Apparatus and methods for direct conversion of gaseous hydrocarbons to liquids

DOEpatents

Kong, Peter C.; Lessing, Paul A.

2006-04-25

A chemical reactor for direct conversion of hydrocarbons includes a dielectric barrier discharge plasma cell and a solid oxide electrochemical cell in fluid communication therewith. The discharge plasma cell comprises a pair of electrodes separated by a dielectric material and passageway therebetween. The electrochemical cell comprises a mixed-conducting solid oxide electrolyte membrane tube positioned between a porous cathode and a porous anode, and a gas inlet tube for feeding oxygen containing gas to the porous cathode. An inlet is provided for feeding hydrocarbons to the passageway of the discharge plasma cell, and an outlet is provided for discharging reaction products from the reactor. A packed bed catalyst may optionally be used in the reactor to increase efficiency of conversion. The reactor can be modified to allow use of a light source for directing ultraviolet light into the discharge plasma cell and the electrochemical cell.

Method for direct conversion of gaseous hydrocarbons to liquids

DOEpatents

Kong, Peter C.; Lessing, Paul A.

2006-03-07

A chemical reactor for direct conversion of hydrocarbons includes a dielectric barrier discharge plasma cell and a solid oxide electrochemical cell in fluid communication therewith. The discharge plasma cell comprises a pair of electrodes separated by a dielectric material and passageway therebetween. The electrochemical cell comprises a mixed-conducting solid oxide electrolyte membrane tube positioned between a porous cathode and a porous anode, and a gas inlet tube for feeding oxygen containing gas to the porous cathode. An inlet is provided for feeding hydrocarbons to the passageway of the discharge plasma cell, and an outlet is provided for discharging reaction products from the reactor. A packed bed catalyst may optionally be used in the reactor to increase efficiency of conversion. The reactor can be modified to allow use of a light source for directing ultraviolet light into the discharge plasma cell and the electrochemical cell.

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

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

This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s (BETO’s) efforts to enable the development of technologies for the production of infrastructure-compatible, cost-competitive liquid hydrocarbon fuels from lignocellulosic biomass feedstocks. The research funded by BETO is designed to advance the state of technology of biomass feedstock supply and logistics, conversion, and overall system sustainability. It is expected that these research improvements will be made within the 2022 timeframe. As part of their involvement in this research and development effort, the National Renewable Energy Laboratory and the Pacific Northwest National Laboratory investigate the economics ofmore » conversion pathways through the development of conceptual biorefinery process models and techno-economic analysis models. This report 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 or syngas via indirect gasification, gas cleanup, catalytic conversion of syngas to methanol intermediate, methanol dehydration to dimethyl ether (DME), and catalytic conversion of DME to high-octane, gasoline-range hydrocarbon blendstock product. The conversion process configuration leverages technologies previously advanced by research funded by BETO and demonstrated in 2012 with the production of mixed alcohols from biomass. Biomass-derived syngas cleanup via reforming of tars and other hydrocarbons is one of the key technology advancements realized as part of this prior research and 2012 demonstrations. The process described in this report evaluates a new technology area for the downstream utilization of clean biomass-derived syngas for the production of high-octane hydrocarbon products through methanol and DME intermediates. In this process, methanol undergoes dehydration to DME, which is subsequently converted via homologation reactions to high-octane, gasoline-range hydrocarbon products.« less

Thermal conversion of biomass to valuable fuels, chemical feedstocks and chemicals

DOEpatents

Peters, William A [Lexington, MA; Howard, Jack B [Winchester, MA; Modestino, Anthony J [Hanson, MA; Vogel, Fredreric [Villigen PSI, CH; Steffin, Carsten R [Herne, DE

2009-02-24

A continuous process for the conversion of biomass to form a chemical feedstock is described. The biomass and an exogenous metal oxide, preferably calcium oxide, or metal oxide precursor are continuously fed into a reaction chamber that is operated at a temperature of at least 1400.degree. C. to form reaction products including metal carbide. The metal oxide or metal oxide precursor is capable of forming a hydrolizable metal carbide. The reaction products are quenched to a temperature of 800.degree. C. or less. The resulting metal carbide is separated from the reaction products or, alternatively, when quenched with water, hydolyzed to provide a recoverable hydrocarbon gas feedstock.

Heterogeneous kinetic modeling of the catalytic conversion of cycloparaffins

NASA Astrophysics Data System (ADS)

Al-Sabawi, Mustafa N.

The limited availability of high value light hydrocarbon feedstocks along with the rise in crude prices has resulted in the international recognition of the vast potential of Canada's oil sands. With the recent expansion of Canadian bitumen production come, however, many technical challenges, one of which is the significant presence of aromatics and cycloparaffins in bitumen-derived feedstocks. In addition to their negative environmental impact, aromatics limit fluid catalytic cracking (FCC) feedstock conversion, decrease the yield and quality of valuable products such as gasoline and middle distillates, increase levels of polyaromatic hydrocarbons prone to form coke on the catalyst, and ultimately compromise the FCC unit performance. Although cycloparaffins do not have such negative impacts, they are precursors of aromatics as they frequently undergo hydrogen transfer reactions. However, cycloparaffin cracking chemistry involves other competing reactions that are complex and need much investigation. This dissertation provides insights and understanding of the fundamentals of the catalytic cracking of cycloparaffins using carefully selected model compounds such as methylcyclohexane (MCH) and decalin. Thermal and catalytic cracking of these cycloparaffins on FCC-type catalysts are carried out using the CREC Riser Simulator under operating conditions similar to those of the industrial FCC units in terms of temperature, reaction time, reactant partial pressure and catalyst-to-hydrocarbon ratio. The crystallite size of the supported zeolites is varied between 0.4 and 0.9 microns, with both activity and selectivity being monitored. Catalytic conversions ranged between 4 to 16 wt% for MCH and between 8 to 27 wt% for decalin. Reaction pathways of cycloparaffins are determined, and these include ring-opening, protolytic cracking, isomerization, hydrogen transfer and transalkylation. The yields and selectivities of over 60 and 140 products, formed during MCH and decalin catalytic conversions respectively, are reported. Using these data, heterogeneous kinetic models accounting for intracrystallite molecular transport, adsorption and thermal and catalytic cracking of both cycloparaffin reactants are established. Results show that undesirable hydrogen transfer reactions are more pronounced and selectively favoured against other reactions at lower reaction temperatures, while the desirable ring-opening and cracking reactions predominate at the higher reaction temperatures. Moreover, results of the present work show that while crystallite size may have an effect on the overall conversion in some situations, there is a definite effect on the selectivity of products obtained during the cracking of MCH and decalin and the cracking of MCH in a mixture with co-reactants such as 1,3,5-triisopropylbenzene. Keywords. cycloparaffins, naphthenes, fluid catalytic cracking, kinetic modeling, Y-zeolites, diffusion, adsorption, ring-opening, hydrogen transfer, catalyst selectivity.

Coupling of exothermic and endothermic reactions in oxidative conversion of natural gas into ethylene/olefins over diluted SrO/La{sub 2}O{sub 3}/SA5205 catalyst

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

Choudhary, V.R.; Mulla, S.A.R.

1997-09-01

In the oxidative conversion of natural gas to ethylene/lower olefins over SrO (17.3 wt.%)/La{sub 2}O{sub 3} (17.9 wt.%)/SA5205 catalyst diluted with inert solid particles (inerts/catalyst(w/w) = 2.0) in the presence of limited O{sub 2}, the exothermic oxidative conversion reactions of natural gas are coupled with the endothermic C{sub 2+} hydrocarbon thermal cracking reactions for avoiding hot spot formation and eliminating heat removal problems. Because of this, the process is operated in the most energy-efficient and safe manner. The influence of various process variables (viz. temperature, NG/O{sub 2} and steam/NG ratios in feed, and space velocity) on the conversion of carbonmore » and also of the individual hydrocarbons in natural gas, the selectivity for C{sub 2}-C{sub 4} olefins, and also on the net heat of reactions in the process has been thoroughly investigated. By carrying out the process at 800--850 C in the presence of steam (H{sub 2}O/NG {le} 0.2) and using limited O{sub 2} in the feed (NG/O{sub 2} = 12--18), high selectivity for ethylene (about 60%) or C{sub 2}-C{sub 4} olefins (above 80%) at the carbon conversion (>15%) of practical interest could be achieved at high space velocity ({ge}34,000 cm{sup 3}/g (catalyst) h), requiring no external energy and also without forming coke or tar-like products. The net heat of reactions can be controlled and the process can be made mildly exothermic or even close to thermoneutral by manipulating the O{sub 2} concentration in the feed.« less

One-step catalytic conversion of biomass-derived carbohydrates to liquid fuels

DOEpatents

Sen, Ayusman; Yang, Weiran

2014-03-18

The invention relates to a method for manufacture of hydrocarbon fuels and oxygenated hydrocarbon fuels such as alkyl substituted tetrahydrofurans such as 2,5-dimethyltetrahydrofuran, 2-methyltetrahydrofuran, 5-methylfurfural and mixtures thereof. The method generally entails forming a mixture of reactants that includes carbonaceous material, water, a metal catalyst and an acid reacting that mixture in the presence of hydrogen. The reaction is performed at a temperature and for a time sufficient to produce a furan type hydrocarbon fuel. The process may be adapted to provide continuous manufacture of hydrocarbon fuels such as a furan type fuel.

One-step preparation of biological aviation kerosene by catalytic hydrogenation of waste lard over Pt/SAPO-11

NASA Astrophysics Data System (ADS)

Zhang, X.; Chen, Y. B.; Li, X. Y.; Souliyathai, D.; Zhang, S. P.; Wang, Q.; Liu, Q.; Du, J. C.; Zhang, A. M.

2017-11-01

Biological aviation kerosene was produced by one-step catalytic hydrotreatment of waste lard oil over Pt/SAPO-11 in a high-pressure fixed bed micro reactor. The influence of reaction conditions such as temperature, pressure, hydrogen oil ratio, and space velocity on the deoxygenation rate, the selectivity of C8-C16 hydrocarbons and the isomerization rate of C8-C16 hydrocarbons have been investigated. The experimental results showed that the temperature of 400°C, pressure of 5 MPa, hydrogen oil ratio of 1000 and space velocity of 1.2 h-1 were the best experimental reaction conditions. Under these conditions, the conversion rate is 96.62%, the selectivity of C8-C16 hydrocarbons is 50.25%, and the isomerization rate of C8-C16 hydrocarbons is 35.68%.

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

Kim, Dongwook; Vardon, Derek R.; Murali, Dheeptha

We demonstrate hydrothermal (300 degrees C, 10 MPa) catalytic conversion of real waste lipids (e.g., waste vegetable oil, sewer trap grease) to liquid hydrocarbon fuels without net need for external chemical inputs (e.g., H2 gas, methanol). A supported bimetallic catalyst (Pt-Re/C; 5 wt % of each metal) previously shown to catalyze both aqueous phase reforming of glycerol (a triacylglyceride lipid hydrolysis coproduct) to H2 gas and conversion of oleic and stearic acid, model unsaturated and saturated fatty acids, to linear alkanes was applied to process real waste lipid feedstocks in water. For reactions conducted with an initially inert headspace gasmore » (N2), waste vegetable oil (WVO) was fully converted into linear hydrocarbons (C15-C17) and other hydrolyzed byproducts within 4.5 h, and H2 gas production was observed. Addition of H2 to the initial reactor headspace accelerated conversion, but net H2 production was still observed, in agreement with results obtained for aqueous mixtures containing model fatty acids and glycerol. Conversion to liquid hydrocarbons with net H2 production was also observed for a range of other waste lipid feedstocks (animal fat residuals, sewer trap grease, dry distiller's grain oil, coffee oil residual). These findings demonstrate potential for valorization of waste lipids through conversion to hydrocarbons that are more compatible with current petroleum-based liquid fuels than the biodiesel and biogas products of conventional waste lipid processing technologies.« less

Photocatalytic destruction of automobile exhaust emissions

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

Kaviranta, P.D.; Peden, C.H.F.

1996-10-01

Hydrocarbons, carbon monoxide, and nitrogen oxides contained in automobile exhaust emissions are among the major atmospheric air pollutants. During the first few minutes of a cold start of the engine, the emission levels of unburned hydrocarbon and CO pollutants are very high due to the inefficiency of the cold engine and the poor activity of the catalysts lower temperatures. Therefore, it is necessary to provide an alternative approach to deal with this specific problem in order to meet near-term regulatory requirements. Our approach has been to use known photocatalytic reactions obtainable on semiconducting powders such as titanium dioxide. In thismore » presentation we describe our recent studies aimed at the photocatalytic reduction of unburned hydrocarbons and carbon monoxide in automobile exhaust emissions. Our results demonstrate the effective destruction of propylene into water and carbon dioxide. The conversion was found to be dependent on the propylene flow rate. The reaction rate was studied as a function of time, humidity and temperature. The effect of the power of the UV source on conversion will also be presented.« less

Activation of carbon-hydrogen bonds and dihydrogen by 1,2-CH-addition across metal-heteroatom bonds.

PubMed

Webb, Joanna R; Burgess, Samantha A; Cundari, Thomas R; Gunnoe, T Brent

2013-12-28

The controlled conversion of hydrocarbons to functionalized products requires selective C-H bond cleavage. This perspective provides an overview of 1,2-CH-addition of hydrocarbons across d(0) transition metal imido complexes and compares and contrasts these to examples of analogous reactions that involve later transition metal amide, hydroxide and alkoxide complexes with d(6) and d(8) metals.

Influence of the Reaction Temperature on the Nature of the Active and Deactivating Species During Methanol-to-Olefins Conversion over H-SAPO-34

PubMed Central

2017-01-01

The selectivity toward lower olefins during the methanol-to-olefins conversion over H-SAPO-34 at reaction temperatures between 573 and 773 K has been studied with a combination of operando UV–vis diffuse reflectance spectroscopy and online gas chromatography. It was found that the selectivity toward propylene increases in the temperature range of 573–623 K, while it decreases in the temperature range of 623–773 K. The high degree of incorporation of olefins, mainly propylene, into the hydrocarbon pool affects the product selectivity at lower reaction temperatures. The nature and dynamics of the active and deactivating hydrocarbon species with increasing reaction temperature were revealed by a non-negative matrix factorization of the time-resolved operando UV–vis diffuse reflectance spectra. The active hydrocarbon pool species consist of mainly highly methylated benzene carbocations at temperatures between 573 and 598 K, of both highly methylated benzene carbocations and methylated naphthalene carbocations at 623 K, and of only methylated naphthalene carbocations at temperatures between 673 and 773 K. The operando spectroscopy results suggest that the nature of the active species also influences the olefin selectivity. In fact, monoenylic and highly methylated benzene carbocations are more selective to the formation of propylene, whereas the formation of the group of low methylated benzene carbocations and methylated naphthalene carbocations at higher reaction temperatures (i.e., 673 and 773 K) favors the formation of ethylene. At reaction temperatures between 573 and 623 K, catalyst deactivation is caused by the gradual filling of the micropores with methylated naphthalene carbocations, while between 623 and 773 K the formation of neutral poly aromatics and phenanthrene/anthracene carbocations are mainly responsible for catalyst deactivation, their respective contribution increasing with increasing reaction temperature. Methanol pulse experiments at different temperatures demonstrate the dynamics between methylated benzene and methylated naphthalene carbocations. It was found that methylated naphthalene carbocations species are deactivating and block the micropores at low reaction temperatures, while acting as the active species at higher reaction temperatures, although they give rise to the formation of extended hydrocarbon deposits. PMID:28824823

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

NASA Astrophysics Data System (ADS)

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

2014-01-01

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

Fundamentals of Hydrocarbon Upgrading to Liquid Fuels and Commodity Chemicals over Catalytic Metallic Nanoparticles

NASA Astrophysics Data System (ADS)

Chen, Tao

Promising new technologies for biomass conversion into fuels and chemical feedstocks rely on the production of bio-oils, which need to be upgraded in order to remove oxygen-containing hydrocarbons and water. A high oxygen concentration makes bio-oils acidic and corrosive, unstable during storage, and less energetically valuable per unit weight than petroleum-derived hydrocarbons. Although there are efficient processes for the production of bio-oils, there are no efficient technologies for their upgrading. Current technologies utilize traditional petroleum refining catalysts, which are not optimized for biomass processing. New upgrading technologies are, therefore, urgently needed for development of sustainable energy resources. Development of such new technologies, however, is severely hindered by a lack of fundamental understanding of how oxygen and oxygen-containing hydrocarbons derived from biomass interact with promising noble-metal catalysts. In this study, kinetic reaction measurements, catalyst characterization and quantum chemical calculations using density functional theory were combined for determining adsorption modes and reaction mechanisms of hydrocarbons in the presence of oxygen on surfaces of catalytic noble-metal nanoparticles. The results were used for developing improved catalyst formulations and optimization of reaction conditions. The addition of molybdenum to platinum catalysts was shown to improve catalytic activity, stability, and selectivity in hydrodeoxygenation of acetic acid, which served as a model biomass compound. The fundamental results that describe interactions of oxygen and hydrocarbons with noble-metal catalysts were extended to other reactions and fields of study: evaluation of the reaction mechanism for hydrogen peroxide decomposition, development of improved hydrogenation catalysts and determination of adsorption modes of a spectroscopic probe molecule.

Catalytic conversion of alcohols to hydrocarbons with low benzene content

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2016-09-06

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

Catalytic conversion of alcohols to hydrocarbons with low benzene content

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2016-03-08

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

Hydrodeoxygenation of lignin-derived phenolic compounds to hydrocarbons over Ni/SiO2-ZrO2 catalysts.

PubMed

Zhang, Xinghua; Zhang, Qi; Wang, Tiejun; Ma, Longlong; Yu, Yuxiao; Chen, Lungang

2013-04-01

Inexpensive non-sulfided Ni-based catalysts were evaluated for hydrodeoxygenation (HDO) using guaiacol as model compound. SiO2-ZrO2 (SZ), a complex oxide synthesized by precipitation method with different ratio of Si/Zr, was impregnated with Ni(NO3)2·6H2O and calcined at 500°C. Conversion rates and product distribution for guaiacol HDO at 200-340°C were determined. Guaiacol conversion reached the maximum at 300°C in the presence of Ni/SZ-3. When HDO reaction was carried out with real lignin-derived phenolic compounds under the optimal conditions determined for guaiacol, the total yield of hydrocarbons was 62.81%. These hydrocarbons were comprised of cyclohexane, alkyl-substituted cyclohexane and alkyl-substituted benzene. They have high octane number, would be the most desirable components for fungible liquid transportation fuel. Copyright © 2013 Elsevier Ltd. All rights reserved.

Cobalt carbide nanoprisms for direct production of lower olefins from syngas

NASA Astrophysics Data System (ADS)

Zhong, Liangshu; Yu, Fei; An, Yunlei; Zhao, Yonghui; Sun, Yuhan; Li, Zhengjia; Lin, Tiejun; Lin, Yanjun; Qi, Xingzhen; Dai, Yuanyuan; Gu, Lin; Hu, Jinsong; Jin, Shifeng; Shen, Qun; Wang, Hui

2016-10-01

Lower olefins—generally referring to ethylene, propylene and butylene—are basic carbon-based building blocks that are widely used in the chemical industry, and are traditionally produced through thermal or catalytic cracking of a range of hydrocarbon feedstocks, such as naphtha, gas oil, condensates and light alkanes. With the rapid depletion of the limited petroleum reserves that serve as the source of these hydrocarbons, there is an urgent need for processes that can produce lower olefins from alternative feedstocks. The ‘Fischer-Tropsch to olefins’ (FTO) process has long offered a way of producing lower olefins directly from syngas—a mixture of hydrogen and carbon monoxide that is readily derived from coal, biomass and natural gas. But the hydrocarbons obtained with the FTO process typically follow the so-called Anderson-Schulz-Flory distribution, which is characterized by a maximum C2-C4 hydrocarbon fraction of about 56.7 per cent and an undesired methane fraction of about 29.2 per cent (refs 1, 10, 11, 12). Here we show that, under mild reaction conditions, cobalt carbide quadrangular nanoprisms catalyse the FTO conversion of syngas with high selectivity for the production of lower olefins (constituting around 60.8 per cent of the carbon products), while generating little methane (about 5.0 per cent), with the ratio of desired unsaturated hydrocarbons to less valuable saturated hydrocarbons amongst the C2-C4 products being as high as 30. Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syngas into lower olefins.

Metabolic engineering of Saccharomyces cerevisiae for production of fatty acid-derived hydrocarbons.

PubMed

Zhang, Yiming; Nielsen, Jens; Liu, Zihe

2018-06-05

Fatty acid-derived hydrocarbons attract increasing attention as biofuels due to their immiscibility with water, high-energy content, low freezing point, and high compatibility with existing refineries and end-user infrastructures. Yeast Saccharomyces cerevisiae has advantages for production of fatty acid-derived hydrocarbons as its native routes toward fatty acid synthesis involve only a few reactions that allow more efficient conversion of carbon substrates. Here we describe major biosynthetic pathways of fatty acid-derived hydrocarbons in yeast, and summarize key metabolic engineering strategies, including enhancing precursor supply, eliminating competing pathways, and expressing heterologous pathways. With recent advances in yeast production of fatty acid-derived hydrocarbons, our review identifies key research challenges and opportunities for future optimization, and concludes with perspectives and outlooks for further research directions. © 2018 Wiley Periodicals, Inc.

The thermal degradation of 5 alpha (H)-cholestane during closed-system pyrolysis

NASA Astrophysics Data System (ADS)

Abbott, Geoffrey D.; Bennett, Barry; Stuart Fetch, G.

1995-06-01

Involatile hydrocarbons were identified following the heating of 5α(H)-cholestane in water with reaction vessel walls composed of 316 grade stainless steel and borosilicate glass. These analyses were compared with the hydrocarbon product compositions from closed-system pyrolysis experiments with no added water. Unsaturated hydrocarbons dominate their saturated counterparts following hydrous pyrolysis in both stainless steel-316 and borosilicate glass. In the absence of added water the converse is true in that saturated components dominate the hydrocarbon mixture. Backbone rearrangement in the steroid nucleus leading to spirosterene formation was only observed under aqueous conditions in both borosilicate glass and stainless steel-316 vessels. These comparisons demonstrate that water, as opposed to reaction vessel surface catalytic effects, plays a central role in mediating hydrocarbon degradation during closed-system hydrous pyrolysis. 5α(H)-cholestane degradation under aqueous conditions is a complex composite of dissociative and rearrangement processes. These include (I) carbon-carbon bond cleavage in the sidechains as well as the ring system, (2) dehydrogenation, and (3) backbone rearrangement. These laboratory experiments provide a product description of the involatile hydrocarbons which will be the basis for a mechanistic study of 5α(H)-cholestane degradation in hot water.

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

Dagle, Robert A.; Lizarazo Adarme, Jair A.; Lebarbier, Vanessa MC

A composite Pd/ZnO/Al2O3-HZSM-5 (Si/Al=40) catalytic system was evaluated for the synthesis of gasoline-range hydrocarbons directly from synthesis gas. Bifunctional catalyst comprising PdZn metal and acid sites present the required catalytically active sites necessary for the methanol synthesis, methanol dehydration, and methanol-to-gasoline reactions. This system provides a unique catalytic pathway for the production of liquid hydrocarbons directly from syngas. However, selectivity control is difficult and poses many challenges. The composite catalytic system was evaluated under various process conditions. Investigated were the effects of temperature (310-375oC), pressure (300-1000 psig), time-on-stream (50 hrs), and gas-hour space velocity (740-2970 hr-1), using a H2/CO molarmore » syngas ratio of 2.0. By operating at the lower end of the temperature range investigated, liquid hydrocarbon formation was favored, as was decreased amounts of undesirable light hydrocarbons. However, lower operating temperatures also facilitated undesirable CO2 formation via the water-gas shift reaction. Higher operating pressures slightly favored liquid synthesis. Operating at relatively low pressures (e.g. 300 psig) was made possible, whereas for methanol synthesis alone higher pressure are usually required to achieve similar conversion levels (e.g. 1000 psig). Thermodynamic constraints on methanol synthesis are eased by pushing the equilibrium through hydrocarbon formation. Catalytic performance was also evaluated by altering Pd and Zn composition of the Pd/ZnO/Al2O3 catalyst. Of the catalysts and conditions tested, selectivity toward liquid hydrocarbon was highest when using a 5% Pd metal loading and Pd/Zn molar ratio of 0.25 and mixed with HZMS-5, operating at 310oC and 300 psig, CO conversion was 43 % and selectivity (carbon weight basis) to hydrocarbons was 49 wt. %. Of the hydrocarbon fraction, 44wt. % was in the C5-C12 liquid product range and consisted primarily of aromatic polymethylbenzenes. However, as syngas conversion increases with increasing temperature, selectivity to liquid product diminished. This is attributed, in large part, to increased saturation of the olefinic intermediates over PdZn metal sites. Under all the conditions and catalysts evaluated in this study, generating liquid product in high yield was challenging (<10 wt. % C5+ yield).« 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 experimental results indicating that the underlying assumption of the simple model of conversion of hydrocarbons to CO and H 2 followed by equilibrium reconstitution to methane appears to be reasonable one.

Understanding of Electrochemical Mechanisms for CO2 Capture and Conversion into Hydrocarbon Fuels in Transition-Metal Carbides (MXenes).

PubMed

Li, Neng; Chen, Xingzhu; Ong, Wee-Jun; MacFarlane, Douglas R; Zhao, Xiujian; Cheetham, Anthony K; Sun, Chenghua

2017-11-28

Two-dimensional (2D) transition-metal (groups IV, V, VI) carbides (MXenes) with formulas M 3 C 2 have been investigated as CO 2 conversion catalysts with well-resolved density functional theory calculations. While MXenes from the group IV to VI series have demonstrated an active behavior for the capture of CO 2 , the Cr 3 C 2 and Mo 3 C 2 MXenes exhibit the most promising CO 2 to CH 4 selective conversion capabilities. Our results predicted the formation of OCHO • and HOCO • radical species in the early hydrogenation steps through spontaneous reactions. This provides atomic level insights into the computer-aided screening for high-performance catalysts and the understanding of electrochemical mechanisms for CO 2 reduction to energy-rich hydrocarbon fuels, which is of fundamental significance to elucidate the elementary steps for CO 2 fixation.

Tailoring gas-phase CO2 electroreduction selectivity to hydrocarbons at Cu nanoparticles

NASA Astrophysics Data System (ADS)

Merino-Garcia, I.; Albo, J.; Irabien, A.

2018-01-01

Copper-based surfaces appear as the most active catalysts for CO2 electroreduction to hydrocarbons, even though formation rates and efficiencies still need to be improved. The aim of the present work is to evaluate the continuous gas-phase CO2 electroreduction to hydrocarbons (i.e. ethylene and methane) at copper nanoparticulated-based surfaces, paying attention to particle size influence (ranging from 25-80 nm) on reaction productivity, selectivity, and Faraday efficiency (FE) for CO2 conversion. The effect of the current density and the presence of a microporous layer within the working electrode are then evaluated. Copper-based gas diffusion electrodes are prepared by airbrushing the catalytic ink onto carbon supports, which are then coupled to a cation exchange membrane (Nafion) in a membrane electrode assembly. The results show that the use of smaller copper nanoparticles (25 nm) leads to a higher ethylene production (1148 μmol m-2 s-1) with a remarkable high FE (92.8%), at the same time, diminishing the competitive hydrogen evolution reaction in terms of FE. This work demonstrates the importance of nanoparticle size on reaction selectivity, which may be of help to design enhanced electrocatalytic materials for CO2 valorization to hydrocarbons.

The nature of the active surface of the Cu/ZSM-5 catalyst in the reaction of NO reduction with hydrocarbons

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

Ilichev, A.N.; Ukharskii, A.A.; Matyshak, V.A.

1995-03-01

Data are obtained on the concentration of Cu{sup 2+}{sub isol}, Cu{sub ass}, and Cu{sup +} ions and the activity in the reaction of NO reduction with propane on copper-containing zeolites (0.15-2.86% Cu/ZSM-5). A correlation between the NO conversion and Cu{sup 2+}{sub isol} concentration is found and discussed.

Low-temperature gas from marine shales: wet gas to dry gas over experimental time.

PubMed

Mango, Frank D; Jarvie, Daniel M

2009-11-09

Marine shales exhibit unusual behavior at low temperatures under anoxic gas flow. They generate catalytic gas 300 degrees below thermal cracking temperatures, discontinuously in aperiodic episodes, and lose these properties on exposure to trace amounts of oxygen. Here we report a surprising reversal in hydrocarbon generation. Heavy hydrocarbons are formed before light hydrocarbons resulting in wet gas at the onset of generation grading to dryer gas over time. The effect is moderate under gas flow and substantial in closed reactions. In sequential closed reactions at 100 degrees C, gas from a Cretaceous Mowry shale progresses from predominately heavy hydrocarbons (66% C5, 2% C1) to predominantly light hydrocarbons (56% C1, 8% C5), the opposite of that expected from desorption of preexisting hydrocarbons. Differences in catalyst substrate composition explain these dynamics. Gas flow should carry heavier hydrocarbons to catalytic sites, in contrast to static conditions where catalytic sites are limited to in-place hydrocarbons. In-place hydrocarbons and their products should become lighter with conversion thus generating lighter hydrocarbon over time, consistent with our experimental results. We recognize the similarities between low-temperature gas generation reported here and the natural progression of wet gas to dry gas over geologic time. There is now substantial evidence for natural catalytic activity in source rocks. Natural gas at thermodynamic equilibrium and the results reported here add to that evidence. Natural catalysis provides a plausible and unique explanation for the origin and evolution of gas in sedimentary basins.

Storage of Renewable Energy by Reduction of CO2 with Hydrogen.

PubMed

Züttel, Andreas; Mauron, Philippe; Kato, Shunsuke; Callini, Elsa; Holzer, Marco; Huang, Jianmei

2015-01-01

The main difference between the past energy economy during the industrialization period which was mainly based on mining of fossil fuels, e.g. coal, oil and methane and the future energy economy based on renewable energy is the requirement for storage of the energy fluxes. Renewable energy, except biomass, appears in time- and location-dependent energy fluxes as heat or electricity upon conversion. Storage and transport of energy requires a high energy density and has to be realized in a closed materials cycle. The hydrogen cycle, i.e. production of hydrogen from water by renewable energy, storage and use of hydrogen in fuel cells, combustion engines or turbines, is a closed cycle. However, the hydrogen density in a storage system is limited to 20 mass% and 150 kg/m(3) which limits the energy density to about half of the energy density in fossil fuels. Introducing CO(2) into the cycle and storing hydrogen by the reduction of CO(2) to hydrocarbons allows renewable energy to be converted into synthetic fuels with the same energy density as fossil fuels. The resulting cycle is a closed cycle (CO(2) neutral) if CO(2) is extracted from the atmosphere. Today's technology allows CO(2) to be reduced either by the Sabatier reaction to methane, by the reversed water gas shift reaction to CO and further reduction of CO by the Fischer-Tropsch synthesis (FTS) to hydrocarbons or over methanol to gasoline. The overall process can only be realized on a very large scale, because the large number of by-products of FTS requires the use of a refinery. Therefore, a well-controlled reaction to a specific product is required for the efficient conversion of renewable energy (electricity) into an easy to store liquid hydrocarbon (fuel). In order to realize a closed hydrocarbon cycle the two major challenges are to extract CO(2) from the atmosphere close to the thermodynamic limit and to reduce CO(2) with hydrogen in a controlled reaction to a specific hydrocarbon. Nanomaterials with nanopores and the unique surface structures of metallic clusters offer new opportunities for the production of synthetic fuels.

Flash Cracking Reactor for Waste Plastic Processing

NASA Technical Reports Server (NTRS)

Timko, Michael T.; Wong, Hsi-Wu; Gonzalez, Lino A.; Broadbelt, Linda; Raviknishan, Vinu

2013-01-01

Conversion of waste plastic to energy is a growing problem that is especially acute in space exploration applications. Moreover, utilization of heavy hydrocarbon resources (wastes, waxes, etc.) as fuels and chemicals will be a growing need in the future. Existing technologies require a trade-off between product selectivity and feedstock conversion. The objective of this work was to maintain high plastic-to-fuel conversion without sacrificing the liquid yield. The developed technology accomplishes this goal with a combined understanding of thermodynamics, reaction rates, and mass transport to achieve high feed conversion without sacrificing product selectivity. The innovation requires a reaction vessel, hydrocarbon feed, gas feed, and pressure and temperature control equipment. Depending on the feedstock and desired product distribution, catalyst can be added. The reactor is heated to the desired tempera ture, pressurized to the desired pressure, and subject to a sweep flow at the optimized superficial velocity. Software developed under this project can be used to determine optimal values for these parameters. Product is vaporized, transferred to a receiver, and cooled to a liquid - a form suitable for long-term storage as a fuel or chemical. An important NASA application is the use of solar energy to convert waste plastic into a form that can be utilized during periods of low solar energy flux. Unlike previous work in this field, this innovation uses thermodynamic, mass transport, and reaction parameters to tune product distribution of pyrolysis cracking. Previous work in this field has used some of these variables, but never all in conjunction for process optimization. This method is useful for municipal waste incinerator operators and gas-to-liquids companies.

Underground thermal generation of hydrocarbons from dry, southwestern coals

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

Vanderborgh, N.E.; Elliott, G.R.B.

1978-01-01

The LASL underground coal conversion concept produces intermediate-BTU fuel gas for nearby industries such as ''minemouth'' electric power plants, plus major byproducts in the form of liquid and gaseous hydrocarbons for feedstocks to chemical plants e.g., substitute natural gas (SNG) producers. The concept involves controlling the water influx and drying the coal, generating hydrocarbons, by pyrolysis and finally gasifying the residual char with O/sub 2//CO/sub 2/ or air/CO/sub 2/ mixtures to produce industrial fuel gases. Underground conversion can be frustrated by uncontrolled water in the coal bed. Moisture can (a) prevent combustion, (b) preclude fuel gas formation by lowering reactionmore » zone temperatures and creating kinetic problems, (c) ruin product gas quality by dropping temperatures into a thermodynamically unsatisfactory regime, (d) degrade an initially satisfactory fuel gas by consuming carbon monoxide, (e) waste large amounts of heat, and (f) isolate reaction zones so that the processing will bypass blocks of coal.« less

Aromatic Radicals-Acetylene Particulate Matter Chemistry

DTIC Science & Technology

2011-12-01

in the fuel itself. For example, alkylated aromatic hydrocarbons form major constituents of gasoline, diesel and jet fuels due to their high energy... jet stirred reactor data at stoichiometric conditions the model shows greater consumption of fuel , oxygen and earlier formation of the intermediates...reaction time of 0.1s, which are the typical reaction times for complete conversion of the fuel in a plug flow reactor or the residence time in a jet

Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

NASA Astrophysics Data System (ADS)

Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A.; Wäckerlin, Aneliia; Meyer, Ernst

2017-03-01

Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect - oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

Improving hydrocarbon yield from catalytic fast co-pyrolysis of hemicellulose and plastic in the dual-catalyst bed of CaO and HZSM-5.

PubMed

Ding, Kuan; Zhong, Zhaoping; Wang, Jia; Zhang, Bo; Fan, Liangliang; Liu, Shiyu; Wang, Yunpu; Liu, Yuhuan; Zhong, Daoxu; Chen, Paul; Ruan, Roger

2018-08-01

The high concentration of oxygenated compounds in pyrolytic products prohibits the conversion of hemicellulose to important biofuels and chemicals via fast pyrolysis. Herein a dual-catalyst bed of CaO and HZSM-5 was developed to convert acids in the pyrolytic products of xylan to valuable hydrocarbons. Meanwhile, LLDPE was co-pyrolyzed with xylan to supplement hydrogen during the catalysis of HZSM-5. The results showed that CaO could effectively transform acids into ketones. A minimum yield of acids (2.74%) and a maximum yield of ketones (42.93%) were obtained at a catalyst to feedstock ratio of 2:1. The dual-catalyst bed dramatically increased the yield of aromatics. Moreover, hydrogen-rich fragments derived from LLDPE promoted the Diels-Alder reactions of furans and participated in the hydrocarbon pool reactions of non-furanic compounds. As a result, a higher yield of hydrocarbons was achieved. This study provides a fundamental for recovering energy and chemicals from pyrolysis of hemicellulose. Copyright © 2018 Elsevier Ltd. All rights reserved.

Catalysts for conversion of methane to higher hydrocarbons

DOEpatents

Siriwardane, Ranjani V.

1993-01-01

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

Investigation of Thermochemistry Associated with the Carbon–Carbon Coupling Reactions of Furan and Furfural Using ab Initio Methods

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

Liu, Cong; Assary, Rajeev S.; Curtiss, Larry A.

2014-06-26

Upgrading of furan and small oxygenates obtained from the decomposition of cellulosic materials via formation of carbon-carbon bonds is critical to effective conversion of biomass to liquid transportation fuels. Simulation-driven molecular level understanding of carbon-carbon bond formation is required to design efficient catalysts and processes. Accurate quantum chemical methods are utilized here to predict the reaction energetics for conversion of furan (C4H4O) to C5-C8 ethers and the transformation of furfural (C5H6O2) to C13-C26 alkanes. Furan, can be coupled with various C1 to C4 lower molecular weight carbohydrates obtained from the pyrolysis via Diels-Alder type reactions in the gas phase tomore » produce C5-C8 cyclic ethers. The computed reaction barriers for these reactions (~25 kcal/mol) are lower than the cellulose activation or decomposition reactions (~50 kcal/mol). Cycloaddition of C5-C8 cyclo-ethers with furans can also occur in the gas phase, and the computed activation energy is similar to that of the first Diels-Alder reaction. Furfural, obtained from biomass, can be coupled with aldehydes or ketones with α-hydrogen atoms to form longer chain aldol products and these aldol products can undergo vapor phase hydrocycloaddition (activation barrier of ~20 kcal/mol) to form the precursors of C26 cyclic hydrocarbons. These thermochemical studies provide the basis for further vapor phase catalytic studies required for upgrading of furans/furfurals to longer chain hydrocarbons.« less

Mixed Alcohol Dehydration over Bronsted and Lewis Acidic Catalysts

DOE PAGES

Nash, Connor P.; Ramanathan, Anand; Ruddy, Daniel A.; ...

2015-12-01

Mixed alcohols are attractive oxygenated products of biomass-derived syngas because they may be catalytically converted to a range of hydrocarbon products, including liquid hydrocarbon fuels. Catalytic dehydration to form olefins is a potential first step in the conversion of C 2–C 4 alcohols into longer-chain hydrocarbons. Here, we describe the physical and chemical characterization along with catalytic activity and selectivity of 4 Brønsted and Lewis acidic catalysts for the dehydration of two mixed alcohol feed streams that are representative of products from syngas conversion over K-CoMoS type catalysts (i.e., ethanol, 1-propanol, 1-butanol and 2-methyl-1-propanol). Specifically, a Lewis acidic Zr-incorporated mesoporousmore » silicate (Zr-KIT-6), a commercial Al-containing mesoporous silicate (Al-MCM-41), a commercial microporous aluminosilicate (HZSM-5), and a commercial microporous silicoaluminophosphate (SAPO-34) were tested for mixed alcohol dehydration at 250, 300 and 350 °C. The zeolite materials exhibited high activity (>98% ethanol conversion) at all temperatures while the mesoporous materials only displayed significant activity (>10% ethanol conversion) at or above 300 °C. The turnover frequencies for ethanol dehydration at 300 °C decreased in the following order: HZSM-5 > SAPO-34 > Al-MCM-41 > Zr-KIT-6, suggesting that Brønsted acidic sites are more active than Lewis acidic sites for alcohol dehydration. At 300 °C, SAPO-34 produced the highest yield of olefin products from both a water-free ethanol rich feed stream and a C 3+-alcohol rich feed stream containing water. Post-reaction characterization indicated changes in the Brønsted-to-Lewis acidic site ratios for Zr-KIT-6, Al-MCM-41 and HZSM-5. Ammonia temperature programmed desorption indicated that the acid sites of post-reaction samples could be regenerated following treatment in air. The post-reaction SAPO-34 catalyst contained more aromatic, methylated aromatic and polyaromatic compounds than its zeolite counterpart HZSM-5, while no aromatic compounds were observed on post-reaction Al-MCM-41 or Zr-KIT-6 catalysts. Olefin yield at 300 °C over SAPO-34 (>95%) was comparable to published values for the methanol-to-olefins process, indicating the potential industrial application of mixed alcohol dehydration. Furthermore, the olefin product distribution over SAPO-34 was tunable by the composition of the alcohol feed mixture.« less

Mixed Alcohol Dehydration over Bronsted and Lewis Acidic Catalysts

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

Nash, Connor P.; Ramanathan, Anand; Ruddy, Daniel A.

Mixed alcohols are attractive oxygenated products of biomass-derived syngas because they may be catalytically converted to a range of hydrocarbon products, including liquid hydrocarbon fuels. Catalytic dehydration to form olefins is a potential first step in the conversion of C 2–C 4 alcohols into longer-chain hydrocarbons. Here, we describe the physical and chemical characterization along with catalytic activity and selectivity of 4 Brønsted and Lewis acidic catalysts for the dehydration of two mixed alcohol feed streams that are representative of products from syngas conversion over K-CoMoS type catalysts (i.e., ethanol, 1-propanol, 1-butanol and 2-methyl-1-propanol). Specifically, a Lewis acidic Zr-incorporated mesoporousmore » silicate (Zr-KIT-6), a commercial Al-containing mesoporous silicate (Al-MCM-41), a commercial microporous aluminosilicate (HZSM-5), and a commercial microporous silicoaluminophosphate (SAPO-34) were tested for mixed alcohol dehydration at 250, 300 and 350 °C. The zeolite materials exhibited high activity (>98% ethanol conversion) at all temperatures while the mesoporous materials only displayed significant activity (>10% ethanol conversion) at or above 300 °C. The turnover frequencies for ethanol dehydration at 300 °C decreased in the following order: HZSM-5 > SAPO-34 > Al-MCM-41 > Zr-KIT-6, suggesting that Brønsted acidic sites are more active than Lewis acidic sites for alcohol dehydration. At 300 °C, SAPO-34 produced the highest yield of olefin products from both a water-free ethanol rich feed stream and a C 3+-alcohol rich feed stream containing water. Post-reaction characterization indicated changes in the Brønsted-to-Lewis acidic site ratios for Zr-KIT-6, Al-MCM-41 and HZSM-5. Ammonia temperature programmed desorption indicated that the acid sites of post-reaction samples could be regenerated following treatment in air. The post-reaction SAPO-34 catalyst contained more aromatic, methylated aromatic and polyaromatic compounds than its zeolite counterpart HZSM-5, while no aromatic compounds were observed on post-reaction Al-MCM-41 or Zr-KIT-6 catalysts. Olefin yield at 300 °C over SAPO-34 (>95%) was comparable to published values for the methanol-to-olefins process, indicating the potential industrial application of mixed alcohol dehydration. Furthermore, the olefin product distribution over SAPO-34 was tunable by the composition of the alcohol feed mixture.« less

Chemical Aspects of Astrophysically Observed Extraterrestrial Methanol, Hydrocarbon Derivatives, and Ions.

PubMed

Olah, George A; Mathew, Thomas; Prakash, G K Surya; Rasul, Golam

2016-02-10

Astrophysically observed extraterrestrial molecular matter contains, besides hydrogen and water, methane and methanol as the most abundant species. Feasible pathways and chemical aspects of their formation as well as of derived hydrocarbon homologues and their ions (carbocations and carbanions) are discussed on the basis of observed similarities with our studied terrestrial chemistry. The preferred pathway for converting extraterrestrial methane according to Ali et al. is based on CH5(+) and Olah's related nonclassical carbonium ion chemistry. On the basis of the observed higher reactivity of methanol compared with methane in various chemical reactions, a feasible new pathway is proposed for the conversion of extraterrestrial methanol to hydrocarbons, their derivatives, and carbocations together with a possible connection with methonium ion-based chemistry.

Massachusetts Lowell low speed wind tunnel (LSWT) test section

NASA Astrophysics Data System (ADS)

Anderson, Erik William

The alumina and hybrid alumina-silica FT catalyst were prepared by one-step solgel/oil-drop methods using metal-nitrate-solutions (method-I), and nanoparticle-metaloxides (method-2). The nanoparticle-metal-oxides did not participate in solubility equilibria in contrast to metal nitrate in method-1 causing no metal ion seepage; therefore, method-2 yields higher XRF metal loading efficiency than method-1. The thermal analysis confirmed that the metal loading by method-1 and method-2 involved two different pathways. Method-1 involves solubility equilibria in the conversion of metal-nitrate to metal- hydroxide and finally to metal-oxide, while in method-2 nanoparticle-metal-oxide remained intact during sol-gel-oil-drop and calcination steps. The alumina supported catalysts were dominated by gamma-alumina PXRD peaks in alumina catalysts while amorphous alumino-silicate phase was the bulk of hybrid alumina-silica catalysts. The presence of cobalt oxides (CoO, Co3O4) and iron oxides (FeO, Fe2O3) phases are confirmed in the catalysts prepared by method-1 and method-2. The PXRD analysis indicated weak peak intensities in catalysts with 5 wt. % total metal loading. PXRD pattern confirmed alloy formation in the bimetallic catalysts (CoFe2O4) on alumina support phase gamma-A12 O3. The surface area and pore diameter of hybrid alumina-silica granules (301 - 372 m2/g and 7.3 nm) showed better values than the alumina granules (251 - 256 m2/g and 6.5 nm). The support pore diameter of both types of granules is within the mesoporous range (1 - 50 nm). The morphology of all the catalysts is preserved upon metal loading and heat treatments. The surface characteristics of the sol-gel-oil-drop method prepared catalysts indicate there was no significant pore blockage of the support below 10 wt % total metal loading. The CO conversion of the FT catalysts was measured to screen catalytic active metals and determine the optimum temperatures of the FT reaction for the alumina catalysts. The alumina FT catalysts showed an optimum reaction temperature of 250 °C. Hydrocarbon production and CO conversion of alumina and hybrid alumina-silica FT catalysts were investigated. Among monometallic alumina catalysts, Co(5%) showed a higher CO conversion. The incorporation of Fe to Co increased CO conversion and hydrocarbon production. Increased Fe content in the bimetallic catalysts prepared by combined method-1&2, decreased CO conversion and hydrocarbon production, and increased CO 2 production. The bimetallic nano-Co(2.5%)nano-Fe(2.5%) prepared by method-2 alone showed higher CO conversion comparable to the Co(4%)nano-Fe(l %). Hybrid alumina-silica FT catalysts showed a higher CO conversion than the alumina FT catalysts due to better surface characteristics. The monometallic catalysts showed higher selectivity to C1-C4 hydrocarbon than bimetallic. The bimetallic alumina FT catalysts prepared by method-2 showed slightly higher C5+ selectivity compared to the higher Co catalysts prepared by combined method- I &2. The Ru promotion showed a significant effect on the CO conversion and 11 product distribution of the monometallic catalysts. There was no significant effect on the CO conversion on the (Co-Fe) bimetallic catalysts, but hydrocarbon production slightly increased when promoted by 0.5 wt.% Ru.

Synthesis, characterization, and activity of Co/Fe alumina/silica supported Ft catalysts and the study of promoter effect of ruthenium

NASA Astrophysics Data System (ADS)

Esumike, Sunday Azubike

The alumina and hybrid alumina-silica FT catalyst were prepared by one-step solgel/oil-drop methods using metal-nitrate-solutions (method-I), and nanoparticle-metaloxides (method-2). The nanoparticle-metal-oxides did not participate in solubility equilibria in contrast to metal nitrate in method-1 causing no metal ion seepage; therefore, method-2 yields higher XRF metal loading efficiency than method-1. The thermal analysis confirmed that the metal loading by method-1 and method-2 involved two different pathways. Method-1 involves solubility equilibria in the conversion of metal-nitrate to metal- hydroxide and finally to metal-oxide, while in method-2 nanoparticle-metal-oxide remained intact during sol-gel-oil-drop and calcination steps. The alumina supported catalysts were dominated by gamma-alumina PXRD peaks in alumina catalysts while amorphous alumino-silicate phase was the bulk of hybrid alumina-silica catalysts. The presence of cobalt oxides (CoO, Co3O4) and iron oxides (FeO, Fe2O3) phases are confirmed in the catalysts prepared by method-1 and method-2. The PXRD analysis indicated weak peak intensities in catalysts with 5 wt. % total metal loading. PXRD pattern confirmed alloy formation in the bimetallic catalysts (CoFe2O4) on alumina support phase gamma-A12 O3. The surface area and pore diameter of hybrid alumina-silica granules (301 - 372 m2/g and 7.3 nm) showed better values than the alumina granules (251 - 256 m2/g and 6.5 nm). The support pore diameter of both types of granules is within the mesoporous range (1 - 50 nm). The morphology of all the catalysts is preserved upon metal loading and heat treatments. The surface characteristics of the sol-gel-oil-drop method prepared catalysts indicate there was no significant pore blockage of the support below 10 wt % total metal loading. The CO conversion of the FT catalysts was measured to screen catalytic active metals and determine the optimum temperatures of the FT reaction for the alumina catalysts. The alumina FT catalysts showed an optimum reaction temperature of 250 °C. Hydrocarbon production and CO conversion of alumina and hybrid alumina-silica FT catalysts were investigated. Among monometallic alumina catalysts, Co(5%) showed a higher CO conversion. The incorporation of Fe to Co increased CO conversion and hydrocarbon production. Increased Fe content in the bimetallic catalysts prepared by combined method-1&2, decreased CO conversion and hydrocarbon production, and increased CO 2 production. The bimetallic nano-Co(2.5%)nano-Fe(2.5%) prepared by method-2 alone showed higher CO conversion comparable to the Co(4%)nano-Fe(l %). Hybrid alumina-silica FT catalysts showed a higher CO conversion than the alumina FT catalysts due to better surface characteristics. The monometallic catalysts showed higher selectivity to C1-C4 hydrocarbon than bimetallic. The bimetallic alumina FT catalysts prepared by method-2 showed slightly higher C5+ selectivity compared to the higher Co catalysts prepared by combined method- I &2. The Ru promotion showed a significant effect on the CO conversion and 11 product distribution of the monometallic catalysts. There was no significant effect on the CO conversion on the (Co-Fe) bimetallic catalysts, but hydrocarbon production slightly increased when promoted by 0.5 wt.% Ru.

Chemicals and energy co-generation from direct hydrocarbons/oxygen proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Li, W. S.; Lu, D. S.; Luo, J. L.; Chuang, K. T.

A proton exchange membrane fuel cell for chemicals and energy co-generation was set up with hydrocarbons ethane, propane and butane as fuels, and the electrochemical performance of the cell was studied by using linear potential sweep, alternating current impedance and gas chromatography. The cell performance can be improved to a great extent by increasing the platinum load in the catalyst, by treating the membrane with phosphoric acid and by elevating temperature. The improvement of cell performance by the increase of platinum load is ascribed to the increase of reaction sites for hydrocarbon oxidation, that by phosphoric acid treatment to the increase of proton conductivity in Nafion membrane, and that by elevating temperature to the improvement in thermodynamic as well as kinetic aspects. Only a small fraction of the hydrocarbon is converted to carbon dioxide in this cell during its power generation. The current efficiency is 5% for the conversion of ethane to carbon dioxide in the ethane/oxygen fuel cell with 20% carbon-supported platinum as catalyst and phosphoric acid-treated membrane as proton exchange membrane at 0.2 V, 80 °C and ambient pressure. The reaction activity of hydrocarbons at the anode is in the order of propane, butane and ethane. The possible chemicals produced from the cell were hydrocarbons with more than six carbons, which are inactive at the anode under cell conditions.

Methane Pyrolysis and Disposing Off Resulting Carbon

NASA Technical Reports Server (NTRS)

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

1999-01-01

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

Performance of ultraviolet photocatalytic oxidation for indoor air cleaning applications.

PubMed

Hodgson, A T; Destaillats, H; Sullivan, D P; Fisk, W J

2007-08-01

Ultraviolet photocatalytic oxidation (UVPCO) systems for removal of volatile organic compounds (VOCs) from air are being considered for use in office buildings. Here, we report an experimental evaluation of a UVPCO device with tungsten oxide modified titanium dioxide (TiO2) as the photocatalyst. The device was challenged with complex VOC mixtures. One mixture contained 27 VOCs characteristic of office buildings and another comprised 10 VOCs emitted by cleaning products, in both cases at realistic concentrations (low ppb range). VOC conversion efficiencies varied widely, usually exceeded 20%, and were as high as approximately 80% at about 0.03 s residence time. Conversion efficiency generally diminished with increased airflow rate, and followed the order: alcohols and glycol ethers > aldehydes, ketones, and terpene hydrocarbons > aromatic and alkane hydrocarbons > halogenated aliphatic hydrocarbons. Conversion efficiencies correlated with the Henry's law constant more closely than with other physicochemical parameters. An empirical model based on the Henry's law constant and the gas-phase reaction rate with hydroxyl radical provided reasonable estimates of pseudo-first order photocatalytic reaction rates. Formaldehyde, acetaldehyde, acetone, formic acid and acetic acid were produced by the device due to incomplete mineralization of common VOCs. Formaldehyde outlet/inlet concentration ratios were in the range 1.9-7.2. Implementation of air cleaning technologies for both VOCs and particles in office buildings may improve indoor air quality, or enable indoor air quality levels to be maintained with reduced outdoor air supply and concomitant energy savings. One promising air cleaning technology is ultraviolet photocatalytic oxidation (UVPCO) air cleaning. For the prototype device evaluated here with realistic mixtures of VOCs, conversion efficiencies typically exceeded the minimum required to counteract predicted VOC concentration increases from a 50% reduction in ventilation. However, the device resulted in the net generation of formaldehyde and acetaldehyde from the partial oxidation of ubiquitous VOCs. Further development of the technology is needed to eliminate these hazardous air pollutants before such a UVPCO device can be deployed in buildings.

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

Not Available

Phillips Petroleum Co. is poised to license its high conversion process to produce fuel ethers for blending in reformulated gasolines. The technology has been proven in a Phillips semiworks at Bartlesville, Okla. The process can produce methyl tertiary butyl ether, ethyl tertiary butyl ether, tertiary amyl methyl ether, or tertiary amyl ethyl ether with typical refinery process equipment and techniques. Phillips said it can achieve conversion levels of 92-99%, depending on the ether. The ether produced is determined by which hydrocarbon fraction is used for feedstock and which alcohol is chosen for reaction. The process is described.

Heterobimetallic Zeolite, InV-ZSM-5, Enables Efficient Conversion of Biomass Derived Ethanol to Renewable Hydrocarbons

NASA Astrophysics Data System (ADS)

Narula, Chaitanya K.; Li, Zhenglong; Casbeer, Erik M.; Geiger, Robert A.; Moses-Debusk, Melanie; Keller, Martin; Buchanan, Michelle V.; Davison, Brian H.

2015-11-01

Direct catalytic conversion of ethanol to hydrocarbon blend-stock can increase biofuels use in current vehicles beyond the ethanol blend-wall of 10-15%. Literature reports describe quantitative conversion of ethanol over zeolite catalysts but high C2 hydrocarbon formation renders this approach unsuitable for commercialization. Furthermore, the prior mechanistic studies suggested that ethanol conversion involves endothermic dehydration step. Here, we report the complete conversion of ethanol to hydrocarbons over InV-ZSM-5 without added hydrogen and which produces lower C2 (<13%) as compared to that over H-ZSM-5. Experiments with C2H5OD and in situ DRIFT suggest that most of the products come from the hydrocarbon pool type mechanism and dehydration step is not necessary. Thus, our method of direct conversion of ethanol offers a pathway to produce suitable hydrocarbon blend-stock that may be blended at a refinery to produce fuels such as gasoline, diesel, JP-8, and jet fuel, or produce commodity chemicals such as BTX.

Heterobimetallic Zeolite, InV-ZSM-5, Enables Efficient Conversion of Biomass Derived Ethanol to Renewable Hydrocarbons.

PubMed

Narula, Chaitanya K; Li, Zhenglong; Casbeer, Erik M; Geiger, Robert A; Moses-Debusk, Melanie; Keller, Martin; Buchanan, Michelle V; Davison, Brian H

2015-11-03

Direct catalytic conversion of ethanol to hydrocarbon blend-stock can increase biofuels use in current vehicles beyond the ethanol blend-wall of 10-15%. Literature reports describe quantitative conversion of ethanol over zeolite catalysts but high C2 hydrocarbon formation renders this approach unsuitable for commercialization. Furthermore, the prior mechanistic studies suggested that ethanol conversion involves endothermic dehydration step. Here, we report the complete conversion of ethanol to hydrocarbons over InV-ZSM-5 without added hydrogen and which produces lower C2 (<13%) as compared to that over H-ZSM-5. Experiments with C2H5OD and in situ DRIFT suggest that most of the products come from the hydrocarbon pool type mechanism and dehydration step is not necessary. Thus, our method of direct conversion of ethanol offers a pathway to produce suitable hydrocarbon blend-stock that may be blended at a refinery to produce fuels such as gasoline, diesel, JP-8, and jet fuel, or produce commodity chemicals such as BTX.

A new technique for measuring gas conversion factors for hydrocarbon mass flowmeters

NASA Technical Reports Server (NTRS)

Singh, J. J.; Sprinkle, D. R.

1983-01-01

A technique for measuring calibration conversion factors for hydrocarbon mass flowmeters was developed. It was applied to a widely used type of commercial thermal mass flowmeter for hydrocarbon gases. The values of conversion factors for two common hydrocarbons measured using this technique are in good agreement with the empirical values cited by the manufacturer. Similar agreements can be expected for all other hydrocarbons. The technique is based on Nernst theorem for matching the partial pressure of oxygen in the combustion product gases with that in normal air. It is simple, quick and relatively safe--particularly for toxic/poisonous hydrocarbons.

Conversion of oligomeric starch, cellulose, or sugars to hydrocarbons

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

Silks, Louis A.; Sutton, Andrew; Kim, Jin Kyung

The present invention is directed to the one step selective conversion of starch, cellulose, or glucose to molecules containing 7 to 26 contiguous carbon atoms. The invention is also directed to the conversion of those intermediates to saturated hydrocarbons. Such saturated hydrocarbons are useful as, for example, fuels.

Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbons: Dilute-Acid and Enzymatic Deconstruction of Biomass to Sugars and Biological Conversion of Sugars to Hydrocarbons

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

Davis, R.; Tao, L.; Tan, E. C. D.

2013-10-01

This report describes one potential conversion process to hydrocarbon products by way of biological conversion of lingnocellulosic-dervied sugars. The process design converts biomass to a hydrocarbon intermediate, a free fatty acid, using dilute-acid pretreatement, enzymatic saccharification, and bioconversion. Ancillary areas--feed handling, hydrolysate conditioning, product recovery and upgrading (hydrotreating) to a final blendstock material, wastewater treatment, lignin combusion, and utilities--are also included in the design.

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

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

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

2010-11-30

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

Catalytic conversion of syngas to mixed alcohols over Zn-Mn promoted Cu-Fe based catalyst

DOE PAGES

Lu, Yongwu; Yu, Fei; Hu, Jin; ...

2012-04-12

Zn-Mn promoted Cu-Fe based catalyst was synthesized by the co-precipitation method. Mixed alcohols synthesis from syngas was studied in a half-inch tubular reactor system after the catalyst was reduced. Zn-Mn promoted Cu-Fe based catalyst was characterized by SEM-EDS, TEM, XRD, and XPS. The liquid phase products (alcohol phase and hydrocarbon phase) were analyzed by GC-MS and the gas phase products were analyzed by GC. The results showed that Zn-Mn promoted Cu-Fe based catalyst had high catalytic activity and high alcohol selectivity. The maximal CO conversion rate was 72%, and the yield of alcohol and hydrocarbons were also very high. Cumore » (111) was the active site for mixed alcohols synthesis, Fe 2C (101) was the active site for olefin and paraffin synthesis. The reaction mechanism of mixed alcohols synthesis from syngas over Zn-Mn promoted Cu-Fe based catalyst was proposed. Here, Zn-Mn promoted Cu-Fe based catalyst can be regarded as a potential candidate for catalytic conversion of biomass-derived syngas to mixed alcohols.« less

Heterobimetallic Zeolite, InV-ZSM-5, Enables Efficient Conversion of Biomass Derived Ethanol to Renewable Hydrocarbons

PubMed Central

Narula, Chaitanya K.; Li, Zhenglong; Casbeer, Erik M.; Geiger, Robert A.; Moses-Debusk, Melanie; Keller, Martin; Buchanan, Michelle V.; Davison, Brian H.

2015-01-01

Direct catalytic conversion of ethanol to hydrocarbon blend-stock can increase biofuels use in current vehicles beyond the ethanol blend-wall of 10–15%. Literature reports describe quantitative conversion of ethanol over zeolite catalysts but high C2 hydrocarbon formation renders this approach unsuitable for commercialization. Furthermore, the prior mechanistic studies suggested that ethanol conversion involves endothermic dehydration step. Here, we report the complete conversion of ethanol to hydrocarbons over InV-ZSM-5 without added hydrogen and which produces lower C2 (<13%) as compared to that over H-ZSM-5. Experiments with C2H5OD and in situ DRIFT suggest that most of the products come from the hydrocarbon pool type mechanism and dehydration step is not necessary. Thus, our method of direct conversion of ethanol offers a pathway to produce suitable hydrocarbon blend-stock that may be blended at a refinery to produce fuels such as gasoline, diesel, JP-8, and jet fuel, or produce commodity chemicals such as BTX. PMID:26526963

Heterobimetallic zeolite, InV-ZSM-5, enables efficient conversion of biomass derived ethanol to renewable hydrocarbons

DOE PAGES

Narula, Chaitanya K.; Li, Zhenglong; Casbeer, Erik M.; ...

2015-11-03

Here, direct catalytic conversion of ethanol to hydrocarbon blend-stock can increase biofuels use in current vehicles beyond the ethanol blend-wall of 10–15%. Literature reports describe quantitative conversion of ethanol over zeolite catalysts but high C 2 hydrocarbon formation renders this approach unsuitable for commercialization. Furthermore, the prior mechanistic studies suggested that ethanol conversion involves endothermic dehydration step. Here, we report the complete conversion of ethanol to hydrocarbons over InV-ZSM-5 without added hydrogen and which produces lower C 2 (<13%) as compared to that over H-ZSM-5. Experiments with C 2H 5OD and in situ DRIFT suggest that most of the productsmore » come from the hydrocarbon pool type mechanism and dehydration step is not necessary. Thus, our method of direct conversion of ethanol offers a pathway to produce suitable hydrocarbon blend-stock that may be blended at a refinery to produce fuels such as gasoline, diesel, JP-8, and jet fuel, or produce commodity chemicals such as BTX.« less

Comparative techno-economic analysis and process design for indirect liquefaction pathways to distillate-range fuels via biomass-derived oxygenated intermediates upgrading

DOE PAGES

Tan, Eric C. D.; Snowden-Swan, Lesley J.; Talmadge, Michael; ...

2016-09-27

This paper presents a comparative techno-economic analysis (TEA) of five conversion pathways from biomass to gasoline-, jet-, and diesel-range hydrocarbons via indirect liquefaction with a specific focus on pathways utilizing oxygenated intermediates. The four emerging pathways of interest are compared with one conventional pathway (Fischer-Tropsch) for the production of the hydrocarbon blendstocks. The processing steps of the four emerging pathways include biomass-to-syngas via indirect gasification, syngas clean-up, conversion of syngas to alcohols/oxygenates followed by conversion of alcohols/oxygenates to hydrocarbon blendstocks via dehydration, oligomerization, and hydrogenation. Conversion of biomass-derived syngas to oxygenated intermediates occurs via three different pathways, producing: (i) mixedmore » alcohols over a MoS 2 catalyst, (ii) mixed oxygenates (a mixture of C 2+ oxygenated compounds, predominantly ethanol, acetic acid, acetaldehyde, ethyl acetate) using an Rh-based catalyst, and (iii) ethanol from syngas fermentation. This is followed by the conversion of oxygenates/alcohols to fuel-range olefins in two approaches: (i) mixed alcohols/ethanol to 1-butanol rich mixture via Guerbet reaction, followed by alcohol dehydration, oligomerization, and hydrogenation, and (ii) mixed oxygenates/ethanol to isobutene rich mixture and followed by oligomerization and hydrogenation. The design features a processing capacity of 2000 tonnes/day (2205 short tons) of dry biomass. The minimum fuel selling prices (MFSPs) for the four developing pathways range from 3.40 dollars to 5.04 dollars per gasoline-gallon equivalent (GGE), in 2011 US dollars. Sensitivity studies show that MFSPs can be improved with co-product credits and are comparable to the commercial Fischer-Tropsch benchmark ($3.58/GGE). Altogether, this comparative TEA study documents potential economics for the developmental biofuel pathways via mixed oxygenates.« less

Comparative techno-economic analysis and process design for indirect liquefaction pathways to distillate-range fuels via biomass-derived oxygenated intermediates upgrading

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

Tan, Eric C. D.; Snowden-Swan, Lesley J.; Talmadge, Michael

This paper presents a comparative techno-economic analysis (TEA) of five conversion pathways from biomass to gasoline-, jet-, and diesel-range hydrocarbons via indirect liquefaction with a specific focus on pathways utilizing oxygenated intermediates. The four emerging pathways of interest are compared with one conventional pathway (Fischer-Tropsch) for the production of the hydrocarbon blendstocks. The processing steps of the four emerging pathways include biomass-to-syngas via indirect gasification, syngas clean-up, conversion of syngas to alcohols/oxygenates followed by conversion of alcohols/oxygenates to hydrocarbon blendstocks via dehydration, oligomerization, and hydrogenation. Conversion of biomass-derived syngas to oxygenated intermediates occurs via three different pathways, producing: (i) mixedmore » alcohols over a MoS 2 catalyst, (ii) mixed oxygenates (a mixture of C 2+ oxygenated compounds, predominantly ethanol, acetic acid, acetaldehyde, ethyl acetate) using an Rh-based catalyst, and (iii) ethanol from syngas fermentation. This is followed by the conversion of oxygenates/alcohols to fuel-range olefins in two approaches: (i) mixed alcohols/ethanol to 1-butanol rich mixture via Guerbet reaction, followed by alcohol dehydration, oligomerization, and hydrogenation, and (ii) mixed oxygenates/ethanol to isobutene rich mixture and followed by oligomerization and hydrogenation. The design features a processing capacity of 2000 tonnes/day (2205 short tons) of dry biomass. The minimum fuel selling prices (MFSPs) for the four developing pathways range from 3.40 dollars to 5.04 dollars per gasoline-gallon equivalent (GGE), in 2011 US dollars. Sensitivity studies show that MFSPs can be improved with co-product credits and are comparable to the commercial Fischer-Tropsch benchmark ($3.58/GGE). Altogether, this comparative TEA study documents potential economics for the developmental biofuel pathways via mixed oxygenates.« less

Experimental Study on Interactions Between H Atoms and Organic Haze

NASA Technical Reports Server (NTRS)

Sekine, Y.; Imanaka, H.; Khare, B. N.; Bakes, E. L. O.; McKay, C. P.; Sugita, S.; Matsui, T.

