohar, Andrej; Petrovčič, Janko; Musizza, Bojan

2014-12-01

A miniature methanol reformer system has been designed and built to technology readiness level exceeding a laboratory prototype. It is intended to feed fuel cells with electric power up to 100 W and contains a complete setup of the technological elements: catalytic reforming and PROX reactors, a combustor, evaporators, actuation and sensing elements, and a control unit. The system is engineered not only for performance and quality of the reformate, but also for its lightweight and compact design, seamless integration of elements, low internal electric consumption, and safety. In the paper, the design of the system is presented by focussing on its miniaturisation, integration, and process control.

Determination of dichloroacetic acid and trichloroacetic acid in drinking water by acidic methanol esterification and headspace gas chromatography.

PubMed

Wang, Y H; Wong, P K

2005-05-01

A simple and rapid headspace method for gas chromatographic determination of dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) in drinking water was developed. Acidic methanol esterification followed by a headspace technique using a capillary column gas chromatograph (GC) equipped with an electron capture detector (ECD) was applied to determine the levels of DCAA and TCAA in drinking water. The major advantages of this method are the use of acidic methanol as the derivatization agent instead of the hazardous diazomethane, and esterification is carried out in water instead of organic solvent. DCAA and TCAA methyl esters produced in the reaction were determined directly by a headspace GC/ECD method. The linear correlation coefficients at concentrations ranging from 0 to 60 microg/L were 0.992 and 0.996 for DCAA and TCAA, respectively. The relative standard deviations (RSD, %) for the determination of DCAA and TCAA in drinking water were 15 and 21.3%, respectively (n=3). The detection limits of this method were 3 and 0.5 microg/L for DCAA and TCAA, respectively, and the recovery was 68-103.2% for DCAA and TCAA.

Hydrocarbon reforming catalyst material and configuration of the same

DOEpatents

Singh, Prabhakar; Shockling, Larry A.; George, Raymond A.; Basel, Richard A.

1996-01-01

A hydrocarbon reforming catalyst material comprising a catalyst support impregnated with catalyst is provided for reforming hydrocarbon fuel gases in an electrochemical generator. Elongated electrochemical cells convert the fuel to electrical power in the presence of an oxidant, after which the spent fuel is recirculated and combined with a fresh hydrocarbon feed fuel forming the reformable gas mixture which is fed to a reforming chamber containing a reforming catalyst material, where the reforming catalyst material includes discrete passageways integrally formed along the length of the catalyst support in the direction of reformable gas flow. The spent fuel and/or combusted exhaust gases discharged from the generator chamber transfer heat to the catalyst support, which in turn transfers heat to the reformable gas and to the catalyst, preferably via a number of discrete passageways disposed adjacent one another in the reforming catalyst support. The passageways can be slots extending inwardly from an outer surface of the support body, which slots are partly defined by an exterior confining wall. According to a preferred embodiment, the catalyst support is non-rigid, porous, fibrous alumina, wherein the fibers are substantially unsintered and compressible, and the reforming catalyst support is impregnated, at least in the discrete passageways with Ni and MgO, and has a number of internal slot passageways for reformable gas, the slot passageways being partly closed by a containing outer wall.

Hydrocarbon reforming catalyst material and configuration of the same

DOEpatents

Singh, P.; Shockling, L.A.; George, R.A.; Basel, R.A.

1996-06-18

A hydrocarbon reforming catalyst material comprising a catalyst support impregnated with catalyst is provided for reforming hydrocarbon fuel gases in an electrochemical generator. Elongated electrochemical cells convert the fuel to electrical power in the presence of an oxidant, after which the spent fuel is recirculated and combined with a fresh hydrocarbon feed fuel forming the reformable gas mixture which is fed to a reforming chamber containing a reforming catalyst material, where the reforming catalyst material includes discrete passageways integrally formed along the length of the catalyst support in the direction of reformable gas flow. The spent fuel and/or combusted exhaust gases discharged from the generator chamber transfer heat to the catalyst support, which in turn transfers heat to the reformable gas and to the catalyst, preferably via a number of discrete passageways disposed adjacent one another in the reforming catalyst support. The passageways can be slots extending inwardly from an outer surface of the support body, which slots are partly defined by an exterior confining wall. According to a preferred embodiment, the catalyst support is non-rigid, porous, fibrous alumina, wherein the fibers are substantially unsintered and compressible, and the reforming catalyst support is impregnated, at least in the discrete passageways with Ni and MgO, and has a number of internal slot passageways for reformable gas, the slot passageways being partly closed by a containing outer wall. 5 figs.

Thermally efficient melting and fuel reforming for glass making

DOEpatents

Chen, M.S.; Painter, C.F.; Pastore, S.P.; Roth, G.S.; Winchester, D.C.

1991-10-15

An integrated process is described for utilizing waste heat from a glass making furnace. The hot off-gas from the furnace is initially partially cooled, then fed to a reformer. In the reformer, the partially cooled off-gas is further cooled against a hydrocarbon which is thus reformed into a synthesis gas, which is then fed into the glass making furnace as a fuel. The further cooled off-gas is then recycled back to absorb the heat from the hot off-gas to perform the initial cooling. 2 figures.

Photolysis of oxyfluorfen in aqueous methanol.

PubMed

Chakraborty, Subhasish K; Chakraborty, Savitri; Bhattacharyya, Anjan; Chowdhury, Ashim

2013-01-01

Photolysis of oxyfluorfen, an herbicide of the nitrodiphenyl ether class, was studied in aqueous methanol under UV and sunlight. UV irradiation was carried out in a borosilicate glass photoreactor (containing 250 ppm oxyfluorfen in 50% aqueous methanol) equipped with a quartz filter and 125 watt mercury lamp (maximum output 254 nm) at 25 ± 1°C. Sunlight irradiation was conducted at 28 ± 1°C in borosilicate Erlenmeyer flasks containing 250 ppm oxyfluorfen in 50% aqueous methanol. The samples from both the irradiated conditions were withdrawn at a definite time interval and extracted to measure oxyfluorfen content by gas chromatography-flame ionization detector for rate study. The half-life values were 20 hours and 2.7 days under UV and sunlight exposure, respectively. Photolysis of oxyfluorfen yielded 13 photoproducts of which three were characterized by infrared spectrophotometer and (1)H NMR and (13)C NMR spectroscopy. The rest of the photoproducts were identified by gas chromatography-mass spectrometry (GC-MS) and thin layer chromatography (TLC). An ionization potential 70 eV was used for electron impact-mass spectrometry (EI-MS) and methane was used as reagent gas for chemical ionization-mass spectrometry (CI-MS). Two of the photoproducts were also synthesized for comparison. The main phototransformation pathways of oxyfluorfen involved nitro reduction, dechlorination, and hydrolysis as well as nucleophiles displacement reaction.

Catalytic decomposition of methanol for onboard hydrogen generation

NASA Technical Reports Server (NTRS)

Brabbs, T.

1978-01-01

The steam reformation of an equimolar mixture of methanol and water on a copper chromite catalyst was studied at three furnace temperatures and at feed space velocities from 800 to 2600 per hour. The hydrogen space velocity could be related to the reactor temperature by the equation Sv = A exp (-omega T), where A and omega are constants determined for each value of alpha and T is temperature. At a methanol conversion of 0.87 and a reactor temperature of 589 K, the extrapolated value of the hydrogen space velocity was 9400 per hour. This velocity was used to estimate the size of an onboard hydrogen reactor for automotive applications. Such a reactor would need only about 0.8 liter of catalyst to produce 7630 STP liters (1.5 lb) of hydrogen per hour. This quantity of catalyst would fit into nine tubes 17.8 centimeters along and 2.54 centimeters in inside diameter, which is smaller than most mufflers. The reactor products would contain 12 to 13 percent more chemical energy than the incoming methanol and water.

Room temperature stable COx-free H2 production from methanol with magnesium oxide nanophotocatalysts

PubMed Central

Liu, Zhengqing; Yin, Zongyou; Cox, Casandra; Bosman, Michel; Qian, Xiaofeng; Li, Na; Zhao, Hongyang; Du, Yaping; Li, Ju; Nocera, Daniel G.

2016-01-01

Methanol, which contains 12.6 weight percent hydrogen, is a good hydrogen storage medium because it is a liquid at room temperature. However, by releasing the hydrogen, undesirable CO and/or CO2 byproducts are formed during catalytic fuel reforming. We show that alkaline earth metal oxides, in our case MgO nanocrystals, exhibit stable photocatalytic activity for CO/CO2-free H2 production from liquid methanol at room temperature. The performance of MgO nanocrystals toward methanol dehydrogenation increases with time and approaches ~320 μmol g−1 hour−1 after a 2-day photocatalytic reaction. The COx-free H2 production is attributed to methanol photodecomposition to formaldehyde, photocatalyzed by surface electronic states of unique monodispersed, porous MgO nanocrystals, which were synthesized with a novel facile colloidal chemical strategy. An oxygen plasma treatment allows for the removal of organic surfactants, producing MgO nanocrystals that are well dispersible in methanol. PMID:28508036

Reforming results of a novel radial reactor for a solid oxide fuel cell system with anode off-gas recirculation

NASA Astrophysics Data System (ADS)

Bosch, Timo; Carré, Maxime; Heinzel, Angelika; Steffen, Michael; Lapicque, François

2017-12-01

A novel reactor of a natural gas (NG) fueled, 1 kW net power solid oxide fuel cell (SOFC) system with anode off-gas recirculation (AOGR) is experimentally investigated. The reactor operates as pre-reformer, is of the type radial reactor with centrifugal z-flow, has the shape of a hollow cylinder with a volume of approximately 1 L and is equipped with two different precious metal wire-mesh catalyst packages as well as with an internal electric heater. Reforming investigations of the reactor are done stand-alone but as if the reactor would operate within the total SOFC system with AOGR. For the tests presented here it is assumed that the SOFC system runs on pure CH4 instead of NG. The manuscript focuses on the various phases of reactor operation during the startup process of the SOFC system. Startup process reforming experiments cover reactor operation points at which it runs on an oxygen to carbon ratio at the reactor inlet (ϕRI) of 1.2 with air supplied, up to a ϕRI of 2.4 without air supplied. As confirmed by a Monte Carlo simulation, most of the measured outlet gas concentrations are in or close to equilibrium.

Methanol from Wood Waste: A Technical and Economic Study.

DTIC Science & Technology

1977-06-01

percent of the gas is converted to methanol , the balance passing as inerts to the boiler. The reaction is as follows: catalyst 2H + CO ’ CH3OH 2 *-3...the boiler. Catalyst life is expected to be 6 years for methanol synthesis and 2 to 3 years for the shift reactor . PLANT SIZE In a chemical processing...percent of methyl alcohol ( methanol ) in gasoline for automotive use. / At a current consumption rate of 110 billion gallons per year (gpy), 11 billion

Towards an Understanding of Atmospheric Methanol

NASA Astrophysics Data System (ADS)

Millet, D. B.; Jacob, D. J.; de Gouw, J.; Warneke, C.; Holloway, J. S.; Blake, D. R.; Karl, T.; Campos, T.; Singh, H. B.; Diskin, G. S.

2007-12-01

Methanol, the most abundant non-methane organic gas in the atmosphere, is an important global source of tropospheric CO and formaldehyde, and plays a significant role in the tropical HOx and ozone budgets. The atmospheric methanol budget is highly uncertain, with estimates of the global source ranging from 75 to 490 Tg/yr. New measurements from recent field experiments (INTEX-B, MILAGRO, TEXAQS-II, INTEX-A, and ICARTT) provide quantitative constraints on methanol sources and sinks. Here we use a 3D model of atmospheric chemistry (GEOS-Chem) to interpret these datasets and their implications for the global methanol budget. We find that emissions from terrestrial plants (thought to be the main source) are overestimated by 40-50%; the discrepancy appears specific to certain plant functional types (broadleaf trees and crops). Recent measurements in the surface ocean imply a large in situ biotic source, so that methanol emissions from the ocean biosphere are comparable in magnitude to those from terrestrial ecosystems. The oceans are also a large gross sink for atmospheric methanol (similar to oxidation by OH). Even with the plant growth source decreased by 40-50% according to these new constraints, we find that methanol emissions from the terrestrial biosphere still dominate over those from urban and industrial sources, in contrast to other recent studies.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1993-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces

NASA Astrophysics Data System (ADS)

Murphy, Colin J.; Carrasco, Javier; Lawton, Timothy J.; Liriano, Melissa L.; Baber, Ashleigh E.; Lewis, Emily A.; Michaelides, Angelos; Sykes, E. Charles H.

2014-07-01

Methanol is a versatile chemical feedstock, fuel source, and energy storage material. Many reactions involving methanol are catalyzed by transition metal surfaces, on which hydrogen-bonded methanol overlayers form. As with water, the structure of these overlayers is expected to depend on a delicate balance of hydrogen bonding and adsorbate-substrate bonding. In contrast to water, however, relatively little is known about the structures methanol overlayers form and how these vary from one substrate to another. To address this issue, herein we analyze the hydrogen bonded networks that methanol forms as a function of coverage on three catalytically important surfaces, Au(111), Cu(111), and Pt(111), using a combination of scanning tunneling microscopy and density functional theory. We investigate the effect of intermolecular interactions, surface coverage, and adsorption energies on molecular assembly and compare the results to more widely studied water networks on the same surfaces. Two main factors are shown to direct the structure of methanol on the surfaces studied: the surface coverage and the competition between the methanol-methanol and methanol-surface interactions. Additionally, we report a new chiral form of buckled hexamer formed by surface bound methanol that maximizes the interactions between methanol monomers by sacrificing interactions with the surface. These results serve as a direct comparison of interaction strength, assembly, and chirality of methanol networks on Au(111), Cu(111), and Pt(111) which are catalytically relevant for methanol oxidation, steam reforming, and direct methanol fuel cells.

The JPL Direct Methanol Liquid-feed PEM Fuel Cell

NASA Technical Reports Server (NTRS)

Halpert, G.; Surampudi, S.

1994-01-01

Recently, there has been a breakthrough in fuel cell technology in the Energy Storage Systems Group at the Jet Propulsion Laboratory with the develpment of a direct methanol, liquid-feed, solid polymer electrolyte membrane (PEM) fuel cell... The methanol liquid-feed, solid polymer electrolyte (PEM) design has numerous system level advantages over the gas-feed design. These include:...

A novel multiple headspace extraction gas chromatographic method for measuring the diffusion coefficient of methanol in water and in olive oil.

PubMed

Zhang, Chun-Yun; Chai, Xin-Sheng

2015-03-13

A novel method for the determination of the diffusion coefficient (D) of methanol in water and olive oil has been developed. Based on multiple headspace extraction gas chromatography (MHE-GC), the methanol released from the liquid sample of interest in a closed sample vial was determined in a stepwise fashion. A theoretical model was derived to establish the relationship between the diffusion coefficient and the GC signals from MHE-GC measurements. The results showed that the present method has an excellent precision (RSD<1%) in the linear fitting procedure and good accuracy for the diffusion coefficients of methanol in both water and olive oil, when compared with data reported in the literature. The present method is simple and practical and can be a valuable tool for the determination of the diffusion coefficient of volatile analyte(s) into food simulants from food and beverage packaging material, both in research studies and in actual applications. Copyright © 2015 Elsevier B.V. All rights reserved.

Room temperature stable CO x -free H2 production from methanol with magnesium oxide nanophotocatalysts.

PubMed

Liu, Zhengqing; Yin, Zongyou; Cox, Casandra; Bosman, Michel; Qian, Xiaofeng; Li, Na; Zhao, Hongyang; Du, Yaping; Li, Ju; Nocera, Daniel G

2016-09-01

Methanol, which contains 12.6 weight percent hydrogen, is a good hydrogen storage medium because it is a liquid at room temperature. However, by releasing the hydrogen, undesirable CO and/or CO 2 byproducts are formed during catalytic fuel reforming. We show that alkaline earth metal oxides, in our case MgO nanocrystals, exhibit stable photocatalytic activity for CO/CO 2 -free H 2 production from liquid methanol at room temperature. The performance of MgO nanocrystals toward methanol dehydrogenation increases with time and approaches ~320 μmol g -1 hour -1 after a 2-day photocatalytic reaction. The CO x -free H 2 production is attributed to methanol photodecomposition to formaldehyde, photocatalyzed by surface electronic states of unique monodispersed, porous MgO nanocrystals, which were synthesized with a novel facile colloidal chemical strategy. An oxygen plasma treatment allows for the removal of organic surfactants, producing MgO nanocrystals that are well dispersible in methanol.

Partial Reform Equilibrium in Russia: A Case Study of the Political Interests of and in the Russian Gas and Oil Industry

NASA Astrophysics Data System (ADS)

Everett, Rabekah

While several theories abound that attempt to explain the obstacles to democracy in Russia, Joel Hellman's partial reform equilibrium model is an institutional theory that illustrates how weak institutions, combined with an instrumentalist cultural approach to the law and authoritarian-minded leadership, allowed the struggle over interests to craft and determine the nature of Russia's political structure. This thesis builds on the work of Hellman by using the partial reform theory to understand the evolution of interest infiltration and their impact on the formation of policies and institutions in favour of the elites or winners from 2004 to the present time period that allow them to wield law as a political weapon. The hypothesis posits that through their vested interests in state politics, the political and economic elites of the oil and gas industry have successfully stalled reform in Russia resulting in partial reform equilibrium. This is illustrated in a case study that was designed to collect the names, backgrounds, and social networks of gas and oil executives in order to determine how many of them have a history of, or are currently working as, ministers in the government or representatives in the Federation Council. The objective being to measure the degree to which gas and oil interests are present in government decision-making and conversely, the degree to which the government is present in the gas and oil industry. The thesis stresses the importance of institutional structure in determining Russia's political evolution, and uses vested interests as a primary source of structural institutional change, while also stressing on the social and international implications of this evolution.

Reformer Fuel Injector

NASA Technical Reports Server (NTRS)

Suder, Jennifer L.

2004-01-01

Today's form of jet engine power comes from what is called a gas turbine engine. This engine is on average 14% efficient and emits great quantities of green house gas carbon dioxide and air pollutants, Le. nitrogen oxides and sulfur oxides. The alternate method being researched involves a reformer and a solid oxide fuel cell (SOFC). Reformers are becoming a popular area of research within the industry scale. NASA Glenn Research Center's approach is based on modifying the large aspects of industry reforming processes into a smaller jet fuel reformer. This process must not only be scaled down in size, but also decrease in weight and increase in efficiency. In comparison to today's method, the Jet A fuel reformer will be more efficient as well as reduce the amount of air pollutants discharged. The intent is to develop a 10kW process that can be used to satisfy the needs of commercial jet engines. Presently, commercial jets use Jet-A fuel, which is a kerosene based hydrocarbon fuel. Hydrocarbon fuels cannot be directly fed into a SOFC for the reason that the high temperature causes it to decompose into solid carbon and Hz. A reforming process converts fuel into hydrogen and supplies it to a fuel cell for power, as well as eliminating sulfur compounds. The SOFC produces electricity by converting H2 and CO2. The reformer contains a catalyst which is used to speed up the reaction rate and overall conversion. An outside company will perform a catalyst screening with our baseline Jet-A fuel to determine the most durable catalyst for this application. Our project team is focusing on the overall research of the reforming process. Eventually we will do a component evaluation on the different reformer designs and catalysts. The current status of the project is the completion of buildup in the test rig and check outs on all equipment and electronic signals to our data system. The objective is to test various reformer designs and catalysts in our test rig to determine the most

Studying the characteristics of a 5 kW power installation on solid-oxide fuel cells with steam reforming of natural gas

NASA Astrophysics Data System (ADS)

Munts, V. A.; Volkova, Yu. V.; Plotnikov, N. S.; Dubinin, A. M.; Tuponogov, V. G.; Chernishev, V. A.

2015-11-01

The results from tests of a 5 kW power plant on solid-oxide fuel cells (SOFCs), in which natural gas is used as fuel, are presented. The installation's process circuit, the test procedure, and the analysis of the obtained results are described. The characteristics of the power plant developed by the Ural Industrial Company are investigated in four steady-state modes of its operation: with the SOFC nominal power capacity utilized by 40% (2 kW), 60% (3 kW), 90% (4.5 kW) and 110% (5.4 kW) (the peaking mode). The electrical and thermodynamic efficiencies are calculated for all operating modes, and the most efficient mode, in which the electrical efficiency reached almost 70%, is determined. The air excess coefficient and heat loss with flue gases q 2 are determined, and it is revealed that the heat loss q 5 decreases from 40 to 25% with increasing the load. Thermal balances are drawn up for the following components of the system the reformer, the SOFC battery, the catalytic burner for afterburning anode gases, the heat exchanger for heating the cathode air and the mixture of natural gas and steam, and the actual fuel utilization rates in the electrochemical generator are calculated. An equation for the resulting natural gas steam reforming reaction was obtained based on the results from calculating the equilibrium composition of reforming products for the achieved temperatures at the reformer outlet t 3.

DFT Studies of Adsorption of Cu7-atom Nanoclusters on TiO2 Surfaces and Application to Methanol Steam Reforming Reactions

NASA Astrophysics Data System (ADS)

Taft, Michael J., Sr.

Alcohol conversion to hydrogen, via steam reforming, is an alternative energy process that is promising for the future of clean energy economies. With advancements in fuel cell technologies, on-board hydrogen reforming could leverage already existing automotive designs and fuel infrastructure. The design of catalytic materials with tunable properties requires a level of insight that has yet to be achieved experimentally. The central objective of this project is to develop a working model of metal-oxide surface mediated copper clusters, since such catalytic beds have a wide-range of applications. More specifically, we investigate the catalytic framework of this process with theoretical models of the active metal (Cu) and metal­oxide support (TiO2). We employ a Density Functional Theory (DFT)-Generalized Gradient Approximation (GGA) approach for the quantum level electronic structure calculations of Cu, TiO2 and CH3OH. Additionally, we have generated anatase (A(001), A(101)) and rutile (R(100), R(110)) surface morphologies and 7­atom copper cluster complexes with those planes. To examine the possible influence of TiO2 on the adsorption properties of our active metal, Cu7, we have carried out adsorption studies with CH3OH. Our final data and observations predict that the Cu7 cluster adopts a symmetric pentagonal bipyramidal geometry with D5h symmetry. We find that the anatase morphology has a greater overall stability than rutile. The adsorption strength of the Cu7 cluster has been predicted in this study to be according to the following order: A(001) > A(101)> R(110). Indeed, the R(100) surface appears to be an unfavorable surface for metal cluster binding. Our data indicates that copper cluster stabilization on the metal-oxide surface depends on the nature of the crystal face. Again, we studied the adsorption properties of methanol on nascent Cu7 cluster, Cu7-TiO 2 complex and on pure TiO2-surface in A(001) polymorphic form. The calculations revealed that methanol

Combustion synthesized copper-ion substituted FeAl2O4 (Cu0.1Fe0.9Al2O4): A superior catalyst for methanol steam reforming compared to its impregnated analogue

NASA Astrophysics Data System (ADS)

Maiti, Sayantani; Llorca, Jordi; Dominguez, Montserrat; Colussi, Sara; Trovarelli, Alessandro; Priolkar, Kaustubh R.; Aquilanti, Giuliana; Gayen, Arup

2016-02-01

A series of copper ion substituted MAl2O4 (M = Mg, Mn, Fe and Zn) spinels is prepared by a single step solution combustion synthesis (SCS) and tested for methanol steam reforming (MSR). The copper ion substituted Cu0.1Fe0.9Al2O4 appears to be the most active, showing ∼98% methanol conversion at 300 °C with ∼5% CO selectivity at GHSV = 30,000 h-1 and H2O:CH3OH = 1.1. The analogous impregnated catalyst, CuO (10 at%)/FeAl2O4, is found to be much less active. These materials are characterized by XRD, H2-TPR, BET, HRTEM, XPS and XANES analyses. Spinel phase formation is highly facilitated upon Cu-ion substitution and Cu loading beyond 10 at% leads to the formation of CuO as an additional phase. The ionic substitution of copper in FeAl2O4 leads to the highly crystalline SCS catalyst containing Cu2+ ion sites that are shown to be more active than the dispersed CuO nano-crystallites on the FeAl2O4 impregnated catalyst, despite its lower surface area. The as prepared SCS catalyst contains also a portion of copper as Cu1+ that increases when subjected to reforming atmosphere. The MSR activity of the SCS catalyst decreases with time-on-stream due to the sintering of catalyst crystallites as established from XPS and HRTEM analyses.

Effect of cooled EGR on performance and exhaust gas emissions in EFI spark ignition engine fueled by gasoline and wet methanol blends

NASA Astrophysics Data System (ADS)

Rohadi, Heru; Syaiful, Bae, Myung-Whan

2016-06-01

Fuel needs, especially the transport sector is still dominated by fossil fuels which are non-renewable. However, oil reserves are very limited. Furthermore, the hazardous components produced by internal combustion engine forces many researchers to consider with alternative fuel which is environmental friendly and renewable sources. Therefore, this study intends to investigate the impact of cooled EGR on the performance and exhaust gas emissions in the gasoline engine fueled by gasoline and wet methanol blends. The percentage of wet methanol blended with gasoline is in the range of 5 to 15% in a volume base. The experiment was performed at the variation of engine speeds from 2500 to 4000 rpm with 500 intervals. The re-circulated exhaust gasses into combustion chamber was 5%. The experiment was performed at the constant engine speed. The results show that the use of cooled EGR with wet methanol of 10% increases the brake torque up to 21.3%. The brake thermal efficiency increases approximately 39.6% using cooled EGR in the case of the engine fueled by 15% wet methanol. Brake specific fuel consumption for the engine using EGR fueled by 10% wet methanol decreases up to 23% at the engine speed of 2500 rpm. The reduction of CO, O2 and HC emissions was found, while CO2 increases.

Ceramic oxygen transport membrane array reactor and reforming method

DOEpatents

Kelly, Sean M.; Christie, Gervase Maxwell; Rosen, Lee J.; Robinson, Charles; Wilson, Jamie R.; Gonzalez, Javier E.; Doraswami, Uttam R.

2016-09-27

A commercially viable modular ceramic oxygen transport membrane reforming reactor for producing a synthesis gas that improves the thermal coupling of reactively-driven oxygen transport membrane tubes and catalyst reforming tubes required to efficiently and effectively produce synthesis gas.

Efficient utilization of greenhouse gases in a gas-to-liquids process combined with CO2/steam-mixed reforming and Fe-based Fischer-Tropsch synthesis.

PubMed

Zhang, Chundong; Jun, Ki-Won; Ha, Kyoung-Su; Lee, Yun-Jo; Kang, Seok Chang

2014-07-15

Two process models for carbon dioxide utilized gas-to-liquids (GTL) process (CUGP) mainly producing light olefins and Fischer-Tropsch (F-T) synthetic oils were developed by Aspen Plus software. Both models are mainly composed of a reforming unit, an F-T synthesis unit and a recycle unit, while the main difference is the feeding point of fresh CO2. In the reforming unit, CO2 reforming and steam reforming of methane are combined together to produce syngas in flexible composition. Meanwhile, CO2 hydrogenation is conducted via reverse water gas shift on the Fe-based catalysts in the F-T synthesis unit to produce hydrocarbons. After F-T synthesis, the unreacted syngas is recycled to F-T synthesis and reforming units to enhance process efficiency. From the simulation results, it was found that the carbon efficiencies of both CUGP options were successfully improved, and total CO2 emissions were significantly reduced, compared with the conventional GTL processes. The process efficiency was sensitive to recycle ratio and more recycle seemed to be beneficial for improving process efficiency and reducing CO2 emission. However, the process efficiency was rather insensitive to split ratio (recycle to reforming unit/total recycle), and the optimum split ratio was determined to be zero.

Advances in catalysts for internal reforming in high temperature fuel cells

NASA Astrophysics Data System (ADS)

Dicks, A. L.

Catalytic steam reforming of natural gas is an attractive method of producing the hydrogen required by the present generation of fuel cells. The molten carbonate (MCFC) and solid oxide (SOFC) fuel cells operate at high enough temperatures for the endothermic steam reforming reaction to be carried out within the stack. For the MCFC, the conventional anodes have insufficient activity to catalyse the steam reforming of natural gas. For these cells, internal reforming can be achieved only with the addition of a separate catalyst, preferably located in close proximity to the anode. However, in the so-called `Direct Internal Reforming' configuration, attack from alkali in the MCFC may severely limit catalyst lifetime. In the case of the state-of-the-art SOFC, natural gas can be reformed directly on the nickel cermet anode. However, in the SOFC, temperature variations in the cell caused by the reforming reaction may limit the amount of internal reforming that can be allowed in practice. In addition, some external pre-reforming may be desirable to remove high molecular weight hydrocarbons from the fuel gas, which would otherwise crack to produce elemental carbon. Degradation of the SOFC anode may also be a problem when internal reforming is carried out. This has prompted several research groups to investigate the use of alternative anode materials.

A rapid method for simultaneously determining ethanol and methanol content in wines by full evaporation headspace gas chromatography.

PubMed

Zhang, Chun-Yun; Lin, Neng-Biao; Chai, Xin-Sheng; Zhong-Li; Barnes, Donald G

2015-09-15

This work reports on a full evaporation headspace gas chromatographic (FE HS-GC) method for simultaneously determining the ethanol (EtOH) and methanol (MeOH) content in wines. A small sample (10μL) was placed in a headspace sample vial, and a near-complete mass transfer of ethanol and methanol from the liquid sample to the vapor phase was obtained within three minutes at a temperature of 105°C, which allowed the measurement of the EtOH and MeOH content in the sample by GC. The results showed excellent precision and accuracy, as shown by the reproducibilities of 1.02% and 2.11% for EtOH and MeOH, respectively, and recoveries that ranged from 96.1% to 104% for both alcohols. The method is efficient, accurate and suitable for the determination of EtOH and MeOH in wine production and quality control. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Study of Catalyst Variation Effect in Glycerol Conversion Process to Hydrogen Gas by Steam Reforming

NASA Astrophysics Data System (ADS)

Widayat; Hartono, R.; Elizabeth, E.; Annisa, A. N.

2018-04-01

Along with the economic development, needs of energy being increase too. Hydrogen as alternative energy has many usages. Besides that, hydrogen is one source of energy that is a clean fuel, but process production of hydrogen from natural gas as a raw material has been used for a long time. Therefore, there is need new invention to produce hydrogen from the others raw material. Glycerol, a byproduct of biodiesel production, is a compound which can be used as a raw material for hydrogen production. By using glycerol as a raw material of hydrogen production, we can get added value of glycerol as well as an energy source solution. The process production of hydrogen by steam reforming is a thermochemical process with efficiency 70%. This process needs contribution of catalyst to improve its efficiency and selectivity of the process. In this study will be examined the effect variation of catalyst for glycerol conversion process to hydrogen by steam reforming. The method for catalyst preparation was variation of catalyst impregnation composition, catalyst calcined with difference concentration of hydrochloric acid and calcined with difference hydrochloric acid ratio. After that, all of catalyst which have been prepared, used for steam reforming process for hydrogen production from glycerol as a raw material. From the study, the highest yield of hydrogen gas showed in the process production by natural zeolite catalyst with 1:15 Hydrochloric acid ratio was 42.28%. Hydrogen yield for 2M calcined natural zeolite catalyst was 38.37%, for ZSM-5 catalyst was 15.83%, for 0.5M calcined natural zeolite was 13.09% and for ultrasonic natural zeolite was 11.43%. The lowest yield of hydrogen gas showed in catalyst 2Zn/ZSM-5 with 11.22%. This result showed that hydrogen yield product was affected by catalyst variation because of the catalyst has difference characteristic and difference catalytic activity after the catalyst preparation process.

Microfluidic distillation chip for methanol concentration detection.

PubMed

Wang, Yao-Nan; Liu, Chan-Chiung; Yang, Ruey-Jen; Ju, Wei-Jhong; Fu, Lung-Ming

2016-03-17

An integrated microfluidic distillation system is proposed for separating a mixed ethanol-methanol-water solution into its constituent components. The microfluidic chip is fabricated using a CO2 laser system and comprises a serpentine channel, a boiling zone, a heating zone, and a cooled collection chamber filled with de-ionized (DI) water. In the proposed device, the ethanol-methanol-water solution is injected into the microfluidic chip and driven through the serpentine channel and into the collection chamber by means of a nitrogen carrier gas. Following the distillation process, the ethanol-methanol vapor flows into the collection chamber and condenses into the DI water. The resulting solution is removed from the collection tank and reacted with a mixed indicator. Finally, the methanol concentration is inversely derived from the absorbance measurements obtained using a spectrophotometer. The experimental results show the proposed microfluidic system achieves an average methanol distillation efficiency of 97%. The practicality of the proposed device is demonstrated by detecting the methanol concentrations of two commercial fruit wines. It is shown that the measured concentration values deviate by no more than 3% from those obtained using a conventional bench top system. Copyright © 2016 Elsevier B.V. All rights reserved.

Slab reformer

DOEpatents

Spurrier, Francis R.; DeZubay, Egon A.; Murray, Alexander P.; Vidt, Edward J.

1984-02-07

Slab-shaped high efficiency catalytic reformer configurations particularly useful for generation of fuels to be used in fuel cell based generation systems. A plurality of structures forming a generally rectangular peripheral envelope are spaced about one another to form annular regions, an interior annular region containing a catalytic bed and being regeneratively heated on one side by a hot comubstion gas and on the other side by the gaseous products of the reformation. An integrally mounted combustor is cooled by impingement of incoming oxidant.

Slab reformer

DOEpatents

Spurrier, Francis R.; DeZubay, Egon A.; Murray, Alexander P.; Vidt, Edward J.

1985-03-12

Slab-shaped high efficiency catalytic reformer configurations particularly useful for generation of fuels to be used in fuel cell based generation systems. A plurality of structures forming a generally rectangular peripheral envelope are spaced about one another to form annular regions, an interior annular region containing a catalytic bed and being regeneratively heated on one side by a hot combustion gas and on the other side by the gaseous products of the reformation. An integrally mounted combustor is cooled by impingement of incoming oxidant.

Slab reformer

NASA Technical Reports Server (NTRS)

Spurrier, Francis R. (Inventor); DeZubay, Egon A. (Inventor); Murray, Alexander P. (Inventor); Vidt, Edward J. (Inventor)

1984-01-01

Slab-shaped high efficiency catalytic reformer configurations particularly useful for generation of fuels to be used in fuel cell based generation systems. A plurality of structures forming a generally rectangular peripheral envelope are spaced about one another to form annular regions, an interior annular region containing a catalytic bed and being regeneratively heated on one side by a hot comubstion gas and on the other side by the gaseous products of the reformation. An integrally mounted combustor is cooled by impingement of incoming oxidant.

Slab reformer

NASA Technical Reports Server (NTRS)

Spurrier, Francis R. (Inventor); DeZubay, Egon A. (Inventor); Murray, Alexander P. (Inventor); Vidt, Edward J. (Inventor)

1985-01-01

Slab-shaped high efficiency catalytic reformer configurations particularly useful for generation of fuels to be used in fuel cell based generation systems. A plurality of structures forming a generally rectangular peripheral envelope are spaced about one another to form annular regions, an interior annular region containing a catalytic bed and being regeneratively heated on one side by a hot combustion gas and on the other side by the gaseous products of the reformation. An integrally mounted combustor is cooled by impingement of incoming oxidant.

Methanol production method and system

DOEpatents

Chen, Michael J.; Rathke, Jerome W.

1984-01-01

Ethanol is selectively produced from the reaction of methanol with carbon monoxide and hydrogen in the presence of a transition metal carbonyl catalyst. Methanol serves as a solvent and may be accompanied by a less volatile co-solvent. The solution includes the transition metal carbonyl catalysts and a basic metal salt such as an alkali metal or alkaline earth metal formate, carbonate or bicarbonate. A gas containing a high carbon monoxide to hydrogen ratio, as is present in a typical gasifer product, is contacted with the solution for the preferential production of ethanol with minimal water as a byproduct. Fractionation of the reaction solution provides substantially pure ethanol product and allows return of the catalysts for reuse.

Alternative Fuels Data Center: Methanol

Science.gov Websites

(CH3OH), also known as wood alcohol, is considered an alternative fuel under the Energy Policy Act of 1992. As an engine fuel, methanol has chemical and physical fuel properties similar to ethanol Ethanol Hydrogen Natural Gas Propane Emerging Fuels Fuel Prices Conserve Fuel Idle Reduction Parts &

Auxiliary reactor for a hydrocarbon reforming system

DOEpatents

Clawson, Lawrence G.; Dorson, Matthew H.; Mitchell, William L.; Nowicki, Brian J.; Bentley, Jeffrey M.; Davis, Robert; Rumsey, Jennifer W.

2006-01-17

An auxiliary reactor for use with a reformer reactor having at least one reaction zone, and including a burner for burning fuel and creating a heated auxiliary reactor gas stream, and heat exchanger for transferring heat from auxiliary reactor gas stream and heat transfer medium, preferably two-phase water, to reformer reaction zone. Auxiliary reactor may include first cylindrical wall defining a chamber for burning fuel and creating a heated auxiliary reactor gas stream, the chamber having an inlet end, an outlet end, a second cylindrical wall surrounding first wall and a second annular chamber there between. The reactor being configured so heated auxiliary reactor gas flows out the outlet end and into and through second annular chamber and conduit which is disposed in second annular chamber, the conduit adapted to carry heat transfer medium and being connectable to reformer reaction zone for additional heat exchange.

Slab reformer

DOEpatents

Spurrier, F.R.; DeZubay, E.A.; Murray, A.P.; Vidt, E.J.