2005-01-01

In Titan s atmosphere composed of N2 and CH4, irradiations of both solar ultraviolet light and charged particles induce active chemical reactions. In the processes of these reactions, a large amount of hydrogen (H) atoms are expected to be formed by dissociation of CH4 and other hydrocarbons [e.g., 1, 2]. Theoretical models suggest that these active H atoms need to be converted to stable hydrogen molecules (H2) efficiently to maintain unsaturated hydrocarbons and organic haze in Titan s atmosphere [e.g., 1]. Furthermore, molecular hydrogen is an important greenhouse effect gas in Titan s atmosphere, and small variation in its abundance strongly affects Titan s surface temperature [3]. Thus, the formation of H2 molecules from H atoms is a key reaction for both the atmospheric chemistry and the surface environment of Titan. Although several numerical calculations have been conducted to investigate the atmospheric chemistry of Titan with hypothesized recombination reactions of H atoms, such as catalytic scheme of C4H2 [e.g., 1, 2], it is still unclear what chemical reaction is responsible for the conversion of H atoms to H2 molecules in Titan s atmosphere.

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.

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.

High-throughput investigation of catalysts for JP-8 fuel cracking to liquefied petroleum gas.

PubMed

Bedenbaugh, John E; Kim, Sungtak; Sasmaz, Erdem; Lauterbach, Jochen

2013-09-09

Portable power technologies for military applications necessitate the production of fuels similar to LPG from existing feedstocks. Catalytic cracking of military jet fuel to form a mixture of C₂-C₄ hydrocarbons was investigated using high-throughput experimentation. Cracking experiments were performed in a gas-phase, 16-sample high-throughput reactor. Zeolite ZSM-5 catalysts with low Si/Al ratios (≤25) demonstrated the highest production of C₂-C₄ hydrocarbons at moderate reaction temperatures (623-823 K). ZSM-5 catalysts were optimized for JP-8 cracking activity to LPG through varying reaction temperature and framework Si/Al ratio. The reducing atmosphere required during catalytic cracking resulted in coking of the catalyst and a commensurate decrease in conversion rate. Rare earth metal promoters for ZSM-5 catalysts were screened to reduce coking deactivation rates, while noble metal promoters reduced onset temperatures for coke burnoff regeneration.

Liquid Hydrocarbon Production from CO2 : Recent Development in Metal-Based Electrocatalysis.

PubMed

Daiyan, Rahman; Lu, Xunyu; Ng, Yun Hau; Amal, Rose

2017-11-23

Rising levels of CO 2 accumulation in the atmosphere have attracted considerable interest in technologies capable of CO 2 capture, storage and conversion. The electrochemical reduction of CO 2 into high-value liquid organic products could be of vital importance to mitigate this issue. The conversion of CO 2 into liquid fuels by using photovoltaic cells, which can readily be integrated in the current infrastructure, will help realize the creation of a sustainable cycle of carbon-based fuel that will promote zero net CO 2 emissions. Despite promising findings, significant challenges still persist that must be circumvented to make the technology profitable for large-scale utilization. With such possibilities, this Minireview presents the current high-performing catalysts for the electrochemical reduction of CO 2 to liquid hydrocarbons, address the limitations and unify the current understanding of the different reaction mechanisms. The Minireview also explores current research directions to improve process efficiencies and production rate and discusses the scope of using photo-assisted electrochemical reduction systems to find stable, highly efficient catalysts that can harvest solar energy directly to convert CO 2 into liquid hydrocarbons. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of coal-related model compounds using a tandem mass spectrometry.

PubMed

Li, Guo-Sheng; Dong, Xueming; Fan, Xing; You, Chun-Yan; Wu, Ge; Zhao, Yun-Peng; Lu, Yao; Wei, Xian-Yong; Ma, Feng-Yun

2018-05-08

Gas chromotography/mass spectrometry (GC/MS) is a routine and basic instrumental method for the analysis of complex coal conversion products in chemical industry. To further enhance practical potentials of GC/MS in chemical industry, a tandem MS method for the selection of ion pair applied in monitoring coal conversions was established by using GC/quadrupole time-of-flight MS (GC/Q-TOF MS). The corresponding fragmentation pathways were explored and suitable ion pairs were screened. Fourteen coal-related model compounds (CRMCs) were analyzed using a GC/Q-TOF MS with different collision induced dissociation (CID) energies (5-20 eV). The fragmentation pathways can offer a better understanding of chemical bond breaking, hydrogen transfer, rearrangement reactions and elimination of neutral fragments for CRMCs during the CID process. The precursor ions of aromatic hydrocarbons without alkyl chain were hard to fragment with a CID energy of 20 eV. But aromatic hydrocarbons with branched chains were prone to fragment via the loss of alkyl chains and further fragmented through ring-open reactions. Compared to C alk -C ar bond, C ar -C ar bond was hard to fragment duo to its high bond dissociation energy. The existence of heteroatoms facilitated fragmentation that was conducive to screening ion pair. The CID technique of GC/Q-TOF MS will contribute to the studies on the organic composition of coals and building monitoring methods for coal conversions via fragmentation and ion pair selection. This article is protected by copyright. All rights reserved.

In situ high temperature MAS NMR study of the mechanisms of catalysis. Ethane aromatization on Zn-modified zeolite BEA.

PubMed

Arzumanov, Sergei S; Gabrienko, Anton A; Freude, Dieter; Stepanov, Alexander G

2009-04-01

Ethane conversion into aromatic hydrocarbons over Zn-modified zeolite BEA has been analyzed by high-temperature MAS NMR spectroscopy. Information about intermediates (Zn-ethyl species) and reaction products (mainly toluene and methane), which were formed under the conditions of a batch reactor, was obtained by (13)C MAS NMR. Kinetics of the reaction, which was monitored by (1)H MAS NMR in situ at the temperature of 573K, provided information about the reaction mechanism. Simulation of the experimental kinetics within the frames of the possible kinetic schemes of the reaction demonstrates that a large amount of methane evolved under ethane aromatization arises from the stage of direct ethane hydrogenolysis.

Catalytic Chemistry of Hydrocarbon Conversion Reactions on Metallic Single Crystals

NASA Astrophysics Data System (ADS)

Tysoe, Wilfred T.

The ability to be able to follow the chemistry of adsorbates on model catalyst surfaces has, in principle, allowed us to peer inside the “black box” of a catalytic reaction and understand the pathway. Such a strategy is most simply implemented for well-ordered single crystal model catalysts for which the catalytic reaction proceeds in ultrahigh vacuum. Thus, in order to be a good model for the supported catalyst, the single crystal should catalyze the reactions with kinetics identical to those for the supported system. This chapter focuses on catalytic systems that fulfill these criteria, namely alkene and alkyne hydrogenation and acetylene cyclotrimerization on Pd(111). The surface chemistry and geometries of the reactants in ultrahigh vacuum are explored in detail allowing fundamental insights into the catalytic reaction pathways to be obtained.

Directly converting CO2 into a gasoline fuel

PubMed Central

Wei, Jian; Ge, Qingjie; Yao, Ruwei; Wen, Zhiyong; Fang, Chuanyan; Guo, Lisheng; Xu, Hengyong; Sun, Jian

2017-01-01

The direct production of liquid fuels from CO2 hydrogenation has attracted enormous interest for its significant roles in mitigating CO2 emissions and reducing dependence on petrochemicals. Here we report a highly efficient, stable and multifunctional Na–Fe3O4/HZSM-5 catalyst, which can directly convert CO2 to gasoline-range (C5–C11) hydrocarbons with selectivity up to 78% of all hydrocarbons while only 4% methane at a CO2 conversion of 22% under industrial relevant conditions. It is achieved by a multifunctional catalyst providing three types of active sites (Fe3O4, Fe5C2 and acid sites), which cooperatively catalyse a tandem reaction. More significantly, the appropriate proximity of three types of active sites plays a crucial role in the successive and synergetic catalytic conversion of CO2 to gasoline. The multifunctional catalyst, exhibiting a remarkable stability for 1,000 h on stream, definitely has the potential to be a promising industrial catalyst for CO2 utilization to liquid fuels. PMID:28462925

Directly converting CO2 into a gasoline fuel.

PubMed

Wei, Jian; Ge, Qingjie; Yao, Ruwei; Wen, Zhiyong; Fang, Chuanyan; Guo, Lisheng; Xu, Hengyong; Sun, Jian

2017-05-02

The direct production of liquid fuels from CO 2 hydrogenation has attracted enormous interest for its significant roles in mitigating CO 2 emissions and reducing dependence on petrochemicals. Here we report a highly efficient, stable and multifunctional Na-Fe 3 O 4 /HZSM-5 catalyst, which can directly convert CO 2 to gasoline-range (C 5 -C 11 ) hydrocarbons with selectivity up to 78% of all hydrocarbons while only 4% methane at a CO 2 conversion of 22% under industrial relevant conditions. It is achieved by a multifunctional catalyst providing three types of active sites (Fe 3 O 4 , Fe 5 C 2 and acid sites), which cooperatively catalyse a tandem reaction. More significantly, the appropriate proximity of three types of active sites plays a crucial role in the successive and synergetic catalytic conversion of CO 2 to gasoline. The multifunctional catalyst, exhibiting a remarkable stability for 1,000 h on stream, definitely has the potential to be a promising industrial catalyst for CO 2 utilization to liquid fuels.

Reactive Transport of Petroleum Hydrocarbon Constituents in a Shallow Aquifer: Modeling Geochemical Interactions Between Organic and Inorganic Species

NASA Astrophysics Data System (ADS)

McNab, W. W.; Narasimhan, T. N.

1995-08-01

Dissolved organic contaminants such as petroleum hydrocarbon constituents are often observed to degrade in groundwater environments through biologically mediated transformation reactions into carbon dioxide, methane, or intermediate organic compounds. Such transformations are closely tied to local geochemical conditions. Favorable degradation pathways depend upon local redox conditions through thermodynamic constraints and the availability of appropriate mediating microbial populations. Conversely, the progress of the degradation reactions may affect the chemical composition of groundwater through changes in electron donor/acceptor speciation and pH, possibly inducing mineral precipitation/dissolution reactions. Transport of reactive organic and inorganic aqueous species through open systems may enhance the reaction process by mixing unlike waters and producing a state of general thermodynamic disequilibrium. In this study, field data from an aquifer contaminated by petroleum hydrocarbons have been analyzed using a mathematical model which dynamically couples equilibrium geochemistry of inorganic constituents, kinetically dominated sequential degradation of organic compounds, and advective-dispersive chemical transport. Simulation results indicate that coupled geochemical processes inferred from field data, such as organic biodegradation, iron reduction and dissolution, and methanogenesis, can be successfully modeled using a partial-redox-disequilibrium approach. The results of this study also suggest how the modeling approach can be used to study system sensitivity to various physical and chemical parameters, such as the effect of dispersion on the position of chemical fronts and the impact of alternative buffering mineral phases (e.g., goethite versus amorphous Fe(OH)3) on water chemistry.

Hydrogenation of carbonaceous materials

DOEpatents

Friedman, Joseph; Oberg, Carl L.; Russell, Larry H.

1980-01-01

A method for reacting pulverized coal with heated hydrogen-rich gas to form hydrocarbon liquids suitable for conversion to fuels wherein the reaction involves injection of pulverized coal entrained in a minimum amount of gas and mixing the entrained coal at ambient temperature with a separate source of heated hydrogen. In accordance with the present invention, the hydrogen is heated by reacting a small portion of the hydrogen-rich gas with oxygen in a first reaction zone to form a gas stream having a temperature in excess of about 1000.degree. C. and comprising a major amount of hydrogen and a minor amount of water vapor. The coal particles then are reacted with the hydrogen in a second reaction zone downstream of the first reaction zone. The products of reaction may be rapidly quenched as they exit the second reaction zone and are subsequently collected.

Characterization of MoVTeNbO x catalysts during oxidation reactions using in situ/operando techniques: A review

DOE PAGES

Lwin, Soe; Diao, Weijian; Baroi, Chinmoy; ...

2017-04-08

The domestic fossil feedstock in recent years is shifting towards light hydrocarbons due to abundance of shale gas from hydraulic fracturing. This shift induces a need for greater flexibility in both new and existing processing plants to produce consumer products (polymers, paints, lubricants, etc.) from new feedstocks. The oxidative catalytic reactions operate at milder conditions than the processing of feedstocks through steam cracking. The conversion of light feedstocks (C3 and shorter hydrocarbons) to high value chemicals through highly selective catalysts in the presence of oxygen plays a crucial role in eliminating wastes, reducing greenhouse gas emissions and lowering market prices.more » Among all catalysts for light hydrocarbon processing through oxidation reactions, bulk mixed metal oxides such as MoVTe(Sb)NbO x catalysts are the most promising due to their performance under favorable reaction conditions (temperature, pressure, etc). Here, state-of-the-art in situ/operando techniques along with transient kinetics can revolutionize the development of catalysts by providing information about the nature of active sites, intermediates and kinetics under realistic industrial conditions. Only through detailed understanding of these catalyst behaviors can new synthesis methods be developed that will improve reactivity, selectivity and lifetimes of these catalysts. In this review, dynamic changes of this mixed oxide catalyst during the reaction (such as changes in surface composition, oxidation states, acidity, etc) are discussed mainly from knowledge and insights obtained from these in situ/operando approaches. The most common oxidation reactions driven by the MoVTeNbO x catalysts and studied under operando/in situ conditions to be discussed here are: (1) oxidative dehydrogenation of light alkanes (ethane and propane), (2) propane ammoxidation to acrylonitrile and (3) selective oxidation of propane to acrylic acid.« less

Characterization of MoVTeNbO x catalysts during oxidation reactions using in situ/operando techniques: A review

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

Lwin, Soe; Diao, Weijian; Baroi, Chinmoy

The domestic fossil feedstock in recent years is shifting towards light hydrocarbons due to abundance of shale gas from hydraulic fracturing. This shift induces a need for greater flexibility in both new and existing processing plants to produce consumer products (polymers, paints, lubricants, etc.) from new feedstocks. The oxidative catalytic reactions operate at milder conditions than the processing of feedstocks through steam cracking. The conversion of light feedstocks (C3 and shorter hydrocarbons) to high value chemicals through highly selective catalysts in the presence of oxygen plays a crucial role in eliminating wastes, reducing greenhouse gas emissions and lowering market prices.more » Among all catalysts for light hydrocarbon processing through oxidation reactions, bulk mixed metal oxides such as MoVTe(Sb)NbO x catalysts are the most promising due to their performance under favorable reaction conditions (temperature, pressure, etc). Here, state-of-the-art in situ/operando techniques along with transient kinetics can revolutionize the development of catalysts by providing information about the nature of active sites, intermediates and kinetics under realistic industrial conditions. Only through detailed understanding of these catalyst behaviors can new synthesis methods be developed that will improve reactivity, selectivity and lifetimes of these catalysts. In this review, dynamic changes of this mixed oxide catalyst during the reaction (such as changes in surface composition, oxidation states, acidity, etc) are discussed mainly from knowledge and insights obtained from these in situ/operando approaches. The most common oxidation reactions driven by the MoVTeNbO x catalysts and studied under operando/in situ conditions to be discussed here are: (1) oxidative dehydrogenation of light alkanes (ethane and propane), (2) propane ammoxidation to acrylonitrile and (3) selective oxidation of propane to acrylic acid.« less

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

DOEpatents

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

2012-01-24

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

In-use catalyst surface area and its relation to HC conversion efficiency and FTP emissions

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

Donahue, K.S.; Sabourin, M.A.; Larson, R.E.

1986-01-01

Surface area data, steady-state hydrocarbon conversion efficiency data, and hydrocarbon emissions results have been determined for catalysts collected by the U.S. Environmental Protection Agency from properly maintained 1981 and 1982 model year vehicles. Catalysts covered in this study were limited to those with three-way-plus-oxidation monolith technologies. Catalyst surface areas were measured using the BET method, conversion efficiencies were measured on an exhaust gas generator, and emissions results were determined using the Urban Driving Schedule of the Federal Test Procedure. Results indicate that correlation of catalyst surface area data with hydrocarbon conversion efficiency data and hydrocarbon emissions results is significant formore » the sample studied.« less

Cocatalysts in Semiconductor-based Photocatalytic CO2 Reduction: Achievements, Challenges, and Opportunities.

PubMed

Ran, Jingrun; Jaroniec, Mietek; Qiao, Shi-Zhang

2018-02-01

Ever-increasing fossil-fuel combustion along with massive CO 2 emissions has aroused a global energy crisis and climate change. Photocatalytic CO 2 reduction represents a promising strategy for clean, cost-effective, and environmentally friendly conversion of CO 2 into hydrocarbon fuels by utilizing solar energy. This strategy combines the reductive half-reaction of CO 2 conversion with an oxidative half reaction, e.g., H 2 O oxidation, to create a carbon-neutral cycle, presenting a viable solution to global energy and environmental problems. There are three pivotal processes in photocatalytic CO 2 conversion: (i) solar-light absorption, (ii) charge separation/migration, and (iii) catalytic CO 2 reduction and H 2 O oxidation. While significant progress is made in optimizing the first two processes, much less research is conducted toward enhancing the efficiency of the third step, which requires the presence of cocatalysts. In general, cocatalysts play four important roles: (i) boosting charge separation/transfer, (ii) improving the activity and selectivity of CO 2 reduction, (iii) enhancing the stability of photocatalysts, and (iv) suppressing side or back reactions. Herein, for the first time, all the developed CO 2 -reduction cocatalysts for semiconductor-based photocatalytic CO 2 conversion are summarized, and their functions and mechanisms are discussed. Finally, perspectives in this emerging area are provided. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparative techno-economic analysis and process design for indirect liquefaction pathways to distillate-range fuels via biomass-derived oxygenated intermediates upgrading: Liquid Transportation Fuel Production via Biomass-derived Oxygenated Intermediates Upgrading

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

Tan, Eric C. D.; Snowden-Swan, Lesley J.; Talmadge, Michael

This paper presents a comparative techno-economic analysis (TEA) of five conversion pathways from biomass to gasoline-, jet-, and diesel-range hydrocarbons via indirect liquefaction with specific focus on pathways utilizing oxygenated intermediates. The four emerging pathways of interest are compared with one conventional pathway (Fischer-Tropsch) for the production of the hydrocarbon blendstocks. The processing steps of the four emerging pathways include: biomass to syngas via indirect gasification, gas cleanup, conversion of syngas to alcohols/oxygenates followed by conversion of alcohols/oxygenates to hydrocarbon blendstocks via dehydration, oligomerization, and hydrogenation. Conversion of biomass-derived syngas to oxygenated intermediates occurs via three different pathways, producing: 1)more » mixed alcohols over a MoS2 catalyst, 2) mixed oxygenates (a mixture of C2+ oxygenated compounds, predominantly ethanol, acetic acid, acetaldehyde, ethyl acetate) using an Rh-based catalyst, and 3) ethanol from syngas fermentation. This is followed by the conversion of oxygenates/alcohols to fuel-range olefins in two approaches: 1) mixed alcohols/ethanol to 1-butanol rich mixture via Guerbet reaction, followed by alcohol dehydration, oligomerization, and hydrogenation, and 2) mixed oxygenates/ethanol to isobutene rich mixture and followed by oligomerization and hydrogenation. The design features a processing capacity of 2,000 tonnes/day (2,205 short tons) of dry biomass. The minimum fuel selling prices (MFSPs) for the four developing pathways range from $3.40 to $5.04 per gasoline-gallon equivalent (GGE), in 2011 US dollars. Sensitivity studies show that MFSPs can be improved with co-product credits and are comparable to the commercial Fischer-Tropsch benchmark ($3.58/GGE). Overall, this comparative TEA study documents potential economics for the developmental biofuel pathways via mixed oxygenates.« less

The conversion process of hydrocarbon hydrates into CO2 hydrates and vice versa: thermodynamic considerations.

PubMed

Schicks, J M; Luzi, M; Beeskow-Strauch, B

2011-11-24

Microscopy, confocal Raman spectroscopy and powder X-ray diffraction (PXRD) were used for in situ investigations of the CO(2)-hydrocarbon exchange process in gas hydrates and its driving forces. The study comprises the exposure of simple structure I CH(4) hydrate and mixed structure II CH(4)-C(2)H(6) and CH(4)-C(3)H(8) hydrates to gaseous CO(2) as well as the reverse reaction, i.e., the conversion of CO(2)-rich structure I hydrate into structure II mixed hydrate. In the case of CH(4)-C(3)H(8) hydrates, a conversion in the presence of gaseous CO(2) from a supposedly more stable structure II hydrate to a less stable structure I CO(2)-rich hydrate was observed. PXRD data show that the reverse process requires longer initiation times, and structural changes seem to be less complete. Generally, the exchange process can be described as a decomposition and reformation process, in terms of a rearrangement of molecules, and is primarily induced by the chemical potential gradient between hydrate phase and the provided gas phase. The results show furthermore the dependency of the conversion rate on the surface area of the hydrate phase, the thermodynamic stability of the original and resulting hydrate phase, as well as the mobility of guest molecules and formation kinetics of the resulting hydrate phase.

Coke formation in a zeolite crystal during the methanol-to-hydrocarbons reaction as studied with atom probe tomography

DOE PAGES

Schmidt, Joel E.; Poplawsky, Jonathan D.; Mazumder, Baishakhi; ...

2016-08-03

Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub-nm length scale in a single zeolite ZSM-5 crystal, which has been partially deactivated by the methanol-to-hydrocarbons reaction using 13C-labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30–60 13C atoms. These clusters correlate with local increases in Brønsted acid sitemore » density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. Here, this nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation.« less

Catalytic conversion of biomass-derived ethanol to liquid hydrocarbon blend-stock: Effect of light gas recirculation

DOE PAGES

Li, Zhenglong; Lepore, Andrew W.; Davison, Brian H.; ...

2016-01-01

Here, we describe a light gas recirculation (LGR) method to increase the liquid hydrocarbon yield with reduced aromatic content from catalytic conversion of ethanol to hydrocarbons. The previous liquid hydrocarbon yield is ~40% from one-pass ethanol conversion over V-ZSM-5 at 350 C and atmospheric pressure where the remaining ~60% yield is light gas hydrocarbons. In comparison, the liquid hydrocarbon yield increases to 80% when a simulated light gas hydrocarbon stream is co-fed at a rate of 0.053 mol g-1 h-1 with ethanol due to the conversion of most of the light olefins. The LGR also significantly improves the quality ofmore » the liquid hydrocarbon blend-stock by reducing aromatic content and overall benzene concentration. For 0.027 mol g-1 h-1 light gas mixture co-feeding, the average aromatic content in liquid hydrocarbons is 51.5% compared with 62.5% aromatic content in ethanol only experiment. Average benzene concentration decreases from 3.75% to 1.5% which is highly desirable since EPA limits benzene concentration in gasoline to 0.62%. As a result of low benzene concentration, the blend-wall for ethanol derived liquid hydrocarbons changes from ~18% to 43%. The remaining light paraffins and olefins can be further converted to valuable BTX products (94% BTX in the liquid) over Ga-ZSM-5 at 500 C. Thus, the LGR is an effective approach to convert ethanol to liquid hydrocarbons with higher liquid yield and low aromatic content, especially low benzene concentration, which could be blended with gasoline in a much higher ratio than ethanol or ethanol derived hydrocarbon blend-stock.« less

Catalytic conversion of biomass-derived ethanol to liquid hydrocarbon blend-stock: Effect of light gas recirculation

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

Li, Zhenglong; Lepore, Andrew W.; Davison, Brian H.

Here, we describe a light gas recirculation (LGR) method to increase the liquid hydrocarbon yield with reduced aromatic content from catalytic conversion of ethanol to hydrocarbons. The previous liquid hydrocarbon yield is ~40% from one-pass ethanol conversion over V-ZSM-5 at 350 C and atmospheric pressure where the remaining ~60% yield is light gas hydrocarbons. In comparison, the liquid hydrocarbon yield increases to 80% when a simulated light gas hydrocarbon stream is co-fed at a rate of 0.053 mol g-1 h-1 with ethanol due to the conversion of most of the light olefins. The LGR also significantly improves the quality ofmore » the liquid hydrocarbon blend-stock by reducing aromatic content and overall benzene concentration. For 0.027 mol g-1 h-1 light gas mixture co-feeding, the average aromatic content in liquid hydrocarbons is 51.5% compared with 62.5% aromatic content in ethanol only experiment. Average benzene concentration decreases from 3.75% to 1.5% which is highly desirable since EPA limits benzene concentration in gasoline to 0.62%. As a result of low benzene concentration, the blend-wall for ethanol derived liquid hydrocarbons changes from ~18% to 43%. The remaining light paraffins and olefins can be further converted to valuable BTX products (94% BTX in the liquid) over Ga-ZSM-5 at 500 C. Thus, the LGR is an effective approach to convert ethanol to liquid hydrocarbons with higher liquid yield and low aromatic content, especially low benzene concentration, which could be blended with gasoline in a much higher ratio than ethanol or ethanol derived hydrocarbon blend-stock.« less

The chemical kinetics and thermodynamics of sodium species in oxygen-rich hydrogen flames

NASA Technical Reports Server (NTRS)

Hynes, A. J.; Steinberg, M.; Schofield, K.

1984-01-01

Results are presented which, it is claimed, lead to a correction of previous misconceptions over the relative importance and kinetics of NaO2. It is shown that its rapid conversion to NaO and NaOH is such that it can severely perturb the NaOH/Na ratio and produce significant concentration overshoots over that predicted from the balance of the reaction of Na with H2O. This becomes increasingly the case in flames of large O2 concentrations and temperatures below 2500 K; and the corresponding large rate constants for the termolecular formation of the other alkali peroxides imply that similar considerations will be necessary for them. Depending on the rate constants for the exothermic conversions of MO2 to MO or MOH, the steady-state concentrations of MO2 could be more or less significant than for sodium. Owing to numerous reactions that produce these conversions, the MOH species will probably be the dominant species in all cases in oxygen-rich hydrogen or hydrocarbon flames, with MO concentrations at not greater than 1 percent of the bound metal.

Microorganism mediated liquid fuels

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

Troiano, Richard

Herein disclosed is a method for producing liquid hydrocarbon product, the method comprising disintegrating a hydrocarbon source; pretreating the disintegrated hydrocarbon source; solubilizing the disintegrated hydrocarbon source to form a slurry comprising a reactant molecule of the hydrocarbon source; admixing a biochemical liquor into the slurry, wherein the biochemical liquor comprises at least one conversion enzyme configured to facilitate bond selective photo-fragmentation of said reactant molecule of the hydrocarbon source, to form liquid hydrocarbons via enzyme assisted bond selective photo-fragmentation, wherein said conversion enzyme comprises reactive sites configured to restrict said reactant molecule such that photo-fragmentation favorably targets a preselectedmore » internal bond of said reactant molecule; separating the liquid hydrocarbons from the slurry, wherein contaminants remain in the slurry; and enriching the liquid hydrocarbons to form a liquid hydrocarbon product. Various aspects of such method/process are also discussed.« less

Fischer-Tropsch synthesis in near-critical n-hexane: Pressure-tuning effects

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

Bochniak, D.J.; Subramaniam, B.

For Fe-catalyzed Fischer-Tropsch (FT) synthesis with near-critical n-hexane (P{sub c} = 29.7 bar; T{sub c} = 233.7 C) as the reaction medium, isothermal pressure tuning from 1.2--2.4 P{sub c} (for n-hexane) at the reaction temperature (240 C) significantly changes syngas conversion and product selectivity. For fixed feed rates of syngas (H{sub 2}/CO = 0.5; 50 std. cm{sup 3}/g catalyst) and n-hexane (1 mL/min), syngas conversion attains a steady state at all pressures, increasing roughly threefold in this pressure range. Effective rate constants, estimated assuming a first-order dependence of syngas conversion on hydrogen, reveal that the catalyst effectiveness increases with pressuremore » implying the alleviation of pore-diffusion limitations. Pore accessibilities increase at higher pressures because the extraction of heavier hydrocarbons from the catalyst pores is enhanced by the liquid-like densities, yet better-than-liquid transport properties, of n-hexane. This explanation is consistent with the single {alpha} (= 0.78) Anderson-Schulz-Flory product distribution, the constant chain termination probability, and the higher primary product (1-olefin) selectivities ({approximately}80%) observed at the higher pressures. Results indicate that the pressure tunability of the density and transport properties of near-critical reaction media offers a powerful tool to optimize catalyst activity and product selectivity during FT reactions on supported catalysts.« less

Use of 2,4-dinitrophenylhydrazine for the purification of technical isoprene from carbonyl compounds

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

Kuznetsova, Y.V.; Taranenko, S.A.; Mil'kina, T.N.

1983-01-01

Technical isoprene can be freed from carbonyl compounds by conversion into non-volatile derivatives - hydrazones, with subsequent liberation of the purified isoprene during re-evaporation. The reaction takes place at room temperature with a molar ratio of 2,4-dinitrophenylhydrazine/carbonyl compounds in the range 2-10 to 1. This method of purification may also be used in other situations where a hydrocarbon flow freed from aldehydes and ketones is required.

Green technology for conversion of renewable hydrocarbon based on plasma-catalytic approach

NASA Astrophysics Data System (ADS)

Fedirchyk, Igor; Nedybaliuk, Oleg; Chernyak, Valeriy; Demchina, Valentina

2016-09-01

The ability to convert renewable biomass into fuels and chemicals is one of the most important steps on our path to green technology and sustainable development. However, the complex composition of biomass poses a major problem for established conversion technologies. The high temperature of thermochemical biomass conversion often leads to the appearance of undesirable byproducts and waste. The catalytic conversion has reduced yield and feedstock range. Plasma-catalytic reforming technology opens a new path for biomass conversion by replacing feedstock-specific catalysts with free radicals generated in the plasma. We studied the plasma-catalytic conversion of several renewable hydrocarbons using the air plasma created by rotating gliding discharge. We found that plasma-catalytic hydrocarbon conversion can be conducted at significantly lower temperatures (500 K) than during the thermochemical ( 1000 K) and catalytic (800 K) conversion. By using gas chromatography, we determined conversion products and found that conversion efficiency of plasma-catalytic conversion reaches over 85%. We used obtained data to determine the energy yield of hydrogen in case of plasma-catalytic reforming of ethanol and compared it with other plasma-based hydrogen-generating systems.

Biological Conversion of Sugars to Hydrocarbons Technology Pathway

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

Davis, R.; Biddy, M.; Tan, E.

2013-03-01

This technology pathway case investigates the biological conversion of biomass-derived sugars to hydrocarbon biofuels, utilizing data from recent literature references and information consistent with recent pilot-scale demonstrations at NREL. Technical barriers and key research needs have been identified that should be pursued for the pathway to become competitive with petroleum-derived gasoline-, diesel-, and jet-range hydrocarbon blendstocks.

Conversion of oligomeric starch, cellulose, hydrolysates or sugars to hydrocarbons

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

Silks, Louis A; Sutton, Andrew; Kim, Jin Kyung

Embodiments of the present invention are directed to the conversion of a source material (e.g., a depolymerized oligosaccharide mixture, a monomeric sugar, a hydrolysate, or a mixture of monomeric sugars) to intermediate molecules containing 7 to 26 contiguous carbon atoms. These intermediates may also be converted to saturated hydrocarbons. Such saturated hydrocarbons are useful as, for example, fuels.

Formation of fatty acids in photochemical conversions of saturated hydrocarbons

NASA Technical Reports Server (NTRS)

Telegina, T. A.; Pavlovskaya, T. Y.; Ladyzhenskaya, A. I.

1977-01-01

Abiogenic synthesis of fatty acids was studied in photochemical conversions of saturated hydrocarbons. It was shown that, in a hydrocarbon water CaCO3 suspension, the action of 254 nm UV rays caused the formation of fatty acids with a maximum number of carbon atoms in the chain not exceeding that in the initial hydrocarbon. Synthesis of acetic, propionic, butyric, valeric, caproic, enanthic and caprylic (in the case of octane) acids occurs in heptane water CaCO3 and octane water CaCO3 systems.

Syngas Conversion to Hydrocarbon Fuels through Mixed Alcohol Intermediates

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

Dagle, Robert A.; Lebarbier, Vanessa M.; Albrecht, Karl O.

2013-05-13

Synthesis gas (syngas) can be used to synthesize a variety of fuels and chemicals. Domestic transportation and military operational interests have driven continued focus on domestic syngas-based fuels production. Liquid transportation fuels may be made from syngas via four basic processes: 1) higher alcohols, 2) Fischer-Tropsch (FT), 3) methanol-to-gasoline (MTG), and 4) methanol-to-olefins (MTO) and olefins-to-gasoline/distillate (MOGD). Compared to FT and higher alcohols, MTG and MTO-MOGD have received less attention in recent years. Due to the high capital cost of these synthetic fuel plants, the production cost of the finished fuel cannot compete with petroleum-derived fuel. Pacific Northwest National Laboratorymore » has recently evaluated one way to potentially reduce capital cost and overall production cost for MTG by combining the methanol and MTG syntheses in a single reactor. The concept consists of mixing the conventional MTG catalyst (i.e. HZSM-5) with an alcohol synthesis catalyst. It was found that a methanol synthesis catalyst, stable at high temperature (i.e. Pd/ZnO/Al2O3) [1], when mixed with ZSM-5, was active for syngas conversion. Relatively high syngas conversion can be achieved as the equilibrium-driven conversion limitations for methanol and dimethyl ether are removed as they are intermediates to the final hydrocarbon product. However, selectivity control was difficult to achieve as formation of undesirable durene and light hydrocarbons was problematic [2]. The objective of the present study was thus to evaluate other potential composite catalyst systems and optimize the reactions conditions for the conversion of syngas to hydrocarbon fuels, through the use of mixed alcohol intermediates. Mixed alcohols are of interest as they have recently been reported to produce higher yields of gasoline compared to methanol [3]. 1. Lebarbier, V.M., Dagle, R.A., Kovarik, L., Lizarazo-Adarme, J.A., King, D.L., Palo, D.R., Catalyst Science & Technology, 2012, 2, 2116-2127. 2. Zhu, Y., Jones, S.B., Biddy, M.J., Dagle, R.A., Palo, D.P., Bioresource Technology, 2012, 117, 341-351. 3. Gujar, A.C., Guda, V.K., Nolan, M., Yan W., Toghiani, H., White, M.G., Applied Catalysis A: General, 2009, 363, 115-121.« less

An investigation of the treatment of particulate matter from gasoline engine exhaust using non-thermal plasma.

PubMed

Ye, Dan; Gao, Dengshan; Yu, Gang; Shen, Xianglin; Gu, Fan

2005-12-09

A plasma reactor with catalysts was used to treat exhaust gas from a gasoline engine in order to decrease particulate matter (PM) emissions. The effect of non-thermal plasma (NTP) of the dielectric discharges on the removal of PM from the exhaust gas was investigated experimentally. The removal efficiency of PM was based on the concentration difference in PM for particle diameters ranging from 0.3 to 5.0 microm as measured by a particle counter. Several factors affecting PM conversion, including the density of plasma energy, reaction temperature, flow rate of exhaust gas, were investigated in the experiment. The results indicate that PM removal efficiency ranged approximately from 25 to 57% and increased with increasing energy input in the reactor, reaction temperature and residence time of the exhaust gas in the reactor. Enhanced removal of the PM was achieved by filling the discharge gap of the reactor with Cu-ZSM-5 catalyst pellets. In addition, the removal of unburned hydrocarbons was studied. Finally, available approaches for PM conversion were analyzed involving the interactions between discharge and catalytic reactions.

Production of Furfural from Process-Relevant Biomass-Derived Pentoses in a Biphasic Reaction System

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

Mittal, Ashutosh; Black, Stuart K.; Vinzant, Todd B.

Furfural is an important fuel precursor which can be converted to hydrocarbon fuels and fuel intermediates. In this work, the production of furfural by dehydration of process-relevant pentose rich corn stover hydrolyzate using a biphasic batch reaction system has been investigated. Methyl isobutyl ketone (MIBK) and toluene have been used to extract furfural and enhance overall furfural yield by limiting its degradation to humins. The effects of reaction time, temperature, and acid concentration (H 2SO 4) on pentose conversion and furfural yield were investigated. For the dehydration of 8 wt % pentose-rich corn stover hydrolyzate under optimum reaction conditions, 0.05more » M H 2SO 4, 170 degrees C for 20 min with MIBK as the solvent, complete conversion of xylose (98-100%) and a furfural yield of 80% were obtained. Under these same conditions, except with toluene as the solvent, the furfural yield was 77%. Additionally, dehydration of process-relevant pentose rich corn stover hydrolyzate using solid acid ion-exchange resins under optimum reaction conditions has shown that Purolite CT275 is as effective as H 2SO 4 for obtaining furfural yields approaching 80% using a biphasic batch reaction system. In conclusion, this work has demonstrated that a biphasic reaction system can be used to process biomass-derived pentose rich sugar hydrolyzates to furfural in yields approaching 80%.« less

Production of Furfural from Process-Relevant Biomass-Derived Pentoses in a Biphasic Reaction System

DOE PAGES

Mittal, Ashutosh; Black, Stuart K.; Vinzant, Todd B.; ...

2017-05-16

Furfural is an important fuel precursor which can be converted to hydrocarbon fuels and fuel intermediates. In this work, the production of furfural by dehydration of process-relevant pentose rich corn stover hydrolyzate using a biphasic batch reaction system has been investigated. Methyl isobutyl ketone (MIBK) and toluene have been used to extract furfural and enhance overall furfural yield by limiting its degradation to humins. The effects of reaction time, temperature, and acid concentration (H 2SO 4) on pentose conversion and furfural yield were investigated. For the dehydration of 8 wt % pentose-rich corn stover hydrolyzate under optimum reaction conditions, 0.05more » M H 2SO 4, 170 degrees C for 20 min with MIBK as the solvent, complete conversion of xylose (98-100%) and a furfural yield of 80% were obtained. Under these same conditions, except with toluene as the solvent, the furfural yield was 77%. Additionally, dehydration of process-relevant pentose rich corn stover hydrolyzate using solid acid ion-exchange resins under optimum reaction conditions has shown that Purolite CT275 is as effective as H 2SO 4 for obtaining furfural yields approaching 80% using a biphasic batch reaction system. In conclusion, this work has demonstrated that a biphasic reaction system can be used to process biomass-derived pentose rich sugar hydrolyzates to furfural in yields approaching 80%.« less

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

Tan, Eric C.D.

This paper presents a comparative techno-economic analysis of four emerging conversion pathways from biomass to gasoline-, jet-, and diesel-range hydrocarbons via indirect liquefaction with specific focus on pathways utilizing oxygenated intermediates. The processing steps include: biomass-to-syngas via indirect gasification, gas cleanup, conversion of syngas to alcohols/oxygenates followed by conversion of alcohols/oxygenates to hydrocarbon blendstocks via dehydration, oligomerization, and hydrogenation.

Kinetic aspects of chain growth in Fischer-Tropsch synthesis.

PubMed

Filot, Ivo A W; Zijlstra, Bart; Broos, Robin J P; Chen, Wei; Pestman, Robert; Hensen, Emiel J M

2017-04-28

Microkinetics simulations are used to investigate the elementary reaction steps that control chain growth in the Fischer-Tropsch reaction. Chain growth in the FT reaction on stepped Ru surfaces proceeds via coupling of CH and CR surface intermediates. Essential to the growth mechanism are C-H dehydrogenation and C hydrogenation steps, whose kinetic consequences have been examined by formulating two novel kinetic concepts, the degree of chain-growth probability control and the thermodynamic degree of chain-growth probability control. For Ru the CO conversion rate is controlled by the removal of O atoms from the catalytic surface. The temperature of maximum CO conversion rate is higher than the temperature to obtain maximum chain-growth probability. Both maxima are determined by Sabatier behavior, but the steps that control chain-growth probability are different from those that control the overall rate. Below the optimum for obtaining long hydrocarbon chains, the reaction is limited by the high total surface coverage: in the absence of sufficient vacancies the CHCHR → CCHR + H reaction is slowed down. Beyond the optimum in chain-growth probability, CHCR + H → CHCHR and OH + H → H 2 O limit the chain-growth process. The thermodynamic degree of chain-growth probability control emphasizes the critical role of the H and free-site coverage and shows that at high temperature, chain depolymerization contributes to the decreased chain-growth probability. That is to say, during the FT reaction chain growth is much faster than chain depolymerization, which ensures high chain-growth probability. The chain-growth rate is also fast compared to chain-growth termination and the steps that control the overall CO conversion rate, which are O removal steps for Ru.

Effects of hydrocarbon contamination on ozone generation with dielectric barrier discharges

NASA Astrophysics Data System (ADS)

Lopez, Jose L.; Vezzu, Guido; Freilich, Alfred; Paolini, Bernhard

2013-08-01

The increasing usage of the feed gases of lower grade liquid oxygen (LOX) containing higher levels of trace hydrocarbon impurities in dielectric barrier discharge (DBD) for ozone generation requires a better understanding of the kinetics of the by-product formation resulting from reactions involving these hydrocarbon impurities. As a case study of hydrocarbon impurities, the kinetics of CH4 conversion in DBDs and the subsequent HNO3 formation were investigated by means of gas-phase plasma diagnostics, supported by detailed process modeling, and extensive in-situ and ex-situ by-product analysis. The by-products formation in the plasma with the presence of CH4, were found to differ significantly in oxygen-fed generators as compared to generators fed with oxygen/nitrogen mixtures. The amount of HNO3 formed depends on the concentration of NOx formed in the plasma and the amount of CH4 that is converted, but not on the O3 concentration. In the present work we have investigated CH4 concentrations of up to 1.95 wt% of the feed gas. The rate of deterioration of the overall ozone generator performance was found to be affected by the concentration of nitrogen in the oxygen/nitrogen mixture.

Comparative TEA for Indirect Liquefaction Pathways to Distillate-Range Fuels via Oxygenated Intermediates

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

Tan, Eric; Snowden-Swan, Lesley J.; Talmadge, Michael

This paper presents a comparative techno-economic analysis of five conversion pathways from biomass to gasoline-, jet-, and diesel-range hydrocarbons via indirect liquefaction with specific focus on pathways utilizing oxygenated intermediates (derived either via thermochemical or biochemical conversion steps). The four emerging pathways of interest are compared with one conventional pathway (Fischer-Tropsch) for the production of the hydrocarbon blendstocks. The processing steps of the four emerging pathways include: biomass-to-syngas via indirect gasification, gas cleanup, conversion of syngas to alcohols/oxygenates, followed by conversion of alcohols/oxygenates to hydrocarbon blendstocks via dehydration, oligomerization, and hydrogenation. We show that the emerging pathways via oxygenated intermediatesmore » have the potential to be cost competitive with the conventional Fischer-Tropsch process. The evaluated pathways and the benchmark process generally exhibit similar fuel yields and carbon conversion efficiencies. The resulting minimum fuel selling prices are comparable to the benchmark at approximately $3.60 per gallon-gasoline equivalent, with potential for two new pathways to be more economically competitive. Additionally, the coproduct values can play an important role in the economics of the processes with oxygenated intermediates derived via syngas fermentation. Major cost drivers for the integrated processes are tied to achievable fuel yields and conversion efficiency of the intermediate steps, i.e., the production of oxygenates/alcohols from syngas and the conversion of oxygenates/alcohols to hydrocarbon fuels.« less

Catalytic properties of volcanic rocks in the synthesis of hydrocarbons from carbon monoxide and hydrogen

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

Taran, Yu.A.; Novak, F.I.; Antoshchuk, I.A.

1981-10-01

Results obtained from studying the catalytic properties of effusive rocks of various chemical compositions, extracted from lava flows of several Kamchatka volcanos, in the process of synthesis from carbon monoxide and hydrogen, are presented. It was evident that samples of volcanic rock display catalytic properties in the process of synthesis from CO and H/sub 2/ in which liquid and gaseous hydrocarbons and an insignificant amount of oxygen-containing compounds are formed as products of the reactions. At a synthesis temperature of 350/sup 0/C the catalytic activity of the samples is characterized by the conversion of CO at a level of 70more » to 80%, and H/sub 2/ at 50 to 60%. The yield of oil, gasoline, and natural gas reached 40, 11, and 3 ml/m/sup 3/, respectively. The light synthetic products were presented based on saturated hydrocarbons of an aliphatic series with significant contents of olefins and insignificant quantities of alcohols and carbonyl compounds. The composition of gaseous products is characterized by significant unsaturation (approx. 33%) and a high content of butane-butylenic fractions (to approx. 55%). The data obtained showed that volcanic rocks were able to catalyze the synthesis of hydrocarbons from CO and H/sub 2/. The sources of the catalytic properties of the rocks shown are evidently iron compounds, and the remaining ingredients of the rocks are able to fulfill the role of structural or chemical promoters influencing the properties of the catalysts and the composition of the reaction products formed. 2 tables. (DP)« less

Method and apparatus for detecting gem-polyhalogenated hydrocarbons

DOEpatents

Anderson, deceased, William G.; Anderson, legal representative, Johanna S.

1990-01-01

A method and optrode for detecting gem polyhalogenated hydrocarbons in a sample fluid based on a single phase Fujiwara reaction as provided. The method comprises contacting a reaction mixture with a sample fluid which contains the gem-polyhalogenated hydrocarbons. The reaction mixture comprises an aqueous solution of pyridine or derivative thereof and a hindered nitrogen base. Upon contact a fluorescent and/or chromgenic reaction product forms whose fluorescence and/or absorbance is related to the concentration of gem-polyhalogenated hydrocarbons in the sample fluid.

Polycyclic aromatic hydrocarbon formation during the gasification of sewage sludge in sub- and supercritical water: Effect of reaction parameters and reaction pathways.

PubMed

Gong, Miao; Wang, Yulan; Fan, Yujie; Zhu, Wei; Zhang, Huiwen; Su, Ying

2018-02-01

The formation of polycyclic aromatic hydrocarbon is a widespread issue during the supercritical water gasification of sewage sludge, which directly reduces the gasification efficiency and restricts the technology practical application. The changes of the concentrations and forms as well as the synthesis rate of polycyclic aromatic hydrocarbons in the residues from supercritical water gasification of dewatered sewage sludge were investigated to understand influence factors and the reaction pathways. Results showed that the increase of reaction temperature during the heating period favours directly concentration of polycyclic aromatic hydrocarbon (especially higher-molecular-weight), especially when it raise above 300 °C. Lower heating and cooling rate essentially extend the total reaction time. Higher polycyclic aromatic hydrocarbon concentration and higher number of rings were generally promoted by lower heating and cooling rate, longer reaction time and higher reaction temperature. The lower-molecular-weight polycyclic aromatic hydrocarbons can be directly generated through the decomposition of aromatic-containing compounds in sewage sludge, as well as 3-ring and 4-ring polycyclic aromatic hydrocarbons can be formed by aromatization of steroids. Possible mechanisms of reaction pathways of supercritical water gasification of sewage sludge were also proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Direct catalytic conversion of methane and light hydrocarbon gases. Quarterly report No. 10, January 1--March 31, 1989

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

Wilson, R.B. Jr.; Posin, B.M.; Chan, Yee Wai

The goal of this research is to develop catalysts that directly convert methane and light hydrocarbons to intermediates that later can be converted to either liquid fuels or value-added chemicals, as economics dictate. In this reporting period, we have utilized samples of magnesia differing in their pretreatment temperature. Both the hydrido-ruthenium complex H{sub 4}Ru{sub 4}(CO){sub 12} and its reaction product with triethyl aluminum were reacted with these samples. The two ruthenium clusters are expected to react with the magnesia surface in different ways: by deprotonation of the hydride through an acid-base reaction with the basic surface, or by hydrolysis ofmore » the aluminum-carbon bond of the triethyl aluminum adduct. The concentration of hydroxyl groups on the magnesia surface able to hydrolyze the aluminum-carbon bond for immobilation should vary depending on the temperature of the pretreatment; the concentration of basic sites which can deprotonate the cluster should also vary with temperature. These differences were borne out by the experiment. We also compared the activity of two batches of AlRu{sub 4}/MgO which had been synthesized at different times in the project. Both batches had approximately the same activity, but the newer batch had greater selectivity for C{sub 6+} hydrocarbons.« less

Confinement Effects on Carbon Dioxide Methanation: A Novel Mechanism for Abiotic Methane Formation

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

Le, Thu; Striolo, Alberto; Turner, C. Heath

An important scientific debate focuses on the possibility of abiotic synthesis of hydrocarbons during oceanic crust-seawater interactions. While on-site measurements near hydrothermal vents support this possibility, laboratory studies have provided data that are in some cases contradictory. At conditions relevant for sub-surface environments it has been shown that classic thermodynamics favour the production of CO 2 from CH 4, while abiotic methane synthesis would require the opposite. However, confinement effects are known to alter reaction equilibria. This report shows that indeed thermodynamic equilibrium can be shifted towards methane production, suggesting that thermal hydrocarbon synthesis near hydrothermal vents and deeper inmore » the magma-hydrothermal system is possible. We report reactive ensemble Monte Carlo simulations for the CO 2 methanation reaction. We compare the predicted equilibrium composition in the bulk gaseous phase to that expected in the presence of confinement. In the bulk phase we obtain excellent agreement with classic thermodynamic expectations. When the reactants can exchange between bulk and a confined phase our results show strong dependency of the reaction equilibrium conversions, X CO2, on nanopore size, nanopore chemistry, and nanopore morphology. Some physical conditions that could shift significantly the equilibrium composition of the reactive system with respect to bulk observations are discussed.« less

Confinement Effects on Carbon Dioxide Methanation: A Novel Mechanism for Abiotic Methane Formation

DOE PAGES

Le, Thu; Striolo, Alberto; Turner, C. Heath; ...

2017-08-21

An important scientific debate focuses on the possibility of abiotic synthesis of hydrocarbons during oceanic crust-seawater interactions. While on-site measurements near hydrothermal vents support this possibility, laboratory studies have provided data that are in some cases contradictory. At conditions relevant for sub-surface environments it has been shown that classic thermodynamics favour the production of CO 2 from CH 4, while abiotic methane synthesis would require the opposite. However, confinement effects are known to alter reaction equilibria. This report shows that indeed thermodynamic equilibrium can be shifted towards methane production, suggesting that thermal hydrocarbon synthesis near hydrothermal vents and deeper inmore » the magma-hydrothermal system is possible. We report reactive ensemble Monte Carlo simulations for the CO 2 methanation reaction. We compare the predicted equilibrium composition in the bulk gaseous phase to that expected in the presence of confinement. In the bulk phase we obtain excellent agreement with classic thermodynamic expectations. When the reactants can exchange between bulk and a confined phase our results show strong dependency of the reaction equilibrium conversions, X CO2, on nanopore size, nanopore chemistry, and nanopore morphology. Some physical conditions that could shift significantly the equilibrium composition of the reactive system with respect to bulk observations are discussed.« less

Catalytic conversion of light alkanes: Quarterly report, January 1-March 31, 1992

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

Biscardi, J.; Bowden, P.T.; Durante, V.A.

The first Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between January 1. 1992 and March 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products which can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon transportation fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mildmore » selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient porphryinic macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE III).« less

Selective photooxidation of hydrocarbons in zeolites by oxygen

DOEpatents

Frei, Heinz; Blatter, Fritz; Sun, Hai

1998-01-01

A selective photooxidation process for the conversion of hydrocarbon molecules to partially oxygenated derivatives, which comprises the steps of adsorbing a hydrocarbon and oxygen onto a dehydrated zeolite support matrix to form a hydrocarbon-oxygen contact pair, and subsequently exposing the hydrocarbon-oxygen contact pair to visible light, thereby forming a partially oxygenated derivative.

Organics in hydrothermal fluids from ultramafics on the Mid-Atlantic Ridge (MAR) - Abiogenic and/or biogenic origin?

NASA Astrophysics Data System (ADS)

Charlou, J.; Donval, J.; Fouquet, Y.; Jean-Baptiste, P.; Dehairs, F.; Holm, N.; Godfroy, A.

2005-12-01

Between 12°N and the Azores Triple Junction along the MAR, CH4 anomalies over axial ultramafic sites are common and point to the association of high or low temperature hydrothermal activity and mantle degassing indicative of ongoing serpentinization process. The general occurrence of isotopically-heavy methane shows the possible abiogenic synthesis of hydrocarbons in hydrothermal systems. The abiogenic formation of CH4 and more complex organic compounds is related to the process of serpentinization of mantellic rocks. Three sites (Logachev, 14°45'N; Rainbow, 36°14'N; Lost City Field, 30°N) are known on the MAR. New fresh fluids were recently sampled at Rainbow and Lost City by the French ROV-Victor during EXOMAR cruise (July 24 to August 28, 2005). The Rainbow and Lost City fluids issued from contrasted ultramafic environments are both enriched in H2, CH4 and hydrocarbons. Hydrogen gas represents more than 40 per cent total gas volume extracted from fluids. SPME (Solid Phase Micro-Extraction) and SBSE (Stir-Bar Sorptive Extraction) extraction techniques were used on board for organic recovery and the analysis was performed on shore by direct GC/MS or by Thermo-Desorption/GC/MS. The hydration of olivine and pyroxen minerals with conversion of Fe(II) to Fe(III) in magnetite during serpentinization leads to production of H2 and conversion of dissolved CO2 to reduced-C species including methane, ethane, propane. In addition heavier straight chain hydrocarbons as alcohols, aldehydes, ketones, aromatics, and cyclic compounds are identified at Rainbow. These compounds may be generated in ultramafic rocks through catalytic reactions (Fischer-Tropsch type reactions), but a biogenic contribution cannot be excluded. Abiogenic organic compounds may be produced from crystalline basement, from volcanic structures, from riftogenic zones and probably from sedimented margins.

Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst.

PubMed

Gao, Peng; Li, Shenggang; Bu, Xianni; Dang, Shanshan; Liu, Ziyu; Wang, Hui; Zhong, Liangshu; Qiu, Minghuang; Yang, Chengguang; Cai, Jun; Wei, Wei; Sun, Yuhan

2017-10-01

Although considerable progress has been made in carbon dioxide (CO 2 ) hydrogenation to various C 1 chemicals, it is still a great challenge to synthesize value-added products with two or more carbons, such as gasoline, directly from CO 2 because of the extreme inertness of CO 2 and a high C-C coupling barrier. Here we present a bifunctional catalyst composed of reducible indium oxides (In 2 O 3 ) and zeolites that yields a high selectivity to gasoline-range hydrocarbons (78.6%) with a very low methane selectivity (1%). The oxygen vacancies on the In 2 O 3 surfaces activate CO 2 and hydrogen to form methanol, and C-C coupling subsequently occurs inside zeolite pores to produce gasoline-range hydrocarbons with a high octane number. The proximity of these two components plays a crucial role in suppressing the undesired reverse water gas shift reaction and giving a high selectivity for gasoline-range hydrocarbons. Moreover, the pellet catalyst exhibits a much better performance during an industry-relevant test, which suggests promising prospects for industrial applications.

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

Tan, Eric; Talmadge, M.; Dutta, Abhijit

The U.S. Department of Energy (DOE) promotes research for enabling cost-competitive liquid fuels production from lignocellulosic biomass feedstocks. The research is geared to advance the state of technology (SOT) of biomass feedstock supply and logistics, conversion, and overall system sustainability. As part of their involvement in this program, the National Renewable Energy Laboratory (NREL) and the Pacific Northwest National Laboratory (PNNL) investigate the economics of conversion pathways through the development of conceptual biorefinery process models. This report describes in detail one potential conversion process for the production of high octane gasoline blendstock via indirect liquefaction (IDL). The steps involve themore » conversion of biomass to syngas via indirect gasification followed by gas cleanup and catalytic syngas conversion to a methanol intermediate; methanol is then further catalytically converted to high octane hydrocarbons. The conversion process model leverages technologies previously advanced by research funded by the Bioenergy Technologies Office (BETO) and demonstrated in 2012 with the production of mixed alcohols from biomass. Biomass-derived syngas cleanup via tar and hydrocarbons reforming was one of the key technology advancements as part of that research. The process described in this report evaluates a new technology area with downstream utilization of clean biomass-syngas for the production of high octane hydrocarbon products through a methanol intermediate, i.e., dehydration of methanol to dimethyl ether (DME) which subsequently undergoes homologation to high octane hydrocarbon products.« less

Conversion of 2,3-butanediol to 2-butanol, olefins and fuels

DOEpatents

Lilga, Michael A.; Lee, Guo-Shuh; Lee, Suh-Jane

2016-12-13

Embodiments of an integrated method for step-wise conversion of 2,3-butanediol to 2-butanol, and optionally to hydrocarbons, are disclosed. The method includes providing an acidic catalyst, exposing a composition comprising aqueous 2,3-butanediol to the acidic catalyst to produce an intermediate composition comprising methyl ethyl ketone, providing a hydrogenation catalyst that is spatially separated from the acidic catalyst, and subsequently exposing the intermediate composition to the hydrogenation catalyst to produce a composition comprising 2-butanol. The method may further include subsequently exposing the composition comprising 2-butanol to a deoxygenation catalyst, and deoxygenating the 2-butanol to form hydrocarbons. In some embodiments, the hydrocarbons comprise olefins, such as butenes, and the method may further include subsequently exposing the hydrocarbons to a hydrogenation catalyst to form saturated hydrocarbons.

Hydrogen production from methane using oxygen-permeable ceramic membranes

NASA Astrophysics Data System (ADS)

Faraji, Sedigheh

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

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

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

Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei

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

Steam reforming of heptane in a fluidized bed membrane reactor

NASA Astrophysics Data System (ADS)

Rakib, Mohammad A.; Grace, John R.; Lim, C. Jim; Elnashaie, Said S. E. H.

n-Heptane served as a model compound to study steam reforming of naphtha as an alternative feedstock to natural gas for production of pure hydrogen in a fluidized bed membrane reactor. Selective removal of hydrogen using Pd 77Ag 23 membrane panels shifted the equilibrium-limited reactions to greater conversion of the hydrocarbons and lower yields of methane, an intermediate product. Experiments were conducted with no membranes, with one membrane panel, and with six panels along the height of the reactor to understand the performance improvement due to hydrogen removal in a reactor where catalyst particles were fluidized. Results indicate that a fluidized bed membrane reactor (FBMR) can provide a compact reformer for pure hydrogen production from a liquid hydrocarbon feedstock at moderate temperatures (475-550 °C). Under the experimental conditions investigated, the maximum achieved yield of pure hydrogen was 14.7 moles of pure hydrogen per mole of heptane fed.

Biological Conversion of Sugars to Hydrocarbons Technology Pathway

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

Davis, Ryan; Biddy, Mary J.; Tan, Eric

2013-03-31

In support of the Bioenergy Technologies Office, the National Renewable Energy Laboratory (NREL) and the Pacific Northwest National Laboratory (PNNL) are undertaking studies of biomass conversion technologies to identify barriers and target research toward reducing conversion costs. Process designs and preliminary economic estimates for each of these pathway cases were developed using rigorous modeling tools (Aspen Plus and Chemcad). These analyses incorporated the best information available at the time of development, including data from recent pilot and bench-scale demonstrations, collaborative industrial and academic partners, and published literature and patents. This technology pathway case investigates the biological conversion of biomass derivedmore » sugars to hydrocarbon biofuels, utilizing data from recent literature references and information consistent with recent pilot scale demonstrations at NREL. Technical barriers and key research needs have been identified that should be pursued for the pathway to become competitive with petroleum-derived gasoline, diesel and jet range hydrocarbon blendstocks.« less

Biogeochemistry: Hexadecane decay by methanogenesis

USGS Publications Warehouse

Anderson, Robert T.; Lovely, Derek R.

2000-01-01

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

Fractional Multistage Hydrothermal Liquefaction of Biomass and Catalytic Conversion into Hydrocarbons

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

Cortright, Randy; Rozmiarek, Robert; Dally, Brice

2017-08-31

The objective of this project was to develop an improved multistage process for the hydrothermal liquefaction (HTL) of biomass to serve as a new front-end, deconstruction process ideally suited to feed Virent’s well-proven catalytic technology, which is already being scaled up. This process produced water soluble, partially de-oxygenated intermediates that are ideally suited for catalytic finishing to fungible distillate hydrocarbons. Through this project, Virent, with its partners, demonstrated the conversion of pine wood chips to drop-in hydrocarbon distillate fuels using a multi-stage fractional conversion system that is integrated with Virent’s BioForming® process. The majority of work was in the liquefactionmore » task and included temperature scoping, solvent optimization, and separations.« less

Single-Atom Electrocatalysts.

PubMed

Zhu, Chengzhou; Fu, Shaofang; Shi, Qiurong; Du, Dan; Lin, Yuehe

2017-11-06

Recent years have witnessed a dramatic increase in the production of sustainable and renewable energy. However, the electrochemical performances of the various systems are limited, and there is an intensive search for highly efficient electrocatalysts by more rational control over the size, shape, composition, and structure. Of particular interest are the studies on single-atom catalysts (SACs), which have sparked new interests in electrocatalysis because of their high catalytic activity, stability, selectivity, and 100 % atom utilization. In this Review, we introduce innovative syntheses and characterization techniques for SACs, with a focus on their electrochemical applications in the oxygen reduction/evolution reaction, hydrogen evolution reaction, and hydrocarbon conversion reactions for fuel cells (electrooxidation of methanol, ethanol, and formic acid). The electrocatalytic performance is further considered at an atomic level and the underlying mechanisms are discussed. The ultimate goal is the tailoring of single atoms for electrochemical applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

HIgh Temperature Photocatalysis over Semiconductors

NASA Astrophysics Data System (ADS)

Westrich, Thomas A.

Due in large part to in prevalence of solar energy, increasing demand of energy production (from all sources), and the uncertain future of petroleum energy feedstocks, solar energy harvesting and other photochemical systems will play a major role in the developing energy market. This dissertation focuses on a novel photochemical reaction process: high temperature photocatalysis (i.e., photocatalysis conducted above ambient temperatures, T ≥ 100°C). The overarching hypothesis of this process is that photo-generated charge carriers are able to constructively participate in thermo-catalytic chemical reactions, thereby increasing catalytic rates at one temperature, or maintaining catalytic rates at lower temperatures. The photocatalytic oxidation of carbon deposits in an operational hydrocarbon reformer is one envisioned application of high temperature photocatalysis. Carbon build-up during hydrocarbon reforming results in catalyst deactivation, in the worst cases, this was shown to happen in a period of minutes with a liquid hydrocarbon. In the presence of steam, oxygen, and above-ambient temperatures, carbonaceous deposits were photocatalytically oxidized over very long periods (t ≥ 24 hours). This initial experiment exemplified the necessity of a fundamental assessment of high temperature photocatalytic activity. Fundamental understanding of the mechanisms that affect photocatalytic activity as a function of temperatures was achieved using an ethylene photocatalytic oxidation probe reaction. Maximum ethylene photocatalytic oxidation rates were observed between 100 °C and 200 °C; the maximum photocatalytic rates were approximately a factor of 2 larger than photocatalytic rates at ambient temperatures. The loss of photocatalytic activity at temperatures above 200 °C is due to a non-radiative multi-phonon recombination mechanism. Further, it was shown that the fundamental rate of recombination (as a function of temperature) can be effectively modeled as a temperature-dependent quantum efficiency term, and is directly driven by bulk photocatalyst crystal parameters: maximum phonon energy and the number of phonons allowed per unit cell. This analysis extends to multiple photocatalysts and can explain experimental observations of photocatalytic oxidation rates with varied reactant concentrations. Lastly, this dissertation applies this knowledge to a thermo-catalytic reaction (CO-oxidation) using a Au/TiO 2 catalyst. The combined photo/thereto-catalytic reaction showed a 10-25% increase in CO conversion during a temperature programmed reaction experiment.

Hydrothermal catalytic deoxygenation of palmitic acid over nickel catalyst

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

Miao, Chao; Marin-Flores, Oscar; Davidson, Stephen D.

2016-02-01

Fatty acid has recently received considerable interest as a possible precursor for producing renewable hydrocarbon. In this study, we investigated hydrothermal catalytic deoxygenation of palmitic acid to produce paraffin over a Ni/ZrO2 catalyst with no or low-pressure (100 psi) external supply of H2. The results show that the presence of water greatly improved conversion of palmitic acid and paraffin yield. Significant improvement was attributed to the formation of in-situ H2. Without an external H2 supply, a 64.2 C% conversion of palmitic acid was achieved in the presence of water, while only a 17.2 C% conversion was achieved without water. Themore » results also show that the presence of water suppressed the side reactions of palmitic acid, specifically ketonization and esterification. We concluded that, compared with decarboxylation and hydrodeoxygenation, decarbonylation was the major route for palmitic acid deoxygenation catalyzed by Ni/ZrO2. Varieties of shorter-chain paraffin (C8–C14) were formed through hydrogenolysis, which also produced a considerable amount of CH4. A viable reaction pathway for hydrothermal catalytic deoxygenation of palmitic acid in the presence of Ni/ZrO2 was suggested. The results show that hydrogenolysis and decarbonylation were the major reactions that occurred. This study demonstrates that this hydrothermal catalytic process is a promising approach for producing liquid paraffin (C8–C15) from fatty acids under no or low-pressure H2.« less

Analysis of Reaction Mechanisms in Flames Using Combined - and Lif-Spectroscopy

NASA Astrophysics Data System (ADS)

Brockhinke, Andreas; Nau, Patrick; Köhler, Markus; Kohse-Höinghaus, Katharina

2009-06-01

Laser-based non-intrusive diagnostic techniques are firmly established as the most versatile tools to study high-temperature gas-phase reactions in general and combustion processes in particular. While fossil fuels remain the most important primary energy carriers, alternative fuels gain in importance. Usually, these fuels contain significant amounts of oxygen, nitrogen and sulphur, leading to different reaction pathways than in the established combustion of hydrocarbons. In order to minimize the formation of pollutants and hazardous compounds (soot, CO, NO_{x}) and increase efficiency, a deeper understanding of these reaction processes is essential. Optical measurements, in particular Cavity Ring-Down Spectroscopy (CRDS) and Laser Induced Fluorescence spectroscopy (LIF), have proven to be well suited for quantitative radical measurements in flames (e.g. OH, ^1CH_2, C_2, HCO). Both techniques provide high sensitivity and selectivity. Our revised experimental setup is designed for quasi-simultaneous measurements, combining the positive features of both complementary techniques. In addition, invasive methods like mass-spectrometry are performed in order to gain a complete understanding of the flame species. In this contribution, we will focus on the quantitative determination of important minor species such as CN, NH_2, CH and formaldehyde in low-pressure flat flames. In addition to investigations of flames with hydrocarbon fuels, we present the first optical measurements in morpholine- and ethylamine-flames. Aim of these measurements is to study the conversion of fuel nitrogen to NO_{x}. Experimental results will be compared with numerical CHEMKIN-II simulations.

Photocatalytic conversion of CO(2) into renewable hydrocarbon fuels: state-of-the-art accomplishment, challenges, and prospects.

PubMed

Tu, Wenguang; Zhou, Yong; Zou, Zhigang

2014-07-16

Photocatalytic reduction of CO2 into hydrocarbon fuels, an artificial photosynthesis, is based on the simulation of natural photosynthesis in green plants, whereby O2 and carbohydrates are produced from H2 O and CO2 using sunlight as an energy source. It couples the reductive half-reaction of CO2 fixation with a matched oxidative half-reaction such as water oxidation, to achieve a carbon neutral cycle, which is like killing two birds with one stone in terms of saving the environment and supplying future energy. The present review provides an overview and highlights recent state-of-the-art accomplishments of overcoming the drawback of low photoconversion efficiency and selectivity through the design of highly active photocatalysts from the point of adsorption of reactants, charge separation and transport, light harvesting, and CO2 activation. It specifically includes: i) band-structure engineering, ii) nanostructuralization, iii) surface oxygen vacancy engineering, iv) macro-/meso-/microporous structuralization, v) exposed facet engineering, vi) co-catalysts, vii) the development of a Z-scheme system. The challenges and prospects for future development of this field are also present. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polynuclear aromatic hydrocarbons for fullerene synthesis in flames

DOEpatents

Alford, J. Michael; Diener, Michael D.

2006-12-19

This invention provides improved methods for combustion synthesis of carbon nanomaterials, including fullerenes, employing multiple-ring aromatic hydrocarbon fuels selected for high carbon conversion to extractable fullerenes. The multiple-ring aromatic hydrocarbon fuels include those that contain polynuclear aromatic hydrocarbons. More specifically, multiple-ring aromatic hydrocarbon fuels contain a substantial amount of indene, methylnapthalenes or mixtures thereof. Coal tar and petroleum distillate fractions provide low cost hydrocarbon fuels containing polynuclear aromatic hydrocarbons, including without limitation, indene, methylnapthalenes or mixtures thereof.

Towards an understanding of the role of clay minerals in crude oil formation, migration and accumulation

NASA Astrophysics Data System (ADS)

Wu, Lin Mei; Zhou, Chun Hui; Keeling, John; Tong, Dong Shen; Yu, Wei Hua

2012-12-01

This article reviews progress in the understanding of the role of clay minerals in crude oil formation, migration and accumulation. Clay minerals are involved in the formation of kerogen, catalytic cracking of kerogen into petroleum hydrocarbon, the migration of crude oil, and the continued change to hydrocarbon composition in underground petroleum reservoirs. In kerogen formation, clay minerals act as catalysts and sorbents to immobilize organic matter through ligand exchange, hydrophobic interactions and cation bridges by the mechanisms of Maillard reactions, polyphenol theory, selective preservation and sorptive protection. Clay minerals also serve as catalysts in acid-catalyzed cracking of kerogen into petroleum hydrocarbon through Lewis and Brønsted acid sites on the clay surface. The amount and type of clay mineral affect the composition of the petroleum. Brønsted acidity of clay minerals is affected by the presence and state of interlayer water, and displacement of this water is a probable driver in crude oil migration from source rocks. During crude oil migration and accumulation in reservoirs, the composition of petroleum is continually modified by interaction with clay minerals. The clays continue to function as sorbents and catalysts even while they are being transformed by diagenetic processes. The detail of chemical interactions and reaction mechanisms between clay minerals and crude oil formation remains to be fully explained but promises to provide insights with broader application, including catalytic conversion of biomass as a source of sustainable energy into the future.

Some features of the oxidative conversion of Mo(CO)/sub 6/ in a medium of hydroperoxide or tert-butyl hydroperoxide and an aromatic hydrocarbon

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

Fomin, V.M.; Lunin, A.V.; Aleksandrov, Yu.A.

1988-03-10

Occurrence of the reaction under study was followed from the decrease in hydroperoxide or of Mo(CO)/sub 6/. The Mo(CO)/sub 6/ content of the reaction was found by determining either the concentration of this compound directly or by determining the concentration of the gaseous products from its transformations (CO + CO/sub 2/). Hydroperoxides (I) and (II) were determined iodometrically. Metal-containing products of the oxidation of Mo(CO)/sub 6/, molybdenum oxides and peroxides, were analyzed by IR and ESR spectroscopy, elemental analysis, and iodometry. Analysis of transformation products of the hydroperoxides (phenol, acetone, dimethylphenylcarbinol, acetophenone, tert-butyl alcohol, water, and oxygen) was performed usingmore » gas chromatography. Results are presented.« less

Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn

DOE PAGES

Liu, Yifei; Göeltl, Florian; Ro, Insoo; ...

2017-06-13

Rh/SiO2 catalysts promoted with Fe and Mn are selective for synthesis gas conversion to oxygenates and light hydrocarbons at 523 K and 580 psi. Selective anchoring of Fe and Mn species on Rh nanoparticles was achieved by controlled surface reactions and was evidenced by ultraviolet–visible absorption spectroscopy, scanning transmission electron microscopy, and inductively coupled plasma absorption emission spectroscopy. The interaction between Rh and Fe promotes the selective production of ethanol through hydrogenation of acetaldehyde and enhances the selectivity toward C2 oxygenates, which include ethanol and acetaldehyde. The interaction between Rh and Mn increases the overall reaction rate and the selectivitymore » toward C2+ hydrocarbons. The combination of Fe and Mn on Rh/SiO2 results in trimetallic Rh-Fe-Mn catalysts that surpass the performance of their bimetallic counterparts. The highest selectivities toward ethanol (36.9%) and C2 oxygenates (39.6%) were achieved over the Rh-Fe-Mn ternary system with a molar ratio of 1:0.15:0.10, as opposed to the selectivities obtained over Rh/SiO2, which were 3.5% and 20.4%, respectively. The production of value-added oxygenates and C2+ hydrocarbons over this trimetallic catalyst accounted for 55% of the total products. X-ray photoelectron spectroscopy measurements suggest that significant fractions of the Fe and Mn species exist as metallic iron and manganese oxides on the Rh surface upon reduction. These findings are rationalized by density functional theory (DFT) calculations, which reveal that the exact state of metals on the surfaces is condition-dependent, with Mn present as Mn(I) and Mn(II) oxide on the Rh (211) step edges and Fe present as Fe(I) oxide on the step edge and metallic subsurface iron on both Rh steps and terraces. CO Fourier transform infrared spectroscopy and DFT calculations suggest that the binding of CO to Rh (211) step edges modified by Fe and/or manganese oxide is altered in comparison to CO adsorption on a clean Rh (211) surface. These results suggest that Mn2Ox species and Fe and Fe2O modify bonding at Rh step edges and shift reaction selectivity away from CH4.« less

Pyrolysis characteristics and kinetics of acid tar waste from crude benzol refining: A thermogravimetry-mass spectrometry analysis.

PubMed

Chihobo, Chido H; Chowdhury, Arindrajit; Kuipa, Pardon K; Simbi, David J

2016-12-01

Pyrolysis is an attractive thermochemical conversion technology that may be utilised as a safe disposal option for acid tar waste. The kinetics of acid tar pyrolysis were investigated using thermogravimetry coupled with mass spectrometry under a nitrogen atmosphere at different heating rates of 10, 15 and 20 K min -1 The thermogravimetric analysis shows three major reaction peaks centred around 178 °C, 258 °C, and 336 °C corresponding to the successive degradation of water soluble lower molecular mass sulphonic acids, sulphonated high molecular mass hydrocarbons, and high molecular mass hydrocarbons. The kinetic parameters were evaluated using the iso-conversional Kissinger-Akahira-Sunose method. A variation in the activation energy with conversion revealed that the pyrolysis of the acid tar waste progresses through complex multi-step kinetics. Mass spectrometry results revealed a predominance of gases such as hydrogen, methane and carbon monoxide, implying that the pyrolysis of acid tar waste is potentially an energy source. Thus the pyrolysis of acid tar waste may present a viable option for its environmental treatment. There are however, some limitations imposed by the co-evolution of corrosive gaseous components for which appropriate considerations must be provided in both pyrolysis reactor design and selection of construction materials. © The Author(s) 2016.

THERMOCHEMICAL CONVERSION OF FERMENTATION-DERIVED OXYGENATES TO FUELS

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

Ramasamy, Karthikeyan K.; Wang, Yong

2013-06-01

At present ethanol generated from renewable resources through fermentation process is the dominant biofuel. But ethanol suffers from undesirable fuel properties such as low energy density and high water solubility. The production capacity of fermentation derived oxygenates are projected to rise in near future beyond the current needs. The conversion of oxygenates to hydrocarbon compounds that are similar to gasoline, diesel and jet fuel is considered as one of the viable option. In this chapter the thermo catalytic conversion of oxygenates generated through fermentation to fuel range hydrocarbons will be discussed.

Process for light-driven hydrocarbon oxidation at ambient temperatures

DOEpatents

Shelnutt, John A.

1990-01-01

A photochemical reaction for the oxidation of hydrocarbons uses molecular oxygen as the oxidant. A reductive photoredox cycle that uses a tin(IV)- or antimony(V)-porphyrin photosensitizer generates the reducing equivalents required to activate oxygen. This artificial photosynthesis system drives a catalytic cycle, which mimics the cytochrome P.sub.450 reaction, to oxidize hydrocarbons. An iron(III)- or manganese(III)-porphyrin is used as the hydrocarbon-oxidation catalyst. Methylviologen can be used as a redox relay molecule to provide for electron-transfer from the reduced photosensitizer to the Fe or Mn porphyrin. The system is long-lived and may be used in photo-initiated spectroscopic studies of the reaction to determine reaction rates and intermediates.

Heterogeneous OH oxidation of motor oil particles causes selective depletion of branched and less cyclic hydrocarbons.

PubMed

Isaacman, Gabriel; Chan, Arthur W H; Nah, Theodora; Worton, David R; Ruehl, Chris R; Wilson, Kevin R; Goldstein, Allen H

2012-10-02

Motor oil serves as a useful model system for atmospheric oxidation of hydrocarbon mixtures typical of anthropogenic atmospheric particulate matter, but its complexity often prevents comprehensive chemical speciation. In this work we fully characterize this formerly "unresolved complex mixture" at the molecular level using recently developed soft ionization gas chromatography techniques. Nucleated motor oil particles are oxidized in a flow tube reactor to investigate the relative reaction rates of observed hydrocarbon classes: alkanes, cycloalkanes, bicycloalkanes, tricycloalkanes, and steranes. Oxidation of hydrocarbons in a complex aerosol is found to be efficient, with approximately three-quarters (0.72 ± 0.06) of OH collisions yielding a reaction. Reaction rates of individual hydrocarbons are structurally dependent: compared to normal alkanes, reaction rates increased by 20-50% with branching, while rates decreased ∼20% per nonaromatic ring present. These differences in rates are expected to alter particle composition as a function of oxidation, with depletion of branched and enrichment of cyclic hydrocarbons. Due to this expected shift toward ring-opening reactions heterogeneous oxidation of the unreacted hydrocarbon mixture is less likely to proceed through fragmentation pathways in more oxidized particles. Based on the observed oxidation-induced changes in composition, isomer-resolved analysis has potential utility for determining the photochemical age of atmospheric particulate matter with respect to heterogeneous oxidation.

First Principles Simulations of Hydrocarbon Conversion Processes in Functionalized Zeolitic Materials

NASA Astrophysics Data System (ADS)

Mazar, Mark Nickolaus

With increasing demand for chemicals and fuels, and finite traditional crude oil resources, there is a growing need to invent, establish, or optimize chemical processes that convert gasifiable carbon-based feedstocks (e.g., coal, natural gas, oil sands, or biomass) into the needed final products. Catalysis is central to almost every industrial chemical process, including alkane metathesis (AM) and the methanol-to-hydrocarbons (MTH) process, which represent final steps in a sequence of hydrocarbon conversion reactions. An in depth understanding of AM and MTH is essential to the selective production of the desired end products. In this dissertation, ab initio density functional theory simulations provide unique mechanistic and thermodynamic insight of specific elementary steps involved in AM and MTH as performed on zeolite supports. Zeolites have been employed throughout the petroleum industry because of their ability to perform acid-catalyzed reactions (e.g., cracking or MTH). The crystalline structure of zeolites imparts regular microporous networks and, in turn, the selective passage of molecules based on shape and functionality. Many different elements can be grafted onto or substituted into zeolites, resulting in a broad range of catalytic behavior. However, due to the variety of competing and secondary reactions that occur at experimental conditions, it is often difficult to extract quantitative information regarding individual elementary steps. ab initio calculations can be particularly useful for this purpose. Alkane metathesis (i.e., the molecular redistribution or chain length averaging of alkanes) is typically performed by transition metal hydrides on amorphous alumina or silica supports. In Chapter 3, the feasibility of AM in zeolites is assessed by using a grafted Ta-hydride complex to explore the full catalytic cycle in the self-metathesis of ethane. The decomposition of a Ta-metallacyclobutane reaction intermediate that forms during olefin metathesis is responsible for the largest activation energy of the catalytic cycle. This assessment is similar to the findings of alkane metathesis studies on alumina/silica supports and indicates that the entire AM cycle can be performed in zeolites by isolated single-atom transition metal hydrides. Performed over acid form zeolites, MTH is used in the conversion of methanol into a broad range of hydrocarbons, including alkenes, alkanes, and aromatics. For reasons that are not yet rigorously quantified, product selectivities vary dramatically based on the choice of catalyst and reaction conditions. The methylation of species containing double bonds (i.e., co-catalysts) is central to the overall process. Distinct structure-function relationships were found with respect to the elementary steps in the methylation and beta-scission of olefins. In Chapter 4, the role of zeolite topology in the step-wise methylation of ethene by surface methoxides is investigated. Elementary steps are studied across multiple frameworks (i.e., BEA, CHA, FER, MFI, and MOR) constituting a wide variety of confinement environments. The reaction of surface methoxides with ethene is found to require a transition state containing a primary carbocation. The barrier height is found to decrease nearly monotonically with respect to the degree of dispersion interactions stabilizing the primary carbocationic species in the transition state. In addition, quantification of the ``local'' dispersion energy indicates that confinement effects can not be simply correlated to pore size. The beta-scission of olefins plays an important role in the product selectivities of many important chemical processes, including MTH. In Chapter 5, beta-scission modes involving C6 and C8 isomers are investigated at a single, isolated Bronsted acid site within H-ZSM-5. We find that the relative enthalpic barriers of beta-scission elementary steps can be rationalized by the substitution order of the two different carbocationic carbon atoms that are present in the reactant (C+) and transition states (betaC). In fact, the increase in charge required by the betaC atom to go from the physi/chemi-sorbed reactant state to the beta-scission transition state (+0.23e-0.33e) is found to correlate almost linearly with the intrinsic activation energy (89-233 kJ mol-1). The charge of the betaC atom depends, to a large extent, on the substitution order of both the C+ and betaC atoms and, therefore, each beta-scission mode is a sub-category onto itself. Isomerization reactions, which are fast with respect to beta-scission, enable reactant hydrocarbons to explore and find low barrier beta-scission pathways. Selectivities predicted on the basis of the relative barrier heights of beta-scission modes accessible to C6 and C8 species indicate general agreement with experimental observations.

Effects of non-thermal plasmas and electric field on hydrocarbon/air flames

NASA Astrophysics Data System (ADS)

Ganguly, Biswa

2009-10-01

Need to improve fuel efficiency, and reduce emission from hydrocarbon combustor in automotive and gas turbine engines have reinvigorated interest in reducing combustion instability of a lean flame. The heat generation rate in a binary reaction is HQ =N^2 c1c2 Q exp(-E/RT), where N is the density, c1 and c2 are mol fractions of the reactants, Q is the reaction heat release, E is the activation energy, R is the gas constant and T is the average temperature. For hydrocarbon-air reactions, the typical value of E/R ˜20, so most heat release reactions are confined to a thin reaction sheet at T >=1400 K. The lean flame burning condition is susceptible to combustion instability due to a critical balance between heat generation and heat loss rates, especially at high gas flow rate. Radical injection can increase flame speed by reducing the hydrocarbon oxidation reaction activation barrier and it can improve flame stability. Advances in nonequilibrium plasma generation at high pressure have prompted its application for energy efficient radical production to enhance hydrocarbon-air combustion. Dielectric barrier discharges and short pulse excited corona discharges have been used to enhance combustion stability. Direct electron impact dissociation of hydrocarbon and O2 produces radicals with lower fuel oxidation reaction activation barriers, initiating heat release reaction CnHm+O <-> CnHm-1+ OH (and other similar sets of reactions with partially dissociated fuel) below the typical cross-over temperature. Also, N2 (A) produced in air discharge at a moderate E/n can dissociate O2 leading to oxidation of fuel at lower gas temperature. Low activation energy reactions are also possible by dissociation of hydrocarbon CnHm+e -> CnHm-2+H2+e, where a chain propagation reaction H2+ O<-> OH+H can be initiated at lower gas temperature than possible under thermal equilibrium kinetics. Most of heat release comes from the reaction CO+OH-> CO2 +H, nonthermal OH production seem to improve combustion stability The effect of applied voltage in a flame below self-sustained plasma generation is known to enhance flame holding through induced turbulence. Review of recent results will be presented to show future research opportunities in quantitative measurements and modeling of hydrocarbon/air plasma enhanced combustion.

Methane on Titan: Photochemical-Meteorological-Hydrogeochemical Cycle

NASA Astrophysics Data System (ADS)

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

2005-08-01

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

Conversion of organic solids to hydrocarbons

DOEpatents

Greenbaum, E.

1995-05-23

A method of converting organic solids to liquid and gaseous hydrocarbons includes impregnating an organic solid with photosensitizing ions and exposing the impregnated solid to light in a non-oxidizing atmosphere for a time sufficient to photocatalytically reduce the solid to at least one of a liquid and a gaseous hydrocarbon. 5 Figs.

Conversion of organic solids to hydrocarbons

DOEpatents

Greenbaum, Elias

1995-01-01

A method of converting organic solids to liquid and gaseous hydrocarbons includes impregnating an organic solid with photosensitizing ions and exposing the impregnated solid to light in a non-oxidizing atmosphere for a time sufficient to photocatalytically reduce the solid to at least one of a liquid and a gaseous hydrocarbon.

Process and apparatus for the production of hydrogen by steam reforming of hydrocarbon

DOEpatents

Sircar, Shivaji; Hufton, Jeffrey Raymond; Nataraj, Shankar

2000-01-01

In the steam reforming of hydrocarbon, particularly methane, under elevated temperature and pressure to produce hydrogen, a feed of steam and hydrocarbon is fed into a first reaction volume containing essentially only reforming catalyst to partially reform the feed. The balance of the feed and the reaction products of carbon dioxide and hydrogen are then fed into a second reaction volume containing a mixture of catalyst and adsorbent which removes the carbon dioxide from the reaction zone as it is formed. The process is conducted in a cycle which includes these reactions followed by countercurrent depressurization and purge of the adsorbent to regenerate it and repressurization of the reaction volumes preparatory to repeating the reaction-sorption phase of the cycle.

Takovite-aluminosilicate-Cr materials prepared by adsorption of Cr3+ from industrial effluents as catalysts for hydrocarbon oxidation reactions.

PubMed

Ciuffi, Katia J; de Faria, Emerson H; Marçal, Liziane; Rocha, Lucas A; Calefi, Paulo S; Nassar, Eduardo J; Pepe, Iuri; da Rocha, Zênis N; Vicente, Miguel A; Trujillano, Raquel; Gil, Antonio; Korili, Sophia A

2012-05-01

The catalytic efficiency of takovite-aluminosilicate-chromium catalysts obtained by adsorption of Cr(3+) ions from aqueous solutions by a takovite-aluminosilicate nanocomposite adsorbent is reported. The adsorbent was synthesized by the coprecipitation method. The catalytic activity of the final Cr-catalysts depended on the amount of adsorbed chromium. (Z)-cyclooctene conversion up to 90% with total selectivity for the epoxide was achieved when the oxidation was carried out with hydrogen peroxide, at room temperature. After five consecutive runs, the catalysts maintained high activity, although after the sixth reuse, the epoxide yields strongly decreased to 35%. The catalysts were also efficient for cyclohexane oxidation, reaching up to 18% conversion, with cyclohexanone/cyclohexanol selectivity close to 1.2. On the whole, their use as catalysts gives a very interesting application for the solids obtained by adsorption of a contaminant cation such as Cr(3+).

Non-thermal plasma conversion of hydrocarbons

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

Strohm, James J.; Skoptsov, George L.; Musselman, Evan T.

A non-thermal plasma is generated to selectively convert a precursor to a product. More specifically, plasma forming material and a precursor material are provided to a reaction zone of a vessel. The reaction zone is exposed to microwave radiation, including exposing the plasma forming material and the precursor material to the microwave radiation. The exposure of the plasma forming material to the microwave radiation selectively converts the plasma forming material to a non-thermal plasma including formation of one or more streamers. The precursor material is mixed with the plasma forming material and the precursor material is exposed to the non-thermalmore » plasma including exposing the precursor material to the one or more streamers. The exposure of the precursor material to the streamers and the microwave radiation selectively converts the precursor material to a product.« less

Discerning the Location and Nature of Coke Deposition from Surface to Bulk of Spent Zeolite Catalysts

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

Devaraj, Arun; Vijayakumar, Murugesan; Bao, Jie

The nanoscale compositional mapping of fresh HZSM-5 catalyst synthesized using hydrothermal process as well as after just steaming and after ethanol conversion reaction for 72 hours at realistic catalytic conditions was investigated using atom probe tomography. Atom probe tomography permitted direct atomic scale imaging of non-uniform distribution of Al within the HZSM-5 as well as for the first time image the hydrocarbon coking after ethanol reaction. Clear evidences for existence of multiple C-H molecular species which appear to aggregate as clusters within the pores of spent HZSM-5 catalyst materials is provided. These results provide evidence for the ability of atommore » probe tomography, a powerful 3D characterization tool in interrogating the atomic scale chemistry of zeolite catalyst materials at industrially relevant catalytic conditions.« less

Laboratory Investigation of Organic Aerosol Formation from Aromatic Hydrocarbons

DOE R&D Accomplishments Database

Molina, Luisa T.; Molina, Mario J.; Zhang, Renyi

2006-08-23

Our work for this DOE funded project includes: (1) measurements of the kinetics and mechanism of the gas-phase oxidation reactions of the aromatic hydrocarbons initiated by OH; (2) measurements of aerosol formation from the aromatic hydrocarbons; and (3) theoretical studies to elucidate the OH-toluene reaction mechanism using quantum-chemical and rate theories.

Hydrocarbon-soluble calcium hydride: a "worker-bee" in calcium chemistry.

PubMed

Spielmann, Jan; Harder, Sjoerd

2007-01-01

The reactivity of the hydrocarbon-soluble calcium hydride complex [{CaH(dipp-nacnac)(thf)}(2)] (1; dipp-nacnac=CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)) with a large variety of substrates has been investigated. Addition of 1 to C=O and C=N functionalities gave easy access to calcium alkoxide and amide complexes. Similarly, reduction of the C[triple chemical bond]N bond in a cyanide or an isocyanide resulted in the first calcium aldimide complexes [Ca{N=C(H)R}(dipp-nacnac)] and [Ca{C(H)=NR}(dipp-nacnac)], respectively. Complexation of 1 with borane or alane Lewis acids gave the borates and alanates as contact ion pairs. In reaction with epoxides, nucleophilic ring-opening is observed as the major reaction. The high reactivity of hydrocarbon-soluble 1 with most functional groups contrasts strongly with that of insoluble CaH(2), which is essentially inert and is used as a common drying agent. Crystal structures of the following products are presented: [{Ca{OC(H)Ph(2)}(dipp-nacnac)}(2)], [{Ca{N=C(H)Ph}(dipp-nacnac)}(2)], [{Ca{C(H)=NC(Me)(2)CH(2)C(Me)(3)}(dipp-nacnac)}(2)], [{Ca{C(H)=NCy}(dipp-nacnac)}(2)], [Ca(dipp-nacnac)(thf)](+)[H(2)BC(8)H(14)](-) and [{Ca(OCy)(dipp-nacnac)}(2)]. The generally smooth and clean conversions of 1 with a variety of substrates and the stability of most intermediates against ligand exchange make 1 a valuable key precursor in the syntheses of a wide variety of beta-diketiminate calcium complexes.

Plasma-assisted conversion of solid hydrocarbon to diamond

DOEpatents

Valone, Steven M.; Pattillo, Stevan G.; Trkula, Mitchell; Coates, Don M.; Shah, S. Ismat

1996-01-01

A process of preparing diamond, e.g., diamond fiber, by subjecting a hydrocarbon material, e.g., a hydrocarbon fiber, to a plasma treatment in a gaseous feedstream for a sufficient period of time to form diamond, e.g., a diamond fiber is disclosed. The method generally further involves pretreating the hydrocarbon material prior to treatment with the plasma by heating within an oxygen-containing atmosphere at temperatures sufficient to increase crosslinking within said hydrocarbon material, but at temperatures insufficient to melt or decompose said hydrocarbon material, followed by heating at temperatures sufficient to promote outgassing of said crosslinked hydrocarbon material, but at temperatures insufficient to convert said hydrocarbon material to carbon.

Enhanced conversion of syngas to liquid motor fuels

DOEpatents

Coughlin, Peter K.; Rabo, Jule A.

1986-01-01

Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

Systems and processes for conversion of ethylene feedstocks to hydrocarbon fuels

DOEpatents

Lilga, Michael A.; Hallen, Richard T.; Albrecht, Karl O.; Cooper, Alan R.; Frye, John G.; Ramasamy, Karthikeyan Kallupalayam

2018-04-03

Systems, processes, and catalysts are disclosed for obtaining fuel and fuel blends containing selected ratios of open-chain and closed-chain fuel-range hydrocarbons suitable for production of alternate fuels including gasolines, jet fuels, and diesel fuels. Fuel-range hydrocarbons may be derived from ethylene-containing feedstocks and ethanol-containing feedstocks.

Systems and processes for conversion of ethylene feedstocks to hydrocarbon fuels

DOEpatents

Lilga, Michael A.; Hallen, Richard T.; Albrecht, Karl O.; Cooper, Alan R.; Frye, John G.; Ramasamy, Karthikeyan Kallupalayam

2017-05-30

Systems, processes, and catalysts are disclosed for obtaining fuel and fuel blends containing selected ratios of open-chain and closed-chain fuel-range hydrocarbons suitable for production of alternate fuels including gasolines, jet fuels, and diesel fuels. Fuel-range hydrocarbons may be derived from ethylene-containing feedstocks and ethanol-containing feedstocks.

Systems and processes for conversion of ethylene feedstocks to hydrocarbon fuels

DOEpatents

Lilga, Michael A.; Hallen, Richard T.; Albrecht, Karl O.; Cooper, Alan R.; Frye, John G.; Ramasamy, Karthikeyan Kallupalayam

2017-09-26

Systems, processes, and catalysts are disclosed for obtaining fuels and fuel blends containing selected ratios of open-chain and closed-chain fuel-range hydrocarbons suitable for production of alternate fuels including gasolines, jet fuels, and diesel fuels. Fuel-range hydrocarbons may be derived from ethylene-containing feedstocks and ethanol-containing feedstocks.

Removal of polycyclic aromatic hydrocarbons in aqueous environment by chemical treatments: a review.

PubMed

Rubio-Clemente, Ainhoa; Torres-Palma, Ricardo A; Peñuela, Gustavo A

2014-04-15

Due to their carcinogenic, mutagenic and teratogenic potential, the removal of polycyclic aromatic hydrocarbons (PAHs) from aqueous environment using physical, biological and chemical processes has been studied by several researchers. This paper reviews the current state of knowledge concerning PAHs including their physico-chemical properties, input sources, occurrence, adverse effects and conventional and alternative chemical processes applied for their removal from water. The mechanisms and reactions involved in each treatment method are reported, and the effects of various variables on the PAH degradation rate as well as the extent of degradation are also discussed. Extensive literature analysis has shown that an effective way to perform the conversion and mineralization of this type of substances is the application of advanced oxidation processes (AOPs). Furthermore, combined processes, particularly AOPs coupled with biological treatments, seem to be one of the best solutions for the treatment of effluents containing PAHs. Copyright © 2013 Elsevier B.V. All rights reserved.

ZnCl 2 induced catalytic conversion of softwood lignin to aromatics and hydrocarbons

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

Wang, Hongliang; Zhang, Libing; Deng, Tiansheng

2016-01-01

Selective cleavage of C-O-C bonds in lignin without disrupting C-C linkages can result in releasing aromatic monomers and dimers that can be subsequently converted into chemicals and fuels. Results showed that both biomass-derived lignin and lignin model compounds were depolymerized in a highly concentrated ZnCl2 solution. Zn2+ ions in highly concentrated ZnCl2 solutions appeared to selectively coordinate with C-O-C bonds to cause key linkages of lignin much easier to cleave. In 63 wt.% ZnCl2 solution at 200 °C for 6 h, nearly half of the softwood technical lignin was converted to liquid products, of which the majority was alkylphenols. Resultsmore » indicated that most β-O-4 and Cmethyl-OAr bonds of model compounds were cleaved undersame conditions, providing a foundation towards understanding lignin depolymerization in a concentrated ZnCl2 solution. The phenolic products were further converted into cyclic hydrocarbons via hydrodeoxygenation and coupling reactions by co-catalyst Ru/C.« less

Transition metal catalysis in the generation of petroleum and natural gas. Progress report, [1992--1993

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

Mango, F.

1993-08-01

A new hypothesis is introduced for the generation of petroleum and natural gas. The transition metals, activated under the reducing conditions of diagenesis, are proposed as catalysts in the generation of light hydrocarbons. The objective of this proposal is to test that hypothesis. Transition metals (Ni, V, Ti, Co, Fe), in kerogen, porphyrins, and as pure compounds, will be tested under catagenic conditions for catalytic activity in the conversion of normal paraffins and hydrogen into light hydrocarbons. If the hypothesis is correct, kerogenous transition metals should become catalytically active under the reducing conditions of diagenesis and catalyze the conversion ofmore » paraffins into the light hydrocarbons seen in petroleum. Moreover, the C{sub 1}-C{sub 4} hydrocarbons generated catalytically should be similar in molecular and isotopic compositions to natural gas.« less

Partial oxidation of methane by pulsed corona discharges

NASA Astrophysics Data System (ADS)

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

2014-09-01

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

Performance characterization of CNTs and γ-Al2O3 supported cobalt catalysts in Fischer-Tropsch reaction

NASA Astrophysics Data System (ADS)

Ali, Sardar; Zabidi, Noor Asmawati Mohd; Subbarao, Duvvuri

2014-10-01

Catalysts were prepared via a wet impregnation method. Different physicochemical properties of the samples were revealed by transmission electron microscope (TEM), temperature programmed reduction (H2-TPR) and carbon dioxide desorption (CO2-desorption). Fischer-Tropsch reaction (FTS) was carried out in a fixed-bed microreactor at 220°C and 1 atm, with H2/ CO = 2v / v and space velocity, SV of 12L/g.h for 5 h. Various characterization techniques revealed that there was a stronger interaction between Co and Al2O3 support compared to that of CNTs support. CNTs support increased the reducibility and decreased Co particle size. A significant increase in % CO conversion and FTS reaction rate was observed over CNTs support compared to that of Co / Al2O3. Co/CNTs resulted in higher C5+ hydrocarbons selectivity compared to that of Co / Al2O3 catalyst. CNTs are a better support for Co compared to Al2O3.

Enhanced catalyst for conversion of syngas to liquid motor fuels

DOEpatents

Coughlin, Peter K.; Rabo, Jule A.

1985-01-01

Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

Enhanced catalyst for conversion of syngas to liquid motor fuels

DOEpatents

Coughlin, P.K.; Rabo, J.A.

1985-12-03

Synthesis gas comprising carbon monoxide and hydrogen is converted to C[sub 5][sup +] hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising a SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

40 CFR Appendix F to Part 75 - Conversion Procedures

Code of Federal Regulations, 2010 CFR

2010-07-01

...-00, Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter, or ASTM D4809-00, Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb...

Provisional Guidance for Quantitative Risk Assessment of Polycyclic Aromatic Hydrocarbons

EPA Science Inventory

Polycyclic Aromatic Hydrocarbons (PAHs) are products of incomplete combustion of organic materials; sources are, thus, widespread,including cigarette smoke, municipal waste incineration, wood stove emissions, coal conversion, energy production form fossil fuels, and automobile an...

Solar-thermal fluid-wall reaction processing

DOEpatents

Weimer, Alan W.; Dahl, Jaimee K.; Lewandowski, Allan A.; Bingham, Carl; Buechler, Karen J.; Grothe, Willy

2006-04-25

The present invention provides a method for carrying out high temperature thermal dissociation reactions requiring rapid-heating and short residence times using solar energy. In particular, the present invention provides a method for carrying out high temperature thermal reactions such as dissociation of hydrocarbon containing gases and hydrogen sulfide to produce hydrogen and dry reforming of hydrocarbon containing gases with carbon dioxide. In the methods of the invention where hydrocarbon containing gases are dissociated, fine carbon black particles are also produced. The present invention also provides solar-thermal reactors and solar-thermal reactor systems.

Solar-Thermal Fluid-Wall Reaction Processing

DOEpatents

Weimer, A. W.; Dahl, J. K.; Lewandowski, A. A.; Bingham, C.; Raska Buechler, K. J.; Grothe, W.

2006-04-25

The present invention provides a method for carrying out high temperature thermal dissociation reactions requiring rapid-heating and short residence times using solar energy. In particular, the present invention provides a method for carrying out high temperature thermal reactions such as dissociation of hydrocarbon containing gases and hydrogen sulfide to produce hydrogen and dry reforming of hydrocarbon containing gases with carbon dioxide. In the methods of the invention where hydrocarbon containing gases are dissociated, fine carbon black particles are also produced. The present invention also provides solar-thermal reactors and solar-thermal reactor systems.

Upgrade of Long-chain Hydrocarbons by Low Pressure Oxygen Plasmas

NASA Astrophysics Data System (ADS)

Patiño, Pedro; Méndez, Bernardo; Gambús, Gloria

1998-10-01

Huge known heavy oil deposits in many countries remain largely untapped. The API gravity of crude oils has been decreasing by about 0.17% per year, this meaning that there will be an urgent need for economically viable new technologies to upgrade the heavy oil for the refineries. The same applies to the residues of several refineries processes. This work will present the results of the application of a plasma process to upgrade long-chain hydrocarbons, namely, tridecane, tetradecane, and squalane (shark oil). They are high boiling point alkanes, the latter being a C_30H_62 with six methyl groups attached to various carbon positions on the chain. An oxygen plasma, created by a high voltage glow discharge, reached the low vapor pressure surface of each liquid hydrocarbon. This (2 mL) was cooled down to temperatures close to its freezing point in a glass reactor. Applied power was 24 W for times of reaction between 30 and 60 minutes and oxygen pressures from 0.1 to 0.4 mbar. Products were analyzed by IR and NMR spectroscopies. The ^1H and ^13C NMR spectra showed that the most important products were secondary alcohols and the corresponding ketones, for tridecane and tetradecane. For squalane, tertiary alcohols were first. Total conversions are tipically 90 to 100%

Heterogeneous Photocatalytic Oxidation of Atmospheric Trace Contaminants

NASA Technical Reports Server (NTRS)

Ollis, David F.

1996-01-01

Heterogeneous photocatalysis involves the use of a light-activated catalyst at room temperature in order to carry out a desired reaction. In the presence of molecular oxygen, illumination of the n-type semiconductor oxide titanium dioxide (TiO2) provides for production of highly active forms of oxygen, such as hydroxyl radicals, which are able to carry out the complete oxidative destruction of simple hydrocarbons such as methane, ethane, ethylene, propylene, and carbon monoxide. This broad oxidation potential, coupled with the ability with sufficient residence time to achieve complete oxidation of simple hydrocarbon contaminants to carbon dioxide and water, indicated that heterogeneous photocatalysis should be examined for its potential for purification of spacecraft air. If a successful catalyst and photoreactor could be demonstrated at the laboratory level, such results would allow consideration of photocatalysts as a partial or complete replacement of adsorption systems, thereby allowing for reduction in lift-off weight of a portion of the life support system for the spacecraft, or other related application such as a space station or a conventional commercial aircraft. The present research was undertaken to explore this potential through achievement of the following plan of work: (a) ascertain the intrinsic kinetics of conversion of pollutants of interest in spacecraft, (b) ascertain the expected lifetime of catalysts through examination of most likely routes of catalyst deactivation and regeneration, (c) model and explore experimentally the low pressure drop catalytic monolith, a commercial configuration for automotive exhaust control, and (d) examine the kinetics of multicomponent conversions. In the recent course of this work, we have also discovered how to increase catalyst activity via halide promotion which has allowed us to achieve approximately 100% conversion of an aromatic contaminant (toluene) in a very short residence time of 5-6 milliseconds.

Heterogeneous Photocatalytic Oxidation of Atmospheric Trace Contaminants

NASA Technical Reports Server (NTRS)

Ollis, David F.

1996-01-01

Heterogeneous photocatalysis involves the use of a light-activated catalyst at room temperature in order to carry out a desired reaction. In the presence of molecular oxygen, illumination of the n-type semiconductor oxide titanium dioxide (TiO2) provides for production of highly active forms of oxygen, such as hydroxyl radicals, which are able to carry out the complete oxidative destruction of simple hydrocarbons such as methane, ethane, ethylene, propylene, and carbon monoxide. This broad oxidation potential, coupled with the ability with sufficient residence time to achieve complete oxidation of simple hydrocarbon contaminants to carbon dioxide and water, indicated that heterogeneous photocatalysis should be examined for its potential for purification of spacecraft air. If a successful catalyst and photoreactor could be demonstrated at the laboratory level, such results would allow consideration of photocatalysts as a partial or complete replacement of adsorption systems, thereby allowing for reduction in lift-off weight of a portion of the life support system for the spacecraft, or other related application such as a space station or a conventional commercial aircraft. The present research was undertaken to explore this potential through achievement of the following plan of work: (a) ascertain the intrinsic kinetics of conversion of pollutants of interest in spacecraft, (b) ascertain the expected lifetime of catalysts through examination of most likely routes of catalyst deactivation and regeneration (c) model and explore experimentally the low pressure drop catalytic monolith, a commercial configuration for automotive exhaust control (d) examine the kinetics of multicomponent conversions. In the recent course of this work, we have also discovered how to increase catalyst activity via halide promotion which has allowed us to achieve approximately 100% conversion of an aromatic contaminant (toluene) in a very short residence time of 5-6 milliseconds.

Combustion process for synthesis of carbon nanomaterials from liquid hydrocarbon

DOEpatents

Diener, Michael D.; Alford, J. Michael; Nabity, James; Hitch, Bradley D.

2007-01-02

The present invention provides a combustion apparatus for the production of carbon nanomaterials including fullerenes and fullerenic soot. Most generally the combustion apparatus comprises one or more inlets for introducing an oxygen-containing gas and a hydrocarbon fuel gas in the combustion system such that a flame can be established from the mixed gases, a droplet delivery apparatus for introducing droplets of a liquid hydrocarbon feedstock into the flame, and a collector apparatus for collecting condensable products containing carbon nanomaterials that are generated in the combustion system. The combustion system optionally has a reaction zone downstream of the flame. If this reaction zone is present the hydrocarbon feedstock can be introduced into the flame, the reaction zone or both.

The future of oil: unconventional fossil fuels.

PubMed

Chew, Kenneth J

2014-01-13

Unconventional fossil hydrocarbons fall into two categories: resource plays and conversion-sourced hydrocarbons. Resource plays involve the production of accumulations of solid, liquid or gaseous hydro-carbons that have been generated over geological time from organic matter in source rocks. The character of these hydrocarbons may have been modified subsequently, especially in the case of solids and extra-heavy liquids. These unconventional hydrocarbons therefore comprise accumulations of hydrocarbons that are trapped in an unconventional manner and/or whose economic exploitation requires complex and technically advanced production methods. This review focuses primarily on unconventional liquid hydro-carbons. The future potential of unconventional gas, especially shale gas, is also discussed, as it is revolutionizing the energy outlook in North America and elsewhere.

Catalytic co-aromatization of ethanol and methane

DOE PAGES

Wang, Aiguo; He, Peng; Yung, Matthew; ...

2016-06-06

This study demonstrates the technical feasibility of simultaneously converting ethanol and methane into liquid hydrocarbons at mild reaction conditions (400 °C and 1 atm) over silver and/or zinc modified zeolite catalysts. After GC-MS analysis, it is worth noting that aromatics are the major compounds contained in the liquid product collected from the run when 1%Ag/ZSM-5, particularly after H 2 pretreatment, is charged. Compared to the performance exhibited from the run with pure HZSM-5 support engaged, Ag addition into the HZSM-5 framework favors aromatics formation, which might be closely associated with better Ag dispersion and more abundance of strong surface acidicmore » sites where aromatization might take place while Zn loading exerts a detrimental effect on the production of aromatics but promotes the ether generation possibly through dehydration reaction. Referred to that from its N 2 counterpart, the increased aromatics formation of the collected liquid product when methane is present indicates that methane existence might facilitate ethanol aromatization. Moreover, combined with the increased carbon number in the formed aromatics from CH 4 run when H 2 run is referred and zero liquid formation from CH 4-alone test as well as more prominent endothermic feature of methane run and more importantly the notably increased 13C signals in 13C NMR spectra of the liquid product collected during ethanol conversion under 13CH 4 environment, all the observations suggest that methane might be activated nonoxidatively and converted into higher hydrocarbons, preferentially into aromatics if suitable catalyst is charged under the assistance of co-existing oxygenated hydrocarbon. Lastly, the reported synergetic effect could potentially lead to the more economic utilization of abundant natural gas and cellulosic ethanol.« less

Kinetic modeling of ethane pyrolysis at high conversion.

PubMed

Xu, Chen; Al Shoaibi, Ahmed Sultan; Wang, Chenguang; Carstensen, Hans-Heinrich; Dean, Anthony M

2011-09-29

The primary objective of this study is to develop an improved first-principle-based mechanism that describes the molecular weight growth kinetics observed during ethane pyrolysis. A proper characterization of the kinetics of ethane pyrolysis is a prerequisite for any analysis of hydrocarbon pyrolysis and oxidation. Flow reactor experiments were performed with ~50/50 ethane/nitrogen mixtures with temperatures ranging from 550 to 850 °C at an absolute pressure of ~0.8 atm and a residence time of ~5 s. These conditions result in ethane conversions ranging from virtually no reaction to ~90%. Comparisons of predictions using our original mechanism to these data yielded very satisfactory results in terms of the temperature dependence of ethane conversion and prediction of the major products ethylene and hydrogen. However, there were discrepancies in some of the minor species concentrations that are involved in the molecular weight growth kinetics. We performed a series of CBS-QB3 analyses for the C(3)H(7), C(4)H(7), and C(4)H(9) potential energy surfaces to better characterize the radical addition reactions that lead to molecular weight growth. We also extended a published C(6)H(9) PES to include addition of vinyl to butadiene. The results were then used to calculate pressure-dependent rate constants for the multiple reaction pathways of these addition reactions. Inclusion of the unadjusted rate constants resulting from these analyses in the mechanism significantly improved the description of several of the species involved in molecular weight growth kinetics. We compare the predictions of this improved model to those obtained with a consensus model recently published as well as to ethane steam cracking data. We find that a particularly important reaction is that of vinyl addition to butadiene. Another important observation is that several radical addition reactions are partially equilibrated. Not only does this mean that reliable thermodynamic parameters are essential for an accurate model, but also that the reaction set describing molecular weight growth chemistry must include a final product that is sufficiently stable to shift the equilibrium toward this product despite the decrease in entropy that accompanies molecular weight growth. Another reaction, H addition to olefins, was found to inhibit molecular weight growth by leading to the production of a lower olefin plus methyl radicals.

Theoretical Studies of Elementary Hydrocarbon Species and Their Reactions

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

Allen, Wesley D.; Schaefer, III, Henry F.

2015-11-14

This is the final report of the theoretical studies of elementary hydrocarbon species and their reactions. Part A has a bibliography of publications supported by DOE from 2010 to 2016 and Part B goes into recent research highlights.

Current Status and Bioinspired Perspective of Electrochemical Conversion of CO2 to a Long-Chain Hydrocarbon.

PubMed

Yang, Ki Dong; Lee, Chan Woo; Jin, Kyoungsuk; Im, Sang Won; Nam, Ki Tae

2017-01-19

Electrocatalytic conversion of CO 2 into a long-chain hydrocarbon represents an important research direction in adding value to CO 2 -based chemicals and realizing its practical application. Long-chain hydrocarbons may change the current fossil fuel-based industry in that those chemicals have a similar energy density as gasoline, high compatibility with the current infrastructure, and low hydroscopicity for pipeline distribution. However, most of the electrocatalysts produce C 1 , C 2 , and C 3 chemicals, and methods for producing long-chain hydrocarbons are not available thus far. Interestingly, nature utilizes many enzymes to generate long-chain hydrocarbons using C 2 building blocks and suggests key mechanisms, inspiring new perspective in the design of electrocatalysts. In this Perspective, we present case studies to demonstrate how CO 2 and its reductive derivatives interact with the electrode surface during C-C bond formation and introduce how these issues are addressed in biological systems. We end this Perspective by outlining possible strategies to translate the natural mechanism into a heterogeneous electrode.

Catalyst for selective conversion of synthesis gas and method of making the catalyst

DOEpatents

Dyer, Paul N.; Pierantozzi, Ronald

1986-01-01

A Fischer-Tropsch (F-T) catalyst, a method of making the catalyst and an F-T process utilizing the catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas is selectively converted to higher hydrocarbons of relatively narrow carbon number range. In general, the selective and notably stable catalyst, consists of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of an F-T metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

Photochemical reactions of water and carbon monoxide in earth's primitive atmosphere

NASA Technical Reports Server (NTRS)

Bar-Nun, A.; Chang, S.

1983-01-01

The gas-phase photolysis of H2O at 1849 A in the presence of CO yields mainly CO2 and H2 and a variety of organic compounds, including C1-C3 hydrocarbons, alcohols, aldehydes, acetone, and acetic acid. The overall quantum yield for conversion of CO to organic compounds varies between 0.23 and 0.03 as a function of the CO abundance. These results indicate that even if primitive earth's atmosphere initially contained no molecular hydrogen and contained carbon only in the form of CO or a mixture of CO and CO2, the prebiotic environment would have become enriched with a variety of organic compounds produced by photochemical processes.

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

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

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

Comprehensive kinetic model for the low-temperature oxidation of hydrocarbons

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

Gaffuri, P.; Faravelli, T.; Ranzi, E.

1997-05-01

The oxidation chemistry in the low- and intermediate-temperature regimes (600--900 K) is important and plays a significant role in the overall combustion process. Autoignition in diesel engines as well as end-gas autoignition and knock phenomena in s.i. engines are initiated at these low temperatures. The low-temperature oxidation chemistry of linear and branched alkanes is discussed with the aim of unifying their complex behavior in various experimental systems using a single detailed kinetic model. New experimental data, obtained in a pressurized flow reactor, as well as in batch- and jet-stirred reactors, are useful for a better definition of the region ofmore » cool flames and negative temperature coefficient (NTC) for pure hydrocarbons from propane up to isooctane. Thermochemical oscillations and the NTC region of the reaction rate of the low-temperature oxidation of n-heptane and isooctane in a jet-stirred flow reactor are reproduced quite well by the model, not only in a qualitative way but in terms of the experimental frequencies and intensities of cool flames. Very good agreement is also observed for fuel conversion and intermediate-species formation. Irrespective of the experimental system, the same critical reaction steps always control these phenomena. The results contribute to the definition of a limited set of fundamental kinetic parameters that should be easily extended to model heavier alkanes.« less

Catalysis in high-temperature fuel cells.

PubMed

Föger, K; Ahmed, K

2005-02-17

Catalysis plays a critical role in solid oxide fuel cell systems. The electrochemical reactions within the cell--oxygen dissociation on the cathode and electrochemical fuel combustion on the anode--are catalytic reactions. The fuels used in high-temperature fuel cells, for example, natural gas, propane, or liquid hydrocarbons, need to be preprocessed to a form suitable for conversion on the anode-sulfur removal and pre-reforming. The unconverted fuel (economic fuel utilization around 85%) is commonly combusted using a catalytic burner. Ceramic Fuel Cells Ltd. has developed anodes that in addition to having electrochemical activity also are reactive for internal steam reforming of methane. This can simplify fuel preprocessing, but its main advantage is thermal management of the fuel cell stack by endothermic heat removal. Using this approach, the objective of fuel preprocessing is to produce a methane-rich fuel stream but with all higher hydrocarbons removed. Sulfur removal can be achieved by absorption or hydro-desulfurization (HDS). Depending on the system configuration, hydrogen is also required for start-up and shutdown. Reactor operating parameters are strongly tied to fuel cell operational regimes, thus often limiting optimization of the catalytic reactors. In this paper we discuss operation of an authothermal reforming reactor for hydrogen generation for HDS and start-up/shutdown, and development of a pre-reformer for converting propane to a methane-rich fuel stream.

Final technical report for the Center for Catalytic Hydrocarbon Functionalization (an EFRC)

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

Gunnoe, Thomas Brent

Greater than 95% of all materials produced by the chemical industry are derived from a small slate of simple hydrocarbons that are derived primarily from natural gas and petroleum, predominantly through oxygenation, C–C bond formation, halogenation or amination. Yet, current technologies for hydrocarbon conversion are typically high temperature, multi-step processes that are energy and capital intensive and result in excessive emissions (including carbon dioxide). The Center for Catalytic Hydrocarbon Functionalization (CCHF) brought together research teams with the broad coalition of skills and knowledge needed to make the fundamental advances in catalysis required for next-generation technologies to convert hydrocarbons (particularly lightmore » alkanes and methane) at high efficiency and low cost. Our new catalyst technologies offer many opportunities including enhanced utilization of natural gas in the transportation sector (via conversion to liquid fuels), more efficient generation of electricity from natural gas using direct methane fuel cells, reduced energy consumption and waste production for large petrochemical processes, and the preparation of high value molecules for use in biological/medical applications or the agricultural sector. The five year collaborative project accelerated fundamental understanding of catalyst design for the conversion of C–H bonds to functionalized products, essential to achieve the goals listed above, as evidenced by the publication of 134 manuscripts. Many of these fundamental advancements provide a foundation for potential commercialization, as evidenced by the submission of 11 patents from research support by the CCHF.« less

Molecular-beam, mass-spectrometric studies of wood vapor and model compounds over HZSM-5 catalyst

NASA Astrophysics Data System (ADS)

Evans, Robert J.; Milne, Thomas A.

1987-11-01

The use of molecular beam mass spectrometry (MBMS) for the real time screening of wood pyrolysis product conversion over Mobil's HZSM-5 catalyst allows the evaluation of the performance of different catalysts, reaction conditions and feedstocks. This information can help guide more extensive testing at the bench scale level and provide insight into the chemistry of conversion. The following conclusions can be drawn from the work to date: (1) there can be no breakthrough of primary wood vapor organics until the weight of wood/weight of the catalyst is 1; (2) there are few intermediates from wood on the way to alkenes, light aromatics, and naphthalenes; (3) the light aromatics/alkenes ration is 1 for the nonoptimized conditions studied to date; (4) much of the oxygen is favorably rejected as CO and CO sub 2; (5) the coke yield is about 10 percent in these experiments; and (6) methanol is a poor model for wood because the mechanism of hydrocarbon formation is apparently different.

Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbon Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy

PubMed Central

Nordvang, Emily C; Borodina, Elena; Ruiz-Martínez, Javier; Fehrmann, Rasmus; Weckhuysen, Bert M

2015-01-01

The catalytic activity of large zeolite H-ZSM-5 crystals in methanol (MTO) and ethanol-to-olefins (ETO) conversions was investigated and, using operando UV/Vis measurements, the catalytic activity and deactivation was correlated with the formation of coke. These findings were related to in situ single crystal UV/Vis and confocal fluorescence micro-spectroscopy, allowing the observation of the spatiotemporal formation of intermediates and coke species during the MTO and ETO conversions. It was observed that rapid deactivation at elevated temperatures was due to the fast formation of aromatics at the periphery of the H-ZSM-5 crystals, which are transformed into more poly-aromatic coke species at the external surface, preventing the diffusion of reactants and products into and out of the H-ZSM-5 crystal. Furthermore, we were able to correlate the operando UV/Vis spectroscopy results observed during catalytic testing with the single crystal in situ results. PMID:26463581

The diagenetic fate of taraxer-14-ene and oleanene isomers

NASA Astrophysics Data System (ADS)

ten Haven, H. L.; Rullkötter, J.

1988-10-01

The extractable organic matter in Holocene to early Miocene deep-sea sediments from Site 645 (ODP Leg 105) in Baffin Bay contains almost exclusively biological markers of terrigenous origin. Pentacyclic triterpenoids of the α-(ursene) and β-amyrin (oleanene) type often occur as the most abundant compounds in the aliphatic hydrocarbon, ketone and alcohol fractions of the sediment extract. A specific diagenetic reaction involves the conversion of taraxer-14-ene into olean-12-ene in the upper 700 metres of the sedimentary sequence. The taraxerene-to-oleanene conversion is complete before the onset of isomerisation of diasterenes at C-20. In the sediment as well as in laboratory simulation experiments, olean-12-ene further isomerises to olean-13(18)-ene and olean-18-ene, the latter of which may be the direct precursor of 18β(H)- and 18α(H)-oleanane found in sediments containing more mature organic matter and in crude oils. The subsurface interconversion of these triterpenoid skeletons indicate that oleanane does not necessarily start life as an oleanoid.

Organic chemistry. A rhodium catalyst for single-step styrene production from benzene and ethylene.

PubMed

Vaughan, Benjamin A; Webster-Gardiner, Michael S; Cundari, Thomas R; Gunnoe, T Brent

2015-04-24

Rising global demand for fossil resources has prompted a renewed interest in catalyst technologies that increase the efficiency of conversion of hydrocarbons from petroleum and natural gas to higher-value materials. Styrene is currently produced from benzene and ethylene through the intermediacy of ethylbenzene, which must be dehydrogenated in a separate step. The direct oxidative conversion of benzene and ethylene to styrene could provide a more efficient route, but achieving high selectivity and yield for this reaction has been challenging. Here, we report that the Rh catalyst ((Fl)DAB)Rh(TFA)(η(2)-C2H4) [(Fl)DAB is N,N'-bis(pentafluorophenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene; TFA is trifluoroacetate] converts benzene, ethylene, and Cu(II) acetate to styrene, Cu(I) acetate, and acetic acid with 100% selectivity and yields ≥95%. Turnover numbers >800 have been demonstrated, with catalyst stability up to 96 hours. Copyright © 2015, American Association for the Advancement of Science.

Recent developments and key barriers to advanced biofuels: A short review.

PubMed

Oh, You-Kwan; Hwang, Kyung-Ran; Kim, Changman; Kim, Jung Rae; Lee, Jin-Suk

2018-06-01

Biofuels are regarded as one of the most viable options for reduction of CO 2 emissions in the transport sector. However, conventional plant-based biofuels (e.g., biodiesel, bioethanol)'s share of total transportation-fuel consumption in 2016 was very low, about 4%, due to several major limitations including shortage of raw materials, low CO 2 mitigation effect, blending wall, and poor cost competitiveness. Advanced biofuels such as drop-in, microalgal, and electro biofuels, especially from inedible biomass, are considered to be a promising solution to the problem of how to cope with the growing biofuel demand. In this paper, recent developments in oxy-free hydrocarbon conversion via catalytic deoxygenation reactions, the selection of and lipid-content enhancement of oleaginous microalgae, electrochemical biofuel conversion, and the diversification of valuable products from biomass and intermediates are reviewed. The challenges and prospects for future development of eco-friendly and economically advanced biofuel production processes also are outlined herein. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

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

Wolf, E.E.

1996-09-30

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

Chemical kinetic models for combustion of hydrocarbons and formation of nitric oxide

NASA Technical Reports Server (NTRS)

Jachimowski, C. J.; Wilson, C. H.

1980-01-01

The formation of nitrogen oxides NOx during combustion of methane, propane, and a jet fuel, JP-4, was investigated in a jet stirred combustor. The results of the experiments were interpreted using reaction models in which the nitric oxide (NO) forming reactions were coupled to the appropriate hydrocarbon combustion reaction mechanisms. Comparison between the experimental data and the model predictions reveals that the CH + N2 reaction process has a significant effect on NO formation especially in stoichiometric and fuel rich mixtures. Reaction models were assembled that predicted nitric oxide levels that were in reasonable agreement with the jet stirred combustor data and with data obtained from a high pressure (5.9 atm (0.6 MPa)), prevaporized, premixed, flame tube type combustor. The results also suggested that the behavior of hydrocarbon mixtures, like JP-4, may not be significantly different from that of pure hydrocarbons. Application of the propane combustion and nitric oxide formation model to the analysis of NOx emission data reported for various aircraft gas turbines showed the contribution of the various nitric oxide forming processes to the total NOx formed.

Aromatic ring generation as a dust precursor in acetylene discharges

NASA Astrophysics Data System (ADS)

De Bleecker, Kathleen; Bogaerts, Annemie; Goedheer, Wim

2006-04-01

Production of aromatic hydrocarbon compounds as an intermediate step for particle formation in low-pressure acetylene discharges is investigated via a kinetic approach. The detailed chemical reaction mechanism contains 140 reactions among 55 species. The cyclic hydrocarbon chemistry is mainly based on studies of polycyclic aromatic hydrocarbon formation in cosmic environments. The model explicitly includes organic chain, cyclic molecules, radicals, and ions up to a size of 12 carbon atoms. The calculated density profiles show that the aromatic formation yields are quite significant, suggesting that aromatic compounds play a role in the underlying mechanisms of particle formation in hydrocarbon plasmas.

Using supercritical fluids to refine hydrocarbons

DOEpatents

Yarbro, Stephen Lee

2015-06-09

A system and method for reactively refining hydrocarbons, such as heavy oils with API gravities of less than 20 degrees and bitumen-like hydrocarbons with viscosities greater than 1000 cp at standard temperature and pressure, using a selected fluid at supercritical conditions. A reaction portion of the system and method delivers lightweight, volatile hydrocarbons to an associated contacting unit which operates in mixed subcritical/supercritical or supercritical modes. Using thermal diffusion, multiphase contact, or a momentum generating pressure gradient, the contacting unit separates the reaction products into portions that are viable for use or sale without further conventional refining and hydro-processing techniques.

Laser cutting with chemical reaction assist

DOEpatents

Gettemy, Donald J.

1992-01-01

A method for cutting with a laser beam where an oxygen-hydrocarbon reaction is used to provide auxiliary energy to a metal workpiece to supplement the energy supplied by the laser. Oxygen is supplied to the laser focus point on the workpiece by a nozzle through which the laser beam also passes. A liquid hydrocarbon is supplied by coating the workpiece along the cutting path with the hydrocarbon prior to laser irradiation or by spraying a stream of hydrocarbon through a nozzle aimed at a point on the cutting path which is just ahead of the focus point during irradiation.

Laser cutting with chemical reaction assist

DOEpatents

Gettemy, D.J.

1992-11-17

A method is described for cutting with a laser beam where an oxygen-hydrocarbon reaction is used to provide auxiliary energy to a metal workpiece to supplement the energy supplied by the laser. Oxygen is supplied to the laser focus point on the workpiece by a nozzle through which the laser beam also passes. A liquid hydrocarbon is supplied by coating the workpiece along the cutting path with the hydrocarbon prior to laser irradiation or by spraying a stream of hydrocarbon through a nozzle aimed at a point on the cutting path which is just ahead of the focus point during irradiation. 1 figure.

Composition and Chemical Stability of Motor Fuels,

DTIC Science & Technology

Fuels, *Hydrocarbons, Cycloalkanes, Chemical analysis, Gasoline, Diesel fuels, Fuel additives, Chemical reactions, Stability, Jet engine fuels...Aviation gasoline, Aviation fuels, Chemical composition, Aromatic hydrocarbons, Unsaturated hydrocarbons, Storage, USSR, Translations, Fuel systems, Alkanes

Chemical Compositional Analysis of Catalytic Hydroconversion Products of Heishan Coal Liquefaction Residue

PubMed Central

Wu, Yajun; Zhang, Shuangquan; Yang, Xiaoqin; Wei, Xianyong

2017-01-01

Liquefaction residue of Heishan bituminous coal (HLR) was subject to two hydroconversion reactions under 5 MPa initial pressure of hydrogen at 300°C for 3 h, without catalyst and with acid supported catalyst (ASC), respectively. The reaction products were analyzed with gas chromatography/mass spectrometer (GC/MS). The results show that 222 organic compounds were detected totally in the products and they can be divided into alkanes, aromatic hydrocarbons (AHCs), phenols, ketones, ethers, and other species (OSs). The yield of hydroconversion over the ASC is much higher than that without catalyst. The most abundant products are aromatic hydrocarbons in the reaction products from both catalytic and noncatalytic reactions of HLR. The yield of aromatic hydrocarbons in the reaction product from hydroconversion with the ACS is considerably higher than that from hydroconversion without a catalyst. PMID:28250770

Microwave pyrolysis of distillers dried grain with solubles (DDGS) for biofuel production.