1984-02-07

Slab-shaped high efficiency catalytic reformer configurations are disclosed particularly useful for generation of fuels to be used in fuel cell based generation systems. A plurality of structures forming a generally rectangular peripheral envelope are spaced about one another to form annular regions, an interior annular region containing a catalytic bed and being regeneratively heated on one side by a hot combustion gas and on the other side by the gaseous products of the reformation. An integrally mounted combustor is cooled by impingement of incoming oxidant. 14 figs.

Process for the conversion of carbonaceous feedstocks to particulate carbon and methanol

DOEpatents

Steinberg, M.; Grohse, E.W.

1995-06-27

A process is described for the production of a pollutant-free particulate carbon (i.e., a substantially ash-, sulfur- and nitrogen-free carbon) from carbonaceous feedstocks. The basic process involves de-oxygenating one of the gas streams formed in a cyclic hydropyrolysis-methane pyrolysis process in order to improve conversion of the initial carbonaceous feedstock. De-oxygenation is effected by catalytically converting carbon monoxide, carbon dioxide, and hydrogen contained in one of the pyrolysis gas streams, preferably the latter, to a methanol co-product. There are thus produced two products whose use is known per se, viz., a substantially pollutant-free particulate carbon black and methanol. These products may be admixed in the form of a liquid slurry of carbon black in methanol. 3 figs.

Process for the conversion of carbonaceous feedstocks to particulate carbon and methanol

DOEpatents

Steinberg, Meyer; Grohse, Edward W.

1995-01-01

A process for the production of a pollutant-free particulate carbon (i.e., a substantially ash-, sulfur- and nitrogen-free carbon) from carbonaceous feedstocks. The basic process involves de-oxygenating one of the gas streams formed in a cyclic hydropyrolysis-methane pyrolysis process in order to improve conversion of the initial carbonaceous feedstock. De-oxygenation is effected by catalytically converting carbon monoxide, carbon dioxide, and hydrogen contained in one of the pyrolysis gas streams, preferably the latter, to a methanol co-product. There are thus produced two products whose use is known per se, viz., a substantially pollutant-free particulate carbon black and methanol. These products may be admixed in the form of a liquid slurry of carbon black in methanol.

A techno-economic & environmental analysis of a novel technology utilizing an internal combustion engine as a compact, inexpensive micro-reformer for a distributed gas-to-liquids system

NASA Astrophysics Data System (ADS)

Browne, Joshua B.

Anthropogenic greenhouse gas emissions (GHG) contribute to global warming, and must be mitigated. With GHG mitigation as an overarching goal, this research aims to study the potential for newfound and abundant sources of natural gas to play a role as part of a GHG mitigation strategy. However, recent work suggests that methane leakage in the current natural gas system may inhibit end-use natural gas as a robust mitigation strategy, but that natural gas as a feedstock for other forms of energy, such as electricity generation or liquid fuels, may support natural-gas based mitigation efforts. Flaring of uneconomic natural gas, or outright loss of natural gas to the atmosphere results in greenhouse gas emissions that could be avoided and which today are very large in aggregate. A central part of this study is to look at a new technology for converting natural gas into methanol at a unit scale that is matched to the size of individual natural gas wells. The goal is to convert stranded or otherwise flared natural gas into a commercially valuable product and thereby avoid any unnecessary emission to the atmosphere. A major part of this study is to contribute to the development of a novel approach for converting natural gas into methanol and to assess the environmental impact (for better or for worse) of this new technology. This Ph. D. research contributes to the development of such a system and provides a comprehensive techno-economic and environmental assessment of this technology. Recognizing the distributed nature of methane leakage associated with the natural gas system, this work is also intended to advance previous research at the Lenfest Center for Sustainable Energy that aims to show that small, modular energy systems can be made economic. This thesis contributes to and analyzes the development of a small-scale gas-to-liquids (GTL) system aimed at addressing flared natural gas from gas and oil wells. This thesis includes system engineering around a design that

Fuel and power coproduction: The Liquid Phase Methanol (LPMEOH{trademark}) process demonstration at Kingsport

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

Drown, D.P.; Brown, W.R.; Heydorn, E.C.

1997-12-31

The Liquid Phase Methanol (LPMEOH{trademark}) process uses a slurry bubble column reactor to convert syngas (primarily a mixture of carbon monoxide and hydrogen) to methanol. Because of its superior heat management, the process is able to be designed to directly handle the carbon monoxide (CO)-rich syngas characteristic of the gasification of coal, petroleum coke, residual oil, wastes, or of other hydrocarbon feedstocks. When added to an integrated gasification combined cycle (IGCC) power plant, the LPMEOH{trademark} process converts a portion of the CO-rich syngas produced by the gasifier to methanol, and the remainder of the unconverted gas is used to fuelmore » the gas turbine combined-cycle power plant. The LPMEOH{trademark} process has the flexibility to operate in a daily electricity demand load-following manner. Coproduction of power and methanol via IGCC and the LPMEOH{trademark} process provides opportunities for energy storage for electrical demand peak shaving, clean fuel for export, and/or chemical methanol sales.« less

Improving formaldehyde consumption drives methanol assimilation in engineered E. coli.

PubMed

Woolston, Benjamin M; King, Jason R; Reiter, Michael; Van Hove, Bob; Stephanopoulos, Gregory

2018-06-19

Due to volatile sugar prices, the food vs fuel debate, and recent increases in the supply of natural gas, methanol has emerged as a promising feedstock for the bio-based economy. However, attempts to engineer Escherichia coli to metabolize methanol have achieved limited success. Here, we provide a rigorous systematic analysis of several potential pathway bottlenecks. We show that regeneration of ribulose 5-phosphate in E. coli is insufficient to sustain methanol assimilation, and overcome this by activating the sedoheptulose bisphosphatase variant of the ribulose monophosphate pathway. By leveraging the kinetic isotope effect associated with deuterated methanol as a chemical probe, we further demonstrate that under these conditions overall pathway flux is kinetically limited by methanol dehydrogenase. Finally, we identify NADH as a potent kinetic inhibitor of this enzyme. These results provide direction for future engineering strategies to improve methanol utilization, and underscore the value of chemical biology methodologies in metabolic engineering.

A novel methanol sensor based on gas-penetration through a porous polypyrrole-coated polyacrylonitrile nanofiber mat.

PubMed

Jun, Tae-Sun; Ho, Thi Anh; Rashid, Muhammad; Kim, Yong Shin

2013-09-01

In this work, we propose a novel chemoresistive gas sensor operated under a vertical analyte flow passing through a permeable sensing membrane. Such a configuration is different from the use of a planar sensor implemented under a conventional horizontal flow. A highly porous core-shell polyacrylonitrile-polypyrrole (PAN@PPy) nanofiber mat was prepared as the sensing element via electrospinning and two-step vapor-phase polymerization (VPP). Various analysis methods such as SEM, TEM, FT-IR and XPS measurements were employed in order to characterize structural features of the porous sensing mat. These analyses confirmed that very thin (ca. 10 nm) conductive PPy sheath layers were deposited by VPP on electrospun PAN nanofibers with an average diameter of 258 nm. Preliminary results revealed that the gas penetration-type PAN@PPy sensor had a higher sensor response and shorter detection and recovery times upon exposure to methanol analyte when compared with a conventional horizontal flow sensor due to efficient and fast analyte transfer into the sensing layer.

Intermittent hemodialysis is superior to continuous veno-venous hemodialysis/hemodiafiltration to eliminate methanol and formate during treatment for methanol poisoning

PubMed Central

Zakharov, Sergey; Pelclova, Daniela; Navratil, Tomas; Belacek, Jaromir; Kurcova, Ivana; Komzak, Ondrej; Salek, Tomas; Latta, Jiri; Turek, Radovan; Bocek, Robert; Kucera, Cyril; Hubacek, Jaroslav A; Fenclova, Zdenka; Petrik, Vit; Cermak, Martin; Hovda, Knut Erik

2014-01-01

During an outbreak of methanol poisonings in the Czech Republic in 2012, we were able to study methanol and formate elimination half-lives during intermittent hemodialysis (IHD) and continuous veno-venous hemodialysis/hemodiafiltration (CVVHD/HDF) and the relative impact of dialysate and blood flow rates on elimination. Data were obtained from 11 IHD and 13 CVVHD/HDF patients. Serum methanol and formate concentrations were measured by gas chromatography and an enzymatic method. The groups were relatively comparable, but the CVVHD/HDF group was significantly more acidotic (mean pH 6.9 vs. 7.1 IHD). The mean elimination half-life of methanol was 3.7 and formate 1.6 h with IHD, versus 8.1 and 3.6 h, respectively, with CVVHD/HDF (both significant). The 54% greater reduction in methanol and 56% reduction in formate elimination half-life during IHD resulted from the higher blood and dialysate flow rates. Increased blood and dialysate flow on the CVVHD/HDF also increased elimination significantly. Thus, IHD is superior to CVVHD/HDF for more rapid methanol and formate elimination, and if CVVHD/HDF is the only treatment available then elimination is greater with greater blood and dialysate flow rates. PMID:24621917

Hydrogen-based power generation from bioethanol steam reforming

NASA Astrophysics Data System (ADS)

Tasnadi-Asztalos, Zs.; Cormos, C. C.; Agachi, P. S.

2015-12-01

This paper is evaluating two power generation concepts based on hydrogen produced from bioethanol steam reforming at industrial scale without and with carbon capture. The power generation from bioethanol conversion is based on two important steps: hydrogen production from bioethanol catalytic steam reforming and electricity generation using a hydrogen-fuelled gas turbine. As carbon capture method to be assessed in hydrogen-based power generation from bioethanol steam reforming, the gas-liquid absorption using methyl-di-ethanol-amine (MDEA) was used. Bioethanol is a renewable energy carrier mainly produced from biomass fermentation. Steam reforming of bioethanol (SRE) provides a promising method for hydrogen and power production from renewable resources. SRE is performed at high temperatures (e.g. 800-900°C) to reduce the reforming by-products (e.g. ethane, ethene). The power generation from hydrogen was done with M701G2 gas turbine (334 MW net power output). Hydrogen was obtained through catalytic steam reforming of bioethanol without and with carbon capture. For the evaluated plant concepts the following key performance indicators were assessed: fuel consumption, gross and net power outputs, net electrical efficiency, ancillary consumptions, carbon capture rate, specific CO2 emission etc. As the results show, the power generation based on bioethanol conversion has high energy efficiency and low carbon footprint.

Coke formation and carbon atom economy of methanol-to-olefins reaction.

PubMed

Wei, Yingxu; Yuan, Cuiyu; Li, Jinzhe; Xu, Shutao; Zhou, You; Chen, Jingrun; Wang, Quanyi; Xu, Lei; Qi, Yue; Zhang, Qing; Liu, Zhongmin

2012-05-01

The methanol-to-olefins (MTO) process is becoming the most important non-petrochemical route for the production of light olefins from coal or natural gas. Maximizing the generation of the target products, ethene and propene, and minimizing the production of byproducts and coke, are major considerations in the efficient utilization of the carbon resource of methanol. In the present work, the heterogeneous catalytic conversion of methanol was evaluated by performing simultaneous measurements of the volatile products generated in the gas phase and the confined coke deposition in the catalyst phase. Real-time and complete reaction profiles were plotted to allow the comparison of carbon atom economy of methanol conversion over the catalyst SAPO-34 at varied reaction temperatures. The difference in carbon atom economy was closely related with the coke formation in the SAPO-34 catalyst. The confined coke compounds were determined. A new type of confined organics was found, and these accounted for the quick deactivation and low carbon atom economy under low-reaction-temperature conditions. Based on the carbon atom economy evaluation and coke species determination, optimized operating conditions for the MTO process are suggested; these conditions guarantee high conversion efficiency of methanol. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Natural gas reforming of carbon dioxide for syngas over Ni–Ce–Al catalysts

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

Han, Jun; Zhan, Yiqiu; Street, Jason

A series of Ni–Ce–Al composite oxides with various Ni molar contents were synthesized via the refluxed co-precipitation method and used for natural gas reforming of CO 2 (NGRC) for syngas production. The effect of Ni molar content, reaction temperature, feed gas ratio and gas hourly space velocity (GHSV) on the Ni–Ce–Al catalytic performance was investigated. The Ni 10CeAl catalyst was selected to undergo 30 h stability test and the conversion of CH 4 and CO 2 decreased by 2.8% and 2.6%, respectively. The characterization of the reduced and used Ni10CeAl catalyst was performed using BET, H 2-TPR, in-situ XRD, TEM,more » and TGA-DTG techniques. The in-situ XRD results revealed that Ce 2O 3, CeO 2 and CeAlO 3 coexisted in the Ni10CeAl catalyst after reduction at 850 °C for 2 h. The results of the TEM analysis revealed that the Ni particle size increased after the NGRC reaction, which mainly caused the catalyst deactivation.« less

JP8 Reformation for Combat Vehicles

DTIC Science & Technology

2007-08-07

phase (fuel), and a gas phase (hydrogen) at elevated pressures. • Trickle - bed configuration is difficult to model and scale down—not practical for...gases output from HDS reactor are used to fuel the reformer. Current Technology Status: •Integrated desulfurization/reforming system successfully

Methanol injection and recovery in a large turboexpander plant. [Canada

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

Nelson, K.; Wolfe, L.

1981-01-01

Methanol is used to prevent hydrate formation in Petro-Canada's 2000 MMSCFD Empress expander plant. Injection and recovery facilities have operated essentially trouble-free since start-up late in 1979. A portion of the methanol recovery section has been modified to provide removal of the H/sub 2/S and most of the COS from the propane product stream, concurrent with methanol recovery. The Empress straddle plant strips natural gas liquids from pipeline gas leaving Alberta for eastern Canadian and U.S. markets. The original cold oil absorption plant, started up in 1964 and expanded in 1967, recovered over 90% of the propane and virtually allmore » of the heavier components. In 1976, a market for ethane was secured as feedstock for the world-scale ethylene complex under construction in Alberta, and it was decided to replace the cold oil plant with a turboexpander facility. The plant and its operations are described in some detail. 2 refs.« less

40 CFR 86.1509 - Exhaust gas sampling system.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Otto-Cycle Heavy-Duty Engines, New Methanol-Fueled Natural Gas-Fueled, and Liquefied Petroleum Gas-Fueled Diesel-Cycle Heavy-Duty Engines, New Otto-Cycle Light-Duty Trucks, and New Methanol-Fueled Natural Gas-Fueled, and Liquefied Petroleum Gas-Fueled Diesel-Cycle Light-Duty Trucks; Idle Test Procedures...

Hydrogen Generation Via Fuel Reforming

NASA Astrophysics Data System (ADS)

Krebs, John F.

2003-07-01

Reforming is the conversion of a hydrocarbon based fuel to a gas mixture that contains hydrogen. The H2 that is produced by reforming can then be used to produce electricity via fuel cells. The realization of H2-based power generation, via reforming, is facilitated by the existence of the liquid fuel and natural gas distribution infrastructures. Coupling these same infrastructures with more portable reforming technology facilitates the realization of fuel cell powered vehicles. The reformer is the first component in a fuel processor. Contaminants in the H2-enriched product stream, such as carbon monoxide (CO) and hydrogen sulfide (H2S), can significantly degrade the performance of current polymer electrolyte membrane fuel cells (PEMFC's). Removal of such contaminants requires extensive processing of the H2-rich product stream prior to utilization by the fuel cell to generate electricity. The remaining components of the fuel processor remove the contaminants in the H2 product stream. For transportation applications the entire fuel processing system must be as small and lightweight as possible to achieve desirable performance requirements. Current efforts at Argonne National Laboratory are focused on catalyst development and reactor engineering of the autothermal processing train for transportation applications.

Electrochemical fuel cell generator having an internal and leak tight hydrocarbon fuel reformer

DOEpatents

Dederer, J.T.; Hager, C.A.

1998-03-31

An electrochemical fuel cell generator configuration is made having a generator section which contains a plurality of axially elongated fuel cells, each cell containing a fuel electrode, air electrode, and solid oxide electrolyte between the electrodes, in which axially elongated dividers separate portions of the fuel cells from each other, and where at least one divider also reforms a reformable fuel gas mixture prior to electricity generation reactions, the at least one reformer-divider is hollow having a closed end and an open end entrance for a reformable fuel mixture to pass to the closed end of the divider and then reverse flow and pass back along the hollowed walls to be reformed, and then finally to pass as reformed fuel out of the open end of the divider to contact the fuel cells, and further where the reformer-divider is a composite structure having a gas diffusion barrier of metallic foil surrounding the external walls of the reformer-divider except at the entrance to prevent diffusion of the reformable gas mixture through the divider, and further housed in an outer insulating jacket except at the entrance to prevent short-circuiting of the fuel cells by the gas diffusion barrier. 10 figs.

Electrochemical fuel cell generator having an internal and leak tight hydrocarbon fuel reformer

DOEpatents

Dederer, Jeffrey T.; Hager, Charles A.

1998-01-01

An electrochemical fuel cell generator configuration is made having a generator section which contains a plurality of axially elongated fuel cells, each cell containing a fuel electrode, air electrode, and solid oxide electrolyte between the electrodes, in which axially elongated dividers separate portions of the fuel cells from each other, and where at least one divider also reforms a reformable fuel gas mixture prior to electricity generation reactions, the at least one reformer-divider is hollow having a closed end and an open end entrance for a reformable fuel mixture to pass to the closed end of the divider and then reverse flow and pass back along the hollowed walls to be reformed, and then finally to pass as reformed fuel out of the open end of the divider to contact the fuel cells, and further where the reformer-divider is a composite structure having a gas diffusion barrier of metallic foil surrounding the external walls of the reformer-divider except at the entrance to prevent diffusion of the reformable gas mixture through the divider, and further housed in an outer insulating jacket except at the entrance to prevent short-circuiting of the fuel cells by the gas diffusion barrier.

40 CFR 86.1509 - Exhaust gas sampling system.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Regulations for Otto-Cycle Heavy-Duty Engines, New Methanol-Fueled Natural Gas-Fueled, and Liquefied Petroleum Gas-Fueled Diesel-Cycle Heavy-Duty Engines, New Otto-Cycle Light-Duty Trucks, and New Methanol-Fueled Natural Gas-Fueled, and Liquefied Petroleum Gas-Fueled Diesel-Cycle Light-Duty Trucks; Idle Test...

40 CFR 86.1509 - Exhaust gas sampling system.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Regulations for Otto-Cycle Heavy-Duty Engines, New Methanol-Fueled Natural Gas-Fueled, and Liquefied Petroleum Gas-Fueled Diesel-Cycle Heavy-Duty Engines, New Otto-Cycle Light-Duty Trucks, and New Methanol-Fueled Natural Gas-Fueled, and Liquefied Petroleum Gas-Fueled Diesel-Cycle Light-Duty Trucks; Idle Test...

40 CFR 86.1511 - Exhaust gas analysis system.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Regulations for Otto-Cycle Heavy-Duty Engines, New Methanol-Fueled Natural Gas-Fueled, and Liquefied Petroleum Gas-Fueled Diesel-Cycle Heavy-Duty Engines, New Otto-Cycle Light-Duty Trucks, and New Methanol-Fueled Natural Gas-Fueled, and Liquefied Petroleum Gas-Fueled Diesel-Cycle Light-Duty Trucks; Idle Test...

40 CFR 86.1509 - Exhaust gas sampling system.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Regulations for Otto-Cycle Heavy-Duty Engines, New Methanol-Fueled Natural Gas-Fueled, and Liquefied Petroleum Gas-Fueled Diesel-Cycle Heavy-Duty Engines, New Otto-Cycle Light-Duty Trucks, and New Methanol-Fueled Natural Gas-Fueled, and Liquefied Petroleum Gas-Fueled Diesel-Cycle Light-Duty Trucks; Idle Test...

Scaffoldless engineered enzyme assembly for enhanced methanol utilization

DOE PAGES

Price, J. Vincent; Chen, Long; Whitaker, W. Brian; ...

2016-10-24

Methanol is an important feedstock derived from natural gas and can be chemically converted into commodity and specialty chemicals at high pressure and temperature. Although biological conversion of methanol can proceed at ambient conditions, there is a dearth of engineered microorganisms that use methanol to produce metabolites. In nature, methanol dehydrogenase (Mdh), which converts methanol to formaldehyde, highly favors the reverse reaction. Thus, efficient coupling with the irreversible sequestration of formaldehyde by 3-hexulose-6-phosphate synthase (Hps) and 6-phospho-3-hexuloseisomerase (Phi) serves as the key driving force to pull the pathway equilibrium toward central metabolism. An emerging strategy to promote efficient substrate channelingmore » is to spatially organize pathway enzymes in an engineered assembly to provide kinetic driving forces that promote carbon flux in a desirable direction. Here, we report a scaffoldless, self-assembly strategy to organize Mdh, Hps, and Phi into an engineered supramolecular enzyme complex using an SH3–ligand interaction pair, which enhances methanol conversion to fructose-6-phosphate (F6P). To increase methanol consumption, an “NADH Sink” was created using Escherichia coli lactate dehydrogenase as an NADH scavenger, thereby preventing reversible formaldehyde reduction. Combination of the two strategies improved in vitro F6P production by 97-fold compared with unassembled enzymes. The beneficial effect of supramolecular enzyme assembly was also realized in vivo as the engineered enzyme assembly improved whole-cell methanol consumption rate by ninefold. This approach will ultimately allow direct coupling of enhanced F6P synthesis with other metabolic engineering strategies for the production of many desired metabolites from methanol.« less

Scaffoldless engineered enzyme assembly for enhanced methanol utilization

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

Price, J. Vincent; Chen, Long; Whitaker, W. Brian

Methanol is an important feedstock derived from natural gas and can be chemically converted into commodity and specialty chemicals at high pressure and temperature. Although biological conversion of methanol can proceed at ambient conditions, there is a dearth of engineered microorganisms that use methanol to produce metabolites. In nature, methanol dehydrogenase (Mdh), which converts methanol to formaldehyde, highly favors the reverse reaction. Thus, efficient coupling with the irreversible sequestration of formaldehyde by 3-hexulose-6-phosphate synthase (Hps) and 6-phospho-3-hexuloseisomerase (Phi) serves as the key driving force to pull the pathway equilibrium toward central metabolism. An emerging strategy to promote efficient substrate channelingmore » is to spatially organize pathway enzymes in an engineered assembly to provide kinetic driving forces that promote carbon flux in a desirable direction. Here, we report a scaffoldless, self-assembly strategy to organize Mdh, Hps, and Phi into an engineered supramolecular enzyme complex using an SH3–ligand interaction pair, which enhances methanol conversion to fructose-6-phosphate (F6P). To increase methanol consumption, an “NADH Sink” was created using Escherichia coli lactate dehydrogenase as an NADH scavenger, thereby preventing reversible formaldehyde reduction. Combination of the two strategies improved in vitro F6P production by 97-fold compared with unassembled enzymes. The beneficial effect of supramolecular enzyme assembly was also realized in vivo as the engineered enzyme assembly improved whole-cell methanol consumption rate by ninefold. This approach will ultimately allow direct coupling of enhanced F6P synthesis with other metabolic engineering strategies for the production of many desired metabolites from methanol.« less

Scaffoldless engineered enzyme assembly for enhanced methanol utilization

PubMed Central

Price, J. Vincent; Chen, Long; Whitaker, W. Brian; Papoutsakis, Eleftherios; Chen, Wilfred

2016-01-01

Methanol is an important feedstock derived from natural gas and can be chemically converted into commodity and specialty chemicals at high pressure and temperature. Although biological conversion of methanol can proceed at ambient conditions, there is a dearth of engineered microorganisms that use methanol to produce metabolites. In nature, methanol dehydrogenase (Mdh), which converts methanol to formaldehyde, highly favors the reverse reaction. Thus, efficient coupling with the irreversible sequestration of formaldehyde by 3-hexulose-6-phosphate synthase (Hps) and 6-phospho-3-hexuloseisomerase (Phi) serves as the key driving force to pull the pathway equilibrium toward central metabolism. An emerging strategy to promote efficient substrate channeling is to spatially organize pathway enzymes in an engineered assembly to provide kinetic driving forces that promote carbon flux in a desirable direction. Here, we report a scaffoldless, self-assembly strategy to organize Mdh, Hps, and Phi into an engineered supramolecular enzyme complex using an SH3–ligand interaction pair, which enhances methanol conversion to fructose-6-phosphate (F6P). To increase methanol consumption, an “NADH Sink” was created using Escherichia coli lactate dehydrogenase as an NADH scavenger, thereby preventing reversible formaldehyde reduction. Combination of the two strategies improved in vitro F6P production by 97-fold compared with unassembled enzymes. The beneficial effect of supramolecular enzyme assembly was also realized in vivo as the engineered enzyme assembly improved whole-cell methanol consumption rate by ninefold. This approach will ultimately allow direct coupling of enhanced F6P synthesis with other metabolic engineering strategies for the production of many desired metabolites from methanol. PMID:27791059

Hydrogen-based power generation from bioethanol steam reforming

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

Tasnadi-Asztalos, Zs., E-mail: tazsolt@chem.ubbcluj.ro; Cormos, C. C., E-mail: cormos@chem.ubbcluj.ro; Agachi, P. S.

This paper is evaluating two power generation concepts based on hydrogen produced from bioethanol steam reforming at industrial scale without and with carbon capture. The power generation from bioethanol conversion is based on two important steps: hydrogen production from bioethanol catalytic steam reforming and electricity generation using a hydrogen-fuelled gas turbine. As carbon capture method to be assessed in hydrogen-based power generation from bioethanol steam reforming, the gas-liquid absorption using methyl-di-ethanol-amine (MDEA) was used. Bioethanol is a renewable energy carrier mainly produced from biomass fermentation. Steam reforming of bioethanol (SRE) provides a promising method for hydrogen and power production frommore » renewable resources. SRE is performed at high temperatures (e.g. 800-900°C) to reduce the reforming by-products (e.g. ethane, ethene). The power generation from hydrogen was done with M701G2 gas turbine (334 MW net power output). Hydrogen was obtained through catalytic steam reforming of bioethanol without and with carbon capture. For the evaluated plant concepts the following key performance indicators were assessed: fuel consumption, gross and net power outputs, net electrical efficiency, ancillary consumptions, carbon capture rate, specific CO{sub 2} emission etc. As the results show, the power generation based on bioethanol conversion has high energy efficiency and low carbon footprint.« less

On-line monitoring of methanol and methyl formate in the exhaust gas of an industrial formaldehyde production plant by a mid-IR gas sensor based on tunable Fabry-Pérot filter technology.

PubMed

Genner, Andreas; Gasser, Christoph; Moser, Harald; Ofner, Johannes; Schreiber, Josef; Lendl, Bernhard

2017-01-01

On-line monitoring of key chemicals in an industrial production plant ensures economic operation, guarantees the desired product quality, and provides additional in-depth information on the involved chemical processes. For that purpose, rapid, rugged, and flexible measurement systems at reasonable cost are required. Here, we present the application of a flexible mid-IR filtometer for industrial gas sensing. The developed prototype consists of a modulated thermal infrared source, a temperature-controlled gas cell for absorption measurement and an integrated device consisting of a Fabry-Pérot interferometer and a pyroelectric mid-IR detector. The prototype was calibrated in the research laboratory at TU Wien for measuring methanol and methyl formate in the concentration ranges from 660 to 4390 and 747 to 4610 ppmV. Subsequently, the prototype was transferred and installed at the project partner Metadynea Austria GmbH and linked to their Process Control System via a dedicated micro-controller and used for on-line monitoring of the process off-gas. Up to five process streams were sequentially monitored in a fully automated manner. The obtained readings for methanol and methyl formate concentrations provided useful information on the efficiency and correct functioning of the process plant. Of special interest for industry is the now added capability to monitor the start-up phase and process irregularities with high time resolution (5 s).

Bridging the Gap: From Model Surfaces to Nanoparticle Analogs for Selective Oxidation and Steam Reforming of Methanol and Selective Hydrogenation Catalysis

NASA Astrophysics Data System (ADS)

Boucher, Matthew B.

Most industrial catalysts are very complex, comprising of non-uniform materials with varying structures, impurities, and interaction between the active metal and supporting substrate. A large portion of the ongoing research in heterogeneous catalysis focuses on understanding structure-function relationships in catalytic materials. In parallel, there is a large area of surface science research focused on studying model catalytic systems for which structural parameters can be tuned and measured with high precision. It is commonly argued, however, that these systems are oversimplified, and that observations made in model systems do not translate to robust catalysts operating in practical environments; this discontinuity is often referred to as a "gap." The focus of this thesis is to explore the mutual benefits of surface science and catalysis, or "bridge the gap," by studying two catalytic systems in both ultra-high vacuum (UHV) and near ambient-environments. The first reaction is the catalytic steam reforming of methanol (SRM) to hydrogen and carbon dioxide. The SRM reaction is a promising route for on-demand hydrogen production. For this catalytic system, the central hypothesis in this thesis is that a balance between redox capability and weak binding of reaction intermediates is necessary for high SRM activity and selectivity to carbon dioxide. As such, a new catalyst for the SRM reaction is developed which incorporates very small amounts of gold (<1 atomic %) supported on zinc oxide nanoparticles with controlled crystal structures. The performance of these catalysts was studied in a fixed-bed micro-reactor system at ambient pressures, and their structure was characterized by high-resolution microscopic and spectroscopic techniques. Pre-existing oxygen defects in zinc oxide {0001} surfaces, and those created by a perturbation of the defect equilibrium by addition of gold, provide an anchoring site for highly dispersed gold species. By utilizing shape control of

Co-treatment of hydrogen sulfide and methanol in a single-stage biotrickling filter under acidic conditions.

PubMed

Jin, Yaomin; Veiga, María C; Kennes, Christian

2007-06-01

Biofiltration of waste gases is cost-effective and environment-friendly compared to the conventional techniques for treating large flow rates of gas streams with low concentrations of pollutants. Pulp and paper industry off-gases usually contain reduced sulfur compounds, such as hydrogen sulfide and a wide range of volatile organic compounds (VOCs), e.g., methanol. It is desirable to eliminate both of these groups of compounds. Since the co-treatment of inorganic sulfur compounds and VOCs in biotrickling filters is a relatively unexplored area, the simultaneous biotreatment of H2S and methanol as the model VOC was investigated. The results showed that, after adaptation, the elimination capacity of methanol could reach around 236 g m(-3) h(-1) with the simultaneous complete removal (100%) of 12 ppm H2S when the empty bed residence time is 24 s. The pH of the system was around 2. Methanol removal was hardly affected by the presence of hydrogen sulfide, despite the low pH. Conversely, the presence of the VOC in the waste gas reduced the efficiency of H2S biodegradation. The maximal methanol removal decreased somewhat when increasing the gas flow rate. This is the first report on the degradation of methanol at such low pH in a biotrickling filter and on the co-treatment of H2S and VOCs under such conditions.

Discovery of Methanol in a Planetary Birthplace

NASA Astrophysics Data System (ADS)

Kohler, Susanna

2016-05-01

Data from the Atacama Large Millimeter/submillimeter Array (ALMA) has recently revealed the first detection of gas-phase methanol, a derivative of methane, in a protoplanetary disk. This milestone discovery is an important step in understanding the conditions for planet formation that can lead to life-supporting planets like Earth.Planetary ChemistryOne major goal in the study of exoplanets is to find planets that orbit in their host stars habitable zones, a measure that determines whether the planet receives the right amount of sunlight to support liquid water. But theres another crucial element in the formation of a life-supporting planet: chemistry.To understand the chemistry of newly born planets, we need to study protoplanetary disks because its from these that young planets form. The elements and molecules contained in these dusty disks are what initially make up the atmospheres of planets forming within the disks.The Atacama Large Millimeter/submillimeter Array under the southern sky. [ESO/B. Tafreshi]The Hunt for ComplexityThe detection of complex molecules in protoplanetary disks is an important milestone, because complex molecules are necessary to build the correct chemistry to support life. Unfortunately, detecting these molecules is very difficult, requiring observations with both high spatial resolution and high sensitivity. Thus far, though weve observed elements and simple molecules in protoplanetary disks, detections of complex molecules have been elusive with only one success before now.Luckily, we now have an observatory up to the challenge! ALMAs unprecedented spatial resolution and sensitivity has recently allowed a team of scientists led by Catherine Walsh (Leiden University) to observe gas-phase methanol in a protoplanetary disk for the first time. This detection was made in the disk around the young star TW Hya, and it represents one of the largest molecules that has ever been observed in a disk to date.Locating IcesThe model (purple line

Recycling of carbon dioxide to methanol and derived products - closing the loop.

PubMed

Goeppert, Alain; Czaun, Miklos; Jones, John-Paul; Surya Prakash, G K; Olah, George A

2014-12-07

Starting with coal, followed by petroleum oil and natural gas, the utilization of fossil fuels has allowed the fast and unprecedented development of human society. However, the burning of these resources in ever increasing pace is accompanied by large amounts of anthropogenic CO2 emissions, which are outpacing the natural carbon cycle, causing adverse global environmental changes, the full extent of which is still unclear. Even through fossil fuels are still abundant, they are nevertheless limited and will, in time, be depleted. Chemical recycling of CO2 to renewable fuels and materials, primarily methanol, offers a powerful alternative to tackle both issues, that is, global climate change and fossil fuel depletion. The energy needed for the reduction of CO2 can come from any renewable energy source such as solar and wind. Methanol, the simplest C1 liquid product that can be easily obtained from any carbon source, including biomass and CO2, has been proposed as a key component of such an anthropogenic carbon cycle in the framework of a "Methanol Economy". Methanol itself is an excellent fuel for internal combustion engines, fuel cells, stoves, etc. It's dehydration product, dimethyl ether, is a diesel fuel and liquefied petroleum gas (LPG) substitute. Furthermore, methanol can be transformed to ethylene, propylene and most of the petrochemical products currently obtained from fossil fuels. The conversion of CO2 to methanol is discussed in detail in this review.

Environmental information volume: Liquid Phase Methanol (LPMEOH{trademark}) project

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

NONE

1996-05-01

The purpose of this project is to demonstrate the commercial viability of the Liquid Phase Methanol Process using coal-derived synthesis gas, a mixture of hydrogen and carbon monoxide. This report describes the proposed actions, alternative to the proposed action, the existing environment at the coal gasification plant at Kingsport, Tennessee, environmental impacts, regulatory requirements, offsite fuel testing, and DME addition to methanol production. Appendices include the air permit application, solid waste permits, water permit, existing air permits, agency correspondence, and Eastman and Air Products literature.

Production of methanol from heat-stressed pepper and corn leaf disks

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

Anderson, J.A.

Early Calwonder'' pepper (Capsicum annuum L.) and Jubilee'' corn (Zea mays L.) leaf disks exposed to high temperature stress produced ethylene, ethane, methanol, acetaldehyde, and ethanol based on comparison of retention times during gas chromatography to authentic standards. Methanol, ethanol, and acetaldehyde were also identified by mass spectroscopy. Corn leaf disks produced lower levels of ethylene, ethane, and methanol, but more acetaldehyde and ethanol than pepper. Production of ethane, a by-product of lipid peroxidation, coincided with an increase in electrolyte leakage (EL) in pepper but not in corn. Compared with controls, pepper leaf disks infiltrated with linolenic acid evolved significantlymore » greater amounts of ethane, acetaldehyde, and methanol and similar levels of ethanol. EL and volatile hydrocarbon production were not affected by fatty acid infiltration in corn. Infiltration of pepper leaves with buffers increasing in pH from 5.5 to 9.5 increased methanol production.« less

Soil moisture by extraction and gas chromatography

NASA Technical Reports Server (NTRS)

Merek, E. L.; Carle, G. C.

1973-01-01

To determine moisture content of soils rapidly and conveniently extract moisture with methanol and determine water content of methanol extract by gas chromatography. Moisture content of sample is calculated from weight of water and methanol in aliquot and weight of methanol added to sample.

Romania program targets methanol and Fischer-Tropsch research

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

Not Available

1987-03-01

Currently, the chemical organic industry, the petrochemical and engine fuels industry in Romania are entirely based on hydrocarbons from oil. To reduce the oil dependence of this sector and to ensure the stipulated growth rate of 8-9%, research and development programs have been set up with a view to the diversification of raw materials. In research on hydrocarbons from alcohol conversion, three process variants are known, i.e. olefins from methanol, gasolines from methanol and a combined gasolines and aromatic hydrocarbons from methanol. The Romanian process of methanol conversion to hydrocarbons is very flexible, with all the variants mentioned being carriedmore » out in the same plant by modifying the catalysts. In research on hydrocarbons from synthesis gas a modern process is being developed for gasification of brown coal in a fluidized bed, under pressure, in the presence of oxygen and water vapors. In the field of carbon oxide hydrogenation, studies have been carried out on selective Fischer-Tropsch processes in which the reaction products are high value hydrocarbon fractions.« less

Stress corrosion behavior of Ru-enhanced alpha-beta titanium alloys in methanol solutions

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

Schutz, R.W.; Horrigan, J.M.; Bednarowicz, T.A.

1998-12-31

Conservative, practical guidelines for the minimum water content required to prevent methanolic stress corrosion cracking (SCC) of Ti-6Al-4V-Ru and Ti-3Al-2.5V-Ru alloy tubulars have been developed from slow strain rate testing in plain and acidified NaCl-saturated methanol-water solutions at 25 C. A minimum methanol water content of 10 wt.% is proposed for Ti-6Al-4V-Ru, whereas 2-3 wt.% is sufficient for the lower strength Ti-3Al-2.5V-Ru alloy. Although HCl-acidification aggravated methanolic SCC, intermixing of methanol with crude oil or pure hydrocarbons, H{sub 2}S gas saturation, and/or increasing temperature diminished cracking susceptibility in these alloy tubulars.