PubMed

Lei, Hanwu; Ren, Shoujie; Wang, Lu; Bu, Quan; Julson, James; Holladay, John; Ruan, Roger

2011-05-01

Microwave pyrolysis of distillers dried grain with solubles (DDGS) was investigated to determine the effects of pyrolytic conditions on the yields of bio-oil, syngas, and biochar. Pyrolysis process variables included reaction temperature, time, and power input. Microwave pyrolysis of DDGS was analyzed using response surface methodology to find out the effect of process variables on the biofuel (bio-oil and syngas) conversion yield and establish prediction models. Bio-oil recovery was in the range of 26.5-50.3 wt.% of the biomass. Biochar yields were 23.5-62.2% depending on the pyrolysis conditions. The energy content of DDGS bio-oils was 28 MJ/kg obtained at the 650°C and 8 min, which was about 66.7% of the heating value of gasoline. GC/MS analysis indicated that the biooil contained a series of important and useful chemical compounds: aliphatic and aromatic hydrocarbons. At least 13% of DDGS bio-oil was the same hydrocarbon compounds found in regular unleaded gasoline. Copyright © 2011 Elsevier Ltd. All rights reserved.

Microwave pyrolysis of distillers dried grain with solubles (DDGS) for biofuel production

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

Lei, Hanwu; Ren, Shoujie; Wang, Lu

2011-05-01

Microwave pyrolysis of distillers dried grain with solubles (DDGS) was investigated to determine the effects of pyrolytic conditions on the yields of bio-oil, syngas, and biochar. Pyrolysis process variables included reaction temperature, time, and power input. Microwave pyrolysis of DDGS was analyzed using response surface methodology to find out the effect of process variables on the biofuel (bio-oil and syn- gas) conversion yield and establish prediction models. Bio-oil recovery was in the range of 26.5–50.3 wt.% of the biomass. Biochar yields were 23.5–62.2% depending on the pyrolysis conditions. The energy con- tent of DDGS bio-oils was 28 MJ/kg obtained atmore » the 650 oC and 8 min, which was about 66.7% of the heat- ing value of gasoline. GC/MS analysis indicated that the biooil contained a series of important and useful chemical compounds: aliphatic and aromatic hydrocarbons. At least 13% of DDGS bio-oil was the same hydrocarbon compounds found in regular unleaded gasoline.« less

Investigation of the combustion kinetics and polycyclic aromatic hydrocarbon emissions from polycaprolactone combustion.

PubMed

Chien, Y C; Yang, S H

2013-01-01

Polycaprolactone (PCL) is one of the most attractive biodegradable plastics that has been widely used in medicine and agriculture fields. Because of the large increase in biodegradable plastics usage, the production of waste biodegradable plastics will be increasing dramatically, producing a growing environmental problem. Generally, waste PCL is collected along with municipal solid wastes and then incinerated. This study investigates the combustion kinetics and emission factors of 16 US Environmental Protection Agency (EPA) priority polycyclic aromatic hydrocarbons (PAHs) in the PCL combustion. Experimentally, two reactions are involved in the PCL combustion process, possibly resulting in the emission of carbon dioxide, propanal, protonated caprolactone and very small amounts of PAH produced by incomplete combustion. The intermediate products may continuously be oxidized to form CO2. The emission factors for 16 US EPA priority PAHs are n.d. -2.95 microg/g, which are much lower than those of poly lactic acid and other plastics combustion. The conversion of PCL is 100%. Results from this work suggest that combustion is a good choice for the waste PCL disposal.

Biodegradation of polycyclic aromatic hydrocarbons (PAHs) by laccase from Trametes versicolor covalently immobilized on amino-functionalized SBA-15.

PubMed

Bautista, Luis Fernando; Morales, Gabriel; Sanz, Raquel

2015-10-01

A covalent immobilization method based on glutaraldehyde and amino-functionalized SBA-15 supports has been successfully applied to covalently and stably immobilize laccase from Trametes versicolor. The resultant biocatalysts displayed high incorporation yields of enzyme and led to excellent biodegradation rates of selected HPAs models, i.e. naphthalene, phenanthrene and anthracene, in water. The nature of the hydrocarbon chain accompanying the amino group has been shown as determinant for the immobilization as well as for the activity and reusability of the materials. Thus, alkyl moieties displayed higher enzyme loadings than phenyl moieties, being more adequate the larger n-butyl tethering residue likely due to its higher mobility. Using the aminobutyl-based laccase-SBA-15, 82%, 73%, and 55% conversion of naphthalene, phenanthrene and anthracene, respectively, were achieved after 48 h, very close to the values obtained with free laccase under the same reaction conditions. On the other hand, aminopropyl-based laccase-SBA-15 biocatalysts displayed the best reusability properties, retaining higher activity after four repeated uses than the corresponding aminobutyl-based materials. Copyright © 2015 Elsevier Ltd. All rights reserved.

Photosynthesis of organic compounds in the atmosphere of Jupiter

NASA Technical Reports Server (NTRS)

Ferris, J. P.; Chen, C. T.

1975-01-01

An efficient conversion of CH4 to hydrocarbons and HCN takes place when NH3 is photolysed in the presence of CH4, H2, and He using a 184.9 nm light source. The extent of NH3 decomposition after a 1 hr exposure was determined spectrophotometrically; CH4, N2, and C2 and C3 hydrocarbons were detected and analyzed by mass spectrometry. Photolysis of one molar equivalent of NH3 results in the loss of 0.84 molar equivalent of CH4, which apparently reacts with hot hydrogen atoms produced by photolysis. The 8% of the NH3 which is not converted to N2 probably is converted to organic amines and nitrile derivatives. The results indicate that NH3 photolysis is a highly probable mechanism for the conversion of methane to more complex hydrocarbons in the upper atmosphere of Jupiter, and predict the occurrence of HCN, NH2NH2, and higher hydrocarbons in the Jovian atmosphere above the NH3 clouds.

Optrode for sensing hydrocarbons

DOEpatents

Miller, Holly; Milanovich, Fred P.; Hirschfeld, Tomas B.; Miller, Fred S.

1987-01-01

A two-phase system employing the Fujiwara reaction is provided for the fluorometric detection of halogenated hydrocarbons. A fiber optic is utilized to illuminate a column of pyridine trapped in a capillary tube coaxially attached at one end to the illuminating end of the fiber optic. A strongly alkaline condition necessary for the reaction is maintained by providing a reservoir of alkali in contact with the column of pyridine, the surface of contact being adjacent to the illuminating end of the fiber optic. A semipermeable membrane caps the other end of the capillary tube, the membrane being preferentially permeable to the halogenated hydrocarbon and but preferentially impermeable to water and pyridine. As the halogenated hydrocarbon diffuses through the membrane and into the column of pyridine, fluorescent reaction products are formed. Light propagated by the fiber optic from a light source, excites the fluorescent products. Light from the fluorescence emission is also collected by the same fiber optic and transmitted to a detector. The intensity of the fluorescence gives a measure of the concentration of the halogenated hydrocarbons.

Optrode for sensing hydrocarbons

DOEpatents

Miller, H.; Milanovich, F.P.; Hirschfeld, T.B.; Miller, F.S.

1987-05-19

A two-phase system employing the Fujiwara reaction is provided for the fluorometric detection of halogenated hydrocarbons. A fiber optic is utilized to illuminate a column of pyridine trapped in a capillary tube coaxially attached at one end to the illuminating end of the fiber optic. A strongly alkaline condition necessary for the reaction is maintained by providing a reservoir of alkali in contact with the column of pyridine, the surface of contact being adjacent to the illuminating end of the fiber optic. A semipermeable membrane caps the other end of the capillary tube, the membrane being preferentially permeable to the halogenated hydrocarbon but preferentially impermeable to water and pyridine. As the halogenated hydrocarbon diffuses through the membrane and into the column of pyridine, fluorescent reaction products are formed. Light propagated by the fiber optic from a light source, excites the fluorescent products. Light from the fluorescence emission is also collected by the same fiber optic and transmitted to a detector. The intensity of the fluorescence gives a measure of the concentration of the halogenated hydrocarbons. 6 figs.

Optrode for sensing hydrocarbons

DOEpatents

Miller, H.; Milanovich, F.P.; Hirschfeld, T.B.; Miller, F.S.

1988-09-13

A two-phase system employing the Fujiwara reaction is provided for the fluorometric detection of halogenated hydrocarbons. A fiber optic is utilized to illuminate a column of pyridine trapped in a capillary tube coaxially attached at one end to the illuminating end of the fiber optic. A strongly alkaline condition necessary for the reaction is maintained by providing a reservoir of alkali in contact with the column of pyridine, the surface of contact being adjacent to the illuminating end of the fiber optic. A semipermeable membrane caps the other end of the capillary tube, the membrane being preferentially permeable to the halogenated hydrocarbon and but preferentially impermeable to water and pyridine. As the halogenated hydrocarbon diffuses through the membrane and into the column of pyridine, fluorescent reaction products are formed. Light propagated by the fiber optic from a light source, excites the fluorescent products. Light from the fluorescence emission is also collected by the same fiber optic and transmitted to a detector. The intensity of the fluorescence gives a measure of the concentration of the halogenated hydrocarbons. 5 figs.

Optrode for sensing hydrocarbons

DOEpatents

Miller, Holly; Milanovich, Fred P.; Hirschfeld, Tomas B.; Miller, Fred S.

1988-01-01

A two-phase system employing the Fujiwara reaction is provided for the fluorometric detection of halogenated hydrocarbons. A fiber optic is utilized to illuminate a column of pyridine trapped in a capillary tube coaxially attached at one end to the illuminating end of the fiber optic. A strongly alkaline condition necessary for the reaction is maintained by providing a reservoir of alkali in contact with the column of pyridine, the surface of contact being adjacent to the illuminating end of the fiber optic. A semipermeable membrane caps the other end of the capillary tube, the membrane being preferentially permeable to the halogenated hydrocarbon and but preferentially impermeable to water and pyridine. As the halogenated hydrocarbon diffuses through the membrane and into the column of pyridine, fluorescent reaction products are formed. Light propagated by the fiber optic from a light source, excites the fluorescent products. Light from the fluorescence emission is also collected by the same fiber optic and transmitted to a detector. The intensity of the fluorescence gives a measure of the concentration of the halogenated hydrocarbons.

One-step production of long-chain hydrocarbons from waste-biomass-derived chemicals using bi-functional heterogeneous catalysts.

PubMed

Wen, Cun; Barrow, Elizabeth; Hattrick-Simpers, Jason; Lauterbach, Jochen

2014-02-21

In this study, we demonstrate the production of long-chain hydrocarbons (C8+) from 2-methylfuran (2MF) and butanal in a single step reactive process by utilizing a bi-functional catalyst with both acid and metallic sites. Our approach utilizes a solid acid for the hydroalkylation function and as a support as well as a transition metal as hydrodeoxygenation catalyst. A series of solid acids was screened, among which MCM-41 demonstrated the best combination of activity and stability. Platinum nanoparticles were then incorporated into the MCM-41. The Pt/MCM-41 catalyst showed 96% yield for C8+ hydrocarbons and the catalytic performance was stable over four reaction cycles of 20 hour each. The reaction pathways for the production of long-chain hydrocarbons is probed with a combination of infrared spectroscopy and steady-state reaction experiments. It is proposed that 2MF and butanal go through hydroalkylation first on the acid site followed by hydrodeoxygenation to produce the hydrocarbon fuels.

Zeolitic catalytic conversion of alochols to hydrocarbons

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2017-01-03

A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.

Zeolitic catalytic conversion of alcohols to hydrocarbons

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2018-04-10

A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.

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

Duration of the hydrocarbon fluid formation under thermobaric conditions of the Earth's upper mantle

NASA Astrophysics Data System (ADS)

Mukhina, Elena; Kolesnikov, Anton; Kutcherov, Vladimir

2016-04-01

Deep abiogenic formation of hydrocarbons is an inherent part of the Earth's global carbon cycle. It was experimentally confirmed that natural gas could be formed from inorganic carbon and hydrogen containing minerals at pressure and temperature corresponding to the Earth's upper mantle conditions. Reaction between calcite, wustite and water in the large volume device was studied in several works. It was previously proposed that reaction is possible only after 40 minutes of exposure at high pressure and temperature. In this work similar experiment at P = 60 kbar and T = 1200 K were carried out in "Toroid" type chamber with the 5 seconds duration of thermobaric exposure. Gas chromatographic analysis of the reaction products has shown the presence of hydrocarbon mixture comparable to 5 minutes and 6 hours exposure experiments. Based on this fact it is possible to conclude that the reaction of natural gas formation is instant at least at given thermobaric conditions. This experiment will help to better understand the process of deep hydrocarbon generation, particularly its kinetics.

Performance characterization of CNTs and γ-Al{sub 2}O{sub 3} supported cobalt catalysts in Fischer-Tropsch reaction

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

Ali, Sardar, E-mail: alikhan-635@yahoo.com; Zabidi, Noor Asmawati Mohd, E-mail: noorasmawati-mzabidi@petronas.com.my; Subbarao, Duvvuri, E-mail: duvvuri-subbarao@petronas.com.my

2014-10-24

Catalysts were prepared via a wet impregnation method. Different physicochemical properties of the samples were revealed by transmission electron microscope (TEM), temperature programmed reduction (H{sub 2}-TPR) and carbon dioxide desorption (CO{sub 2}-desorption). Fischer-Tropsch reaction (FTS) was carried out in a fixed-bed microreactor at 220°C and 1 atm, with H{sub 2}/CO = 2v/v and space velocity, SV of 12L/g.h for 5 h. Various characterization techniques revealed that there was a stronger interaction between Co and Al{sub 2}O{sub 3} support compared to that of CNTs support. CNTs support increased the reducibility and decreased Co particle size. A significant increase in % CO conversion andmore » FTS reaction rate was observed over CNTs support compared to that of Co/Al{sub 2}O{sub 3}. Co/CNTs resulted in higher C{sub 5+} hydrocarbons selectivity compared to that of Co/Al{sub 2}O{sub 3} catalyst. CNTs are a better support for Co compared to Al{sub 2}O{sub 3}.« less

Multi-element isotope fractionation concepts to characterize the biodegradation of hydrocarbons - from enzymes to the environment.

PubMed

Vogt, Carsten; Dorer, Conrad; Musat, Florin; Richnow, Hans-Hermann

2016-10-01

Multi-element compound-specific isotope fractionation (ME-CSIA) has become a state-of-the-art approach for identifying biotransformation reactions. In the last decade, several studies focused on the combined analysis of carbon and hydrogen stable isotopes upon biodegradation of hydrocarbons due to its widespread environmental occurrence as contaminants, often in high concentrations. Most known initial transformation reactions of hydrocarbons have been isotopically characterized in laboratory experiments using model cultures. The data suggest that several of these reactions - especially those occurring under anoxic conditions - can be identified by ME-CSIA, although a number of constraints have been realized which may lead to wrong ME-CSIA data interpretations in field studies. Generally, the applicability of ME-CSIA regarding hydrocarbon biodegradation needs to be corroborated in future field studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Insights into the Activity and Deactivation of the Methanol-to-Olefins Process over Different Small-Pore Zeolites As Studied with Operando UV-vis Spectroscopy.

PubMed

Goetze, Joris; Meirer, Florian; Yarulina, Irina; Gascon, Jorge; Kapteijn, Freek; Ruiz-Martínez, Javier; Weckhuysen, Bert M

2017-06-02

The nature and evolution of the hydrocarbon pool (HP) species during the Methanol-to-Olefins (MTO) process for three small-pore zeolite catalysts, with a different framework consisting of large cages interconnected by small eight-ring windows (CHA, DDR, and LEV) was studied at reaction temperatures between 350 and 450 °C using a combination of operando UV-vis spectroscopy and online gas chromatography. It was found that small differences in cage size, shape, and pore structure of the zeolite frameworks result in the generation of different hydrocarbon pool species. More specifically, it was found that the large cage of CHA results in the formation of a wide variety of hydrocarbon pool species, mostly alkylated benzenes and naphthalenes. In the DDR cage, 1-methylnaphthalene is preferentially formed, while the small LEV cage generally contains fewer hydrocarbon pool species. The nature and evolution of these hydrocarbon pool species was linked with the stage of the reaction using a multivariate analysis of the operando UV-vis spectra. In the 3-D pore network of CHA, the reaction temperature has only a minor effect on the performance of the MTO catalyst. However, for the 2-D pore networks of DDR and LEV, an increase in the applied reaction temperature resulted in a dramatic increase in catalytic activity. For all zeolites in this study, the role of the hydrocarbon species changes with reaction temperature. This effect is most clear in DDR, in which diamantane and 1-methylnaphthalene are deactivating species at a reaction temperature of 350 °C, whereas at higher temperatures diamantane formation is not observed and 1-methylnaphthalene is an active species. This results in a different amount and nature of coke species in the deactivated catalyst, depending on zeolite framework and reaction temperature.

Insights into the Activity and Deactivation of the Methanol-to-Olefins Process over Different Small-Pore Zeolites As Studied with Operando UV–vis Spectroscopy

PubMed Central

2017-01-01

The nature and evolution of the hydrocarbon pool (HP) species during the Methanol-to-Olefins (MTO) process for three small-pore zeolite catalysts, with a different framework consisting of large cages interconnected by small eight-ring windows (CHA, DDR, and LEV) was studied at reaction temperatures between 350 and 450 °C using a combination of operando UV–vis spectroscopy and online gas chromatography. It was found that small differences in cage size, shape, and pore structure of the zeolite frameworks result in the generation of different hydrocarbon pool species. More specifically, it was found that the large cage of CHA results in the formation of a wide variety of hydrocarbon pool species, mostly alkylated benzenes and naphthalenes. In the DDR cage, 1-methylnaphthalene is preferentially formed, while the small LEV cage generally contains fewer hydrocarbon pool species. The nature and evolution of these hydrocarbon pool species was linked with the stage of the reaction using a multivariate analysis of the operando UV–vis spectra. In the 3-D pore network of CHA, the reaction temperature has only a minor effect on the performance of the MTO catalyst. However, for the 2-D pore networks of DDR and LEV, an increase in the applied reaction temperature resulted in a dramatic increase in catalytic activity. For all zeolites in this study, the role of the hydrocarbon species changes with reaction temperature. This effect is most clear in DDR, in which diamantane and 1-methylnaphthalene are deactivating species at a reaction temperature of 350 °C, whereas at higher temperatures diamantane formation is not observed and 1-methylnaphthalene is an active species. This results in a different amount and nature of coke species in the deactivated catalyst, depending on zeolite framework and reaction temperature. PMID:28603658

Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.

2018-04-17

A method for producing a hydrocarbon blendstock, the method comprising contacting at least one saturated acyclic alcohol having at least three and up to ten carbon atoms with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein the metal is a positively-charged metal ion, and the metal-loaded zeolite catalyst is catalytically active for converting the alcohol to the hydrocarbon blendstock, wherein the method directly produces a hydrocarbon blendstock having less than 1 vol % ethylene and at least 35 vol % of hydrocarbon compounds containing at least eight carbon atoms.

Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.

2015-11-13

A method for producing a hydrocarbon blendstock, the method comprising contacting at least one saturated acyclic alcohol having at least three and up to ten carbon atoms with a metal-loaded zeolite catalyst at a temperature of at least 100°C and up to 550°C, wherein the metal is a positively-charged metal ion, and the metal-loaded zeolite catalyst is catalytically active for converting the alcohol to the hydrocarbon blendstock, wherein the method directly produces a hydrocarbon blendstock having less than 1 vol % ethylene and at least 35 vol % of hydrocarbon compounds containing at least eight carbon atoms.

Kerosene combustion at pressures up to 40 atm: Experimental study and detailed chemical kinetic modeling

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

Dagaut, P.; Reuillon, M.; Boettner, J.C.

1994-12-31

The oxidation of TR0 kerosene (jet A1 aviation fuel) was studied in a jet-stirred reactor (JSR) at pressures extending from 10 to 40 atm, in the temperature range 750--1,150 K. A large number of reaction intermediates were identified, and their concentrations were followed for reaction yields ranging from low conversion to the formation of the final products. A reference hydrocarbon, n-decane, studied under the same experimental conditions gave very similar experimental concentration profiles for the main oxidation products. Because of the strong analogy between n-decane and kerosene oxidation kinetics, a detailed chemical kinetic reaction mechanisms describing the oxidation of n-decanemore » was built to reproduce the present experimental results. This mechanisms includes 573 elementary reactions, most of them being reversible, among 90 chemical species. A reasonably good prediction of the concentrations of major species was obtained by computation, covering the whole range of temperature, pressures, and equivalence ratios of the experiments. A kinetic analysis performed to identify the dominant reaction steps of the mechanism shows that, under the conditions of the present study (intermediate temperature and high pressure), HO{sub 2} radicals are important chain carriers leading to the formation of the branching agent H{sub 2}O{sub 2}.« less

Aqueous geochemistry of low molecular weight hydrocarbons at elevated temperatures and pressures: constraints from mineral buffered laboratory experiments

NASA Astrophysics Data System (ADS)

Seewald, Jeffrey S.

2001-05-01

Organic matter, water, and minerals coexist at elevated temperatures and pressures in sedimentary basins and participate in a wide range of geochemical processes that includes the generation of oil and natural gas. A series of laboratory experiments were conducted at 300 to 350°C and 350 bars to examine chemical interactions involving low molecular weight aqueous hydrocarbons with water and Fe-bearing minerals under hydrothermal conditions. Mineral buffers composed of hematite-magnetite-pyrite, hematite-magnetite, and pyrite-pyrrhotite-magnetite were added to each experiment to fix the redox state of the fluid and the activity of reduced sulfur species. During each experiment the chemical system was externally modified by addition of ethene, ethane, propene, 1-butene, or n-heptane, and variations in the abundance of aqueous organic species were monitored as a function of time and temperature. Results of the experiments indicate that decomposition of aqueous n-alkanes proceeds through a series of oxidation and hydration reactions that sequentially produce alkenes, alcohols, ketones, and organic acids as reaction intermediaries. Organic acids subsequently undergo decarboxylation and/or oxidation reactions to form carbon dioxide and shorter chain saturated hydrocarbons. This alteration assemblage is compositionally distinct from that produced by thermal cracking under anhydrous conditions, indicating that the presence of water and minerals provide alternative reaction pathways for the decomposition of hydrocarbons. The rate of hydrocarbon oxidation decreases substantially under reducing conditions and in the absence of catalytically active aqueous sulfur species. These results represent compelling evidence that the stability of aqueous hydrocarbons at elevated temperatures in natural environments is not a simple function of time and temperature alone. Under the appropriate geochemical conditions, stepwise oxidation represents a mechanism for the decomposition of low molecular weight hydrocarbons and the production of methane-rich ("dry") natural gas. Evaluation of aqueous reaction products generated during the experiments within a thermodynamic framework indicates that alkane-alkene, alkene-ketone, and alkene-alcohol reactions attained metastable thermodynamic equilibrium states. This equilibrium included water and iron-bearing minerals, demonstrating the direct involvement of inorganic species as reactants during organic transformations. The high reactivity of water and iron-bearing minerals suggests that they represent abundant sources of hydrogen and oxygen available for the formation of hydrocarbons and oxygenated alteration products. Thus, variations in elemental kerogen composition may not accurately reflect the timing and extent of hydrocarbon, carbon dioxide, and organic acid generation in sedimentary basins. This study demonstrates that the stabilities of aqueous hydrocarbons are strongly influenced by inorganic sediment composition at elevated temperatures. Incorporation of such interactions into geochemical models will greatly improve prediction of the occurrence of hydrocarbons in natural environments over geologic time.

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.

FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND THEIR GROWTH TO SOOT -A REVIEW OF CHEMICAL REACTION PATHWAYS. (R824970)

EPA Science Inventory

The generation by combustion processes of airborne species of current health concern such as polycyclic aromatic hydrocarbons (PAH) and soot particles necessitates a detailed understanding of chemical reaction pathways responsible for their formation. The present review discus...

Varying potential silicon carbide gas sensor

NASA Technical Reports Server (NTRS)

Shields, Virgil B. (Inventor); Ryan, Margaret A. (Inventor); Williams, Roger M. (Inventor)

1997-01-01

A hydrocarbon gas detection device operates by dissociating or electro-chemically oxidizing hydrocarbons adsorbed to a silicon carbide detection layer. Dissociation or oxidation are driven by a varying potential applied to the detection layer. Different hydrocarbon species undergo reaction at different applied potentials so that the device is able to discriminate among various hydrocarbon species. The device can operate at temperatures between 100.degree. C. and at least 650.degree. C., allowing hydrocarbon detection in hot exhaust gases. The dissociation reaction is detected either as a change in a capacitor or, preferably, as a change of current flow through an FET which incorporates the silicon carbide detection layers. The silicon carbide detection layer can be augmented with a pad of catalytic material which provides a signal without an applied potential. Comparisons between the catalytically produced signal and the varying potential produced signal may further help identify the hydrocarbon present.

Role of Pt during hydrodeoxygenation of biomass pyrolysis vapors over Pt/HBEA

DOE PAGES

Yung, Matthew M.; Foo, Guo Shiou; Sievers, Carsten

2017-03-27

1.3 wt% Pt/HBEA and HBEA were studied as catalysts for the hydrodeoxygenation of pine pyrolysis vapors at 500 °C. Both catalysts showed high initial conversion of oxygenated pyrolysis products into aromatic hydrocarbons, while Pt/HBEA showed higher stability in terms of hydrocarbon productivity and deferred breakthrough of oxygenated compounds. Among 1-, 2- and 3-ring aromatic hydrocarbons, Pt/HBEA had a significantly higher selectivity than HBEA towards unalkylated aromatics (e.g., benzene) as compared to the corresponding alkylated aromatics (e.g., toluene and xylene). Additionally, Pt addition to HBEA decreased coke deposition and improved resistance to pore and acid site blockage as determined by TPO,more » N 2 physisorption, and NH 3 TPD. The ability of Pt to promote cleavage and hydrogenation of methoxy and methyl groups was observed by increased methane production over Pt/HBEA relative to HBEA. A progressive decrease in the methane production over Pt/HBEA correlated with deactivation in terms of reduced benzene formation, breakthrough of oxygenated products, and increased formation of polynuclear aromatics and their degree of substitution, which indicate coke formation. In conclusion, the increased methane yield and suppressed coke formation with the addition of Pt is attributed to hydrogen spillover, through which hydrogen activated on Pt can subsequently migrate to the HBEA support to reverse the coke-forming hydrogen abstraction reaction.« less

Role of Pt during hydrodeoxygenation of biomass pyrolysis vapors over Pt/HBEA

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

Yung, Matthew M.; Foo, Guo Shiou; Sievers, Carsten

1.3 wt% Pt/HBEA and HBEA were studied as catalysts for the hydrodeoxygenation of pine pyrolysis vapors at 500 °C. Both catalysts showed high initial conversion of oxygenated pyrolysis products into aromatic hydrocarbons, while Pt/HBEA showed higher stability in terms of hydrocarbon productivity and deferred breakthrough of oxygenated compounds. Among 1-, 2- and 3-ring aromatic hydrocarbons, Pt/HBEA had a significantly higher selectivity than HBEA towards unalkylated aromatics (e.g., benzene) as compared to the corresponding alkylated aromatics (e.g., toluene and xylene). Additionally, Pt addition to HBEA decreased coke deposition and improved resistance to pore and acid site blockage as determined by TPO,more » N 2 physisorption, and NH 3 TPD. The ability of Pt to promote cleavage and hydrogenation of methoxy and methyl groups was observed by increased methane production over Pt/HBEA relative to HBEA. A progressive decrease in the methane production over Pt/HBEA correlated with deactivation in terms of reduced benzene formation, breakthrough of oxygenated products, and increased formation of polynuclear aromatics and their degree of substitution, which indicate coke formation. In conclusion, the increased methane yield and suppressed coke formation with the addition of Pt is attributed to hydrogen spillover, through which hydrogen activated on Pt can subsequently migrate to the HBEA support to reverse the coke-forming hydrogen abstraction reaction.« less

Direct catalytic conversion of methane and light hydrocarbon gases. Quarterly report No. 9, October 1--December 31, 1988

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

Wilson, R.B. Jr.; Posin, B.M.; Chan, Yee Wai

The goal of this research is to develop catalysts that directly convert methane and light hydrocarbons to intermediates that later can be converted to either liquid fuels or value-added chemicals, as economics dictate. During this reporting period, we completed our IR spectroscopic examination of the Ru{sub 4}/MgO and FeRu{sub 3}/MgO systems under nitrogen and methane by examining FeRu{sub 3}/MgO under methane. This system behaved quite differently than the same system under nitrogen. Under methane, only one very broad peak is observed at room temperature. Upon heating, the catalyst transformed so that by 300{degrees}C, the spectrum of FeRu{sub 3}/MgO under methanemore » was the same as that of Ru{sub 4}/MgO. This suggests that methane promotes the segregation of the metals in the mixed metal system. The differences in catalytic activity between the FeRu{sub 3}/MgO and Ru{sub 4}/MgO systems may then be due to the presence of IR transparent species such as iron ions which cause different nucleation in the ruthenium clusters. We examined several systems for activity in the methane dehydrogenation reaction. Focusing on systems which produce C{sub 6} hydrocarbons since this is the most useful product. These systems all displayed low activity so that the amount of hydrocarbon product is very low. Some C{sub 6} hydrocarbon is observed over zeolite supports, but its production ceases after the first few hours of reaction. We prepared a new system, Ru{sub 4} supported on carbon, and examined its reactivity. Its activity was very low and in fact the carbon support had the same level of activity. We synthesized four new systems for examination as catalysts in the partial oxidation of methane. Three of these (PtTSPC/MgO, PtTSPC and PdTSPC on carbon) are analogs of PdTSPC/MgO. This system is of interest because we have observed the production of ethane from methane oxidation over PdTSPC/MgO at relatively low temperatures and we wished to explore its generality among close analogs.« less

Improving the hydrocarbon production via co-pyrolysis of bagasse with bio-plastic and dual-catalysts layout.

PubMed

Zhang, Huiyan; Likun, Peter Keliona Wani; Xiao, Rui

2018-03-15

Catalytic fast pyrolysis (CFP) of bagasse and bio-plastic (chicken feather keratin) and their mixtures were conducted to produce aromatic hydrocarbons over a HZSM-5, USY, and dual-catalysts layout. The effects of temperature, co-feeding ratios, feed-to-catalyst ratios and dual catalysts on hydrocarbon yields and selectivities were investigated. The results show a general improvement in the aromatic hydrocarbons yields in all cases compared to non-catalytic and pure biomass pyrolysis. The aromatic hydrocarbons increased by 10 fold with the increase of temperature from 400°C to 700°C. The aromatic yields increased 1.5 times at co-feeding, 2.0 greater at feed/HZSM-5 ratio of 1:6, 1.2 times at feed/USY ratio of 1:16, and 2.66 times at USY/HZSM-5 scenario. The selectivities towards benzene increased, at higher co-feeding ratios, while that of toluene shows an opposite trend. Xylenes selectivities were less sensitive to the changes of co-feeding ratios. In contrast, the USY catalyst only produced little amount of toluene and xylenes. The dual catalyst design (USY/HZSM-5) resulted in the highest aromatic yields, than other catalyst design scenarios. The pyrolysis temperature is a significant parameter for hydrocarbon production. Co-feeding bagasse and bio-plastic enhanced biomass conversion to aromatic compounds. For any type of zeolite catalyst, there was an optimum feed-to-catalyst ratio that generated maximum hydrocarbons. Dual catalyst layout shows a new opportunity for efficient conversion of biomass materials into hydrocarbons. Copyright © 2017 Elsevier B.V. All rights reserved.

Reaction pathway in vapour phase hydrogenation of maleic anhydride and its esters to {gamma}-butyrolactone

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

Messori, M.; Vaccari, A.

1994-11-01

The catalytic reactivity of maleic anhydride (MA), succinic anhydride (SA) and their dimethyl esters (dimethyl maleate and dimethyl succinate) in the vapour phase hydrogenation to {gamma}-butyrolacetone (GBL) was investigated. In order to obtain general data, both a multicomponent catalyst (CAT 1: Cu/Zn/Mg/Cr = 40:5:5:50, atomic ratio %), obtained by reduction of a nonstoichiometric spinel-type precursor, and a commercial catalyst (CAT 2: Cu/Mn/Ba/Cr = 44:8:1:47, atomic ratio %) were used. The MA/GBL solution exhibited the highest GBL production, while the SA/GBL solution was converted only partially due to a competitive adsorption of GBL on the active sites, as evidenced by themore » similar reactivities observed with pure anhydrides. The best carbon balances were observed with the esters, probably the result of lowest light hydrocarbon synthesis and tar formation. With all the feedstocks, the activity of CAT 2 is higher than that of CAT 1, which, however, gives the best yield in GBL due its lower activity in the overhydrogenation and hydrogenolysis reaction. It was found that n-butanol (BuOH) and butyric acid (BuA) derived mainly from GBL. On this basis, the reactivities of the main products observed were investigated separately, confirming the stability of tetrahydrofuran (THF), which reacted only at high temperature with low conversions to ethanol. On the other hand, GBL gave rise to overhydrogenation and/or hydrogenolysis, with high conversion (mainly with CAT 2), confirming its key role in both reactions. Furthermore, the formation in the catalytic tests with BuA and BuOH of n-butanal, notwithstanding the high H{sub 2}/organic ratio, implies that it is the main intermediate in the hydrogenolysis reactions. A new reaction scheme is proposed, pointing out the key role of GBL as the {open_quotes}intersection{close_quotes} of two possible reaction pathways, giving rise to THF or overhydrogenation and hydrogenolysis products, respectively. 44 refs., 4 figs., 6 tabs.« less

Application of mesoporous Al-MCM-48 material to the conversion of lignin.

PubMed

Lee, Hyung Won; Lee, In-Gu; Park, Sung Hoon; Jeon, Jong-Ki; Suh, Dong Jin; Jung, Jinho; Park, Young-Kwon

2014-04-01

Al-MCM-48 was applied to the catalytic pyrolysis of lignin for the first time. The pyrolysis reaction and in-situ product were analyzed by pyrolysis gas chromatography/mass spectrometry. The main products of the non-catalytic pyrolysis of lignin were phenols. The use of Al-MCM-48 increased the production of light phenols considerably. The yields of high-value-added compounds, such as hydrocarbons and aromatics, were also increased by catalytic upgrading. Al-MCM-48 is believed to promote cracking, aromatization and deoxygenation, such as decarbonylation. On the other hand, Si-MCM-48, which has no acid sites, showed lower deoxygenation efficiency than Al-MCM-48. Al-MCM-48 could be regenerated by calcining in air.

Electron and Ion Reactions in Molecular Solids: from astrochemistry to radiobiology

NASA Astrophysics Data System (ADS)

Huels, Michael A.

2001-05-01

Wherever ionizing radiation interacts with matter, it initiates reaction cascades involving ions, radicals, and ballistic secondary electrons; these reactions occur on fs time-scales, and may lead to substantial physical and chemical modifications of a medium. Here I present measurements of 0-80 eV electron and ion reactions in condensed films ranging from simple to complex, and astrophysical to biological in nature. Targets contain either: small molecules, hydrocarbons of increasing complexity (incl. bases, sugars, single/double stranded DNA), molecules on rare gas matrices, or mixed cryogenic films resembling astrophysical or planetary surface ices containing O2, H2O, methane, and aromatic hydrocarbons. The basic electron or ion reaction mechanisms and pathways are found to be fundamentally universal, but are modulated by the physical and chemical nature of the medium; depending on the latter, a reaction cascade may lead to different end-points, e.g. a decrease in molecular complexity via molecular fragmentations, or increases in complexity via secondary ion collision induced synthesis of larger molecules in hydrocarbon rich surface ices.

Waterflooding injectate design systems and methods

DOEpatents

Brady, Patrick V.; Krumhansl, James L.

2014-08-19

A method of designing an injectate to be used in a waterflooding operation is disclosed. One aspect includes specifying data representative of chemical characteristics of a liquid hydrocarbon, a connate, and a reservoir rock, of a subterranean reservoir. Charged species at an interface of the liquid hydrocarbon are determined based on the specified data by evaluating at least one chemical reaction. Charged species at an interface of the reservoir rock are determined based on the specified data by evaluating at least one chemical reaction. An extent of surface complexation between the charged species at the interfaces of the liquid hydrocarbon and the reservoir rock is determined by evaluating at least one surface complexation reaction. The injectate is designed and is operable to decrease the extent of surface complexation between the charged species at interfaces of the liquid hydrocarbon and the reservoir rock. Other methods, apparatus, and systems are disclosed.

Temperature-dependent ozone chemiluminescence: A new approach for hydrocarbon monitoring

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

Marley, N.; Gaffney, J.

1996-12-31

Ozone chemiluminescent reactions have been used for some time to detect oxides of nitrogen, ozone, and olefins in air quality studies. Current procedures use non-methane hydrocarbon analyzers based on the flame ionization detector (FID), which quantitate total non-methane hydrocarbons but do not differentiate between the wide variety of volatile organic classes and oxygenates. The other methodology that has been used, gas chromatography/mass spectroscopy (GC/MS), can measure a variety of individual hydrocarbon species and classes, but it is costly, time-consuming, and labor intensive and is not amenable to real-time measurements. Presented here is preliminary research aimed at the development of anmore » alternative to FID and GC/MS: the ozone chemiluminescent detector (OCD) for measurement of a variety of hydrocarbon species and classes by use of the temperature dependence of ozone chemiluminescent reactions. Responses for various hydrocarbon classes obtained with an OCD operated at 170 C or the FID were compared. The results indicate that the OCD detector responds like a total carbon detector at this temperature, with sensitivities 10-100 times higher than those of a FID. Use of the temperature dependence of the chemiluminescent reaction and prereactors will apparently make a real-time hydrocarbon analyzer based on this approach feasible for determination of high-, moderate-, and low-reactivity hydrocarbon levels in ambient air. The OCD approach may be very useful in determining oxygenate emissions from motor vehicles, particularly alternative fuels. The OCD may also be useful in monitoring of ambient air for natural hydrocarbon emissions.« less

Catalytic combustion of volatile organic compounds.

PubMed

Everaert, K; Baeyens, J

2004-06-18

Despite the success of adsorption and thermal incineration of (C)VOC emissions, there is still a need for research on techniques which are both economically more favorable and actually destroy the pollutants rather than merely remove them for recycling elsewhere in the biosphere. The catalytic destruction of (C)VOC to CO2, H2O and HCl/Cl2 appears very promising in this context and is the subject of the present paper. The experiments mainly investigate the catalytic combustion of eight target compounds, all of which are commonly encountered in (C)VOC emissions and/or act as precursors for the formation of PCDD/F. Available literature on the different catalysts active in the oxidation of (C)VOC is reviewed and the transition metal oxide complex V2O5-WO3/TiO2 appears most suitable for the current application. Different reactor geometries (e.g. fixed pellet beds, honeycombs, etc.) are also described. In this research a novel catalyst type is introduced, consisting of a V2O5-WO3/TiO2 coated metal fiber fleece. The conversion of (C)VOC by thermo-catalytic reactions is governed by both reaction kinetics and reaction equilibrium. Full conversion of all investigated VOC to CO2, Cl2, HCl and H2O is thermodynamically feasible within the range of experimental conditions used in this work (260-340 degrees C, feed concentrations 30-60 ppm). A first-order rate equation is proposed for the (C)VOC oxidation reactions. The apparent rate constant is a combination of reaction kinetics and mass transfer effects. The oxidation efficiencies were measured with various (C)VOC in the temperature range of 260-340 degrees C. Literature data for oxidation reactions in fixed beds and honeycomb reactors are included in the assessment. Mass transfer resistances are calculated and are generally negligible for fleece reactors and fixed pellet beds, but can be of importance for honeycomb monoliths. The experimental investigations demonstrate: (i) that the conversion of the hydrocarbons is independent of the oxygen concentration, corresponding to a zero-order dependency of the reaction rate; (ii) that the conversion of the hydrocarbons is a first-order reaction in the (C)VOC; (iii) that the oxidation of the (C)VOC proceeds to a higher extent with increasing temperature, with multiple chlorine substitution enhancing the reactivity; (iv) that the reaction rate constant follows an Arrhenius dependency. The reaction rate constant kr (s(-1)) and the activation energy E (kJ/mol) are determined from the experimental results. The activation energy is related to the characteristics of the (C)VOC under scrutiny and correlated in terms of the molecular weight. The kr-values are system-dependent and hence limited in design application to the specific VOC-catalyst combination being studied. To achieve system-independency, kr-values are transformed into an alternative kinetic constant K (m3/(m2u)) expressed per unit of catalyst surface and thus independent of the amount of catalyst present in the reactor. Largely different experimental data can be fitted in terms of this approach. Results are thereafter used to define the Arrhenius pre-exponential factor A*, itself expressed in terms of the activation entropy. Destruction efficiencies for any given reactor set-up can be predicted from E- and A*-correlations. The excellent comparison of predicted and measured destruction efficiencies for a group of chlorinated aromatics stresses the validity of the design approach. Since laboratory-scale experiments using PCDD/F are impossible, pilot and full-scale tests of PCDD/F oxidation undertaken in Flemish MSWIs and obtained from literature are reported. From the data it is clear that: (i) destruction efficiencies are normally excellent; (ii) the efficiencies increase with increasing operating temperature; (iii) the higher degree of chlorination does not markedly affect the destruction efficiency. Finally, all experimental findings are used in design recommendations for the catalytic oxidation of (C)VOC and PCDD/F. Predicted values of the a)VOC and PCDD/F. Predicted values of the acceptable space velocity correspond with the cited industrial values, thus stressing the validity of the design strategy and equations developed in the present paper.

Hydrocarbon activation under sulfate-reducing and methanogenic conditions proceeds by different mechanisms.

NASA Astrophysics Data System (ADS)

Head, Ian; Gray, Neil; Aitken, Caroline; Sherry, Angela; Jones, Martin; Larter, Stephen

2010-05-01

Microbial degradation of alkanes typically involves their conversion to fatty acids which are then catabolised by beta-oxidation. The critical step in this process is activation of the hydrocarbon. Under oxic conditions this is catalyzed by monooxygenase enzymes with the formation of long chain alcohols. In the absence of oxygen alternative alkane activation mechanisms have been observed or proposed. Fumarate addition to alkanes to form alkyl succinates is considered a central process in anaerobic hydrocarbon degradation. Comparative studies of crude oil degradation under sulphate-reducing and methanogenic conditions revealed distinctive patterns of compound class removal and metabolite formation. Alkyl succinates derived from C7 to C26 n-alkanes and branched chain alkanes were found in abundance in sulfate-reducing systems but these were not detected during methanogenic crude oil degradation. Only one other mechanism of alkane activation has been elucidated to date. This involves addition of carbon derived from bicarbonate/CO2 to C-3 of an alkane chain to form a 2-ethylalkane with subsequent removal of the ethyl group leading to the formation of a fatty acid 1 carbon shorter than the original alkane. 2-ethylalkanes have never been detected as metabolites of anaerobic alkane degradation and were not detected in crude oil-degrading methanogenic systems. Due to the range of alkanes present in crude oil it was not possible to infer the generation of C-odd acids from C-even alkanes which is characteristic of the C-3 carboxylation mechanism. Furthermore genes homologous to alkysuccinate synthetases were not detected in the methanogenic hydrocarbon degrading community by pyrosequencing of total DNA extracted from methanogenic enrichments cultures. beta-oxidation genes were detected and intriguingly, alcohol and aldehyde dehydrogenase genes were present. This offers the possibility that alkane activation in the methanogenic system does not proceed via acid metabolites, but may be initiated by an anaerobic hydroxylation reaction. This is not unprecedented and hydroxylation of ethylbenzene has been demonstrated. However the C-H bond dissociation energy of alkanes is typically considered too high to readily permit alkane hydroxylation. It is however clear that alkane activation in these methanogenic crude oil-degrading systems involves mechanisms other than the well-known fumarate-addition reactions.

Multitasking mesoporous nanomaterials for biorefinery applications

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

Kandel, Kapil

2013-01-01

Mesoporous silica nanoparticles (MSNs) have attracted great interest for last two decades due to their unique and advantageous structural properties, such as high surface area, pore volume, stable mesostructure, tunable pore size and controllable particle morphology. The robust silica framework provides sites for organic modifications, making MSNs ideal platforms for adsorbents and supported organocatalysts. In addition, the pores of MSNs provide cavities/ channels for incorporation of metal and metal oxide nanoparticle catalysts. These supported metal nanoparticle catalysts benefit from confined local environments to enhance their activity and selectivity for various reactions. Biomass is considered as a sustainable feedstock with potentialmore » to replace diminishing fossil fuels for the production of biofuels. Among several strategies, one of the promising methods of biofuel production from biomass is to reduce the oxygen content of the feedstock in order to improve the energy density. This can be achieved by creating C-C bonds between biomass derived intermediates to increase the molecular weight of the final hydrocarbon molecules. In this context, pore size and organic functionality of MSNs are varied to obtain the ideal catalyst for a C-C bond forming reaction: the aldol condensation. The mechanistic aspects of this reaction in supported heterogeneous catalysts are explored. The modification of supported organocatalyst and the effect of solvent on the reaction are rationalized. The significance of two functional surfaces of MSNs is exploited by enzyme immobilization on the external surface and organo catalyst functionalization on the internal surface. Using this bifunctional catalyst, the tandem conversion of small chain alcohols into longer chain hydrocarbon molecules is demonstrated. The ability to incorporate metal and metal oxide nanoparticles in the pores and subsequent functionalization led to develop organic modified magnetic MSNs (OM-MSNs) for applications in microalgae biorefinery. Two different integrated biorefinery systems are highlighted. (i) OM-MSNs are used to harvest microalgae and selectively sequester free fatty acids (FFAs). (ii) OM-MSNs are shown to selectively sequester FFAs and convert them into diesel-range liquid hydrocarbon fuels. A similar MSN supported metal nanoparticle catalyst is demonstrated to transform FFAs into green diesel with even greater activity and selectivity. The incorporation of a different organic functional group into MSN provides a selective adsorbent for separation and purification of α-tocopherol from microalgae oil. The functional group with electron deficient aromatic rings demonstrated high sequestration capacity and selectivity of {alpha}-tocopherol.« less

Heterogeneous Reactions of Limonene on Mineral Dust: Impacts of Adsorbed Water and Nitric Acid.

PubMed

Lederer, Madeline R; Staniec, Allison R; Coates Fuentes, Zoe L; Van Ry, Daryl A; Hinrichs, Ryan Z

2016-12-08

Biogenic volatile organic compounds (BVOCs), including the monoterpene limonene, are a major source of secondary organic aerosol (SOA). While gas-phase oxidation initiates the dominant pathway for BVOC conversion to SOA, recent studies have demonstrated that biogenic hydrocarbons can also directly react with acidic droplets. To investigate whether mineral dust may facilitate similar reactive uptake of biogenic hydrocarbons, we studied the heterogeneous reaction of limonene with mineral substrates using condensed-phase infrared spectroscopy and identified the formation of irreversibly adsorbed organic products. For kaolinite, Arizona Test Dust, and silica at 30% relative humidity, GC-MS identified limonene-1,2-diol as the dominant product with total organic surface concentrations on the order of (3-5) × 10 18 molecules m -2 . Experiments with 18 O-labeled water support a mechanism initiated by oxidation of limonene by surface redox sites forming limonene oxide followed by water addition to the epoxide to form limonenediol. Limonene uptake on α-alumina, γ-alumina, and montmorillonite formed additional products in high yield, including carveol, carvone, limonene oxide, and α-terpineol. To model tropospheric processing of mineral aerosol, we also exposed each mineral substrate to gaseous nitric acid prior to limonene uptake and identified similar surface adsorbed products that were formed at rates 2 to 5 times faster than without nitrate coatings. The initial rate of reaction was linearly dependent on gaseous limonene concentration between 5 × 10 12 and 5 × 10 14 molecules cm -3 (0.22-20.5 ppm) consistent with an Eley-Rideal-type mechanism in which gaseous limonene reacts directly with reactive surface sites. Increasing relative humidity decreased the amount of surface adsorbed products indicating competitive adsorption of surface adsorbed water. Using a laminar flow tube reactor we measured the uptake coefficient for limonene on kaolinite at 25% RH to range from γ = 5.1 × 10 -6 to 9.7 × 10 -7 . After adjusting for reactive surface areas, we estimate uptake coefficients for limonene on HNO 3 -processed mineral aerosol on the order of (1-6) × 10 -6 . Although this heterogeneous reaction will not impact the atmospheric lifetime of gaseous limonene, it does provide a new pathway for mineral aerosol to acquire secondary organic matter from biogenic hydrocarbons, which in turn will alter the physical properties of mineral dust.

Direct Carbon Conversion: Review of Production and Electrochemical Conversion of Reactive Carbons, Economics and Potential Impact on the Carbon Cycle

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

Cooper, J F; Cherepy, N; Upadhye, R

Concerns over global warning have motivated the search for more efficient technologies for electric power generation from fossil fuels. Today, 90% of electric power is produced from coal, petroleum or natural gas. Higher efficiency reduces the carbon dioxide emissions per unit of electric energy. Exercising an option of deep geologic or ocean sequestration for the CO{sub 2} byproduct would reduce emissions further and partially forestall global warming. We introduce an innovative concept for conversion of fossil fuels to electricity at efficiencies in the range of 70-85% (based on standard enthalpy of the combustion reaction). These levels exceed the performance ofmore » common utility plants by up to a factor of two. These levels are also in excess of the efficiencies of combined cycle plants and of advanced fuel cells now operated on the pilot scale. The core of the concept is direct carbon conversion a process that is similar to that a fuel cell but differs in that synthesized forms of carbon, not hydrogen, are used as fuel. The cell sustains the reaction, C + O{sub 2} = CO{sub 2} (E {approx} 1.0 V, T = 800 C). The fuel is in the form of fine particulates ({approx}100 nm) distributed by entrainment in a flow of CO{sub 2} to the cells to form a slurry of carbon in the melt. The byproduct stream of CO{sub 2} is pure. It affords the option of sequestration without additional separation costs, or can be reused in secondary oil or gas recovery. Our experimental program has discovered carbon materials with orders of magnitude spreads in anode reactivity reflected in cell power density. One class of materials yields energy at about 1 kW/m{sup 2} sufficiently high to make practical the use of the cell in electric utility applications. The carbons used in such cells are highly disordered on the nanometer scale (2-30 nm), relative to graphite. Such disordered or turbostratic carbons can be produced by controlled pyrolysis (thermal decomposition) of hydrocarbons extracted from coal, petroleum or natural gas. For coal and lignite, such hydrocarbons may be produced by cyclic hydrogenation (hydropyrolysis), with the recycle of the hydrogen intermediate following pyrolysis. Starting with common CH{sub x} feedstock for carbon black manufacture, the ash entrained into the carbon (<0.03%) does not jeopardize cell life or enter into the economic estimates for power generation. The value of carbon (relative to hydrogen) as an electrochemical fuel derives from thermodynamic aspects of the C/O{sub 2} reaction. First, the entropy change of the C/O{sub 2} reaction is nearly zero, allowing theoretical efficiencies ({Delta}G(T)/{Delta}H{sub i298}) of 100% (cf. H{sub 2}/O{sub 2} theoretical efficiency of 70%). Second, the thermodynamic activity of the carbon fuel and the CO{sub 2} product are spatially and temporally invariant. This allows 100% utilization of the carbon fuel in single pass (cf. hydrogen utilizations of 75-85%). The carbodmelt slurry is non-explosive at operating temperatures. The total energy efficiency for the C/O{sub 2} is roughly 80% for cell operation at practical rates. In summary, what gives this route its fundamental advantage in energy conversion is that it derives the greatest possible fraction of energy of the fossil resource from an electrochemical reaction (C+O{sub 2} = CO{sub 2}) that is comparatively simple to operate at efficiencies of 80%, in a single-pass cell configuration without bottoming turbine cycles.« less

Site-selective oxidation, amination and epimerization reactions of complex polyols enabled by transfer hydrogenation

NASA Astrophysics Data System (ADS)

Hill, Christopher K.; Hartwig, John F.

2017-12-01

Polyoxygenated hydrocarbons that bear one or more hydroxyl groups comprise a large set of natural and synthetic compounds, often with potent biological activity. In synthetic chemistry, alcohols are important precursors to carbonyl groups, which then can be converted into a wide range of oxygen- or nitrogen-based functionality. Therefore, the selective conversion of a single hydroxyl group in natural products into a ketone would enable the selective introduction of unnatural functionality. However, the methods known to convert a simple alcohol, or even an alcohol in a molecule that contains multiple protected functional groups, are not suitable for selective reactions of complex polyol structures. We present a new ruthenium catalyst with a unique efficacy for the selective oxidation of a single hydroxyl group among many in unprotected polyol natural products. This oxidation enables the introduction of nitrogen-based functional groups into such structures that lack nitrogen atoms and enables a selective alcohol epimerization by stepwise or reversible oxidation and reduction.

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

Yung, Matthew M.; Starace, Anne K.; Mukarakate, Calvin

Here in this work, Ni/ZSM-5 catalysts with varied nickel loadings were evaluated for their ability to produce aromatic hydrocarbons by upgrading of pine pyrolysis vapors. The effect of catalyst pretreatment by hydrogen reduction was also investigated. Results indicate that the addition of nickel increases the yield of aromatic hydrocarbons while simultaneously increasing the conversion of oxygenates, relative to ZSM-5, and these effects are more pronounced with increasing nickel loading. Additionally, while initial activity differences were observed between the oxidized and reduced forms of nickel on ZSM-5 (i.e., NiO/ZSM-5 versus Ni/ZSM-5), the activity of both catalysts converges with increasing time onmore » stream. These reaction results coupled with characterization of pristine and spent catalysts suggest that the catalysts reach similar active states during catalytic pyrolysis, regardless of pretreatment, as NiO undergoes in situ reduction to Ni by biomass pyrolysis vapors. This reduction of NiO to Ni was confirmed by reaction results and characterization by NH 3 temperature-programmed desorption, temperature-programmed reduction, and X-ray diffraction. This finding is significant in that the ability to reduce or eliminate the need for a pre-reaction H 2 reduction of Ni-modified zeolite catalysts could reduce process complexity and operating costs in a biorefinery-based vapor-phase upgrading process to produce biomass-derived fuels and chemicals. The ability to monitor catalyst activity in real time with a molecular beam mass spectrometer used to measure uncondensed, hot pyrolysis vapors allows for an improved understanding of the mechanism for improved activity with Ni addition to ZSM-5, which is attributed to the ability to prevent deactivation by deposition of coke and capping of zeolite micropores.« less

Biomass Catalytic Pyrolysis on Ni/ZSM-5: Effects of Nickel Pretreatment and Loading

DOE PAGES

Yung, Matthew M.; Starace, Anne K.; Mukarakate, Calvin; ...

2016-04-25

Here in this work, Ni/ZSM-5 catalysts with varied nickel loadings were evaluated for their ability to produce aromatic hydrocarbons by upgrading of pine pyrolysis vapors. The effect of catalyst pretreatment by hydrogen reduction was also investigated. Results indicate that the addition of nickel increases the yield of aromatic hydrocarbons while simultaneously increasing the conversion of oxygenates, relative to ZSM-5, and these effects are more pronounced with increasing nickel loading. Additionally, while initial activity differences were observed between the oxidized and reduced forms of nickel on ZSM-5 (i.e., NiO/ZSM-5 versus Ni/ZSM-5), the activity of both catalysts converges with increasing time onmore » stream. These reaction results coupled with characterization of pristine and spent catalysts suggest that the catalysts reach similar active states during catalytic pyrolysis, regardless of pretreatment, as NiO undergoes in situ reduction to Ni by biomass pyrolysis vapors. This reduction of NiO to Ni was confirmed by reaction results and characterization by NH 3 temperature-programmed desorption, temperature-programmed reduction, and X-ray diffraction. This finding is significant in that the ability to reduce or eliminate the need for a pre-reaction H 2 reduction of Ni-modified zeolite catalysts could reduce process complexity and operating costs in a biorefinery-based vapor-phase upgrading process to produce biomass-derived fuels and chemicals. The ability to monitor catalyst activity in real time with a molecular beam mass spectrometer used to measure uncondensed, hot pyrolysis vapors allows for an improved understanding of the mechanism for improved activity with Ni addition to ZSM-5, which is attributed to the ability to prevent deactivation by deposition of coke and capping of zeolite micropores.« less

Reductive deconstruction of organosolv lignin catalyzed by zeolite supported nickel nanoparticles

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

Kasakov, Stanislav; Shi, Hui; Camaioni, Donald M.

2015-11-01

Mechanistic aspects of deconstruction and hydrodeoxygenation of organosolv lignin using supported Ni catalysts with (Ni/HZSM-5 and Ni/HBEA) and without Brønsted acid sites (Ni/SiO2) are reported. Lignin was deconstructed and converted to saturated cyclic hydrocarbons ranging from C5 to C14. In the one-stage reaction, full conversion with total yield of 70 ± 5 wt.% saturated hydrocarbons was achieved at 593 K and 20 bar H2. The organosolv lignin used consists of seven to eight monolignol subunits and has an average molecular weight of ca. 1200 g mol-1. The monolignols were mainly guaiacyl, syringyl and phenylcoumaran, randomly interconnected through β-O-4, 4-O-5, β-1,more » 5-5’ and β-β ether bonds. In situ IR spectroscopy was used to follow the changes in lignin constituents during reaction. The proposed reaction pathways for the catalytic transformation of this organosolv lignin to alkanes start with the hydrogenolysis of aryl alkyl ether bonds, followed by hydrogenation of the aromatic compounds on Ni to cyclic alcohols. Oxygen is removed from the alcohols via dehydration on Brønsted acid sites to yield cyclic alkenes that are further hydrogenated to alkanes. Formation of condensation products may occur via intermolecular recombination of aromatic monomers or alkylation of aromatic compounds by alkenes. The financial support from TUM-PNNL cooperation project “Development of new methods for in situ characterization in liquid phase reactions” (CN-177939) is highly appreciated. The work by S.K., H.S., and J.A.L was partially supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.« less

Optimizing catalysis conditions to decrease aromatic hydrocarbons and increase alkanes for improving jet biofuel quality.

PubMed

Cheng, Jun; Li, Tao; Huang, Rui; Zhou, Junhu; Cen, Kefa

2014-04-01

To produce quality jet biofuel with high amount of alkanes and low amount of aromatic hydrocarbons, two zeolites of HY and HZSM-5 supporting Ni and Mo were used as catalysts to convert soybean oil into jet fuel. Zeolite HY exhibited higher jet range alkane selectivity (40.3%) and lower jet range aromatic hydrocarbon selectivity (23.8%) than zeolite HZSM-5 (13.8% and 58.9%). When reaction temperature increased from 330 to 390°C, yield of jet fuel over Ni-Mo/HY catalyst at 4 MPa hydrogen pressure increased from 0% to 49.1% due to the shift of reaction pathway from oligomerization to cracking reaction. Further increase of reaction temperature from 390 to 410°C resulted in increased yield of jet range aromatic hydrocarbons from 18.7% to 30%, which decreased jet fuel quality. A high yield of jet fuel (48.2%) was obtained at 1 MPa low hydrogen pressure over Ni (8 wt.%)-Mo (12 wt.%)/HY catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

Final Technical Report: Tandem and Bimetallic Catalysts for Oxidative Dehydrogenation of Light Hydrocarbon with Renewable Feedstock

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

Abu-Omar, Mahdi

2017-01-06

An estimated 490 million metric tons of lignocellulosic biomass is available annually from U.S. agriculture and forestry. With continuing concerns over greenhouse gas emission, the development of efficient catalytic processes for conversion of biomass derived compounds is an important area of research. Since carbohydrates and polyols are rich in oxygen, approximately one oxygen atom per carbon, removal of hydroxyl groups via deoxygenation is needed. The necessary hydrogen required for hydrodeoxygenation (HDO) would either come from reforming biomass itself or from steam reforming of natural gas. Both processes contribute to global CO2 emission. The hope is that eventually renewable sources suchmore » as wind and solar for hydrogen production will become more viable and economic in the future. In the meantime, unconventional natural gas production in North America has boomed. As a result, light hydrocarbons present an opportunity when coupled with biomass derived oxygenates to generate valuable products from both streams without co-production of carbon dioxide. This concept is the focus of our current funding period. The objective of the project requires coupling two different types of catalysis, HDO and dehydrogenation. Our hypothesis was formulated around our success in establishing oxorhenium catalysts for polyol HDO reactions and known literature precedence for the use of iridium hydrides in alkane dehydrogenation. To examine our hypothesis we set out to investigate the reaction chemistry of binuclear complexes of oxorhenium and iridium hydride.« less

Green diesel production via catalytic hydrogenation/decarboxylation of triglycerides and fatty acids of vegetable oil and brown grease

NASA Astrophysics Data System (ADS)

Sari, Elvan

Increase in the petroleum prices, projected increases in the world's energy demand and environmental awareness have shifted the research interest to the alternative fuel technologies. In particular, green diesel, vegetable oil/animal fat/waste oil and grease derived hydrocarbons in diesel boiling range, has become an attractive alternative to biodiesel---a mixture of fatty acid methyl esters, particularly due to its superior fuel properties that are similar to petroleum diesel. Hence, green diesel can be used as a drop-in fuel in the current diesel engines. The current technology for production of green diesel-hydrodeoxygenation of triglycerides and fatty acids over conventional hydrotreating catalysts suffers from fast catalyst deactivation in the absence of hydrogen combined with high temperatures and high fatty acid content in the feedstock. Additionally, excess hydrogen requirement for hydrodeoxygenation technique leads to high production costs. This thesis proposes a new technology-selective decarboxylation of brown grease, which is a mixture of fats and oils collected from waste water trap and rich in fatty acids, over a supported noble metal catalyst that overcomes the green diesel production challenges. In contrast to other feedstocks used for liquid biofuel production, brown grease is inexpensive and non-food competing feedstock, therefore the process finds solution to waste management issues, reduces the renewable fuel production cost and does not add to the global food shortage problems. Special catalyst formulations were developed to have a high activity and stability in the absence of hydrogen in the fatty acid decarboxylation process. The study shows how catalyst innovations can lead to a new technology that overcomes the process challenges. First, the effect of reaction parameters on the activity and the selectivity of brown grease decarboxylation with minimum hydrogen consumption over an activated carbon supported palladium catalyst were investigated. A 90% conversion of brown grease in a semi-batch mode was obtained in 7 hours. In contrast, in a batch reaction the conversion was roughly 40% in the same reaction time. However, by pre-treating the "as received" brown grease with H 2, the conversion in a batch reactor was increased 1.4--fold; and when the H2 to BG ratio was increased to 3/1 (mol/mol), the conversion was further improved. Therefore, such a two-step processing with selective hydrogenation prior to the decarboxylation of BG improves the product selectivity. The commercial 5% Pd/C catalyst was highly active for the decarboxylation of brown grease to green diesel at 300 °C and 1.5 MPa. Second, a class of Pd catalyst supported on a silica-activated carbon nanocomposite for free fatty acid decarboxylation was developed, and displayed excellent activity and operation stability selectively for the green diesel hydrocarbons formation in the absence of hydrogen under mild reaction conditions. The decarboxylation activities of different amount of silica containing catalysts were investigated in a batch reactor under inert gas. Among them, the formulation with the fewer oxygen surface groups (Pd/Si--C--4) was the most active catalyst for the decarboxylation of an unsaturated fatty acid. The high activity of the Pd/Si--C--4 catalyst is attributed to its accessible and well-distributed metallic Pd nanoparticles inside hybrid mesopores as well as to its low acidity, weak surface interactions and inertness. Thus, Pd supported on carbon modified with silica may be regarded as a prospective decarboxylation catalyst for the removal of oxygen from vegetable oil/animal fat without the need of additional hydrogen. Third, in order to design a suitable catalyst for conversion of brown grease to green diesel, a systematic study of the model compounds--oleic acid was conducted on various catalysts in super-critical water to understand the reaction pathways in the absence of hydrogen. A Si--C support was more effective than activated carbon itself for both decarboxylation of oleic acid and hydrogenation of alkenes. In an additional effort to reduce Pd amount in the catalyst, Pd2Co/C catalysts with various Pd content were prepared and the catalytic activity study showed that 0.5 wt% Pd2Co/C catalyst performs even better than a 5 wt% Pd/C catalyst. Pd and Co alloys were very well dispersed and formed fine clusters, which led to a higher active metal surface area and hence favored the decarboxylation of oleic acid. This study showed that an alloy of Pd on carbon with a significantly low Pd content is much more active and selective to diesel hydrocarbons production from an unsaturated fatty acid in super-critical water and may be regarded as a prospective feasible decarboxylation catalyst for the removal of oxygen from vegetable oil/animal fat without the need of additional hydrogen.

A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

NASA Astrophysics Data System (ADS)

Wu, Jingjie; Ma, Sichao; Sun, Jing; Gold, Jake I.; Tiwary, Chandrasekhar; Kim, Byoungsu; Zhu, Lingyang; Chopra, Nitin; Odeh, Ihab N.; Vajtai, Robert; Yu, Aaron Z.; Luo, Raymond; Lou, Jun; Ding, Guqiao; Kenis, Paul J. A.; Ajayan, Pulickel M.

2016-12-01

Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts.

Direct Production of Propene from the Thermolysis of Poly(..beta..-hydroxybutyrate)

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

Mittal, Ashutosh; Pilath, Heidi M.; Johnson, David K.