Methanol Production by a Broad Phylogenetic Array of Marine Phytoplankton.

PubMed

Mincer, Tracy J; Aicher, Athena C

2016-01-01

Methanol is a major volatile organic compound on Earth and serves as an important carbon and energy substrate for abundant methylotrophic microbes. Previous geochemical surveys coupled with predictive models suggest that the marine contributions are exceedingly large, rivaling terrestrial sources. Although well studied in terrestrial ecosystems, methanol sources are poorly understood in the marine environment and warrant further investigation. To this end, we adapted a Purge and Trap Gas Chromatography/Mass Spectrometry (P&T-GC/MS) method which allowed reliable measurements of methanol in seawater and marine phytoplankton cultures with a method detection limit of 120 nanomolar. All phytoplankton tested (cyanobacteria: Synechococcus spp. 8102 and 8103, Trichodesmium erythraeum, and Prochlorococcus marinus), and Eukarya (heterokont diatom: Phaeodactylum tricornutum, coccolithophore: Emiliania huxleyi, cryptophyte: Rhodomonas salina, and non-diatom heterokont: Nannochloropsis oculata) produced methanol, ranging from 0.8-13.7 micromolar in culture and methanol per total cellular carbon were measured in the ranges of 0.09-0.3%. Phytoplankton culture time-course measurements displayed a punctuated production pattern with maxima near early stationary phase. Stabile isotope labeled bicarbonate incorporation experiments confirmed that methanol was produced from phytoplankton biomass. Overall, our findings suggest that phytoplankton are a major source of methanol in the upper water column of the world's oceans.

Methanol Production by a Broad Phylogenetic Array of Marine Phytoplankton

PubMed Central

Mincer, Tracy J.; Aicher, Athena C.

2016-01-01

Methanol is a major volatile organic compound on Earth and serves as an important carbon and energy substrate for abundant methylotrophic microbes. Previous geochemical surveys coupled with predictive models suggest that the marine contributions are exceedingly large, rivaling terrestrial sources. Although well studied in terrestrial ecosystems, methanol sources are poorly understood in the marine environment and warrant further investigation. To this end, we adapted a Purge and Trap Gas Chromatography/Mass Spectrometry (P&T-GC/MS) method which allowed reliable measurements of methanol in seawater and marine phytoplankton cultures with a method detection limit of 120 nanomolar. All phytoplankton tested (cyanobacteria: Synechococcus spp. 8102 and 8103, Trichodesmium erythraeum, and Prochlorococcus marinus), and Eukarya (heterokont diatom: Phaeodactylum tricornutum, coccolithophore: Emiliania huxleyi, cryptophyte: Rhodomonas salina, and non-diatom heterokont: Nannochloropsis oculata) produced methanol, ranging from 0.8–13.7 micromolar in culture and methanol per total cellular carbon were measured in the ranges of 0.09–0.3%. Phytoplankton culture time-course measurements displayed a punctuated production pattern with maxima near early stationary phase. Stabile isotope labeled bicarbonate incorporation experiments confirmed that methanol was produced from phytoplankton biomass. Overall, our findings suggest that phytoplankton are a major source of methanol in the upper water column of the world’s oceans. PMID:26963515

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.

Conceptual process design and economics for the production of high-octane gasoline blendstock via indirect liquefaction of biomass through methanol/dimethyl ether intermediates

DOE PAGES

Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit; ...

2015-10-28

This paper describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas via indirect gasification, gas clean-up via reforming of tars and other hydrocarbons, catalytic conversion of syngas to methanol, methanol dehydration to dimethyl ether (DME), and the homologation of DME over a zeolite catalyst to high-octane gasoline-range hydrocarbon products. The current process configuration has similarities to conventional methanol-to-gasoline (MTG) technologies, but there are key distinctions, specifically regarding the product slate, catalysts, and reactor conditions. A techno-economicmore » analysis is performed to investigate the production of high-octane gasoline blendstock. The design features a processing daily capacity of 2000 tonnes (2205 short tons) of dry biomass. The process yields 271 liters of liquid fuel per dry tonne of biomass (65 gal/dry ton), for an annual fuel production rate of 178 million liters (47 MM gal) at 90% on-stream time. The estimated total capital investment for an nth-plant is $438 million. The resulting minimum fuel selling price (MFSP) is $0.86 per liter or $3.25 per gallon in 2011 US dollars. A rigorous sensitivity analysis captures uncertainties in costs and plant performance. Sustainability metrics for the conversion process are quantified and assessed. The potential premium value of the high-octane gasoline blendstock is examined and found to be at least as competitive as fossil-derived blendstocks. A simple blending strategy is proposed to demonstrate the potential for blending the biomass-derived blendstock with petroleum-derived intermediates. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.« less

Infrared spectroscopy of the methanol cation and its methylene-oxonium isomer

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

Mosley, J. D.; Young, J. W.; Duncan, M. A., E-mail: mccoy@chemistry.ohio-state.edu, E-mail: maduncan@uga.edu

2015-03-21

The carbenium ion with nominal formula [C,H{sub 4},O]{sup +} is produced from methanol or ethylene glycol in a pulsed-discharge supersonic expansion source. The ion is mass selected, and its infrared spectrum is measured from 2000 to 4000 cm{sup −1} using laser photodissociation spectroscopy and the method of rare gas atom tagging. Computational chemistry predicts two isomers, the methanol and methylene-oxonium cations. Predicted vibrational spectra based on scaled harmonic and reduced dimensional treatments are compared to the experimental spectra. The methanol cation is the only isomer produced when methanol is used as a precursor. When ethylene glycol is used as themore » precursor, methylene-oxonium is produced in addition to the methanol cation. Theoretical results at the CCSD(T)/cc-pVTZ level show that methylene-oxonium is lower in energy than methanol cation by 6.4 kcal/mol, and is in fact the global minimum isomer on the [C,H{sub 4},O]{sup +} potential surface. Methanol cation is trapped behind an isomerization barrier in our source, providing a convenient method to produce and characterize this transient species. Analysis of the spectrum of the methanol cation provides evidence for strong CH stretch vibration/torsion coupling in this molecular ion.« less

Integrated hydrocarbon reforming system and controls

DOEpatents

Clawson, Lawrence G.; Dorson, Matthew H.; Mitchell, William L.; Nowicki, Brian J.; Thijssen, Johannes; Davis, Robert; Papile, Christopher; Rumsey, Jennifer W.; Longo, Nathan; Cross, III, James C.; Rizzo, Vincent; Kleeburg, Gunther; Rindone, Michael; Block, Stephen G.; Sun, Maria; Morriseau, Brian D.; Hagan, Mark R.; Bowers, Brian

2003-11-04

A hydrocarbon reformer system including a first reactor configured to generate hydrogen-rich reformate by carrying out at least one of a non-catalytic thermal partial oxidation, a catalytic partial oxidation, a steam reforming, and any combinations thereof, a second reactor in fluid communication with the first reactor to receive the hydrogen-rich reformate, and having a catalyst for promoting a water gas shift reaction in the hydrogen-rich reformate, and a heat exchanger having a first mass of two-phase water therein and configured to exchange heat between the two-phase water and the hydrogen-rich reformate in the second reactor, the heat exchanger being in fluid communication with the first reactor so as to supply steam to the first reactor as a reactant is disclosed. The disclosed reformer includes an auxiliary reactor configured to generate heated water/steam and being in fluid communication with the heat exchanger of the second reactor to supply the heated water/steam to the heat exchanger.

Performance of a biotrickling filter for the anaerobic utilization of gas-phase methanol coupled to thiosulphate reduction and resource recovery through volatile fatty acids production.

PubMed

Eregowda, Tejaswini; Matanhike, Luck; Rene, Eldon R; Lens, Piet N L

2018-04-25

The anaerobic removal of continuously fed gas-phase methanol (2.5-30 g/m 3 .h) and the reduction of step-fed thiosulphate (1000 mg/L) was investigated in a biotrickling filter (BTF) operated for 123 d at an empty bed residence time (EBRT) of 4.6 and 2.3 min. The BTF performance during steady step-feed and special operational phases like intermittent liquid trickling in 6 and 24 h cycles and operation without pH regulation were evaluated. Performance of the BTF was not affected and nearly 100% removal of gas-phase methanol was achieved with an EC max of 21 g/m 3 .h. Besides, >99% thiosulphate reduction was achieved, in all the phases of operation. The production of sulphate, H 2 S and volatile fatty acids (VFA) was monitored and a maximum of 2500 mg/L of acetate, 200 mg/L of propionate, 150 mg/L of isovalerate and 100 mg/L isobutyrate was produced. Copyright © 2018 Elsevier Ltd. All rights reserved.

METHANOL PRODUCTION FROM BIOMASS AND NATURAL GAS AS TRANSPORTATION FUEL

EPA Science Inventory

Two processes are examined for production of methanol. They are assessed against the essential requirements of a future alternative fuel for road transport: that it (i) is producible in amounts comparable to the 19 EJ of motor fuel annually consumed in the U.S., (ii) minimizes em...

Fuel processing requirements and techniques for fuel cell propulsion power

NASA Astrophysics Data System (ADS)

Kumar, R.; Ahmed, S.; Yu, M.

Fuels for fuel cells in transportation systems are likely to be methanol, natural gas, hydrogen, propane, or ethanol. Fuels other than hydrogen will need to be reformed to hydrogen on-board the vehicle. The fuel reformer must meet stringent requirements for weight and volume, product quality, and transient operation. It must be compact and lightweight, must produce low levels of CO and other byproducts, and must have rapid start-up and good dynamic response. Catalytic steam reforming, catalytic or noncatalytic partial oxidation reforming, or some combination of these processes may be used. This paper discusses salient features of the different kinds of reformers and describes the catalysts and processes being examined for the oxidation reforming of methanol and the steam reforming of ethanol. Effective catalysts and reaction conditions for the former have been identified; promising catalysts and reaction conditions for the latter are being investigated.

Pyrochlore catalysts for hydrocarbon fuel reforming

DOEpatents

Berry, David A.; Shekhawat, Dushyant; Haynes, Daniel; Smith, Mark; Spivey, James J.

2012-08-14

A method of catalytically reforming a reactant gas mixture using a pyrochlore catalyst material comprised of one or more pyrochlores having the composition A₂B_2-y-zB'_yB"_zO_7-.DELTA., where y>0 and z.gtoreq.0. Distribution of catalytically active metals throughout the structure at the B site creates an active and well dispersed metal locked into place in the crystal structure. This greatly reduces the metal sintering that typically occurs on supported catalysts used in reforming reactions, and reduces deactivation by sulfur and carbon. Further, oxygen mobility may also be enhanced by elemental exchange of promoters at sites in the pyrochlore. The pyrochlore catalyst material may be utilized in catalytic reforming reactions for the conversion of hydrocarbon fuels into synthesis gas (H₂+CO) for fuel cells, among other uses.

Methanol Oxidation on Pt3Sn(111) for Direct Methanol Fuel Cells: Methanol Decomposition.

PubMed

Lu, Xiaoqing; Deng, Zhigang; Guo, Chen; Wang, Weili; Wei, Shuxian; Ng, Siu-Pang; Chen, Xiangfeng; Ding, Ning; Guo, Wenyue; Wu, Chi-Man Lawrence

2016-05-18

PtSn alloy, which is a potential material for use in direct methanol fuel cells, can efficiently promote methanol oxidation and alleviate the CO poisoning problem. Herein, methanol decomposition on Pt3Sn(111) was systematically investigated using periodic density functional theory and microkinetic modeling. The geometries and energies of all of the involved species were analyzed, and the decomposition network was mapped out to elaborate the reaction mechanisms. Our results indicated that methanol and formaldehyde were weakly adsorbed, and the other derivatives (CHxOHy, x = 1-3, y = 0-1) were strongly adsorbed and preferred decomposition rather than desorption on Pt3Sn(111). The competitive methanol decomposition started with the initial O-H bond scission followed by successive C-H bond scissions, (i.e., CH3OH → CH3O → CH2O → CHO → CO). The Brønsted-Evans-Polanyi relations and energy barrier decomposition analyses identified the C-H and O-H bond scissions as being more competitive than the C-O bond scission. Microkinetic modeling confirmed that the vast majority of the intermediates and products from methanol decomposition would escape from the Pt3Sn(111) surface at a relatively low temperature, and the coverage of the CO residue decreased with an increase in the temperature and decrease in partial methanol pressure.

Three-dimensional graphene as gas diffusion layer for micro direct methanol fuel cell

NASA Astrophysics Data System (ADS)

Zhu, Yingli; Zhang, Xiaojian; Li, Jianyu; Qi, Gary

2018-05-01

The gas diffusion layer (GDL), as an important structure of the membrane electrode assembly (MEA) of the direct methanol fuel cell (DMFC), provides a support layer for the catalyst and the fuel and the product channel. Traditionally, the material of GDL is generally carbon paper (CP). In this paper, a new material, namely three-dimensional graphene (3DG) is used as GDL for micro DMFC. The experimental results reveal that the performance of the DMFC has been improved significantly by application of 3DG. The peak powers increase from 25 mW to 31.2 mW and 32 mW by using 3DG as the anode and cathode GDL instead of CP, respectively. The reason may be the decrease of charge and mass transfer resistance of the cell. This means that the unique 3D porous architecture of the 3DG can provide lower contact resistance and sufficient fuel diffusion paths. The output performance of the cell will be further improved when porous metal current collectors is used.

Approach to the Treatment of Methanol Intoxication.

PubMed

Kraut, Jeffrey A

2016-07-01

Methanol intoxication is an uncommon but serious poisoning. Its adverse effects are due primarily to the impact of its major metabolite formic acid and lactic acid resulting from cellular hypoxia. Symptoms including abdominal pain and loss of vision can appear a few hours to a few days after exposure, reflecting the time necessary for accumulation of the toxic byproducts. In addition to a history of exposure, increases in serum osmolal and anion gaps can be clues to its presence. However, increments in both parameters can be absent depending on the nature of the toxic alcohol, time of exposure, and coingestion of ethanol. Definitive diagnosis requires measurement with gas or liquid chromatography, which are laborious and expensive procedures. Tests under study to detect methanol or its metabolite formate might facilitate the diagnosis of this poisoning. Treatment can include administration of ethanol or fomepizole, both inhibitors of the enzyme alcohol dehydrogenase to prevent formation of its metabolites, and hemodialysis to remove methanol and formate. In this Acid-Base and Electrolyte Teaching Case, a patient with methanol intoxication due to ingestion of model airplane fuel is described, and the value and limitations of current and new diagnostic and treatment measures are discussed. Published by Elsevier Inc.

Breath alcohol analyzer mistakes methanol poisoning for alcohol intoxication.

PubMed

Caravati, E Martin; Anderson, Kathleen T

2010-02-01

Breath alcohol analyzers are used to detect ethanol in motorists and others suspected of public intoxication. One concern is their ability to detect interfering substances that may falsely increase the ethanol reading. A 47-year-old-man was found in a public park, acting intoxicated. A breath analyzer test (Intoxilyzer 5000EN) measured 0.288 g/210 L breath ethanol, without an interferent noted. In the emergency department, the patient admitted to drinking HEET Gas-Line antifreeze, which contains 99% methanol. Two to three hours after ingestion, serum and urine toxicology screen results were negative for ethanol and multiple other substances. His serum methanol concentration was 589 mg/dL, serum osmolality 503 mOsm/kg, osmolar gap 193 mOsm/kg, and anion gap 17 mmol/L. The patient was treated with intravenous ethanol, fomepizole, and hemodialysis without complication. This is a unique clinical case of a breath alcohol analyzer reporting methanol as ethanol. Intoxilyzer devices have been shown to indicate some substances (acetone) as interferents in humans but not methanol. Increased serum concentrations of methanol can be reported as ethanol by a commonly used breath alcohol analyzer, which can result in a delayed diagnosis or misdiagnosis and subsequent methanol toxicity if antidotal treatment is not administered in a timely manner. Copyright (c) 2009 American College of Emergency Physicians. Published by Mosby, Inc. All rights reserved.

Chemical recycling of carbon dioxide to methanol and dimethyl ether: from greenhouse gas to renewable, environmentally carbon neutral fuels and synthetic hydrocarbons.

PubMed

Olah, George A; Goeppert, Alain; Prakash, G K Surya

2009-01-16

Nature's photosynthesis uses the sun's energy with chlorophyll in plants as a catalyst to recycle carbon dioxide and water into new plant life. Only given sufficient geological time can new fossil fuels be formed naturally. In contrast, chemical recycling of carbon dioxide from natural and industrial sources as well as varied human activities or even from the air itself to methanol or dimethyl ether (DME) and their varied products can be achieved via its capture and subsequent reductive hydrogenative conversion. The present Perspective reviews this new approach and our research in the field over the last 15 years. Carbon recycling represents a significant aspect of our proposed Methanol Economy. Any available energy source (alternative energies such as solar, wind, geothermal, and atomic energy) can be used for the production of needed hydrogen and chemical conversion of CO(2). Improved new methods for the efficient reductive conversion of CO(2) to methanol and/or DME that we have developed include bireforming with methane and ways of catalytic or electrochemical conversions. Liquid methanol is preferable to highly volatile and potentially explosive hydrogen for energy storage and transportation. Together with the derived DME, they are excellent transportation fuels for internal combustion engines (ICE) and fuel cells as well as convenient starting materials for synthetic hydrocarbons and their varied products. Carbon dioxide thus can be chemically transformed from a detrimental greenhouse gas causing global warming into a valuable, renewable and inexhaustible carbon source of the future allowing environmentally neutral use of carbon fuels and derived hydrocarbon products.

Surface-Bound Intermediates in Low-Temperature Methanol Synthesis on Copper. Participants and Spectators

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

Yang, Yong; Mei, Donghai; Peden, Charles H.F.

The reactivity of surface adsorbed species present on copper catalysts during methanol synthesis at low temperatures was studied by simultaneous infrared spectroscopy (IR) and mass spectroscopy (MS) measurements during “titration” (transient surface reaction) experiments with isotopic tracing. The results show that adsorbed formate is a major bystander species present on the surface under steady-state methanol synthesis reaction conditions, but it cannot be converted to methanol by reaction with pure H 2, nor with H 2 plus added water. Formate-containing surface adlayers for these experiments were produced during steady state catalysis in (a) H 2:CO 2 (with substantial formate coverage) andmore » (b) moist H 2:CO (with no IR visible formate species). Both these reaction conditions produce methanol at steady state with relatively high rates. Adlayers containing formate were also produced by (c) formic acid adsorption. Various "titration" gases were used to probe these adlayers at modest temperatures (T = 410-450K) and 6 bar total pressure. Methanol gas (up to ~1% monolayer equivalent) was produced in "titration" from the H 2:CO 2 catalytic adlayers by H 2 plus water, but not by dry hydrogen. The decay in the formate IR features accelerated in the presence of added water vapor. The H 2:CO:H 2O catalytic adlayer produced similar methanol titration yields in H 2 plus water but showed no surface formate features in IR (less than 0.2% monolayer coverage). Finally, formate from formic acid chemisorption produced no methanol under any titration conditions. Even under (H 2:CO 2) catalytic reaction conditions, isotope tracing showed that pre-adsorbed formate from formic acid did not contribute to the methanol produced. Although non-formate intermediates exist during low temperature methanol synthesis on copper which can be converted to methanol gas by titration with pure H 2 plus water in sufficient quantities for that intermediate to be observable by IR, formate

UV Photodesorption of Methanol in Pure and CO-rich Ices: Desorption Rates of the Intact Molecule and of the Photofragments

NASA Astrophysics Data System (ADS)

Bertin, Mathieu; Romanzin, Claire; Doronin, Mikhail; Philippe, Laurent; Jeseck, Pascal; Ligterink, Niels; Linnartz, Harold; Michaut, Xavier; Fillion, Jean-Hugues

2016-02-01

Wavelength-dependent photodesorption rates have been determined using synchrotron radiation for condensed pure and mixed methanol ice in the 7-14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10-5 molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower (<10-6 molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH3OH ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH3, OH, H2CO, and CH3O/CH2OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH3O, therefore, opening new gas phase chemical routes for the formation of complex molecules.

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

A validated near-infrared spectroscopic method for methanol detection in biodiesel

NASA Astrophysics Data System (ADS)

Paul, Andrea; Bräuer, Bastian; Nieuwenkamp, Gerard; Ent, Hugo; Bremser, Wolfram

2016-06-01

Biodiesel quality control is a relevant issue as biodiesel properties influence diesel engine performance and integrity. Within the European metrology research program (EMRP) ENG09 project ‘Metrology for Biofuels’, an on-line/at-site suitable near-infrared spectroscopy (NIRS) method has been developed in parallel with an improved EN14110 headspace gas chromatography (GC) analysis method for methanol in biodiesel. Both methods have been optimized for a methanol content of 0.2 mass% as this represents the maximum limit of methanol content in FAME according to EN 14214:2009. The NIRS method is based on a mobile NIR spectrometer equipped with a fiber-optic coupled probe. Due to the high volatility of methanol, a tailored air-tight adaptor was constructed to prevent methanol evaporation during measurement. The methanol content of biodiesel was determined from evaluation of NIRS spectra by partial least squares regression (PLS). Both GC analysis and NIRS exhibited a significant dependence on biodiesel feedstock. The NIRS method is applicable to a content range of 0.1% (m/m) to 0.4% (m/m) of methanol with uncertainties at around 6% relative for the different feedstocks. A direct comparison of headspace GC and NIRS for samples of FAMEs yielded that the results of both methods are fully compatible within their stated uncertainties.

ATOM-ECONOMICAL PATHWAYS TO METHANOL FUEL CELL FROM BIOMASS

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

MAHAJAN,D.; WEGRZYN,J.E.

1999-03-01

An economical production of alcohol fuels from biomass, a feedstock low in carbon and high in water content, is of interest. At Brookhaven National Laboratory (BNL), a Liquid Phase Low Temperature (LPLT) concept is under development to improve the economics by maximizing the conversion of energy carrier atoms (C,H) into energy liquids (fuel). So far, the LPLT concept has been successfully applied to obtain highly efficient methanol synthesis. This synthesis was achieved with specifically designed soluble catalysts, at temperatures < 150 C. A subsequent study at BNL yielded a water-gas-shift (WGS) catalyst for the production of hydrogen from a feedstockmore » of carbon monoxide and H{sub 2}O at temperatures < 120 C. With these LPLT technologies as a background, this paper extends the discussion of the LPLT concept to include methanol decomposition into 3 moles of H{sub 2} per mole of methanol. The implication of these technologies for the atom-economical pathways to methanol fuel cell from biomass is discussed.« less

Torsion-rotation intensities in methanol

NASA Astrophysics Data System (ADS)

Pearson, John

Methanol exists in numerous kinds of astronomical objects featuring a wide range of local conditions. The light nature of the molecule coupled with the internal rotation of the methyl group with respect to the hydroxyl group results in a rich, strong spectrum that spans the entire far-infrared region. As a result, any modest size observational window will have a number of strong methanol transitions. This has made it the gas of choice for testing THz receivers and to extract the local physical conditions from observations covering small frequency windows. The latter has caused methanol to be dubbed the Swiss army knife of astrophysics. Methanol has been increasingly used in this capacity and will be used even more for subsequent investigations into the Herschel archive, and with SOFIA and ALMA. Interpreting physical conditions on the basis of a few methanol lines requires that the molecular data, line positions, intensities, and collision rates, be complete, consistent and accurate to a much higher level than previously required for astrophysics. The need for highly reliable data is even more critical for modeling the two classes of widespread maser action and many examples of optical pumping through the torsional bands. Observation of the torsional bands in the infrared will be a unique opportunity to directly connect JWST observations with those of Herschel, SOFIA, and ALMA. The theory for the intensities of torsion-rotation transitions in a molecule featuring a single internally rotating methyl group is well developed after 70 years of research. However, other than a recent very preliminary and not completely satisfactory investigation of a few CH3OH torsional bands, this theory has never been experimentally tested for any C3V internal rotor. More alarming is a set of recent intensity calibrated microwave measurements that showed deviations relative to calculations of up to 50% in some ground state rotational transitions commonly used by astronomers to extract

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.

Liquid-Phase Electrical Discharges: Fundamental Mechanisms and Applications

NASA Astrophysics Data System (ADS)

Franclemont, Joshua

The increased demand in alternative energy in recent decades has generated significant interest in cleaner fuel sources including hydrogen and syngas (hydrogen and carbon monoxide). Hydrogen and syngas are both primarily produced through the steam reforming of hydrocarbons, specifically natural gas. Although other processes are known, the cheapest source of these fuels is currently through the heating of natural gas in the presence of steam and a catalyst. However, due to the emissions associated with the steam reforming of natural gas and the lack of low cost, efficient, and reliable onboard hydrogen storage technologies for fuel cell powered vehicles, attention has been focused on plasma-assisted reforming of hydrocarbons. Plasma processes can be implemented onboard and are able to directly reform liquid hydrocarbons and alcohols without external heating or catalysts. In addition to hydrogen and syngas, the plasma-assisted reforming of hydrocarbons and alcohols offers other desirable products such as C2 gases (ethane, ethylene, and acetylene), methanol and ethanol. The primary goal of this study is to investigate the fundamental chemical reactions occurring during plasma-assisted reforming of liquid hydrocarbons and alcohols using streamer-like pulsed electrical discharges. Due to the relatively unexplored field of chemical reactions in liquid plasmas, the focus of this study is on elucidating chemical pathways responsible for the formation of hydrogen, syngas, and other products during the direct reforming of liquid methanol, glycerol, and pentane as model species.

Heat exchanger for fuel cell power plant reformer

DOEpatents

Misage, Robert; Scheffler, Glenn W.; Setzer, Herbert J.; Margiott, Paul R.; Parenti, Jr., Edmund K.

1988-01-01

A heat exchanger uses the heat from processed fuel gas from a reformer for a fuel cell to superheat steam, to preheat raw fuel prior to entering the reformer and to heat a water-steam coolant mixture from the fuel cells. The processed fuel gas temperature is thus lowered to a level useful in the fuel cell reaction. The four temperature adjustments are accomplished in a single heat exchanger with only three heat transfer cores. The heat exchanger is preheated by circulating coolant and purge steam from the power section during startup of the latter.

Hydrogen generation utilizing integrated CO2 removal with steam reforming

DOEpatents

Duraiswamy, Kandaswamy; Chellappa, Anand S

2013-07-23

A steam reformer may comprise fluid inlet and outlet connections and have a substantially cylindrical geometry divided into reforming segments and reforming compartments extending longitudinally within the reformer, each being in fluid communication. With the fluid inlets and outlets. Further, methods for generating hydrogen may comprise steam reformation and material adsorption in one operation followed by regeneration of adsorbers in another operation. Cathode off-gas from a fuel cell may be used to regenerate and sweep the adsorbers, and the operations may cycle among a plurality of adsorption enhanced reformers to provide a continuous flow of hydrogen.

Solubility of methanol in low-temperature aqueous sulfuric acid and implications for atmospheric particle composition

NASA Technical Reports Server (NTRS)

Iraci, Laura T.; Essin, Andrew M.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

2001-01-01

Using traditional Knudsen cell techniques, we find well-behaved Henry's law uptake of methanol in aqueous 45 - 70 wt% H2SO4 solutions at temperatures between 197 and 231 K. Solubility of methanol increases with decreasing temperature and increasing acidity, with an effective Henry's law coefficient ranging from 10(exp 5) - 10(exp 8) M/atm. Equilibrium uptake of methanol into sulfuric acid aerosol particles in the upper troposphere and lower stratosphere will not appreciably alter gas-phase concentrations of methanol. The observed room temperature reaction between methanol and sulfuric acid is too slow to provide a sink for gaseous methanol at the temperatures of the upper troposphere and lower stratosphere. It is also too slow to produce sufficient quantities of soluble reaction products to explain the large amount of unidentified organic material seen in particles of the upper troposphere.

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

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

Ethanol internal steam reforming in intermediate temperature solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Diethelm, Stefan; Van herle, Jan

This study investigates the performance of a standard Ni-YSZ anode supported cell under ethanol steam reforming operating conditions. Therefore, the fuel cell was directly operated with a steam/ethanol mixture (3 to 1 molar). Other gas mixtures were also used for comparison to check the conversion of ethanol and of reformate gases (H 2, CO) in the fuel cell. The electrochemical properties of the fuel cell fed with four different fuel compositions were characterized between 710 and 860 °C by I- V and EIS measurements at OCV and under polarization. In order to elucidate the limiting processes, impedance spectra obtained with different gas compositions were compared using the derivative of the real part of the impedance with respect of the natural logarithm of the frequency. Results show that internal steam reforming of ethanol takes place significantly on Ni-YSZ anode only above 760 °C. Comparisons of results obtained with reformate gas showed that the electrochemical cell performance is dominated by the conversion of hydrogen. The conversion of CO also occurs either directly or indirectly through the water-gas shift reaction but has a significant impact on the electrochemical performance only above 760 °C.

UV PHOTODESORPTION OF METHANOL IN PURE AND CO-RICH ICES: DESORPTION RATES OF THE INTACT MOLECULE AND OF THE PHOTOFRAGMENTS

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

Bertin, Mathieu; Doronin, Mikhail; Philippe, Laurent

2016-02-01

Wavelength-dependent photodesorption rates have been determined using synchrotron radiation for condensed pure and mixed methanol ice in the 7–14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10{sup −5} molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower (<10{sup −6} molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH{sub 3}OHmore » ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH{sub 3}, OH, H{sub 2}CO, and CH{sub 3}O/CH{sub 2}OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH{sub 3}O, therefore, opening new gas phase chemical routes for the formation of complex molecules.« less

Syngas Production from CO2 Reforming and CO2-steam Reforming of Methane over Ni/Ce-SBA-15 Catalyst

NASA Astrophysics Data System (ADS)

Tan, J. S.; Danh, H. T.; Singh, S.; Truong, Q. D.; Setiabudi, H. D.; Vo, D.-V. N.

2017-06-01

This study compares the catalytic performance of mesoporous 10 Ni/Ce-SBA-15 catalyst for CO2 reforming and CO2-steam reforming of methane reactions in syngas production. The catalytic performance of 10 Ni/Ce-SBA-15 catalyst for CO2 reforming and CO2-steam reforming of methane was evaluated in a temperature-controlled tubular fixed-bed reactor at stoichiometric feed composition, 1023 K and atmospheric pressure for 12 h on-stream with gas hourly space velocity (GHSV) of 36 L gcat -1 h-1. The 10 Ni/Ce-SBA-15 catalyst possessed a high specific BET surface area and average pore volume of 595.04 m2 g-1. The XRD measurement revealed the presence of NiO phase with crystallite dimension of about 13.60 nm whilst H2-TPR result indicates that NiO phase was completely reduced to metallic Ni0 phase at temperature beyond 800 K and the reduction temperature relied on different degrees of metal-support interaction associated with the location and size of NiO particles. The catalytic reactivity was significantly enhanced with increasing H2O/CO2 feed ratio. Interestingly, the H2/CO ratio for CO2-steam reforming of methane varied between 1 and 3 indicated the occurrence of parallel reactions, i.e., CH4 steam reforming giving a H2/CO of 3 whilst reverse water-gas shift (RWGS) reaction consuming H2 to produce CO gaseous product.

The shock sensitivity of nitromethane/methanol mixtures

NASA Astrophysics Data System (ADS)

Bartram, Brian; Dattelbaum, Dana; Sheffield, Steve; Gibson, Lee

2013-06-01

The dilution of liquid explosives has multiple effects on detonation properties including an increase in critical diameter, spatiotemporal lengthening of the chemical reaction zone, and the development of propagating wave instabilities. Earlier detonation studies of NM/methanol mixtures have shown several effects of increasing dilution, including: 1) a continual increase in the critical diameter, 2) lowering of the Chapman-Jouguet detonation pressure, and 3) slowing of the steady detonation velocity (Koldunov et al., Comb. Expl. Shock Waves). Here, we present the results of a series of gas gun-driven plate-impact experiments to study the shock-to-detonation transition in NM/methanol mixtures. Embedded electromagnetic gauges were used to obtain in situ particle velocity wave profiles at multiple Lagrangian positions in the initiating explosive mixture. From the wave profiles obtained in each experiment, an unreacted Hugoniot locus, the initiation mechanism, and the overtake-time-to-detonation were obtained as a function of shock input condition for mixture concentrations from 100% NM to 50 wt%/50 wt% NM/methanol. Desensitization with dilution is less than expected. For example, little change in overtake time occurs in 80 wt%/20 wt% NM/methanol when compared with neat NM. Furthermore, the shock wave profiles from the gauges indicate that wave instabilities grow in as the overdriven detonation wave settles down following the shock-to-detonation transition.

Alternative technologies to steam-methane reforming

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

Tindall, B.M.; Crews, M.A.

1995-11-01

Steam-methane reforming (SMR) has been the conventional route for hydrogen and carbon monoxide production from natural gas feedstocks. However, several alternative technologies are currently finding favor for an increasing number of applications. The competing technologies include: steam-methane reforming combined with oxygen secondary reforming (SMR/O2R); autothermal reforming (ATR); thermal partial oxidation (POX). Each of these alternative technologies uses oxygen as a feedstock. Accordingly, if low-cost oxygen is available, they can be an attractive alternate to SMR with natural gas feedstocks. These technologies are composed technically and economically. The following conclusions can be drawn: (1) the SMR/O2R, ATR and POX technologies canmore » be attractive if low-cost oxygen is available; (2) for competing technologies, the H{sub 2}/CO product ratio is typically the most important process parameter; (3) for low methane slip, the SMR/O2R, ATR and POX technologies are favored; (4) for full CO{sub 2} recycle, POX is usually better than ATR; (5) relative to POX, the ATR is a nonlicensed technology that avoids third-party involvement; (6) economics of each technology are dependent on the conditions and requirements for each project and must be evaluated on a case-by-case basis.« less

Infrared Spectrum of Methanol: A First-Year Student Experiment.

ERIC Educational Resources Information Center

Boehm, Garth; Dwyer, Mark

1981-01-01

Describes an experiment providing an experimental introduction to vibrational spectroscopy and experience in using an elementary vacuum line. The experiment, using a gas cell charged with methanol, is completed in a three-hour laboratory period and is directed toward understanding vibrational spectroscopy rather than the diagnostic value of the…

Catalytic Exhaust Gas Recirculation-Loop Reforming for High Efficiency in a Stoichiometric Spark-Ignited Engine through Thermochemical Recuperation and Dilution Limit Extension, Part 2: Engine Performance

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

Chang, Yan; Szybist, James P.; Pihl, Josh A.

This is the second part of a two-part investigation of on-board catalytic fuel reforming to increase the brake efficiency of a multicylinder, stoichiometric spark-ignited (SI) engine. In Part 1 of the investigation, we analytically and experimentally characterized the energetics and kinetics of a candidate reforming catalyst over a range of reforming equivalence ratios and oxygen concentration conditions to identify the best conditions for efficient reforming. In the present part of our investigation, we studied an engine strategy that combined exhaust gas recirculation (EGR)–loop reforming with dilution limit extension of the combustion. In our experiments, we found that, under an enginemore » operating condition of 2000 rpm and brake mean effective pressure (4 bar), catalytic EGR reforming made it possible to sustain stable combustion with a volumetric equivalent of 45%–55% EGR. Under this same operating condition with stoichiometric engine exhaust (and no reforming), we were only able to sustain stable combustion with EGR under 25%. In conclusion, these results indicate that multicylinder gasoline engine efficiency can be increased substantially with catalytic reforming combined with and higher EGR operation, resulting in a decrease of more than 8% in fuel consumption, compared to baseline operation.« less

Catalytic Exhaust Gas Recirculation-Loop Reforming for High Efficiency in a Stoichiometric Spark-Ignited Engine through Thermochemical Recuperation and Dilution Limit Extension, Part 2: Engine Performance

DOE PAGES

Chang, Yan; Szybist, James P.; Pihl, Josh A.; ...

2018-01-17

This is the second part of a two-part investigation of on-board catalytic fuel reforming to increase the brake efficiency of a multicylinder, stoichiometric spark-ignited (SI) engine. In Part 1 of the investigation, we analytically and experimentally characterized the energetics and kinetics of a candidate reforming catalyst over a range of reforming equivalence ratios and oxygen concentration conditions to identify the best conditions for efficient reforming. In the present part of our investigation, we studied an engine strategy that combined exhaust gas recirculation (EGR)–loop reforming with dilution limit extension of the combustion. In our experiments, we found that, under an enginemore » operating condition of 2000 rpm and brake mean effective pressure (4 bar), catalytic EGR reforming made it possible to sustain stable combustion with a volumetric equivalent of 45%–55% EGR. Under this same operating condition with stoichiometric engine exhaust (and no reforming), we were only able to sustain stable combustion with EGR under 25%. In conclusion, these results indicate that multicylinder gasoline engine efficiency can be increased substantially with catalytic reforming combined with and higher EGR operation, resulting in a decrease of more than 8% in fuel consumption, compared to baseline operation.« less

Recent Studies on Methanol Crossover in Liquid-Feed Direct Methanol Fuel Cells

NASA Technical Reports Server (NTRS)

Valdez, T. I.; Narayanan, S. R.

2000-01-01

In this work, the effects of methanol crossover and airflow rates on the cathode potential of an operating direct methanol fuel cell are explored. Techniques for quantifying methanol crossover in a fuel cell and for separating the electrical performance of each electrode in a fuel cell are discussed. The effect of methanol concentration on cathode potential has been determined to be significant. The cathode is found to be mass transfer limited when operating on low flow rate air and high concentrations of methanol. Improvements in cathode structure and operation at low methanol concentration have been shown to result in improved cell performance.