To transform biomass components into hydrocarbon fuels it is clear that there are two main transformations that need to occur, i.e., deoxygenation and carbon chain extension. The potential routes for decreasing the oxygen content of biomass intermediates include dehydration, hydrodeoxygenation and decarboxylation. One route that is examined here is the conversion of polyhydroxyalkanoates (PHA) to alkenes that would be intermediates to hydrocarbon fuels.Thermal breakdown of PHA proceeds via an intermediate carboxylic acid, which can then be decarboxylated to an alkene. Oligomerization of alkenes by well-known commercial technologies would permit production of a range of hydrocarbon fuels from a carbohydrate derivedmore » intermediate. Moreover, polyhydroxybutyrate (PHB) can be produced in Cupriavidus necator (formerly known as Ralstonia eutropha) and Alcaligenes eutrophus on a variety of carbon sources including glucose, fructose and glycerol with PHB accumulation reaching 75 percent of dry cell mass. We conducted thermal conversion of PHB and pure crotonic acid (CA), the intermediate carboxylic acid produced by thermal depolymerization of PHB, in a flow-through reactor. The results of initial experiments on the thermal conversion of CA showed that up to 75 mole percent yields of propene could be achieved by optimizing the residence time and temperature of the reactor. Further experiments are being investigated to optimize the reactor parameters and enhance propene yields via thermal conversion of PHB.« less

Global investigation of potential energy surfaces for the pyrolysis of C(1)-C(3) hydrocarbons: toward the development of detailed kinetic models from first principles.

PubMed

Ryazantsev, Mikhail N; Jamal, Adeel; Maeda, Satoshi; Morokuma, Keiji

2015-11-07

Detailed kinetic models (DKMs) are the most fundamental "bottom-up" approaches to computational investigation of the pyrolysis and oxidation of fuels. The weakest points of existing DKMs are incomplete information about the reaction types that can be involved in the potential energy surfaces (PESs) in pyrolysis and oxidation processes. Also, the computational thermodynamic parameters available in the literature vary widely with the level of theory employed. More sophisticated models require improvement both in our knowledge of the type of the reactions involved and the consistency of thermodynamic and kinetic parameters. In this paper, we aim to address these issues by developing ab initio models that can be used to describe early stages of pyrolysis of C1-C3 hydrocarbons. We applied a recently developed global reaction route mapping (GRRM) strategy to systematically investigate the PES of the pyrolysis of C1-C3 hydrocarbons at a consistent level of theory. The reactions are classified into 14 reaction types. The critical points on the PES for all reactions in the network are calculated at the highly accurate UCCSD(T)-F12b/cc-pVTZ//UM06-2X/cc-pVTZ level of theory. The data reported in this paper can be used for first principle calculations of kinetic constants and for a subsequent study on modeling the evolution of the species from the reaction network of the pyrolysis and oxidation of C1-C3 hydrocarbons.

Synthesis of hydrocarbons by CO2 fluid conversion with hydrogen: Experimental modeling at 7.8 GPa and 1350°C

NASA Astrophysics Data System (ADS)

Sokol, A. G.; Tomilenko, A. A.; Bul'bak, T. A.; Sobolev, N. V.

2017-12-01

Synthesis of hydrocarbons by the interaction of a CO2 fluid with hydrogen mantle domains has been simulated in an experiment at 7.8 GPa and 1350°C. The synthesized fluid contains mainly aldehydes; lower amounts of ketones, alcohols, esters, and ethers; as well as noticeable amounts of isobutane and butane, alkenes, arenes, and polycyclic aromatic and heterocyclic hydrocarbons. The fluid is compositionally close to volatiles found in inclusions from mantle olivines and picroilmenites.

A Field Scale Investigation of Enhanced Petroleum Hydrocarbon Biodegradation in the Vadose Zone Combining Soil Venting as an Oxygen Source with Moisture and Nutrient Addition

DTIC Science & Technology

1990-01-01

herbicides, insecticides, and fungicides is dependent upon both biotic and abiotic reactions, and the rate of these reactions determines the required...The most commonly isolated I hydrocarbon degrading fungi in decreasing order include: Trichoderma , i Penicillium, Aspergillus, and Mortierella (Dragun

Aspen Plus Model for In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors for the Conversion of Biomass to Hydrocarbon Fuels

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

This is an Aspen Plus process model for in situ and ex situ upgrading of fast pyrolysis vapors for the conversion of biomass to hydrocarbon fuels. It is based on conceptual designs that allow projections of future commercial implementations of the technologies based on a combination of research and existing commercial technologies. The process model was developed from the ground up at NREL. Results from the model are documented in a detailed design report NREL/TP-5100-62455 (available at http://www.nrel.gov/docs/fy15osti/62455.pdf).

Catalytic two-stage coal hydrogenation and hydroconversion process

DOEpatents

MacArthur, James B.; McLean, Joseph B.; Comolli, Alfred G.

1989-01-01

A process for two-stage catalytic hydrogenation and liquefaction of coal to produce increased yields of low-boiling hydrocarbon liquid and gas products. In the process, the particulate coal is slurried with a process-derived liquid solvent and fed at temperature below about 650.degree. F. into a first stage catalytic reaction zone operated at conditions which promote controlled rate liquefaction of the coal, while simultaneously hydrogenating the hydrocarbon recycle oils at conditions favoring hydrogenation reactions. The first stage reactor is maintained at 650.degree.-800.degree. F. temperature, 1000-4000 psig hydrogen partial pressure, and 10-60 lb coal/hr/ft.sup.3 reactor space velocity. The partially hydrogenated material from the first stage reaction zone is passed directly to the close-coupled second stage catalytic reaction zone maintained at a temperature at least about 25.degree. F. higher than for the first stage reactor and within a range of 750.degree.-875.degree. F. temperature for further hydrogenation and thermal hydroconversion reactions. By this process, the coal feed is successively catalytically hydrogenated and hydroconverted at selected conditions, which results in significantly increased yields of desirable low-boiling hydrocarbon liquid products and minimal production of undesirable residuum and unconverted coal and hydrocarbon gases, with use of less energy to obtain the low molecular weight products, while catalyst life is substantially increased.

Blow-Out Velocities of Solutions of Hydrocarbons and Boron Hydride - Hydrocarbon Reaction Products in a 1 7/8-Inch-Diameter Combustor

NASA Technical Reports Server (NTRS)

Morris, James F.; Lord, Albert M.

1957-01-01

Blow-out velocities were determined for JP-4 solutions containing: (1) 10 % ethylene - decaborane reaction product, (2) 10% and 20% acetylene - diborane reaction product, and (3) 5.5%, 15.7%, and 30.7% methylacetylene - diborane reaction product. These were compared with blow-out velocities for JP-4, propylene oxide, and neohexane and previously reported data for JP-4 solutions of pentaborane. For those reaction products investigated, the blow-out velocities at a fixed equivalence ratio were higher for those materials containing higher boron concentrations; that is, blow-out velocity increased in the following order: (1) methylacetylene - diborane, (2) acetylene - diborane, and (3) ethylene - decaborane reaction products.

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.

Reaction Mechanism of Oxygen Atoms with Unsaturated Hydrocarbons by the Crossed-Molecular-Beams Method

DOE R&D Accomplishments Database

Buss, R. J.; Baseman, R. J.; Guozhong, H.; Lee, Y. T.

1982-04-01

From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

Detailed surface reaction mechanism in a three-way catalyst.

PubMed

Chatterjee, D; Deutschmann, O; Warnatz, J

2001-01-01

Monolithic three-way catalysts are applied to reduce the emission of combustion engines. The design of such a catalytic converter is a complex process involving the optimization of different physical and chemical parameters (in the simplest case, e.g., length, cell densities or metal coverage of the catalyst). Numerical simulation can be used as an effective tool for the investigation of the catalytic properties of a catalytic converter and for the prediction of the performance of the catalyst. To attain this goal, a two-dimensional flow-field description is coupled with a detailed surface reaction model (gas-phase reactions can be neglected in three-way catalysts). This surface reaction mechanism (with C3H6 taken as representative of unburnt hydrocarbons) was developed using sub-mechanisms recently developed for hydrogen, carbon monoxide and methane oxidation, literature values for C3H6 oxidation, and estimates for the remaining unknown reactions. Results of the simulation of a monolithic single channel are used to validate the surface reaction mechanism. The performance of the catalyst was simulated under lean, nearly stoichiometric and rich conditions. For these characteristic conditions, the oxidation of propene and carbon monoxide and the reduction of NO on a typical Pt/Rh coated three-way catalyst were simulated as a function of temperature. The numerically predicted conversion data are compared with experimentally measured data. The simulation further reveals the coupling between chemical reactions and transport processes within the monolithic channel.

Performance of Ni/dolomite pellet catalyst on gas distribution from cassava rhizome gasification with a modular fixed-bed gasifier.

PubMed

Sricharoenchaikul, V; Atong, D; Sornkade, P; Nisamaneenate, J

2017-05-01

Thermal conversion of cassava rhizome was performed using a modular downdraft gasifier with the addition of Ni-based catalysts as promising tar eliminating and produced gas upgrading techniques. The activities of a synthesized 5% Ni/dolomite pellet catalyst prepared by impregnation method were investigated in a secondary reactor downstream of the gasifier. High reforming activity of the Ni/dolomite pellet catalyst on tar reduction was achieved. The conversion to H 2 and CO was improved via steam reforming of methane and char reaction with CO 2 . Moreover, the formation of CH 4 and C x H y was diminished through the tar or condensable hydrocarbon reformed on the catalyst surface. The carbon and hydrogen conversions of cassava rhizome with prepared catalyst were 83.79% and 61.78%, respectively, at an air flow rate of 1.98 m 3 /hr. At this condition, tar formation was low, while the lower heating value was 4.39 MJ/m 3 and H 2 to CO molar ratio was 1.22. Generally, the addition of a catalyst not only enhanced gas production, but also reduced tar and particulate matter generation; thus, its implementation should help lessen the pollution control requirement and cost of operation, while allowing higher quality fuel gas production.

Potassium-Promoted Molybdenum Carbide as a Highly Active and Selective Catalyst for CO2 Conversion to CO.

PubMed

Porosoff, Marc D; Baldwin, Jeffrey W; Peng, Xi; Mpourmpakis, Giannis; Willauer, Heather D

2017-06-09

The high concentration of CO 2 bound in seawater represents a significant opportunity to extract and use this CO 2 as a C 1 feedstock for synthetic fuels. Using an existing process, CO 2 and H 2 can be concurrently extracted from seawater and then catalytically reacted to produce synthetic fuel. Hydrogenating CO 2 directly into liquid hydrocarbons is exceptionally difficult, but by first identifying a catalyst for selective CO production through the reverse water-gas shift (RWGS) reaction, CO can then be hydrogenated to fuel through Fischer-Tropsch (FT) synthesis. Results of this study demonstrate that potassium-promoted molybdenum carbide supported on γ-Al 2 O 3 (K-Mo 2 C/γ-Al 2 O 3 ) is a low-cost, stable, and highly selective catalyst for RWGS over a wide range of conversions. These findings are supported by X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reaction of a (Salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (Salen)ruthenium(IV) sulfilamido species.

PubMed

Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Peng, Shie-Ming; Wong, Wing-Tak; Lau, Tai-Chu

2010-01-04

The reaction of [Ru(VI)(N)(L)(MeOH)](PF(6)) [1; L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH(3)CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [Ru(IV){N(H)SR}(L)(NCCH(3))](PF(6)) (2a, R = (t)Bu; 2b, R = Ph). Metathesis of 2a with NaN(3) in methanol affords [Ru(IV){N(H)S(t)Bu}(L)(N(3))] (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(III) sulfilamine species, [Ru(III){N(H)(2)S(t)Bu}(L)(NCCH(3))](PF(6)) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(III) ammine species [Ru(III)(NH(3))(L)(NCCH(3))](PF(6)) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 --> 2a --> 3 (R = (t)Bu), 1 --> 2b --> 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4-cyclohexadiene, and fluorene by 2a are 51, 56, and 11, respectively.

Development of new generation of perovskite based noble metal/semiconductor photocatalysts for visible-light-driven hydrogen production

NASA Astrophysics Data System (ADS)

Shen, Peichuan

In recent decades, semiconductor photocatalysis has attracted a growing attention as a possible alternative to existing methods of hydrogen production, hydrocarbon conversion and organic compound oxidation. Many types of photocatalysts have been developed and tested for photocatalytic applications. However, most of them do not have notable activity in visible light region, which limits their practical applications. Development of photocatalysts, which can be activated by visible light provides a promising way forward to utilize both UV and visible portions of solar spectrum. In this thesis, two main methods to advance visible light driven photocatalysis, such as bandgap modification through doping and co-catalyst development, are investigated. The photocatalysts studied in this thesis included CdS and SrTiO3, which were extensively investigated and characterized. Rhodium doped strontium titanate was synthesized through different preparation methods. The synthesized samples have been investigated by various characterization techniques including XRD, TEM, STEM, XPS and UV-Vis spectroscopy. The effect of preparation conditions, such as doping concentration, calcination temperature and pH have been investigated and optimized. In addition, the photocatalytic activities for hydrogen production of the samples synthesized by different preparation methods were also studied. Among the preparation methods, polymerizable complex (PC) method was found to be the most effective synthesis method for SrTiO3: Rh. The samples prepared by PC method had higher photocatalytic activity as compared to that of samples synthesized by solid state reaction method and hydrothermal method. The reasons might be attributed to more effective doping and higher surface area. The results of this work suggest that PC method can also be applied to develop other perovskite materials for photocatalytic applications. Co-catalyst development for enhancement of photocatalytic hydrogen production is also described in this dissertation. Noble metal nanoparticles have been proved to be effective co-catalysts due to their unique physical and chemical properties. Au and Pt nanoparticles with different sizes were synthesized and deposited on CdS. Sub-nanometer Au and Pt were found to be promising co-catalysts for photocatalytic hydrogen production reaction. Specifically, sub-nm Au and sub-nm Pt nanoparticles were found to enhance the photocatalytic activity in hydrogen production of CdS by 35 and 15 times respectively. Other noble metal co-catalysts, such as Ru, Pd and Rh were also deposited on CdS and their photocatalytic activities were investigated. Additionally, a novel chamber for photocatalytic reactions was developed as a part of this dissertation. The reaction chamber has several unique features allowing different reactions and measurements. The reactor was proved to be suitable for future projects in photocatalysis such as photocatalytic CO2 conversion into hydrocarbons.

Catalytic Deoxydehydration of Carbohydrates and Polyols to Chemicals and Fuels

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

Nicholas, Kenneth M.

As the world's fossil fuel resources are being depleted and their costs increase, there is an urgent need to discover and develop new processes for the conversion of renewable, biomass resources into fuels and chemical feedstocks. Research and development in this area have been given high priority by both governmental agencies and industry. To increase the energy content and decrease the boiling points of biomass-derived carbohydrates and polyols to the useful liquid range it is necessary to chemically remove water (dehydrate) and, preferably, oxygen (deoxygenate/reduce). The poly-hydroxylic nature of carbohydrates is attractive for their use as functionalized chemical building blocks,more » but it presents a daunting challenge for their selective conversion to single product chemicals or fuels. The long term, practical objective of this project is to develop catalytic processes for the deoxydehydration (DODH) of biomass-derived carbohydrates and polyols to produce unsaturated alcohols and hydrocarbons of value as chemical feedstocks and fuels; DODH: polyol + reductant --(LMOx catalyst)--> unsaturate + oxidized reductant + H2O. Limited prior studies have established the viability of the DODH process with expensive phosphine reductants and rhenium-catalysts. Initial studies in the PI's laboratory have now demonstrated: 1) the moderately efficient conversion of glycols to olefins by the economical sulfite salts is catalyzed by MeReO3 and Z+ReO4-; 2) effective phosphine-based catalytic DODH of representative glycols to olefins by cheap LMoO2 complexes; and 3) computational studies (with K. Houk, UCLA) have identified several Mo-, W-, and V-oxo complexes that are likely to catalyze glycol DODH. Seeking practically useful DODH reactions of complex polyols and new understanding of the reactivity of polyoxo-metal species with biomass-oxygenates we will employ a two-pronged approach: 1) investigate experimentally the reactivity, both stoichiometric and catalytic, of polyoxo-complexes and practical reductants with representative polyols to establish structure/reactivity relationships and reaction mechanisms; and b) carry out parallel computational studies of these reactions and their mechanisms- both analytical and predictive. Our prioritized action plan is: (1) to optimize the catalytic efficiency, assess the substrate scope/selectivity, and address key mechanistic aspects of Re-catalyzed, sulfite-driven DODH reactions; (2) use the findings from (1), together with computational predictions, to discover new, effective non-precious metal catalysts for sulfite-driven DODH reactions; and 3) to initiate exploratory studies of CO- and H2-driven DODH. Successful execution of this research project will: 1) provide practical chemical processes for the conversion of biomass into useful chemicals and fuels: 2) bring fundamental new understanding of chemical reactions involving metal-oxo catalysts; and 3) provide educational and technical training of future energy scientists.« less

Plant hydrocarbon recovery process

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

Dzadzic, P.M.; Price, M.C.; Shih, C.J.

1982-01-26

A process for production and recovery of hydrocarbons from hydrocarbon-containing whole plants in a form suitable for use as chemical feedstocks or as hydrocarbon energy sources which process comprises: (A) pulverizing by grinding or chopping hydrocarbon-containing whole plants selected from the group consisting of euphorbiaceae, apocynaceae, asclepiadaceae, compositae, cactaceae and pinaceae families to a suitable particle size, (B) drying and preheating said particles in a reducing atmosphere under positive pressure (C) passing said particles through a thermal conversion zone containing a reducing atmosphere and with a residence time of 1 second to about 30 minutes at a temperature within themore » range of from about 200* C. To about 1000* C., (D) separately recovering the condensable vapors as liquids and the noncondensable gases in a condition suitable for use as chemical feedstocks or as hydrocarbon fuels.« less

An analytical study of nitrogen oxides and carbon monoxide emissions in hydrocarbon combustion with added nitrogen, preliminary results

NASA Technical Reports Server (NTRS)

Bittker, D. A.

1979-01-01

The effect of combustor operating conditions on the conversion of fuel-bound nitrogen (FBN) to nitrogen oxides NO sub x was analytically determined. The effect of FBN and of operating conditions on carbon monoxide (CO) formation was also studied. For these computations, the combustor was assumed to be a two stage, adiabatic, perfectly-stirred reactor. Propane-air was used as the combustible mixture and fuel-bound nitrogen was simulated by adding nitrogen atoms to the mixture. The oxidation of propane and formation of NO sub x and CO were modeled by a fifty-seven reaction chemical mechanism. The results for NO sub x and CO formation are given as functions of primary and secondary stage equivalence ratios and residence times.

A unifying picture of gas-phase formation and growth of PAH (Polycyclic Aromatic Hydrocarbons), soot, diamond and graphite

NASA Technical Reports Server (NTRS)

Frenklach, Michael

1990-01-01

A variety of seemingly different carbon formation processes -- polycyclic aromatic hydrocarbons and diamond in the interstellar medium, soot in hydrocarbon flames, graphite and diamond in plasma-assisted-chemical vapor deposition reactors -- may all have closely related underlying chemical reaction mechanisms. Two distinct mechanisms for gas-phase carbon growth are discussed. At high temperatures it proceeds via the formation of carbon clusters. At lower temperatures it follows a polymerization-type kinetic sequence of chemical reactions of acetylene addition to a radical, and reactivation of the resultant species through H-abstraction by a hydrogen atom.

Transition metal sulfide loaded catalyst

DOEpatents

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

1994-01-01

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

Estimation of hydrocarbon biodegradation rates in gasoline-contaminated sediment from measured respiration rates

USGS Publications Warehouse

Baker, R.J.; Baehr, A.L.; Lahvis, M.A.

2000-01-01

An open microcosm method for quantifying microbial respiration and estimating biodegradation rates of hydrocarbons in gasoline-contaminated sediment samples has been developed and validated. Stainless-steel bioreactors are filled with soil or sediment samples, and the vapor-phase composition (concentrations of oxygen (O2), nitrogen (N2), carbon dioxide (CO2), and selected hydrocarbons) is monitored over time. Replacement gas is added as the vapor sample is taken, and selection of the replacement gas composition facilitates real-time decision-making regarding environmental conditions within the bioreactor. This capability allows for maintenance of field conditions over time, which is not possible in closed microcosms. Reaction rates of CO2 and O2 are calculated from the vapor-phase composition time series. Rates of hydrocarbon biodegradation are either measured directly from the hydrocarbon mass balance, or estimated from CO2 and O2 reaction rates and assumed reaction stoichiometries. Open microcosm experiments using sediments spiked with toluene and p-xylene were conducted to validate the stoichiometric assumptions. Respiration rates calculated from O2 consumption and from CO2 production provide estimates of toluene and p- xylene degradation rates within about ??50% of measured values when complete mineralization stoichiometry is assumed. Measured values ranged from 851.1 to 965.1 g m-3 year-1 for toluene, and 407.2-942.3 g m-3 year-1 for p- xylene. Contaminated sediment samples from a gasoline-spill site were used in a second set of microcosm experiments. Here, reaction rates of O2 and CO2 were measured and used to estimate hydrocarbon respiration rates. Total hydrocarbon reaction rates ranged from 49.0 g m-3 year-1 in uncontaminated (background) to 1040.4 g m-3 year-1 for highly contaminated sediment, based on CO2 production data. These rate estimates were similar to those obtained independently from in situ CO2 vertical gradient and flux determinations at the field site. In these experiments, aerobic conditions were maintained in the microcosms by using air as the replacement gas, thus preserving the ambient aerobic environment of the subsurface near the capillary zone. This would not be possible with closed microcosms.

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

Underwood, R.P.

As part of the DOE-sponsored contract Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal-Derived Syngas'' experimental evaluations of the one-step synthesis of alternative fuels were carried out. The objective of this work was to develop novel processes for converting coal-derived syngas to fuels or fuel additives. Building on a technology base acquired during the development of the Liquid Phase Methanol (LPMEOH) process, this work focused on the development of slurry reactor based processes. The experimental investigations, which involved bench-scale reactor studies, focused primarily on three areas: (1) One-step, slurry-phase syngas conversion to hydrocarbons or methanol/hydrocarbonmore » mixtures using a mixture of methanol synthesis catalyst and methanol conversion catalyst in the same slurry reactor. (2) Slurry-phase conversion of syngas to mixed alcohols using various catalysts. (3) One-step, slurry-phase syngas conversion to mixed ethers using a mixture of mixed alcohols synthesis catalyst and dehydration catalyst in the same slurry reactor. The experimental results indicate that, of the three types of processes investigated, slurry phase conversion of syngas to mixed alcohols shows the most promise for further process development. Evaluations of various mixed alcohols catalysts show that a cesium-promoted Cu/ZnO/Al[sub 2]O[sub 3] methanol synthesis catalyst, developed in Air Products' laboratories, has the highest performance in terms of rate and selectivity for C[sub 2+]-alcohols. In fact, once-through conversion at industrially practical reaction conditions yielded a mixed alcohols product potentially suitable for direct gasoline blending. Moreover, an additional attractive aspect of this catalyst is its high selectivity for branched alcohols, potential precursors to iso-olefins for use in etherification.« less

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

Underwood, R.P.

As part of the DOE-sponsored contract ``Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal-Derived Syngas`` experimental evaluations of the one-step synthesis of alternative fuels were carried out. The objective of this work was to develop novel processes for converting coal-derived syngas to fuels or fuel additives. Building on a technology base acquired during the development of the Liquid Phase Methanol (LPMEOH) process, this work focused on the development of slurry reactor based processes. The experimental investigations, which involved bench-scale reactor studies, focused primarily on three areas: (1) One-step, slurry-phase syngas conversion to hydrocarbons or methanol/hydrocarbonmore » mixtures using a mixture of methanol synthesis catalyst and methanol conversion catalyst in the same slurry reactor. (2) Slurry-phase conversion of syngas to mixed alcohols using various catalysts. (3) One-step, slurry-phase syngas conversion to mixed ethers using a mixture of mixed alcohols synthesis catalyst and dehydration catalyst in the same slurry reactor. The experimental results indicate that, of the three types of processes investigated, slurry phase conversion of syngas to mixed alcohols shows the most promise for further process development. Evaluations of various mixed alcohols catalysts show that a cesium-promoted Cu/ZnO/Al{sub 2}O{sub 3} methanol synthesis catalyst, developed in Air Products` laboratories, has the highest performance in terms of rate and selectivity for C{sub 2+}-alcohols. In fact, once-through conversion at industrially practical reaction conditions yielded a mixed alcohols product potentially suitable for direct gasoline blending. Moreover, an additional attractive aspect of this catalyst is its high selectivity for branched alcohols, potential precursors to iso-olefins for use in etherification.« less

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

Davis, R.; Tao, L.; Scarlata, C.

This report describes one potential conversion process to hydrocarbon products by way of catalytic conversion of lignocellulosic-derived hydrolysate. This model leverages expertise established over time in biomass deconstruction and process integration research at NREL, while adding in new technology areas for sugar purification and catalysis. The overarching process design converts biomass to die die diesel- and naphtha-range fuels using dilute-acid pretreatment, enzymatic saccharification, purifications, and catalytic conversion focused on deoxygenating and oligomerizing biomass hydrolysates.

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

Schachtl, Eva; Yoo, Jong Suk; Gutiérrez, Oliver Y.

The reaction network and elementary steps of the hydrogenation of phenanthrene are explored on parent and Ni-promoted MoS2/c-Al2O3. Two pathways were identified, i.e., Path 1: Phenanthrene _ 9,10-dihydrophenanthrene (DiHPhe)?1,2,3,4,4a,9,10,10a-octahydro-phenanthrene (asymOHPhe), and Path 2: Phenanthrene ?1,2,3,4-tetrahydrophenanthrene (TetHPhe)?1,2,3,4,5,6,7,8-octahydrophenan threne. The steps TetHPhe?asymOHPhe (hydrogenation), and DiHPhe?TetHPhe (hydrogenationisomerization) become notable at phenanthrene conversions above 20%. The reaction preferentially proceeds via Path 1 (90% selectivity) on MoS2/Al2O3. Ni promotion (Ni/(Ni + Mo) molar ratio of 0.3 at the edges on MoS2) increases the hydrogenation activity per active edge twofold and leads to 50% selectivity to both pathways. The reaction orders in H2 vary from _0.8more » on MoS2/Al2O3 to _1.2 on Ni-MoS2/Al2O3, whereas the reaction orders in phenanthrene (_0.6) hardly depend on Ni promotion. The reaction orders in H2S are zero on MoS2/Al2O3 and slightly negative on Ni-MoS2/Al2O3. DFT calculations indicate that phenanthrene is preferentially adsorbed parallel to the basal planes, while H is located at the edges perpendicular to the basal planes. Theory also suggests that Ni atoms, incorporated preferentially on the S-edges, increase the stability of hydrogenated intermediates. Hydrogenation of phenanthrene proceeds through quasi-equilibrated adsorption of the reactants followed by consecutive addition of hydrogen pairs to the adsorbed hydrocarbon. The rate determining steps for the formation of DiHPhe and TetHPhe are the addition of the first and second hydrogen pair, respectively. The concentration of SH groups (activated H at the edges) increases with Ni promotion linearly correlating the rates of Path 1 and Path 2, albeit with different functions. The enhancing effect of Ni on Path 2 is attributed to accelerated hydrogen addition to adsorbed hydrocarbons without important changes in their coverages.« less

Using supercritical fluids to refine hydrocarbons

DOEpatents

Yarbro, Stephen Lee

2014-11-25

This is a method to reactively refine hydrocarbons, such as heavy oils with API gravities of less than 20.degree. and bitumen-like hydrocarbons with viscosities greater than 1000 cp at standard temperature and pressure using a selected fluid at supercritical conditions. The reaction portion of the method delivers lighter weight, more volatile hydrocarbons to an attached contacting device that operates in mixed subcritical or supercritical modes. This separates the reaction products into portions that are viable for use or sale without further conventional refining and hydro-processing techniques. This method produces valuable products with fewer processing steps, lower costs, increased worker safety due to less processing and handling, allow greater opportunity for new oil field development and subsequent positive economic impact, reduce related carbon dioxide, and wastes typical with conventional refineries.

Influence of Gas Feed Composition and Pressure on the Catalytic Conversion of CO2 to Hydrocarbons Using a Traditional Cobalt-Based Fischer-Tropsch Catalyst

DTIC Science & Technology

2009-06-25

this supply by supporting the development of synthetic hydrocarbon fuel from the vast natural resources, such as coal, shale , gas hydrates, and CO2 ...the ability to convert CO2 to hydrocarbons,13-19 the objective of this study was to change experimental conditions to improve the production...R.; Lewis, M. K.; Williams, F. W. Recovery of [ CO2 ]T from aqueous bicarbonate using a gas permeable membrane. NRL Memorandum Report 6180-08-9129, June

An improved light hydrocarbon analysis system. Interim report

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

Lamontagne, R.A.

1982-05-11

A system for extracting and measuring ambient levels of C1-C4 hydrocarbons and carbon monoxide (CO) in seawater is described. The analytical instrument is a gas chromatograph with flame ionization detectors that incorporates a catalytic conversion of CO to CH4 (methane). The samples are concentrated prior to introduction to the chromatographic system. The volatile hydrocarbons are extracted from the seawater by the use of a helium flow stream and concentrated on dry ice-acetone cold traps. Air samples can be processed in a similar way.

Hydrogenation of CO 2 to methanol: Importance of metal–oxide and metal–carbide interfaces in the activation of CO 2

DOE PAGES

Rodriguez, José A.; Liu, Ping; Stacchiola, Dario J.; ...

2015-09-30

In this study, the high thermochemical stability of CO 2 makes it very difficult to achieve the catalytic conversion of the molecule into alcohols or other hydrocarbon compounds, which can be used as fuels or the starting point for the generation of fine chemicals. Pure metals and bimetallic systems used for the CO 2 → CH 3OH conversion usually bind CO 2 too weakly and, thus, show low catalytic activity. Here, we discuss a series of recent studies that illustrate the advantages of metal–oxide and metal–carbide interfaces when aiming at the conversion of CO2 into methanol. CeO x/Cu(111), Cu/CeO x/TiOmore » 2(110), and Au/CeO x/TiO 2(110) exhibit an activity for the CO 2 → CH 3OH conversion that is 2–3 orders of magnitude higher than that of a benchmark Cu(111) catalyst. In the Cu–ceria and Au–ceria interfaces, the multifunctional combination of metal and oxide centers leads to complementary chemical properties that open active reaction pathways for methanol synthesis. Efficient catalysts are also generated after depositing Cu and Au on TiC(001). In these cases, strong metal–support interactions modify the electronic properties of the admetals and make them active for the binding of CO 2 and its subsequent transformation into CH 3OH at the metal–carbide interfaces.« less

A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

PubMed Central

Wu, Jingjie; Ma, Sichao; Sun, Jing; Gold, Jake I.; Tiwary, ChandraSekhar; Kim, Byoungsu; Zhu, Lingyang; Chopra, Nitin; Odeh, Ihab N.; Vajtai, Robert; Yu, Aaron Z.; Luo, Raymond; Lou, Jun; Ding, Guqiao; Kenis, Paul J. A.; Ajayan, Pulickel M.

2016-01-01

Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts. PMID:27958290

George A. Olah, Carbocation and Hydrocarbon Chemistry

Science.gov Websites

. Final Technical Report. [HF:BF{sub 2}/H{sub 2}] , DOE Technical Report, 1980 Superacid Catalyzed Coal Conversion Chemistry. 1st and 2nd Quarterly Technical Progress Reports, September 1, 1983-March 30, 1984 , DOE Technical Report, 1984 Superacid Catalyzed Coal Conversion Chemistry. Final Technical Report

Transition metal sulfide loaded catalyst

DOEpatents

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

1994-04-26

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

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.

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

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

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

1995-12-31

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

Heterogeneous reaction of SO2 with soot: The roles of relative humidity and surface composition of soot in surface sulfate formation

NASA Astrophysics Data System (ADS)

Zhao, Yan; Liu, Yongchun; Ma, Jinzhu; Ma, Qingxin; He, Hong

2017-03-01

The conversion of SO2 to sulfates on the surface of soot is still poorly understood. Soot samples with different fractions of unsaturated hydrocarbons and oxygen-containing groups were prepared by combusting n-hexane under well-controlled conditions. The heterogeneous reaction of SO2 with soot was investigated using in situ attenuated total internal reflection infrared (ATR-IR) spectroscopy, ion chromatography (IC) and a flow tube reactor at the ambient pressure and relative humidity (RH). Water promoted SO2 adsorption and sulfate formation at the RH range from 6% to 70%, while exceeded water condensed on soot was unfavorable for sulfate formation due to inhibition of SO2 adsorption when RH was higher than 80%. The surface composition of soot, which was governed by combustion conditions, also played an important role in the heterogeneous reaction of SO2 with soot. This effect was found to greatly depend on RH. At low RH of 6%, soot with the highest fuel/oxygen ratio of 0.162 exhibited a maximum uptake capacity for SO2 because it contained a large amount of aromatic Csbnd H groups, which acted as active sites for SO2 adsorption. At RH of 54%, soot produced with a fuel/oxygen ratio of 0.134 showed the highest reactivity toward SO2 because it contained appropriate amounts of aromatic Csbnd H groups and oxygen-containing groups, subsequently leading to the optimal surface concentrations of both SO2 and water. These results suggest that variation in the surface composition of soot from different sources and/or resulting from chemical aging in the atmosphere likely affects the conversion of SO2 to sulfates.

Formation of Alkenes via Degradation of tert-Alkyl Ethers and Alcohols by Aquincola tertiaricarbonis L108 and Methylibium spp. ▿†

PubMed Central

Schäfer, Franziska; Muzica, Liudmila; Schuster, Judith; Treuter, Naemi; Rosell, Mònica; Harms, Hauke; Müller, Roland H.; Rohwerder, Thore

2011-01-01

Bacterial degradation pathways of fuel oxygenates such as methyl tert-butyl and tert-amyl methyl ether (MTBE and TAME, respectively) have already been studied in some detail. However, many of the involved enzymes are still unknown, and possible side reactions have not yet been considered. In Aquincola tertiaricarbonis L108, Methylibium petroleiphilum PM1, and Methylibium sp. strain R8, we have now detected volatile hydrocarbons as by-products of the degradation of the tert-alkyl ether metabolites tert-butyl and tert-amyl alcohol (TBA and TAA, respectively). The alkene isobutene was formed only during TBA catabolism, while the beta and gamma isomers of isoamylene were produced only during TAA conversion. Both tert-alkyl alcohol degradation and alkene production were strictly oxygen dependent. However, the relative contribution of the dehydration reaction to total alcohol conversion increased with decreasing oxygen concentrations. In resting-cell experiments where the headspace oxygen content was adjusted to less than 2%, more than 50% of the TAA was converted to isoamylene. Isobutene formation from TBA was about 20-fold lower, reaching up to 4% alcohol turnover at low oxygen concentrations. It is likely that the putative tert-alkyl alcohol monooxygenase MdpJ, belonging to the Rieske nonheme mononuclear iron enzymes and found in all three strains tested, or an associated enzymatic step catalyzed the unusual elimination reaction. This was also supported by the detection of mdpJK genes in MTBE-degrading and isobutene-emitting enrichment cultures obtained from two treatment ponds operating at Leuna, Germany. The possible use of alkene formation as an easy-to-measure indicator of aerobic fuel oxygenate biodegradation in contaminated aquifers is discussed. PMID:21742915

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

NASA Astrophysics Data System (ADS)

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

2003-11-01

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

Improving Catalyst Efficiency in Bio-Based Hydrocarbon Fuels; NREL (National Renewable Energy Laboratory)

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

None

This article investigates upgrading biomass pyrolysis vapors to form hydrocarbon fuels and chemicals using catalysts with different concentrations of acid sites. It shows that greater separation of acid sites makes catalysts more efficient at producing hydrocarbon fuels and chemicals. The conversion of biomass into liquid transportation fuels has attracted significant attention because of depleting fossil fuel reserves and environmental concerns resulting from the use of fossil fuels. Biomass is a renewable resource, which is abundant worldwide and can potentially be exploited to produce transportation fuels that are less damaging to the environment. This renewable resource consists of cellulose (40–50%), hemicellulosemore » (25–35%), and lignin (16–33%) biopolymers in addition to smaller quantities of inorganic materials such as silica and alkali and alkaline earth metals (calcium and potassium). Fast pyrolysis is an attractive thermochemical technology for converting biomass into precursors for hydrocarbon fuels because it produces up to 75 wt% bio-oil,1 which can be upgraded to feedstocks and/or blendstocks for further refining to finished fuels. Bio-oil that has not been upgraded has limited applications because of the presence of oxygen-containing functional groups, derived from cellulose, hemicellulose and lignin, which gives rise to high acidity, high viscosity, low heating value, immiscibility with hydrocarbons and aging during storage. Ex situ catalytic vapor phase upgrading is a promising approach for improving the properties of bio-oil. The goal of this process is to reject oxygen and produce a bio-oil with improved properties for subsequent downstream conversion to hydrocarbons.« less

Computations and estimates of rate coefficients for hydrocarbon reactions of interest to the atmospheres of outer solar system

NASA Technical Reports Server (NTRS)

Laufer, A. H.; Gardner, E. P.; Kwok, T. L.; Yung, Y. L.

1983-01-01

The rate coefficients, including Arrhenius parameters, have been computed for a number of chemical reactions involving hydrocarbon species for which experimental data are not available and which are important in planetary atmospheric models. The techniques used to calculate the kinetic parameters include the Troe and semiempirical bond energy-bond order (BEBO) or bond strength-bond length (BSBL) methods.

High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

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

Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.

2016-12-01

High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group bymore » dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.« less

Effect of structural promoters on Fe-based Fischer-Tropsch synthesis of biomass derived syngas

Treesearch

Pratibha Sharma; Thomas Elder; Leslie H. Groom; James J. Spivey

2014-01-01

Biomass gasification and subsequent conversion of this syngas to liquid hydrocarbons using Fischer–Tropsch (F–T) synthesis is a promising source of hydrocarbon fuels. However, biomass-derived syngas is different from syngas obtained from other sources such as steam reforming of methane. Specifically the H2/CO ratio is less than 1/1 and the CO

MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction.

PubMed

Liu, Guoliang; Robertson, Alex W; Li, Molly Meng-Jung; Kuo, Winson C H; Darby, Matthew T; Muhieddine, Mohamad H; Lin, Yung-Chang; Suenaga, Kazu; Stamatakis, Michail; Warner, Jamie H; Tsang, Shik Chi Edman

2017-08-01

The conversion of oxygen-rich biomass into hydrocarbon fuels requires efficient hydrodeoxygenation catalysts during the upgrading process. However, traditionally prepared CoMoS 2 catalysts, although efficient for hydrodesulfurization, are not appropriate due to their poor activity, sulfur loss and rapid deactivation at elevated temperature. Here, we report the synthesis of MoS 2 monolayer sheets decorated with isolated Co atoms that bond covalently to sulfur vacancies on the basal planes that, when compared with conventionally prepared samples, exhibit superior activity, selectivity and stability for the hydrodeoxygenation of 4-methylphenol to toluene. This higher activity allows the reaction temperature to be reduced from the typically used 300 °C to 180 °C and thus allows the catalysis to proceed without sulfur loss and deactivation. Experimental analysis and density functional theory calculations reveal a large number of sites at the interface between the Co and Mo atoms on the MoS 2 basal surface and we ascribe the higher activity to the presence of sulfur vacancies that are created local to the observed Co-S-Mo interfacial sites.

MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction

NASA Astrophysics Data System (ADS)

Liu, Guoliang; Robertson, Alex W.; Li, Molly Meng-Jung; Kuo, Winson C. H.; Darby, Matthew T.; Muhieddine, Mohamad H.; Lin, Yung-Chang; Suenaga, Kazu; Stamatakis, Michail; Warner, Jamie H.; Tsang, Shik Chi Edman

2017-08-01

The conversion of oxygen-rich biomass into hydrocarbon fuels requires efficient hydrodeoxygenation catalysts during the upgrading process. However, traditionally prepared CoMoS2 catalysts, although efficient for hydrodesulfurization, are not appropriate due to their poor activity, sulfur loss and rapid deactivation at elevated temperature. Here, we report the synthesis of MoS2 monolayer sheets decorated with isolated Co atoms that bond covalently to sulfur vacancies on the basal planes that, when compared with conventionally prepared samples, exhibit superior activity, selectivity and stability for the hydrodeoxygenation of 4-methylphenol to toluene. This higher activity allows the reaction temperature to be reduced from the typically used 300 °C to 180 °C and thus allows the catalysis to proceed without sulfur loss and deactivation. Experimental analysis and density functional theory calculations reveal a large number of sites at the interface between the Co and Mo atoms on the MoS2 basal surface and we ascribe the higher activity to the presence of sulfur vacancies that are created local to the observed Co-S-Mo interfacial sites.

Oxidative coupling of methane using inorganic membrane reactor

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

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

1995-12-31

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

Mechanistic and kinetic studies on the OH-initiated atmospheric oxidation of fluoranthene.

PubMed

Dang, Juan; Shi, Xiangli; Zhang, Qingzhu; Hu, Jingtian; Chen, Jianmin; Wang, Wenxing

2014-08-15

The atmospheric oxidation of polycyclic aromatic hydrocarbons (PAHs) can generate toxic derivatives which contribute to the carcinogenic potential of particulate organic matter. In this work, the mechanism of the OH-initiated atmospheric oxidation of fluoranthene (Flu) was investigated by using high-accuracy molecular orbital calculations. All of the possible oxidation pathways were discussed, and the theoretical results were compared with the available experimental observation. The rate constants of the crucial elementary reactions were evaluated by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The main oxidation products are a range of ring-retaining and ring-opening chemicals containing fluoranthols, fluoranthones, fluoranthenequinones, nitro-fluoranthenes, dialdehydes and epoxides. The overall rate constant of the OH addition reaction is 1.72×10(-11) cm(3) molecule(-1) s(-1) at 298 K and 1 atm. The atmospheric lifetime of Flu determined by OH radicals is about 0.69 days. This work provides a comprehensive investigation of the OH-initiated oxidation of Flu and should help to clarify its atmospheric conversion. Copyright © 2014 Elsevier B.V. All rights reserved.

Technique for measuring gas conversion factors

NASA Technical Reports Server (NTRS)

Singh, J. J.; Sprinkle, D. R. (Inventor)

1985-01-01

A method for determining hydrocarbon conversion factors for a flowmeter. A mixture of air, O2 and C sub x H sub y is burned and the partial paressure of O2 in the resulting gas is forced to equal the partial pressure of O2 in air. The flowrate of O2 flowing into the mixture is measured by flowmeter and the flowrate of C sub x H sub y flowing into the mixture is measured by the flowmeter conversion factor is to be determined. These measured values are used to calculate the conversion factor.

MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds

DOE PAGES

Stavila, Vitalie; Parthasarathi, Ramakrishnan; Davis, Ryan W.; ...

2015-11-23

We demonstrate that metal–organic frameworks (MOFs) can catalyze hydrogenolysis of aryl ether bonds under mild conditions. Mg-IRMOF-74(I) and Mg-IRMOF-74(II) are stable under reducing conditions and can cleave phenyl ethers containing β-O-4, α-O-4, and 4-O-5 linkages to the corresponding hydrocarbons and phenols. Reaction occurs at 10 bar H 2 and 120 °C without added base. DFT-optimized structures and charge transfer analysis suggest that the MOF orients the substrate near Mg 2+ ions on the pore walls. Ti and Ni doping further increase conversions to as high as 82% with 96% selectivity for hydrogenolysis versus ring hydrogenation. Thus repeated cycling induces nomore » loss of activity, making this a promising route for mild aryl-ether bond scission.« less

Anaerobic Microbial Degradation of Hydrocarbons: From Enzymatic Reactions to the Environment.

PubMed

Rabus, Ralf; Boll, Matthias; Heider, Johann; Meckenstock, Rainer U; Buckel, Wolfgang; Einsle, Oliver; Ermler, Ulrich; Golding, Bernard T; Gunsalus, Robert P; Kroneck, Peter M H; Krüger, Martin; Lueders, Tillmann; Martins, Berta M; Musat, Florin; Richnow, Hans H; Schink, Bernhard; Seifert, Jana; Szaleniec, Maciej; Treude, Tina; Ullmann, G Matthias; Vogt, Carsten; von Bergen, Martin; Wilkes, Heinz

2016-01-01

Hydrocarbons are abundant in anoxic environments and pose biochemical challenges to their anaerobic degradation by microorganisms. Within the framework of the Priority Program 1319, investigations funded by the Deutsche Forschungsgemeinschaft on the anaerobic microbial degradation of hydrocarbons ranged from isolation and enrichment of hitherto unknown hydrocarbon-degrading anaerobic microorganisms, discovery of novel reactions, detailed studies of enzyme mechanisms and structures to process-oriented in situ studies. Selected highlights from this program are collected in this synopsis, with more detailed information provided by theme-focused reviews of the special topic issue on 'Anaerobic biodegradation of hydrocarbons' [this issue, pp. 1-244]. The interdisciplinary character of the program, involving microbiologists, biochemists, organic chemists and environmental scientists, is best exemplified by the studies on alkyl-/arylalkylsuccinate synthases. Here, research topics ranged from in-depth mechanistic studies of archetypical toluene-activating benzylsuccinate synthase, substrate-specific phylogenetic clustering of alkyl-/arylalkylsuccinate synthases (toluene plus xylenes, p-cymene, p-cresol, 2-methylnaphthalene, n-alkanes), stereochemical and co-metabolic insights into n-alkane-activating (methylalkyl)succinate synthases to the discovery of bacterial groups previously unknown to possess alkyl-/arylalkylsuccinate synthases by means of functional gene markers and in situ field studies enabled by state-of-the-art stable isotope probing and fractionation approaches. Other topics are Mo-cofactor-dependent dehydrogenases performing O2-independent hydroxylation of hydrocarbons and alkyl side chains (ethylbenzene, p-cymene, cholesterol, n-hexadecane), degradation of p-alkylated benzoates and toluenes, glycyl radical-bearing 4-hydroxyphenylacetate decarboxylase, novel types of carboxylation reactions (for acetophenone, acetone, and potentially also benzene and naphthalene), W-cofactor-containing enzymes for reductive dearomatization of benzoyl-CoA (class II benzoyl-CoA reductase) in obligate anaerobes and addition of water to acetylene, fermentative formation of cyclohexanecarboxylate from benzoate, and methanogenic degradation of hydrocarbons. © 2016 S. Karger AG, Basel.

Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2011-01-01

We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

Selective Conversion of Lignin-Derivable 4-Alkylguaiacols to 4-Alkylcyclohexanols over Noble and Non-Noble-Metal Catalysts

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

Schutyser, Wouter; Van den Bossche, Gil; Raaffels, Anton

2016-10-03

Recent lignin-first catalytic lignocellulosic biorefineries produce large quantities of two potential platform chemicals, 4-n-propylguaiacol (PG) and 4-n-propylsyringol. Because conversion into 4-n-propylcyclohexanol (PCol), a precursor for novel polymer building blocks, presents a promising valorization route, reductive demethoxylation of PG was examined here in the liquid-phase over three commercial hydrogenation catalysts, viz. 5 wt % Ru/C, 5 wt % Pd/C and 65 wt % Ni/SiO2-Al2O3, at elevated temperatures ranging from 200 to 300 degrees C under hydrogen atmosphere. Kinetic profiles suggest two parallel conversion pathways: Pathway I involves PG hydrogenation to 4-n-propyl-2-methoxycyclohexanol (PMCol), followed by its demethoxylation to PCol, whereas Pathway IImore » constitutes PG hydrodemethoxylation to 4-n-propylphenol (PPh), followed by its hydrogenation into PCol. The slowest step in the catalytic formation of PCol is the reductive methoxy removal from PMCol. Moreover, under the applied reaction conditions, PCol may react further into hydrocarbons. The following criteria are therefore essential to reach a high PCol yield: (i) catalytic pathway II is preferred as this route does not involve stable intermediates; (ii) reactivity of PMCol should be higher than that of PCol, and (iii) the overall carbon balance should be high. Both the catalyst type and the reaction conditions have a substantial impact on the PCol yield. Only the commercial Ni catalyst meets the three criteria, provided the reaction is performed at 250 degrees C in hexadecane. Additional advantages of this solvent choice are a high boiling point (low operational pressure in closed reactor systems), high solubility of PG and derived products, high thermal, reductive stability, and easy derivability from fatty biomass feedstock. This Ni catalyst also showed an excellent stability in recycling runs and is capable of converting highly concentrated (up to 20 wt %) PG in hexadecane. Ru and Pd on carbon showed a low PCol yield, as they are not conform the three criteria. Low hydrogen pressure favors Pathway II, resulting in a very high PCol yield of 85% at 10 bar. Catalytic conversion of guaiacol, 4-methyl- and 4-ethylguaiacol in comparable circumstances showed similarly high yields of the corresponding cyclohexanols.« less

Polycyclic aromatic hydrocarbons - Primitive pigment systems in the prebiotic environment

NASA Technical Reports Server (NTRS)

Deamer, D. W.

1992-01-01

The chemical evolution of meteoritic organics in the primitive earth is examined experimentally with attention given to the photochemical effects of hydrocarbon/water mixtures. Also addressed are the generation of amphiphilic products by photochemical reactions and the transduction of light energy into potentially useful forms. Polycyclic aromatic hydrocarbons (PAHs) absorb light and exist in carbonaceous chondrites; PAHs are therefore examined as primitive pigments by means of salt solutions with pyrene, fluoranthene, and pyrene derivatives with hexadecane. The hexadecane undergoes photochemical oxidation and yields long-chain amphiphiles with oxygen supplied by water, and acid pH shifts also occur. PAHs are also tested in lipid bilayer membranes to examine light-energy transduction. Protons are found to accumulate within the membrane-bounded volume to form proton gradients, and this reaction is theorized to be a good model of primitive photochemical reactions that related to the transduction of light energy into useable forms.

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.

Closed system Fischer-Tropsch synthesis over meteoritic iron, iron ore and nickel-iron alloy. [deuterium-carbon monoxide reaction catalysis

NASA Technical Reports Server (NTRS)

Nooner, D. W.; Gibert, J. M.; Gelpi, E.; Oro, J.

1976-01-01

Experiments were performed in which meteoritic iron, iron ore and nickel-iron alloy were used to catalyze (in Fischer-Tropsch synthesis) the reaction of deuterium and carbon monoxide in a closed vessel. Normal alkanes and alkenes and their monomethyl substituted isomers and aromatic hydrocarbons were synthesized. Iron oxide and oxidized-reduced Canyon Diablo used as Fischer-Tropsch catalysts were found to produce aromatic hydrocarbons in distributions having many of the features of those observed in carbonaceous chondrites, but only at temperatures and reaction times well above 300 C and 6-8 h.

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.

Process for preparing a chemical compound enriched in isotope content

DOEpatents

Michaels, Edward D.

1982-01-01

A process to prepare a chemical enriched in isotope content which includes: (a) A chemical exchange reaction between a first and second compound which yields an isotopically enriched first compound and an isotopically depleted second compound; (b) the removal of a portion of the first compound as product and the removal of a portion of the second compound as spent material; (c) the conversion of the remainder of the first compound to the second compound for reflux at the product end of the chemical exchange reaction region; (d) the conversion of the remainder of the second compound to the first compound for reflux at the spent material end of the chemical exchange region; and the cycling of the additional chemicals produced by one conversion reaction to the other conversion reaction, for consumption therein. One of the conversion reactions is an oxidation reaction, and the energy that it yields is used to drive the other conversion reaction, a reduction. The reduction reaction is carried out in a solid polymer electrolyte electrolytic reactor. The overall process is energy efficient and yields no waste by-products.

A comparison of flame ionization and ozone chemiluminescence for the determination of atmospheric hydrocarbons.

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

Marley, N. A.; Gaffney, J. S.; Environmental Research

A reactive hydrocarbon analyzer has been constructed on the basis of chemiluminescence reaction with ozone. This detector is designed to operate at varying temperatures which take advantage of the different rates of reaction of the hydrocarbon classes with ozone to yield a measure of their atmospheric reactivity. When operated at high temperatures (170 C), all hydrocarbons will give a chemiluminescence signal. Reported here is a direct comparison of the ozone chemiluminescent detector (operated at a temperature of 170 C) with a flame ionization detector. This comparison was accomplished by connecting a capillary gas chromatograph to each of the two detectorsmore » by means of a switching valve. Twenty-seven compounds representing alkanes, alkenes, aromatics, and oxygenated hydrocarbons (aldehydes, ketones, alcohols, and ethers) were studied. For the compounds studied, analytical sensitivities were 10-1000 times better for the chemiluminescence detector. The results of this comparison indicate that the response of the chemiluminescent detector at 170 C correlates with a total carbon detector (flame ionization detection) and that total response is a measure of total carbon in the sample. The chemiluminescent system will be very useful for gas chromatographic detection of atmospheric hydrocarbons, particularly of oxygenates in complex mixtures.« less

Hydrocarbons and energy from plants: Final report, 1984-1987

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

Calvin, M.; Otvos, J.; Taylor, S.E.

1988-08-01

Plant hydrocarbon (isoprenoid) production was investigated as an alternative source to fossil fuels. Because of their high triterpenoid (hydrocarbon) content of 4--8%, Euphorbia lathyris plants were used as a model system for this study. The structure of the E. lathyris triterpenoids was determined, and triterpenoid biosynthesis studied to better understand the metabolic regulation of isoprenoid production. Triterpenoid biosynthesis occurs in two distinct tissue types in E. lathyris plants: in the latex of the laticifer cells; and in the mesophyll cells of the leaf and stem. The latex has been fractionated by centrifugation, and it has been determined that the latermore » steps of isoprenoid biosynthesis, the conversion of mevalonic acid to the triterpenes, are compartmentized within a vacuole. Also identified was the conversion of hydroxymethyl glutaryl-CoA to mevalonic acid, catalyzed by the enzyme Hydroxymethyl glutaryl-CoA Reductase, as a key rate limiting step in isoprenoid biosynthesis. At least two isozymes of this enzyme, one in the latex and another in the leaf plastids, have been identified. Environmental stress has been applied to plants to study changes in carbon allocation. Salinity stress caused a large decrease in growth, smaller decreases in photosynthesis, resulting in a larger allocation of carbon to both hydrocarbon and sugar production. An increase in Hydroxymethyl glutaryl-CoA Reductase activity was also observed when isoprenoid production increased. Other species where also screened for the production of hydrogen rich products such as isoprenoids and glycerides, and their hydrocarbon composition was determined.« less

Model compound study of the pathways for aromatic hydrocarbon formation in soot.

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

Tomczyk, N. A.; Hunt, J. E.; Winans, R. E.

2002-04-29

To explore the mechanisms for formation of aromatic hydrocarbons as precursors to soot, a model system using combustion of biphenyl in a fuel rich flame is studied. The soots acquired at three different temperatures are solvent extracted and the extract characterized by both GCMS and high resolution mass spectrometry. A description of the NMR results for the whole soots has been published (1). The production of most products could be rationalized from the coupling of biphenyls and subsequent aromatic species and the addition of acetylenes to existing aromatic molecules. Early work by Badger on pyrolysis of hydrocarbons is used inmore » developing these schemes (2). The reaction schemes to produce larger aromatic hydrocarbons will be discussed. Richter and Howard have discussed in detail potential reaction mechanisms in the formation of aromatics as precursors to soot (3).« less

Method to monitor HC-SCR catalyst NOx reduction performance for lean exhaust applications

DOEpatents

Viola, Michael B [Macomb Township, MI; Schmieg, Steven J [Troy, MI; Sloane, Thompson M [Oxford, MI; Hilden, David L [Shelby Township, MI; Mulawa, Patricia A [Clinton Township, MI; Lee, Jong H [Rochester Hills, MI; Cheng, Shi-Wai S [Troy, MI

2012-05-29

A method for initiating a regeneration mode in selective catalytic reduction device utilizing hydrocarbons as a reductant includes monitoring a temperature within the aftertreatment system, monitoring a fuel dosing rate to the selective catalytic reduction device, monitoring an initial conversion efficiency, selecting a determined equation to estimate changes in a conversion efficiency of the selective catalytic reduction device based upon the monitored temperature and the monitored fuel dosing rate, estimating changes in the conversion efficiency based upon the determined equation and the initial conversion efficiency, and initiating a regeneration mode for the selective catalytic reduction device based upon the estimated changes in conversion efficiency.

The Effects of Sooting and Radiation on Droplet Combustion

NASA Technical Reports Server (NTRS)

Lee, Kyeong-Ook; Manzello, Samuel L.; Choi, Mun Young

1997-01-01

The burning of liquid hydrocarbon fuels accounts for a significant portion of global energy production. With predicted future increases in demand and limited reserves of hydrocarbon fuel, it is important to maximize the efficiency of all processes that involve conversion of fuel. With the exception of unwanted fires, most applications involve introduction of liquid fuels into an oxidizing environment in the form of sprays which are comprised of groups of individual droplets. Therefore, tremendous benefits can result from a better understanding of spray combustion processes. Yet, theoretical developments and experimental measurements of spray combustion remains a daunting task due to the complex coupling of a turbulent, two-phase flow with phase change and chemical reactions. However, it is recognized that individual droplet behavior (including ignition, evaporation and combustion) is a necessary component for laying the foundation for a better understanding of spray processes. Droplet combustion is also an ideal problem for gaining a better understanding of non-premixed flames. Under the idealized situation producing spherically-symmetric flames (produced under conditions of reduced natural and forced convection), it represents the simplest geometry in which to formulate and solve the governing equations of mass, species and heat transfer for a chemically reacting two phase flow with phase change. The importance of this topic has promoted extensive theoretical investigations for more than 40 years.

Influence of the Crystal Structure of Titanium Oxide on the Catalytic Activity of Rh/TiO2 in Steam Reforming of Propane at Low Temperature.

PubMed

Yu, Lin; Sato, Katsutoshi; Toriyama, Takaaki; Yamamoto, Tomokazu; Matsumura, Syo; Nagaoka, Katsutoshi

2018-06-21

Solid oxide fuel cells (SOFCs) with liquefied petroleum gas (LPG) reduce CO 2 emissions due to their high-energy-conversion efficiency. Although SOFCs can convert LPG directly, coking occurs easily by decomposition of hydrocarbons, including C-C bonds on the electrode of fuel cell stacks. It is therefore necessary to develop an active steam pre-reforming catalyst that eliminates the hydrocarbons at low temperature, in which waste heat of SOFCs is used. Herein, we show that the crystal structure of the TiO 2 that anchors Rh particles is crucial for catalytic activity of Rh/TiO 2 catalysts for propane pre-reforming. Our experimental results revealed that strong metal support interaction (SMSI) induced during H 2 pre-reduction were optimized over Rh/TiO 2 with a rutile structure; this catalyst catalyzed the reaction much more effectively than conventional Rh/γ-Al 2 O 3 . In contrast, the SMSI was too strong for Rh/TiO 2 with an anatase structure, and the surface of the Rh particles was therefore covered mostly with partially reduced TiO 2 . The result was very low activity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Defining a Materials Database for the Design of Copper Binary Alloy Catalysts for Electrochemical CO2 Conversion.

PubMed

Lee, Chan Woo; Yang, Ki Dong; Nam, Dae-Hyun; Jang, Jun Ho; Cho, Nam Heon; Im, Sang Won; Nam, Ki Tae

2018-01-24

While Cu electrodes are a versatile material in the electrochemical production of desired hydrocarbon fuels, Cu binary alloy electrodes are recently proposed to further tune reaction directionality and, more importantly, overcome the intrinsic limitation of scaling relations. Despite encouraging empirical demonstrations of various Cu-based metal alloy systems, the underlying principles of their outstanding performance are not fully addressed. In particular, possible phase segregation with concurrent composition changes, which is widely observed in the field of metallurgy, is not at all considered. Moreover, surface-exposed metals can easily form oxide species, which is another pivotal factor that determines overall catalytic properties. Here, the understanding of Cu binary alloy catalysts for CO 2 reduction and recent progress in this field are discussed. From the viewpoint of the thermodynamic stability of the alloy system and elemental mixing, possible microstructures and naturally generated surface oxide species are proposed. These basic principles of material science can help to predict and understand metal alloy structure and, moreover, act as an inspiration for the development of new binary alloy catalysts to further improve CO 2 conversion and, ultimately, achieve a carbon-neutral cycle. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct liquefaction proof-of-concept facility

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

Alfred G. Comolli; Peizheng Zhou; HTI Staff

2000-01-01

The main objective of the U.S. DOE, Office of Fossil Energy, is to ensure the US a secure energy supply at an affordable price. An integral part of this program was the demonstration of fully developed coal liquefaction processes that could be implemented if market and supply considerations so required, Demonstration of the technology, even if not commercialized, provides a security factor for the country if it is known that the coal to liquid processes are proven and readily available. Direct liquefaction breaks down and rearranges complex hydrocarbon molecules from coal, adds hydrogen, and cracks the large molecules to thosemore » in the fuel range, removes hetero-atoms and gives the liquids characteristics comparable to petroleum derived fuels. The current processes being scaled and demonstrated are based on two reactor stages that increase conversion efficiency and improve quality by providing the flexibility to adjust process conditions to accommodate favorable reactions. The first stage conditions promote hydrogenation and some oxygen, sulfur and nitrogen removal. The second stage hydrocracks and speeds the conversion to liquids while removing the remaining sulfur and nitrogen. A third hydrotreatment stage can be used to upgrade the liquids to clean specification fuels.« less

Precursor soot synthesis of fullerenes and nanotubes without formation of carbonaceous soot

DOEpatents

Reilly, Peter T. A.

2007-03-20

The present invention is a method for the synthesis of fullerenes and/or nanotubes from precursor soot without the formation of carbonaceous soot. The method comprises the pyrolysis of a hydrocarbon fuel source by heating the fuel source at a sufficient temperature to transform the fuel source to a condensed hydrocarbon. The condensed hydrocarbon is a reaction medium comprising precursor soot wherein hydrogen exchange occurs within the reaction medium to form reactive radicals which cause continuous rearrangement of the carbon skeletal structure of the condensed hydrocarbon. Then, inducing dehydrogenation of the precursor soot to form fullerenes and/or nanotubes free from the formation of carbonaceous soot by continued heating at the sufficient temperature and by regulating the carbon to hydrogen ratio within the reaction medium. The dehydrogenation process produces hydrogen gas as a by-product. The method of the present invention in another embodiment is also a continuous synthesis process having a continuous supply of the fuel source. The method of the present invention can also be a continuous cyclic synthesis process wherein the reaction medium is fed back into the system as a fuel source after extraction of the fullerenes and/or nanotube products. The method of the present invention is also a method for producing precursor soot in bulk quantity, then forming fullerenes and/or nanotubes from the precursor bulk.

Finely controlled multimetallic nanocluster catalysts for solvent-free aerobic oxidation of hydrocarbons

PubMed Central

Takahashi, Masaki; Koizumi, Hiromu; Chun, Wang-Jae; Kori, Makoto; Imaoka, Takane; Yamamoto, Kimihisa

2017-01-01

The catalytic activity of alloy nanoparticles depends on the particle size and composition ratio of different metals. Alloy nanoparticles composed of Pd, Pt, and Au are widely used as catalysts for oxidation reactions. The catalytic activities of Pt and Au nanoparticles in oxidation reactions are known to increase as the particle size decreases and to increase on the metal-metal interface of alloy nanoparticles. Therefore, multimetallic nanoclusters (MNCs) around 1 nm in diameter have potential as catalysts for oxidation reactions. However, there have been few reports describing the preparation of uniform alloy nanoclusters. We report the synthesis of finely controlled MNCs (around 1 nm) using a macromolecular template with coordination sites arranged in a gradient of basicity. We reveal that Cu-Pt-Au MNCs supported on graphitized mesoporous carbon show catalytic activity that is 24 times greater than that of a commercially available Pt catalyst for aerobic oxidation of hydrocarbons. In addition, solvent-free aerobic oxidation of hydrocarbons to ketones at room temperature, using small amounts of a radical initiator, was achieved as a heterogeneous catalytic reaction for the first time. PMID:28782020

Extraction of Carbon Dioxide and Hydrogen from Seawater and Hydrocarbon Production Therefrom

DTIC Science & Technology

2016-04-05

extracted from the acidified seawater. Optionally, the ion exchange reaction can be conducted under conditions which produce hydrogen as well as carbon dioxide. The carbon dioxide and hydrogen may be used to produce hydrocarbons.

Geochemical signatures of thermochemical sulfate reduction in controlled hydrous pyrolysis experiments

USGS Publications Warehouse

Zhang, T.; Ellis, G.S.; Walters, C.C.; Kelemen, S.R.; Wang, K.-s.; Tang, Y.