Experimental and Numerical Observations of Hydrate Reformation during Depressurization in a Core-Scale Reactor

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

Seol, Yongkoo; Myshakin, Evgeniy

2011-01-01

Gas hydrate has been predicted to reform around a wellbore during depressurization-based gas production from gas hydrate-bearing reservoirs. This process has an adverse effect on gas production rates and it requires time and sometimes special measures to resume gas flow to producing wells. Due to lack of applicable field data, laboratory scale experiments remain a valuable source of information to study hydrate reformation. In this work, we report laboratory experiments and complementary numerical simulations executed to investigate the hydrate reformation phenomenon. Gas production from a pressure vessel filled with hydrate-bearing sand was induced by depressurization with and without heat fluxmore » through the boundaries. Hydrate decomposition was monitored with a medical X-ray CT scanner and pressure and temperature measurements. CT images of the hydrate-bearing sample were processed to provide 3-dimensional data of heterogeneous porosity and phase saturations suitable for numerical simulations. In the experiments, gas hydrate reformation was observed only in the case of no-heat supply from surroundings, a finding consistent with numerical simulation. By allowing gas production on either side of the core, numerical simulations showed that initial hydrate distribution patterns affect gas distribution and flow inside the sample. This is a direct consequence of the heterogeneous pore network resulting in varying hydraulic properties of the hydrate-bearing sediment.« less

Effect of methanol on the liquefaction reaction of biomass in hot compressed water under microwave energy

Treesearch

Junming Xu; Jianchun Jiang; Chun-Yun Hse; Todd F. Shupe

2013-01-01

Liquefaction of sawdust was studied in methanol-water solutions using an acid catalyst under microwave energy. The effect of the methanol concentration on the changes of components in the liquefied products was analyzed by gas chromatography−mass spectrometry (GC−MS). It was found that 5-hydroxymethylfurfural (HMF) and levulinic acid are the...

Reforming of natural gas—hydrogen generation for small scale stationary fuel cell systems

NASA Astrophysics Data System (ADS)

Heinzel, A.; Vogel, B.; Hübner, P.

The reforming of natural gas to produce hydrogen for fuel cells is described, including the basic concepts (steam reforming or autothermal reforming) and the mechanisms of the chemical reactions. Experimental work has been done with a compact steam reformer, and a prototype of an experimental reactor for autothermal reforming was tested, both containing a Pt-catalyst on metallic substrate. Experimental results on the steam reforming system and a comparison of the steam reforming process with the autothermal process are given.

Synthesis gas and olefins from the catalytic autothermal reforming of volatile and non-volatile liquids

NASA Astrophysics Data System (ADS)

Dreyer, Bradon Justin

2007-12-01

The research presented in this thesis develops an understanding of a clean energy process technology, catalytic partial oxidation (CPO). CPO is a process in which a carbon containing fuel, such as a hydrocarbon, is passed over a noble metal catalyst (e.g. rhodium and platinum) to efficiently generate synthesis gas (H2 and CO) and olefins (e.g. ethylene and propylene) in millisecond contact times. Chapter 1 introduces CPO and compares this technology with conventional methods for synthesis gas and olefin production. CPO has several advantages over the traditional synthesis gas and olefin production methods. One advantage includes autothermal operation, requiring no external heat input from furnaces or heat exchangers. Autothermal operation allows these reactors to be built compactly. The short contact-times associated with CPO further enable for high throughput in relatively small reactor systems, and more compact reactors typically translate to faster response times if transient operation is required. Nobel metal based CPO catalysts are also resistant to deactivation, resulting in less catalyst replacement, regeneration, and maintenance, and an increase in operating efficiency. An overview of the many applications of the chemicals produced from CPO is also presented in Chapter 1. The chemicals produced are crucial in generating valuable chemical intermediates that are eventually incorporated in consumer products, medical devices, building structures, and fertilizers. Additionally, H2 can be used as a source of energy in mobile fuel applications. Fuel cells convert H2 and O2 into electricity and water at higher efficiencies than thermal engine generators. Due to the difficulties in H2 storage, these more efficient energy generators are dependent on hydrogen obtained from synthesis gas production in compact, portable fuel reformers, such as CPO reactors. Furthermore, H2 and CO can be used in reducing environmentally harmful emissions. Particularly, the implementation

A self-sustained, complete and miniaturized methanol fuel processor for proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Yang, Mei; Jiao, Fengjun; Li, Shulian; Li, Hengqiang; Chen, Guangwen

2015-08-01

A self-sustained, complete and miniaturized methanol fuel processor has been developed based on modular integration and microreactor technology. The fuel processor is comprised of one methanol oxidative reformer, one methanol combustor and one two-stage CO preferential oxidation unit. Microchannel heat exchanger is employed to recover heat from hot stream, miniaturize system size and thus achieve high energy utilization efficiency. By optimized thermal management and proper operation parameter control, the fuel processor can start up in 10 min at room temperature without external heating. A self-sustained state is achieved with H2 production rate of 0.99 Nm3 h-1 and extremely low CO content below 25 ppm. This amount of H2 is sufficient to supply a 1 kWe proton exchange membrane fuel cell. The corresponding thermal efficiency of whole processor is higher than 86%. The size and weight of the assembled reactors integrated with microchannel heat exchangers are 1.4 L and 5.3 kg, respectively, demonstrating a very compact construction of the fuel processor.

NEW MATERIAL NEEDS FOR HYDROCARBON FUEL PROCESSING: Generating Hydrogen for the PEM Fuel Cell

NASA Astrophysics Data System (ADS)

Farrauto, R.; Hwang, S.; Shore, L.; Ruettinger, W.; Lampert, J.; Giroux, T.; Liu, Y.; Ilinich, O.

2003-08-01

The hydrogen economy is fast approaching as petroleum reserves are rapidly consumed. The fuel cell promises to deliver clean and efficient power by combining hydrogen and oxygen in a simple electrochemical device that directly converts chemical energy to electrical energy. Hydrogen, the most plentiful element available, can be extracted from water by electrolysis. One can imagine capturing energy from the sun and wind and/or from the depths of the earth to provide the necessary power for electrolysis. Alternative energy sources such as these are the promise for the future, but for now they are not feasible for power needs across the globe. A transitional solution is required to convert certain hydrocarbon fuels to hydrogen. These fuels must be available through existing infrastructures such as the natural gas pipeline. The present review discusses the catalyst and adsorbent technologies under development for the extraction of hydrogen from natural gas to meet the requirements for the proton exchange membrane (PEM) fuel cell. The primary market is for residential applications, where pipeline natural gas will be the source of H2 used to power the home. Other applications including the reforming of methanol for portable power applications such as laptop computers, cellular phones, and personnel digital equipment are also discussed. Processing natural gas containing sulfur requires many materials, for example, adsorbents for desulfurization, and heterogeneous catalysts for reforming (either autothermal or steam reforming) water gas shift, preferential oxidation of CO, and anode tail gas combustion. All these technologies are discussed for natural gas and to a limited extent for reforming methanol.

Biocatalytic conversion of methane to methanol as a key step for development of methane-based biorefineries.

PubMed

Hwang, In Yeub; Lee, Seung Hwan; Choi, Yoo Seong; Park, Si Jae; Na, Jeong Geol; Chang, In Seop; Kim, Choongik; Kim, Hyun Cheol; Kim, Yong Hwan; Lee, Jin Won; Lee, Eun Yeol

2014-12-28

Methane is considered as a next-generation carbon feedstock owing to the vast reserves of natural and shale gas. Methane can be converted to methanol by various methods, which in turn can be used as a starting chemical for the production of value-added chemicals using existing chemical conversion processes. Methane monooxygenase is the key enzyme that catalyzes the addition of oxygen to methane. Methanotrophic bacteria can transform methane to methanol by inhibiting methanol dehydrogenase. In this paper, we review the recent progress made on the biocatalytic conversion of methane to methanol as a key step for methane-based refinery systems and discuss future prospects for this technology.

Methanol Fuel Cell

NASA Technical Reports Server (NTRS)

Voecks, G. E.

1985-01-01

In proposed fuel-cell system, methanol converted to hydrogen in two places. External fuel processor converts only part of methanol. Remaining methanol converted in fuel cell itself, in reaction at anode. As result, size of fuel processor reduced, system efficiency increased, and cost lowered.

Methanol-tolerant cathode catalyst composite for direct methanol fuel cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-09-05

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of Pt.sub.3Cr/C so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-03-21

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Ruling in the diagnosis of methanol intoxication in a young heavy drinker: a case report

PubMed Central

Anyfantakis, D; Symvoulakis, EK; Cristodoulakis, EV; Frantzeskakis, G

2012-01-01

Methanol poisoning is a relatively rare but potentially serious medical emergency. Toxicity results when methanol is successively oxidized to the active metabolites formaldehyde and formic acid. We report a case of a 23-year-old male, a high daily alcohol consumer, who attended the local primary health care centre complaining of sudden visual loss. A presumed diagnosis of methanol intoxication was suggested based on the patient’s visual impairment and the history of alcohol ingestion. Specific therapy was initiated before a definitive diagnosis. Gas chromatographic determination of methanol levels confirmed the initial diagnostic suspicion. In this case, prompt recognition of methanol intoxication and treatment conditioned a favorable clinical outcome. Given that timely diagnosis and antidote administration are crucial issues in terms of prognosis, we underline the necessity for physicians to be alert for entities provoked by rare environmental factors. PMID:23049639

A methodology for thermodynamic simulation of high temperature, internal reforming fuel cell systems

NASA Astrophysics Data System (ADS)

Matelli, José Alexandre; Bazzo, Edson

This work presents a methodology for simulation of fuel cells to be used in power production in small on-site power/cogeneration plants that use natural gas as fuel. The methodology contemplates thermodynamics and electrochemical aspects related to molten carbonate and solid oxide fuel cells (MCFC and SOFC, respectively). Internal steam reforming of the natural gas hydrocarbons is considered for hydrogen production. From inputs as cell potential, cell power, number of cell in the stack, ancillary systems power consumption, reformed natural gas composition and hydrogen utilization factor, the simulation gives the natural gas consumption, anode and cathode stream gases temperature and composition, and thermodynamic, electrochemical and practical efficiencies. Both energetic and exergetic methods are considered for performance analysis. The results obtained from natural gas reforming thermodynamics simulation show that the hydrogen production is maximum around 700 °C, for a steam/carbon ratio equal to 3. As shown in the literature, the found results indicate that the SOFC is more efficient than MCFC.

Solar central receiver reformer system for ammonia plants

NASA Astrophysics Data System (ADS)

1980-07-01

An overview of a study to retrofit the Valley Nitrogen Producers, Inc., El Centro, California 600 ST/SD Ammonia Plant with Solar Central Receiver Technology is presented. The retrofit system consists of a solar central receiver reformer (SCRR) operating in parallel with the existing fossil fired reformer. Steam and hydrocarbon react in the catalyst filled tubes of the inner cavity receiver to form a hydrogen rich mixture which is the syngas feed for the ammonia production. The SCRR system will displace natural gas presently used in the fossil reformer combustion chamber.

Methanol synthesis on ZnO(0001{sup ¯}). IV. Reaction mechanisms and electronic structure

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

Frenzel, Johannes, E-mail: johannes.frenzel@theochem.rub.de; Marx, Dominik

2014-09-28

Methanol synthesis from CO and H{sub 2} over ZnO, which requires high temperatures and high pressures giving rise to a complex interplay of physical and chemical processes over this heterogeneous catalyst surface, is investigated using ab initio simulations. The redox properties of the surrounding gas phase are known to directly impact on the catalyst properties and thus, set the overall catalytic reactivity of this easily reducible oxide material. In Paper III of our series [J. Kiss, J. Frenzel, N. N. Nair, B. Meyer, and D. Marx, J. Chem. Phys. 134, 064710 (2011)] we have qualitatively shown that for the partiallymore » hydroxylated and defective ZnO(0001{sup ¯}) surface there exists an intricate network of surface chemical reactions. In the present study, we employ advanced molecular dynamics techniques to resolve in detail this reaction network in terms of elementary steps on the defective surface, which is in stepwise equilibrium with the gas phase. The two individual reduction steps were investigated by ab initio metadynamics sampling of free energy landscapes in three-dimensional reaction subspaces. By also sampling adsorption and desorption processes and thus molecular species that are in the gas phase but close to the surface, our approach successfully generated several alternative pathways of methanol synthesis. The obtained results suggest an Eley-Rideal mechanism for both reduction steps, thus involving “near-surface” molecules from the gas phase, to give methanol preferentially over a strongly reduced catalyst surface, while important side reactions are of Langmuir-Hinshelwood type. Catalyst re-reduction by H{sub 2} stemming from the gas phase is a crucial process after each reduction step in order to maintain the catalyst's activity toward methanol formation and to close the catalytic cycle in some reaction channels. Furthermore, the role of oxygen vacancies, side reactions, and spectator species is investigated and mechanistic details are

Control of autothermal reforming reactor of diesel fuel

NASA Astrophysics Data System (ADS)

Dolanc, Gregor; Pregelj, Boštjan; Petrovčič, Janko; Pasel, Joachim; Kolb, Gunther

2016-05-01

In this paper a control system for autothermal reforming reactor for diesel fuel is presented. Autothermal reforming reactors and the pertaining purification reactors are used to convert diesel fuel into hydrogen-rich reformate gas, which is then converted into electricity by the fuel cell. The purpose of the presented control system is to control the hydrogen production rate and the temperature of the autothermal reforming reactor. The system is designed in such a way that the two control loops do not interact, which is required for stable operation of the fuel cell. The presented control system is a part of the complete control system of the diesel fuel cell auxiliary power unit (APU).

Thermochemically recuperated and steam cooled gas turbine system

DOEpatents

Viscovich, Paul W.; Bannister, Ronald L.

1995-01-01

A gas turbine system in which the expanded gas from the turbine section is used to generate the steam in a heat recovery steam generator and to heat a mixture of gaseous hydrocarbon fuel and the steam in a reformer. The reformer converts the hydrocarbon gas to hydrogen and carbon monoxide for combustion in a combustor. A portion of the steam from the heat recovery steam generator is used to cool components, such as the stationary vanes, in the turbine section, thereby superheating the steam. The superheated steam is mixed into the hydrocarbon gas upstream of the reformer, thereby eliminating the need to raise the temperature of the expanded gas discharged from the turbine section in order to achieve effective conversion of the hydrocarbon gas.

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

Integrated anode structure for passive direct methanol fuel cells with neat methanol operation

NASA Astrophysics Data System (ADS)

Wu, Huijuan; Zhang, Haifeng; Chen, Peng; Guo, Jing; Yuan, Ting; Zheng, Junwei; Yang, Hui

2014-02-01

A microporous titanium plate based integrated anode structure (Ti-IAS) suitable for passive direct methanol fuel cells (DMFCs) fueled with neat methanol is reported. This anode structure incorporates a porous titanium plate as a methanol mass transfer barrier and current collector, pervaporation film for passively vaporizing methanol, vaporous methanol cavity for evenly distributing fuel, and channels for carbon dioxide venting. With the effective control of methanol delivery rate, the Ti-IAS based DMFC allows the direct use of neat methanol as the fuel source. In the meantime, the required water for methanol-oxidation reaction at the anode can also be fully recovered from the cathode with the help of the highly hydrophobic microporous layer in the cathode. DMFCs incorporating this new anode structure exhibit a power density as high as 40 mW cm-2 and a high volumetric energy density of 489 Wh L-1 operating with neat methanol and at 25 °C. Importantly, no obvious performance degradation of the passive DMFC system is observed after more than 90 h of continuous operation. The experimental results reveal that the compact DMFC based on the Ti-IAS exhibits a substantial potential as power sources for portable applications.

Development of a Soldier-Portable Fuel Cell Power System, Part I: A Bread-Board Methanol Fuel Processor

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

Palo, Daniel R.; Holladay, Jamelyn D.; Rozmiarek, Robert T.

A 15-We portable power system is being developed for the US Army, comprised of a hydrogen-generating fuel reformer coupled to a hydrogen-converting fuel cell. As a first phase of this project, a methanol steam reformer system was developed and demonstrated. The reformer system included a combustor, two vaporizers, and a steam-reforming reactor. The device was demonstrated as a thermally independent unit over the range of 14 to 80 Wt output. Assuming a 14-day mission life and an ultimate 1-kg fuel processor/fuel cell assembly, a base case was chosen to illustrate the expected system performance. Operating at 13 We, the systemmore » yielded a fuel processor efficiency of 45% (LHV of H2 out/LHV of fuel in) and an estimated net efficiency of 22% (assuming a fuel cell efficiency of 48%). The resulting energy density of 720 W-hr/kg is several times the energy density of the best lithium-ion batteries. Some immediate areas of improvement in thermal management also have been identified and an integrated fuel processor is under development. The final system will be a hybrid, containing a fuel reformer, fuel cell, and rechargeable battery. The battery will provide power for startup and added capacity for times of peak power demand.« less

Attrition resistant fluidizable reforming catalyst

DOEpatents

Parent, Yves O [Golden, CO; Magrini, Kim [Golden, CO; Landin, Steven M [Conifer, CO; Ritland, Marcus A [Palm Beach Shores, FL

2011-03-29

A method of preparing a steam reforming catalyst characterized by improved resistance to attrition loss when used for cracking, reforming, water gas shift and gasification reactions on feedstock in a fluidized bed reactor, comprising: fabricating the ceramic support particle, coating a ceramic support by adding an aqueous solution of a precursor salt of a metal selected from the group consisting of Ni, Pt, Pd, Ru, Rh, Cr, Co, Mn, Mg, K, La and Fe and mixtures thereof to the ceramic support and calcining the coated ceramic in air to convert the metal salts to metal oxides.

Advanced PEFC development for fuel cell powered vehicles

NASA Astrophysics Data System (ADS)

Kawatsu, Shigeyuki

Vehicles equipped with fuel cells have been developed with much progress. Outcomes of such development efforts include a Toyota fuel cell electric vehicle (FCEV) using hydrogen as the fuel which was developed and introduced in 1996, followed by another Toyota FCEV using methanol as the fuel, developed and introduced in 1997. In those Toyota FCEVs, a fuel cell system is installed under the floor of each RAV4L, to sports utility vehicle. It has been found that the CO concentration in the reformed gas of methanol reformer can be reduced to 100 ppm in wide ranges of catalyst temperature and gas flow rate, by using the ruthenium (Ru) catalyst as the CO selective oxidizer, instead of the platinum (Pt) catalyst known from some time ago. It has been also found that a fuel cell performance equivalent to that with pure hydrogen can be ensured even in the reformed gas with the carbon monoxide (CO) concentration of 100 ppm, by using the Pt-Ru (platinum ruthenium alloy) electrocatalyst as the anode electrocatalyst of a polymer electrolyte fuel cell (PEFC), instead of the Pt electrocatalyst known from some time ago.

Gas chromatography/isotope ratio mass spectrometry: analysis of methanol, ethanol and acetic acid by direct injection of aqueous alcoholic and acetic acid samples.

PubMed

Ai, Guomin; Sun, Tong; Dong, Xiuzhu

2014-08-15

Methanol, ethanol, and acetic acid are not easily extracted from aqueous samples and are susceptible to isotope fractionation in gas chromatography/isotope ratio mass spectrometry (GC/IRMS) analysis. Developing a direct dilution GC/IRMS method for aqueous samples, by adjusting the sample concentrations in common solvents to be similar to each other and using a fixed GC split ratio, is very convenient and important because any linearity effects caused by amount-dependent isotope fractionation can be avoided. The suitability of acetonitrile and acetone solvents for the GC/IRMS analysis of pure methanol, ethanol and acetic acid, and commercial liquor and vinegar samples was evaluated using n-hexane and water as control solvents. All the solvents including water were separated from the analyte on a HP-INNOWAX column and were diverted away from the combustion interface. The influence of liquor matrix on the ethanol GC/IRMS analyses was evaluated by adding pure ethanol to liquor samples. Acetonitrile and acetone gave similar δ(13) C values for pure ethanol and pure acetic acid to those obtained in water and n-hexane, and also gave similar δ(13) C values of ethanol in liquor and acetic acid in white vinegar to that obtained in water. For methanol analysis, acetonitrile and refined acetone gave similar δ(13) C values to that obtained in water, but n-hexane was not a suitable solvent. In addition, isotopic fractionation caused by solvent and solute interactions was observed. We recommend using acetonitrile for the GC/IRMS analysis of aqueous alcoholic samples, and acetone for the analysis of aqueous acetic acid samples. This direct dilution method can provide high accurate and precise GC/IRMS analysis of the relative changes in δ(13) C values of methanol, ethanol, and acetic acid. Copyright © 2014 John Wiley & Sons, Ltd.

Thermal chemical recuperation method and system for use with gas turbine systems

DOEpatents

Yang, W.C.; Newby, R.A.; Bannister, R.L.

1999-04-27

A system and method are disclosed for efficiently generating power using a gas turbine, a steam generating system and a reformer. The gas turbine receives a reformed fuel stream and an air stream and produces shaft power and exhaust. Some of the thermal energy from the turbine exhaust is received by the reformer. The turbine exhaust is then directed to the steam generator system that recovers thermal energy from it and also produces a steam flow from a water stream. The steam flow and a fuel stream are directed to the reformer that reforms the fuel stream and produces the reformed fuel stream used in the gas turbine. 2 figs.

Thermal chemical recuperation method and system for use with gas turbine systems

DOEpatents

Yang, Wen-Ching; Newby, Richard A.; Bannister, Ronald L.

1999-01-01

A system and method for efficiently generating power using a gas turbine, a steam generating system (20, 22, 78) and a reformer. The gas turbine receives a reformed fuel stream (74) and an air stream and produces shaft power and exhaust. Some of the thermal energy from the turbine exhaust is received by the reformer (18). The turbine exhaust is then directed to the steam generator system that recovers thermal energy from it and also produces a steam flow from a water stream. The steam flow and a fuel stream are directed to the reformer that reforms the fuel stream and produces the reformed fuel stream used in the gas turbine.

Temporal variations in rainwater methanol

NASA Astrophysics Data System (ADS)

Felix, J. D.; Jones, S. B.; Avery, G. B.; Willey, J. D.; Mead, R. N.; Kieber, R. J.

2014-10-01

This work reports the first comprehensive analysis of methanol concentrations in rainwater. Methanol concentrations measured in 49 rain events collected between 28 August 2007 and 10 July 2008 in Wilmington, NC, USA, ranged from below the detection limit of 6 nM to 9.3 μM with a volume-weighted average concentration of 1 ± 0.2 μM. Methanol concentrations in rainwater were up to ~200 times greater than concentrations reported previously in marine waters, indicating wet deposition as a potentially significant source of methanol to marine waters. Assuming that these methanol concentrations are an appropriate proxy for global methanol rainwater concentrations, the global methanol wet deposition sink is estimated as 20 Tg yr-1, which implies that previous methanol budgets underestimate removal by precipitation. Methanol concentrations in rainwater did not correlate significantly with H+, NO3-, and NSS, which suggests that the dominant source of the alcohol to rainwater is not anthropogenic. However, methanol concentrations were strongly correlated with acetaldehyde, which has a primarily biogenic input. The methanol volume-weighted concentration during the summer (2.7 ± 0.9 μM) was ~3 times that of the winter (0.9 ± 0.2 μM), further promoting biogenic emissions as the primary cause of temporal variations of methanol concentrations. Methanol concentrations peaked in rainwater collected during the time period 12 p.m.-6 p.m. Peaking during this period of optimal sunlight implies a possible relationship with photochemical methanol production, but there are also increases in biogenic activity during this time period. Rain events with terrestrial origin had greater concentrations than those of marine origin, demonstrating the significance of the continental source of methanol in rainwater.

Integrated reformer and shift reactor

DOEpatents

Bentley, Jeffrey M.; Clawson, Lawrence G.; Mitchell, William L.; Dorson, Matthew H.

2006-06-27

A hydrocarbon fuel reformer for producing diatomic hydrogen gas is disclosed. The reformer includes a first reaction vessel, a shift reactor vessel annularly disposed about the first reaction vessel, including a first shift reactor zone, and a first helical tube disposed within the first shift reactor zone having an inlet end communicating with a water supply source. The water supply source is preferably adapted to supply liquid-phase water to the first helical tube at flow conditions sufficient to ensure discharge of liquid-phase and steam-phase water from an outlet end of the first helical tube. The reformer may further include a first catalyst bed disposed in the first shift reactor zone, having a low-temperature shift catalyst in contact with the first helical tube. The catalyst bed includes a plurality of coil sections disposed in coaxial relation to other coil sections and to the central longitudinal axis of the reformer, each coil section extending between the first and second ends, and each coil section being in direct fluid communication with at least one other coil section.

Method for converting hydrocarbon fuel into hydrogen gas and carbon dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

2000-01-01

A method for converting hydrocarbon fuel into hydrogen gas and carbon dioxide within a reformer 10 is disclosed. According to the method, a stream including an oxygen-containing gas is directed adjacent to a first vessel 18 and the oxygen-containing gas is heated. A stream including unburned fuel is introduced into the oxygen-containing gas stream to form a mixture including oxygen-containing gas and fuel. The mixture of oxygen-containing gas and unburned fuel is directed tangentially into a partial oxidation reaction zone 24 within the first vessel 18. The mixture of oxygen-containing gas and fuel is further directed through the partial oxidation reaction zone 24 to produce a heated reformate stream including hydrogen gas and carbon monoxide. Steam may also be mixed with the oxygen-containing gas and fuel, and the reformate stream from the partial oxidation reaction zone 24 directed into a steam reforming zone 26. High- and low-temperature shift reaction zones 64,76 may be employed for further fuel processing.

Thermochemically recuperated and steam cooled gas turbine system

DOEpatents

Viscovich, P.W.; Bannister, R.L.

1995-07-11

A gas turbine system is described in which the expanded gas from the turbine section is used to generate the steam in a heat recovery steam generator and to heat a mixture of gaseous hydrocarbon fuel and the steam in a reformer. The reformer converts the hydrocarbon gas to hydrogen and carbon monoxide for combustion in a combustor. A portion of the steam from the heat recovery steam generator is used to cool components, such as the stationary vanes, in the turbine section, thereby superheating the steam. The superheated steam is mixed into the hydrocarbon gas upstream of the reformer, thereby eliminating the need to raise the temperature of the expanded gas discharged from the turbine section in order to achieve effective conversion of the hydrocarbon gas. 4 figs.

Combinatorial discovery of new methanol-tolerant non-noble metal cathode electrocatalysts for direct methanol fuel cells.

PubMed

Yu, Jong-Sung; Kim, Min-Sik; Kim, Jung Ho

2010-12-14

Combinatorial synthesis and screening were used to identify methanol-tolerant non-platinum cathode electrocatalysts for use in direct methanol fuel cells (DMFCs). Oxygen reduction consumes protons at the surface of DMFC cathode catalysts. In combinatorial screening, this pH change allows one to differentiate active catalysts using fluorescent acid-base indicators. Combinatorial libraries of carbon-supported catalyst compositions containing Ru, Mo, W, Sn, and Se were screened. Ternary and quaternary compositions containing Ru, Sn, Mo, Se were more active than the "standard" Alonso-Vante catalyst, Ru(3)Mo(0.08)Se(2), when tested in liquid-feed DMFCs. Physical characterization of the most active catalysts by powder X-ray diffraction, gas adsorption, and X-ray photoelectron spectroscopy revealed that the predominant crystalline phase was hexagonal close-packed (hcp) ruthenium, and showed a surface mostly covered with oxide. The best new catalyst, Ru(7.0)Sn(1.0)Se(1.0), was significantly more active than Ru(3)Se(2)Mo(0.08), even though the latter contained smaller particles.

OXIDATION OF METHANOL USING OZONE ON TITANIA-SUPPORTED VANADIUM CATALYST

EPA Science Inventory

Catalytic ozone decomposition of methanol has been conducted at mild temperatures of 100 to 250°C using V2O5/TiO2 catalyst prepared by either sol-gel or wet impregnation methods. The catalysts were characterized using XRD, surface area measurements, and desorption of CH3OH. Gas p...

Conversion of Methanol, Ethanol and Propanol over Zeolites

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

Ramasamy, Karthikeyan K.; Wang, Yong

2013-06-04

Renewable fuel from lignocellulosic biomass has recently attracted more attention due to its environmental and the potential economic benefits over the crude oil [1]. In particular the production of fuel range hydrocarbon (HC) from alcohol generated lots of interest since the alcohol can be produced from biomass via thermochemical [2] (mixed alcohol from gasification derived synthesis gas) as well as the biochemical routes [3] (alcohol fermentation). Along with the development of ZSM5 synthesis and the discovery of methanol-to-gasoline (MTG) process by Mobil in 1970’s triggered lots of interest in research and development arena to understand the reaction mechanisms of alcoholsmore » over zeolites in particular ZSM5 [4]. More detailed research on methanol conversion was extensively reported [5] and in recent times the research work can be found on ethanol [6] and other alcohols as well but comprehensive comparison of catalyst activity and the deactivation mechanism of the conversion of various alcohols over zeolites has not been reported. The experiments were conducted on smaller alcohols such as methanol, ethanol and 1-propanol over HZSM5. The experimental results on the catalyst activity and the catalyst deactivation mechanism will be discussed.« less

Fuel cell generator with fuel electrodes that control on-cell fuel reformation

DOEpatents

Ruka, Roswell J [Pittsburgh, PA; Basel, Richard A [Pittsburgh, PA; Zhang, Gong [Murrysville, PA

2011-10-25

A fuel cell for a fuel cell generator including a housing including a gas flow path for receiving a fuel from a fuel source and directing the fuel across the fuel cell. The fuel cell includes an elongate member including opposing first and second ends and defining an interior cathode portion and an exterior anode portion. The interior cathode portion includes an electrode in contact with an oxidant flow path. The exterior anode portion includes an electrode in contact with the fuel in the gas flow path. The anode portion includes a catalyst material for effecting fuel reformation along the fuel cell between the opposing ends. A fuel reformation control layer is applied over the catalyst material for reducing a rate of fuel reformation on the fuel cell. The control layer effects a variable reformation rate along the length of the fuel cell.

Thermodynamic analyses of hydrogen production from sub-quality natural gas. Part II: Steam reforming and autothermal steam reforming

NASA Astrophysics Data System (ADS)

Huang, Cunping; T-Raissi, Ali

Part I of this paper analyzed sub-quality natural gas (SQNG) pyrolysis and autothermal pyrolysis. Production of hydrogen via direct thermolysis of SQNGs produces only 2 mol of hydrogen and 1 mol of carbon per mole of methane (CH 4). Steam reforming of SQNG (SRSQNG) could become a more effective approach because the processes produce two more moles of hydrogen via water splitting. A Gibbs reactor unit operation in the AspenPlus™ chemical process simulator was employed to accomplish equilibrium calculations for the SQNG + H 2O and SQNG + H 2O + O 2 systems. The results indicate that water and oxygen inlet flow rates do not significantly affect the decomposition of hydrogen sulfide (H 2S) at temperatures lower than 1000 °C. The major co-product of the processes is carbonyl sulfide (COS) while sulfur dimer (S 2) and carbon disulfide (CS 2) are minor by-products within this temperature range. At higher temperatures (>1300 °C), CS 2 and S 2 become major co-products. No sulfur dioxide (SO 2) or sulfur trioxide (SO 3) is formed during either SRSQNG or autothermal SRSQNG processes, indicating that no environmentally harmful acidic gases are generated.

Pyrochlore-type catalysts for the reforming of hydrocarbon fuels

DOEpatents

Berry, David A [Morgantown, WV; Shekhawat, Dushyant [Morgantown, WV; Haynes, Daniel [Morgantown, WV; Smith, Mark [Morgantown, WV; Spivey, James J [Baton Rouge, LA

2012-03-13

A method of catalytically reforming a reactant gas mixture using a pyrochlore catalyst material comprised of one or more pyrochlores having the composition A.sub.2-w-xA'.sub.wA''.sub.xB.sub.2-y-zB'.sub.yB''.sub.zO.sub.7-.DELTA.. Distribution of catalytically active metals throughout the structure at the B site creates an active and well dispersed metal locked into place in the crystal structure. This greatly reduces the metal sintering that typically occurs on supported catalysts used in reforming reactions, and reduces deactivation by sulfur and carbon. Further, oxygen mobility may also be enhanced by elemental exchange of promoters at sites in the pyrochlore. The pyrochlore catalyst material may be utilized in catalytic reforming reactions for the conversion of hydrocarbon fuels into synthesis gas (H.sub.2+CO) for fuel cells, among other uses.

Short-term inhalation toxicity of methanol, gasoline, and methanol/gasoline in the rat.

PubMed

Poon, R; Chu, I; Bjarnason, S; Vincent, R; Potvin, M; Miller, R B; Valli, V E

1995-01-01

Four- to five-week-old male and female Sprague Dawley rats were exposed to vapors of methanol (2500 ppm), gasoline (3200 ppm), and methanol/gasoline (2500/3200 ppm, 570/3200 ppm) six hours per day, five days per week for four weeks. Control animals were exposed to filtered room air only. Depression in body weight gain and reduced food consumption were observed in male rats, and increased relative liver weight was detected in rats of both sexes exposed to gasoline or methanol/gasoline mixtures. Rats of both sexes exposed to methanol/gasoline mixtures had increased relative kidney weight and females exposed to gasoline and methanol/gasoline mixtures had increased kidney weight. Decreased serum glucose and cholesterol were detected in male rats exposed to gasoline and methanol/gasoline mixtures. Decreased hemoglobin was observed in females inhaling vapors of gasoline and methanol/gasoline at 570/3200 ppm. Urine from rats inhaling gasoline or methanol/gasoline mixtures had up to a fourfold increase in hippuric acid, a biomarker of exposure to the toluene constituent of gasoline, and up to a sixfold elevation in ascorbic acid, a noninvasive biomarker of hepatic response. Hepatic mixed-function oxidase (aniline hydroxylase, aminopyrine N-demethylase and ethoxyresorufin O-deethylase) activities and UDP-glucuronosyltransferase activity were elevated in rats exposed to gasoline and methanol/gasoline mixtures. Histopathological changes were confined to very mild changes in the nasal passages and in the uterus, where decreased incidence or absence of mucosal and myometrial eosinophilia was observed in females inhaling gasoline and methanol/gasoline at 570/3200 ppm. It was concluded that gasoline was largely responsible for the adverse effects, the most significant of which included depression in weight gain in the males, increased liver weight and hepatic microsomal enzyme activities in both sexes, and suppression of uterine eosinophilia. No apparent interactive effects

Fabrication and Characterization of a Micro Methanol Sensor Using the CMOS-MEMS Technique.

PubMed

Fong, Chien-Fu; Dai, Ching-Liang; Wu, Chyan-Chyi

2015-10-23

A methanol microsensor integrated with a micro heater manufactured using the complementary metal oxide semiconductor (CMOS)-microelectromechanical system (MEMS) technique was presented. The sensor has a capability of detecting low concentration methanol gas. Structure of the sensor is composed of interdigitated electrodes, a sensitive film and a heater. The heater located under the interdigitated electrodes is utilized to provide a working temperature to the sensitive film. The sensitive film prepared by the sol-gel method is tin dioxide doped cadmium sulfide, which is deposited on the interdigitated electrodes. To obtain the suspended structure and deposit the sensitive film, the sensor needs a post-CMOS process to etch the sacrificial silicon dioxide layer and silicon substrate. The methanol senor is a resistive type. A readout circuit converts the resistance variation of the sensor into the output voltage. The experimental results show that the methanol sensor has a sensitivity of 0.18 V/ppm.

Fabrication and Characterization of a Micro Methanol Sensor Using the CMOS-MEMS Technique

PubMed Central

Fong, Chien-Fu; Dai, Ching-Liang; Wu, Chyan-Chyi

2015-01-01

A methanol microsensor integrated with a micro heater manufactured using the complementary metal oxide semiconductor (CMOS)-microelectromechanical system (MEMS) technique was presented. The sensor has a capability of detecting low concentration methanol gas. Structure of the sensor is composed of interdigitated electrodes, a sensitive film and a heater. The heater located under the interdigitated electrodes is utilized to provide a working temperature to the sensitive film. The sensitive film prepared by the sol-gel method is tin dioxide doped cadmium sulfide, which is deposited on the interdigitated electrodes. To obtain the suspended structure and deposit the sensitive film, the sensor needs a post-CMOS process to etch the sacrificial silicon dioxide layer and silicon substrate. The methanol senor is a resistive type. A readout circuit converts the resistance variation of the sensor into the output voltage. The experimental results show that the methanol sensor has a sensitivity of 0.18 V/ppm. PMID:26512671

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.

A three-dimensional non-isothermal model for a membraneless direct methanol redox fuel cell

NASA Astrophysics Data System (ADS)

Wei, Lin; Yuan, Xianxia; Jiang, Fangming

2018-05-01

In the membraneless direct methanol redox fuel cell (DMRFC), three-dimensional electrodes contribute to the reduction of methanol crossover and the open separator design lowers the system cost and extends its service life. In order to better understand the mechanisms of this configuration and further optimize its performance, the development of a three-dimensional numerical model is reported in this work. The governing equations of the multi-physics field are solved based on computational fluid dynamics methodology, and the influence of the CO2 gas is taken into consideration through the effective diffusivities. The numerical results are in good agreement with experimental data, and the deviation observed for cases of large current density may be related to the single-phase assumption made. The three-dimensional electrode is found to be effective in controlling methanol crossover in its multi-layer structure, while it also increases the flow resistance for the discharging products. It is found that the current density distribution is affected by both the electronic conductivity and the concentration of reactants, and the temperature rise can be primarily attributed to the current density distribution. The sensitivity and reliability of the model are analyzed through the investigation of the effects of cell parameters, including porosity values of gas diffusion layers and catalyst layers, methanol concentration and CO2 volume fraction, on the polarization characteristics.

40 CFR 86.1309-90 - Exhaust gas sampling system; Otto-cycle and non-petroleum-fueled engines.

Code of Federal Regulations, 2011 CFR

2011-07-01

... gasoline-fueled, natural gas-fueled, liquefied petroleum gas-fueled or methanol-fueled engines. In the CVS... test period. (2) Engine exhaust to CVS duct. For methanol-fueled engines, reactions of the exhaust... samples for the bag sample, the methanol sample (Figure N90-2), and the formaldehyde sample (Figure N90-3...

A selective electrocatalyst–based direct methanol fuel cell operated at high concentrations of methanol

PubMed Central

Feng, Yan; Liu, Hui; Yang, Jun

2017-01-01

Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag2S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm−2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol. PMID:28695199

A selective electrocatalyst-based direct methanol fuel cell operated at high concentrations of methanol.

PubMed

Feng, Yan; Liu, Hui; Yang, Jun

2017-06-01

Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag 2 S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm -2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol.

Fabrication of a Flexible Micro CO Sensor for Micro Reformer Applications

PubMed Central

Lee, Chi-Yuan; Chang, Chi-Chung; Lo, Yi-Man

2010-01-01

Integration of a reformer and a proton exchange membrane fuel cell (PEMFC) is problematic due to the presence in the gas from the reforming process of a slight amount of carbon monoxide. Carbon monoxide poisons the catalyst of the proton exchange membrane fuel cell subsequently degrading the fuel cell performance, and necessitating the sublimation of the reaction gas before supplying to fuel cells. Based on the use of micro-electro-mechanical systems (MEMS) technology to manufacture flexible micro CO sensors, this study elucidates the relation between a micro CO sensor and different SnO2 thin film thicknesses. Experimental results indicate that the sensitivity increases at temperatures ranging from 100–300 °C. Additionally, the best sensitivity is obtained at a specific temperature. For instance, the best sensitivity of SnO2 thin film thickness of 100 nm at 300 °C is 59.3%. Moreover, a flexible micro CO sensor is embedded into a micro reformer to determine the CO concentration in each part of a micro reformer in the future, demonstrating the inner reaction of a micro reformer in depth and immediate detection. PMID:22163494

Plasma-catalyzed fuel reformer

DOEpatents

Hartvigsen, Joseph J.; Elangovan, S.; Czernichowski, Piotr; Hollist, Michele

2013-06-11

A reformer is disclosed that includes a plasma zone to receive a pre-heated mixture of reactants and ionize the reactants by applying an electrical potential thereto. A first thermally conductive surface surrounds the plasma zone and is configured to transfer heat from an external heat source into the plasma zone. The reformer further includes a reaction zone to chemically transform the ionized reactants into synthesis gas comprising hydrogen and carbon monoxide. A second thermally conductive surface surrounds the reaction zone and is configured to transfer heat from the external heat source into the reaction zone. The first thermally conductive surface and second thermally conductive surface are both directly exposed to the external heat source. A corresponding method and system are also disclosed and claimed herein.

Gas-to-gasoline plant half complete

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

Williams, B.

New Zealand has reached the midpoint in construction of the world's first commercial natural gas-to-gasoline (GTG) plant. Plans call for mid-1985 mechanical completion of the $1.475 billion GTG project in Motunui; limited production would begin by year-end 1985 with the plant fully on-stream by 1986, yielding about 628,000 tons (570,000 metric tons)/yr or about 14,450 bbl/stream-day of high-octane, low-sulfur gasoline. The process configuration combines for the first time on a commercial scale the ICI low-pressure gas-to-methanol scheme with Mobil's fixed bed zeolite catalyst process for converting methanol to gasoline. The GTG plant will be the world's biggest methanol plant andmore » New Zealand's largest grassroots industrial facility.« less

Development of a soldier-portable fuel cell power system. Part I: A bread-board methanol fuel processor

NASA Astrophysics Data System (ADS)

Palo, Daniel R.; Holladay, Jamie D.; Rozmiarek, Robert T.; Guzman-Leong, Consuelo E.; Wang, Yong; Hu, Jianli; Chin, Ya-Huei; Dagle, Robert A.; Baker, Eddie G.

A 15-W e portable power system is being developed for the US Army that consists of a hydrogen-generating fuel reformer coupled to a proton-exchange membrane fuel cell. In the first phase of this project, a methanol steam reformer system was developed and demonstrated. The reformer system included a combustor, two vaporizers, and a steam reforming reactor. The device was demonstrated as a thermally independent unit over the range of 14-80 W t output. Assuming a 14-day mission life and an ultimate 1-kg fuel processor/fuel cell assembly, a base case was chosen to illustrate the expected system performance. Operating at 13 W e, the system yielded a fuel processor efficiency of 45% (LHV of H 2 out/LHV of fuel in) and an estimated net efficiency of 22% (assuming a fuel cell efficiency of 48%). The resulting energy density of 720 Wh/kg is several times the energy density of the best lithium-ion batteries. Some immediate areas of improvement in thermal management also have been identified, and an integrated fuel processor is under development. The final system will be a hybrid, containing a fuel reformer, a fuel cell, and a rechargeable battery. The battery will provide power for start-up and added capacity for times of peak power demand.

Activity Tests of Macro-Meso Porous Catalysts over Metal Foam Plate for Steam Reforming of Bio-Ethanol.

PubMed

Park, No-Kuk; Jeong, Yong Han; Kang, Misook; Lee, Tae Jin

2018-09-01

The catalytic activity of a macro-mesoporous catalyst coated on a metal foam plate in the reforming of bio-ethanol to synthesis gas was investigated. The catalysts were prepared by coating a support with a noble metal and transition metal. The catalytic activity for the production of synthetic gas by the reforming of bio-ethanol was compared according to the support material, reaction temperature, and steam/carbon ratio. The catalysts coated on the metal foams were prepared using a template method, in which macro-pores and meso-pores were formed by mixing polymer beads. In particular, the thermodynamic equilibrium composition of bio-ethanol reforming with the reaction temperature and steam/carbon ratio to produce synthetic gas was examined using the HSC (Enthalpy-Entropy-Heat capacity) chemistry program in this study. The composition of hydrogen and carbon monoxide in the reformate gas produced by steam reforming over the Rh/Ni-Ce-Zr/Al2O3-based pellet type catalysts and metal foam catalysts that had been coated with the Rh/Al-Ce-Zr-based catalysts was investigated by experimental activity tests. The activity of the metal foam catalyst was higher than that of the pellet type catalyst.

Design and Operation of an Electrochemical Methanol Concentration Sensor for Direct Methanol Fuel Cell Systems

NASA Technical Reports Server (NTRS)

Narayanan, S. R.; Valdez, T. I.; Chun, W.

2000-01-01

The development of a 150-Watt packaged power source based on liquid feed direct methanol fuel cells is being pursued currently at the Jet propulsion Laboratory for defense applications. In our studies we find that the concentration of methanol in the fuel circulation loop affects the electrical performance and efficiency the direct methanol fuel cell systems significantly. The practical operation of direct methanol fuel cell systems, therefore, requires accurate monitoring and control of methanol concentration. The present paper reports on the principle and demonstration of an in-house developed electrochemical sensor suitable for direct methanol fuel cell systems.

First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation.

PubMed

Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter; Fehrmann, Rasmus

2006-03-07

A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)2I2]-[BMIM]I-SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.

Methanol ice VUV photoprocessing: GC-MS analysis of volatile organic compounds

NASA Astrophysics Data System (ADS)

Abou Mrad, Ninette; Duvernay, Fabrice; Chiavassa, Thierry; Danger, Grégoire

2016-05-01

Next to water, methanol is one of the most abundant molecules in astrophysical ices. A new experimental approach is presented here for the direct monitoring via gas chromatography coupled to mass spectrometry (GC-MS) of a sublimating photoprocessed pure methanol ice. Unprecedentedly, in a same analysis, compelling evidences for the formation of 33 volatile organic compounds are provided. The latter are C1-C6 products including alcohols, aldehydes, ketones, esters, ethers and carboxylic acids. Few C3 and all C4 detected compounds have been identified for the first time. Tentative detections of few C5 and C6 compounds are also presented. GC-MS allows for the first time the direct quantification of C2-C4 photoproducts and shows that their abundances decrease with the increase of their carbon chain length. These qualitative and quantitative measurements provide important complementary results to previous experiments, and present interesting similarities with observations of sources rich in methanol.

Synthetic methylotrophy: engineering the production of biofuels and chemicals based on the biology of aerobic methanol utilization.

PubMed

Whitaker, William B; Sandoval, Nicholas R; Bennett, Robert K; Fast, Alan G; Papoutsakis, Eleftherios T

2015-06-01

Synthetic methylotrophy is the development of non-native methylotrophs that can utilize methane and methanol as sole carbon and energy sources or as co-substrates with carbohydrates to produce metabolites as biofuels and chemicals. The availability of methane (from natural gas) and its oxidation product, methanol, has been increasing, while prices have been decreasing, thus rendering them as attractive fermentation substrates. As they are more reduced than most carbohydrates, methane and methanol, as co-substrates, can enhance the yields of biologically produced metabolites. Here we discuss synthetic biology and metabolic engineering strategies based on the native biology of aerobic methylotrophs for developing synthetic strains grown on methanol, with Escherichia coli as the prototype. Copyright © 2015. Published by Elsevier Ltd.

Production of synthetic fuels using syngas from a steam hydrogasification and reforming process

NASA Astrophysics Data System (ADS)

Raju, Arun Satheesh Kumar

This thesis is aimed at the research, optimization and development of a thermo-chemical process aimed at the production of synthesis gas (mixture of H2 and CO) with a flexible H2 to CO ratio using coupled steam hydrogasification and steam reforming processes. The steam hydrogasification step generates a product gas containing significant amounts of methane by gasifying a carbonaceous feed material with steam and internally generated H2. This product gas is converted to synthesis gas with an excess H2 to CO using the steam reformer. Research involving experimental and simulation work has been conducted on steam hydrogasification, steam reforming and the Fischer-Tropsch reaction. The Aspen Plus simulation tool has been used to develop a process model that can perform heat and mass balance calculations of the whole process using built-in reactor modules and an empirical FT model available in the literature. This model has been used to estimate optimum feed ratios and process conditions for specific feedstocks and products. Steam hydrogasification of coal and wood mixtures of varying coal to wood ratios has been performed in a stirred batch reactor. The carbon conversion of the feedstocks to gaseous products is around 60% at 700°C and 80% at 800°C. The coal to wood ratio of the feedstock does not exert a significant influence on the carbon conversion. The rates of formation of CO, CO 2 and CH4 during gasification have been calculated based on the experimental results using a simple kinetic model. Experimental research on steam reforming has been performed. It has been shown that temperature and the feed CO2/CH4 ratio play a dominant role in determining the product gas H2/CO ratio. Reforming of typical steam hydrogasification product-gas stream has been investigated over a commercial steam reforming catalyst. The results demonstrate that the combined use of steam hydrogasification process with a reformer can generate a synthesis gas with a predetermined H2/CO ratio

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-24

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Properties of a soft-core model of methanol: An integral equation theory and computer simulation study

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

Huš, Matej; Urbic, Tomaz, E-mail: tomaz.urbic@fkkt.uni-lj.si; Munaò, Gianmarco

Thermodynamic and structural properties of a coarse-grained model of methanol are examined by Monte Carlo simulations and reference interaction site model (RISM) integral equation theory. Methanol particles are described as dimers formed from an apolar Lennard-Jones sphere, mimicking the methyl group, and a sphere with a core-softened potential as the hydroxyl group. Different closure approximations of the RISM theory are compared and discussed. The liquid structure of methanol is investigated by calculating site-site radial distribution functions and static structure factors for a wide range of temperatures and densities. Results obtained show a good agreement between RISM and Monte Carlo simulations.more » The phase behavior of methanol is investigated by employing different thermodynamic routes for the calculation of the RISM free energy, drawing gas-liquid coexistence curves that match the simulation data. Preliminary indications for a putative second critical point between two different liquid phases of methanol are also discussed.« less

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Hydrogen generation from biogenic and fossil fuels by autothermal reforming

NASA Astrophysics Data System (ADS)

Rampe, Thomas; Heinzel, Angelika; Vogel, Bernhard

Hydrogen generation for fuel cell systems by reforming technologies from various fuels is one of the main fields of investigation of the Fraunhofer ISE. Suitable fuels are, on the one hand, gaseous hydrocarbons like methane, propane but also, on the other hand, liquid hydrocarbons like gasoline and alcohols, e.g., ethanol as biogenic fuel. The goal is to develop compact systems for generation of hydrogen from fuel being suitable for small-scale membrane fuel cells. The most recent work is related to reforming according to the autothermal principle — fuel, air and steam is supplied to the reactor. Possible applications of such small-scale autothermal reformers are mobile systems and also miniature fuel cell as co-generation plant for decentralised electricity and heat generation. For small stand-alone systems without a connection to the natural gas grid liquid gas, a mixture of propane and butane is an appropriate fuel.

Method And Apparatus For Converting Hydrocarbon Fuel Into Hydrogen Gas And Carbon Dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

2001-03-27

A hydrocarbon fuel reforming method is disclosed suitable for producing synthesis hydrogen gas from reactions with hydrocarbons fuels, oxygen, and steam. A first mixture of an oxygen-containing gas and a first fuel is directed into a first tube 108 to produce a first reaction reformate. A second mixture of steam and a second fuel is directed into a second tube 116 annularly disposed about the first tube 108 to produce a second reaction reformate. The first and second reaction reformates are then directed into a reforming zone 144 and subject to a catalytic reforming reaction. In another aspect of the method, a first fuel is combusted with an oxygen-containing gas in a first zone 108 to produce a reformate stream, while a second fuel under steam reforming in a second zone 116. Heat energy from the first zone 108 is transferred to the second zone 116.

Process Evaluation - Steam Reforming of Diesel Fuel Oil

DTIC Science & Technology

1980-02-15

Table 9. HIDROGEN CONVERSION RELATIVE TO TEMPERATURE, SPACE, VELOCITY, AND H20/C RATIO Oil Feed, Gas Product ,Run No. Temperature, *F H2,O/C Ratio igram...steam reforming diesel fuel, but with the production of naphthalene after 30 hours. Hydrogen production remained stable through the 86 hours of the test...79-C-0048. Hydrogen-rich gas was produced over a wide range of reaction conditions. This product gas contained small amounts of ethylene and !nzene

Transesterification of waste vegetable oil under pulse sonication using ethanol, methanol and ethanol-methanol mixtures.

PubMed

Martinez-Guerra, Edith; Gude, Veera Gnaneswar

2014-12-01

This study reports on the effects of direct pulse sonication and the type of alcohol (methanol and ethanol) on the transesterification reaction of waste vegetable oil without any external heating or mechanical mixing. Biodiesel yields and optimum process conditions for the transesterification reaction involving ethanol, methanol, and ethanol-methanol mixtures were evaluated. The effects of ultrasonic power densities (by varying sample volumes), power output rates (in W), and ultrasonic intensities (by varying the reactor size) were studied for transesterification reaction with ethanol, methanol and ethanol-methanol (50%-50%) mixtures. The optimum process conditions for ethanol or methanol based transesterification reaction of waste vegetable oil were determined as: 9:1 alcohol to oil ratio, 1% wt. catalyst amount, 1-2 min reaction time at a power output rate between 75 and 150 W. It was shown that the transesterification reactions using ethanol-methanol mixtures resulted in biodiesel yields as high as >99% at lower power density and ultrasound intensity when compared to ethanol or methanol based transesterification reactions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermodynamic and Structural Properties of Methanol-Water Solutions Using Non-Additive Interaction Models

PubMed Central

Zhong, Yang; Warren, G. Lee; Patel, Sandeep

2014-01-01

We study bulk structural and thermodynamic properties of methanol-water solutions via molecular dynamics simulations using novel interaction potentials based on the charge equilibration (fluctuating charge) formalism to explicitly account for molecular polarization at the atomic level. The study uses the TIP4P-FQ potential for water-water interactions, and the CHARMM-based (Chemistry at HARvard Molecular Mechanics) fluctuating charge potential for methanol-methanol and methanol-water interactions. In terms of bulk solution properties, we discuss liquid densities, enthalpies of mixing, dielectric constants, self-diffusion constants, as well as structural properties related to local hydrogen bonding structure as manifested in radial distribution functions and cluster analysis. We further explore the electronic response of water and methanol in the differing local environments established by the interaction of each species predominantly with molecules of the other species. The current force field for the alcohol-water interaction performs reasonably well for most properties, with the greatest deviation from experiment observed for the excess mixing enthalpies, which are predicted to be too favorable. This is qualitatively consistent with the overestimation of the methanol-water gas-phase interaction energy for the lowest-energy conformer (methanol as proton donor). Hydration free energies for methanol in TIP4P-FQ water are predicted to be −5.6±0.2 kcal/mole, in respectable agreement with the experimental value of −5.1 kcal/mole. With respect to solution micro-structure, the present cluster analysis suggests that the micro-scale environment for concentrations where select thermodynamic quantities reach extremal values is described by a bi-percolating network structure. PMID:18074339

Reformer assisted lean NO.sub.x catalyst aftertreatment system and method

DOEpatents

Kalyanaraman, Mohan [Media, PA; Park, Paul W [Peoria, IL; Ragle, Christie S [Havana, IL

2010-06-29

A method and apparatus for catalytically processing a gas stream passing therethrough to reduce the presence of NO.sub.x therein, wherein the apparatus includes a first catalyst composed of a silver-containing alumina that is adapted for catalytically processing the gas stream at a first temperature range, a second catalyst composed of a copper-containing zeolite located downstream from the first catalyst, wherein the second catalyst is adapted for catalytically processing the gas stream at a lower second temperature range relative to the first temperature range, a hydrocarbon compound for injection into the gas stream upstream of the first catalyst to provide a reductant, and a reformer for reforming a portion of the hydrocarbon compound into H.sub.2 and/or oxygenated hydrocarbon for injection into the gas stream upstream of the first catalyst. The second catalyst is adapted to facilitate the reaction of reducing NOx into N.sub.2, whereby the intermediates are produced via the first catalyst reacting with NOx and hydrocarbons.

Antiproliferative effect of methanolic extraction of tualang honey on human keloid fibroblasts

PubMed Central

2011-01-01

Background Keloid is a type of scar which extends beyond the boundaries of the original wound. It can spread to the surrounding skin by invasion. The use of Tualang honey is a possible approach for keloid treatment. The objective of this study was to determine the antiproliferative effect of methanolic extraction of Tualang honey to primary human keloid fibroblasts and to identify the volatile compounds in methanol extraction of Tualang honey. Methods Crude Tualang honey was extracted with methanol and then dried using rota vapor to remove remaining methanol from honey. Normal and keloid fibroblasts were verified and treated with the extracted honey. Cell proliferation was tested with [3-(4,5-dimethylthiazol-2-yi)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium, inner salt] (MTS) assay. Extraction of Tualang honey using methanol was carried out and the extracted samples were analysed using gas chromatography-mass spectrometry (GC-MS). The result was analysed using SPSS and tested with Kruskal-Wallis and Mann-Whitney tests. Results Methanolic extraction of honey has positive anti proliferative effect on keloid fibroblasts in a dose-dependent manner. The presence of fatty acids such as palmitic acid, stearic acid, oleic acid, linoleic acid and octadecanoic acid may contribute to the anti-proliferative effect in keloid fibroblasts. Conclusions The methanolic honey extraction has an antiproliferative effect on keloid fibroblasts and a range of volatile compounds has been identified from Tualang honey. The antiproliferative effect of keloid fibroblasts towards Tualang honey may involve cell signaling pathway. Identifying other volatile compounds from different organic solvents should be carried out in future. PMID:21943200

A study of the region of massive star formation L379IRS1 in radio lines of methanol and other molecules

NASA Astrophysics Data System (ADS)

Kalenskii, S. V.; Shchurov, M. A.

2016-04-01

The results of spectral observations of the region of massive star formation L379IRS1 (IRAS18265-1517) are presented. The observations were carried out with the 30-m Pico Veleta radio telescope (Spain) at seven frequencies in the 1-mm, 2-mm, and 3-mm wavelength bands. Lines of 24 molecules were detected, from simple diatomic or triatomic species to complex eight- or nine-atom compounds such as CH3OCHO or CH3OCH3. Rotation diagrams constructed from methanol andmethyl cyanide lines were used to determine the temperature of the quiescent gas in this region, which is about 40-50 K. In addition to this warm gas, there is a hot component that is revealed through high-energy lines of methanol and methyl cyanide, molecular lines arising in hot regions, and the presence of H2O masers and Class II methanol masers at 6.7 GHz, which are also related to hot gas. One of the hot regions is probably a compact hot core, which is located near the southern submillimeter peak and is related to a group of methanol masers at 6.7 GHz. High-excitation lines at other positions may be associated with other hot cores or hot post-shock gas in the lobes of bipolar outflows. The rotation diagrams can be use to determine the column densities and abundances of methanol (10-9) and methyl cyanide (about 10-11) in the quiescent gas. The column densities of A- and E-methanol in L379IRS1 are essentually the same. The column densities of other observedmolecules were calculated assuming that the ratios of the molecular level abundances correspond to a temperature of 40 K. The molecular composition of the quiescent gas is close to that in another region of massive star formation, DR21(OH). The only appreciable difference is that the column density of SO2 in L379IRS1 is at least a factor of 20 lower than the value in DR21(OH). The SO2/CS and SO2/OCS abundance ratios, which can be used as chemical clocks, are lower in L379IRS1 than in DR21(OH), suggesting that L379IRS1 is probably younger than DR21(OH).

A high selective methanol gas sensor based on molecular imprinted Ag-LaFeO3 fibers.

PubMed

Rong, Qian; Zhang, Yumin; Wang, Chao; Zhu, Zhongqi; Zhang, Jin; Liu, Qingju

2017-09-21

Ag-LaFeO 3 molecularly imprinted polymers (ALMIPs) were fabricated, which provided special recognition sites to methanol. Then ALMIPs fiber 1, fiber 2 and fiber 3 were prepared using filter paper, silk and carbon fibers template, respectively. Based on the observation of X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), and Nitrogen adsorption surface area analyzer (BET), the structure, morphology and surface area of the fibers were characterized. The ALMIPs fibers (fiber 1, fiber 2 and fiber 3) show excellent selectivity and good response to methanol. The responses to 5 ppm methanol and the optimal operating temperature of ALMIPs fibers are 23.5 and 175 °C (fiber 1), 19.67 and 125 °C (fiber 2), 17.59 and 125 °C (fiber 3), and a lower response (≤10, 3, 2) to other test gases including formaldehyde, acetone, ethanol, ammonia, gasoline and benzene was measured, respectively.

GC-MS analysis of bio-active compounds in methanolic extract of Lactuca runcinata DC

PubMed Central

Kanthal, Lakshmi Kanta; Dey, Akalanka; Satyavathi, K.; Bhojaraju, P.

2014-01-01

Background: The presence of phytochemical constitutes has been reported from species of the Compositae (Asteraceae). Hitherto no reports exist on the phytochemical components and biological activity of Lactuca runcinata DC. Objective: The present study was designed to determine the bioactive compounds in the whole plant methanol extract of Lactuca runcinata. Materials and Methods: Phytochemical screening of the entire herb of Lactuca runcinata DC revealed the presence of some bio-active components. Gas chromatography-mass spectrometry (GC-MS) analysis of the whole plant methanol extract of Lactuca runcinata was performed on a GC-MS equipment (Thermo Scientific Co.) Thermo GC-TRACE ultra ver.: 5.0, Thermo MS DSQ II. Results: The phytochemical tests showed the presence of alkaloids, cardiac glycosides, flavonoids, phenols, phlobatannin, reducing sugars, saponins, steroids, tannins, terpenoids, volatile oils, carbohydrates, and protein/amino acids in methanolic extract of L. runcinata. The GC-MS analysis has shown the presence of different phytochemical compounds in the methanolic extract of Lactuca runcinata. A total of 21 compounds were identified representing 84.49% of total methanolic extract composition. Conclusion: From the results, it is evident that Lactuca runcinata contains various phytocomponents and is recommended as a plant of phytopharmaceutical importance. PMID:24497744

Biofiltration of methanol vapor

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

Shareefdeen, Z.; Baltzis, B.C.; Oh, Youngsook

1993-03-05

Biofiltration of solvent and fuel vapors may offer a cost-effective way to comply with increasingly strict air emission standards. An important step in the development of this technology is to derive and validate mathematical models of the biofiltration process for predictive and scaleup calculations. For the study of methanol vapor biofiltration, an 8-membered bacterial consortium was obtained from methanol-exposed soil. The bacteria were immobilized on solid support and packed into a 5-cm diameter, 60-cm-high column provided with appropriate flowmeters and sampling ports. The solid support was prepared by mixing two volumes of peat with three volumes of perlite particles. Twomore » series of experiments were performed. In the first, the inlet methanol concentration was kept constant while the superficial air velocity was varied from run to run. In the second series, the air flow rate (velocity) was kept constant while the inlet methanol concentration was varied. The unit proved effective in removing methanol at rates up to 112.8 g h[sup [minus]1] m[sup [minus]3] packing. A mathematical model has been derived and validated. The model described and predicted experimental results closely. Both experimental data and model predictions suggest that the methanol biofiltration process was limited by oxygen diffusion and methanol degradation kinetics.« less

Interstellar Methanol from the Lab to Protoplanetary Disks

NASA Astrophysics Data System (ADS)

Drozdovskaya, Maria; Walsh, Catherine; Visser, Ruud; Harsono, Daniel; van Dishoeck, Ewine

2015-08-01

Interstellar methanol is considered to be a parent species of larger, more complex organic molecules. It holds a central role in many astrochemical models [e.g. 1]. Methanol has also been the focus of several laboratory studies [e.g. 2, 3] in an effort to gain insight into grain-surface chemistry, which potentially builds chemical complexity already in the cold, dark phases of protostellar evolution. The case of methanol is a prime example of experimental work having implications on astronomical scales. For this meeting, I would like to highlight how physical and chemical models can be unified to simulate infalling material during the birth of a low-mass protostar. An axisymmetric 2D semi-analytic collapse model [4], wavelength-dependent radiative transfer calculations with RADMC3D [5] and a comprehensive gas-grain chemical network [6] are used to study two physical scenarios. In the first case, the dominant disc growth mechanism is viscous spreading, while in the second, continuous infall of matter prevails. The results show that the infall path influences the abundance of methanol entering each type of disk, ranging from complete loss of methanol to an enhancement by a factor of >1 relative to the prestellar phase [7]. This work illustrates how the experimentally verified hydrogenation sequence of carbon monoxide leading to methanol influences the delivery of methanol ice to the planet- and comet-forming zones of protoplanetary disks. Such intriguing links will soon be tested by upcoming cometary data from the Rosetta mission and ALMA observations.[1] Garrod R. T., Herbst E., 2006, A&A, 457, 927[2] Watanabe N., Nagaoka A., Shiraki T., Kouchi A., 2004, ApJ, 616, 638[3] Fuchs G. W., Cuppen H. M., Ioppolo S., Romanzin C., Bisschop S. E., Andersson S., van Dishoeck E. F., Linnartz H., 2009, A&A, 505, 629[4] Visser R., van Dishoeck E. F., Doty S. D., Dullemond C. P., 2009, A&A, 495, 881[5] Dullemond C. P., Dominik C., 2004, A&A, 417, 159[6] Walsh C., Millar T. J

Liquid phase methanol reactor staging process for the production of methanol

DOEpatents

Bonnell, Leo W.; Perka, Alan T.; Roberts, George W.

1988-01-01

The present invention is a process for the production of methanol from a syngas feed containing carbon monoxide, carbon dioxide and hydrogen. Basically, the process is the combination of two liquid phase methanol reactors into a staging process, such that each reactor is operated to favor a particular reaction mechanism. In the first reactor, the operation is controlled to favor the hydrogenation of carbon monoxide, and in the second reactor, the operation is controlled so as to favor the hydrogenation of carbon dioxide. This staging process results in substantial increases in methanol yield.

Dynamic Modeling and Plantwide Control of a Hybrid Power and Chemical Plant: An Integrated Gasification Combined Cycle Coupled with a Methanol Plant

NASA Astrophysics Data System (ADS)

Robinson, Patrick J.

Gasification has been used in industry on a relatively limited scale for many years, but it is emerging as the premier unit operation in the energy and chemical industries. The switch from expensive and insecure petroleum to solid hydrocarbon sources (coal and biomass) is occurring due to the vast amount of domestic solid resources, national security and global warming issues. Gasification (or partial oxidation) is a vital component of "clean coal" technology. Sulfur and nitrogen emissions can be reduced, overall energy efficiency is increased and carbon dioxide recovery and sequestration are facilitated. Gasification units in an electric power generation plant produce a fuel gas for driving combustion turbines. Gasification units in a chemical plant generate synthesis gas, which can be used to produce a wide spectrum of chemical products. Future plants are predicted to be hybrid power/chemical plants with gasification as the key unit operation. The coupling of an Integrated Gasification Combined Cycle (IGCC) with a methanol plant can handle swings in power demand by diverting hydrogen gas from a combustion turbine and synthesis gas from the gasifier to a methanol plant for the production of an easily-stored, hydrogen-consuming liquid product. An additional control degree of freedom is provided with this hybrid plant, fundamentally improving the controllability of the process. The idea is to base-load the gasifier and use the more responsive gas-phase units to handle disturbances. During the summer days, power demand can fluctuate up to 50% over a 12-hour period. The winter provides a different problem where spikes of power demand can go up 15% within the hour. The following dissertation develops a hybrid IGCC / methanol plant model, validates the steady-state results with a National Energy Technical Laboratory study, and tests a proposed control structure to handle these significant disturbances. All modeling was performed in the widely used chemical process

California methanol assessment. Volume 2: Technical report

NASA Technical Reports Server (NTRS)

Otoole, R.; Dutzi, E.; Gershman, R.; Heft, R.; Kalema, W.; Maynard, D.

1983-01-01

Energy feedstock sources for methanol; methanol and other synfuels; transport, storage, and distribution; air quality impact of methanol use in vehicles, chemical methanol production and use; methanol utilization in vehicles; methanol utilization in stationary applications; and environmental and regulatory constraints are discussed.

Aerobic methanol-oxidizing bacteria in soil.

PubMed

Kolb, Steffen

2009-11-01

Methanol is an atmospheric compound that is primarily released from plant polymers and impacts ozone formation. The global methanol emission rate from terrestrial ecosystems is of the same order of magnitude (4.9 x 10(12) mol year(-1)) as that of methane (10 x 10(12) mol year(-1)). The major proportion of the annual plant-released methanol does not enter the atmosphere, but may be reoxidized by biological methanol oxidation, which is catalyzed by methanol-oxidizing prokaryotes. Fifty-six aerobic methanol-oxidizing species have been isolated from soils. These methylotrophs belong to the Alpha-, Beta-, and Gammaproteobacteria, Verrucomicrobia, Firmicutes, and Actinobacteria. Their ecological niches are determined by oxygen and methanol concentration, temperature, pH, the capability to utilize nitrate as an electron acceptor, and the spectrum of nitrogen sources and utilizable multicarbon substrates. Recently discovered interactions with eukaryotes indicate that their ecological niches may not solely be defined by physicochemical parameters. Nonetheless, there are still gaps in knowledge; based on global methanol budgets, methanol oxidation in soil is important, but has not been addressed adequately by biogeochemical studies. Ratios of above-ground and soil-internal methanol oxidation are not known. The contribution to methanol-oxidation by aerobic and anaerobic methylotrophs in situ also needs further research.

High performance internal reforming unit for high temperature fuel cells

DOEpatents

Ma, Zhiwen [Sandy Hook, CT; Venkataraman, Ramakrishnan [New Milford, CT; Novacco, Lawrence J [Brookfield, CT

2008-10-07

A fuel reformer having an enclosure with first and second opposing surfaces, a sidewall connecting the first and second opposing surfaces and an inlet port and an outlet port in the sidewall. A plate assembly supporting a catalyst and baffles are also disposed in the enclosure. A main baffle extends into the enclosure from a point of the sidewall between the inlet and outlet ports. The main baffle cooperates with the enclosure and the plate assembly to establish a path for the flow of fuel gas through the reformer from the inlet port to the outlet port. At least a first directing baffle extends in the enclosure from one of the sidewall and the main baffle and cooperates with the plate assembly and the enclosure to alter the gas flow path. Desired graded catalyst loading pattern has been defined for optimized thermal management for the internal reforming high temperature fuel cells so as to achieve high cell performance.

Control of methanol vapours in a biotrickling filter: performance analysis and experimental determination of partition coefficient.

PubMed

Avalos Ramirez, Antonio; Peter Jones, J; Heitz, Michéle

2009-02-01

Methanol vapours were treated in a biotrickling filter (BTF) packed with inert polypropylene spheres. The effects of the nitrogen concentration in the nutrient solution, the empty bed residence time (EBRT) and the methanol inlet concentration, on the BTF performance, were all examined. The elimination capacity (EC), the biomass and the carbon dioxide production rates were all increased with the rising of the nitrogen concentration and the EBRT. The EC also rose with increasing methanol inlet load (IL) when the methanol inlet concentration and the EBRT were varied, from 0.3 to 37.0 g m(-3), and from 20 to 65 s, respectively. The BTF reached its maximum EC level of 2160 g m(-3) h(-1) when it was operated at an IL level of 3700 g m(-3) h(-1). The input methanol was removed through two mechanisms: biodegradation and absorption in the liquid phase. The partition coefficient for the methanol in the BTF was determined at five EBRTs and along the packed bed. It generally followed the Henry model, having an average value of 2.64 x 10(-4)[mol L(-1)](gas)/[mol L(-1)](liquid).

A multi-level simulation platform of natural gas internal reforming solid oxide fuel cell-gas turbine hybrid generation system - Part II. Balancing units model library and system simulation

NASA Astrophysics Data System (ADS)

Bao, Cheng; Cai, Ningsheng; Croiset, Eric

2011-10-01

Following our integrated hierarchical modeling framework of natural gas internal reforming solid oxide fuel cell (IRSOFC), this paper firstly introduces the model libraries of main balancing units, including some state-of-the-art achievements and our specific work. Based on gPROMS programming code, flexible configuration and modular design are fully realized by specifying graphically all unit models in each level. Via comparison with the steady-state experimental data of Siemens-Westinghouse demonstration system, the in-house multi-level SOFC-gas turbine (GT) simulation platform is validated to be more accurate than the advanced power system analysis tool (APSAT). Moreover, some units of the demonstration system are designed reversely for analysis of a typically part-load transient process. The framework of distributed and dynamic modeling in most of units is significant for the development of control strategies in the future.

Towards neat methanol operation of direct methanol fuel cells: a novel self-assembled proton exchange membrane.

PubMed

Li, Jing; Cai, Weiwei; Ma, Liying; Zhang, Yunfeng; Chen, Zhangxian; Cheng, Hansong

2015-04-18

We report here a novel proton exchange membrane with remarkably high methanol-permeation resistivity and excellent proton conductivity enabled by carefully designed self-assembled ionic conductive channels. A direct methanol fuel cell utilizing the membrane performs well with a 20 M methanol solution, very close to the concentration of neat methanol.

A thermally self-sustained micro-power plant with integrated micro-solid oxide fuel cells, micro-reformer and functional micro-fluidic carrier

NASA Astrophysics Data System (ADS)

Scherrer, Barbara; Evans, Anna; Santis-Alvarez, Alejandro J.; Jiang, Bo; Martynczuk, Julia; Galinski, Henning; Nabavi, Majid; Prestat, Michel; Tölke, René; Bieberle-Hütter, Anja; Poulikakos, Dimos; Muralt, Paul; Niedermann, Philippe; Dommann, Alex; Maeder, Thomas; Heeb, Peter; Straessle, Valentin; Muller, Claude; Gauckler, Ludwig J.

2014-07-01

Low temperature micro-solid oxide fuel cell (micro-SOFC) systems are an attractive alternative power source for small-size portable electronic devices due to their high energy efficiency and density. Here, we report on a thermally self-sustainable reformer-micro-SOFC assembly. The device consists of a micro-reformer bonded to a silicon chip containing 30 micro-SOFC membranes and a functional glass carrier with gas channels and screen-printed heaters for start-up. Thermal independence of the device from the externally powered heater is achieved by exothermic reforming reactions above 470 °C. The reforming reaction and the fuel gas flow rate of the n-butane/air gas mixture controls the operation temperature and gas composition on the micro-SOFC membrane. In the temperature range between 505 °C and 570 °C, the gas composition after the micro-reformer consists of 12 vol.% to 28 vol.% H2. An open-circuit voltage of 1.0 V and maximum power density of 47 mW cm-2 at 565 °C is achieved with the on-chip produced hydrogen at the micro-SOFC membranes.

Formaldehyde and methanol formation from reaction of carbon monoxide and hydrogen on neutral Fe2S2 clusters in the gas phase.