2008-01-01

A series of gold tube hydrous pyrolysis experiments was conducted in order to investigate the effect of thermochemical sulfate reduction (TSR) on gas generation, residual saturated hydrocarbon compositional alteration, and solid pyrobitumen formation. The intensity of TSR significantly depends on the H2O/MgSO4 mole ratio, the smaller the ratio, the stronger the oxidizing conditions. Under highly oxidizing conditions (MgSO4/hydrocarbon wt/wt 20/1 and hydrocarbon/H2O wt/wt 1/1), large amounts of H2S and CO2 are generated indicating that hydrocarbon oxidation coupled with sulfate reduction is the dominant reaction. Starting with a mixture of C21-C35 n-alkanes, these hydrocarbons are consumed totally at temperatures below the onset of hydrocarbon thermal cracking in the absence of TSR (400 ??C). Moreover, once the longer chain length hydrocarbons are oxidized, secondarily formed hydrocarbons, even methane, are oxidized to CO2. Using whole crude oils as the starting reactants, the TSR reaction dramatically lowers the stability of hydrocarbons leading to increases in gas dryness and gas/oil ratio. While their concentrations decrease, the relative distributions of n-alkanes do not change appreciably from the original composition, and consequently, are non-diagnostic for TSR. However, distinct molecular changes related to TSR are observed, Pr/n-C17 and Ph/n-C18 ratios decrease at a faster rate under TSR compared to thermal chemical alteration (TCA) alone. TSR promotes aromatization and the incorporation of sulfur and oxygen into hydrocarbons leading to a decrease in the saturate to aromatic ratio in the residual oil and in the generation of sulfur and oxygen rich pyrobitumen. These experimental findings could provide useful geochemical signatures to identify TSR in settings where TSR has occurred in natural systems. ?? 2008 Elsevier Ltd. All rights reserved.

Process for preparing a chemical compound enriched in isotope content. [nitrogen 15-enriched nitric acid

DOEpatents

Michaels, E.D.

1981-02-25

A process to prepare a chemical enriched in isotope content includes: a chemical exchange reaction between a first and second compound which yields an isotopically enriched first compound and an isotopically depleted second compound; the removal of a portion of the first compound as product and the removal of a portion of the second compound as spent material; the conversion of the remainder of the first compound to the second compound for reflux at the product end of the chemical exchange reaction region; the conversion of the remainder of the second compound to the first compound for reflux at the spent material end of the chemical exchange region; and the cycling of the additional chemicals produced by one conversion reaction to the other conversion reaction, for consumption therein. One of the conversion reactions is an oxidation reaction, and the energy that it yields is used to drive the other conversion reaction, a reduction. The reduction reaction is carried out in a solid polymer electrolyte electrolytic reactor. The overall process is energy efficient and yields no waste by-products. A particular embodiment of the process in the production of nitrogen-15-enriched nitric acid.

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.

Biomimetic catalytic system driven by electron transfer for selective oxygenation of hydrocarbon.

PubMed

Yang, Guanyu; Ma, Yinfa; Xu, Jie

2004-09-01

Hydrocarbon oxyfunctionalization is a crucial industrial process. Most metallic catalysts require higher temperatures and often show lower selectivities. One of the intellectual approaches is the mimicry for bio-oxidation. We have established a biomimetic system with a nonmetallic redox center, composed of anthraquinones, N-hydroxyphthalimide, and zeolite HY, for selective hydrocarbon oxygenation by molecular oxygen. Selectivity of 95.8% for acetophenone and 66.2% conversion were accomplished for oxygenation of ethylbenzene at temperatures as low as 80 degrees C. The redox cycle, driven by one-electron transfer and product orientation by Zeolite HY, opens up the possibility of mimicking bio-oxidation under mild conditions.

Methanol and ethanol conversion into hydrocarbons over H-ZSM-5 catalyst

NASA Astrophysics Data System (ADS)

Hamieh, S.; Canaff, C.; Tayeb, K. Ben; Tarighi, M.; Maury, S.; Vezin, H.; Pouilloux, Y.; Pinard, L.

2015-07-01

Ethanol and methanol are converted using H-ZSM-5 zeolite at 623 K and 3.0 MPa into identical hydrocarbons (paraffins, olefins and aromatics) and moreover with identical selectivities. The distribution of olefins as paraffins follows the Flory distribution with a growth probability of 0.53. Regardless of the alcohol, the catalyst lifetime and selectivity into hydrocarbons C3+ are high in spite of an important coke content. The coke that poisons the Brønsted acid sites without blocking their access is composed in part of radical polyalkylaromatics. The addition of hydroquinone, an inhibitor of radicals, to the feed, provokes an immediate catalyst deactivation.

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS: Application to Analysis of Experimentally Derived Hydrothermal Mineral-Catalyzed Organic Products

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.; Gibson, Everett K., Jr.

2012-01-01

We report results of experiments to measure the H isotope composition of organic acids and alcohols. These experiments make use of a pyroprobe interfaced with a GC and high temperature extraction furnace to make quantitative H isotope measurements. This work compliments our previous work that focused on the extraction and analysis of C isotopes from the same compounds [1]. Together with our carbon isotope analyses our experiments serve as a "proof of concept" for making C and H isotope measurements on more complex mixtures of organic compounds on mineral surfaces in abiotic hydrocarbon formation processes at elevated temperatures and pressures. Our motivation for undertaking this work stems from observations of methane detected within the Martian atmosphere [2-5], coupled with evidence showing extensive water-rock interaction during Mars history [6-8]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization [9,10]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [11-13]. Our H isotope measurements utilize an analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). This technique is designed to carry a split of the pyrolyzed GC-separated product to a Thermo DSQII quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

One step Pd(0)-catalyzed synthesis, X-ray analysis, and photophysical properties of cyclopent[hi]aceanthrylene: fullerene-like properties in a nonalternant cyclopentafused aromatic hydrocarbon.

PubMed

Dang, Hung; Levitus, Marcia; Garcia-Garibay, Miguel A

2002-01-09

A simple procedure for the synthesis of cyclopentafused polycyclic aromatic hydrocarbons (CP-PAH) with Pd(PPh(3))(2)Cl(2) catalyst has been applied to the one-pot palladium(0)-catalyzed coupling of 9,10-dibromoanthracene (1) with 2-methyl-3-butyn-2-ol. Reactions carried out in refluxing benzene in the presence of CuSO(4)/Al(2)O(3) yielded 9,10-dialkynylanthracene 2a, alkynyl aceanthrylene 2b, and 2,7-disubstituted cyclopent[hi]aceanthrylene 2c in 13%, 23%, and 19% purified yields, respectively, with total conversions of 80-90%. Sealed tube reactions without copper at 110 degrees C improved the yield of 2c up to >75%. Single-crystal X-ray analyses of 2a and 2c reveal a three-dimensional hydrogen bonding network, producing a unique crystal packing. The packing structure of 2b is dominated by pi-pi stacking interactions between two aceanthrylene molecules. CP-PAHs 2b and 2c have potentially interesting fullerene-like photophysics. While the UV-vis and fluorescence spectra of 2a (Phi(F) = 0.87) show the characteristic vibronic structure of anthracene, the UV-vis spectra of ruby-red aceanthrylene 2b and greenish-black cyclopent[hi]aceanthrylene 2c extend well into the visible range. Isomers 2b and 2c showed no detectable fluorescence emission. Unlike fullerenes, compounds 2b and 2c are poor singlet oxygen sensitizers with measured (1)O(2) quantum yields of 0.02 and 0.06, respectively. As expected from a simple Hückel analysis, 2c has relatively low two-electron reduction potentials as determined by cyclic voltammetry.

Is Photolytic Production a Viable Source of HCN and HNC in Astrophysical Environments? A Laboratory-based Feasibility Study of Methyl Cyanoformate

NASA Astrophysics Data System (ADS)

Wilhelm, Michael J.; Martínez-Núñez, Emilio; González-Vázquez, Jesús; Vázquez, Saulo A.; Smith, Jonathan M.; Dai, Hai-Lung

2017-11-01

Motivated by the possibility that cyano-containing hydrocarbons may act as photolytic sources for HCN and HNC in astrophysical environments, we conducted a combined experimental and theoretical investigation of the 193 nm photolysis of the cyano-ester, methyl cyanoformate (MCF). Experimentally, nanosecond time-resolved infrared emission spectroscopy was used to detect the emission from nascent products generated in the photolysis reaction. The time-resolved spectra were analyzed using a recently developed spectral reconstruction analysis, which revealed spectral bands assignable to HCN and HNC. Fitting of the emission band shape and intensity allowed determination of the photolysis quantum yields of HCN, HNC, and {CN}({A}2{{{\\Pi }}}1) and an HNC/HCN ratio of ˜0.076 ± 0.059. Additionally, multiconfiguration self-consistent field calculations were used to characterize photoexcitation-induced reactions in the ground and four lowest singlet excited states of MCF. At 193 nm excitation, dissociation is predicted to occur predominantly on the repulsive S 2 state, with minor pathways via internal conversion from S 2 to highly excited ground state. An automated transition-state search algorithm was employed to identify the corresponding ground-state dissociation channels, and Rice-Ramsperger-Kassel-Marcus and Kinetic Monte Carlo simulations were used to calculate the associated branching ratios. The proposed mechanisms were validated using the experimentally measured and quasi-classical trajectory-deduced nascent internal energy distributions of HCN and HNC. This work, along with previous studies, illustrates the propensity for cyano-containing hydrocarbons to act as photolytic sources for astrophysical HCN and HNC and may help explain the observed overabundance of HNC in astrophysical environments.

Catalytic Upgrading of Biomass Pyrolysis Oxygenates with Vacuum Gas Oil Using a Davison Circulating Riser Reactor

DOE PAGES

Jarvis, Mark W.; Olstad, Jessica; Parent, Yves; ...

2018-01-02

We investigate and quantitate the changes in hydrocarbon product composition while evaluating the performance and operability of the National Renewable Energy Laboratory's Davison Circulating Riser (DCR) reactor system when biomass model compounds are cofed with traditional fluid catalyst cracking (FCC) feeds and catalyst: vacuum gas oil (VGO) and equilibrium zeolite catalyst (E-Cat). Three compounds (acetic acid, guaiacol, and sorbitan monooleate) were selected to represent the major classes of oxygenates present in biomass pyrolysis vapors. These vapors can contain 30-50% oxygen as oxygenates, which create conversion complications (increased reactivity and coking) when integrating biomass vapors and liquids into fuel and chemicalmore » processes long dominated by petroleum feedstocks. We used these model compounds to determine the appropriate conditions for coprocessing with petroleum and ultimately pure pyrolysis vapors only as compared with standard baseline conditions obtained with VGO and E-Cat only in the DCR. Model compound addition decreased the DCR catalyst circulation rate, which controls reactor temperature and measures reaction heat demand, while increasing catalyst coking rates. Liquid product analyses included 2-dimensional gas chromatography time-of-flight mass spectroscopy (2D GCxGC TOFS), simulated distillation (SIM DIST), 13C NMR, and carbonyl content. Aggregated results indicated that the model compounds were converted during reaction, and despite functional group differences, product distributions for each model compound were very similar. In addition, we determined that adding model compounds to the VGO feed did not significantly affect the DCR's operability or performance. Future work will assess catalytic upgrading of biomass pyrolysis vapor to fungible hydrocarbon products using upgrading catalysts currently being developed at NREL and at Johnson Matthey.« less

Catalytic Upgrading of Biomass Pyrolysis Oxygenates with Vacuum Gas Oil Using a Davison Circulating Riser Reactor

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

Jarvis, Mark W.; Olstad, Jessica; Parent, Yves

We investigate and quantitate the changes in hydrocarbon product composition while evaluating the performance and operability of the National Renewable Energy Laboratory's Davison Circulating Riser (DCR) reactor system when biomass model compounds are cofed with traditional fluid catalyst cracking (FCC) feeds and catalyst: vacuum gas oil (VGO) and equilibrium zeolite catalyst (E-Cat). Three compounds (acetic acid, guaiacol, and sorbitan monooleate) were selected to represent the major classes of oxygenates present in biomass pyrolysis vapors. These vapors can contain 30-50% oxygen as oxygenates, which create conversion complications (increased reactivity and coking) when integrating biomass vapors and liquids into fuel and chemicalmore » processes long dominated by petroleum feedstocks. We used these model compounds to determine the appropriate conditions for coprocessing with petroleum and ultimately pure pyrolysis vapors only as compared with standard baseline conditions obtained with VGO and E-Cat only in the DCR. Model compound addition decreased the DCR catalyst circulation rate, which controls reactor temperature and measures reaction heat demand, while increasing catalyst coking rates. Liquid product analyses included 2-dimensional gas chromatography time-of-flight mass spectroscopy (2D GCxGC TOFS), simulated distillation (SIM DIST), 13C NMR, and carbonyl content. Aggregated results indicated that the model compounds were converted during reaction, and despite functional group differences, product distributions for each model compound were very similar. In addition, we determined that adding model compounds to the VGO feed did not significantly affect the DCR's operability or performance. Future work will assess catalytic upgrading of biomass pyrolysis vapor to fungible hydrocarbon products using upgrading catalysts currently being developed at NREL and at Johnson Matthey.« less

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

PubMed

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

2013-08-20

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

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

Schmidt, Joel E.; Poplawsky, Jonathan D.; Mazumder, Baishakhi

Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub-nm length scale in a single zeolite ZSM-5 crystal, which has been partially deactivated by the methanol-to-hydrocarbons reaction using 13C-labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30–60 13C atoms. These clusters correlate with local increases in Brønsted acid sitemore » density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. Here, this nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation.« less

Upgrading producer gas quality from rubber wood gasification in a radio frequency tar thermocatalytic treatment reactor.

PubMed

Anis, Samsudin; Zainal, Z A

2013-12-01

This study focused on improving the producer gas quality using radio frequency (RF) tar thermocatalytic treatment reactor. The producer gas containing tar, particles and water was directly passed at a particular flow rate into the RF reactor at various temperatures for catalytic and thermal treatments. Thermal treatment generates higher heating value of 5.76 MJ Nm(-3) at 1200°C. Catalytic treatments using both dolomite and Y-zeolite provide high tar and particles conversion efficiencies of about 97% on average. The result also showed that light poly-aromatic hydrocarbons especially naphthalene and aromatic compounds particularly benzene and toluene were still found even at higher reaction temperatures. Low energy intensive RF tar thermocatalytic treatment was found to be effective for upgrading the producer gas quality to meet the end user requirements and increasing its energy content. Copyright © 2013 Elsevier Ltd. All rights reserved.

Separation of catalyst from Fischer-Tropsch slurry

DOEpatents

White, Curt M.; Quiring, Michael S.; Jensen, Karen L.; Hickey, Richard F.; Gillham, Larry D.

1998-10-27

In a catalytic process for converting synthesis gas including hydrogen and carbon monoxide to hydrocarbons and oxygenates by a slurry Fischer-Tropsch synthesis, the wax product along with dispersed catalyst is removed from the slurry and purified by removing substantially all of the catalyst prior to upgrading the wax and returning a portion to the Fischer-Tropsch reaction. Separation of the catalyst particles from the wax product is accomplished by dense gas and/or liquid extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic in nature. The purified catalyst free wax product can be subsequently upgraded by various methods such as hydrogenation, isomerization, hydrocracking, conversion to gasoline and other products over ZSM-5 aluminosilicate zeolite, etc. The catalyst particles are returned to the Fischer-Tropsch Reactor by slurring them with a wax fraction of appropriate molecular weight, boiling point and viscosity to avoid reactor gelation.

Catalytic dehydroaromatization of n-alkanes by pincer-ligated iridium complexes

NASA Astrophysics Data System (ADS)

Ahuja, Ritu; Punji, Benudhar; Findlater, Michael; Supplee, Carolyn; Schinski, William; Brookhart, Maurice; Goldman, Alan S.

2011-02-01

Aromatic hydrocarbons are among the most important building blocks in the chemical industry. Benzene, toluene and xylenes are obtained from the high temperature thermolysis of alkanes. Higher alkylaromatics are generally derived from arene-olefin coupling, which gives branched products—that is, secondary alkyl arenes—with olefins higher than ethylene. The dehydrogenation of acyclic alkanes to give alkylaromatics can be achieved using heterogeneous catalysts at high temperatures, but with low yields and low selectivity. We present here the first catalytic conversion of n-alkanes to alkylaromatics using homogeneous or molecular catalysts—specifically ‘pincer’-ligated iridium complexes—and olefinic hydrogen acceptors. For example, the reaction of n-octane affords up to 86% yield of aromatic product, primarily o-xylene and secondarily ethylbenzene. In the case of n-decane and n-dodecane, the resulting alkylarenes are exclusively unbranched (that is, n-alkyl-substituted), with selectivity for the corresponding o-(n-alkyl)toluene.

Autogenic reaction synthesis of photocatalysts for solar fuel generation

DOEpatents

Ingram, Brian J.; Pol, Vilas G.; Cronauer, Donald C.; Ramanathan, Muruganathan

2016-04-19

In one preferred embodiment, a photocatalyst for conversion of carbon dioxide and water to a hydrocarbon and oxygen comprises at least one nanoparticulate metal or metal oxide material that is substantially free of a carbon coating, prepared by heating a metal-containing precursor compound in a sealed reactor under a pressure autogenically generated by dissociation of the precursor material in the sealed reactor at a temperature of at least about 600.degree. C. to form a nanoparticulate carbon-coated metal or metal oxide material, and subsequently substantially removing the carbon coating. The precursor material comprises a solid, solvent-free salt comprising a metal ion and at least one thermally decomposable carbon- and oxygen-containing counter-ion, and the metal of the salt is selected from the group consisting of Mn, Ti, Sn, V, Fe, Zn, Zr, Mo, Nb, W, Eu, La, Ce, In, and Si.

Identification of persulfate oxidation products of polycyclic aromatic hydrocarbon during remediation of contaminated soil

EPA Science Inventory

The extent of PAH transformation, the formation and transformation of reaction byproducts during persulfate oxidation of polycyclic aromatic hydrocarbons (PAHs) in coking plant soil was investigated. Pre-oxidation analyses indicated that oxygen-containing PAHs (oxy-PAHs) existed ...

Fuel-rich, catalytic reaction experimental results

NASA Technical Reports Server (NTRS)

Rollbuhler, R. James

1991-01-01

Future aeropropulsion gas turbine combustion requirements call for operating at very high inlet temperatures, pressures, and large temperature rises. At the same time, the combustion process is to have minimum pollution effects on the environment. Aircraft gas turbine engines utilize liquid hydrocarbon fuels which are difficult to uniformly atomize and mix with combustion air. An approach for minimizing fuel related problems is to transform the liquid fuel into gaseous form prior to the completion of the combustion process. Experimentally obtained results are presented for vaporizing and partially oxidizing a liquid hydrocarbon fuel into burnable gaseous components. The presented experimental data show that 1200 to 1300 K reaction product gas, rich in hydrogen, carbon monoxide, and light-end hydrocarbons, is formed when flowing 0.3 to 0.6 fuel to air mixes through a catalyst reactor. The reaction temperatures are kept low enough that nitrogen oxides and carbon particles (soot) do not form. Results are reported for tests using different catalyst types and configurations, mass flowrates, input temperatures, and fuel to air ratios.

Pyrolytic conversion of plastic and rubber waste to hydrocarbons with basic salt catalysts

DOEpatents

Wingfield, Jr., Robert C.; Braslaw, Jacob; Gealer, Roy L.

1985-01-01

The invention relates to a process for improving the pyrolytic conversion of waste selected from rubber and plastic to low molecular weight olefinic materials by employing basis salt catalysts in the waste mixture. The salts comprise alkali or alkaline earth compounds, particularly sodium carbonate, in an amount of greater than about 1 weight percent based on the waste feed.

A Detailed Chemical Kinetic Model for TNT

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

Pitz, W J; Westbrook, C K

2005-01-13

A detailed chemical kinetic mechanism for 2,4,6-tri-nitrotoluene (TNT) has been developed to explore problems of explosive performance and soot formation during the destruction of munitions. The TNT mechanism treats only gas-phase reactions. Reactions for the decomposition of TNT and for the consumption of intermediate products formed from TNT are assembled based on information from the literature and on current understanding of aromatic chemistry. Thermodynamic properties of intermediate and radical species are estimated by group additivity. Reaction paths are developed based on similar paths for aromatic hydrocarbons. Reaction-rate constant expressions are estimated from the literature and from analogous reactions where themore » rate constants are available. The detailed reaction mechanism for TNT is added to existing reaction mechanisms for RDX and for hydrocarbons. Computed results show the effect of oxygen concentration on the amount of soot precursors that are formed in the combustion of RDX and TNT mixtures in N{sub 2}/O{sub 2} mixtures.« less

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

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

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

Catalysts and process for liquid hydrocarbon fuel production

DOEpatents

White, Mark G.; Ranaweera, Samantha A.; Henry, William P.

2016-08-02

The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality distillates, gasoline components, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel supported bimetallic ion complex catalyst for conversion, and provides methods of preparing such novel catalysts and use of the novel catalysts in the process and system of the invention.

Studies of the effect of selected nondonor solvents on coal liquefaction yields

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

Jolley, R. L.; Rodgers, B. R.; Benjamin, B. M.

The objective of this research program was to evaluate the effectiveness of selected nondonor solvents (i.e., solvents that are not generally considered to have hydrogen available for hydrogenolysis reactions) for the solubilization of coals. Principal criteria for selection of candidate solvents were that the compound should be representative of a major chemical class, should be present in reasonable concentration in coal liquid products, and should have the potential to participate in hydrogen redistribution reactions. Naphthalene, phenanthrene, pyrene, carbazole, phenanthridine, quinoline, 1-naphthol, and diphenyl ether were evaluated to determine their effect on coal liquefaction yields and were compared with phenol andmore » two high-quality process solvents, Wilsonville SRC-I recycle solvent and Lummus ITSL heavy oil solvent. The high conversion efficacy of 1-naphthol may be attributed to its condensation to binaphthol and the consequent availability of hydrogen. The effectiveness of both the nitrogen heterocycles and the polycyclic aromatic hydrocarbon (PAH) compounds may be due to their polycyclic aromatic nature (i.e., possible hydrogen shuttling or transfer agents) and their physical solvent properties. The relative effectiveness for coal conversion of the Lummus ITSL heavy oil solvent as compared with the Wilsonville SRC-I process solvent may be attributed to the much higher concentration of 3-, 4-, and 5-ring PAH and hydroaromatic constituents in Lummus solvent. The chemistry of coal liquefaction and the development of recycle, hydrogen donor, and nondonor solvents are reviewed. The experimental methodology for tubing-bomb tests is outlined, and experimental problem areas are discussed.« less

Catalytic two-stage coal hydrogenation process using extinction recycle of heavy liquid fraction

DOEpatents

MacArthur, J.B.; Comolli, A.G.; McLean, J.B.

1989-10-17

A process is described for catalytic two-stage hydrogenation and liquefaction of coal with selective extinction recycle of all heavy liquid fractions boiling above a distillation cut point of about 600--750 F to produce increased yields of low-boiling hydrocarbon liquid and gas products. In the process, the particulate coal feed is slurried with a process-derived liquid solvent normally boiling above about 650 F and fed into a first stage catalytic reaction zone operated at conditions which promote controlled rate liquefaction of the coal, while simultaneously hydrogenating the hydrocarbon recycle oils. The first stage reactor is maintained at 710--800 F temperature, 1,000--4,000 psig hydrogen partial pressure, and 10-90 lb/hr per ft[sup 3] catalyst space velocity. Partially hydrogenated material withdrawn from the first stage reaction zone is passed directly to the second stage catalytic reaction zone maintained at 760--860 F temperature for further hydrogenation and hydroconversion reactions. A 600--750 F[sup +] fraction containing 0--20 W % unreacted coal and ash solids is recycled to the coal slurrying step. If desired, the cut point lower boiling fraction can be further catalytically hydrotreated. By this process, the coal feed is successively catalytically hydrogenated and hydroconverted at selected conditions, to provide significantly increased yields of desirable low-boiling hydrocarbon liquid products and minimal production of hydrocarbon gases, and no net production of undesirable heavy oils and residuum materials. 2 figs.

Catalytic two-stage coal hydrogenation process using extinction recycle of heavy liquid fraction

DOEpatents

MacArthur, James B.; Comolli, Alfred G.; McLean, Joseph B.

1989-01-01

A process for catalytic two-stage hydrogenation and liquefaction of coal with selective extinction recycle of all heavy liquid fractions boiling above a distillation cut point of about 600.degree.-750.degree. F. to produce increased yields of low-boiling hydrocarbon liquid and gas products. In the process, the particulate coal feed is slurried with a process-derived liquid solvent normally boiling above about 650.degree. F. and fed into a first stage catalytic reaction zone operated at conditions which promote controlled rate liquefaction of the coal, while simultaneously hydrogenating the hydrocarbon recycle oils. The first stage reactor is maintained at 710.degree.-800.degree. F. temperature, 1000-4000 psig hydrogen partial pressure, and 10-90 lb/hr per ft.sup.3 catalyst space velocity. Partially hydrogenated material withdrawn from the first stage reaction zone is passed directly to the second stage catalytic reaction zone maintained at 760.degree.-860.degree. F. temperature for further hydrogenation and hydroconversion reactions. A 600.degree.-750.degree. F..sup.+ fraction containing 0-20 W % unreacted coal and ash solids is recycled to the coal slurrying step. If desired, the cut point lower boiling fraction can be further catalytically hydrotreated. By this process, the coal feed is successively catalytically hydrogenated and hydroconverted at selected conditions, to provide significantly increased yields of desirable low-boiling hydrocarbon liquid products and minimal production of hydrocarbon gases, and no net production of undesirable heavy oils and residuum materials.

Novel Fischer-Tropsch catalysts. [DOE patent

DOEpatents

Vollhardt, K.P.C.; Perkins, P.

Novel compounds are described which are used as improved Fischer-Tropsch catalysts particularly for the conversion of CO + H/sub 2/ to gaseous and liquid hydrocarbons at milder conditions than with prior catalysts.

Contribution of first- versus second-generation products to secondary organic aerosols formed in the oxidation of biogenic hydrocarbons.

PubMed

Ng, Nga L; Kroll, Jesse H; Keywood, Melita D; Bahreini, Roya; Varutbangkul, Varuntida; Flagan, Richard C; Seinfeld, John H; Lee, Anita; Goldstein, Allen H

2006-04-01

Biogenic hydrocarbons emitted by vegetation are important contributors to secondary organic aerosol (SOA), but the aerosol formation mechanisms are incompletely understood. In this study, the formation of aerosols and gas-phase products from the ozonolysis and photooxidation of a series of biogenic hydrocarbons (isoprene, 8 monoterpenes, 4 sesquiterpenes, and 3 oxygenated terpenes) are examined. By comparing aerosol growth (measured by Differential Mobility Analyzers, DMAs) and gas-phase concentrations (monitored by a Proton Transfer Reaction Mass Spectrometer, PTR-MS), we study the general mechanisms of SOA formation. Aerosol growth data are presented in terms of a "growth curve", a plot of aerosol mass formed versus the amount of hydrocarbon reacted. From the shapes of the growth curves, it is found that all the hydrocarbons studied can be classified into two groups based entirely on the number of double bonds of the hydrocarbon, regardless of the reaction systems (ozonolysis or photooxidation) and the types of hydrocarbons studied: compounds with only one double bond and compounds with more than one double bond. For compounds with only one double bond, the first oxidation step is rate-limiting, and aerosols are formed mainly from low volatility first-generation oxidation products; whereas for compounds with more than one double bond, the second oxidation step may also be rate-limiting and second-generation products contribute substantially to SOA growth. This behavior is characterized by a vertical section in the growth curve, in which continued aerosol growth is observed even after all the parent hydrocarbon is consumed.

Comparative analysis of metagenomes from three methanogenic hydrocarbon-degrading enrichment cultures with 41 environmental samples.

PubMed

Tan, Boonfei; Fowler, S Jane; Abu Laban, Nidal; Dong, Xiaoli; Sensen, Christoph W; Foght, Julia; Gieg, Lisa M

2015-09-01

Methanogenic hydrocarbon metabolism is a key process in subsurface oil reservoirs and hydrocarbon-contaminated environments and thus warrants greater understanding to improve current technologies for fossil fuel extraction and bioremediation. In this study, three hydrocarbon-degrading methanogenic cultures established from two geographically distinct environments and incubated with different hydrocarbon substrates (added as single hydrocarbons or as mixtures) were subjected to metagenomic and 16S rRNA gene pyrosequencing to test whether these differences affect the genetic potential and composition of the communities. Enrichment of different putative hydrocarbon-degrading bacteria in each culture appeared to be substrate dependent, though all cultures contained both acetate- and H2-utilizing methanogens. Despite differing hydrocarbon substrates and inoculum sources, all three cultures harbored genes for hydrocarbon activation by fumarate addition (bssA, assA, nmsA) and carboxylation (abcA, ancA), along with those for associated downstream pathways (bbs, bcr, bam), though the cultures incubated with hydrocarbon mixtures contained a broader diversity of fumarate addition genes. A comparative metagenomic analysis of the three cultures showed that they were functionally redundant despite their enrichment backgrounds, sharing multiple features associated with syntrophic hydrocarbon conversion to methane. In addition, a comparative analysis of the culture metagenomes with those of 41 environmental samples (containing varying proportions of methanogens) showed that the three cultures were functionally most similar to each other but distinct from other environments, including hydrocarbon-impacted environments (for example, oil sands tailings ponds and oil-affected marine sediments). This study provides a basis for understanding key functions and environmental selection in methanogenic hydrocarbon-associated communities.

Sustainable production of green feed from carbon dioxide and hydrogen.

PubMed

Landau, Miron V; Vidruk, Roxana; Herskowitz, Moti

2014-03-01

Carbon dioxide hydrogenation to form hydrocarbons was conducted on two iron-based catalysts, prepared according to procedures described in the literature, and on a new iron spinel catalyst. The CO2 conversion measured in a packed-bed reactor was limited to about 60% because of excessive amounts of water produced in this process. Switching to a system of three packed-bed reactors in series with interim removal of water and condensed hydrocarbons increased CO2 conversion to as much as 89%. The pure spinel catalyst displayed a significantly higher activity and selectivity than those of the other iron catalysts. This process produces a product called green feed, which is similar in composition to the product of a high-temperature, iron-based Fischer–Tropsch process from syngas. The green feed can be readily converted into renewable fuels by well-established technologies.

FTIR Study of Comustion Species in Several Regions of a Candle Flame

NASA Astrophysics Data System (ADS)

White, Allen R.

2013-06-01

The complex chemical structure of the fuel in a candle flame, parafin, is broken down into smaller hydrocarbons in the dark region just above the candle wick during combustion. This creates fuel-rich, fuel-lean, hydrocarbon reaction, and combustion product regions in the flame during combustion that are spectroscopically rich, particularly in the infrared. IR emissions were measured for each reaction region via collection optics focused into an FTIR and used to identify IR active species present in that region and, when possible, temperature of the sampling region. The results of the measurements are useful for combustion reaction modeling as well as for future validation of mass spectroscopy sampling systems.

Fast co-pyrolysis of waste newspaper with high-density polyethylene for high yields of alcohols and hydrocarbons.

PubMed

Chen, Weimin; Shi, Shukai; Chen, Minzhi; Zhou, Xiaoyan

2017-09-01

Waste newspaper (WP) was first co-pyrolyzed with high-density polyethylene (HDPE) using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) to enhance the yields of alcohols and hydrocarbons. The effects of WP: HDPE feed ratio (100:0, 75:25, 50:50, 25:75, 0:100) and temperature (500-800°C) on products distribution were investigated and the interaction mechanism during co-pyrolysis was also proposed. Maximum yields of alcohols and hydrocarbons reached 85.88% (feed ratio 50:50wt.%, 600°C). Hydrogen supplements and deoxidation by HDPE and subsequently fragments recombination result in the conversion of aldehydes and ketones into branched hydrocarbons. Radicals from WP degradation favor the secondary crack for HDPE products resulting in the formation of linear hydrocarbons with low carbon number. Hydrocarbons with activated radical site from HDPE degradation were interacted with hydroxyl from WP degradation promoting the formation of linear long chain alcohols. Moreover, co-pyrolysis significantly enhanced condensable oil qualities, which were close to commercial diesel No. 0. Copyright © 2017 Elsevier Ltd. All rights reserved.

In situ gas fuel production during the treatment of textile wastewater at supercritical conditions.

PubMed

Kıpçak, Ekin; Akgün, Mesut

2013-01-01

Supercritical water gasification has recently received much attention as a potential alternative to energy conversion methods applied to aqueous/non-aqueous biomass sources, industrial wastes or fossil fuels such as coal because of the unique physical properties of water above its critical conditions (i.e. 374.8 °C and 22.1 MPa). This paper presents the results obtained for the hydrothermal gasification of textile wastewater at supercritical conditions. The experiments were carried out at five reaction temperatures (between 450 and 650 °C) and five reaction times (between 30 and 150 s), under a constant pressure of 25 MPa. It was found that the gaseous products contained considerable amounts of hydrogen, carbon monoxide, carbon dioxide, and C(1)-C(4) hydrocarbons, such as methane, ethane, propane and propylene. The maximum amount of the obtained gaseous product was 1.23 mL per mL textile wastewater, at a reaction temperature of 600 °C, with a reaction time of 150 s. At this state, the product comprised 13.02% hydrogen, 38.93% methane, 4.33% ethane, 0.10% propane, 0.01% propylene, 7.97% carbon monoxide, 27.22% carbon dioxide and 8.00% nitrogen. In addition, a 62.88% decrease in the total organic carbon (TOC) content was observed and the color of the wastewater was removed. Moreover, for the hydrothermal decomposition of the textile wastewater, a first-order reaction rate was designated with an activation energy of 50.42 (±2.33) kJ/mol and a pre-exponential factor of 13.29 (±0.41) s(-1).

Kinetic phase evolution of spinel cobalt oxide during lithiation

DOE PAGES

Li, Jing; He, Kai; Meng, Qingping; ...

2016-09-15

Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalationmore » reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.« less

Kinetic phase evolution of spinel cobalt oxide during lithiation

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

Li, Jing; He, Kai; Meng, Qingping

Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalationmore » reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.« less

Molecular Characterization of Thiols in Fossil Fuels by Michael Addition Reaction Derivatization and Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

PubMed

Wang, Meng; Zhao, Suoqi; Liu, Xuxia; Shi, Quan

2016-10-04

Thiols widely occur in sediments and fossil fuels. However, the molecular composition of these compounds is unclear due to the lack of appropriate analytical methods. In this work, a characterization method for thiols in fossil fuels was developed on the basis of Michael addition reaction derivatization followed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). Model thiol compound studies showed that thiols were selectively reacted with phenylvinylsulfone and transformed to sulfones with greater than 98% conversions. This method was applied to a coker naphtha, light and heavy gas oils, and crude oils from various geological sources. The results showed that long alkyl chain thiols are readily present in petroleum, which have up to 30 carbon atoms. Large DBE dispersity of thiols indicates that naphthenic and aromatic thiols are also present in the petroleum. This method is capable of detecting thiol compounds in the part per million range by weight. This method allows characterization of thiols in a complex hydrocarbon matrix, which is complementary to the comprehensive analysis of sulfur compounds in fossil fuels.

Novel Fischer-Tropsch catalysts

DOEpatents

Vollhardt, Kurt P. C.; Perkins, Patrick

1981-01-01

Novel polymer-supported metal complexes of the formula PS -R Me(CO).sub.n H.sub.m where: PS represents a divinylbenzene crosslinked polystyrene in which the divinylbenzene crosslinking is greater than 1% and less than about 18%; R represents a cycloalkadienyl radical of 4 through 6 carbon atoms; Me represents a Group VIII metal; CO represents a carbonyl radical; H represents hydrogen; n represents an integer varying from 0 through 3; m represents an integer varying from 0 through 2 inclusively with the further provision that 2n+m must total 18 when added to the electrons in R and Me, or n+m must total 0; are prepared by: brominating PS -H by treating same with bromine in the presence of a thallium salt in a partially or fully halogenated solvent to form PS -Br; treating said PS -Br so produced with a lithium alkyl of 1 through 12 carbon atoms in an aromatic solvent to produce PS -Li; substituting said PS - Li so produced by reaction with a 2-cycloalkenone of 4 to 6 carbon atoms in the presence of an ether solvent and using a water work-up to form a cycloalkenylalcohol-substituted PS ; dehydrating said alcohol so produced by heating under a vacuum to produce a cycloalkadienyl-substituted PS ; reacting the cycloalkadienyl-substituted PS with metal carbonyl in the presence of a partially or fully halogenated hydrocarbon, aromatic hydrocarbon of 6 through 8 carbon atoms, ethers, or esters of 4 through 10 carbon atoms as a solvent to produce a polystyrene-supported cycloalkadienyl metal carbonyl. The novel compounds are used as improved Fischer-Tropsch catalysts particularly for the conversion of CO+H.sub.2 to gaseous and liquid hydrocarbons at milder conditions than with prior catalysts.

Novel Fischer-Tropsch catalysts

DOEpatents

Vollhardt, Kurt P. C.; Perkins, Patrick

1980-01-01

Novel polymer-supported metal complexes of the formula: PS --R Me(CO).sub.n H.sub.m where: PS represents a divinylbenzene crosslinked polystyrene in which the divinylbenzene crosslinking is greater than 1% and less than about 18%; R represents a cycloalkadienyl radical of 4 through 6 carbon atoms; Me represents a Group VIII metal; CO represents a carbonyl radical; H represents hydrogen; n represents an integer varying from 0 through 3; m represents an integer varying from 0 through 2 inclusively with the further provision that 2n+m must total 18 when added to the electrons in R and Me, or n+m must total 0; are prepared by: brominating PS --H by treating same with bromine in the presence of a thallium salt in a partially or fully halogenated solvent to form PS --Br; treating said PS --Br so produced with a lithium alkyl of 1 through 12 carbon atoms in an aromatic solvent to produce PS --Li; substituting said PS-- Li so produced by reaction with a 2-cycloalkenone of 4 to 6 carbon atoms in the presence of an ether solvent and using a water work-up to form a cycloalkenylalcohol-substituted PS ; dehydrating said alcohol so produced by heating under a vacuum to produce a cycloalkadienyl-substituted PS ; reacting the cycloalkadienyl-substituted PS with metal carbonyl in the presence of a partially or fully halogenated hydrocarbon, aromatic hydrocarbon of 6 through 8 carbon atoms, ethers, or esters of 4 through 10 carbon atoms as a solvent to produce a polystyrene-supported cycloalkadienyl metal carbonyl. The novel compounds are used as improved Fischer-Tropsch catalysts particularly for the conversion of CO+H.sub.2 to gaseous and liquid hydrocarbons at milder conditions than with prior catalysts.

Novel Fischer-Tropsch catalysts

DOEpatents

Vollhardt, Kurt P. C.; Perkins, Patrick

1981-01-01

Novel polymer-supported metal complexes of the formula: PS --R Me(CO).sub.n H.sub.m where: PS represents a divinylbenzene crosslinked polystyrene in which the divinylbenzene crosslinking is greater than 1% and less than about 18%; R represents a cycloalkadienyl radical of 4 through 6 carbon atoms; Me represents a Group VIII metal; CO represents a carbonyl radical; H represents hydrogen; n represents an integer varying from 0 through 3; m represents an integer varying from 0 through 2 inclusively with the further provision that 2n+m must total 18 when added to the electrons in R and Me, or n+m must total 0; are prepared by: brominating PS --H by treating same with bromine in the presence of a thallium salt in a partially or fully halogenated solvent to form PS --Br; treating said PS --Br so produced with a lithium alkyl of 1 through 12 carbon atoms in an aromatic solvent to produce PS --Li; substituting said PS-- Li so produced by reaction with a 2-cycloalkenone of 4 to 6 carbon atoms in the presence of an ether solvent and using a water work-up to form a cycloalkenylalcohol-substituted PS ; dehydrating said alcohol so produced by heating under a vacuum to produce a cycloalkadienyl-substituted PS ; reacting the cycloalkadienyl-substituted PS with metal carbonyl in the presence of a partially or fully halogenated hydrocarbon, aromatic hydrocarbon of 6 through 8 carbon atoms, ethers, or esters of 4 through 10 carbon atoms as a solvent to produce a polystyrene-supported cycloalkadienyl metal carbonyl. The novel compounds are used as improved Fischer-Tropsch catalysts particularly for the conversion of CO+H.sub.2 to gaseous and liquid hydrocarbons at milder conditions than with prior catalysts.

Catalytic conversion of hydrocarbons to hydrogen and high-value carbon

DOEpatents

Shah, Naresh; Panjala, Devadas; Huffman, Gerald P.

2005-04-05

The present invention provides novel catalysts for accomplishing catalytic decomposition of undiluted light hydrocarbons to a hydrogen product, and methods for preparing such catalysts. In one aspect, a method is provided for preparing a catalyst by admixing an aqueous solution of an iron salt, at least one additional catalyst metal salt, and a suitable oxide substrate support, and precipitating metal oxyhydroxides onto the substrate support. An incipient wetness method, comprising addition of aqueous solutions of metal salts to a dry oxide substrate support, extruding the resulting paste to pellet form, and calcining the pellets in air is also discloses. In yet another aspect, a process is provided for producing hydrogen from an undiluted light hydrocarbon reactant, comprising contacting the hydrocarbon reactant with a catalyst as described above in a reactor, and recovering a substantially carbon monoxide-free hydrogen product stream. In still yet another aspect, a process is provided for catalytic decomposition of an undiluted light hydrocarbon reactant to obtain hydrogen and a valuable multi-walled carbon nanotube coproduct.

High surface area graphene-supported metal chalcogenide assembly

DOEpatents

Worsley, Marcus A.; Kuntz, Joshua D.; Orme, Christine A.

2017-04-25

Disclosed here is a method for hydrocarbon conversion, comprising contacting at least one graphene-supported assembly with at least one hydrocarbon feedstock, wherein the graphene-supported assembly comprises (i) a three-dimensional network of graphene sheets crosslinked by covalent carbon bonds and (ii) at least one metal chalcogenide compound disposed on the graphene sheets, wherein the chalcogen of the metal chalcogenide compound is selected from S, Se and Te, and wherein the metal chalcogenide compound accounts for at least 20 wt. % of the graphene-supported assembly.

A new hydrocarbon material based on seabuckthorn ( Hippophae rhamnoides) sawdust: A structural promoter of cobalt catalyst for Fischer-Tropsch synthesis

NASA Astrophysics Data System (ADS)

Pankina, G. V.; Chernavskii, P. A.; Lunin, V. V.

2016-09-01

Aspects of the physicochemical properties of a hydrocarbon material based on seabuckthorn ( Hippophae rhamnoides) sawdust are studied. The use of a hydrocarbon material based on sea buckthorn sawdust as a structural promoter of Co/CHip cobalt catalyst in the reaction of CO hydrogenation is shown to require an additional cycling stage in the mode of reduction and oxidation. The resulting mean size of the Co particles is found to be 18-19 nm and is considered acceptable for the synthesis of C5+ liquid hydrocarbons.

Fire and Pesticides: A Review of Air Quality Considerations

Treesearch

Parshall B. Bush; Daniel G. Neary; Charles K. McMahon

2000-01-01

The classes of primary chemical products naturally produced by the combustion of forest fuels are: carbon dioxide, water, carbon monoxide, particulate matter, methane and non-methane hydrocarbons, polynuclear aromatic hydrocarbons, nitrogen and sulfur oxides, aldehydes, free radicals, and inorganic elements. Secondary chemical products produced by reactions in smoke...

THE PHOTOTOXOICITY OF POLYCYCLIC AROMATIC HYDROCARBONS: A THEORETICAL STUDY OF EXCITED STATES AND CORRELATION TO EXPERIMENT

EPA Science Inventory

Investigators using models to determine the phototoxic effects of sunlight on polycyclic aromatic hydrocarbons (PAHS) have invoked the excited states of the molecule as important in elucidating the mechanism of these reactions. Energies of actual excited states were calcu...

Chemical recycling of scrap composites

NASA Technical Reports Server (NTRS)

Allred, Ronald E.; Salas, Richard M.

1994-01-01

There are no well-developed technologies for recycling composite materials other than grinding to produce fillers. New approaches are needed to reclaim these valuable resources. Chemical or tertiary recycling, conversion of polymers into low molecular weight hydrocarbons for reuse as chemicals or fuels, is emerging as the most practical means for obtaining value from waste plastics and composites. Adherent Technologies is exploring a low-temperature catalytic process for recycling plastics and composites. Laboratory results show that all types of plastics, thermosets as well as thermoplastics, can be converted in high yields to valuable hydrocarbon products. This novel catalytic process runs at 200 C, conversion times are rapid, the process is closed and, thus, nonpolluting, and no highly toxic gas or liquid products have been observed so no negative environmental impact will result from its implementation. Tests on reclamation of composite materials show that epoxy, imide, and engineering thermoplastic matrices can be converted to low molecular weight hydrocarbons leaving behind the reinforcing fibers for reuse as composite reinforcements in secondary, lower-performance applications. Chemical recycling is also a means to dispose of sensitive or classified organic materials without incineration and provides a means to eliminate or reduce mixed hazardous wastes containing organic materials.

An investigation into support cooperativity for the deoxygenation of guaiacol over nanoparticle Ni and Rh 2P

DOE PAGES

Griffin, Michael B.; Baddour, Frederick G.; Habas, Susan E.; ...

2017-06-06

Here, the production of hydrocarbon fuels from biomass pyrolysis requires the development of effective deoxygenation catalysts, and insight into how the properties of the support influence performance is critical for catalyst design. In this report, nanoparticles of Ni and Rh 2P were synthesized using solution-phase techniques and dispersed on high surface area supports. The supports included a relatively inert material (C), an acidic reducible metal-oxide (TiO 2), an acidic irreducible metal-oxide (Al 2O 3), and a basic irreducible metal-oxide (MgO). The eight active phase/support combinations were investigated for the deoxygenation of guaiacol, a pyrolysis vapor model compound, under ex situmore » catalytic fast pyrolysis conditions (350 °C, 0.44 MPa H 2). Compared to the baseline performance of the C-supported catalysts, Ni/TiO 2 and Rh 2P/TiO 2 exhibited higher guaiacol conversion and lower O : C ratios for C 5+ products, highlighting the enhanced activity and greater selectivity to deoxygenated products derived from the use of an acidic reducible metal-oxide support. The Al 2O 3-supported catalysts also exhibited higher conversion than the C-supported catalysts and promoted alkylation reactions, which improve carbon efficiency and increase the carbon number of the C 5+ products. However, Ni/Al 2O 3 and Rh 2P/Al 2O 3 were less selective towards deoxygenated products than the C-supported catalysts. The MgO-supported catalyst exhibited lower conversion and decreased yield of deoxygenated products compared to the C-supported catalysts. The results reported here suggest that basic metal-oxide supports may inhibit deoxygenation of phenolics under CFP conditions. Contrastingly, support acidity and reducibility were demonstrated to promote conversion and selectivity to deoxygenated products, respectively.« less

Bioconversion of R-(+)-limonene to perillic acid by the yeast Yarrowia lipolytica

PubMed Central

Ferrara, Maria Antonieta; Almeida, Débora S.; Siani, Antonio C.; Lucchetti, Leonardo; Lacerda, Paulo S.B.; Freitas, André; Tappin, Marcelo R.R.; Bon, Elba P.S.

2013-01-01

Perillyl derivatives are increasingly important due to their flavouring and antimicrobial properties as well as their potential as anticancer agents. These terpenoid species, which are present in limited amounts in plants, may be obtained via bioconversion of selected monoterpene hydrocarbons. In this study, seventeen yeast strains were screened for their ability to oxidize the exocyclic methyl group in the p-menthene moiety of limonene into perillic acid. Of the yeast tested, the highest efficiency was observed for Yarrowia lipolytica ATCC 18942. The conversion of R (+)-limonene by Y. lipolytica was evaluated by varying the pH (3 to 8) and the temperature (25 to 30 °C) in a reaction medium containing 0.5% v/v limonene and 10 g/L of stationary phase cells (dry weight). The best results, corresponding to 564 mg/L of perillic acid, were obtained in buffered medium at pH 7.1 that was incubated at 25 °C for 48 h. The stepwise addition of limonene increased the perillic acid concentration by over 50%, reaching 855 mg/L, whereas the addition of glucose or surfactant to the reaction medium did not improve the bioconversion process. The use of Y. lipolytica showed promise for ease of further downstream processing, as perillic acid was the sole oxidised product of the bioconversion reaction. Moreover, bioprocesses using safe and easy to cultivate yeast cells have been favoured in industry. PMID:24688495

On the role of resonantly stabilized radicals in polycyclic aromatic hydrocarbon (PAH) formation: pyrene and fluoranthene formation from benzyl-indenyl addition.

PubMed

Sinha, Sourab; Rahman, Ramees K; Raj, Abhijeet

2017-07-26

Resonantly stabilized radicals, such as propargyl, cyclopentadienyl, benzyl, and indenyl, play a vital role in the formation and growth of polycyclic aromatic hydrocarbons (PAHs) that are soot precursors in engines and flames. Pyrene is considered to be an important PAH, as it is thought to nucleate soot particles, but its formation pathways are not well known. This paper presents a reaction mechanism for the formation of four-ring aromatics, pyrene and fluoranthene, through the combination of benzyl and indenyl radicals. The intermediate species and transition structures involved in the elementary reactions of the mechanism were studied using density functional theory, and the reaction kinetics were evaluated using transition state theory. The barrierless addition of benzyl and indenyl to form the adduct, 1-benzyl-1H-indene, was found to be exothermic with a reaction energy of 204.2 kJ mol -1 . The decomposition of this adduct through H-abstraction and H 2 -loss was studied to determine the possible products. The rate-of-production analysis was conducted to determine the most favourable reactions for pyrene and fluoranthene formation. The premixed laminar flames of toluene, ethylbenzene, and benzene were simulated using a well-validated hydrocarbon fuel mechanism with detailed PAH chemistry after adding the proposed reactions to it. The computed and experimentally observed species profiles were compared to determine the effect of the new reactions for pyrene and fluoranthene formation on their concentration profiles. The role of benzyl and indenyl combination in PAH formation and growth is highlighted.

Control of harmful hydrocarbon species in the exhaust of modern advanced GDI engines

NASA Astrophysics Data System (ADS)

Hasan, A. O.; Abu-jrai, A.; Turner, D.; Tsolakis, A.; Xu, H. M.; Golunski, S. E.; Herreros, J. M.

2016-03-01

A qualitative and quantitative analysis of toxic but currently non-regulated hydrocarbon compounds ranging from C5-C11, before and after a zoned three-way catalytic converter (TWC) in a modern gasoline direct injection (GDI) engine has been studied using gas chromatography-mass spectrometry (GC-MS). The GDI engine has been operated under conventional and advanced combustion modes, which result in better fuel economy and reduced levels of NOx with respect to standard SI operation. However, these fuel-efficient conditions are more challenging for the operation of a conventional TWC, and could lead to higher level of emissions released to the environment. Lean combustion leads to the reduction in pumping losses, fuel consumption and in-cylinder emission formation rates. However, lean HCCI will lead to high levels of unburnt HCs while the presence of oxygen will lower the TWC efficiency for NOx control. The effect on the catalytic conversion of the hydrocarbon species of the addition of hydrogen upstream the catalyst has been also investigated. The highest hydrocarbon engine-out emissions were produced for HCCI engine operation at low engine load operation. The catalyst was able to remove most of the hydrocarbon species to low levels (below the permissible exposure limits) for standard and most of the advanced combustion modes, except for naphthalene (classified as possibly carcinogenic to humans by the International Agency for Research on Cancer) and methyl-naphthalene (which has the potential to cause lung damage). However, when hydrogen was added upstream of the catalyst, the catalyst conversion efficiency in reducing methyl-naphthalene and naphthalene was increased by approximately 21%. This results in simultaneous fuel economy and environmental benefits from the effective combination of advanced combustion and novel aftertreatment systems.

EDITORIAL: Non-thermal plasma-assisted fuel conversion for green chemistry Non-thermal plasma-assisted fuel conversion for green chemistry

NASA Astrophysics Data System (ADS)

Nozaki, Tomohiro; Gutsol, Alexander

2011-07-01

This special issue is based on the symposium on Non-thermal Plasma Assisted Fuel Conversion for Green Chemistry, a part of the 240th ACS National Meeting & Exposition held in Boston, MA, USA, 22-26 August 2010. Historically, the Division of Fuel Chemistry of the American Chemical Society (ACS) has featured three plasma-related symposia since 2000, and has launched special issues in Catalysis Today on three occasions: 'Catalyst Preparation using Plasma Technologies', Fall Meeting, Washington DC, USA, 2000. Special issue in Catalysis Today 72 (3-4) with 12 peer-reviewed articles. 'Plasma Technology and Catalysis', Spring Meeting, New Orleans, LA, USA, 2003. Special issue in Catalysis Today 89 (1-2) with more than 30 peer-reviewed articles. 'Utilization of Greenhouse Gases II' (partly focused on plasma-related technologies), Spring Meeting, Anaheim, CA, USA, 2004. Special issue in Catalysis Today 98 (4) with 25 peer-reviewed articles. This time, selected presentations are published in this Journal of Physics D: Applied Physics special issue. An industrial material and energy conversion technology platform is established on thermochemical processes including various catalytic reactions. Existing industry-scale technology is already well established; nevertheless, further improvement in energy efficiency and material saving has been continuously demanded. Drastic reduction of CO2 emission is also drawing keen attention with increasing recognition of energy and environmental issues. Green chemistry is a rapidly growing research field, and frequently highlights renewable bioenergy, bioprocesses, solar photocatalysis of water splitting, and regeneration of CO2 into useful chemicals. We would also like to emphasize 'plasma catalysis' of hydrocarbon resources as an important part of the innovative next-generation green technologies. The peculiarity of non-thermal plasma is that it can generate reactive species almost independently of reaction temperature. Plasma-generated reactive species are used to initiate chemical reactions at unexpectedly lower temperatures than conventional thermochemical reactions, leading to non-equilibrium product distribution or creating unconventional reaction pathways. When non-thermal plasma is combined with catalysts, a synergistic effect is frequently observed. Such unique properties of non-thermal plasma are expected to contribute excellent control over process parameters that meet the need for energy saving, environment protection, and material preservation. This special issue consists of eleven peer-reviewed papers including two invited publications. Professors Alexander Fridman and Alexander Rabinovich from Drexel University, and Dr Gutsol from the Chevron Energy Technology Company present a critical review of various industry-oriented practical plasma fuel conversion processes. Professor Richard Mallinson from University of Oklahoma describes his recent project on E85 (85%-ethanol/15%-gasoline) upgrading using non-thermal plasma and catalyst hybrid reactor, and highlights the synergistic effect on fuel conversion processes. Other papers focus on plasma/catalyst hybrid reactions for methane dry (CO2) reforming, plasma synthesis of carbon suboxide polymer from CO, the gas-to-liquid (GTL) process using a non-thermal plasma-combined micro-chemical reactor, and molecular beam characterization of plasma-generated reactive species. Much research regarding plasma catalysis is ongoing worldwide, but there is plenty of room for further development of plasma fuel processing, which could eventually provide a viable and flexible solution in future energy and material use. Finally, we would like to thank all symposium participants for their active discussion. We appreciate the sponsorship of the Division of Fuel Chemistry of the American Chemical Society. We express special thanks to the program chair of the Fuel Chemistry Division, Professor Chang-jun Liu at Tianjin University, for his dedication to the success of the symposium. We particularly express our appreciation to the Editorial Board of Journal of Physics D: Applied Physics for publication of the special issue.

Tailoring ZSM-5 Zeolites for the Fast Pyrolysis of Biomass to Aromatic Hydrocarbons.

PubMed

Hoff, Thomas C; Gardner, David W; Thilakaratne, Rajeeva; Wang, Kaige; Hansen, Thomas W; Brown, Robert C; Tessonnier, Jean-Philippe

2016-06-22

The production of aromatic hydrocarbons from cellulose by zeolite-catalyzed fast pyrolysis involves a complex reaction network sensitive to the zeolite structure, crystallinity, elemental composition, porosity, and acidity. The interplay of these parameters under the reaction conditions represents a major roadblock that has hampered significant improvement in catalyst design for over a decade. Here, we studied commercial and laboratory-synthesized ZSM-5 zeolites and combined data from 10 complementary characterization techniques in an attempt to identify parameters common to high-performance catalysts. Crystallinity and framework aluminum site accessibility were found to be critical to achieve high aromatic yields. These findings enabled us to synthesize a ZSM-5 catalyst with enhanced activity, which offers the highest aromatic hydrocarbon yield reported to date. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The seasonal variation of nonmethane hydrocarbons in the free troposphere over the North Atlantic Ocean - Possible evidence for extensive reaction of hydrocarbons with the nitrate radical

NASA Astrophysics Data System (ADS)

Penkett, S. A.; Blake, N. J.; Lightman, P.; Marsh, A. R. W.; Anwyl, P.; Butcher, G.

1993-02-01

Observations of the buildup in wintertime of a substantial concentration of hydrocarbons in the free troposphere over the North Atlantic Ocean are extended to the seasonal cycles of a much wider range of hydrocarbons, from C2 to C8. A large seasonal variation was found in the hydrocarbon content in the free troposphere over the north Atlantic Ocean. The maximum carbon concentration occurs in winter and is of the order of 20 ppbv in the form of reactive carbon compounds with lifetimes of days to months. The hydrocarbon content of air in winter over the Atlantic depends greatly on its source area, with polar maritime air containing much higher concentrations than air with a tropical maritime origin. There is evidence from detailed hydrocarbon data that NO3 chemistry may play a significant role in the removal of hydrocarbons from the atmosphere. This is more evident in the wintertime, when the hydroxyl chemistry is less dominant.

The in vivo hydrocarbon formation by vanadium nitrogenase follows a secondary metabolic pathway

DOE PAGES

Rebelein, Johannes G.; Lee, Chi Chung; Hu, Yilin; ...

2016-12-15

The vanadium (V)-nitrogenase of Azotobacter vinelandii catalyses the in vitro conversion of carbon monoxide (CO) to hydrocarbons. Here we show that an A. vinelandii strain expressing the V-nitrogenase is capable of in vivo reduction of CO to ethylene (C 2H 4), ethane (C 2H 6) and propane (C 3H 8). Moreover, we demonstrate that CO is not used as a carbon source for cell growth, being instead reduced to hydrocarbons in a secondary metabolic pathway. These findings suggest a possible role of the ancient nitrogenase as an evolutionary link between the carbon and nitrogen cycles on Earth and establish amore » solid foundation for biotechnological adaptation of a whole-cell approach to recycling carbon wastes into hydrocarbon products. Furthermore, this study has several repercussions for evolution-, environment- and energy-related areas.« less

Plasma chemistry and organic synthesis

NASA Technical Reports Server (NTRS)

Tezuka, M.

1980-01-01

The characteristic features of chemical reactions using low temperature plasmas are described and differentiated from those seen in other reaction systems. A number of examples of applications of plasma chemistry to synthetic reactions are mentioned. The production of amino acids by discharge reactions in hydrocarbon-ammonia-water systems is discussed, and its implications for the origins of life are mentioned.

GC×GC measurements of C7-C11 aromatic and n-alkane hydrocarbons on Crete, in air from Eastern Europe during the MINOS campaign

NASA Astrophysics Data System (ADS)

Xu, X.; Williams, C.; Plass-Dülmer, H.; Berresheim, H.; Salisbury, G.; Lange, L.; Lelieveld, J.

2003-09-01

During the Mediterranean Intensive Oxidant Study (MINOS) campaign in August 2001 gas-phase organic compounds were measured using comprehensive two-dimensional gas chromatography (GCxGC) at the Finokalia ground station, Crete. In this paper, C7-C11 aromatic and n-alkane measurements are presented and interpreted. The mean mixing ratios of the hydrocarbons varied from 1±1 pptv (i-propylbenzene) to 43±36 pptv (toluene). The observed mixing ratios showed strong day-to-day variations and generally higher levels during the first half of the campaign. Mean diel profiles showed maxima at local midnight and late morning, and minima in the early morning and evening. Results from analysis using a simplified box model suggest that both the chemical sink (i.e. reaction with OH) and the variability of source strengths were the causes of the observed variations in hydrocarbon mixing ratios. The logarithms of hydrocarbon concentrations were negatively correlated with the OH concentrations integral over a day prior to the hydrocarbon measurements. Slopes of the regression lines derived from these correlations for different compounds are compared with literature rate constants for their reactions with OH. The slopes for most compounds agree reasonably well with the literature rate constants. A sequential reaction model has been applied to the interpretation of the relationship between ethylbenzene and two of its potential products, i.e. acetophenone and benzeneacetaldehyde. The model can explain the good correlation observed between [acetophenone]/[ethylbenzene] and [benzeneacetaldehyde]/[ethylbenzene]. The model results and field measurements suggest that the reactivity of benzeneacetaldehyde may lie between those of acetophenone and ethylbenzene and that the ratio between yields of acetophenone and benzeneacetaldehyde may be up to 28:1. Photochemical ages of trace gases sampled at Finokalia during the campaign are estimated using the sequential reaction model and related data. They lie in the range of about 0.5-2.5 days.

GC×GC measurements of C7-C11 aromatic and n-alkane hydrocarbons on Crete, in air from Eastern Europe during the MINOS campaign

NASA Astrophysics Data System (ADS)

Xu, X.; Williams, J.; Plass-Dülmer, C.; Berresheim, H.; Salisbury, G.; Lange, L.; Lelieveld, J.

2003-03-01

During the Mediterranean Intensive Oxidant Study (MINOS) campaign in August 2001 gas-phase organic compounds were measured using comprehensive two-dimensional gas chromatography (GC×GC) at the Finokalia ground station, Crete. In this paper, C7-C11 aromatic and n-alkane measurements are presented and interpreted. The mean mixing ratios of the hydrocarbons varied from 1+/-1 pptv (i-propylbenzene) to 43+/-36 pptv (toluene). The observed mixing ratios showed strong day-to-day variations and generally higher levels during the first half of the campaign. Mean diel profiles showed maxima at local midnight and late morning, and minima in the early morning and evening. Results from analysis using a simplified box model suggest that both the chemical sink (i.e. reaction with OH) and the variability of source strengths were the causes of the observed variations in hydrocarbon mixing ratios. The logarithms of hydrocarbon concentrations were negatively correlated with the OH concentrations integral over a day prior to the hydrocarbon measurements. Slopes of the regression lines derived from these correlations for different compounds are compared with literature rate constants for their reactions with OH. The slopes for most compounds agree reasonably well with the literature rate constants. A sequential reaction model has been applied to the interpretation of the relationship between ethylbenzene and two of its potential products, i.e. acetophenone and benzeneacetaldehyde. The model can explain the good correlation observed between [acetophenone]/[ethylbenzene] and [benzeneacetaldehyde]/[ethylbenzene]. The model results and field measurements suggest that the reactivity of benzeneacetaldehyde may lie between those of acetophenone and ethylbenzene and that the ratio between yields of acetophenone and benzeneacetaldehyde may be up to 28:1. Photochemical ages of trace gases sampled at Finokalia during the campaign are estimated using the sequential reaction model and related data. They lie in the range of about 0.5-2.5 days.

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

Krasnokutski, Serge A.; Huisken, Friedrich; Jäger, Cornelia

A very high abundance of atomic carbon in the interstellar medium (ISM), and the high reactivity of these species toward different hydrocarbon molecules including benzene, raise questions regarding the stability of polycyclic aromatic hydrocarbon (PAH) molecules in space. To test the efficiency of destruction of PAH molecules via reactions with atomic carbon, we performed a set of laboratory and computational studies of the reactions of naphthalene, anthracene, and coronene molecules with carbon atoms in the ground state. The reactions were investigated in liquid helium droplets at T = 0.37 K and by quantum chemical computations. Our studies suggest that allmore » small and all large catacondensed PAHs react barrierlessly with atomic carbon, and therefore should be efficiently destroyed by such reactions in a broad temperature range. At the same time, large compact pericondensed PAHs should be more inert toward such a reaction. In addition, taking into account their higher photostability, much higher abundances of pericondensed PAHs should be expected in various astrophysical environments. The barrierless reactions between carbon atoms and small PAHs also suggest that, in the ISM, these reactions could lead to the bottom-up formation of PAH molecules.« less

Remote carboxylation of halogenated aliphatic hydrocarbons with carbon dioxide

NASA Astrophysics Data System (ADS)

Juliá-Hernández, Francisco; Moragas, Toni; Cornella, Josep; Martin, Ruben

2017-05-01

Catalytic carbon-carbon bond formation has enabled the streamlining of synthetic routes when assembling complex molecules. It is particularly important when incorporating saturated hydrocarbons, which are common motifs in petrochemicals and biologically relevant molecules. However, cross-coupling methods that involve alkyl electrophiles result in catalytic bond formation only at specific and previously functionalized sites. Here we describe a catalytic method that is capable of promoting carboxylation reactions at remote and unfunctionalized aliphatic sites with carbon dioxide at atmospheric pressure. The reaction occurs via selective migration of the catalyst along the hydrocarbon side-chain with excellent regio- and chemoselectivity, representing a remarkable reactivity relay when compared with classical cross-coupling reactions. Our results demonstrate that site-selectivity can be switched and controlled, enabling the functionalization of less-reactive positions in the presence of a priori more reactive ones. Furthermore, we show that raw materials obtained in bulk from petroleum processing, such as alkanes and unrefined mixtures of olefins, can be used as substrates. This offers an opportunity to integrate a catalytic platform en route to valuable fatty acids by transforming petroleum-derived feedstocks directly.

Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

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

Enrique Iglesia; Akio Ishikawa; Manual Ojeda

2007-09-30

A detailed study of the catalyst composition, preparation and activation protocol of Fe-based catalysts for the Fischer-Tropsch Synthesis (FTS) have been carried out in this project. We have studied the effects of different promoters on the catalytic performance of Fe-based catalysts. Specifically, we have focused on how their sequence of addition dramatically influences the performance of these materials in the Fischer-Tropsch synthesis. The resulting procedures have been optimized to improve further upon the already unprecedented rates and C{sub 5+} selectivities of the Fe-based catalysts that we have developed as part of this project. Selectivity to C{sub 5+} hydrocarbon was closemore » to 90 % (CO{sub 2}-free basis) and CO conversion rate was about 6.7 mol h{sup -1} g-at Fe{sup -1} at 2.14 MPa, 508 K and with substoichiometric synthesis gas; these rates were larger than any reported previously for Fe-based FTS catalysts at these conditions. We also tested the stability of Fe-based catalysts during FTS reaction (10 days); as a result, the high hydrocarbon formation rates were maintained during 10 days, though the gradual deactivation was observed. Our investigation has also focused on the evaluation of Fe-based catalysts with hydrogen-poor synthesis gas streams (H{sub 2}/CO=1). We have observed that the Fe-based catalysts prepared in this project display also a high hydrocarbon synthesis rate with substoichiometric synthesis gas (H{sub 2}/CO=1) stream, which is a less desirable reactant mixture than stoichiometric synthesis gas (H{sub 2}/CO=2). We have improved the catalyst preparation protocols and achieved the highest FTS reaction rates and selectivities so far reported at the low temperatures required for selectivity and stability. Also, we have characterized the catalyst structural change and active phases formed, and their catalytic behavior during the activation process to evaluate their influences on FTS reaction. The efforts of this project led to (i) structural evolution of Fe-Zn oxide promoted with K and Cu, and (ii) evaluation of hydrocarbon and CH{sub 4} formation rates during activation procedures at various temperature and H{sub 2}/CO ratios. On the basis of the obtained results, we suggest that lower reactor temperature can be sufficient to activate catalysts and lead to the high FTS performance. In this project, we have also carried out a detailed kinetic and mechanistic study of the Fischer-Tropsch Synthesis with Fe-based catalysts. We have proposed a reaction mechanism with two CO activation pathways: unassisted and H-assisted. Both routes lead to the formation of the same surface monomers (CH{sub 2}). However, the oxygen removal mechanism is different. In the H-assisted route, oxygen is removed exclusively as water, while oxygen is rejected as carbon dioxide in the unassisted CO dissociation. The validity of the mechanism here proposed has been found to be in agreement with the experimental observation and with theoretical calculations over a Fe(110) surface. Also, we have studied the validity of the mechanism that we propose by analyzing the H{sub 2}/D{sub 2} kinetic isotope effect (r{sub H}/r{sub D}) over a conventional iron-based Fischer-Tropsch catalyst Fe-Zn-K-Cu. We have observed experimentally that the use of D{sub 2} instead of H{sub 2} leads to higher hydrocarbons formation rates (inverse kinetic isotopic effect). On the contrary, primary carbon dioxide formation is not influenced. These experimental observations can be explained by two CO activation pathways. We have also explored the catalytic performance of Co-based catalysts prepared by using inverse micelles techniques. We have studied several methods in order to terminate the silanol groups on SiO{sub 2} support including impregnation, urea homogeneous deposition-precipitation, or zirconium (IV) ethoxide titration. Although hydroxyl groups on the SiO{sub 2} surface are difficult to be stoichiometrically titrated by ZrO{sub 2}, a requirement to prevent the formation of strongly-interacting Co oxide species on SiO{sub 2}, modification of ZrO{sub 2} on SiO{sub 2} surface can improve the Co clusters dispersion leading to a marked increase in the number of accessible Co sites. Inverse micelle method allowed the synthesis of small Co clusters on SiO{sub 2}, but the required surfactant removal steps led to the re-oxidation of Co metal clusters and to the formation of difficult to reduce CoO{sub x} species.« less

Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels: Thermochemical Research Pathways with In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors

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

Dutta, Abhijit; Sahir, A. H.; Tan, Eric

This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s efforts to enable the development of technologies for the production of infrastructure-compatible, cost-competitive liquid hydrocarbon fuels from biomass. Specifically, this report details two conceptual designs based on projected product yields and quality improvements via catalyst development and process integration. It is expected that these research improvements will be made within the 2022 timeframe. The two conversion pathways detailed are (1) in situ and (2) ex situ upgrading of vapors produced from the fast pyrolysis of biomass. While the base case conceptual designs and underlying assumptionsmore » outline performance metrics for feasibility, it should be noted that these are only two of many other possibilities in this area of research. Other promising process design options emerging from the research will be considered for future techno-economic analysis. Both the in situ and ex situ conceptual designs, using the underlying assumptions, project MFSPs of approximately $3.5/gallon gasoline equivalent (GGE). The performance assumptions for the ex situ process were more aggressive with higher distillate (diesel-range) products. This was based on an assumption that more favorable reaction chemistry (such as coupling) can be made possible in a separate reactor where, unlike in an in situ upgrading reactor, one does not have to deal with catalyst mixing with biomass char and ash, which pose challenges to catalyst performance and maintenance. Natural gas was used for hydrogen production, but only when off gases from the process was not sufficient to meet the needs; natural gas consumption is insignificant in both the in situ and ex situ base cases. Heat produced from the burning of char, coke, and off-gases allows for the production of surplus electricity which is sold to the grid allowing a reduction of approximately 5¢/GGE in the MFSP.« less

GREEN CATALYZED OXIDATION OF HYDROCARBONS IN ALTERNATIVE SOLVENT SYSTEMS GENERATED BY PARIS II DECHEMA; GREEN SOLVENTS FOR CATALYSIS - ENVIRONMENTALLY BENIGN REACTION MEDIA

EPA Science Inventory

Green catalyzed oxidation of hydrocarbons in alternative solvent systems generated by PARIS II
Thomas M. Becker, Michael A. Gonzalez, Paul F. Harten; Sustainable Technology Division, Office of Research and Development; United States Environmental Protection Agency, 26 West Mar...

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

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

Wang, Hongliang; Wang, Huamin; Kuhn, Eric

Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalyticmore » system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.« less

Effect of the ultrasound-Fenton oxidation process with the addition of a chelating agent on the removal of petroleum-based contaminants from soil.

PubMed

Li, Ying; Li, Fangmin; Li, Fanxiu; Yuan, Fuqian; Wei, Pingfang

2015-12-01

The effects of ultrasonic irradiation, the chelating agent modified Fenton reaction, and a combination of ultrasound and the Fenton method in removing petroleum contaminants from a soil were studied. The results showed that the contaminant removal rate of the Fenton treatment combined with an oxalic acid chelating agent was 55.6% higher than that without a chelating agent. The average removal rate of the contaminants using the ultrasound-Fenton treatment was 59.0% higher than that without ultrasonic treatment. A combination of ultrasound and an Fe(2+)/Fe(3+)-oxalate complex-modified Fenton reagent resulted in significantly higher removal rates of n-alkanes (C(n)H(2n+2), n < 28), isoprenoid hydrocarbons, aromatic hydrocarbons, and saturated polycyclic terpenes compared with the ultrasound treatment alone or the Fenton method. The Fenton reaction and the ultrasound-Fenton treatment can unselectively remove multiple components of residual hydrocarbons and a number of benzene rings in polycyclic aromatic hydrocarbons. The chemistry of the heterocyclic compounds and the position and number of substituents can affect the degradation process.

Method of preparing and utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream

DOEpatents

Berry, David A; Shekhawat, Dushyant; Smith, Mark; Haynes, Daniel

2013-07-16

The disclosure relates to a method of utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream with a mitigation of carbon accumulation. The system is comprised of a catalytically active phase deposited onto an oxygen conducting phase, with or without supplemental support. The catalytically active phase has a specified crystal structure where at least one catalytically active metal is a cation within the crystal structure and coordinated with oxygen atoms within the crystal structure. The catalyst system employs an optimum coverage ratio for a given set of oxidation conditions, based on a specified hydrocarbon conversion and a carbon deposition limit. Specific embodiments of the catalyst system are disclosed.

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

Yung, Matthew M.; Stanton, Alexander R.; Iisa, Kristiina

Metal-impregnated (Ni or Ga) ZSM-5 catalysts were studied for biomass pyrolysis vapor upgrading to produce hydrocarbons using three reactors constituting a 100 000x change in the amount of catalyst used in experiments. Catalysts were screened for pyrolysis vapor phase upgrading activity in two small-scale reactors: (i) a Pyroprobe with a 10 mg catalyst in a fixed bed and (ii) a fixed-bed reactor with 500 mg of catalyst. The best performing catalysts were then validated with a larger scale fluidized-bed reactor (using ~1 kg of catalyst) that produced measurable quantities of bio-oil for analysis and evaluation of mass balances. Despite somemore » inherent differences across the reactor systems (such as residence time, reactor type, analytical techniques, mode of catalyst and biomass feed) there was good agreement of reaction results for production of aromatic hydrocarbons, light gases, and coke deposition. Relative to ZSM-5, Ni or Ga addition to ZSM-5 increased production of fully deoxygenated aromatic hydrocarbons and light gases. In the fluidized bed reactor, Ga/ZSM-5 slightly enhanced carbon efficiency to condensed oil, which includes oxygenates in addition to aromatic hydrocarbons, and reduced oil oxygen content compared to ZSM-5. Ni/ZSM-5, while giving the highest yield of fully deoxygenated aromatic hydrocarbons, gave lower overall carbon efficiency to oil but with the lowest oxygen content. Reaction product analysis coupled with fresh and spent catalyst characterization indicated that the improved performance of Ni/ZSM-5 is related to decreasing deactivation by coking, which keeps the active acid sites accessible for the deoxygenation and aromatization reactions that produce fully deoxygenated aromatic hydrocarbons. The addition of Ga enhances the dehydrogenation activity of the catalyst, which leads to enhanced olefin formation and higher fully deoxygenated aromatic hydrocarbon yields compared to unmodified ZSM-5. Catalyst characterization by ammonia temperature programmed desorption, surface area measurements, and postreaction temperature-programmed oxidation (TPO) also showed that the metal-modified zeolites retained a greater percentage of their initial acidity and surface area, which was consistent between the reactor scales. These results demonstrate that the trends observed with smaller (milligram to gram) catalyst reactors are applicable to larger, more industrially relevant (kg) scales to help guide catalyst research toward application.« less

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

NASA Astrophysics Data System (ADS)

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

2010-05-01

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

Pressure-dependent rate constants for PAH growth: formation of indene and its conversion to naphthalene

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

Mebel, Alexander M.; Georgievskii, Yuri; Jasper, Ahren W.

2016-01-01

Unraveling the mechanisms for growth of polycyclic aromatic hydrocarbons (PAHs) requires accurate temperature- and pressure-dependent rate coefficients for a great variety of feasible pathways. Even the pathways for the formation of the simplest PAHs, indene and naphthalene, are fairly complex. These pathways provide important prototypes for modeling larger PAH growth. In this work we employ the ab initio RRKM theory-based master equation approach to predict the rate constants involved in the formation of indene and its conversion to naphthalene. The reactions eventually leading to indene involve C9Hx (x = 8–11) potential energy surfaces (PESs) and include C6H5 + C3H4 (allenemore » and propyne), C6H6 + C3H3, benzyl + C2H2, C6H5 + C3H6, C6H6 + C3H5 and C6H5 + C3H5. These predictions allow us to make a number of valuable observations on the role of various mechanisms. For instance, we demonstrate that reactions which can significantly contribute to the formation of indene include phenyl + allene and H-assisted isomerization to indene of its major product, 3-phenylpropyne, benzyl + acetylene, and the reactions of the phenyl radical with propene and the allyl radical, both proceeding via the 3-phenylpropene intermediate. 3-Phenylpropene can be activated to a 1-phenylallyl radical, which in turn rapidly decomposes to indene. Next, indene can be converted to benzofulvene or naphthalene under typical combustion conditions, via its activation by H atom abstraction and methyl substitution on the five-membered ring followed by isomerization and decomposition of the resulting 1-methylindenyl radical, C10H9 → C10H8 + H. Alternatively, the same region of the C10H9 PES can be accessed through the reaction of benzyl with propargyl, C7H7 + C3H3 → C10H10 → C10H9 + H, which therefore can also contribute to the formation of benzofulvene or naphthalene. Benzofulvene easily transforms to naphthalene by H-assisted isomerization. An analysis of the effect of pressure on the reaction outcome and relative product yields is given, and modified Arrhenius fits of the rate constants are reported for the majority of the considered reactions. Ultimately, the implementation of such expressions in detailed kinetic models will help quantify the role of these reactions for PAH growth in various environments.« less

Laboratory simulated hydrothermal alteration of sedimentary organic matter from Guaymas Basin, Gulf of California. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Leif, Roald N.

1993-01-01

High temperature alteration of sedimentary organic matter associated with marine hydrothermal systems involves complex physical and chemical processes that are not easily measured in most natural systems. Many of these processes can be evaluated indirectly by examining the geochemistry of the hydrothermal system in the laboratory. In this investigation, an experimental organic geochemical approach to studying pyrolysis of sedimentary organic matter is applied to the hydrothermal system in the Guaymas Basin, Gulf of California. A general survey of hydrothermal oils and extractable organic matter (bitumen) in hydrothermally altered sediments identified several homologous series of alkanones associated with a high temperature hydrothermal origin. The alkanones range in carbon number from C11 to C30 with no carbon number preference. Alkan-2-ones are in highest concentrations, with lower amounts of 3-, 4-, 5- (and higher) homologs. The alkanones appear to be pyrolysis products synthesized under extreme hydrothermal conditions. Hydrous pyrolysis and confinement pyrolysis experiments were performed to simulate thermally enhanced diagenetic and catagenetic changes in the immature sedimentary organic matter. The extent of alteration was measured by monitoring the n-alkanes, acyclic isoprenoids, steroid and triterpenoid biomarkers, polycyclic aromatic hydrocarbons and alkanones. The results were compared to bitumen extracts from sediments which have been naturally altered by a sill intrusion and accompanied hydrothermal fluid flow. These pyrolysis experiments duplicated many of the organic matter transformations observed in the natural system. Full hopane and sterane maturation occurred after 48 hr in experiments at 330 deg C with low water/rock mass ratios (0.29). A variety of radical and ionic reactions are responsible for the organic compound conversions which occur under extreme hydrothermal conditions. Short duration pyrolysis experiments revealed that a portion of the hydrocarbons generated from kerogen was observed to go through alkene intermediates, and the rate of alkene isomerization was influenced by the ionic strength and catalytic mineral phases. Confinement of the organic pyrolysate to the bulk sediment accelerated the rates of the biomarker epimerization reactions, suggesting that these reactions are influenced strongly by the association of the inorganic matrix, and that the relative rates of some ionic and radical reactions can be influenced by the water/rock ratio during the pyrolysis experiments.

Catalysts and process for liquid hydrocarbon fuel production

DOEpatents

White, Mark G; Liu, Shetian

2014-12-09

The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality gasoline components, aromatic compounds, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel molybdenum-zeolite catalyst in high pressure hydrogen for conversion, as well as a novel rhenium-zeolite catalyst in place of the molybdenum-zeolite catalyst, and provides for use of the novel catalysts in the process and system of the invention.

Hydrodeoxygenation processes: advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels.

PubMed

De, Sudipta; Saha, Basudeb; Luque, Rafael

2015-02-01

Lignocellulosic biomass provides an attractive source of renewable carbon that can be sustainably converted into chemicals and fuels. Hydrodeoxygenation (HDO) processes have recently received considerable attention to upgrade biomass-derived feedstocks into liquid transportation fuels. The selection and design of HDO catalysts plays an important role to determine the success of the process. This review has been aimed to emphasize recent developments on HDO catalysts in effective transformations of biomass-derived platform molecules into hydrocarbon fuels with reduced oxygen content and improved H/C ratios. Liquid hydrocarbon fuels can be obtained by combining oxygen removal processes (e.g. dehydration, hydrogenation, hydrogenolysis, decarbonylation etc.) as well as by increasing the molecular weight via C-C coupling reactions (e.g. aldol condensation, ketonization, oligomerization, hydroxyalkylation etc.). Fundamentals and mechanistic aspects of the use of HDO catalysts in deoxygenation reactions will also be discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

The role of NH3 and hydrocarbon mixtures in GaN pseudo-halide CVD: a quantum chemical study.

PubMed

Gadzhiev, Oleg B; Sennikov, Peter G; Petrov, Alexander I; Kachel, Krzysztof; Golka, Sebastian; Gogova, Daniela; Siche, Dietmar

2014-11-01

The prospects of a control for a novel gallium nitride pseudo-halide vapor phase epitaxy (PHVPE) with HCN were thoroughly analyzed for hydrocarbons-NH3-Ga gas phase on the basis of quantum chemical investigation with DFT (B3LYP, B3LYP with D3 empirical correction on dispersion interaction) and ab-initio (CASSCF, coupled clusters, and multireference configuration interaction including MRCI+Q) methods. The computational screening of reactions for different hydrocarbons (CH4, C2H6, C3H8, C2H4, and C2H2) as readily available carbon precursors for HCN formation, potential chemical transport agents, and for controlled carbon doping of deposited GaN was carried out with the B3LYP method in conjunction with basis sets up to aug-cc-pVTZ. The gas phase intermediates for the reactions in the Ga-hydrocarbon systems were predicted at different theory levels. The located π-complexes Ga…C2H2 and Ga…C2H4 were studied to determine a probable catalytic activity in reactions with NH3. A limited influence of the carbon-containing atmosphere was exhibited for the carbon doping of GaN crystal in the conventional GaN chemical vapor deposition (CVD) process with hydrocarbons injected in the gas phase. Our results provide a basis for experimental studies of GaN crystal growth with C2H4 and C2H2 as auxiliary carbon reagents for the Ga-NH3 and Ga-C-NH3 CVD systems and prerequisites for reactor design to enhance and control the PHVPE process through the HCN synthesis.

Coupling Oxygen Consumption with Hydrocarbon Oxidation in Bacterial Multicomponent Monooxygenases.

PubMed

Wang, Weixue; Liang, Alexandria D; Lippard, Stephen J

2015-09-15

A fundamental goal in catalysis is the coupling of multiple reactions to yield a desired product. Enzymes have evolved elegant approaches to address this grand challenge. A salient example is the biological conversion of methane to methanol catalyzed by soluble methane monooxygenase (sMMO), a member of the bacterial multicomponent monooxygenase (BMM) superfamily. sMMO is a dynamic protein complex of three components: a hydroxylase, a reductase, and a regulatory protein. The active site, a carboxylate-rich non-heme diiron center, is buried inside the 251 kDa hydroxylase component. The enzyme processes four substrates: O2, protons, electrons, and methane. To couple O2 activation to methane oxidation, timely control of substrate access to the active site is critical. Recent studies of sMMO, as well as its homologues in the BMM superfamily, have begun to unravel the mechanism. The emerging and unifying picture reveals that each substrate gains access to the active site along a specific pathway through the hydroxylase. Electrons and protons are delivered via a three-amino-acid pore located adjacent to the diiron center; O2 migrates via a series of hydrophobic cavities; and hydrocarbon substrates reach the active site through a channel or linked set of cavities. The gating of these pathways mediates entry of each substrate to the diiron active site in a timed sequence and is coordinated by dynamic interactions with the other component proteins. The result is coupling of dioxygen consumption with hydrocarbon oxidation, avoiding unproductive oxidation of the reductant rather than the desired hydrocarbon. To initiate catalysis, the reductase delivers two electrons to the diiron(III) center by binding over the pore of the hydroxylase. The regulatory component then displaces the reductase, docking onto the same surface of the hydroxylase. Formation of the hydroxylase-regulatory component complex (i) induces conformational changes of pore residues that may bring protons to the active site; (ii) connects hydrophobic cavities in the hydroxylase leading from the exterior to the diiron active site, providing a pathway for O2 and methane, in the case of sMMO, to the reduced diiron center for O2 activation and substrate hydroxylation; (iii) closes the pore, as well as a channel in the case of four-component BMM enzymes, restricting proton access to the diiron center during formation of "Fe2O2" intermediates required for hydrocarbon oxidation; and (iv) inhibits undesired electron transfer to the Fe2O2 intermediates by blocking reductase binding during O2 activation. This mechanism is quite different from that adopted by cytochromes P450, a large class of heme-containing monooxygenases that catalyze reactions very similar to those catalyzed by the BMM enzymes. Understanding the timed enzyme control of substrate access has implications for designing artificial catalysts. To achieve multiple turnovers and tight coupling, synthetic models must also control substrate access, a major challenge considering that nature requires large, multimeric, dynamic protein complexes to accomplish this feat.

Biomass Conversion to Produce Hydrocarbon Liquid Fuel Via Hot-vapor Filtered Fast Pyrolysis and Catalytic Hydrotreating.

PubMed

Wang, Huamin; Elliott, Douglas C; French, Richard J; Deutch, Steve; Iisa, Kristiina

2016-12-25

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and the processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. The protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.

Biomass Conversion to Produce Hydrocarbon Liquid Fuel Via Hot-vapor Filtered Fast Pyrolysis and Catalytic Hydrotreating

PubMed Central

Wang, Huamin; Elliott, Douglas C.; French, Richard J.; Deutch, Steve; Iisa, Kristiina

2016-01-01

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and the processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. The protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research. PMID:28060311

Oxidative stress in entomopathogenic fungi grown on insect-like hydrocarbons.

PubMed

Huarte-Bonnet, Carla; Juárez, M Patricia; Pedrini, Nicolás

2015-08-01

Entomopathogenic fungi mostly attack their insect hosts by penetration through the cuticle. The outermost insect surface is covered by a lipid-rich layer, usually composed of very long chain hydrocarbons. These fungi are apt to grow on straight chain hydrocarbons (alkanes) as the sole carbon source. Insect-like hydrocarbons are first hydroxylated by a microsomal P450 monooxygenase system, and then fully catabolized by peroxisomal β-oxidation reactions in Beauveria bassiana. In this review, we will discuss lipid metabolism adaptations in alkane-grown fungi, and how an oxidative stress scenario is established under these conditions. Fungi have to pay a high cost for hydrocarbon utilization; high levels of reactive oxygen species are produced and a concomitant antioxidant response is triggered in fungal cells to cope with this drawback.

The gaseous explosive reaction at constant pressure : the reaction order and reaction rate

NASA Technical Reports Server (NTRS)

Stevens, F W

1931-01-01

The data given in this report covers the explosive limits of hydrocarbon fuels. Incidental to the purpose of the investigation here reported, the explosive limits will be found to be expressed for the condition of constant pressure, in the fundamental terms of concentrations (partial pressures) of fuel and oxygen.

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.

Chloromethane to olefins over H-SAPO-34: Probing the hydrocarbon pool mechanism

DOE PAGES

Fickel, Dustin W.; Sabnis, Kaiwalya D.; Li, Luanyi; ...

2016-09-09

In this paper, by means of in situ FTIR and ex situ 13C NMR studies, the initial periods of the chloromethane-to-olefins (CTO) reaction over SAPO-34 were probed in order to investigate the activation period of the reaction and to elucidate the formation of the catalyst active site. A methylated benzene species has been observed to form during the initial activation period of the reaction, and a direct positive correlation was constructed between the formation of this species and the catalytic activity. The data thus indicate that these methylated benzene species contribute to the formation of active sites within SAPO-34 formore » the CTO reaction. This is the first known report identifying a direct semi-quantitative correlation between the catalyst activity and growth of a methylated benzene active species, during the activation period of the chloromethane to olefins reaction. Finally, the findings here in correspond well to those reported for the methanol to olefins reaction, suggesting that a similar ‘hydrocarbon pool’ mechanism may be responsible for the formation of light olefins in CTO chemistry as well.« less

Bimetallic Catalysts.

ERIC Educational Resources Information Center

Sinfelt, John H.

1985-01-01

Chemical reaction rates can be controlled by varying composition of miniscule clusters of metal atoms. These bimetallic catalysts have had major impact on petroleum refining, where work has involved heterogeneous catalysis (reacting molecules in a phase separate from catalyst.) Experimentation involving hydrocarbon reactions, catalytic…

Capacitively coupled RF diamond-like-carbon reactor

DOEpatents

Devlin, David James; Coates, Don Mayo; Archuleta, Thomas Arthur; Barbero, Robert Steven

2000-01-01

A process of coating a non-conductive fiber with diamond-like carbon, including passing a non-conductive fiber between a pair of parallel metal grids within a reaction chamber, introducing a hydrocarbon gas into the reaction chamber, forming a plasma within the reaction chamber for a sufficient period of time whereby diamond-like carbon is formed upon the non-conductive fiber, is provided together with a reactor chamber for deposition of diamond-like carbon upon a non-conductive fiber, including a vacuum chamber, a cathode assembly including a pair of electrically isolated opposingly parallel metal grids spaced apart at a distance of less than about 1 centimeter, an anode, a means of introducing a hydrocarbon gas into said vacuum chamber, and a means of generating a plasma within said vacuum chamber.

Tested Demonstrations: The Effect of Free Radical Stability on the Rate of Bromination of Hydrocarbons.

ERIC Educational Resources Information Center

Gilbert, George L., Ed.; And Others

1980-01-01

Presents a demonstration of the effect of alkyl free radical stability on the rate of free radical halogenation of hydrocarbons. The arenes toluene, ethylbenzene and comene are photobrominated comparatively, using an overhead projector both to provide a light source for the chemical reaction and to project the results on a screen. (CS)

Process for chemical reaction of amino acids and amides yielding selective conversion products

DOEpatents

Holladay, Jonathan E [Kennewick, WA

2006-05-23

The invention relates to processes for converting amino acids and amides to desirable conversion products including pyrrolidines, pyrrolidinones, and other N-substituted products. L-glutamic acid and L-pyroglutamic acid provide general reaction pathways to numerous and valuable selective conversion products with varied potential industrial uses.

Simplified Modeling of Oxidation of Hydrocarbons

NASA Technical Reports Server (NTRS)

Bellan, Josette; Harstad, Kenneth

2008-01-01

A method of simplified computational modeling of oxidation of hydrocarbons is undergoing development. This is one of several developments needed to enable accurate computational simulation of turbulent, chemically reacting flows. At present, accurate computational simulation of such flows is difficult or impossible in most cases because (1) the numbers of grid points needed for adequate spatial resolution of turbulent flows in realistically complex geometries are beyond the capabilities of typical supercomputers now in use and (2) the combustion of typical hydrocarbons proceeds through decomposition into hundreds of molecular species interacting through thousands of reactions. Hence, the combination of detailed reaction- rate models with the fundamental flow equations yields flow models that are computationally prohibitive. Hence, further, a reduction of at least an order of magnitude in the dimension of reaction kinetics is one of the prerequisites for feasibility of computational simulation of turbulent, chemically reacting flows. In the present method of simplified modeling, all molecular species involved in the oxidation of hydrocarbons are classified as either light or heavy; heavy molecules are those having 3 or more carbon atoms. The light molecules are not subject to meaningful decomposition, and the heavy molecules are considered to decompose into only 13 specified constituent radicals, a few of which are listed in the table. One constructs a reduced-order model, suitable for use in estimating the release of heat and the evolution of temperature in combustion, from a base comprising the 13 constituent radicals plus a total of 26 other species that include the light molecules and related light free radicals. Then rather than following all possible species through their reaction coordinates, one follows only the reduced set of reaction coordinates of the base. The behavior of the base was examined in test computational simulations of the combustion of heptane in a stirred reactor at various initial pressures ranging from 0.1 to 6 MPa. Most of the simulations were performed for stoichiometric mixtures; some were performed for fuel/oxygen mole ratios of 1/2 and 2.

Abiogenic formation of alkanes in the Earth's crust as a minor source for global hydrocarbon reservoirs.

PubMed

Sherwood Lollar, B; Westgate, T D; Ward, J A; Slater, G F; Lacrampe-Couloume, G

2002-04-04

Natural hydrocarbons are largely formed by the thermal decomposition of organic matter (thermogenesis) or by microbial processes (bacteriogenesis). But the discovery of methane at an East Pacific Rise hydrothermal vent and in other crustal fluids supports the occurrence of an abiogenic source of hydrocarbons. These abiogenic hydrocarbons are generally formed by the reduction of carbon dioxide, a process which is thought to occur during magma cooling and-more commonly-in hydrothermal systems during water-rock interactions, for example involving Fischer-Tropsch reactions and the serpentinization of ultramafic rocks. Suggestions that abiogenic hydrocarbons make a significant contribution to economic hydrocarbon reservoirs have been difficult to resolve, in part owing to uncertainty in the carbon isotopic signatures for abiogenic versus thermogenic hydrocarbons. Here, using carbon and hydrogen isotope analyses of abiogenic methane and higher hydrocarbons in crystalline rocks of the Canadian shield, we show a clear distinction between abiogenic and thermogenic hydrocarbons. The progressive isotopic trends for the series of C1-C4 alkanes indicate that hydrocarbon formation occurs by way of polymerization of methane precursors. Given that these trends are not observed in the isotopic signatures of economic gas reservoirs, we can now rule out the presence of a globally significant abiogenic source of hydrocarbons.

High Energy-Density and Reversibility of Iron Fluoride Cathode Enabled Via an Intercalation-Extrusion Reaction

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

Fan, Xiulin; Hu, Enyuan; Ji, Xiao

Iron fluoride, an intercalation-conversion cathode for lithium ion batteries, promises a high theoretical energy density of 1922 Wh Kg –1. However, poor electrochemical reversibility due to repeated breaking/reformation of metal-fluoride bonds poses a grand challenge for its practical application. Here we report that both a high reversibility over 1000 cycles and a high capacity of 420 mAh g –1 can be realized by concerted doping of cobalt and oxygen into iron fluoride. In the doped nanorods, an energy density of ~1000 Wh Kg –1 with a decay rate of 0.03% per cycle is achieved. The anion and cation’s co-substitutions thermodynamicallymore » reduce conversion-reaction potential and shift the reaction from less reversible intercalation-conversion reaction in iron fluoride to a highly reversible intercalation-extrusion reaction in doped material. Furthermore, the co-substitution strategy to tune the thermodynamic features of the reactions could be extended to other high energy conversion materials for improved performance.« less

High Energy-Density and Reversibility of Iron Fluoride Cathode Enabled Via an Intercalation-Extrusion Reaction

DOE PAGES

Fan, Xiulin; Hu, Enyuan; Ji, Xiao; ...

2018-05-30

Iron fluoride, an intercalation-conversion cathode for lithium ion batteries, promises a high theoretical energy density of 1922 Wh Kg –1. However, poor electrochemical reversibility due to repeated breaking/reformation of metal-fluoride bonds poses a grand challenge for its practical application. Here we report that both a high reversibility over 1000 cycles and a high capacity of 420 mAh g –1 can be realized by concerted doping of cobalt and oxygen into iron fluoride. In the doped nanorods, an energy density of ~1000 Wh Kg –1 with a decay rate of 0.03% per cycle is achieved. The anion and cation’s co-substitutions thermodynamicallymore » reduce conversion-reaction potential and shift the reaction from less reversible intercalation-conversion reaction in iron fluoride to a highly reversible intercalation-extrusion reaction in doped material. Furthermore, the co-substitution strategy to tune the thermodynamic features of the reactions could be extended to other high energy conversion materials for improved performance.« less

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Method for silicon carbide production by reacting silica with hydrocarbon gas

DOEpatents

Glatzmaier, G.C.

1994-06-28

A method is described for producing silicon carbide particles using a silicon source material and a hydrocarbon. The method is efficient and is characterized by high yield. Finely divided silicon source material is contacted with hydrocarbon at a temperature of 400 C to 1000 C where the hydrocarbon pyrolyzes and coats the particles with carbon. The particles are then heated to 1100 C to 1600 C to cause a reaction between the ingredients to form silicon carbide of very small particle size. No grinding of silicon carbide is required to obtain small particles. The method may be carried out as a batch process or as a continuous process. 5 figures.

Method for silicon carbide production by reacting silica with hydrocarbon gas

DOEpatents

Glatzmaier, Gregory C.

1994-01-01

A method is described for producing silicon carbide particles using a silicon source material and a hydrocarbon. The method is efficient and is characterized by high yield. Finely divided silicon source material is contacted with hydrocarbon at a temperature of 400.degree. C. to 1000.degree. C. where the hydrocarbon pyrolyzes and coats the particles with carbon. The particles are then heated to 1100.degree. C. to 1600.degree. C. to cause a reaction between the ingredients to form silicon carbide of very small particle size. No grinding of silicon carbide is required to obtain small particles. The method may be carried out as a batch process or as a continuous process.

Catalysts for the production of hydrocarbons from carbon monoxide and water

DOEpatents

Sapienza, Richard S.; Slegeir, William A.; Goldberg, Robert I.

1987-04-07

A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: and for olefinic hydrocarbons: where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Hydrogen and elemental carbon production from natural gas and other hydrocarbons

DOEpatents

Detering, Brent A.; Kong, Peter C.

2002-01-01

Diatomic hydrogen and unsaturated hydrocarbons are produced as reactor gases in a fast quench reactor. During the fast quench, the unsaturated hydrocarbons are further decomposed by reheating the reactor gases. More diatomic hydrogen is produced, along with elemental carbon. Other gas may be added at different stages in the process to form a desired end product and prevent back reactions. The product is a substantially clean-burning hydrogen fuel that leaves no greenhouse gas emissions, and elemental carbon that may be used in powder form as a commodity for several processes.

Distinctive activation and functionalization of hydrocarbon C-H bonds initiated by Cp*W(NO)(η(3)-allyl)(CH2CMe3) complexes.

PubMed

Baillie, Rhett A; Legzdins, Peter

2014-02-18

Converting hydrocarbon feedstocks into value-added chemicals continues to offer challenges to contemporary preparative chemists. A particularly important remaining challenge is the selective activation and functionalization of the C(sp(3))-H linkages of alkanes, which are relatively abundant but chemically inert. This Account outlines the discovery and development of C-H bond functionalization mediated by a family of tungsten organometallic nitrosyl complexes. Specifically, it describes how gentle thermolyses of any of four 18-electron Cp*W(NO)(η(3)-allyl)(CH2CMe3) complexes (Cp* = η(5)-C5Me5; η(3)-allyl = η(3)-H2CCHCHMe, η(3)-H2CCHCHSiMe3, η(3)-H2CCHCHPh, or η(3)-H2CCHCMe2) results in the loss of neopentane and the transient formation of a 16-electron intermediate species, Cp*W(NO)(η(2)-allene) and/or Cp*W(NO)(η(2)-diene). We have never detected any of these species spectroscopically, but we infer their existence based on trapping experiments with trimethylphosphine (PMe3) and labeling experiments using deuterated hydrocarbon substrates. This Account first summarizes the syntheses and properties of the four chiral Cp*W(NO)(η(3)-allyl)(CH2CMe3) complexes. It then outlines the various types of C-H activations we have effected with each of the 16-electron (η(2)-allene) or (η(2)-diene) intermediate nitrosyl complexes, and presents the results of mechanistic investigations of some of these processes. It next describes the characteristic chemical properties of the Cp*W(NO)(η(3)-allyl)(η(1)-hydrocarbyl) compounds formed by the single activations of C(sp(3))-H bonds, with particular emphasis on those reactions that result in the selective functionalization of the original hydrocarbon substrate. We are continuing development of methods to release the acyl ligands from the metal centers while keeping the Cp*W(NO)(η(3)-allyl) fragments intact, with the ultimate aim of achieving these distinctive conversions of alkanes into functionalized organics in a catalytic manner.

Influence of vegetable oils fatty acid composition on reaction temperature and glycerides conversion to biodiesel during transesterification.

PubMed

Pinzi, S; Gandía, L M; Arzamendi, G; Ruiz, J J; Dorado, M P

2011-01-01

Presence of unreacted glycerides in biodiesel may reduce drastically its quality. This is why conversion of raw material in biodiesel through transesterification needs to readjust reaction parameter values to complete. In the present work, monitoring of glycerides transformation in biodiesel during the transesterification of vegetable oils was carried out. To check the influence of the chemical composition on glycerides conversion, selected vegetable oils covered a wide range of fatty acid composition. Reactions were carried out under alkali-transesterification in the presence of methanol. In addition, a multiple regression model was proposed. Results showed that kinetics depends on chemical and physical properties of the oils. It was found that the optimal reaction temperature depends on both length and unsaturation degree of vegetable oils fatty acid chains. Vegetable oils with higher degree of unsaturation exhibit faster monoglycerides conversion to biodiesel. It can be concluded that fatty acid composition influences reaction parameters and glycerides conversion, hence biodiesel yield and economic viability. Copyright © 2010 Elsevier Ltd. All rights reserved.

Diesel particle filter and fuel effects on heavy-duty diesel engine emissions.

PubMed

Ratcliff, Matthew A; Dane, A John; Williams, Aaron; Ireland, John; Luecke, Jon; McCormick, Robert L; Voorhees, Kent J

2010-11-01

The impacts of biodiesel and a continuously regenerated (catalyzed) diesel particle filter (DPF) on the emissions of volatile unburned hydrocarbons, carbonyls, and particle associated polycyclic aromatic hydrocarbons (PAH) and nitro-PAH, were investigated. Experiments were conducted on a 5.9 L Cummins ISB, heavy-duty diesel engine using certification ultra-low-sulfur diesel (ULSD, S ≤ 15 ppm), soy biodiesel (B100), and a 20% blend thereof (B20). Against the ULSD baseline, B20 and B100 reduced engine-out emissions of measured unburned volatile hydrocarbons and PM associated PAH and nitro-PAH by significant percentages (40% or more for B20 and higher percentage for B100). However, emissions of benzene were unaffected by the presence of biodiesel and emissions of naphthalene actually increased for B100. This suggests that the unsaturated FAME in soy-biodiesel can react to form aromatic rings in the diesel combustion environment. Methyl acrylate and methyl 3-butanoate were observed as significant species in the exhaust for B20 and B100 and may serve as markers of the presence of biodiesel in the fuel. The DPF was highly effective at converting gaseous hydrocarbons and PM associated PAH and total nitro-PAH. However, conversion of 1-nitropyrene by the DPF was less than 50% for all fuels. Blending of biodiesel caused a slight reduction in engine-out emissions of acrolein, but otherwise had little effect on carbonyl emissions. The DPF was highly effective for conversion of carbonyls, with the exception of formaldehyde. Formaldehyde emissions were increased by the DPF for ULSD and B20.

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

Dong, Tao; Fei, Qiang; Genelot, Marie

In light of the availability of low-cost methane (CH 4) derived from natural gas and biogas along with increasing concerns of the greenhouse gas emissions, the production of alternative liquid biofuels directly from CH 4 is a promising approach to capturing wasted energy. A novel biorefinery concept integrating biological conversion of CH 4 to microbial lipids together with lipid extraction and generation of hydrocarbon fuels is demonstrated in this study for the first time. An aerobic methanotrophic bacterium, Methylomicrobium buryatense capable of using CH 4 as the sole carbon source was selected on the basis of genetic tractability, cultivation robustness,more » and ability to accumulate phospholipids in membranes. A maximum fatty acid content of 10% of dry cell weight was obtained in batch cultures grown in a continuous gas sparging fermentation system. Although phospholipids are not typically considered as a good feedstock for upgrading to hydrocarbon fuels, we set out to demonstrate that using a combination of novel lipid extraction methodology with advanced catalyst design, we could prove the feasibility of this approach. Up to 95% of the total fatty acids from membrane-bound phospholipids were recovered by a two-stage pretreatment method followed by hexane extraction of the aqueous hydrolysate. The upgrading of extracted lipids was then demonstrated in a hydrodeoxygeation process using palladium on silica as a catalyst. Lipid conversion in excess of 99% was achieved, with a full selectivity to hydrocarbons. Lastly, the final hydrocarbon mixture is dominated by 88% pentadecane (C 15H 32) based on decarbonylation/decarboxylation and hydrogenation of C16 fatty acids, indicating that a biological gas-to-liquid fuel (Bio-GTL) process is technically feasible.« less

Conjugated ladder polymers by a cyclopentannulation polymerization

DOE PAGES

Bheemireddy, Sambasiva R.; Hautzinger, Matthew P.; Li, Tao; ...

2017-04-03

Here, we report a nontraditional synthesis of cyclopentafused-polycyclic aromatic hydrocarbon embedded ladder polymers using a palladium catalyzed cyclopentannulation polymerization followed by a cyclodehydrogenation reaction. Donor–acceptor type polymers containing a cyclopenta[hi]aceanthrylene acceptor groups can be synthesized by a palladium catalyzed copolymerization between 9,10-dibromoanthracene and a variety of bis(arylethynyl)arenes to give polymers with molecular weights (Mn) of 9–22 kDa. The bis(arylethynyl)arenes were composed of benzene, thiophene, or thieno[3,2- b]thiophene moieties, which provided access to a series of four donor–acceptor copolymers. The polymers were subjected to cyclodehydrogenation with FeCl 3 to access rigid ladder type polymers with the conversion investigated by 13C NMRmore » of isotopically labeled polymers. As a result, the ladder polymers possess broad UV–Vis absorptions and narrow optical band gaps of 1.17–1.29 eV and are p-type semiconductors in organic field effect transistors.« less

Conjugated ladder polymers by a cyclopentannulation polymerization

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

Bheemireddy, Sambasiva R.; Hautzinger, Matthew P.; Li, Tao

Here, we report a nontraditional synthesis of cyclopentafused-polycyclic aromatic hydrocarbon embedded ladder polymers using a palladium catalyzed cyclopentannulation polymerization followed by a cyclodehydrogenation reaction. Donor–acceptor type polymers containing a cyclopenta[hi]aceanthrylene acceptor groups can be synthesized by a palladium catalyzed copolymerization between 9,10-dibromoanthracene and a variety of bis(arylethynyl)arenes to give polymers with molecular weights (Mn) of 9–22 kDa. The bis(arylethynyl)arenes were composed of benzene, thiophene, or thieno[3,2- b]thiophene moieties, which provided access to a series of four donor–acceptor copolymers. The polymers were subjected to cyclodehydrogenation with FeCl 3 to access rigid ladder type polymers with the conversion investigated by 13C NMRmore » of isotopically labeled polymers. As a result, the ladder polymers possess broad UV–Vis absorptions and narrow optical band gaps of 1.17–1.29 eV and are p-type semiconductors in organic field effect transistors.« less

Separation of catalyst from Fischer-Tropsch slurry

DOEpatents

White, C.M.; Quiring, M.S.; Jensen, K.L.; Hickey, R.F.; Gillham, L.D.

1998-10-27

In a catalytic process for converting synthesis gas including hydrogen and carbon monoxide to hydrocarbons and oxygenates by a slurry Fischer-Tropsch synthesis, the wax product along with dispersed catalyst is removed from the slurry and purified by removing substantially all of the catalyst prior to upgrading the wax and returning a portion to the Fischer-Tropsch reaction. Separation of the catalyst particles from the wax product is accomplished by dense gas and/or liquid extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic in nature. The purified catalyst-free wax product can be subsequently upgraded by various methods such as hydrogenation, isomerization, hydrocracking, conversion to gasoline and other products over ZSM-5 aluminosilicate zeolite, etc. The catalyst particles are returned to the Fischer-Tropsch Reactor by mixing them with a wax fraction of appropriate molecular weight, boiling point and viscosity to avoid reactor gelation. 2 figs.

A review of catalytic microwave pyrolysis of lignocellulosic biomass for value-added fuel and chemicals.

PubMed

Morgan, Hervan Marion; Bu, Quan; Liang, Jianghui; Liu, Yujing; Mao, Hanping; Shi, Aiping; Lei, Hanwu; Ruan, Roger

2017-04-01

Lignocellulosic biomass is an abundant renewable resource and can be efficiently converted into bio-energy by a bio-refinery. From the various techniques available for biomass thermo-chemical conversion; microwave assisted pyrolysis (MAP) seems to be the very promising. The principles of microwave technology were reviewed and the parameters for the efficient production of bio-oil using microwave technology were summarized. Microwave technology by itself cannot efficiently produce high quality bio-oil products, catalysts are used to improve the reaction conditions and selectivity for valued products during MAP. The catalysts used to optimize MAP are revised in the development of this article. The origins for bio-oils that are phenol rich or hydrocarbon rich are reviewed and their experimental results were summarized. The kinetics of MAP is discussed briefly in the development of the article. Future prospects and scientific development of MAP are also considered in the development of this article. Copyright © 2017 Elsevier Ltd. All rights reserved.

First-principles quantum-mechanical investigations: The role of water in catalytic conversion of furfural on Pd(111)

NASA Astrophysics Data System (ADS)

Xue, Wenhua; Borja, Miguel Gonzalez; Resasco, Daniel E.; Wang, Sanwu

2015-03-01

In the study of catalytic reactions of biomass, furfural conversion over metal catalysts with the presence of water has attracted wide attention. Recent experiments showed that the proportion of alcohol product from catalytic reactions of furfural conversion with palladium in the presence of water is significantly increased, when compared with other solvent including dioxane, decalin, and ethanol. We investigated the microscopic mechanism of the reactions based on first-principles quantum-mechanical calculations. We particularly identified the important role of water and the liquid/solid interface in furfural conversion. Our results provide atomic-scale details for the catalytic reactions. Supported by DOE (DE-SC0004600). This research used the supercomputer resources at NERSC, of XSEDE, at TACC, and at the Tandy Supercomputing Center.

System and process for producing fuel with a methane thermochemical cycle

DOEpatents

Diver, Richard B.

2015-12-15

A thermochemical process and system for producing fuel are provided. The thermochemical process includes reducing an oxygenated-hydrocarbon to form an alkane and using the alkane in a reforming reaction as a reducing agent for water, a reducing agent for carbon dioxide, or a combination thereof. Another thermochemical process includes reducing a metal oxide to form a reduced metal oxide, reducing an oxygenated-hydrocarbon with the reduced metal oxide to form an alkane, and using the alkane in a reforming reaction as a reducing agent for water, a reducing agent for carbon dioxide, or a combination thereof. The system includes a reformer configured to perform a thermochemical process.

Kinetic modeling of secondary organic aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Kroll, J. H.; Ng, N. L.; Seinfeld, J. H.

2007-08-01

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

Kinetic modeling of Secondary Organic Aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Kroll, J. H.; Ng, N. L.; Seinfeld, J. H.

2007-05-01

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

Fate of microbial metabolites of hydrocarbons in a coastal plain aquifer: The role of electron acceptors

USGS Publications Warehouse

Cozzarelli, I.M.; Herman, J.S.; Baedecker, M. Jo

1995-01-01

A combined field and laboratory study was undertaken to understand the distribution and geochemical conditions that influence the prevalence of low molecular weight organic acids in groundwater of a shallow aquifer contaminated with gasoline. Aromatic hydrocarbons from gasoline were degraded by microbially mediated oxidation-reduction reactions, including reduction of nitrate, sulfate, and Fe(III). The biogeochemical reactions changed overtime in response to changes in the hydrogeochemical conditions in the aquifer. Aliphatic and aromatic organic acids were associated with hydrocarbon degradation in anoxic zones of the aquifer. Laboratory microcosms demonstrated that the biogeochemical fate of specific organic acids observed in groundwater varied with the structure of the acid and the availability of electron acceptors. Benzoic and phenylacetic acid were degraded by indigenous aquifer microorganisms when nitrate was supplied as an electron acceptor. Aromatic acids with two or more methyl substituants on the benzene ring persisted under nitrate-reducing conditions. Although iron reduction and sulfate reduction were important processes in situ and occurred in the microcosms, these reactions were not coupled to the biological oxidation of aromatic organic acids that were added to the microcosms as electron donors. ?? 1995 American Chemical Society.

The Preparation and Physical Properties of Several Aliphatic Hydrocarbons and Intermediates

DTIC Science & Technology

1947-05-01

34. •: • : - •’•«-" In’ order to-determine the optimum conditions for conversion of the glycol to 2,3-&imethyl-i,3~’butadiene, a series of- test runs were made...pentene to ^,lt--dimethyl-2-pentanone (methyl neopentyl ketone), (b) oxida- tion of this ketone to t-butylacetic acid, (c) conversion, of the acid to...Kenneth C: The Dehydration of Tertiary Alcohols Containing a Neopentyl System. H - Methyliso- propyl-tert-butylcarbinol, Methyldl-tert-butylcarbinol

Studies Relevent to Catalytic Activation Co & other small Molecules

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

Ford, Peter C

2005-02-22

Detailed annual and triannual reports describing the progress accomplished during the tenure of this grant were filed with the Program Manager for Catalysis at the Office of Basic Energy Sciences. To avoid unnecessary duplication, the present report will provide a brief overview of the research areas that were sponsored by this grant and list the resulting publications and theses based on this DOE supported research. The scientific personnel participating in (and trained by) this grant's research are also listed. Research carried out under this DOE grant was largely concerned with the mechanisms of the homogeneous catalytic and photocatalytic activation ofmore » small molecules such as carbon monoxide, dihydrogen and various hydrocarbons. Much of the more recent effort has focused on the dynamics and mechanisms of reactions relevant to substrate carbonylations by homogeneous organometallic catalysts. A wide range of modern investigative techniques were employed, including quantitative fast reaction methodologies such as time-resolved optical (TRO) and time-resolved infrared (TRIR) spectroscopy and stopped flow kinetics. Although somewhat diverse, this research falls within the scope of the long-term objective of applying quantitative techniques to elucidate the dynamics and understand the principles of mechanisms relevant to the selective and efficient catalytic conversions of fundamental feedstocks to higher value materials.« less

The peroxidase-mediated biodegradation of petroleum hydrocarbons in a H2O2-induced SBR using in-situ production of peroxidase: Biodegradation experiments and bacterial identification.

PubMed

Shekoohiyan, Sakine; Moussavi, Gholamreza; Naddafi, Kazem

2016-08-05

A bacterial peroxidase-mediated oxidizing process was developed for biodegrading total petroleum hydrocarbons (TPH) in a sequencing batch reactor (SBR). Almost complete biodegradation (>99%) of high TPH concentrations (4g/L) was attained in the bioreactor with a low amount (0.6mM) of H2O2 at a reaction time of 22h. A specific TPH biodegradation rate as high as 44.3mgTPH/gbiomass×h was obtained with this process. The reaction times required for complete biodegradation of TPH concentrations of 1, 2, 3, and 4g/L were 21, 22, 28, and 30h, respectively. The catalytic activity of hydrocarbon catalyzing peroxidase was determined to be 1.48U/mL biomass. The biodegradation of TPH in seawater was similar to that in fresh media (no salt). A mixture of bacteria capable of peroxidase synthesis and hydrocarbon biodegradation including Pseudomonas spp. and Bacillus spp. were identified in the bioreactor. The GC/MS analysis of the effluent indicated that all classes of hydrocarbons could be well-degraded in the H2O2-induced SBR. Accordingly, the peroxidase-mediated process is a promising method for efficiently biodegrading concentrated TPH-laden saline wastewater. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Pyrolysis of polyethylene terephthalate containing real waste plastics using Ni loaded zeolite catalysts

NASA Astrophysics Data System (ADS)

Al-asadi, M.; Miskolczi, N.

2018-05-01

In this work the pyrolysis of polyethylene terephthalate (PET) containing real waste plastic was investigated using different Ni loaded catalysts: Ni/ZSM-5, Ni/y-zeolite, Ni/β-zeolite and Ni/natural zeolite (clinoptilolite). Raw materials were pyrolyzed in a horizontal tubular reactor between 600 and 900°C using 10% of catalysts. It was found, that both temperature increasing and catalysts presence can increase the gas yields, however owing to gasification reactions, the pyrolysis oil yield decreased with increasing temperature. Ni/y-zeolite catalyst had the most benefit in gas yield increasing at low temperature; however Ni/ZSM-5 showed advanced property in gas yield increasing at high temperature. Gases contained hydrogen, carbon oxides and hydrocarbons, which composition was significantly affected by catalysts. Ni loaded zeolites favoured to the formation of hydrogen and branched hydrocarbons; furthermore the concentrations of both CO and CO2 were also increased as function of elevated temperature. That phenomenon was attributed to the further decomposition of PET, especially to the side chain scission reactions. Owing to the Boudouard reaction, the ratio of CO2/CO can increased with temperature. Pyrolysis oils were the mixtures of n-saturated, n-unsaturated, branched, oxygen free aromatics and oxygenated hydrocarbons. Temperature increasing has a significant effect to the aromatization and isomerization reactions, while the catalysts can efficiently decreased the concentration of oxygen containing compounds.

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

DOE PAGES

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; ...

2017-11-14

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4, Ln(OTf) 3, In(OTf) 3, Al(OTf) 3] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt %more » of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.« less

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

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

Wang, Hongliang; Wang, Huamin; Kuhn, Eric

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4, Ln(OTf) 3, In(OTf) 3, Al(OTf) 3] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt %more » of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.« less

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

PubMed

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

2018-01-10

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for hydrocracking a heavy polynuclear hydrocarbonaceous feedstock in the presence of a molten metal halide catalyst

DOEpatents

Gorin, Everett

1981-01-01

A method for hydrocracking a heavy polynuclear hydrocarbonaceous feedstock to produce lighter hydrocarbon fuels by contacting the feedstock with hydrogen in the presence of a molten metal halide catalyst, the method comprising: mixing the feedstock with a heavy naphtha fraction which has an initial boiling point from about 100.degree. to about 160.degree. C. with a boiling point difference between the initial boiling point and the final boiling point of no more than about 50.degree. C. to produce a mixture; thereafter contacting the mixture with partially spent molten metal halide and hydrogen under temperature and pressure conditions so that the temperature is near the critical temperature of the heavy naphtha fraction; separating at least a portion of the heavy naphtha fraction and lighter hydrocarbon fuels from the partially spent molten metal halide, unreacted feedstock and reaction products; thereafter contacting the partially spent molten metal halide, unreacted feedstock and reaction products with hydrogen and fresh molten metal halide in a hydrocracking zone to produce additional lighter hydrocarbon fuels and separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide.

Study of parameters affecting the conversion in a plug flow reactor for reactions of the type 2A→B

NASA Astrophysics Data System (ADS)

Beltran-Prieto, Juan Carlos; Long, Nguyen Huynh Bach Son

2018-04-01

Modeling of chemical reactors is an important tool to quantify reagent conversion, product yield and selectivity towards a specific compound and to describe the behavior of the system. Proposal of differential equations describing the mass and energy balance are among the most important steps required during the modeling process as they play a special role in the design and operation of the reactor. Parameters governing transfer of heat and mass have a strong relevance in the rate of the reaction. Understanding this information is important for the selection of reactor and operating regime. In this paper we studied the irreversible gas-phase reaction 2A→B. We model the conversion that can be achieved as function of the reactor volume and feeding temperature. Additionally, we discuss the effect of activation energy and the heat of reaction on the conversion achieved in the tubular reactor. Furthermore, we considered that dimerization occurs instantaneously in the catalytic surface to develop equations for the determination of rate of reaction per unit area of three different catalytic surface shapes. This data can be combined with information about the global rate of conversion in the reactor to improve regent conversion and yield of product.

Hydrocarbon pyrolysis reactor experimentation and modeling for the production of solar absorbing carbon nanoparticles

NASA Astrophysics Data System (ADS)

Frederickson, Lee Thomas

Much of combustion research focuses on reducing soot particulates in emissions. However, current research at San Diego State University (SDSU) Combustion and Solar Energy Laboratory (CSEL) is underway to develop a high temperature solar receiver which will utilize carbon nanoparticles as a solar absorption medium. To produce carbon nanoparticles for the small particle heat exchange receiver (SPHER), a lab-scale carbon particle generator (CPG) has been built and tested. The CPG is a heated ceramic tube reactor with a set point wall temperature of 1100-1300°C operating at 5-6 bar pressure. Natural gas and nitrogen are fed to the CPG where natural gas undergoes pyrolysis resulting in carbon particles. The gas-particle mixture is met downstream with dilution air and sent to the lab scale solar receiver. To predict soot yield and general trends in CPG performance, a model has been setup in Reaction Design CHEMKIN-PRO software. One of the primary goals of this research is to accurately measure particle properties. Mean particle diameter, size distribution, and index of refraction are calculated using Scanning Electron Microscopy (SEM) and a Diesel Particulate Scatterometer (DPS). Filter samples taken during experimentation are analyzed to obtain a particle size distribution with SEM images processed in ImageJ software. These results are compared with the DPS, which calculates the particle size distribution and the index of refraction from light scattering using Mie theory. For testing with the lab scale receiver, a particle diameter range of 200-500 nm is desired. Test conditions are varied to understand effects of operating parameters on particle size and the ability to obtain the size range. Analysis of particle loading is the other important metric for this research. Particle loading is measured downstream of the CPG outlet and dilution air mixing point. The air-particle mixture flows through an extinction tube where opacity of the mixture is measured with a 532 nm laser and detector. Beer's law is then used to calculate particle loading. The CPG needs to produce a certain particle loading for a corresponding receiver test. By obtaining the particle loading in the system, the reaction conversion to solid carbon in the CPG can be calculated to measure the efficiency of the CPG. To predict trends in reaction conversion and particle size from experimentation, the CHEMKIN-PRO computer model for the CPG is run for various flow rates and wall temperature profiles. These predictions were a reason for testing at higher wall set point temperatures. Based on these research goals, it was shown that the CPG consistently produces a mean particle diameter of 200-400 nm at the conditions tested, fitting perfectly inside the desired range. This led to successful lab scale SPHER testing which produced a 10-point efficiency increase and 150°C temperature difference with particles present. Also, at 3 g/s dilution air flow rate, an efficiency of 80% at an outlet temperature above 800°C was obtained. Promise was shown at higher CPG experimental temperatures to produce higher reaction conversion, both experimentally and in the model. However, based on wall temperature data taken during experimentation, it is apparent that the CPG needs to have multiple heating zones with separate temperature controllers in order to have an isothermal zone rather than a parabolic temperature profile. As for the computer model, it predicted much higher reaction conversion at higher temperature. The mass fraction of fuel in the inlet stream was shown to not affect conversion while increasing residence time led to increasing conversion. Particle size distribution in the model was far off and showed a bimodal distribution for one of the statistical methods. Using the results from experimentation and modeling, a preliminary CPG design is presented that will operate in a 5MWth receiver system.

Dermal exposure to jet fuel suppresses delayed-type hypersensitivity: a critical role for aromatic hydrocarbons.

PubMed

Ramos, Gerardo; Limon-Flores, Alberto Yairh; Ullrich, Stephen E

2007-12-01

Dermal exposure to military (JP-8) and/or commercial (Jet-A) jet fuel suppresses cell-mediated immune reactions. Immune regulatory cytokines and biological modifiers, including platelet activating factor (PAF), prostaglandin E(2), and interleukin-10, have been implicated in the pathway of events leading to immune suppression. It is estimated that approximately 260 different hydrocarbons are found in jet fuel, and the exact identity of the active immunotoxic agent(s) is unknown. The recent availability of synthetic jet fuel (S-8), which is refined from natural gas, and is devoid of aromatic hydrocarbons, made it feasible to design experiments to address this problem. Here we tested the hypothesis that the aromatic hydrocarbons present in jet fuel are responsible for immune suppression. We report that applying S-8 to the skin of mice does not upregulate the expression of epidermal cyclooxygenase-2 (COX-2) nor does it induce immune suppression. Adding back a cocktail of seven of the most prevalent aromatic hydrocarbons found in jet fuel (benzene, toluene, ethylbenzene, xylene, 1,2,4-trimethlybenzene, cyclohexylbenzene, and dimethylnaphthalene) to S-8 upregulated epidermal COX-2 expression and suppressed a delayed-type hypersensitivity (DTH) reaction. Injecting PAF receptor antagonists, or a selective cycloozygenase-2 inhibitor into mice treated with S-8 supplemented with the aromatic cocktail, blocked suppression of DTH, similar to data previously reported using JP-8. These findings identify the aromatic hydrocarbons found in jet fuel as the agents responsible for suppressing DTH, in part by the upregulation of COX-2, and the production of immune regulatory factors and cytokines.

Four dimensional X-ray imaging of deformation modes in organic-rich Green River Shale retorted under uniaxial compression

NASA Astrophysics Data System (ADS)

Kobchenko, M.; Pluymakers, A.; Cordonnier, B.; Tairova, A.; Renard, F.

2017-12-01

Time-lapse imaging of fracture network development in organic-rich shales at elevated temperatures while kerogen is retorted allows characterizing the development of microfractures and the onset of primary migration. When the solid organic matter is transformed to hydrocarbons with lower molecular weight, the local pore-pressure increases and drives the propagation of hydro-fractures sub-parallel to the shale lamination. On the scale of samples of several mm size, these fractures can be described as mode I opening, where fracture walls dilate in the direction of minimal compression. However, so far experiments coupled to microtomography in situ imaging have been performed on samples where no load was imposed. Here, an external load was applied perpendicular to the sample laminations and we show that this stress state slows down, but does not stop, the propagation of fracture along bedding. Conversely, microfractures also propagate sub-perpendicular to the shale lamination, creating a percolating network in three dimensions. To monitor this process we have used a uniaxial compaction rig combined with in-situ heating from 50 to 500 deg C, while capturing three-dimensional X-ray microtomography scans at a voxel resolution of 2.2 μm; Data were acquired at beamline ID19 at the European Synchrotron Radiation Facility. In total ten time-resolved experiments were performed at different vertical loading conditions, with and without lateral passive confinement and different heating rates. At high external load the sample fails by symmetric bulging, while at lower external load the reaction-induced fracture network develops with the presence of microfractures both sub-parallel and sub-perpendicular to the bedding direction. In addition, the variation of experimental conditions allows the decoupling of the effects of the hydrocarbon decomposition reaction on the deformation process from the influence of thermal stress heating on the weakening and failure mode of immature shale.

Photo-induced CO2 reduction by CH4/H2O to fuels over Cu-modified g-C3N4 nanorods under simulated solar energy

NASA Astrophysics Data System (ADS)

Tahir, Beenish; Tahir, Muhammad; Amin, Nor Aishah Saidina

2017-10-01

Copper modified polymeric graphitic carbon nitride (Cu/g-C3N4) nanorods for photo-induced CO2 conversion with methane (CH4) and water (H2O) as reducing system under simulated solar energy has been investigated. The nanocatalysts, synthesized by pyrolysis and sonication, were characterized by XRD, FTIR, Raman analysis, XPS, SEM, N2 adsorption-desorption and PL spectroscopy. The presence of Cu2+ ions over the g-C3N4 structure inhibited charge carriers recombination process. The results indicated that photo-activity and selectivity of Cu/g-C3N4 photo-catalyst for CO2 reduction greatly dependent on the type of CO2-reduction system. CO2 was efficiently converted to CH4 and CH3OH with traces of C2H4 and C2H6 hydrocarbons in the CO2-water system. The yield of the main product, CH4 over 3 wt.% Cu/g-C3N4 was 109 μmole g-cata.-1 h-1 under visible light irradiation, significantly higher than the pure g-C3N4 catalyst (60 μmole/g.cat). In photo-induced CO2-CH4 reaction, CO and H2 were detected as the main products with smaller amount of hydrocarbons. The highest efficiency was detected over 3 wt.%Cu-loading of g-C3N4 and at optimal CH4/CO2 feed ratio of 1.0. The maximum yield of CO and H2 detected were 142 and 76 μmole g-catal.-1 h-1, respectively at selectivity 66.6% and 32.5%, respectively. Significantly enhanced CO2/CH4 reduction over Cu/g-C3N4 was attributed to its polymeric structure with efficient charge transfer property and inhibited charges recombination rate. A proposed photo-induced reaction mechanism, corroborated with the experimental data, was also deliberated.

High Temperature Chemistry of Aromatic Hydrocarbons. Final Technical Report

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

Scott, Lawrence T.

The primary goal of this research was to uncover the principal reaction channels available to polycyclic aromatic hydrocarbons (PAHs) at high temperatures in the gas phase and to establish the factors that determine which channels will be followed in varying circumstances. New structure-property relationships for PAHs were also studied. The efficient production of clean energy from fossil fuels will remain a major component of the DOE mission until alternative sources of energy eventually displace coal and petroleum. Hydrocarbons constitute the most basic class of compounds in all of organic chemistry, and as the dominant species in fossil fuels, they figuremore » prominently into the programs of the DOE. Much is already known about the normal chemistry of hydrocarbons under ambient conditions, but far less is known about their intrinsic chemistry at temperatures close to those reached during combustion. An understanding of the fundamental molecular transformations, rearrangements, and interconversions of PAHs at high temperatures in the gas phase, as revealed by careful studies on small, well-designed, molecular systems, provides insights into the underlying chemistry of many important processes that are more complex, such as the generation of energy by the combustion of fossil fuels, the uncatalyzed gasification and liquefaction of coal, the production of fullerenes in fuel-rich flames, and the formation of soot and carcinogenic pollutants in smoke (e.g., benzo[a]pyrene). The rational control of any of these processes, whether it be the optimization of a desirable process or the minimization of an undesirable one, requires a clear knowledge of the basic chemistry that governs the fate of the species involved. Advances in chemistry at the most fundamental level come about primarily from the discovery of new reactions and from new insights into how reactions occur. Harnessing that knowledge is the key to new technologies. The recent commercialization of a combustion synthesis of C 60 and other fullerenes depended critically on a knowledge of hydrocarbon reactions at high temperatures in the gas phase, and the research supported by this project enabled further advances in the realm of carbon-rich materials.« less

Developing clean fuels: Novel techniques for desulfurization

NASA Astrophysics Data System (ADS)

Nehlsen, James P.