PubMed

Yin, Shi; Wang, Zhechen; Bernstein, Elliot R

2013-04-07

Reaction of CO with H2 on neutral FemSn clusters in a fast flow reactor is investigated both experimentally and theoretically. Single photon ionization at 118 nm is used to detect neutral cluster distributions through time of flight mass spectrometry. FemSn clusters are generated through laser ablation of a mixed iron-sulfur target in the presence of a pure helium carrier gas. A strong size dependent reactivity of (FeS)m clusters toward CO is characterized. The reaction FeS + CO → Fe + OCS is found for the FeS cluster, and the association product Fe2S2CO is observed for the Fe2S2 cluster. Products Fe2S2(13)COH2 and Fe2S2(13)COH4 are identified for reactions of (13)CO and H2 on Fe2S2 clusters: this suggests that the Fe2S2 cluster has a high catalytic activity for hydrogenation reactions of CO to form formaldehyde and methanol. Density functional theory (DFT) calculations are performed to explore the potential energy surfaces for the two reactions: Fe2S2 + CO + 2H2 → Fe2S2 + CH3OH; and Fe2S2 + CO + H2 → Fe2S2 + CH2O. A barrierless, thermodynamically favorable pathway is obtained for both catalytic processes. Catalytic cycles for formaldehyde and methanol formation from CO and H2 on a Fe2S2 cluster are proposed based on our experimental and theoretical investigations. The various reaction mechanisms explored by DFT are in good agreement with the experimental results. Condensed phase iron sulfide, which contains exposed Fe2S2 units on its surface, is suggested to be a good catalyst for low temperature formaldehyde/methanol synthesis.

Endogenous Methanol Regulates Mammalian Gene Activity

PubMed Central

Komarova, Tatiana V.; Petrunia, Igor V.; Shindyapina, Anastasia V.; Silachev, Denis N.; Sheshukova, Ekaterina V.; Kiryanov, Gleb I.; Dorokhov, Yuri L.

2014-01-01

We recently showed that methanol emitted by wounded plants might function as a signaling molecule for plant-to-plant and plant-to-animal communications. In mammals, methanol is considered a poison because the enzyme alcohol dehydrogenase (ADH) converts methanol into toxic formaldehyde. However, the detection of methanol in the blood and exhaled air of healthy volunteers suggests that methanol may be a chemical with specific functions rather than a metabolic waste product. Using a genome-wide analysis of the mouse brain, we demonstrated that an increase in blood methanol concentration led to a change in the accumulation of mRNAs from genes primarily involved in detoxification processes and regulation of the alcohol/aldehyde dehydrogenases gene cluster. To test the role of ADH in the maintenance of low methanol concentration in the plasma, we used the specific ADH inhibitor 4-methylpyrazole (4-MP) and showed that intraperitoneal administration of 4-MP resulted in a significant increase in the plasma methanol, ethanol and formaldehyde concentrations. Removal of the intestine significantly decreased the rate of methanol addition to the plasma and suggested that the gut flora may be involved in the endogenous production of methanol. ADH in the liver was identified as the main enzyme for metabolizing methanol because an increase in the methanol and ethanol contents in the liver homogenate was observed after 4-MP administration into the portal vein. Liver mRNA quantification showed changes in the accumulation of mRNAs from genes involved in cell signalling and detoxification processes. We hypothesized that endogenous methanol acts as a regulator of homeostasis by controlling the mRNA synthesis. PMID:24587296

Reforming options for hydrogen production from fossil fuels for PEM fuel cells

NASA Astrophysics Data System (ADS)

Ersoz, Atilla; Olgun, Hayati; Ozdogan, Sibel

PEM fuel cell systems are considered as a sustainable option for the future transport sector in the future. There is great interest in converting current hydrocarbon based transportation fuels into hydrogen rich gases acceptable by PEM fuel cells on-board of vehicles. In this paper, we compare the results of our simulation studies for 100 kW PEM fuel cell systems utilizing three different major reforming technologies, namely steam reforming (SREF), partial oxidation (POX) and autothermal reforming (ATR). Natural gas, gasoline and diesel are the selected hydrocarbon fuels. It is desired to investigate the effect of the selected fuel reforming options on the overall fuel cell system efficiency, which depends on the fuel processing, PEM fuel cell and auxiliary system efficiencies. The Aspen-HYSYS 3.1 code has been used for simulation purposes. Process parameters of fuel preparation steps have been determined considering the limitations set by the catalysts and hydrocarbons involved. Results indicate that fuel properties, fuel processing system and its operation parameters, and PEM fuel cell characteristics all affect the overall system efficiencies. Steam reforming appears as the most efficient fuel preparation option for all investigated fuels. Natural gas with steam reforming shows the highest fuel cell system efficiency. Good heat integration within the fuel cell system is absolutely necessary to achieve acceptable overall system efficiencies.

37 GHz Methanol Masers : Horsemen of the Apocalypse for the Class II Methanol Maser Phase?

NASA Astrophysics Data System (ADS)

Ellingsen, S. P.; Breen, S. L.; Sobolev, A. M.; Voronkov, M. A.; Caswell, J. L.; Lo, N.

2011-12-01

We report the results of a search for class II methanol masers at 37.7, 38.3, and 38.5 GHz toward a sample of 70 high-mass star formation regions. We primarily searched toward regions known to show emission either from the 107 GHz class II methanol maser transition, or from the 6.035 GHz excited OH transition. We detected maser emission from 13 sources in the 37.7 GHz transition, eight of these being new detections. We detected maser emission from three sources in the 38 GHz transitions, one of which is a new detection. We find that 37.7 GHz methanol masers are only associated with the most luminous 6.7 and 12.2 GHz methanol maser sources, which in turn are hypothesized to be the oldest class II methanol sources. We suggest that the 37.7 GHz methanol masers are associated with a brief evolutionary phase (of 1000-4000 years) prior to the cessation of class II methanol maser activity in the associated high-mass star formation region.

Effect of sorbed methanol, current, and temperature on multicomponent transport in nafion-based direct methanol fuel cells.

PubMed

Rivera, Harry; Lawton, Jamie S; Budil, David E; Smotkin, Eugene S

2008-07-24

The CO2 in the cathode exhaust of a liquid feed direct methanol fuel cell (DMFC) has two sources: methanol diffuses through the membrane electrode assembly (MEA) to the cathode where it is catalytically oxidized to CO2; additionally, a portion of the CO2 produced at the anode diffuses through the MEA to the cathode. The potential-dependent CO2 exhaust from the cathode was monitored by online electrochemical mass spectrometry (ECMS) with air and with H2 at the cathode. The precise determination of the crossover rates of methanol and CO2, enabled by the subtractive normalization of the methanol/air to the methanol/H2 ECMS data, shows that methanol decreases the membrane viscosity and thus increases the diffusion coefficients of sorbed membrane components. The crossover of CO2 initially increases linearly with the Faradaic oxidation of methanol, reaches a temperature-dependent maximum, and then decreases. The membrane viscosity progressively increases as methanol is electrochemically depleted from the anode/electrolyte interface. The crossover maximum occurs when the current dependence of the diffusion coefficients and membrane CO2 solubility dominate over the Faradaic production of CO2. The plasticizing effect of methanol is corroborated by measurements of the rotational diffusion of TEMPONE (2,2,6,6-tetramethyl-4-piperidone N-oxide) spin probe by electron spin resonance spectroscopy. A linear inverse relationship between the methanol crossover rate and current density confirms the absence of methanol electro-osmotic drag at concentrations relevant to operating DMFCs. The purely diffusive transport of methanol is explained in terms of current proton solvation and methanol-water incomplete mixing theories.

Hydrogen generation from natural gas for the fuel cell systems of tomorrow

NASA Astrophysics Data System (ADS)

Dicks, Andrew L.

In most cases hydrogen is the preferred fuel for use in the present generation of fuel cells being developed for commercial applications. Of all the potential sources of hydrogen, natural gas offers many advantages. It is widely available, clean, and can be converted to hydrogen relatively easily. When catalytic steam reforming is used to generate hydrogen from natural gas, it is essential that sulfur compounds in the natural gas are removed upstream of the reformer and various types of desulfurisation processes are available. In addition, the quality of fuel required for each type of fuel cell varies according to the anode material used, and the cell temperature. Low temperature cells will not tolerate high concentrations of carbon monoxide, whereas the molten fuel cell (MCFC) and solid oxide fuel cell (SOFC) anodes contain nickel on which it is possible to electrochemically oxidise carbon monoxide directly. The ability to internally reform fuel gas is a feature of the MCFC and SOFC. Internal reforming can give benefits in terms of increased electrical efficiency owing to the reduction in the required cell cooling and therefore parasitic system losses. Direct electrocatalysis of hydrocarbon oxidation has been the elusive goal of fuel cell developers over many years and recent laboratory results are encouraging. This paper reviews the principal methods of converting natural gas into hydrogen, namely catalytic steam reforming, autothermic reforming, pyrolysis and partial oxidation; it reviews currently available purification techniques and discusses some recent advances in internal reforming and the direct use of natural gas in fuel cells.

Verrucomicrobia and their role in soil methanol consumption

NASA Astrophysics Data System (ADS)

Fierer, N.

2015-12-01

Bacteria belonging to the phylum Verrucomicrobia are far more ubiquitous and abundant in soil than previous work would suggest. In many soils, a relatively small number of verrucomicrobial phylotypes or 'species' can represent more than 25% of the bacterial cells in soil. Since these phylotypes are not closely related to any known cultured isolates or any strains for which we have whole-genome data, we have limited information on what these bacteria are actually doing in soil, their metabolic capabilities, or the niches they inhabit. We have recently assembled the genomes of these dominant Verrucomicrobia from soil metagenomic data and found that these taxa appear to be oligotrophs that specialize in methanol oxidation. This is important because we have found in previous work that methanol likely represents an important source of labile organic carbon to soil microbes in many ecosystems with methanol fluxes likely representing an important, but under-studied, mechanism by which organic carbon is transferred from surface litter layers to mineral soils. Ongoing work has focused on using high-throughput cultivation methods to study soil Verrucomicrobia in vitro and better understand their controls on soil carbon dynamics. Together this work demonstrates how we can leverage recent methodological advances in metagenomics, high-throughput cultivation, and soil trace gas analyses to understand the biogeochemical relevance of an abundant, but mysterious, group of soil microorganisms.

Feasibility of flare gas reformation to practical energy in Farashband gas refinery: no gas flaring.

PubMed

Rahimpour, Mohammad Reaza; Jokar, Seyyed Mohammad

2012-03-30

A suggested method for controlling the level of hazardous materials in the atmosphere is prevention of combustion in flare. In this work, three methods are proposed to recover flare gas instead of conventional gas-burning in flare at the Farashband gas refinery. These methods aim to minimize environmental and economical disadvantages of burning flare gas. The proposed methods are: (1) gas to liquid (GTL) production, (2) electricity generation with a gas turbine and, (3) compression and injection into the refinery pipelines. To find the most suitable method, the refinery units that send gas to the flare as well as the required equipment for the three aforementioned methods are simulated. These simulations determine the amount of flare gas, the number of GTL barrels, the power generated by the gas turbine and the required compression horsepower. The results of simulation show that 563 barrels/day of valuable GTL products is produced by the first method. The second method provides 25 MW electricity and the third method provides a compressed natural gas with 129 bar pressure for injection to the refinery pipelines. In addition, the economics of flare gas recovery methods are studied and compared. The results show that for the 4.176MMSCFD of gas flared from the Farashband gas refinery, the electricity production gives the highest rate of return (ROR), the lowest payback period, the highest annual profit and mild capital investment. Therefore, the electricity production is the superior method economically. Copyright © 2012 Elsevier B.V. All rights reserved.

An active micro-direct methanol fuel cell with self-circulation of fuel and built-in removal of CO 2 bubbles

NASA Astrophysics Data System (ADS)

Meng, Dennis Desheng; Kim, C. J.

As an alternative or supplement to small batteries, the much-anticipated micro-direct methanol fuel cell (μDMFC) faces several key technical issues such as methanol crossover, reactant delivery, and byproduct release. This paper addresses two of the issues, removal of CO 2 bubbles and delivery of methanol fuel, in a non-prohibitive way for system miniaturization. A recently reported bubble-driven pumping mechanism is applied to develop active μDMFCs free of an ancillary pump or a gas separator. The intrinsically generated CO 2 bubbles in the anodic microchannels are used to pump and circulate the liquid fuel before being promptly removed as a part of the pumping mechanism. Without a discrete liquid pump or gas separator, the widely known packaging penalty incurred within many micro-fuel-cell systems can be alleviated so that the system's power/energy density does not decrease dramatically as a result of miniaturization. Since the power required for pumping is provided by the byproduct of the fuel cell reaction, the parasitic power loss due to an external pump is also eliminated. The fuel circulation is visually confirmed, and the effectiveness for fuel cell applications is verified during continuous operation of a μDMFC for over 70 min with 1.2 mL of 2 M methanol. The same device was shown to operate for only 5 min if the pumping mechanism is disabled by blocking the gas venting membrane. Methanol consumption while utilizing the reported self-circulation mechanism is estimated to be 46%. Different from common pump-free fuel delivery approaches, the reported mechanism delivers the fuel actively and is independent of gravity.

HIGH EFFICIENCY SYNGAS GENERATION

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

Robert J. Copeland; Yevgenia Gershanovich; Brian Windecker

2005-02-01

This project investigated an efficient and low cost method of auto-thermally reforming natural gas to hydrogen and carbon monoxide. Reforming is the highest cost step in producing products such as methanol and Fisher Tropsch liquids (i.e., gas to liquids); and reducing the cost of reforming is the key to reducing the cost of these products. Steam reforming is expensive because of the high cost of the high nickel alloy reforming tubes (i.e., indirectly fired reforming tubes). Conventional auto-thermal or Partial Oxidation (POX) reforming minimizes the size and cost of the reformers and provides a near optimum mixture of CO andmore » hydrogen. However POX requires pure oxygen, which consumes power and significantly increases the cost to reforming. Our high efficiency process extracts oxygen from low-pressure air with novel oxygen sorbent and transfers the oxygen to a nickel-catalyzed reformer. The syngas is generated at process pressure (typically 20 to 40 bar) without nitrogen dilution and has a 1CO to 2H{sub 2} ratio that is near optimum for the subsequent production of Fisher-Tropsch liquid to liquids and other chemicals (i.e., Gas to Liquids, GTL). Our high process efficiency comes from the way we transfer the oxygen into the reformer. All of the components of the process, except for the oxygen sorbent, are commonly used in commercial practice. A process based on a longlived, regenerable, oxygen transfer sorbent could substantially reduce the cost of natural gas reforming to syngas. Lower cost syngas (CO + 2H{sub 2}) that is the feedstock for GTL would reduce the cost of GTL and for other commercial applications (e.g., methanol, other organic chemicals). The vast gas resources of Alaska's North Slope (ANS) offer more than 22 Tcf of gas and GTL production in this application alone, and could account for as much as 300,000 to 700,000 bpd for 20 to 30+ years. We developed a new sorbent, which is an essential part of the High Efficiency Oxygen Process (HOP). We

Vapor permeation-stepwise injection simultaneous determination of methanol and ethanol in biodiesel with voltammetric detection.

PubMed

Shishov, Andrey; Penkova, Anastasia; Zabrodin, Andrey; Nikolaev, Konstantin; Dmitrenko, Maria; Ermakov, Sergey; Bulatov, Andrey

2016-02-01

A novel vapor permeation-stepwise injection (VP-SWI) method for the determination of methanol and ethanol in biodiesel samples is discussed. In the current study, stepwise injection analysis was successfully combined with voltammetric detection and vapor permeation. This method is based on the separation of methanol and ethanol from a sample using a vapor permeation module (VPM) with a selective polymer membrane based on poly(phenylene isophtalamide) (PA) containing high amounts of a residual solvent. After the evaporation into the headspace of the VPM, methanol and ethanol were transported, by gas bubbling, through a PA membrane to a mixing chamber equipped with a voltammetric detector. Ethanol was selectively detected at +0.19 V, and both compounds were detected at +1.20 V. Current subtractions (using a correction factor) were used for the selective determination of methanol. A linear range between 0.05 and 0.5% (m/m) was established for each analyte. The limits of detection were estimated at 0.02% (m/m) for ethanol and methanol. The sample throughput was 5 samples h(-1). The method was successfully applied to the analysis of biodiesel samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Acute methanol toxicity in minipigs

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

Dorman, D.C.; Dye, J.A.; Nassise, M.P.

1993-01-01

The pig has been proposed as a potential animal model for methanol-induced neuro-ocular toxicosis in humans because of its low liver tetrahydrofolate levels and slower rate of formate metabolism compared to those of humans. To examine the validity of this animal model, 12 4-month-old female minipigs (minipig YU) were given a single oral dose of water or methanol at 1.0, 2.5, or 5.0 g/kg body wt by gavage (n = 3 pigs/dose). Dose-dependent signs of acute methanol intoxication, which included mild CNS depression, tremors, ataxia, and recumbency, developed within 0.5 to 2.0 hr, and resolved by 52 hr. Methanol- andmore » formate-dosed pigs did not develop optic nerve lesions, toxicologically significant formate accumulation, or metabolic acidosis. Based on results following a single dose, female minipigs do not appear to be overtly sensitive to methanol and thus may not be a suitable animal model for acute methanol-induced neuroocular toxicosis.« less

Oxygen sensor for monitoring gas mixtures containing hydrocarbons

DOEpatents

Ruka, Roswell J.; Basel, Richard A.

1996-01-01

A gas sensor measures O.sub.2 content of a reformable monitored gas containing hydrocarbons H.sub.2 O and/or CO.sub.2, preferably in association with an electrochemical power generation system. The gas sensor has a housing communicating with the monitored gas environment and carries the monitored gas through an integral catalytic hydrocarbon reforming chamber containing a reforming catalyst, and over a solid electrolyte electrochemical cell used for sensing purposes. The electrochemical cell includes a solid electrolyte between a sensor electrode that is exposed to the monitored gas, and a reference electrode that is isolated in the housing from the monitored gas and is exposed to a reference gas environment. A heating element is also provided in heat transfer communication with the gas sensor. A circuit that can include controls operable to adjust operations via valves or the like is connected between the sensor electrode and the reference electrode to process the electrical signal developed by the electrochemical cell. The electrical signal varies as a measure of the equilibrium oxygen partial pressure of the monitored gas. Signal noise is effectively reduced by maintaining a constant temperature in the area of the electrochemical cell and providing a monitored gas at chemical equilibria when contacting the electrochemical cell. The output gas from the electrochemical cell of the sensor is fed back into the conduits of the power generating system.

Oxygen sensor for monitoring gas mixtures containing hydrocarbons

DOEpatents

Ruka, R.J.; Basel, R.A.

1996-03-12

A gas sensor measures O{sub 2} content of a reformable monitored gas containing hydrocarbons, H{sub 2}O and/or CO{sub 2}, preferably in association with an electrochemical power generation system. The gas sensor has a housing communicating with the monitored gas environment and carries the monitored gas through an integral catalytic hydrocarbon reforming chamber containing a reforming catalyst, and over a solid electrolyte electrochemical cell used for sensing purposes. The electrochemical cell includes a solid electrolyte between a sensor electrode that is exposed to the monitored gas, and a reference electrode that is isolated in the housing from the monitored gas and is exposed to a reference gas environment. A heating element is also provided in heat transfer communication with the gas sensor. A circuit that can include controls operable to adjust operations via valves or the like is connected between the sensor electrode and the reference electrode to process the electrical signal developed by the electrochemical cell. The electrical signal varies as a measure of the equilibrium oxygen partial pressure of the monitored gas. Signal noise is effectively reduced by maintaining a constant temperature in the area of the electrochemical cell and providing a monitored gas at chemical equilibria when contacting the electrochemical cell. The output gas from the electrochemical cell of the sensor is fed back into the conduits of the power generating system. 4 figs.

Method of dehydrating natural gas

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

Wells, R. E.

1985-01-01

A method for dehydration of natural gas is provided wherein well head gas is supplied to a three-phase inlet separator, the vapor mixture of natural gas and water removed from that inlet separator means is supplied to a turboexpander, and the resulting refrigerated mixture of natural gas and condensed water vapor is supplied to a multi-phase outlet separator. The turboexpander may have integral means for subsequent compression of the refrigerated mixture and may be coupled through reduction gears to a means for generating electricity. A portion of the refrigerated mixture may be connected to a heat exchanger for cooling themore » well head natural gas prior to entry into the inlet separator. The flow of refrigerated mixture to this heat exchanger may be controlled by a temperature sensitive valve downstream of the heat exchanger. Methanol may be injected into the vapor mixture prior to entry into the turboexpander. The flow of methanol into the vapor mixture may be controlled by a valve sensitive to the flow rate of the vapor mixture and the water vapor content of the refrigerated mixture. Natural gas vapor from the outlet separator may be recirculated through the turboexpander if the output water vapor content of the natural gas vapor stream is too high.« less

Hydrogen bond dynamics of superheated water and methanol by ultrafast IR-pump and EUV-photoelectron probe spectroscopy.

PubMed

Vöhringer-Martinez, E; Link, O; Lugovoy, E; Siefermann, K R; Wiederschein, F; Grubmüller, H; Abel, B

2014-09-28

Supercritical water and methanol have recently drawn much attention in the field of green chemistry. It is crucial to an understanding of supercritical solvents to know their dynamics and to what extent hydrogen (H) bonds persist in these fluids. Here, we show that with femtosecond infrared (IR) laser pulses water and methanol can be heated to temperatures near and above their critical temperature Tc and their molecular dynamics can be studied via ultrafast photoelectron spectroscopy at liquid jet interfaces with high harmonics radiation. As opposed to previous studies, the main focus here is the comparison between the hydrogen bonded systems of methanol and water and their interpretation by theory. Superheated water initially forms a dense hot phase with spectral features resembling those of monomers in gas phase water. On longer timescales, this phase was found to build hot aggregates, whose size increases as a function of time. In contrast, methanol heated to temperatures near Tc initially forms a broad distribution of aggregate sizes and some gas. These experimental features are also found and analyzed in extended molecular dynamics simulations. Additionally, the simulations enabled us to relate the origin of the different behavior of these two hydrogen-bonded liquids to the nature of the intermolecular potentials. The combined experimental and theoretical approach delivers new insights into both superheated phases and may contribute to understand their different chemical reactivities.

Solar Reforming of Carbon Dioxide to Produce Diesel Fuel

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

Dennis Schuetzle; Robert Schuetzle

2010-12-31

This project focused on the demonstration of an innovative technology, referred to as the Sunexus CO2 Solar Reformer, which utilizes waste CO2 as a feedstock for the efficient and economical production of synthetic diesel fuel using solar thermal energy as the primary energy input. The Sunexus technology employs a two stage process for the conversion of CO2 to diesel fuel. A solar reforming system, including a specially designed reactor and proprietary CO2 reforming catalyst, was developed and used to convert captured CO2 rich gas streams into syngas (primarily hydrogen and carbon monoxide) using concentrated solar energy at high conversion efficiencies.more » The second stage of the system (which has been demonstrated under other funding) involves the direct conversion of the syngas into synthetic diesel fuel using a proprietary catalyst (Terra) previously developed and validated by Pacific Renewable Fuels and Chemicals (PRFC). The overall system energy efficiency for conversion of CO2 to diesel fuel is 74%, due to the use of solar energy. The results herein describe modeling, design, construction, and testing of the Sunexus CO2 Solar Reformer. Extensive parametric testing of the solar reformer and candidate catalysts was conducted and chemical kinetic models were developed. Laboratory testing of the Solar Reformer was successfully completed using various gas mixtures, temperatures, and gas flow rates/space velocities to establish performance metrics which can be employed for the design of commercial plants. A variety of laboratory tests were conducted including dry reforming (CO2 and CH{sub 4}), combination dry/steam reforming (CO2, CH{sub 4} & H{sub 2}O), and tri-reforming (CO2, CH{sub 4}, H{sub 2}O & O{sub 2}). CH{sub 4} and CO2 conversions averaged 95-100% and 50-90% per reformer cycle, respectively, depending upon the temperatures and gas space velocities. No formation of carbon deposits (coking) on the catalyst was observed in any of these tests. A 16 ft

Toluene, Methanol and Benzaldehyde Removal from Gas Streams by Adsorption onto Natural Clay and Faujasite-Y type Zeolite.

PubMed

Zaitan, Hicham; Mohamed, Elham F; Valdés, Héctor; Nawdali, Mostafa; Rafqah, Salah; Manero, Marie Hélène

2016-12-01

A great number of pollution problems come as a result of the emission of Volatile Organic Compounds (VOCs) into the environment and their control becomes a serious challenge for the global chemical industry. Adsorption is a widely used technique for the removal of VOCs due to its high efficiency, low cost, and convenient operation. In this study, the feasibility to use a locally available clay, as adsorbent material to control VOCs emissions is evaluated. Natural clay is characterised by different physical-chemical methods and adsorptive interaction features between VOCs and natural clay are identified. Toluene (T), methanol (M) and benzaldehyde (B) are used here as representatives of three different kinds of VOCs. Adsorption isotherms onto natural clay and faujasite-Y type zeolite (Fau Y) are obtained at room temperature. According to Langmuir model data, maximum adsorption capacities (qm) of Fez natural clay and zeolite toward methanol (M), toluene (T) and benzaldehyde (B) at 300 K are 8, 0.89 and 3.1 mmol g-1, and 15, 1.91 and 13.9 mmol g-1 respectively. In addition, the effect of temperature on the adsorption of toluene onto natural clay is evaluated in the range from 300 to 323K. An increase on temperature reduces the adsorption capacity of natural clay toward toluene, indicating that an exothermic physical adsorption process takes place. The enthalpy of adsorption of toluene onto Fez natural clay was found to be -54 kJ mol-1. A preliminary cost analysis shows that natural clay could be used as an alternative low cost adsorbent in the control of VOCs from contaminated gas streams with a cost of US$ 0.02 kg-1 compared to Fau Y zeolite with US$ 10 kg-1.

An afterburner-powered methane/steam reformer for a solid oxide fuel cells application

NASA Astrophysics Data System (ADS)

Mozdzierz, Marcin; Chalusiak, Maciej; Kimijima, Shinji; Szmyd, Janusz S.; Brus, Grzegorz

2018-04-01

Solid oxide fuel cell (SOFC) systems can be fueled by natural gas when the reforming reaction is conducted in a stack. Due to its maturity and safety, indirect internal reforming is usually used. A strong endothermic methane/steam reforming process needs a large amount of heat, and it is convenient to provide thermal energy by burning the remainders of fuel from a cell. In this work, the mathematical model of afterburner-powered methane/steam reformer is proposed. To analyze the effect of a fuel composition on SOFC performance, the zero-dimensional model of a fuel cell connected with a reformer is formulated. It is shown that the highest efficiency of a solid oxide fuel cell is achieved when the steam-to-methane ratio at the reforming reactor inlet is high.

THE EXCHANGE OF DEUTERIUM WITH METHANOL OVER RANEY NICKEL CATALYST AND THE EFFECT OF CERTAIN NITRO COMPOUNDS UPON THE EXCHANGE

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

Smith, H.A.; Stewart, B.B.

Deuterium gas exchanges slowly with liquid methanol over Raney nickel catalyst at 35 deg . The reaction is zero order with respect to deuterium pressure and has a low activation energy. The influences of catalyst weight, catalyst treatment, and of the presence of certain nitro compounds were studied. Since active Raney nickel can liberate hydrogen directly, a method for determining the origin of hydrogen which undergoes exchange with the deuterium gas was developed. It was shown that the exchanged hydrogen does originate from the hydroxyl hydrogen of methanol. The results are discussed in the light of the mechanism of catalyticmore » exchange and catalytic hydrogenation reactions. (auth)« less

Proton exchange membrane materials for the advancement of direct methanol fuel-cell technology

DOEpatents

Cornelius, Christopher J [Albuquerque, NM

2006-04-04

A new class of hybrid organic-inorganic materials, and methods of synthesis, that can be used as a proton exchange membrane in a direct methanol fuel cell. In contrast with Nafion.RTM. PEM materials, which have random sulfonation, the new class of materials have ordered sulfonation achieved through self-assembly of alternating polyimide segments of different molecular weights comprising, for example, highly sulfonated hydrophilic PDA-DASA polyimide segment alternating with an unsulfonated hydrophobic 6FDA-DAS polyimide segment. An inorganic phase, e.g., 0.5 5 wt % TEOS, can be incorporated in the sulfonated polyimide copolymer to further improve its properties. The new materials exhibit reduced swelling when exposed to water, increased thermal stability, and decreased O.sub.2 and H.sub.2 gas permeability, while retaining proton conductivities similar to Nafion.RTM.. These improved properties may allow direct methanol fuel cells to operate at higher temperatures and with higher efficiencies due to reduced methanol crossover.

Structural and thermodynamic properties of the Cm III ion solvated by water and methanol

DOE PAGES

Kelley, Morgan P.; Yang, Ping; Clark, Sue B.; ...

2016-04-27

The geometric and electronic structures of the 9-coordinate Cm 3+ ion solvated with both water and methanol are systematically investigated in the gas phase at each possible solvent-shell composition and configuration using density functional theory and second-order Møller–Plesset perturbation theory. Ab initio molecular dynamics simulations are employed to assess the effects of second and third solvent shells on the gas-phase structure. The ion–solvent dissociation energy for methanol is greater than that of water, potentially because of increased charge donation to the ion made possible by the electron-rich methyl group. Further, the ion–solvent dissociation energy and the ion–solvent distance are shownmore » to be dependent on the solvent-shell composition. Furthermore, this has implications for solvent exchange, which is generally the rate-limiting step in complexation reactions utilized in the separation of curium from complex metal mixtures that derive from the advanced nuclear fuel cycle.« less

Thermodynamics of R-(+)-2-(4-Hydroxyphenoxy)propanoic Acid Dissolution in Methanol, Ethanol, and Methanol-Ethanol Mixture

NASA Astrophysics Data System (ADS)

Liu, Wei; Ma, Jinju; Yao, Xinding; Fang, Ruina; Cheng, Liang

2018-05-01

The solubilities of R-(+)-2-(4-hydroxyphenoxy)propanoic acid (D-HPPA) in methanol, ethanol and various methanol-ethanol mixtures are determined in the temperature range from 273.15 to 323.15 K at atmospheric pressure using a laser detecting system. The solubilities of D-HPPA increase with increasing mole fraction of ethanol in the methanol-ethanol mixtures. Experimental data were correlated with Buchowski-Ksiazczak λ h equation and modified Apelblat equation; the first one gives better approximation for the experimental results. The enthalpy, entropy and Gibbs free energy of D-HPPA dissolution in methanol, ethanol and methanol-ethanol mixtures were also calculated from the solubility data.

Temporal and spatial variations in rainwater methanol

NASA Astrophysics Data System (ADS)

Felix, J. D.; Jones, S. B.; Avery, G. B.; Willey, J. D.; Mead, R. N.; Kieber, R. J.

2014-01-01

This work reports the first detailed analysis of methanol concentrations in rainwater. Methanol concentrations measured in 49 rain events collected between 28 August 2007 to 10 July 2008 in Wilmington, NC, USA, ranged from below the detection limit of 6 nM to 9.3 μM with a volume weighted average concentration of 1.2 ± 0.2 μM. Methanol concentrations in rainwater were up to ~200× greater than concentrations observed in marine waters indicating wet deposition as a potential significant source to marine waters. Assuming these methanol concentrations are an appropriate proxy for global methanol rainwater concentrations the global methanol wet deposition sink is estimated as 20 Tg yr-1 which implies previous methanol budgets underestimate removal by precipitation. Methanol concentrations did not correlate with H+, NO3-, and NSS, which suggest that the dominant source of the alcohol to rainwater is not anthropogenic. However, methanol concentrations were strongly correlated with acetaldehyde which has a primarily biogenic input. Methanol volume weighted concentration during the growing season (1.5 + 0.3 μM) was more than double that of the non-growing season (0.7 + 0.1 μM), further promoting biogenic emissions as the primary cause of fluctuating methanol concentrations. Methanol concentrations peaked in rainwater collected between the time period 12:00-06:00 p.m. Peaking during this period of optimal sunlight implies a direct relationship to photochemical methanol production but there are also increases in biogenic activity during this time period. Rain events with terrestrial origins had higher concentrations than those of marine origin demonstrating the significance of the continental source of methanol in rainwater.

First Detection of Methanol in a Class O Protostellar Disk

NASA Technical Reports Server (NTRS)

Velusamy, T.; Langer, William D.; Goldsmith, Paul F.

2000-01-01

We report the detection of emission from methanol in a compact source coincident with the position of the L1157 infrared source, which we attribute to molecules in the disk surrounding this young, Class O protostellar object. In addition, we identify a spectral feature in the outflow corresponding to an ethanol transition. Using the Caltech Owens Valley Millimeter Array with a synthesized beam size of 2", we detect spatially unresolved methanol in the 2(sub k) - 1(sub k) transitions at 3mm, which is coincident in position with the peak of the continuum emission. The gas phase methanol could be located in the central region (< 100 AU radius) of a flat disk, or in an extended heated surface layer (approx. 200 AU radius) of a flared disk. The fractional abundance of methanol X(CH3OH) is approx. 2 x l0(exp -8) in the flat disk model, and 3 x l0(exp -7) for the flared disk. The fractional abundance is small in the disk as a whole, but considerably larger in the warm portions. This difference indicates that substantial chemical processing probably takes place in the disk via depletion and desorption. The methanol desorbed from the grains in the warm surface layers returns to the icy grain mantles in the cooler interior of the disk, where it is available to become part of the composition of solar system-like bodies, such as comets, formed in the outer circumstellar region. This first millimeter-wavelength detection of a complex organic molecule in a young protostellar disk has implications for disk structure and chemical evolution and for potential use as a temperature probe. The research of TV and WL was conducted at the Jet Propulsion Laboratory, California Institute of Technology with support from the National Aeronautics and Space Administration.

Gradients in microbial methanol uptake: productive coastal upwelling waters to oligotrophic gyres in the Atlantic Ocean

PubMed Central

Dixon, Joanna L; Sargeant, Stephanie; Nightingale, Philip D; Colin Murrell, J

2013-01-01

Methanol biogeochemistry and its importance as a carbon source in seawater is relatively unexplored. We report the first microbial methanol carbon assimilation rates (k) in productive coastal upwelling waters of up to 0.117±0.002 d−1 (∼10 nmol l−1 d−1). On average, coastal upwelling waters were 11 times greater than open ocean northern temperate (NT) waters, eight times greater than gyre waters and four times greater than equatorial upwelling (EU) waters; suggesting that all upwelling waters upon reaching the surface (⩽20 m), contain a microbial population that uses a relatively high amount of carbon (0.3–10 nmol l−1 d−1), derived from methanol, to support their growth. In open ocean Atlantic regions, microbial uptake of methanol into biomass was significantly lower, ranging between 0.04–0.68 nmol l−1 d−1. Microbes in the Mauritanian coastal upwelling used up to 57% of the total methanol for assimilation of the carbon into cells, compared with an average of 12% in the EU, and 1% in NT and gyre waters. Several methylotrophic bacterial species were identified from open ocean Atlantic waters using PCR amplification of mxaF encoding methanol dehydrogenase, the key enzyme in bacterial methanol oxidation. These included Methylophaga sp., Burkholderiales sp., Methylococcaceae sp., Ancylobacter aquaticus, Paracoccus denitrificans, Methylophilus methylotrophus, Methylobacterium oryzae, Hyphomicrobium sp. and Methylosulfonomonas methylovora. Statistically significant correlations for upwelling waters between methanol uptake into cells and both chlorophyll a concentrations and methanol oxidation rates suggest that remotely sensed chlorophyll a images, in these productive areas, could be used to derive total methanol biological loss rates, a useful tool for atmospheric and marine climatically active gas modellers, and air–sea exchange scientists. PMID:23178665

Hydrogen production by steam reforming of liquefied natural gas over a nickel catalyst supported on mesoporous alumina xerogel

NASA Astrophysics Data System (ADS)

Seo, Jeong Gil; Youn, Min Hye; Cho, Kyung Min; Park, Sunyoung; Song, In Kyu

Mesoporous alumina xerogel (A-SG) is prepared by a sol-gel method for use as a support for a nickel catalyst. The Ni/A-SG catalyst is then prepared by an impregnation method, and is applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of the mesoporous alumina xerogel support on the catalytic performance of Ni/A-SG catalyst is investigated. For the purpose of comparison, a nickel catalyst supported on commercial alumina (A-C) is also prepared by an impregnation method (Ni/A-C). Both the hydroxyl-rich surface and the electron-deficient sites of the A-SG support enhance the dispersion of the nickel species on the support during the calcination step. The formation of the surface nickel aluminate phase in the Ni/A-SG catalyst remarkably increases the reducibility and stability of the catalyst. Furthermore, the high-surface area and the well-developed mesoporosity of the Ni/A-SG catalyst enhance the gasification of surface hydrocarbons that are adsorbed in the reaction. In the steam reforming of LNG, the Ni/A-SG catalyst exhibits a better catalytic performance than the Ni/A-C catalyst in terms of LNG conversion and hydrogen production. Moreover, the Ni/A-SG catalyst shows strong resistance toward catalyst deactivation.

Determination of formic acid tissue and fluid concentrations in three fatalities due to methanol poisoning.

PubMed

Hantson, P; Haufroid, V; Mahieu, P

2000-12-01

Three fatalities caused by methanol ingestion are reported. Admission blood methanol concentrations ranged from 0.28 to 4.6 g/L. Two patients had been admitted after a significant delay (>20 hours), and one patient was observed within 90 minutes following ingestion. Formic acid levels were determined in blood samples at admission and ranged from 302 to 680 mg/L. The patients died 44, 55, and 82 hours after poisoning. Formic acid determinations in postmortem tissues were performed by a gas chromatograph method. The authors found great variability in formic acid distribution among the patients and among organs.

Catalytic performance of heterogeneous Rh/C3N4 for the carbonylation of methanol

NASA Astrophysics Data System (ADS)

Budiman, Anatta Wahyu; Choi, Myoung Jae; Nur, Adrian

2018-02-01

The excess of water in homogeneous the carbonylation of methanol system could increase the amount of by-products formed through water-gas shift reaction and could accelerate the rusting of equipment. Many scientists tried to decrease the content of water in the carbonylation of methanol system by using lithium and iodide promoter that results a moderate catalytic activity in the water content at 2wt%. The heterogenized catalyst offers several distinct advantages such as it was enables increased catalyst concentration in the reaction mixture, which is directly proportional to acetic acid production rate, without the addition of an alkali iodide salt promoter. The heterogeneous catalyst also results in reduced by-product formation. This study is aimed to produce a novel catalyst (Rh/C3N4) with a high selectivity of acetic acid in a relatively lower water and halide content. This novel catalyst performs high conversion and selectivity of acetic acid as the result of the strong ionic bonding of melamine and rhodium complex species that was caused by the presence of methyl iodide species. The CO2 in feed gas significantly decreases the catalytic activity of Rh-melamine because of its inert characteristics. The kinetic test was performed as that the first order kinetic equation. The kinetic tests revealed the reaction route of the the carbonylation of methanol in this system was performed trough the methyl acetate.

Catalytic Steam and Partial Oxidation Reforming of Liquid Fuels for Application in Improving the Efficiency of Internal Combustion Engines

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

Brookshear, Daniel William; Pihl, Josh A.; Szybist, James P.

Here, this study investigated the potential for catalytically reforming liquid fuels in a simulated exhaust gas recirculation (EGR) mixture loop for the purpose of generating reformate that could be used to increase stoichiometric combustion engine efficiency. The experiments were performed on a simulated exhaust flow reactor using a Rh/Al 2O 3 reformer catalyst, and the fuels evaluated included iso-octane, ethanol, and gasoline. Both steam reforming and partial oxidation reforming were examined as routes for the production of reformate. Steam reforming was determined to be an ineffective option for reforming in an EGR loop, because of the high exhaust temperatures (inmore » excess of 700 °C) required to produce adequate concentrations of reformate, regardless of fuel. However, partial oxidation reforming is capable of producing hydrogen concentrations as high as 10%–16%, depending on fuel and operating conditions in the simulated EGR gas mixture. Meanwhile, measurements of total fuel enthalpy retention were shown to have favorable energetics under a range of conditions, although a tradeoff between fuel enthalpy retention and reformate production was observed. Of the three fuels evaluated, iso-octane exhibited the best overall performance, followed by ethanol and then gasoline. Overall, it was found that partial oxidation reforming of liquid fuels in a simulated EGR mixture over the Rh/Al 2O 3 catalyst demonstrated sufficiently high reformate yields and favorable energetics to warrant further evaluation in the EGR system of a stoichiometric combustion engine.« less

Catalytic Steam and Partial Oxidation Reforming of Liquid Fuels for Application in Improving the Efficiency of Internal Combustion Engines

DOE PAGES

Brookshear, Daniel William; Pihl, Josh A.; Szybist, James P.

2018-02-07

Here, this study investigated the potential for catalytically reforming liquid fuels in a simulated exhaust gas recirculation (EGR) mixture loop for the purpose of generating reformate that could be used to increase stoichiometric combustion engine efficiency. The experiments were performed on a simulated exhaust flow reactor using a Rh/Al 2O 3 reformer catalyst, and the fuels evaluated included iso-octane, ethanol, and gasoline. Both steam reforming and partial oxidation reforming were examined as routes for the production of reformate. Steam reforming was determined to be an ineffective option for reforming in an EGR loop, because of the high exhaust temperatures (inmore » excess of 700 °C) required to produce adequate concentrations of reformate, regardless of fuel. However, partial oxidation reforming is capable of producing hydrogen concentrations as high as 10%–16%, depending on fuel and operating conditions in the simulated EGR gas mixture. Meanwhile, measurements of total fuel enthalpy retention were shown to have favorable energetics under a range of conditions, although a tradeoff between fuel enthalpy retention and reformate production was observed. Of the three fuels evaluated, iso-octane exhibited the best overall performance, followed by ethanol and then gasoline. Overall, it was found that partial oxidation reforming of liquid fuels in a simulated EGR mixture over the Rh/Al 2O 3 catalyst demonstrated sufficiently high reformate yields and favorable energetics to warrant further evaluation in the EGR system of a stoichiometric combustion engine.« less

Hydrogen-bonded ring closing and opening of protonated methanol clusters H(+)(CH3OH)(n) (n = 4-8) with the inert gas tagging.

PubMed

Li, Ying-Cheng; Hamashima, Toru; Yamazaki, Ryoko; Kobayashi, Tomohiro; Suzuki, Yuta; Mizuse, Kenta; Fujii, Asuka; Kuo, Jer-Lai

2015-09-14

The preferential hydrogen bond (H-bond) structures of protonated methanol clusters, H(+)(MeOH)n, in the size range of n = 4-8, were studied by size-selective infrared (IR) spectroscopy in conjunction with density functional theory calculations. The IR spectra of bare clusters were compared with those with the inert gas tagging by Ar, Ne, and N2, and remarkable changes in the isomer distribution with the tagging were found for clusters with n≥ 5. The temperature dependence of the isomer distribution of the clusters was calculated by the quantum harmonic superposition approach. The observed spectral changes with the tagging were well interpreted by the fall of the cluster temperature with the tagging, which causes the transfer of the isomer distribution from the open and flexible H-bond network types to the closed and rigid ones. Anomalous isomer distribution with the tagging, which has been recently found for protonated water clusters, was also found for H(+)(MeOH)5. The origin of the anomaly was examined by the experiments on its carrier gas dependence.

Hydrogen and methanol exchange processes for (TMP)Rh-OCH3(CH3OH) in binary solutions of methanol and benzene.

PubMed

Sarkar, Sounak; Li, Shan; Wayland, Bradford B

2011-04-18

Tetramesityl porphinato rhodium(III) methoxide ((TMP)Rh-OCH(3)) binds with methanol in benzene to form a 1:1 methanol complex ((TMP)Rh-OCH(3)(CH(3)OH)) (1). Dynamic processes are observed to occur for the rhodium(III) methoxide methanol complex (1) that involve both hydrogen and methanol exchange. Hydrogen exchange between coordinated methanol and methoxide through methanol in solution results in an interchange of the environments for the non-equivalent porphyrin faces that contain methoxide and methanol ligands. Interchange of the environments of the coordinated methanol and methoxide sites in 1 produces interchange of the inequivalent mesityl o-CH(3) groups, but methanol ligand exchange occurs on one face of the porphyrin and the mesityl o-CH(3) groups remain inequivalent. Rate constants for dynamic processes are evaluated by full line shape analysis for the (1)H NMR of the mesityl o-CH(3) and high field methyl resonances of coordinated methanol and methoxide groups in 1. The rate constant for interchange of the inequivalent porphyrin faces is associated with hydrogen exchange between 1 and methanol in solution and is observed to increase regularly with the increase in the mole fraction of methanol. The rate constant for methanol ligand exchange between 1 and the solution varies with the solution composition and fluctuates in a manner that parallels the change in the activation energy for methanol diffusion which is a consequence of solution non-ideality from hydrogen bonded clusters.

Selective anaerobic oxidation of methane enables direct synthesis of methanol.

PubMed

Sushkevich, Vitaly L; Palagin, Dennis; Ranocchiari, Marco; van Bokhoven, Jeroen A

2017-05-05

Direct functionalization of methane in natural gas remains a key challenge. We present a direct stepwise method for converting methane into methanol with high selectivity (~97%) over a copper-containing zeolite, based on partial oxidation with water. The activation in helium at 673 kelvin (K), followed by consecutive catalyst exposures to 7 bars of methane and then water at 473 K, consistently produced 0.204 mole of CH 3 OH per mole of copper in zeolite. Isotopic labeling confirmed water as the source of oxygen to regenerate the zeolite active centers and renders methanol desorption energetically favorable. On the basis of in situ x-ray absorption spectroscopy, infrared spectroscopy, and density functional theory calculations, we propose a mechanism involving methane oxidation at Cu II oxide active centers, followed by Cu I reoxidation by water with concurrent formation of hydrogen. Copyright © 2017, American Association for the Advancement of Science.

Fatal methanol poisoning: features of liver histopathology.

PubMed

Akhgari, Maryam; Panahianpour, Mohammad Hadi; Bazmi, Elham; Etemadi-Aleagha, Afshar; Mahdavi, Amirhosein; Nazari, Saeed Hashemi

2013-03-01

Methanol poisoning has become a considerable problem in Iran. Liver can show some features of poisoning after methanol ingestion. Therefore, our concern was to examine liver tissue histopathology in fatal methanol poisoning cases in Iranian population. In this study, 44 cases of fatal methanol poisoning were identified in a year. The histological changes of the liver were reviewed. The most striking features of liver damage by light microscopy were micro-vesicular steatosis, macro-vesicular steatosis, focal hepatocyte necrosis, mild intra-hepatocyte bile stasis, feathery degeneration and hydropic degeneration. Blood and vitreous humor methanol concentrations were examined to confirm the proposed history of methanol poisoning. The majority of cases were men (86.36%). In conclusion, methanol poisoning can cause histological changes in liver tissues. Most importantly in cases with mean blood and vitreous humor methanol levels greater than 127 ± 38.9 mg/dL more than one pathologic features were detected.

Thz and Long Path Fourier Transform Spectroscopy of Methanol; Torsionally Coupled High-K Levels

NASA Astrophysics Data System (ADS)

Pearson, John C.; Yu, Shanshan; Drouin, Brian J.; Lees, Ronald M.; Xu, Li-Hong; Billinghurst, Brant E.

2012-06-01

Methanol is nearly ubiquitous in the interstellar gas. The presence of both a-type and b-type dipole moments, asymmetry, and internal rotation assure that any small astronomical observation window will contain multiple methanol transitions. This often allows a great deal about the local physical conditions to be deduced, but only insofar as the spectra are characterized. The Herschel Space Observatory has detected numerous, clearly beam diluted, methanol transitions with quanta surpassing J = 35 in many regions. Unfortunately, observations of methanol often display strong non-thermal behavior whose modeling requires many additional levels to be included in a radiative transfer analysis. Additionally, the intensities of many more highly excited transitions are strongly dependent on the accuracy of the wave functions used in the calculation. We report a combined Fourier Transform Infrared and THz study targeting the high J and K transitions in the ground torsional manifold. Microwave accuracy energy levels have been derived to J > 40 and K as high as 20. These levels illuminate a number of strongly resonant torsional interactions that dominate the high K spectrum of the molecule. Comparison with levels calculated from the rho-axis method Hamiltonian suggest that the rho-axis method should be able to model v_t = 0, 1 and probably v_t = 2 to experimental accuracy. The challenges in determining methanol wave functions to experimental accuracy will be discussed.

Solar central receiver reformer system for ammonia plants

NASA Astrophysics Data System (ADS)

1980-07-01

Details of the conceptual design, economic analysis, and development plan for a solar central receiver system for retrofitting the Valley Nitrogen Producers, Inc., El Centro, California 600 ST/SD Ammonia Plant are presented. The retrofit system consists of a solar central receiver reformer (SCRR) operating in parallel with the existing fossil fired reformer. Steam and hydrocarbon react in the catalyst filled tubes of the inner cavity receiver to form a hydrogen rich mixture which is the syngas feed for the ammonia production. The SCRR system displaces natural gas presently used in the fossil reformer combustion chamber. The solar reformer retrofit system characteristics and its interface with the existing plant are simple, incorporating state of the art components with proven technology. A northfield composed of one thousand forty second generation heliostats provides solar energy to the receiver which is positioned on top of a 90 meter high steel tower. The overall economics of this system can provide over 20% discount cash flow rate of return with proper investment and market conditions.

Compact hydrogen production systems for solid polymer fuel cells

NASA Astrophysics Data System (ADS)

Ledjeff-Hey, K.; Formanski, V.; Kalk, Th.; Roes, J.

Generally there are several ways to produce hydrogen gas from carbonaceous fuels like natural gas, oil or alcohols. Most of these processes are designed for large-scale industrial production and are not suitable for a compact hydrogen production system (CHYPS) in the power range of 1 kW. In order to supply solid polymer fuel cells (SPFC) with hydrogen, a compact fuel processor is required for mobile applications. The produced hydrogen-rich gas has to have a low level of harmful impurities; in particular the carbon monoxide content has to be lower than 20 ppmv. Integrating the reaction step, the gas purification and the heat supply leads to small-scale hydrogen production systems. The steam reforming of methanol is feasible at copper catalysts in a low temperature range of 200-350°C. The combination of a small-scale methanol reformer and a metal membrane as purification step forms a compact system producing high-purity hydrogen. The generation of a SPFC hydrogen fuel gas can also be performed by thermal or catalytic cracking of liquid hydrocarbons such as propane. At a temperature of 900°C the decomposition of propane into carbon and hydrogen takes place. A fuel processor based on this simple concept produces a gas stream with a hydrogen content of more than 90 vol.% and without CO and CO2.

Determination of Methanol Concentrations in Traditional Herbal Waters of Different Brands in Iran

PubMed Central

Mousavi, Seyed Reza; Namaei-Ghassemi, Mohssen; Layegh, Massomeh; AfzalAghaee, Monavar; vafaee, Manssoreh; Zare, Gholamali; Moghiman, Toktam; Mood, Mahdi Balali

2011-01-01

Objective(s) Herbal waters are extensively used in most parts of including . Visiting a patient with total blindness due to daily ingestion of around 200 ml of herbal water (Plant forty water) per day for six months was the rational for methanol determination in all herbal waters available in markets. Materials and Methods A total of two hundred and nineteen bottles of herbal waters were randomly bought from market. Methanol concentration was determined by gas chromatography, using a Flame Ionized Detector. Benzene (1000 mg/l) was applied as the internal standard. Collected data was analyzed by SPSS software (version 11.5), using appropriate descriptive statistical tests. Results Forty six different herbal waters from three main producing factories (A, B and C) were tested. Highest methanol concentration was measured in dill water of A (1208±202.74 mg/l), concentrated rose water of A (1017.41±59.68 mg/l) and concentrated rose water of B (978.52±92.81 mg/l). Lowest methanol concentration was determined in Trachyspermum copticum water of B (18.93±1.04 mg/l), cinnamon and ginger water of B (29.64±10.88 mg/l) and rice skin water of A (41.33±7.85 mg/l). Mean methanol concentrations of herbal waters including ginger, cinnamon, dill, peppermint, alfalfa, and plant forty from A, B and C were 374.69, 209.81 and 280.12 mg/l, respectively (P< 0.001). Conclusion Methanol concentration in all herbal waters, especially rose water of the three producers was very high that may induce toxicity in people taking these products regularly for a long time. PMID:23493100

Apparatus for converting hydrocarbon fuel into hydrogen gas and carbon dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

2002-01-01

Hydrocarbon fuel reformer 100 suitable for producing synthesis hydrogen gas from reactions with hydrocarbons fuels, oxygen, and steam. A first tube 108 has a first tube inlet 110 and a first tube outlet 112. The first tube inlet 110 is adapted for receiving a first mixture including an oxygen-containing gas and a first fuel. A partially oxidized first reaction reformate is directed out of the first tube 108 into a mixing zone 114. A second tube 116 is annularly disposed about the first tube 108 and has a second tube inlet 118 and a second tube outlet 120. The second tube inlet 118 is adapted for receiving a second mixture including steam and a second fuel. A steam reformed second reaction reformate is directed out of the second tube 116 and into the mixing zone 114. From the mixing zone 114, the first and second reaction reformates may be directed into a catalytic reforming zone 144 containing a reforming catalyst 147.

Gas-Phase Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide Over Co1.5pw12o40 Keggin-Type Heteropolyanion

PubMed Central

Aouissi, Ahmed; Al-Othman, Zeid Abdullah; Al-Amro, Amro

2010-01-01

The reactivity of Co1.5PW12O40 in the direct synthesis of dimethyl carbonate (DMC) from CO2 and CH3OH was investigated. The synthesized catalyst has been characterized by means of FTIR, XRD, TG, and DTA and tested in gas phase under atmospheric pressure. The effects of the reaction temperature, time on stream, and methanol weight hourly space velocity (MWHSV) on the conversion and DMC selectivity were investigated. The highest conversion (7.6%) and highest DMC selectivity (86.5%) were obtained at the lowest temperature used (200 °C). Increasing the space velocity MWHSV increased the selectivity of DMC, but decreased the conversion. A gain of 18.4% of DMC selectivity was obtained when the MWHSV was increased from 0.65 h−1 to 3.2 h−1. PMID:20480023

Characterization of methanol as a magnetic field tracer in star-forming regions

NASA Astrophysics Data System (ADS)

Lankhaar, Boy; Vlemmings, Wouter; Surcis, Gabriele; van Langevelde, Huib Jan; Groenenboom, Gerrit C.; van der Avoird, Ad

2018-02-01

Magnetic fields play an important role during star formation1. Direct magnetic field strength observations have proven particularly challenging in the extremely dynamic protostellar phase2-4. Because of their occurrence in the densest parts of star-forming regions, masers, through polarization observations, are the main source of magnetic field strength and morphology measurements around protostars2. Of all maser species, methanol is one of the strongest and most abundant tracers of gas around high-mass protostellar disks and in outflows. However, as experimental determination of the magnetic characteristics of methanol has remained largely unsuccessful5, a robust magnetic field strength analysis of these regions could hitherto not be performed. Here, we report a quantitative theoretical model of the magnetic properties of methanol, including the complicated hyperfine structure that results from its internal rotation6. We show that the large range in values of the Landé g factors of the hyperfine components of each maser line lead to conclusions that differ substantially from the current interpretation based on a single effective g factor. These conclusions are more consistent with other observations7,8 and confirm the presence of dynamically important magnetic fields around protostars. Additionally, our calculations show that (nonlinear) Zeeman effects must be taken into account to further enhance the accuracy of cosmological electron-to-proton mass ratio determinations using methanol9-12.

Proton conductivity and methanol permeability of Nafion-SiO2/SiWA composite membranes

NASA Astrophysics Data System (ADS)

Thiam, Hui San; Chia, Min Yan; Cheah, Qiao Rou; Koo, Charlene Chai Hoon; Lai, Soon Onn; Chong, Kok Chung

2017-04-01

Proton exchange membranes for a direct methanol fuel cell (DMFC) were prepared by incorporating silica/silicotungstic acid (SiO2/SiWA) inorganic composite into a Nafion polymer. The effects of SiO2/SiWA content on proton conductivity of membranes were investigated by using a four-probe conductivity cell. Methanol permeability of composite membrane was also determined by using a homemade diffusion cell and gas chromatography technique. It was found that proton conductivity of the composite membranes decreased with SiO2/SiWA content, however the highest proton conductivity achieved was 11% greater than the pure recast Nafion membrane. The methanol permeability of composite membrane was much lower than that of pure recast Nafion, in a reduction of 58% which indicated a better resistance to fuel crossover. Nafion-SiO2/SiWA composite membrane showed promising advantages over pure Nafion on electrochemical properties such as proton conductivity and fuel crossover and it is potentially attractive for use in DMFC.

Theoretical Basis for Estimated Test Times and Conditions for Drop Tower and Space-Based Droplet Burning Experiments With Methanol and N-Heptane

NASA Technical Reports Server (NTRS)

Marchese, Anthony J.; Dryer, Fredrick L.; Choi, Mun Y.

1994-01-01

In order to develop an extensive envelope of test conditions for NASA's space-based Droplet Combustion Experiment (DCE) as well those droplet experiments which can be performed using a drop tower, the transient vaporization and combustion of methanol and n-heptane droplets were simulated using a recently developed fully time-dependent, spherically symmetric droplet combustion model. The transient vaporization of methanol and n-heptane was modeled to characterize the instantaneous gas phase composition surrounding the droplet prior to the introduction of an ignition source. The results for methanol/air showed that the entire gas phase surrounding a 2 mm methanol droplet deployed in zero-g .quickly falls outside the lean flammability limit. The gas phase surrounding an identically-sized n-heptane droplet, on the other hand, remains flammable. The combustion of methanol was then modeled considering a detailed gas phase chemical kinetic mechanism (168 steps, 26 species) and the effect of the dissolution of flame-generated water into the liquid droplet. These results were used to determine the critical ignition diameter required to achieve quasi-steady droplet combustion in a given oxidizing environment. For droplet diameters greater than the critical ignition diameter, the model predicted a finite diameter at which the flame would extinguish. These extinction diameters were found to vary significantly with initial droplet diameter. This phenomenon appears to be unique to the transient heat transfer, mass transfer and chemical kinetics of the system and thus has not been reported elsewhere to date. The extinction diameter was also shown to vary significantly with the liquid phase Lewis number since the amount of water present in the droplet at extinction is largely governed by the rate at which water is transported into the droplet via mass diffusion. Finally, the numerical results for n-heptane combustion were obtained using both 2 step and 96 step semi

Reforming of fuel inside fuel cell generator

DOEpatents

Grimble, Ralph E.

1988-01-01

Disclosed is an improved method of reforming a gaseous reformable fuel within a solid oxide fuel cell generator, wherein the solid oxide fuel cell generator has a plurality of individual fuel cells in a refractory container, the fuel cells generating a partially spent fuel stream and a partially spent oxidant stream. The partially spent fuel stream is divided into two streams, spent fuel stream I and spent fuel stream II. Spent fuel stream I is burned with the partially spent oxidant stream inside the refractory container to produce an exhaust stream. The exhaust stream is divided into two streams, exhaust stream I and exhaust stream II, and exhaust stream I is vented. Exhaust stream II is mixed with spent fuel stream II to form a recycle stream. The recycle stream is mixed with the gaseous reformable fuel within the refractory container to form a fuel stream which is supplied to the fuel cells. Also disclosed is an improved apparatus which permits the reforming of a reformable gaseous fuel within such a solid oxide fuel cell generator. The apparatus comprises a mixing chamber within the refractory container, means for diverting a portion of the partially spent fuel stream to the mixing chamber, means for diverting a portion of exhaust gas to the mixing chamber where it is mixed with the portion of the partially spent fuel stream to form a recycle stream, means for injecting the reformable gaseous fuel into the recycle stream, and means for circulating the recycle stream back to the fuel cells.

Reforming of fuel inside fuel cell generator

DOEpatents

Grimble, R.E.

1988-03-08

Disclosed is an improved method of reforming a gaseous reformable fuel within a solid oxide fuel cell generator, wherein the solid oxide fuel cell generator has a plurality of individual fuel cells in a refractory container, the fuel cells generating a partially spent fuel stream and a partially spent oxidant stream. The partially spent fuel stream is divided into two streams, spent fuel stream 1 and spent fuel stream 2. Spent fuel stream 1 is burned with the partially spent oxidant stream inside the refractory container to produce an exhaust stream. The exhaust stream is divided into two streams, exhaust stream 1 and exhaust stream 2, and exhaust stream 1 is vented. Exhaust stream 2 is mixed with spent fuel stream 2 to form a recycle stream. The recycle stream is mixed with the gaseous reformable fuel within the refractory container to form a fuel stream which is supplied to the fuel cells. Also disclosed is an improved apparatus which permits the reforming of a reformable gaseous fuel within such a solid oxide fuel cell generator. The apparatus comprises a mixing chamber within the refractory container, means for diverting a portion of the partially spent fuel stream to the mixing chamber, means for diverting a portion of exhaust gas to the mixing chamber where it is mixed with the portion of the partially spent fuel stream to form a recycle stream, means for injecting the reformable gaseous fuel into the recycle stream, and means for circulating the recycle stream back to the fuel cells. 1 fig.

Hydrogen production by aqueous phase reforming of light oxygenated hydrocarbons

NASA Astrophysics Data System (ADS)

Shabaker, John William

Aqueous phase reforming (APR) of renewable oxygenated hydrocarbons (e.g., methanol, ethylene glycol, glycerol, sorbitol, glucose) is a promising new technology for the catalytic production of high-purity hydrogen for fuel cells and chemical processing. Supported Pt catalysts are effective catalysts for stable and rapid H2 production at temperatures near 500 K (H 2 turnover frequencies near 10 min-1). Inexpensive Raney Ni-based catalysts have been developed using a combination of fundamental and high-throughput studies that have similar catalytic properties as Pt-based materials. Promotion of Raney Ni with Sn by controlled surface reaction of organometallic tin compounds is necessary to control formation of thermodynamically-favorable alkane byproducts. Detailed characterization by Mossbauer spectroscopy, electron microscopy, adsorption studies, and x-ray photoelectron spectroscopy (XPS/ESCA) has shown that NiSn alloys are formed during heat treatment, and may be responsible for enhanced stability and selectivity for hydrogen production. Detailed kinetic studies led to the development of a kinetic mechanism for the APR reaction on Pt and NiSn catalysts, in which the oxygenate decomposes through C--H and O--H cleavage, followed by C--C cleavage and water gas shift of the CO intermediate. The rate limiting step on Pt surfaces is the initial dehydrogenation, while C--C cleavage appears rate limiting over NiSn catalysts. Tin promotion of Raney Ni catalysts suppresses C--O bond scission reactions that lead to alkane formation without inhibiting fast C--C and C--H cleavage steps that are necessary for high rates of reforming. A window of operating temperature, pressure, and reactor residence time has been identified for use of the inexpensive NiSn catalysts as a Pt substitute. Concentrated feed stocks and aggressive pretreatments have been found to counteract catalyst deactivation by sintering in the hydrothermal APR environment and allow stable, long-term production of H

Improved Cathode Structure for a Direct Methanol Fuel Cell

NASA Technical Reports Server (NTRS)

Valdez, Thomas; Narayanan, Sekharipuram

2005-01-01

An improved cathode structure on a membrane/electrode assembly has been developed for a direct methanol fuel cell, in a continuing effort to realize practical power systems containing such fuel cells. This cathode structure is intended particularly to afford better cell performance at a low airflow rate. A membrane/electrode assembly of the type for which the improved cathode structure was developed (see Figure 1) is fabricated in a process that includes brush painting and spray coating of catalyst layers onto a polymer-electrolyte membrane and onto gas-diffusion backings that also act as current collectors. The aforementioned layers are then dried and hot-pressed together. When completed, the membrane/electrode assembly contains (1) an anode containing a fine metal black of Pt/Ru alloy, (2) a membrane made of Nafion 117 or equivalent (a perfluorosulfonic acid-based hydrophilic, proton-conducting ion-exchange polymer), (3) a cathode structure (in the present case, the improved cathode structure described below), and (4) the electrically conductive gas-diffusion backing layers, which are made of Toray 060(TradeMark)(or equivalent) carbon paper containing between 5 and 6 weight percent of poly(tetrafluoroethylene). The need for an improved cathode structure arises for the following reasons: In the design and operation of a fuel-cell power system, the airflow rate is a critical parameter that determines the overall efficiency, cell voltage, and power density. It is desirable to operate at a low airflow rate in order to obtain thermal and water balance and to minimize the size and mass of the system. The performances of membrane/electrode assemblies of prior design are limited at low airflow rates. Methanol crossover increases the required airflow rate. Hence, one way to reduce the required airflow rate is to reduce the effect of methanol crossover. Improvement of the cathode structure - in particular, addition of hydrophobic particles to the cathode - has been

Air breathing direct methanol fuel cell

DOEpatents

Ren, Xiaoming

2002-01-01

An air breathing direct methanol fuel cell is provided with a membrane electrode assembly, a conductive anode assembly that is permeable to air and directly open to atmospheric air, and a conductive cathode assembly that is permeable to methanol and directly contacting a liquid methanol source.

Enhanced methanol utilization in direct methanol fuel cell

DOEpatents

Ren, Xiaoming; Gottesfeld, Shimshon

2001-10-02

The fuel utilization of a direct methanol fuel cell is enhanced for improved cell efficiency. Distribution plates at the anode and cathode of the fuel cell are configured to distribute reactants vertically and laterally uniformly over a catalyzed membrane surface of the fuel cell. A conductive sheet between the anode distribution plate and the anodic membrane surface forms a mass transport barrier to the methanol fuel that is large relative to a mass transport barrier for a gaseous hydrogen fuel cell. In a preferred embodiment, the distribution plate is a perforated corrugated sheet. The mass transport barrier may be conveniently increased by increasing the thickness of an anode conductive sheet adjacent the membrane surface of the fuel cell.

Thermodynamic analysis of tar reforming through auto-thermal reforming process

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

Nurhadi, N., E-mail: nurhadi@tekmira.esdm.go.id; Diniyati, Dahlia; Efendi, M. Ade Andriansyah

2015-12-29

Fixed bed gasification is a simple and suitable technology for small scale power generation. One of the disadvantages of this technology is producing tar. So far, tar is not utilized yet and being waste that should be treated into a more useful product. This paper presents a thermodynamic analysis of tar conversion into gas producer through non-catalytic auto-thermal reforming technology. Tar was converted into components, C, H, O, N and S, and then reacted with oxidant such as mixture of air or pure oxygen. Thus, this reaction occurred auto-thermally and reached chemical equilibrium. The sensitivity analysis resulted that the mostmore » promising process performance occurred at flow rate of air was reached 43% of stoichiometry while temperature of process is 1100°C, the addition of pure oxygen is 40% and preheating of oxidant flow is 250°C. The yield of the most promising process performance between 11.15-11.17 kmol/h and cold gas efficiency was between 73.8-73.9%.The results of this study indicated that thermodynamically the conversion of tar into producer gas through non-catalytic auto-thermal reformingis more promising.« less

Methanol May Function as a Cross-Kingdom Signal

PubMed Central

Dorokhov, Yuri L.; Komarova, Tatiana V.; Petrunia, Igor V.; Kosorukov, Vyacheslav S.; Zinovkin, Roman A.; Shindyapina, Anastasia V.; Frolova, Olga Y.; Gleba, Yuri Y.

2012-01-01

Recently, we demonstrated that leaf wounding results in the synthesis of pectin methylesterase (PME), which causes the plant to release methanol into the air. Methanol emitted by a wounded plant increases the accumulation of methanol-inducible gene mRNA and enhances antibacterial resistance as well as cell-to-cell communication, which facilitates virus spreading in neighboring plants. We concluded that methanol is a signaling molecule involved in within-plant and plant-to-plant communication. Methanol is considered to be a poison in humans because of the alcohol dehydrogenase (ADH)-mediated conversion of methanol into toxic formaldehyde. However, recent data showed that methanol is a natural compound in normal, healthy humans. These data call into question whether human methanol is a metabolic waste product or whether methanol has specific function in humans. Here, to reveal human methanol-responsive genes (MRGs), we used suppression subtractive hybridization cDNA libraries of HeLa cells lacking ADH and exposed to methanol. This design allowed us to exclude genes involved in formaldehyde and formic acid detoxification from our analysis. We identified MRGs and revealed a correlation between increases in methanol content in the plasma and changes in human leukocyte MRG mRNA levels after fresh salad consumption by volunteers. Subsequently, we showed that the methanol generated by the pectin/PME complex in the gastrointestinal tract of mice induces the up- and downregulation of brain MRG mRNA. We used an adapted Y-maze to measure the locomotor behavior of the mice while breathing wounded plant vapors in two-choice assays. We showed that mice prefer the odor of methanol to other plant volatiles and that methanol changed MRG mRNA accumulation in the mouse brain. We hypothesize that the methanol emitted by wounded plants may have a role in plant-animal signaling. The known positive effect of plant food intake on human health suggests a role for physiological methanol in

Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen.

PubMed

Zakzeski, Joseph; Weckhuysen, Bert M

2011-03-21

The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model compounds and the distribution of products obtained during the lignin aqueous phase reforming revealed that lignin was depolymerized through disruption of the abundant β-O-4 linkages and, to a lesser extent, the 5-5' carbon-carbon linkages to form monomeric aromatic compounds. The alkyl chains contained on these monomeric compounds were readily reformed to produce hydrogen and simple aromatic platform chemicals, particularly guaiacol and syringol, with the distribution of each depending on the lignin source. The methoxy groups present on the aromatic rings were subject to hydrolysis to form methanol, which was also readily reformed to produce hydrogen and carbon dioxide. The composition of the isolated yields of monomeric aromatic compounds and overall lignin conversion based on these isolated yields varied from 10-15% depending on the lignin sample, with the balance consisting of gaseous products and residual solid material. Furthermore, we introduce the use of a high-pressure autoclave with optical windows and an autoclave with ATR-IR sentinel for on-line in situ spectroscopic monitoring of biomass conversion processes, which provides direct insight into, for example, the solubilization process and aqueous phase reforming reaction of lignin. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

California methanol assessment. Volume 1: Summary report

NASA Technical Reports Server (NTRS)

Otoole, R.; Dutzi, E.; Gershman, R.; Heft, R.; Kalema, W.; Maynard, D.

1983-01-01

The near term methanol industry, the competitive environment, long term methanol market, the transition period, air quality impacts of methanol, roles of the public and private sectors are considered.

Production of hydrogen from biomass by catalytic steam reforming of fast pyrolysis oil

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

Czernik, S.; Wang, D.; Chornet, E.

1998-08-01

Hydrogen is the prototype of the environmentally cleanest fuel of interest for power generation using fuel cells and for transportation. The thermochemical conversion of biomass to hydrogen can be carried out through two distinct strategies: (a) gasification followed by water-gas shift conversion, and (b) catalytic steam reforming of specific fractions derived from fast pyrolysis and aqueous/steam processes of biomass. This paper presents the latter route that begins with fast pyrolysis of biomass to produce bio-oil. This oil (as a whole or its selected fractions) can be converted to hydrogen via catalytic steam reforming followed by a water-gas shift conversion step.more » Such a process has been demonstrated at the bench scale using model compounds, poplar oil aqueous fraction, and the whole pyrolysis oil with commercial Ni-based steam reforming catalysts. Hydrogen yields as high as 85% have been obtained. Catalyst initial activity can be recovered through regeneration cycles by steam or CO{sub 2} gasification of carbonaceous deposits.« less

Methanol utilizing Desulfotomaculum species utilizes hydrogen in a methanol-fed sulfate-reducing bioreactor.

PubMed

Balk, Melike; Weijma, Jan; Goorissen, Heleen P; Ronteltap, Mariska; Hansen, Theo A; Stams, Alfons J M

2007-01-01

A sulfate-reducing bacterium, strain WW1, was isolated from a thermophilic bioreactor operated at 65 degrees C with methanol as sole energy source in the presence of sulfate. Growth of strain WW1 on methanol or acetate was inhibited at a sulfide concentration of 200 mg l(-1), while on H2/CO2, no apparent inhibition occurred up to a concentration of 500 mg l(-1). When strain WW1 was co-cultured under the same conditions with the methanol-utilizing, non-sulfate-reducing bacteria, Thermotoga lettingae and Moorella mulderi, both originating from the same bioreactor, growth and sulfide formation were observed up to 430 mg l(-1). These results indicated that in the co-cultures, a major part of the electron flow was directed from methanol via H2/CO2 to the reduction of sulfate to sulfide. Besides methanol, acetate, and hydrogen, strain WW1 was also able to use formate, malate, fumarate, propionate, succinate, butyrate, ethanol, propanol, butanol, isobutanol, with concomitant reduction of sulfate to sulfide. In the absence of sulfate, strain WW1 grew only on pyruvate and lactate. On the basis of 16S rRNA analysis, strain WW1 was most closely related to Desulfotomaculum thermocisternum and Desulfotomaculum australicum. However, physiological properties of strain WW1 differed in some aspects from those of the two related bacteria.

ECO LOGIC INTERNATIONAL GAS-PHASE CHEMICAL REDUCTION PROCESS - THE REACTOR SYSTEM - APPLICATIONS ANALYSIS REPORT

EPA Science Inventory

The ELI Eco Logic International Inc. (Eco Logic) process thermally separates organics, then chemically reduces them in a hydrogen atmosphere, converting them to a reformed gas that consists of light hydrocarbons and water. A scrubber treats the reformed gas to remove hydrogen chl...

Improvement of water management in a vapor feed direct methanol fuel cell

NASA Astrophysics Data System (ADS)

Masdar, M. Shahbudin; Tsujiguchi, Takuya; Nakagawa, Nobuyoshi

Water transport in a vapor feed direct methanol fuel cell was improved by fixing a hydrophobic air filter (HAF) at the cathode. Effects of the HAF properties and the fixed positions, i.e., just on the cathode surface or by providing a certain space from the surface, of the HAF on the water transport as well as the power generation performance were investigated. The water transport was evaluated by measuring the partial pressure of water, PH2O , and methanol, PCH3OH , at the anode gas layer using in situ mass spectrometry with a capillary probe and also the water and methanol fluxes across the electrode structure using a conventional method. The HAF with the highest hydrophobicity and the highest flow resistance had the strongest effect on increasing the water back diffusion from the cathode to the anode through the membrane and increasing the current density. It was noted that the HAF fixation by providing a space from the cathode surface was more effective in increasing JWCO and the current density than that of the direct placement on the cathode surface. There was an optimum distance for the HAF placement depending on the humidity of the outside air.

Experimental investigation of regulated and unregulated emissions from a diesel engine fueled with Euro V diesel fuel and fumigation methanol

NASA Astrophysics Data System (ADS)

Zhang, Z. H.; Cheung, C. S.; Chan, T. L.; Yao, C. D.

2010-03-01

Experiments were conducted on a four-cylinder direct-injection diesel engine with part of the engine load taken up by fumigation methanol injected into the air intake of each cylinder to investigate the regulated and unregulated gaseous emissions and particulate emission of the engine under five engine loads at an engine speed of 1920 rev min -1. The fumigation methanol was injected to top up 10%, 20% and 30% of the engine load under different engine operating conditions. The experimental results show that at low engine loads, the brake thermal efficiency (BTE) decreases with increase in fumigation methanol; but at high engine loads, the BTE is not significantly affected by fumigation methanol. The fumigation methanol results in significant increase in hydrocarbon (HC), carbon monoxide (CO) and nitrogen dioxide (NO 2) emissions, but decrease in nitrogen oxides (NO x). For the unregulated gaseous emissions, unburned methanol, formaldehyde and BTX (benzene, toluene and xylene) emissions increase but ethyne, ethene and 1,3-butadiene emissions decrease. Particulate mass and number concentrations also decrease with increase in fumigation methanol. A diesel oxidation catalyst (DOC) is found to reduce significantly most of the pollutants, including the air toxics, when the exhaust gas temperature is sufficiently high.

Simulation of a 250 kW diesel fuel processor/PEM fuel cell system

NASA Astrophysics Data System (ADS)

Amphlett, J. C.; Mann, R. F.; Peppley, B. A.; Roberge, P. R.; Rodrigues, A.; Salvador, J. P.

Polymer-electrolyte membrane (PEM) fuel cell systems offer a potential power source for utility and mobile applications. Practical fuel cell systems use fuel processors for the production of hydrogen-rich gas. Liquid fuels, such as diesel or other related fuels, are attractive options as feeds to a fuel processor. The generation of hydrogen gas for fuel cells, in most cases, becomes the crucial design issue with respect to weight and volume in these applications. Furthermore, these systems will require a gas clean-up system to insure that the fuel quality meets the demands of the cell anode. The endothermic nature of the reformer will have a significant affect on the overall system efficiency. The gas clean-up system may also significantly effect the overall heat balance. To optimize the performance of this integrated system, therefore, waste heat must be used effectively. Previously, we have concentrated on catalytic methanol-steam reforming. A model of a methanol steam reformer has been previously developed and has been used as the basis for a new, higher temperature model for liquid hydrocarbon fuels. Similarly, our fuel cell evaluation program previously led to the development of a steady-state electrochemical fuel cell model (SSEM). The hydrocarbon fuel processor model and the SSEM have now been incorporated in the development of a process simulation of a 250 kW diesel-fueled reformer/fuel cell system using a process simulator. The performance of this system has been investigated for a variety of operating conditions and a preliminary assessment of thermal integration issues has been carried out. This study demonstrates the application of a process simulation model as a design analysis tool for the development of a 250 kW fuel cell system.

Methanol Metabolism in Pseudomonad C

PubMed Central

Stieglitz, B.; Mateles, R. I.

1973-01-01

Cell suspensions of pseudomonad C, a bacterium capable of growth on methanol as sole carbon source, were able to oxidize methanol, formaldehyde, and formate, although the rates of oxidation for the latter two compounds were much slower. The latter compounds also could not serve as sole carbon sources. Through the use of labeled compounds, it was shown that in the presence of methanol, formaldehyde, formate, and bicarbonate were incorporated into trichloroacetic acid-precipitable material. Hexose phosphate synthetase activity was found, indicating the assimilation of methanol via an allulose pathway. No hydroxypyruvate reductase activity was found, nor was any complex membrane structure observed. Such a combination of characteristics has been observed in an obligate methylotroph (Pseudomonas W1), but pseudomonad C can utilize a variety of non-methyl substrates. Images PMID:4349032

Biogeochemical Cycle of Methanol in Anoxic Deep-Sea Sediments

PubMed Central

Yanagawa, Katsunori; Tani, Atsushi; Yamamoto, Naoya; Hachikubo, Akihiro; Kano, Akihiro; Matsumoto, Ryo; Suzuki, Yohey

2016-01-01

The biological flux and lifetime of methanol in anoxic marine sediments are largely unknown. We herein reported, for the first time, quantitative methanol removal rates in subsurface sediments. Anaerobic incubation experiments with radiotracers showed high rates of microbial methanol consumption. Notably, methanol oxidation to CO2 surpassed methanol assimilation and methanogenesis from CO2/H2 and methanol. Nevertheless, a significant decrease in methanol was not observed after the incubation, and this was attributed to the microbial production of methanol in parallel with its consumption. These results suggest that microbial reactions play an important role in the sources and sinks of methanol in subseafloor sediments. PMID:27301420

Apparatus for converting hydrocarbon fuel into hydrogen gas and carbon dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

2001-01-01

A hydrocarbon fuel reformer (200) is disclosed suitable for producing synthesis hydrogen gas from reactions with hydrocarbons fuels, oxygen, and steam. The reformer (200) comprises first and second tubes (208,218). The first tube (208) includes a first catalyst (214) and receives a first mixture of steam and a first fuel. The second tube (218) is annularly disposed about the first tube (208) and receives a second mixture of an oxygen-containing gas and a second fuel. In one embodiment, a third tube (224) is annularly disposed about the second tube (218) and receives a first reaction reformate from the first tube (208) and a second reaction reformate from the second tube (218). A catalyst reforming zone (260) annularly disposed about the third tube (224) may be provided to subject reformate constituents to a shift reaction. In another embodiment, a fractionator is provided to distill first and second fuels from a fuel supply source.

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

Methanol

Integrated Risk Information System (IRIS)

EPA / 635 / R - 11 / 001Fa www.epa.gov / iris TOXICOLOGICAL REVIEW OF METHANOL ( NONCANCER ) ( CAS No . 67 - 56 - 1 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) September 2013 U.S . Environmental Protection Agency Washington , DC ii DISCLAIMER This document

Lignite-to-methanol: an engineering evaluation of Winkler gasification and ICI methanol synthesis route. Final report

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

Goyen, S.; Baily, E.; Mawer, J.

1980-10-01

The objective of the work reported herein was to develop a preliminary conceptual design, capital requirements, and product cost for a lignite-to-methanol plant incorporating Winkler Gasification Technology and ICI Methanol synthesis. The lignite-to-methanol complex described herein is designed to produce 15,000 TPD of fuel grade methanol. The complex is designed to be self-sufficient with respect to all utility services, offsites, and other support facilities, including power generation. Following is a summary of the results of the study: (1) Tons per day (TPD) of Lignite Feedstock and Fuel (as received) was 47,770; (2) TPD of Fuel Grade Methanol Product was 15,000;more » (3) Thermal efficiency, % (HHV) was 47.4; (4) Plant investment expressed in terms of first quarter of 1980 was ($ Million) 1545; and (5) Applying the economic premises used by EPRI for fuel conversion plant utility type financing, the calculated levelized and first year product costs are included.« less

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

A greenhouse gas source of surprising significance: anthropogenic CO2 emissions from use of methanol in sewage treatment.

PubMed

Willis, John L; Al-Omari, Ahmed; Bastian, Robert; Brower, Bill; DeBarbadillo, Christine; Murthy, Sudhir; Peot, Christopher; Yuan, Zhiguo

2017-05-01

The impact of methanol (CH 3 OH) as a source of anthropogenic carbon dioxide (CO 2 ) in denitrification at wastewater treatment plants (WWTPs) has never been quantified. CH 3 OH is the most commonly purchased carbon source for sewage denitrification. Until recently, greenhouse gas (GHG) reporting protocols consistently ignored the liberation of anthropogenic CO 2 attributable to CH 3 OH. This oversight can likely be attributed to a simplifying notion that CO 2 produced through activated-sludge-process respiration is biogenic because most raw-sewage carbon is un-sequestered prior to entering a WWTP. Instead, a biogenic categorization cannot apply to fossil-fuel-derived carbon sources like CH 3 OH. This paper provides a summary of how CH 3 OH use at DC Water's Blue Plains Advanced Wastewater Treatment Plant (AWTP; Washington, DC, USA) amounts to 60 to 85% of the AWTP's Scope-1 emissions. The United States Environmental Protection Agency and Water Environment Federation databases suggest that CH 3 OH CO 2 likely represents one quarter of all Scope-1 GHG emissions attributable to sewage treatment in the USA. Finally, many alternatives to CH 3 OH use exist and are discussed.

Microbial methanol uptake in northeast Atlantic waters

PubMed Central

Dixon, Joanna L; Beale, Rachael; Nightingale, Philip D

2011-01-01

Methanol is the predominant oxygenated volatile organic compound in the troposphere, where it can significantly influence the oxidising capacity of the atmosphere. However, we do not understand which processes control oceanic concentrations, and hence, whether the oceans are a source or a sink to the atmosphere. We report the first methanol loss rates in seawater by demonstrating that 14C-labelled methanol can be used to determine microbial uptake into particulate biomass, and oxidation to 14CO2. We have found that methanol is used predominantly as a microbial energy source, but also demonstrated its use as a carbon source. We report biological methanol oxidation rates between 2.1 and 8.4 nmol l−1 day−1 in surface seawater of the northeast Atlantic. Kinetic experiments predict a Vmax of up to 29 nmol l−1 day−1, with a high affinity Km constant of 9.3 n in more productive coastal waters. We report surface concentrations of methanol in the western English channel of 97±8 n (n=4) between May and June 2010, and for the wider temperate North Atlantic waters of 70±13 n (n=6). The biological turnover time of methanol has been estimated between 7 and 33 days, although kinetic experiments suggest a 7-day turnover in more productive shelf waters. Methanol uptake rates into microbial particles significantly correlated with bacterial and phytoplankton parameters, suggesting that it could be used as a carbon source by some bacteria and possibly some mixotrophic eukaryotes. Our results provide the first methanol loss rates from seawater, which will improve the understanding of the global methanol budget. PMID:21068775

Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) process. Technical progress report number 9, July 1--September 30, 1996

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

NONE

The Liquid Phase Methanol (LPMEOH{trademark}) Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the US Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership). The LPMEOH{trademark} Process Demonstration Unit is being built at a site located at the Eastman Chemical Company (Eastman) complex in Kingsport. The project involves the construction of an 80,000 gallons per day (260 tons per day (TPD)) methanol unit utilizing coal-derived synthesis gas from Eastman`s integrated coal gasification facility. The new equipment consists of synthesis gas feed preparation and compression facilities, the liquid phase reactor and auxiliaries,more » product distillation facilities, and utilities. This liquid phase process suspends fine catalyst particles in an inert liquid, forming a slurry. The slurry dissipates the heat of the chemical reaction away from the catalyst surface, protecting the catalyst and allowing the methanol synthesis reaction to proceed at higher rates. At the Eastman complex, the technology is being integrated with existing coal-gasifiers.« less

Method of plasma enhanced chemical vapor deposition of diamond using methanol-based solutions

NASA Technical Reports Server (NTRS)

Tzeng, Yonhua (Inventor)

2009-01-01

Briefly described, methods of forming diamond are described. A representative method, among others, includes: providing a substrate in a reaction chamber in a non-magnetic-field microwave plasma system; introducing, in the absence of a gas stream, a liquid precursor substantially free of water and containing methanol and at least one carbon and oxygen containing compound having a carbon to oxygen ratio greater than one, into an inlet of the reaction chamber; vaporizing the liquid precursor; and subjecting the vaporized precursor, in the absence of a carrier gas and in the absence in a reactive gas, to a plasma under conditions effective to disassociate the vaporized precursor and promote diamond growth on the substrate in a pressure range from about 70 to 130 Torr.

On-board diesel autothermal reforming for PEM fuel cells: Simulation and optimization

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

Cozzolino, Raffaello, E-mail: raffaello.cozzolino@unicusano.it; Tribioli, Laura

2015-03-10

Alternative power sources are nowadays the only option to provide a quick response to the current regulations on automotive pollutant emissions. Hydrogen fuel cell is one promising solution, but the nature of the gas is such that the in-vehicle conversion of other fuels into hydrogen is necessary. In this paper, autothermal reforming, for Diesel on-board conversion into a hydrogen-rich gas suitable for PEM fuel cells, has investigated using the simulation tool Aspen Plus. A steady-state model has been developed to analyze the fuel processor and the overall system performance. The components of the fuel processor are: the fuel reforming reactor,more » two water gas shift reactors, a preferential oxidation reactor and H{sub 2} separation unit. The influence of various operating parameters such as oxygen to carbon ratio, steam to carbon ratio, and temperature on the process components has been analyzed in-depth and results are presented.« less

Methanol poisoning among travellers to Indonesia.

PubMed

Giovanetti, Franco

2013-01-01

Common Travel Medicine sources generally do not provide information on the risk of methanol poisoning among travellers who visit Indonesia. The aim of this analysis was to increase knowledge on this topic through reports from bibliographic databases and Internet sources. Case reports and studies on methanol poisoning in Indonesia were retrieved through PubMed, Embase and Google Scholar database searching. The Google search was used to retrieve the Web Media articles reporting fatal and non-fatal methanol poisoning in Indonesia, in a timeframe from 01.01.2009 to 03.03.2013. Three case reports of methanol poisoning involving four travellers to Indonesia were found in bibliographic databases. The media sources searching identified 14 articles published online, reporting 22 cases of methanol poisoning among travellers after consumption of local alcohol beverages. The total number of death cases was 18. Some sources report also a large number of cases among the local population. Methanol poisoning is likely to be an emerging public health problem in Indonesia, with an associated morbidity and mortality among travellers and local people. Some strategies can be implemented to prevent or reduce harm among travellers. Copyright © 2013 Elsevier Ltd. All rights reserved.

Air breathing direct methanol fuel cell

DOEpatents

Ren, Xiaoming; Gottesfeld, Shimshon

2002-01-01

An air breathing direct methanol fuel cell is provided with a membrane electrode assembly, a conductive anode assembly that is permeable to air and directly open to atmospheric air, and a conductive cathode assembly that is permeable to methanol and directly contacting a liquid methanol source. Water loss from the cell is minimized by making the conductive cathode assembly hydrophobic and the conductive anode assembly hydrophilic.

Methods of conditioning direct methanol fuel cells

DOEpatents

Rice, Cynthia; Ren, Xiaoming; Gottesfeld, Shimshon

2005-11-08

Methods for conditioning the membrane electrode assembly of a direct methanol fuel cell ("DMFC") are disclosed. In a first method, an electrical current of polarity opposite to that used in a functioning direct methanol fuel cell is passed through the anode surface of the membrane electrode assembly. In a second method, methanol is supplied to an anode surface of the membrane electrode assembly, allowed to cross over the polymer electrolyte membrane of the membrane electrode assembly to a cathode surface of the membrane electrode assembly, and an electrical current of polarity opposite to that in a functioning direct methanol fuel cell is drawn through the membrane electrode assembly, wherein methanol is oxidized at the cathode surface of the membrane electrode assembly while the catalyst on the anode surface is reduced. Surface oxides on the direct methanol fuel cell anode catalyst of the membrane electrode assembly are thereby reduced.

Fuel cell power supply with oxidant and fuel gas switching

DOEpatents

McElroy, James F.; Chludzinski, Paul J.; Dantowitz, Philip

1987-01-01

This invention relates to a fuel cell vehicular power plant. Fuel for the fuel stack is supplied by a hydrocarbon (methanol) catalytic cracking reactor and CO shift reactor. A water electrolysis subsystem is associated with the stack. During low power operation part of the fuel cell power is used to electrolyze water with hydrogen and oxygen electrolysis products being stored in pressure vessels. During peak power intervals, viz, during acceleration or start-up, pure oxygen and pure hydrogen from the pressure vessel are supplied as the reaction gases to the cathodes and anodes in place of air and methanol reformate. This allows the fuel cell stack to be sized for normal low power/air operation but with a peak power capacity several times greater than that for normal operation.

Fuel cell power supply with oxidant and fuel gas switching

DOEpatents

McElroy, J.F.; Chludzinski, P.J.; Dantowitz, P.

1987-04-14

This invention relates to a fuel cell vehicular power plant. Fuel for the fuel stack is supplied by a hydrocarbon (methanol) catalytic cracking reactor and CO shift reactor. A water electrolysis subsystem is associated with the stack. During low power operation part of the fuel cell power is used to electrolyze water with hydrogen and oxygen electrolysis products being stored in pressure vessels. During peak power intervals, viz, during acceleration or start-up, pure oxygen and pure hydrogen from the pressure vessel are supplied as the reaction gases to the cathodes and anodes in place of air and methanol reformate. This allows the fuel cell stack to be sized for normal low power/air operation but with a peak power capacity several times greater than that for normal operation. 2 figs.

Gas production strategy of underground coal gasification based on multiple gas sources.

PubMed

Tianhong, Duan; Zuotang, Wang; Limin, Zhou; Dongdong, Li

2014-01-01

To lower stability requirement of gas production in UCG (underground coal gasification), create better space and opportunities of development for UCG, an emerging sunrise industry, in its initial stage, and reduce the emission of blast furnace gas, converter gas, and coke oven gas, this paper, for the first time, puts forward a new mode of utilization of multiple gas sources mainly including ground gasifier gas, UCG gas, blast furnace gas, converter gas, and coke oven gas and the new mode was demonstrated by field tests. According to the field tests, the existing power generation technology can fully adapt to situation of high hydrogen, low calorific value, and gas output fluctuation in the gas production in UCG in multiple-gas-sources power generation; there are large fluctuations and air can serve as a gasifying agent; the gas production of UCG in the mode of both power and methanol based on multiple gas sources has a strict requirement for stability. It was demonstrated by the field tests that the fluctuations in gas production in UCG can be well monitored through a quality control chart method.

Method And Apparatus For Converting Hydrocarbon Fuel Into Hydrogen Gas And Carbon Dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

2000-09-26

A method is disclosed for synthesizing hydrogen gas from hydrocarbon fuel. A first mixture of steam and a first fuel is directed into a first tube 208 to subject the first mixture to a first steam reforming reaction in the presence of a first catalyst 214. A stream of oxygen-containing gas is pre-heated by transferring heat energy from product gases. A second mixture of the pre-heated oxygen-containing gas and a second fuel is directed into a second tube 218 disposed about the first tube 208 to subject the second mixture to a partial oxidation reaction and to provide heat energy for transfer to the first tube 208. A first reaction reformate from the first tube 208 and a second reaction reformate from the second tube 218 are directed into a third tube 224 disposed about the second tube 218 to subject the first and second reaction reformates to a second steam reforming reaction, wherein heat energy is transferred to the third tube 224 from the second tube 218.

Hydrogen isotope exchanges between water and methanol in interstellar ices

NASA Astrophysics Data System (ADS)

Faure, A.; Faure, M.; Theulé, P.; Quirico, E.; Schmitt, B.

2015-12-01

The deuterium fractionation of gas-phase molecules in hot cores is believed to reflect the composition of interstellar ices. The deuteration of methanol is a major puzzle, however, because the isotopologue ratio [CH2DOH]/[CH3OD], which is predicted to be equal to 3 by standard grain chemistry models, is much larger (~20) in low-mass hot corinos and significantly lower (~1) in high-mass hot cores. This dichotomy in methanol deuteration between low-mass and massive protostars is currently not understood. In this study, we report a simplified rate equation model of the deuterium chemistry occurring in the icy mantles of interstellar grains. We apply this model to the chemistry of hot corinos and hot cores, with IRAS 16293-2422 and the Orion KL Compact Ridge as prototypes, respectively. The chemistry is based on a statistical initial deuteration at low temperature followed by a warm-up phase during which thermal hydrogen/deuterium (H/D) exchanges occur between water and methanol. The exchange kinetics is incorporated using laboratory data. The [CH2DOH]/[CH3OD] ratio is found to scale inversely with the D/H ratio of water, owing to the H/D exchange equilibrium between the hydroxyl (-OH) functional groups of methanol and water. Our model is able to reproduce the observed [CH2DOH]/[CH3OD] ratios provided that the primitive fractionation of water ice [HDO]/[H2O] is ~2% in IRAS 16293-2422 and ~0.6% in Orion KL. We conclude that the molecular D/H ratios measured in hot cores may not be representative of the original mantles because molecules with exchangeable deuterium atoms can equilibrate with water ice during the warm-up phase.

Statistical validation and an empirical model of hydrogen production enhancement found by utilizing passive flow disturbance in the steam-reformation process

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

Erickson, Paul A.; Liao, Chang-hsien

2007-11-15

A passive flow disturbance has been proven to enhance the conversion of fuel in a methanol-steam reformer. This study presents a statistical validation of the experiment based on a standard 2{sup k} factorial experiment design and the resulting empirical model of the enhanced hydrogen producing process. A factorial experiment design was used to statistically analyze the effects and interactions of various input factors in the experiment. Three input factors, including the number of flow disturbers, catalyst size, and reactant flow rate were investigated for their effects on the fuel conversion in the steam-reformation process. Based on the experimental results, anmore » empirical model was developed and further evaluated with an uncertainty analysis and interior point data. (author)« less

Microwave Spectrum of the Ethanol-Methanol Dimer

NASA Astrophysics Data System (ADS)

Finneran, Ian A.; Carroll, Brandon; Mead, Griffin; Blake, Geoffrey

2016-06-01

The hydrogen bond donor/acceptor competition in mixed alcohol clusters remains a fundamental question in physical chemistry. Previous theoretical work on the prototype ethanol-methanol dimer has been inconclusive in predicting the energetically preferred structure. Here, we report the microwave spectrum of the ethanol-methanol dimer between 8-18 GHz, using a chirped pulse Fourier transform microwave spectrometer. With the aid of ab initio calculations, 36 transitions have been fit and assigned to a t-ethanol-acceptor, methanol-donor structure in an argon-backed expansion. In a helium-backed expansion, a second excited conformer has been observed, and tentatively assigned to a g-ethanol-acceptor, methanol-donor structure. No ethanol-donor, methanol-acceptor structures have been found, suggesting such structures are energetically disfavored.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-31

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Photodegradation of organic pollutants in water and green hydrogen production via methanol photoreforming of doped titanium oxide nanoparticles.

PubMed

Rico-Oller, Beatriz; Boudjemaa, Amel; Bahruji, Hasliza; Kebir, Mohammed; Prashar, Sanjiv; Bachari, Khaldoun; Fajardo, Mariano; Gómez-Ruiz, Santiago

2016-09-01

Novel nanomaterials based on doped TiO2 nanoparticles with different morphological, textural and band-gap properties have been synthesized using scalable methods. The influence of synthetic parameters such as titanium source (titanium(IV) isopropoxide and titanium(IV) butoxide), doping quantity (0%, 2% or 5% Zn), acidic solution for the hydrolysis reaction (ascorbic acid, nitric acid) and calcination temperatures (500°C and 600°C) was simultaneously investigated. The obtained nanomaterials were characterized by different methods and photocatalytic tests of methylene blue (MB) degradation under UV-light were conducted to determine their activity. The results revealed that the synthesized nanomaterials are porous aggregates with very high crystallinity and are mainly composed of the anatase phase; although their physical properties vary depending on the different synthetic parameters employed. These changes are able to modify the apparent rate constant of the degradation of MB up to one order of magnitude, indicating, substantial changes in their photoactivity. Hybrid materials TiO2-Pd nanoparticles have also been prepared, characterized and tested for hydrogen production using photocatalytic methanol reforming where supported palladium nanoparticles acted as co-catalyst. Furthermore, the hybrid materials TiO2-Pd nanoparticles were studied in photocatalytic tests of methylene blue degradation under visible LED-light. The results obtained in the production of hydrogen from the photocatalytic reforming of methanol by hybrid materials suggest that the reported hybrid systems could be suitable photocatalysts for future sustainable hydrogen production upon tuning of the morphological, textural and band gap energy properties to allow processes to be carried out under visible light. Copyright © 2015 Elsevier B.V. All rights reserved.

Metabolic Engineering of Corynebacterium glutamicum for Methanol Metabolism

PubMed Central

Witthoff, Sabrina; Schmitz, Katja; Niedenführ, Sebastian; Nöh, Katharina; Noack, Stephan

2015-01-01

Methanol is already an important carbon feedstock in the chemical industry, but it has found only limited application in biotechnological production processes. This can be mostly attributed to the inability of most microbial platform organisms to utilize methanol as a carbon and energy source. With the aim to turn methanol into a suitable feedstock for microbial production processes, we engineered the industrially important but nonmethylotrophic bacterium Corynebacterium glutamicum toward the utilization of methanol as an auxiliary carbon source in a sugar-based medium. Initial oxidation of methanol to formaldehyde was achieved by heterologous expression of a methanol dehydrogenase from Bacillus methanolicus, whereas assimilation of formaldehyde was realized by implementing the two key enzymes of the ribulose monophosphate pathway of Bacillus subtilis: 3-hexulose-6-phosphate synthase and 6-phospho-3-hexuloisomerase. The recombinant C. glutamicum strain showed an average methanol consumption rate of 1.7 ± 0.3 mM/h (mean ± standard deviation) in a glucose-methanol medium, and the culture grew to a higher cell density than in medium without methanol. In addition, [13C]methanol-labeling experiments revealed labeling fractions of 3 to 10% in the m + 1 mass isotopomers of various intracellular metabolites. In the background of a C. glutamicum Δald ΔadhE mutant being strongly impaired in its ability to oxidize formaldehyde to CO2, the m + 1 labeling of these intermediates was increased (8 to 25%), pointing toward higher formaldehyde assimilation capabilities of this strain. The engineered C. glutamicum strains represent a promising starting point for the development of sugar-based biotechnological production processes using methanol as an auxiliary substrate. PMID:25595770

Effect of gasoline/methanol blends on motorcycle emissions: Exhaust and evaporative emissions

NASA Astrophysics Data System (ADS)

Li, Lan; Ge, Yunshan; Wang, Mingda; Li, Jiaqiang; Peng, Zihang; Song, Yanan; Zhang, Liwei

2015-02-01

The emission characteristics of motorcycles using gasoline and M15 (consisting of 85% gasoline and 15% methanol by volume) were investigated in this article. Exhaust and evaporative emissions, including regulated and unregulated emissions, of three motorcycles were investigated on the chassis dynamometer over the Urban Driving Cycle (UDC) and in the Sealed Housing for Evaporative Determination (SHED), respectively. The regulated emissions were detected by an exhaust gas analyzer directly. The unregulated emissions, including carbonyls, volatile organic compounds (VOCs) and methanol, were sampled through battery-operated air pumps using tubes coated with 2,4-dintrophenylhydrazine (DNPH), Tenax TA and silica gel, respectively. The experimental results showed that, for exhaust emission, compared with those from gasoline fueled motorcycles, the concentration of total hydrocarbons (THC) and CO from motorcycles fueled with M15 decreased by 11%-34.5% and 63%-84% respectively, while the concentration of NOx increased by 76.9%-107.7%. Compared with those from gasoline fueled motorcycles, BTEX from motorcycles fueled with M15 decreased by 16%-60% while formaldehyde increased by 16.4%-52.5%. For evaporative emission, diurnal losses were more than hot soak losses and turned out to be dominated in evaporative emissions. In addition, compared with gasoline fueling motorcycles, the evaporative emissions of THC, carbonyls and VOCs from motorcycles fueled with M15 increased by 11.7%-37%, 38%-45% and 16%-42%, respectively. It should be noted that the growth rate of methanol was as high as 297%-1429%. It is important to reduce the evaporative emissions of methanol fueling motorcycles.

Hydrogen production by steam reforming of liquefied natural gas (LNG) over nickel catalysts supported on cationic surfactant-templated mesoporous aluminas

NASA Astrophysics Data System (ADS)

Seo, Jeong Gil; Youn, Min Hye; Park, Sunyoung; Jung, Ji Chul; Kim, Pil; Chung, Jin Suk; Song, In Kyu

Two types of mesoporous γ-aluminas (denoted as A-A and A-S) are prepared by a hydrothermal method under different basic conditions using cationic surfactant (cetyltrimethylammonium bromide, CTAB) as a templating agent. A-A and A-S are synthesized in a medium of ammonia solution and sodium hydroxide solution, respectively. Ni/γ-Al 2O 3 catalysts (Ni/A-A and Ni/A-S) are then prepared by an impregnation method, and are applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of a mesoporous γ-Al 2O 3 support on the catalytic performance of Ni/γ-Al 2O 3 is investigated. The identity of basic solution strongly affects the physical properties of the A-A and A-S supports. The high surface-area of the mesoporous γ-aluminas and the strong metal-support interaction of supported catalysts greatly enhance the dispersion of nickel species on the catalyst surface. The well-developed mesopores of the Ni/A-A and Ni/A-S catalysts prohibit the polymerization of carbon species on the catalyst surface during the reaction. In the steam reforming of LNG, both Ni/A-A and Ni/A-S catalysts give better catalytic performance than the nickel catalyst supported on commercial γ-Al 2O 3 (Ni/A-C). In addition, the Ni/A-A catalyst is superior to the Ni/A-S catalyst. The relatively strong metal-support interaction of Ni/A-A catalyst effectively suppresses the sintering of metallic nickel and the carbon deposition in the steam reforming of LNG. The large pores of the Ni/A-A catalyst also play an important role in enhancing internal mass transfer during the reaction.

Solar hydrogen production: renewable hydrogen production by dry fuel reforming

NASA Astrophysics Data System (ADS)

Bakos, Jamie; Miyamoto, Henry K.

2006-09-01

SHEC LABS - Solar Hydrogen Energy Corporation constructed a pilot-plant to demonstrate a Dry Fuel Reforming (DFR) system that is heated primarily by sunlight focusing-mirrors. The pilot-plant consists of: 1) a solar mirror array and solar concentrator and shutter system; and 2) two thermo-catalytic reactors to convert Methane, Carbon Dioxide, and Water into Hydrogen. Results from the pilot study show that solar Hydrogen generation is feasible and cost-competitive with traditional Hydrogen production. More than 95% of Hydrogen commercially produced today is by the Steam Methane Reformation (SMR) of natural gas, a process that liberates Carbon Dioxide to the atmosphere. The SMR process provides a net energy loss of 30 to 35% when converting from Methane to Hydrogen. Solar Hydrogen production provides a 14% net energy gain when converting Methane into Hydrogen since the energy used to drive the process is from the sun. The environmental benefits of generating Hydrogen using renewable energy include significant greenhouse gas and criteria air contaminant reductions.

On the road to reform: a sociocultural interpretation of reform

NASA Astrophysics Data System (ADS)

Mensah, Felicia Moore

2011-09-01

In this paper I discuss how reform in science education is interpreted by Barma as she recounts the story of Catherine, a grade 9 biology teacher, who reforms her teaching practices in response to a national curriculum reform in Quebec, Canada. Unlike some cases in response to reform, this case is hopeful and positive. Also in this paper, I address some familiar areas that must be considered when teachers undertake curriculum reform and how science educators may fulfill the role of facilitator and advocate in the support of teachers on the road to reform. The commentary focuses on how Barma retells the story through the lens of activity theory.

Methanol test

MedlinePlus

... Safety and Health. Emergency Response Safety and Health Database. Methanol: systemic agent. Updated May 28, 2015. www. ... ADAM Health Solutions. About MedlinePlus Site Map FAQs Customer Support Get email updates Subscribe to RSS Follow ...

Onboard fuel reformers for fuel cell vehicles: Equilibrium, kinetic and system modeling

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

Kreutz, T.G.; Steinbugler, M.M.; Ogden, J.M.

1996-12-31

On-board reforming of liquid fuels to hydrogen for use in proton exchange membrane (PEM) fuel cell electric vehicles (FCEVs) has been the subject of numerous investigations. In many respects, liquid fuels represent a more attractive method of carrying hydrogen than compressed hydrogen itself, promising greater vehicle range, shorter refilling times, increased safety, and perhaps most importantly, utilization of the current fuel distribution infrastructure. The drawbacks of on-board reformers include their inherent complexity [for example a POX reactor includes: a fuel vaporizer, a reformer, water-gas shift reactors, a preferential oxidation (PROX) unit for CO cleanup, heat exchangers for thermal integration, sensorsmore » and controls, etc.], weight, and expense relative to compressed H{sub 2}, as well as degraded fuel cell performance due to the presence of inert gases and impurities in the reformate. Partial oxidation (POX) of automotive fuels is another alternative for hydrogen production. This paper provides an analysis of POX reformers and a fuel economy comparison of vehicles powered by on-board POX and SRM fuel processors.« less

A novel differential electrochemical mass spectrometry method to determine the product distribution from parasitic Methanol oxidation reaction on oxygen reduction reaction catalysts

NASA Astrophysics Data System (ADS)

Jurzinsky, Tilman; Kurzhals, Philipp; Cremers, Carsten

2018-06-01

The oxygen reduction reaction is in research focus since several decades due to its importance for the overall fuel cell performance. In direct methanol fuel cells, the crossover of methanol and its subsequent parasitic oxidation are main issues when it comes to preventing fuel cell performance losses. In this work, we present a novel differential electrochemical mass spectrometry method to evaluate oxygen reduction reaction catalysts on their tolerance to methanol being present at the cathode. Besides this, the setup allows to measure under more realistic fuel cell conditions than typical rotating disc electrode measurements, because the oxygen reduction reaction is evaluated in gaseous phase and a gas diffusion electrode is used as working electrode. Due to the new method, it was possible to investigate the oxygen reduction reaction on two commonly used catalysts (Pt/C and Pt3Co/C) in absence and presence of methanol. It was found, that Pt3Co/C is less prone to parasitic current losses due to methanol oxidation reaction. By connecting a mass spectrometer to the electrochemical cell, the new method allows to determine the products formed on the catalysts due to parasitic methanol electrooxidation.

Methanol production from Eucalyptus wood chips. Working Document 9. Economics of producing methanol from Eucalyptus in Central Florida

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

Fishkind, H.H.

1982-06-01

A detailed feasibility study of producing methanol from Eucalyptus in Central Florida encompasses all phases of production - from seedling to delivery of finished methanol. The project includes the following components: (1) production of 55 million, high quality, Eucalyptus seedlings through tissue culture; (2) establishment of a Eucalyptus energy plantation on approximately 70,000 acres; and (3) engineering for a 100 million gallon-per-year methanol production facility. In addition, the potential environmental impacts of the whole project were examined, safety and health aspects of producing and using methanol were analyzed, and site specific cost estimates were made. The economics of the projectmore » are presented here. Each of the three major components of the project - tissue culture lab, energy plantation, and methanol refinery - are examined individually. In each case a site specific analysis of the potential return on investment was conducted.« less

(Non) formation of methanol by direct hydrogenation of formate on copper catalysts

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

Yang, Yong; Mims, Charles A.; Disselkamp, Robert S.

2010-10-14

We have attempted to hydrogenate adsorbed formate species on copper catalysts to probe the importance of this postulated mechanistic step in methanol synthesis. Surface formate coverages up to 0.25 were produced at temperatures between 413K and 453K on supported (Cu/SiO2) copper and unsupported copper catalysts. The adlayers were produced by various methods including (1) steady state catalytic conditions in CO2-H2 (3:1, 6 bar) atmospheres, and (2) by exposure of the catalysts to formic acid. As reported in earlier work, the catalytic surface at steady state contains bidentate formate species with coverages up to saturation levels of ~ 0.25 at themore » low temperatures of this study. The reactivity of these formate adlayers was investigated at relevant reaction temperatures in atmospheres containing up to 6 bar H2 partial pressure by simultaneous mass spectrometry (MS) and infrared (IR) spectroscopy measurements. The yield of methanol during the attempted hydrogenation (“titration”) of these adlayers was insignificant (<0.2 mol % of the formate adlayer) even in dry hydrogen partial pressures up to 6 bar. Hydrogen titration of formate species produced from formic acid also failed to produce significant quantities of methanol, and attempted titration in gases consisting of CO-hydrogen mixtures or dry CO2 were also unproductive. The formate decomposition kinetics, measured by IR, were also unaffected by these changes in the gas composition. Similar experiments on unsupported copper also failed to show any methanol. From these results, we conclude that methanol synthesis on copper cannot result from the direct hydrogenation of (bidentate) formate species in simple steps involving adsorbed H species alone. Furthermore, experiments performed on both supported (Cu/SiO2) and unsupported copper catalysts gave similar results implying that the methanol synthesis reaction mechanism only involves metal surface chemistry. Pre-exposure of the bidentate formate adlayer to

A simple preparation of very high methanol tolerant cathode electrocatalyst for direct methanol fuel cell based on polymer-coated carbon nanotube/platinum

PubMed Central

Yang, Zehui; Nakashima, Naotoshi

2015-01-01

The development of a durable and methanol tolerant electrocatalyst with a high oxygen reduction reaction activity is highly important for the cathode side of direct methanol fuel cells. Here, we describe a simple and novel methodology to fabricate a practically applicable electrocatalyst with a high methanol tolerance based on poly[2,2′-(2,6-pyridine)-5,5′-bibenzimidazole]-wrapped multi-walled carbon nanotubes, on which Pt nanoparticles have been deposited, then coated with poly(vinylphosphonic acid) (PVPA). The polymer coated electrocatalyst showed an ~3.3 times higher oxygen reduction reaction activity compared to that of the commercial CB/Pt and methanol tolerance in the presence of methanol to the electrolyte due to a 50% decreased methanol adsorption on the Pt after coating with the PVPA. Meanwhile, the peroxide generation of the PVPA coated electrocatalyst was as low as 0.8% with 2 M methanol added to the electrolyte, which was much lower than those of the non-PVPA-coated electrocatalyst (7.5%) and conventional CB/Pt (20.5%). Such a high methanol tolerance is very important for the design of a direct methanol fuel cell cathode electrocatalyst with a high performance. PMID:26192397

A simple preparation of very high methanol tolerant cathode electrocatalyst for direct methanol fuel cell based on polymer-coated carbon nanotube/platinum.

PubMed