The removal of sulfur compounds from petroleum is crucial to producing clean burning fuels. Sulfur compounds poison emission control catalysts and are the source of acid rain. New federal regulations require the removal of sulfur in both gasoline and diesel to very low levels, forcing existing technologies to be pushed into inefficient operating regimes. New technology is required to efficiently produce low sulfur fuels. Two processes for the removal of sulfur compounds from petroleum have been developed: the removal of alkanethiols by heterogeneous reaction with metal oxides; and oxidative desulfurization of sulfides and thiophene by reaction with sulfuric acid. Alkanethiols, common in hydrotreated gasoline, can be selectively removed and recovered from a hydrocarbon stream by heterogeneous reaction with oxides of Pb, Hg(II), and Ba. The choice of reactive metal oxides may be predicted from simple thermodynamic considerations. The reaction is found to be autocatalytic, first order in water, and zero order in thiol in the presence of excess oxide. The thiols are recovered by reactive extraction with dilute oxidizing acid. The potential for using polymer membrane hydrogenation reactors (PEMHRs) to perform hydrogenation reactions such as hydrodesulfurization is explored by hydrogenating ketones and olefins over Pt and Au group metals. The dependence of reaction rate on current density suggests that the first hydrogen addition to the olefin is the rate limiting step, rather than the adsorption of hydrogen, for all of the metals tested. PEMHRs proved unsuccessful in hydrogenating sulfur compounds to perform HDS. For the removal of sulfides, a two-phase reactor is used in which concentrated sulfuric acid oxidizes aromatic and aliphatic sulfides present in a hydrocarbon solvent, generating sulfoxides and other sulfonated species. The polar oxidized species are extracted into the acid phase, effectively desulfurizing the hydrocarbon. A reaction scheme is proposed for this system and is justified with a thermodynamic analysis and an experimental determination of the reaction rate law.

Molecular modelling and quantum biochemistry computations of a naturally occurring bioremediation enzyme: Alkane hydroxylase from Pseudomonas putida P1.

PubMed

de Sousa, B G; Oliveira, J I N; Albuquerque, E L; Fulco, U L; Amaro, V E; Blaha, C A G

2017-10-01

Many species of bacteria involved in degradation of n-alkanes have an important constitutional metabolic enzyme, the alkane hydroxylase called AlkB, specialized in the conversion of hydrocarbons molecules that can be used as carbon and/or energy source. This enzyme plays an important role in the microbial degradation of oil, chlorinated hydrocarbons, fuel additives, and many other compounds. A number of these enzymes has been biochemically characterized in detail because the potential of alkane hydroxylases to catalyse high added-value reactions is widely recognized. Nevertheless, the industrial and process bioremediation application of them is restricted, owing to their complex biochemistry, challenging process requirements, and the limited number of their three-dimensional structures. Furthermore, AlkB has great potential as biocatalysts for selective transformation of a wide range of chemically inert unreactive alkanes into reactive chemical precursors that can be used as tools for bioremediation and bioprocesses. Aiming to understand the possible ways the AlkB enzyme Pseudomonas putida P1 interacts with octane, octanol and 1-octyne, we consider its suitable biochemical structure taking into account a 3-D homology modelling. Besides, by using a quantum chemistry computational model based on the density functional theory (DFT), we determine possible protein-substrate interaction regions measured by means of its binding energy simulated throughout the Molecular Fractionation with Conjugated Caps (MFCC) approach. Copyright © 2017 Elsevier Inc. All rights reserved.

Mixed polyanion glass cathodes: Glass-state conversion reactions

DOE PAGES

Kercher, Andrew K.; Kolopus, James A.; Carroll, Kyler; ...

2015-11-10

Mixed polyanion (MP) glasses can undergo glass-state conversion (GSC) reactions to provide an alternate class of high-capacity cathode materials. GSC reactions have been demonstrated in phosphate/vanadate glasses with Ag, Co, Cu, Fe, and Ni cations. These MP glasses provided high capacity and good high power performance, but suffer from moderate voltages, large voltage hysteresis, and significant capacity fade with cycling. Details of the GSC reaction have been revealed by x-ray absorption spectroscopy, electron microscopy, and energy dispersive x-ray spectroscopy of ex situ cathodes at key states of charge. Using the Open Quantum Materials Database (OQMD), a computational thermodynamic model hasmore » been developed to predict the near-equilibrium voltages of glass-state conversion reactions in MP glasses.« less

Jennifer N. Markham | NREL

Science.gov Websites

-economic analysis Algae cultivation and separation Biomass conversion to fuels and higher values products economic modeling Discounted cash flow rate of return (DCFROR) Capital expenses Operating expense Education ;Techno-Economic Analysis for Upgrading Normal-Butanol to Jet and Hydrocarbon Fuel," presented at

Methods for conversion of lignocellulosic-derived products to transportation fuel precursors

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

Lilga, Michael A.; Padmaperuma, Asanga B.

2017-10-03

Methods are disclosed for converting a biomass-derived product containing levulinic acid and/or gamma-valerolactone to a transportation fuel precursor product containing diesel like hydrocarbons. These methods are expected to produce fuel products at a reduced cost relative to conventional approaches.

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

Catalytic conversion of light alkanes, Phase 3. Topical report, January 1990--December 1992

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

NONE

The mission of this work is to devise a new catalyst which can be used in the first simple, economic process to convert the light alkanes in natural gas to an alcohol-rich oxygenated product which can either be used as an environmentally friendly, high-performance liquid fuel, or a precursor to a liquid hydrocarbon transportation fuel. The authors have entered the proof-of-concept stage for converting isobutane to tert butyl alcohol in a practical process and are preparing to enter proof-of-concept of a propane to isopropyl alcohol process in the near future. Methane and ethane are more refractory and thus more difficultmore » to oxidize than the C{sub 3} and C{sub 4} hydrocarbons. Nonetheless, advances made in this area indicate that further research progress could achieve the goal of their direct conversion to alcohols. Progress in Phase 3 catalytic vapor phase methane and ethane oxidation over metals in regular oxidic lattices are the subject of this topical report.« less

Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels. Thermochemical Research Pathways with In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors

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

Dutta, Abhijit; Sahir, Asad; Tan, Eric

This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s efforts to enable the development of technologies for the production of infrastructurecompatible, cost-competitive liquid hydrocarbon fuels from biomass. Specifically, this report details two conceptual designs based on projected product yields and quality improvements via catalyst development and process integration. It is expected that these research improvements will be made within the 2022 timeframe. The two conversion pathways detailed are (1) in situ and (2) ex situ upgrading of vapors produced from the fast pyrolysis of biomass. While the base case conceptual designs and underlying assumptionsmore » outline performance metrics for feasibility, it should be noted that these are only two of many other possibilities in this area of research. Other promising process design options emerging from the research will be considered for future techno-economic analysis.« less

Process for recovering uranium from waste hydrocarbon oils containing the same. [Uranium contaminated lubricating oils from gaseous diffusion compressors

DOEpatents

Conrad, M.C.; Getz, P.A.; Hickman, J.E.; Payne, L.D.

1982-06-29

The invention is a process for the recovery of uranium from uranium-bearing hydrocarbon oils containing carboxylic acid as a degradation product. In one aspect, the invention comprises providing an emulsion of water and the oil, heating the same to a temperature effecting conversion of the emulsion to an organic phase and to an acidic aqueous phase containing uranium carboxylate, and recovering the uranium from the aqueous phase. The process is effective, simple and comparatively inexpensive. It avoids the use of toxic reagents and the formation of undesirable intermediates.

Method for machining steel with diamond tools

DOEpatents

Casstevens, J.M.

1984-01-01

The present invention is directed to a method for machine optical quality finishes and contour accuracies of workpieces of carbon-containing metals such as steel with diamond tooling. The wear rate of the diamond tooling is significantly reduced by saturating the atmosphere at the interface of the workpiece and the diamond tool with a gaseous hydrocarbon during the machining operation. The presence of the gaseous hydrocarbon effectively eliminates the deterioration of the diamond tool by inhibiting or preventing the conversion of the diamond carbon to graphite carbon at the point of contact between the cutting tool and the workpiece.

Method for machining steel with diamond tools

DOEpatents

Casstevens, John M.

1986-01-01

The present invention is directed to a method for machining optical quality inishes and contour accuracies of workpieces of carbon-containing metals such as steel with diamond tooling. The wear rate of the diamond tooling is significantly reduced by saturating the atmosphere at the interface of the workpiece and the diamond tool with a gaseous hydrocarbon during the machining operation. The presence of the gaseous hydrocarbon effectively eliminates the deterioration of the diamond tool by inhibiting or preventing the conversion of the diamond carbon to graphite carbon at the point of contact between the cutting tool and the workpiece.

Use of zinc and copper (I) salts to reduce sulfur and nitrogen impurities during the pyrolysis of plastic and rubber waste to hydrocarbons

DOEpatents

Wingfield, Jr., Robert C.; Braslaw, Jacob; Gealer, Roy L.

1984-01-01

An improvement in a process for the pyrolytic conversion of rubber and plastic waste to hydrocarbon products which results in reduced levels of nitrogen and sulfur impurities in these products. The improvement comprises pyrolyzing the waste in the presence of at least about 1 weight percent of salts, based on the weight of the waste, preferably chloride or carbonate salts, of zinc or copper (I). This invention was made under contract with or subcontract thereunder of the Department of Energy Contract #DE-AC02-78-ER10049.

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.

2000-01-01

An apparatus and a method are disclosed for converting hydrocarbon fuel or an alcohol into hydrogen gas and carbon dioxide. The apparatus includes a first vessel having a partial oxidation reaction zone and a separate steam reforming reaction zone that is distinct from the partial oxidation reaction zone. The first vessel has a first vessel inlet at the partial oxidation reaction zone and a first vessel outlet at the steam reforming zone. The reformer also includes a helical tube extending about the first vessel. The helical tube has a first end connected to an oxygen-containing source and a second end connected to the first vessel at the partial oxidation reaction zone. Oxygen gas from an oxygen-containing source can be directed through the helical tube to the first vessel. A second vessel having a second vessel inlet and second vessel outlet is annularly disposed about the first vessel. The helical tube is disposed between the first vessel and the second vessel and gases from the first vessel can be directed through second vessel.

Investigating Oil-Prone Kerogen Conversion to Hydrocarbons Using AFM-based Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Eoghan, D.; Cook, D.; Hackley, P. C.; Kjoller, K.; Dawson, D.; Shetty, R.

2016-12-01

Understanding in situ chemical changes occurring during thermal conversion of oil-prone kerogen to hydrocarbons can provide fundamental information regarding the origin of the earth's fossil fuel endowment and reduce uncertainty in hydrocarbon prospecting and resource assessment. Tasmanites algal bodies were studied using an Atomic Force Microscope-based IR spectroscopy technique (AFM-IR) that offers chemical characterization of organic materials with spatial resolution below the diffraction limit. The AFM allows precise positioning within the algal bodies. A tunable IR laser irradiates the sample under the AFM probe. At absorbing wavenumbers, the sample heats up and expands. The AFM detects the expansion of the material under the probe tip to generate local IR spectra. The Tasmanites algal bodies from the Devonian-Mississippian Woodford Shale were contained in two polished rock fragment pellets. To simulate maturation, one was subjected to isothermal hydrous pyrolysis at 320 °C for 72 hours. AFM-IR spectra were collected at multiple sites on algal bodies in both samples (Figure 1). The aromatic C=C ring stretching at 1600 cm-1 (unheated) shifted to 1606 cm-1 with increased absorption in the heated algal bodies, indicating development of increased aromaticity with thermal maturation. The ratio of the 1606 cm-1 peak to peaks at 1708 cm-1 (C=O stretching) and 1460 cm-1 (CH2 wag) was higher in the heated sample, indicating loss of oxygenated functional groups and aliphatic components with thermal advance. A shift of the 1372 cm-1 peak to 1376 cm-1 with lower absorption in the heated samples suggests reduction in the abundance of methyl substituents and development of preferred localization. These results are consistent with extant information from FTIR analysis and demonstrate the ability of AFM-IR to provide in situ characterization of organic matter with respect to thermal maturity advance, and its application to understanding conversion of oil-prone kerogen to hydrocarbons. AFM-IR also showed chemical variations within an algal body, from the central region compared to the folded tips. Future work will examine nanoscale characterization of localized compositional variations in Tasmanites bodies in relation to spectral fluorescence parameters to determine preferred sites of kerogen cracking.

Organic chemistry on Titan

NASA Technical Reports Server (NTRS)

Chang, S.; Scattergood, T.; Aronowitz, S.; Flores, J.

1978-01-01

Observations of nonequilibrium phenomena on the Saturn satellite Titan indicate the occurrence of organic chemical evolution. Greenhouse and thermal inversion models of Titan's atmosphere provide environmental constraints within which various pathways for organic chemical synthesis are assessed. Experimental results and theoretical modeling studies suggest that the organic chemistry of the satellite may be dominated by two atmospheric processes: energetic-particle bombardment and photochemistry. Reactions initiated in various levels of the atmosphere by cosmic ray, Saturn wind, and solar wind particle bombardment of a CH4 - N2 atmospheric mixture can account for the C2-hydrocarbons, the UV-visible-absorbing stratospheric haze, and the reddish color of the satellite. Photochemical reactions of CH4 can also account for the presence of C2-hydrocarbons. In the lower Titan atmosphere, photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. Hot H-atom reactions initiated by photo-dissociation of NH3 can couple the chemical reactions of NH3 and CH4 and produce organic matter.

Chemical reaction and dust formation studies in laboratory hydrocarbon plasmas.

NASA Astrophysics Data System (ADS)

Hippler, Rainer; Majumdar, Abhijit; Thejaswini, H. C.

Plasma chemical reaction studies with relevance to, e.g., Titan's atmosphere have been per-formed in various laboratory plasmas [1,2]. Chemical reactions in a dielectric barrier discharge at medium pressure of 250-300 mbar have been studied in CH4 /N2 and CH4 /Ar gas mixtures by means of mass spectrometry. The main reaction scheme is production of H2 by fragmenta-tion of CH4 , but also production of larger hydrocarbons like Cn Hm with n up to 10 including formation of different functional CN groups is observed. [1] A. Majumdar and R. Hippler, Development of dielectric barrier discharge plasma processing apparatus for mass spectrometry and thin film deposition, Rev. Sci. Instrum. 78, 075103 (2007) [2] H.T. Do, G. Thieme, M. Frühlich, H. Kersten, and R. Hippler, Ion Molecule and Dust Particle Formation in Ar/CH4 , Ar/C2 H2 and Ar/C3 H6 Radio-frequency Plasmas, Contrib. Plasma Phys. 45, No. 5-6, 378-384 (2005)

Global Kinetic Constants for Thermal Oxidative Degradation of a Cellulosic Paper

NASA Technical Reports Server (NTRS)

Kashiwagi, Takashi; Nambu, Hidesaburo

1992-01-01

Values of global kinetic constants for pyrolysis, thermal oxidative degradation, and char oxidation of a cellulosic paper were determined by a derivative thermal gravimetric study. The study was conducted at heating rates of 0.5, 1, 1.5, 3, and 5 C/min in ambient atmospheres of nitrogen, 0.28, 1.08, 5.2 percent oxygen concentrations, and air. Sample weight loss rate, concentrations of CO, CO2, and H2O in the degradation products, and oxygen consumption were continuously measured during the experiment. Values of activation energy, preexponential factor, orders of reaction, and yields of CO, CO2, H2O, total hydrocarbons, and char for each degradation reaction were derived from the results. Heat of reaction for each reaction was determined by differential scanning calorimetry. A comparison of the calculated CO, CO2, H2O, total hydrocarbons, sample weight loss rate, and oxygen consumption was made with the measured results using the derived kinetic constants, and the accuracy of the values of kinetic constants was discussed.

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.

Method and apparatus for producing oxygenates from hydrocarbons

DOEpatents

Kong, Peter C.; Lessing, Paul A.

1995-01-01

A chemical reactor for oxygenating hydrocarbons includes: a) a dielectric barrier discharge plasma cell, the plasma cell comprising a pair of electrodes having a dielectric material and void therebetween, the plasma cell comprising a hydrocarbon gas inlet feeding to the void; b) a solid oxide electrochemical cell, the electrochemical cell comprising a solid oxide electrolyte positioned between a porous cathode and a porous anode, an oxygen containing gas inlet stream feeding to the porous cathode side of the electrochemical cell; c) a first gas passageway feeding from the void to the anode side of the electrochemical cell; and d) a gas outlet feeding from the anode side of the electrochemical cell to expel reaction products from the chemical reactor. A method of oxygenating hydrocarbons is also disclosed.

Multiscale Evaluation of Catalytic Upgrading of Biomass Pyrolysis Vapors on Ni- and Ga-Modified ZSM-5

DOE PAGES

Yung, Matthew M.; Stanton, Alexander R.; Iisa, Kristiina; ...

2016-10-07

Metal-impregnated (Ni or Ga) ZSM-5 catalysts were studied for biomass pyrolysis vapor upgrading to produce hydrocarbons using three reactors constituting a 100 000x change in the amount of catalyst used in experiments. Catalysts were screened for pyrolysis vapor phase upgrading activity in two small-scale reactors: (i) a Pyroprobe with a 10 mg catalyst in a fixed bed and (ii) a fixed-bed reactor with 500 mg of catalyst. The best performing catalysts were then validated with a larger scale fluidized-bed reactor (using ~1 kg of catalyst) that produced measurable quantities of bio-oil for analysis and evaluation of mass balances. Despite somemore » inherent differences across the reactor systems (such as residence time, reactor type, analytical techniques, mode of catalyst and biomass feed) there was good agreement of reaction results for production of aromatic hydrocarbons, light gases, and coke deposition. Relative to ZSM-5, Ni or Ga addition to ZSM-5 increased production of fully deoxygenated aromatic hydrocarbons and light gases. In the fluidized bed reactor, Ga/ZSM-5 slightly enhanced carbon efficiency to condensed oil, which includes oxygenates in addition to aromatic hydrocarbons, and reduced oil oxygen content compared to ZSM-5. Ni/ZSM-5, while giving the highest yield of fully deoxygenated aromatic hydrocarbons, gave lower overall carbon efficiency to oil but with the lowest oxygen content. Reaction product analysis coupled with fresh and spent catalyst characterization indicated that the improved performance of Ni/ZSM-5 is related to decreasing deactivation by coking, which keeps the active acid sites accessible for the deoxygenation and aromatization reactions that produce fully deoxygenated aromatic hydrocarbons. The addition of Ga enhances the dehydrogenation activity of the catalyst, which leads to enhanced olefin formation and higher fully deoxygenated aromatic hydrocarbon yields compared to unmodified ZSM-5. Catalyst characterization by ammonia temperature programmed desorption, surface area measurements, and postreaction temperature-programmed oxidation (TPO) also showed that the metal-modified zeolites retained a greater percentage of their initial acidity and surface area, which was consistent between the reactor scales. These results demonstrate that the trends observed with smaller (milligram to gram) catalyst reactors are applicable to larger, more industrially relevant (kg) scales to help guide catalyst research toward application.« less

Surface Plasmon-Assisted Solar Energy Conversion.

PubMed

Dodekatos, Georgios; Schünemann, Stefan; Tüysüz, Harun

2016-01-01

The utilization of localized surface plasmon resonance (LSPR) from plasmonic noble metals in combination with semiconductors promises great improvements for visible light-driven photocatalysis, in particular for energy conversion. This review summarizes the basic principles of plasmonic photocatalysis, giving a comprehensive overview about the proposed mechanisms for enhancing the performance of photocatalytically active semiconductors with plasmonic devices and their applications for surface plasmon-assisted solar energy conversion. The main focus is on gold and, to a lesser extent, silver nanoparticles in combination with titania as semiconductor and their usage as active plasmonic photocatalysts. Recent advances in water splitting, hydrogen generation with sacrificial organic compounds, and CO2 reduction to hydrocarbons for solar fuel production are highlighted. Finally, further improvements for plasmonic photocatalysts, regarding performance, stability, and economic feasibility, are discussed for surface plasmon-assisted solar energy conversion.

Hydrogen rich gas generator

NASA Technical Reports Server (NTRS)

Houseman, J.; Rupe, J. H.; Kushida, R. O. (Inventor)

1976-01-01

A process and apparatus is described for producing a hydrogen rich gas by injecting air and hydrocarbon fuel at one end of a cylindrically shaped chamber to form a mixture and igniting the mixture to provide hot combustion gases by partial oxidation of the hydrocarbon fuel. The combustion gases move away from the ignition region to another region where water is injected to be turned into steam by the hot combustion gases. The steam which is formed mixes with the hot gases to yield a uniform hot gas whereby a steam reforming reaction with the hydrocarbon fuel takes place to produce a hydrogen rich gas.

Detonability of hydrocarbon fuels in air

NASA Technical Reports Server (NTRS)

Beeson, H. D.; Mcclenagan, R. D.; Bishop, C. V.; Benz, F. J.; Pitz, W. J.; Westbrook, C. K.; Lee, J. H. S.

1991-01-01

Studies were conducted of the detonation of gas-phase mixtures of n-hexane and JP-4, with oxidizers as varied as air and pure oxygen, measuring detonation velocities and cell sizes as a function of stoichiometry and diluent concentration. The induction length of a one-dimensional Zeldovich-von Neumann-Doering detonation was calculated on the basis of a theoretical model that employed the reaction kinetics of the hydrocarbon fuels used. Critical energy and critical tube diameter are compared for a relative measure of the heavy hydrocarbon fuels studied; detonation sensitivity appears to increase slightly with increasing carbon number.

Method for producing hydrocarbon fuels from heavy polynuclear hydrocarbons by use of molten metal halide catalyst

DOEpatents

Gorin, Everett

1979-01-01

In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst, thereafter separating at least a substantial portion of the carbonaceous material associated with the reaction mixture from the spent molten metal halide and thereafter regenerating the metal halide catalyst, an improvement comprising contacting the spent molten metal halide catalyst after removal of a major portion of the carbonaceous material therefrom with an additional quantity of hydrogen is disclosed.

Dry Chemical Development - A Model for the Extinction of Hydrocarbon Flames.

DTIC Science & Technology

1984-02-08

and predicts the suppression effectiveness of a wide variety of gaseous, liquid, and solid agents . The flame extinguishment model is based on the...generalized by consideration of all endothermic reaction sinks, eg., vaporization, dissociation, and decomposition. The general equation correlates...CHEMICAL DEVELOPMENT - A MODEL FOR THE EXTINCTION OF HYDROCARBON FLAMES Various fire-extinguishing agents are carried on board Navy ships to control

Experiments and Reaction Models of Fundamental Combustion Properties

DTIC Science & Technology

2010-05-31

in liquid hydrocarbon flames Lennard - Jones 12-6 potential parameters were estimated for n-alkanes and 1-alkenes with carbon numbers ranging from 5...hydrocarbons, were studied both experimentally and numerically. The fuel mixtures were chosen in order to gain insight into potential kinetic couplings...initio electronic structure theory, transition state theory, and master equation modelling. The potential energy surface was examined with the coupled

Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

DOEpatents

Kung, H.H.; Chaar, M.A.

1988-10-11

Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M[sub 3](VO[sub 4])[sub 2] and MV[sub 2]O[sub 6], M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

DOEpatents

Kung, Harold H.; Chaar, Mohamed A.

1988-01-01

Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M.sub.3 (VO.sub.4).sub.2 and MV.sub.2 O.sub.6, M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

Crossed Molecular Beams Investigations on the Dynamics and Energetics of Elementary Boron Reactions with Unsaturated Hydrocarbons

DTIC Science & Technology

2005-03-17

Is1 maglev pump (Osaka Vacuum; TG2003 and TG430) to the low 10. torr region; the operation of pulsed and continuous sources increases the pressure to...about 10-5 torr and 10.4 torr, respectively. All maglev pumps require no maintenance and are hydrocarbon free. A dry roots pump (Leybold WS505; 140 s

Method of upgrading oils containing hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline

DOEpatents

Baker, Eddie G.; Elliott, Douglas C.

1993-01-01

The present invention is a multi-stepped method of converting an oil which is produced by various biomass and coal conversion processes and contains primarily single and multiple ring hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline. The single and multiple ring hydroxyaromatic hydrocarbon compounds in a raw oil material are first deoxygenated to produce a deoxygenated oil material containing single and multiple ring aromatic compounds. Then, water is removed from the deoxygenated oil material. The next step is distillation to remove the single ring aromatic compouns as gasoline. In the third step, the multiple ring aromatics remaining in the deoxygenated oil material are cracked in the presence of hydrogen to produce a cracked oil material containing single ring aromatic compounds. Finally, the cracked oil material is then distilled to remove the single ring aromatics as gasoline.

Method of upgrading oils containing hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline

DOEpatents

Baker, E.G.; Elliott, D.C.

1993-01-19

The present invention is a multi-stepped method of converting an oil which is produced by various biomass and coal conversion processes and contains primarily single and multiple ring hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline. The single and multiple ring hydroxyaromatic hydrocarbon compounds in a raw oil material are first deoxygenated to produce a deoxygenated oil material containing single and multiple ring aromatic compounds. Then, water is removed from the deoxygenated oil material. The next step is distillation to remove the single ring aromatic compounds as gasoline. In the third step, the multiple ring aromatics remaining in the deoxygenated oil material are cracked in the presence of hydrogen to produce a cracked oil material containing single ring aromatic compounds. Finally, the cracked oil material is then distilled to remove the single ring aromatics as gasoline.

Cleaner Energy for Cars

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

Cropley, Cecelia

Representing the Center for Catalytic Hydrocarbon Functionalization (CCHF), this document is one of the entries in the Ten Hundred and One Word Challenge. As part of the challenge, the 46 Energy Frontier Research Centers were invited to represent their science in images, cartoons, photos, words and original paintings, but any descriptions or words could only use the 1000 most commonly used words in the English language, with the addition of one word important to each of the EFRCs and the mission of DOE: energy. The mission of CCHF is to develop, validate, and optimize new methods to rearrange the bondsmore » of hydrocarbons, implement enzymatic strategies into synthetic systems, and design optimal environments for catalysts that can be used to reversibly functionalize hydrocarbons, especially for more efficient use of natural gas including low temperature conversion to liquid fuels.« less

Process Development for Hydrothermal Liquefaction of Algae Feedstocks in a Continuous-Flow Reactor

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

Elliott, Douglas C.; Hart, Todd R.; Schmidt, Andrew J.

Wet algae slurries can be converted into an upgradeable biocrude by hydrothermal liquefaction (HTL). High levels of carbon conversion to gravity-separable biocrude product were accomplished at relatively low temperature (350 °C) in a continuous-flow, pressurized (sub-critical liquid water) environment (20 MPa). As opposed to earlier work in batch reactors reported by others, direct oil recovery was achieved without the use of a solvent and biomass trace components were removed by processing steps so that they did not cause process difficulties. High conversions were obtained even with high slurry concentrations of up to 35 wt% of dry solids. Catalytic hydrotreating wasmore » effectively applied for hydrodeoxygenation, hydrodenitrogenation, and hydrodesulfurization of the biocrude to form liquid hydrocarbon fuel. Catalytic hydrothermal gasification was effectively applied for HTL byproduct water cleanup and fuel gas production from water soluble organics, allowing the water to be considered for recycle of nutrients to the algae growth ponds. As a result, high conversion of algae to liquid hydrocarbon and gas products was found with low levels of organic contamination in the byproduct water. All three process steps were accomplished in bench-scale, continuous-flow reactor systems such that design data for process scale-up was generated.« less

Biomass conversion to produce hydrocarbon liquid fuel via hot-vapor filtered fast pyrolysis and catalytic hydrotreating

DOE PAGES

Wang, Huamin; Elliott, Douglas C.; French, Richard J.; ...

2016-12-25

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and themore » processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. As a result, the protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.« less

Biomass conversion to produce hydrocarbon liquid fuel via hot-vapor filtered fast pyrolysis and catalytic hydrotreating

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

Wang, Huamin; Elliott, Douglas C.; French, Richard J.

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and themore » processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. As a result, the protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.« less

IMPROVING PHOTOCATALYTIC PROPERTIES OF TIO2 THROUGH THIN FILM COATING AND METAL DOPING VIA FLAME AEROSOL COATING METHOD

EPA Science Inventory

There has been an increasing demand for efficient, economical and environmentally friendly methods for partial oxidation of hydrocarbons by molecular oxygen, to desirable industrial feedstock oxygenates. Current processes are energy intensive, have low conversion efficiencies and...

Method and apparatus for producing synthesis gas

DOEpatents

Hemmings, John William; Bonnell, Leo; Robinson, Earl T.

2010-03-03

A method and apparatus for reacting a hydrocarbon containing feed stream by steam methane reforming reactions to form a synthesis gas. The hydrocarbon containing feed is reacted within a reactor having stages in which the final stage from which a synthesis gas is discharged incorporates expensive high temperature materials such as oxide dispersed strengthened metals while upstream stages operate at a lower temperature allowing the use of more conventional high temperature alloys. Each of the reactor stages incorporate reactor elements having one or more separation zones to separate oxygen from an oxygen containing feed to support combustion of a fuel within adjacent combustion zones, thereby to generate heat to support the endothermic steam methane reforming reactions.

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

Krotov, V.V.; Staroverov, S.M.; Nesterenko, P.N.

A series of heterogeneous catalysts for asymmetric Michael additions was synthesized based on ephedrine chemically bound to the surface of silica. The length of the hydrocarbon chain binding the active center to the support surface affects the sign of rotation of the reaction product from the asymmetric addition of thiophenol to benzylideneacetophenone. Grafting ephedrine to the silica surface via a short hydrocarbon chain results in a change in the configuration of the reaction product. Silanol groups on the silica surface are involved in the transition state, as evidenced by data obtained using silica which has been exhaustively treated with trimethylchlorosilane.more » The absolute specific rotation of 1,3-diphenyl-3-thiophenylpropan-1-one has been established.« less

Kinetics of liquid-solid reactions in naphthenic acid conversion and Kraft pulping

NASA Astrophysics Data System (ADS)

Yang, Ling

Two liquid-solid reactions, in which the morphology of the solid changes as the reactions proceeds, were examined. One is the NA conversion in oil by decarboxylation on metal oxides and carbonates, and the other is the Kraft pulping in which lignin removal by delignification reaction. In the study of the NA conversion, CaO was chosen as the catalyst for the kinetic study from the tested catalysts based on NA conversion. Two reaction mixtures, carrier oil plus commercial naphthenic acids and heavy vacuum gas oil (HVGO) from Athabasca bitumen, were applied in the kinetic study. The influence of TAN, temperature, and catalyst loading on the NA conversion and decarboxylation were studied systematically. The results showed that the removal rate of TAN and the decarboxylation of NA were both independent of the concentration of NA over the range studied, and significantly dependent on reaction temperature. The data from analyzing the spent catalyst demonstrated that calcium naphthenate was an intermediate of the decarboxylation reaction of NA, and the decomposition of calcium naphthenate was a rate-determining step. In the study on the delignification of the Kraft pulping, a new mechanism was proposed for the heterogeneous delignification reaction during the Kraft pulping process. In particular, the chemical reaction mechanism took into account the heterogeneous nature of Kraft pulping. Lignin reacted in parallel with sodium hydroxide and sodium sulfide. The mechanism consists of three key kinetic steps: (1) adsorption of hydroxide and hydrosulfide ions on lignin; (2) surface reaction on the solid surface to produce degraded lignin products; and (3) desorption of degradation products from the solid surface. The most important step for the delignification process is the surface reaction, rather than the reactions occurring in the liquid phase. A kinetic model has, thus, been developed based on the proposed mechanism. The derived kinetic model showed that the mechanism could be employed to predict the pulping behavior under a variety of conditions with good accuracy.

Serpentinization processes: Influence of silica

NASA Astrophysics Data System (ADS)

Huang, R.; Sun, W.; Ding, X.; Song, M.; Zhan, W.

2016-12-01

Serpentinization systems are highly enriched in molecular hydrogen (H2) and hydrocarbons (e.g. methane, ethane and propane). The production of hydrocarbons results from reactions between H2 and oxidized carbon (carbon dioxide and carbon monoxide), which possibly contribute to climate changes during early history of the Earth. However, the influence of silica on the production of H2 and hydrocarbons was poorly constrained. We performed experiments at 311-500 °C and 3.0 kbar using mechanical mixtures of silica and olivine in ratios ranging from 0 to 40%. Molecular hydrogen (H2), methane, ethane and propane were formed, which were analyzed by gas chromatography. It was found that silica largely decreased H2 production. Without any silica, olivine serpentinization produced 94.5 mmol/kg H2 after 20 days of reaction time. By contrast, with the presence of 20% silica, H2 concentrations decreased largely, 8.5 mmol/kg. However, the influence of silica on the production of hydrocarbons is negligible. Moreover, with the addition of 20%-40% silica, the major hydrous minerals are talc, which was quantified according to an established standard curve calibrated by infrared spectroscopy analyses. It shows that silica greatly enhances olivine hydration, especially at 500 °C. Without any addition of silica, reaction extents were <5% at 17 days during olivine serpentinization at 500 °C and 3.0 kbar. By contrast, with the presence of 50% silica, olivine was completely transformed to talc within 9 days. This study indicates that silica impedes the oxidation of ferrous iron into ferric iron, and that rates of olivine hydration in natural geological settings are much faster with silica supply.

Conversion of wood residues to diesel fuel

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

Kuester, J.L.

1981-01-01

The basic approach is indirect liquefaction, i.e., thermal gasification followed by catalytic liquefaction. The indirect approach results in separation of the oxygen in the biomass feedstock, i.e., oxygenated compounds do not appear in the liquid hydrocarbon fuel product. The general conversion scheme is shown. The process is capable of accepting a wide variety of feedstocks. Potential products include medium quality gas, normal propanol, paraffinic fuel and/or high octane gasoline. A flow diagram of the continuous laboratory unit is shown. A fluidized bed pyrolysis system is used for gasification. Capacity is about 10 lbs/h of feedstock. The pyrolyzer can be fluidizedmore » with recycle pyrolysis gas, steam or recycle liquefaction system off gas or some combination thereof. Tars are removed in a wet scrubber. Unseparated pyrolysis gases are utilized as feed to a modified Fischer-Tropsch reactor. The liquid condensate from the reactor consists of a normal propanol-water phase and a paraffinic hydrocarbon phase. The reactor can be operated to optimize for either product. If a high octane gasoline is desired, the paraffinic fuel is passed through a conventional catalytic reformer. The normal propanol could be used as a fuel extender if blended with the hydrocarbon fuel products. Off gases from the downstream reactors are of high quality due to the accumulation of low molecular weight paraffins.« less

A novel integrated biorefinery process for diesel fuel blendstock production using lipids from the methanotroph, Methylomicrobium buryatense

DOE PAGES

Dong, Tao; Fei, Qiang; Genelot, Marie; ...

2017-03-08

In light of the availability of low-cost methane (CH 4) derived from natural gas and biogas along with increasing concerns of the greenhouse gas emissions, the production of alternative liquid biofuels directly from CH 4 is a promising approach to capturing wasted energy. A novel biorefinery concept integrating biological conversion of CH 4 to microbial lipids together with lipid extraction and generation of hydrocarbon fuels is demonstrated in this study for the first time. An aerobic methanotrophic bacterium, Methylomicrobium buryatense capable of using CH 4 as the sole carbon source was selected on the basis of genetic tractability, cultivation robustness,more » and ability to accumulate phospholipids in membranes. A maximum fatty acid content of 10% of dry cell weight was obtained in batch cultures grown in a continuous gas sparging fermentation system. Although phospholipids are not typically considered as a good feedstock for upgrading to hydrocarbon fuels, we set out to demonstrate that using a combination of novel lipid extraction methodology with advanced catalyst design, we could prove the feasibility of this approach. Up to 95% of the total fatty acids from membrane-bound phospholipids were recovered by a two-stage pretreatment method followed by hexane extraction of the aqueous hydrolysate. The upgrading of extracted lipids was then demonstrated in a hydrodeoxygeation process using palladium on silica as a catalyst. Lipid conversion in excess of 99% was achieved, with a full selectivity to hydrocarbons. Lastly, the final hydrocarbon mixture is dominated by 88% pentadecane (C 15H 32) based on decarbonylation/decarboxylation and hydrogenation of C16 fatty acids, indicating that a biological gas-to-liquid fuel (Bio-GTL) process is technically feasible.« less

Experimental and analytical study of nitric oxide formation during combustion of propane in a jet-stirred combustor

NASA Technical Reports Server (NTRS)

Wakelyn, N. T.; Jachimowski, C. J.; Wilson, C. H.

1978-01-01

A jet-stirred combustor, constructed of castable zirconia and with an Inconel injector, was used to study nitric oxide formation in propane-air combustion with residence times in the range from 3.2 to 3.3 msec and equivalence ratios varying from 0.7 to 1.4. Measurements were made of combustor operating temperature and of nitric oxide concentration. Maximum nitric oxide concentrations of the order of 55 ppm were found in the range of equivalence ratio from 1.0 to 1.1. A finite-rate chemical kinetic mechanism for propane combustion and nitric oxide formation was assembled by coupling an existing propane oxidation mechanism with the Zeldovich reactions and reactions of molecular nitrogen with hydrocarbon fragments. Analytical studies using this mechanism in a computer simulation of the experimental conditions revealed that the hydrocarbon-fragment-nitrogen reactions play a significant role in nitric oxide formation during fuel-rich combustion.

Mineral dust aerosols promote the formation of toxic nitropolycyclic aromatic compounds

PubMed Central

Kameda, Takayuki; Azumi, Eri; Fukushima, Aki; Tang, Ning; Matsuki, Atsushi; Kamiya, Yuta; Toriba, Akira; Hayakawa, Kazuichi

2016-01-01

Atmospheric nitrated polycyclic aromatic hydrocarbons (NPAHs), which have been shown to have adverse health effects such as carcinogenicity, are formed in part through nitration reactions of their parent polycyclic aromatic hydrocarbons (PAHs) in the atmosphere. However, little is known about heterogeneous nitration rates of PAHs by gaseous NO2 on natural mineral substrates, such as desert dust aerosols. Herein by employing kinetic experiments using a flow reactor and surface analysis by Fourier transform infrared spectroscopy with pyridine adsorption, we demonstrate that the reaction is accelerated on acidic surfaces of mineral dust, particularly on those of clay minerals. In support of this finding, we show that levels of ambient particle-associated NPAHs in Beijing, China, significantly increased during heavy dust storms. These results suggest that mineral dust surface reactions are an unrecognized source of toxic organic chemicals in the atmosphere and that they enhance the toxicity of mineral dust aerosols in urban environments. PMID:27075250

Site-selective covalent functionalization at interior carbon atoms and on the rim of circumtrindene, a C36H12 open geodesic polyarene

PubMed Central

Cho, Hee Yeon; Ansems, Ronald B M

2014-01-01

Summary Circumtrindene (6, C36H12), one of the largest open geodesic polyarenes ever reported, exhibits fullerene-like reactivity at its interior carbon atoms, whereas its edge carbons react like those of planar polycyclic aromatic hydrocarbons (PAHs). The Bingel–Hirsch and Prato reactions – two traditional methods for fullerene functionalization – afford derivatives of circumtrindene with one of the interior 6:6 C=C bonds modified. On the other hand, functionalization on the rim of circumtrindene can be achieved by normal electrophilic aromatic substitution, the most common reaction of planar PAHs. This peripheral functionalization has been used to extend the π-system of the polyarene by subsequent coupling reactions and to probe the magnetic environment of the concave/convex space around the hydrocarbon bowl. For both classes of functionalization, computational results are reported to complement the experimental observations. PMID:24991245

Special Issue in Honor of Professor S. Ted Oyama: 2014 ACS Distinguished Researcher Award in Petroleum Chemistry and Storch Award in Fuel Science

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

Bravo-Suárez, Juan J.; Wang, Xianqin; Li, Wei

This special issue of Topics in Catalysis honors Professor S. Ted Oyama for his Awards in Petroleum Chemistry and Fuel Science Research. These awards were celebrated at two American Chemical Society (ACS) symposia in 2014. First, the ACS’s Distinguished Research Award in Petroleum Chemistry Symposium, took place at the 247th ACS National Meeting in Dallas, TX, during March 17-19, 2014 and the second one, the ACS’s Storch Award in Fuel Science Symposium, took place at the 248th ACS National Meeting in San Francisco, CA, during August 10-12, 2014. Professor Oyama received the 2014 ACS Distinguished Research Award in Petroleum Chemistrymore » ‘‘for his substantial contributions to the field of heterogeneous catalysis’’ including the discovery of highly active transition metal phosphide catalysts for hydrotreatment of petroleum and coal-derived feedstocks and biomass refining, the development of new compositions, and the understanding of their reaction mechanisms by in situ spectroscopic techniques at high temperatures and pressures of reaction. In light of this recognition, Professor Oyama was also awarded the 2014 ACS Storch Award in Fuel Science ‘‘for his broad contributions to the field of fuel science’’ including the production of hydrogen by catalytic reforming, selective oxidation of hydrocarbons, biomass conversion, their reaction kinetics and mechanisms, and spectrokinetic methods to study catalysts in situ at reaction conditions and theory and application of inorganic membranes for separation of hydrogen and fuel-relevant gases. Finally, this special issue consists of contributions by catalysis researchers who participated in the two ACS symposia honoring Professor Oyama’s Awards.« less

Unlocking the potential of SnS2: Transition metal catalyzed utilization of reversible conversion and alloying reactions

NASA Astrophysics Data System (ADS)

Huang, Zhi Xiang; Wang, Ye; Liu, Bo; Kong, Dezhi; Zhang, Jun; Chen, Tupei; Yang, Hui Ying

2017-01-01

The alloying-dealloying reactions of SnS2 proceeds with the initial conversion reaction of SnS2 with lithium that produces Li2S. Unfortunately, due to the electrochemical inactivity of Li2S, the conversion reaction of SnS2 is irreversible, which significantly limit its potential applications in lithium-ion batteries. Herein, a systematic understanding of transition metal molybdenum (Mo) as a catalyst in SnS2 anode is presented. It is found that Mo catalyst is able to efficiently promote the reversible conversion of Sn to SnS2. This leads to the utilization of both conversion and alloying reactions in SnS2 that greatly increases lithium storage capability of SnS2. Mo catalyst is introduced in the form of MoS2 grown directly onto self-assembled vertical SnS2 nanosheets that anchors on three-dimensional graphene (3DG) creating a hierarchal nanostructured named as SnS2/MoS2/3DG. The catalytic effect results in a significantly enhanced electrochemical properties of SnS2/MoS2/3DG; a high initial Coulombic efficiency (81.5%) and high discharge capacities of 960.5 and 495.6 mA h g-1 at current densities of 50 and 1000 mA g-1, respectively. Post cycling investigations using ex situ TEM and XPS analysis verifies the successful conversion reaction of SnS2 mediated by Mo. The successful integration of catalyst on alloying type metal sulfide anode creates a new avenue towards high energy density lithium anodes.

Unlocking the potential of SnS2: Transition metal catalyzed utilization of reversible conversion and alloying reactions.

PubMed

Huang, Zhi Xiang; Wang, Ye; Liu, Bo; Kong, Dezhi; Zhang, Jun; Chen, Tupei; Yang, Hui Ying

2017-01-19

The alloying-dealloying reactions of SnS 2 proceeds with the initial conversion reaction of SnS 2 with lithium that produces Li 2 S. Unfortunately, due to the electrochemical inactivity of Li 2 S, the conversion reaction of SnS 2 is irreversible, which significantly limit its potential applications in lithium-ion batteries. Herein, a systematic understanding of transition metal molybdenum (Mo) as a catalyst in SnS 2 anode is presented. It is found that Mo catalyst is able to efficiently promote the reversible conversion of Sn to SnS 2 . This leads to the utilization of both conversion and alloying reactions in SnS 2 that greatly increases lithium storage capability of SnS 2 . Mo catalyst is introduced in the form of MoS 2 grown directly onto self-assembled vertical SnS 2 nanosheets that anchors on three-dimensional graphene (3DG) creating a hierarchal nanostructured named as SnS 2 /MoS 2 /3DG. The catalytic effect results in a significantly enhanced electrochemical properties of SnS 2 /MoS 2 /3DG; a high initial Coulombic efficiency (81.5%) and high discharge capacities of 960.5 and 495.6 mA h g -1 at current densities of 50 and 1000 mA g -1 , respectively. Post cycling investigations using ex situ TEM and XPS analysis verifies the successful conversion reaction of SnS 2 mediated by Mo. The successful integration of catalyst on alloying type metal sulfide anode creates a new avenue towards high energy density lithium anodes.

Efficient light hydrocarbon separation and CO2 capture and conversion in a stable MOF with oxalamide-decorated polar tubes.

PubMed

Li, Xiu-Yuan; Li, Yong-Zhi; Yang, Yun; Hou, Lei; Wang, Yao-Yu; Zhu, Zhonghua

2017-11-30

The first strontium-based MOF possessing polar tubular channels embedded with a high density of open Lewis acidic metal sites and basic oxalamide groups was constructed, which shows not only a high CO 2 and C 2 H 6 adsorption capability and significant selectivity for CO 2 over both CH 4 and CO, and for C 2 H 6 over CH 4 , but also size-selective chemical conversion of CO 2 with epoxides producing cyclic carbonates under ambient conditions.

Mass spectrometric identification of intermediates in the O2-driven [4Fe-4S] to [2Fe-2S] cluster conversion in FNR

PubMed Central

Crack, Jason C.; Thomson, Andrew J.

2017-01-01

The iron-sulfur cluster containing protein Fumarate and Nitrate Reduction (FNR) is the master regulator for the switch between anaerobic and aerobic respiration in Escherichia coli and many other bacteria. The [4Fe-4S] cluster functions as the sensory module, undergoing reaction with O2 that leads to conversion to a [2Fe-2S] form with loss of high-affinity DNA binding. Here, we report studies of the FNR cluster conversion reaction using time-resolved electrospray ionization mass spectrometry. The data provide insight into the reaction, permitting the detection of cluster conversion intermediates and products, including a [3Fe-3S] cluster and persulfide-coordinated [2Fe-2S] clusters [[2Fe-2S](S)n, where n = 1 or 2]. Analysis of kinetic data revealed a branched mechanism in which cluster sulfide oxidation occurs in parallel with cluster conversion and not as a subsequent, secondary reaction to generate [2Fe-2S](S)n species. This methodology shows great potential for broad application to studies of protein cofactor–small molecule interactions. PMID:28373574

Catalysts for the production of hydrocarbons from carbon monoxide and water

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

Sapienza, Richard S.; Slegeir, William A.; Goldberg, Robert I.

1987-01-01

A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n+1).gtoreq.x.gtoreq.O and for olefinic hydrocarbons: 2n.gtoreq.x.gtoreq.O where n is the number of carbon atoms in the product and x ismore » the molar amount of water in the reaction mixture.« less

Method and apparatus for producing oxygenates from hydrocarbons

DOEpatents

Kong, P.C.; Lessing, P.A.

1995-06-27

A chemical reactor for oxygenating hydrocarbons includes: (a) a dielectric barrier discharge plasma cell, the plasma cell comprising a pair of electrodes having a dielectric material and void therebetween, the plasma cell comprising a hydrocarbon gas inlet feeding to the void; (b) a solid oxide electrochemical cell, the electrochemical cell comprising a solid oxide electrolyte positioned between a porous cathode and a porous anode, an oxygen containing gas inlet stream feeding to the porous cathode side of the electrochemical cell; (c) a first gas passageway feeding from the void to the anode side of the electrochemical cell; and (d) a gas outlet feeding from the anode side of the electrochemical cell to expel reaction products from the chemical reactor. A method of oxygenating hydrocarbons is also disclosed. 4 figs.

One-step hydroprocessing of fatty acids into renewable aromatic hydrocarbons over Ni/HZSM-5: insights into the major reaction pathways.

PubMed

Xing, Shiyou; Lv, Pengmei; Wang, Jiayan; Fu, Junying; Fan, Pei; Yang, Lingmei; Yang, Gaixiu; Yuan, Zhenhong; Chen, Yong

2017-01-25

For high caloricity and stability in bio-aviation fuels, a certain content of aromatic hydrocarbons (AHCs, 8-25 wt%) is crucial. Fatty acids, obtained from waste or inedible oils, are a renewable and economic feedstock for AHC production. Considerable amounts of AHCs, up to 64.61 wt%, were produced through the one-step hydroprocessing of fatty acids over Ni/HZSM-5 catalysts. Hydrogenation, hydrocracking, and aromatization constituted the principal AHC formation processes. At a lower temperature, fatty acids were first hydrosaturated and then hydrodeoxygenated at metal sites to form long-chain hydrocarbons. Alternatively, the unsaturated fatty acids could be directly deoxygenated at acid sites without first being saturated. The long-chain hydrocarbons were cracked into gases such as ethane, propane, and C 6 -C 8 olefins over the catalysts' Brønsted acid sites; these underwent Diels-Alder reactions on the catalysts' Lewis acid sites to form AHCs. C 6 -C 8 olefins were determined as critical intermediates for AHC formation. As the Ni content in the catalyst increased, the Brønsted-acid site density was reduced due to coverage by the metal nanoparticles. Good performance was achieved with a loading of 10 wt% Ni, where the Ni nanoparticles exhibited a polyhedral morphology which exposed more active sites for aromatization.

THE DYNAMICS OF HYDROGEN ATOM ABSTRACTION FROM POLYATOMIC MOLECULES.

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

LIU,X.; SUITS,A.G.

2002-11-21

The hydrogen atom abstraction reaction is an important fundamental process that is extensively involved in atmospheric and combustion chemistry. The practical significance of this type of reaction with polyatomic hydrocarbons is manifest, which has led to many kinetics studies. The detailed understanding of these reactions requires corresponding dynamics studies. However, in comparison to the A + HX {radical} AH + X reactions, the study of the dynamics of A + HR {yields} AH + R reactions is much more difficult, both experimentally and theoretically (here and in the following, A stands for an atom, X stands for a halogen atom,more » and R stands for a polyatomic hydrocarbon radical). The complication stems from the structured R, in contrast to the structureless X. First of all, there are many internal degrees of freedom in R that can participate in the reaction. In addition, there are different carbon sites from which an H atom can be abstracted, and the dynamics are correspondingly different; there are also multiple identical carbon sites in HR and in the picture of a local reaction, there exist competitions between neighboring H atoms, and so on. Despite this complexity, there have been continuing efforts to obtain insight into the dynamics of these reactions. In this chapter, some examples are presented, including the reactions of ground state H, Cl, and O atoms, with particular focus on our recent work using imaging to obtain the differential cross sections for these reactions.« less

Kinetic Coupling of Water Splitting and Photoreforming on SrTiO 3 -Based Photocatalysts

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

Sanwald, Kai E.; Berto, Tobias F.; Jentys, Andreas

Coupling the anodic half-reactions of overall water splitting and oxygenate photoreforming (i.e., proton reduction and oxygenate oxidations) on Al-doped SrTiO3 decorated with a co-catalyst enables efficient photocatalytic H2 generation along with oxygenate conversion without accumulating undesired intermediates such as formaldehyde. The net H2-evolution rates result from the interplay between water oxidation, oxygenate oxidation, and the back-reaction of H2 and O2 to water. When the latter pathway is quantitatively suppressed (e.g., on RhCrOx co-catalyst or in excess of oxygenated hydrocarbons), the initial H2-evolution rates are independent of the oxygenate nature and concentration. This is a consequence of the reduction equivalents formore » H2-evolution provided by water oxidation compensating changes in the rates of oxygenate conversion. Thus, under conditions of suppressed back-reaction, water and oxygenate oxidations have equal quantum efficiencies. The selectivities to water and oxygenate oxidation depend on oxygenate nature and concentration. Transformations mediated by indirect hole transfer dominate as a result of the water oxidation at the anode and the associated intermediates generated in O2-evolution catalysis (e.g. ·OH, ·O and ·OOH). On the undecorated semiconductor, the O2 produced during overall water splitting is reductively activated to participate in glycerol oxidation without consuming evolved H2. Acknowledgements The authors would like to thank ESRF in Grenoble, France, for providing beam time at the ID26 station for XAFS experiments. K.E.S. gratefully acknowledges financial support by the Fond der Chemischen Industrie (FCI). J.A.L. and O.Y.G. acknowledge support for his contribution by the Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory, a multi-program national laboratory operated by Battelle for the U.S. Department of Energy. The authors thank Xaver Hecht for BET measurements, Martin Neukamm for SEM and AAS measurements and Dr. Udishnu Sanyal for TEM imaging. Christine Schwarz is acknowledged for technical assistance in NMR experiments.« less

Untangling the Energetics and Dynamics of Boron Monoxide Radical Reactions (11BO; X2Sigma+)

DTIC Science & Technology

2015-04-15

Reaction products of isoelectronic boron monoxide (BO), cyano (CN), ethynyl (CCH), and silicon nitride (SiN) radicals with acetylene and ethylene. 3.10...Isoelectronicity in the Reactions of the Cyano (CN), Boron Monoxide (BO), Silicon Nitride (SiN), and Ethynyl (C2H) Radicals with Unsaturated Hydrocarbons...AFRL-OSR-VA-TR-2015-0111 Untangling the Energetics and Dynamics of Boron Monoxide Radical Reactions Ralf Kaiser UNIVERSITY OF HAWAII SYSTEMS HONOLULU

Total reaction cross sections of electronic state-specified transition metal cations: V + +C2H6, C3H8, and C2H4 at 0.2 eV

NASA Astrophysics Data System (ADS)

Sanders, Lary; Hanton, Scott D.; Weisshaar, James C.

1990-03-01

We describe a crossed beam experiment which measures total cross sections for reaction of electronic state-specified V+ with small hydrocarbons at well-defined collision energy E=0.2 eV. The V+ state distribution created at each ionizing wavelength is directly measured by angle-integrated photoelectron spectroscopy (preceding paper). Reactant and product ions are collected and analyzed by pulsed time-of-flight mass spectrometry following a reaction time of 6 μs. Tests of the performance of the apparatus are described in detail. Our experiment defines the reactant V+ electronic state distribution and the collision energy much more precisely than previous work. For all three hydrocarbons C2H6, C3H8, and C2H4, H2 elimination products dominate at 0.2 eV. We observe a dramatic dependence of cross section on the V+ electronic term. The second excited term 3d34s(3F) is more reactive than either lower energy quintet term 3d4(5D) or 3d34s(5F) by a factor of ≥270, 80, and ≥6 for the C2H6, C3H8, and C2H4 reactions, respectively. The 3d34s(3F) reaction cross sections at 0.2 eV are 20±11 Å2, 37±19 Å2, and 2.7±1.6 Å2, respectively, compared with Langevin cross sections of ˜80 Å2. For the C2H6 and C3H8 reactions, cross sections are independent of initial spin-orbit level J within the 3F term to the limits of our accuracy. Comparison with earlier work by Armentrout and co-workers shows that electronic excitation to d3s(3F) is far more effective at promoting H2 elimination than addition of the same total kinetic energy to reactants. Electron spin is clearly a key determinant of V+ reactivity with small hydrocarbons. We suggest that triplet V+ reacts much more efficiently than quintet V+ because of its ability to conserve total electron spin along paths to insertion in a C-H bond of the hydrocarbon.

Accelerated methanogenesis from aliphatic and aromatic hydrocarbons under iron- and sulfate-reducing conditions.

PubMed

Siegert, Michael; Cichocka, Danuta; Herrmann, Steffi; Gründger, Friederike; Feisthauer, Stefan; Richnow, Hans-Hermann; Springael, Dirk; Krüger, Martin

2011-02-01

The impact of four electron acceptors on hydrocarbon-induced methanogenesis was studied. Methanogenesis from residual hydrocarbons may enhance the exploitation of oil reservoirs and may improve bioremediation. The conditions to drive the rate-limiting first hydrocarbon-oxidizing steps for the conversion of hydrocarbons into methanogenic substrates are crucial. Thus, the electron acceptors ferrihydrite, manganese dioxide, nitrate or sulfate were added to sediment microcosms acquired from two brackish water locations. Hexadecane, ethylbenzene or 1-(13)C-naphthalene were used as model hydrocarbons. Methane was released most rapidly from incubations amended with ferrihydrite and hexadecane. Ferrihydrite enhanced only hexadecane-dependent methanogenesis. The rates of methanogenesis were negatively affected by sulfate and nitrate at concentrations of more than 5 and 1 mM, respectively. Metal-reducing Geobacteraceae and potential sulfate reducers as well as Methanosarcina were present in situ and in vitro. Ferrihydrite addition triggered the growth of Methanosarcina-related methanogens. Additionally, methane was removed concomitantly by anaerobic methanotrophy. ANME-1 and -2 methyl coenzyme M reductase genes were detected, indicating anaerobic methanotrophy as an accompanying process [Correction added 16 December after online publication: 'methyl coenzyme A' changed to 'methyl coenzyme M' in this sentence]. The experiments presented here demonstrate the feasibility of enhancing methanogenic alkane degradation by ferrihydrite or sulfate addition in different geological settings. © 2010 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Biofuels Refining Engineering

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

Lobban, Lance

The goal of this project is the development of novel catalysts and knowledge of reaction pathways and mechanisms for conversion of biomass-based compounds to fuels that are compatible with oil-based fuels and with acceptable or superior fuel properties. The research scope included both catalysts to convert lignocellulosic biomass-based molecules (from pyrolysis) and vegetable oil-based molecules (i.e., triglycerides and fatty acid methyl esters). This project comprised five technical tasks. Each task is briefly introduced below, and major technical accomplishments summarized. Technical accomplishments were described in greater detail in the quarterly progress reports, and in even more detail in the >50 publicationsmore » acknowledging this DoE project funding (list of publications and presentations included at the end of this report). The results of this research added greatly to the knowledge base necessary for upgrading of pyrolysis oil to hydrocarbon fuels and chemicals, and for conversion of vegetable oils to fungible diesel fuel. Numerous new catalysts and catalytic reaction systems were developed for upgrading particular compounds or compound families found in the biomass-based pyrolysis oils and vegetable oils. Methods to mitigate catalyst deactivation were investigated, including novel reaction/separation systems. Performance and emission characteristics of biofuels in flames and engines were measured. Importantly, the knowledge developed from this project became the basis for a subsequent collaborative proposal led by our research group, involving researchers from the University of Wisconsin, the University of Pittsburg, and the Idaho National Lab, for the DoE Carbon, Hydrogen and Separations Efficiency (CHASE) program, which was subsequently funded (one of only four projects awarded in the CHASE program). The CHASE project examined novel catalytic processes for lignocellulosic biomass conversion as well as technoeconomic analyses for process options for maximum carbon capture and hydrogen efficiency. Our research approach combined catalyst synthesis, measurements of catalyst activity and selectivity in different reactor systems and conditions, and detailed catalyst characterization to develop fundamental understanding of reaction pathways and the capability to predict product distributions. Nearly all of the candidate catalysts were prepared in-house via standard techniques such as impregnation, co-impregnation, or chemical vapor deposition. Supports were usually purchased, but in some cases coprecipitation was used to simultaneously create the support and active component, which can be advantageous for strong active component-support interactions and for achieving high active component dispersion. In-house synthesis also allowed for studies of the effects on catalyst activity and selectivity of such factors as support porosity, calcination temperature, and reduction/activation conditions. Depending on the physical characteristics of the molecule, catalyst activity measurements were carried out in tubular flow reactors (for vapor phase reactions) or stirred tank reactors (for liquid phase reactions) over a wide range of pressures and temperatures. Reactant and product concentrations were measured using gas chromatography (both on-line and off-line, with TCD, FID, and/or mass spectrometric detection). For promising catalysts, detailed physicochemical characterization was carried out using FTIR, Raman, XPS, and XRD spectroscopies (all available in our laboratories) and TEM spectroscopy (available at OU). Additional methods included temperature programmed techniques (TPD, TPO) and surface area measurements by nitrogen adsorption techniques.« less

Elucidation of the Conversion Reaction of CoMnFeO4 Nanoparticles in Lithium Ion Battery Anode via Operando Studies.

PubMed

Permien, Stefan; Indris, Sylvio; Hansen, Anna-Lena; Scheuermann, Marco; Zahn, Dirk; Schürmann, Ulrich; Neubüser, Gero; Kienle, Lorenz; Yegudin, Eugen; Bensch, Wolfgang

2016-06-22

Conversion reactions deliver much higher capacities than intercalation/deintercalation reactions of commercial Li ion batteries. However, the complex reaction pathways of conversion reactions occurring during Li uptake and release are not entirely understood, especially the irreversible capacity loss of Mn(III)-containing oxidic spinels. Here, we report for the first time on the electrochemical Li uptake and release of Co(II)Mn(III)Fe(III)O4 spinel nanoparticles and the conversion reaction mechanisms elucidated by combined operando X-ray diffraction, operando and ex-situ X-ray absorption spectroscopy, transmission electron microscopy, (7)Li NMR, and molecular dynamics simulation. The combination of these techniques enabled uncovering the pronounced electronic changes and structural alterations on different length scales in a unique way. The spinel nanoparticles undergo a successive phase transition into a mixed monoxide caused by a movement of the reduced cations from tetrahedral to octahedral positions. While the redox reactions Fe(3+) ↔ Fe(0) and Co(2+) ↔ Co(0) occur for many charge/discharge cycles, metallic Mn nanoparticles formed during the first discharge can only be oxidized to Mn(2+) during charge. This finding explains the partial capacity loss reported for Mn(III)-based spinels. Furthermore, the results of the investigations evidence that the reaction mechanisms on the nanoscale are very different from pathways of microcrystalline materials.

Reactions of gas phase H atoms with ethylene, acetylene and ethane adsorbed on Ni( 1 1 1 )

NASA Astrophysics Data System (ADS)

Bürgi, T.; Trautman, T. R.; Gostein, M.; Lahr, D. L.; Haug, K. L.; Ceyer, S. T.

2002-03-01

The products of the reaction of the most energetic form of hydrogen, gas phase H atoms, with ethylene, acetylene and ethane adsorbed on a Ni(1 1 1) surface at 60 K are probed. Adsorbed ethylidyne (CCH 3) is identified by high resolution electron energy loss spectroscopy to be the major product (30% yield) in all three cases. Adsorbed acetylene is a minor product (3% yield) and arises as a consequence of a dynamic equilibrium between CCH 3 and C 2H 2 in the presence of gas phase H atoms. The observation of the same product for the reaction of H atoms with all three hydrocarbons implies that CCH 3 is the most stable C 2 species in the presence of coadsorbed hydrogen. The rates of CCH 3 production are measured as a function of the time of exposure of H atoms to each hydrocarbon. A simple kinetic model treating each reaction as a pseudo-first order reaction in the hydrocarbon coverage is fit to these data. A mechanism for the formation of CCH 3 via a CHCH 2 intermediate common to all three reactants is proposed to describe this model. The observed instability of the CH 2CH 3 species relative to C 2H 4 plays a role in the formulation of this mechanism as does the observed stability of CHCH 2 species in the presence of coadsorbed hydrogen. The CH 2CH 3 and the CHCH 2 species are produced by the translational activation of ethane and the dissociative ionization of ethane and ethylene, respectively. In addition, the binding energy and the vibrational spectrum of ethane adsorbed on Ni(1 1 1) are determined and exceptionally high resolution vibrational spectra of adsorbed ethylene and acetylene are presented.

Mineral-assisted production of benzene under hydrothermal conditions: Insights from experimental studies on C6 cyclic hydrocarbons

NASA Astrophysics Data System (ADS)

Venturi, Stefania; Tassi, Franco; Gould, Ian R.; Shock, Everett L.; Hartnett, Hilairy E.; Lorance, Edward D.; Bockisch, Christiana; Fecteau, Kristopher M.; Capecchiacci, Francesco; Vaselli, Orlando

2017-10-01

Volatile Organic Compounds (VOCs) are ubiquitously present at low but detectable concentrations in hydrothermal fluids from volcanic and geothermal systems. Although their behavior is strictly controlled by physical and chemical parameters, the mechanisms responsible for the production of most VOCs in natural environments are poorly understood. Among them, benzene, whose abundances were found to be relatively high in hydrothermal gases, can theoretically be originated from reversible catalytic reforming processes, i.e. multi-step dehydrogenation reactions, involving saturated hydrocarbons. However, this hypothesis and other hypotheses are difficult to definitively prove on the basis of compositional data obtained by natural gas discharges only. In this study, therefore, laboratory experiments were carried out to investigate the production of benzene from cyclic hydrocarbons at hydrothermal conditions, specifically 300 °C and 85 bar. The results of experiments carried out in the presence of water and selected powdered minerals, suggest that cyclohexane undergoes dehydrogenation to form benzene, with cyclohexene and cyclohexadiene as by-products, and also as likely reaction intermediates. This reaction is slow when carried out in water alone and competes with isomerization and hydration pathways. However, benzene formation was increased compared to these competing reactions in the presence of sulfide (sphalerite and pyrite) and iron oxide (magnetite and hematite) minerals, whereas no enhancement of any reaction products was observed in the presence of quartz. The production of thiols was observed in experiments involving sphalerite and pyrite, suggesting that sulfide minerals may act both to enhance reactivity and also as reactants after dissolution. These experiments demonstrate that benzene can be effectively produced at hydrothermal conditions through dehydrogenation of saturated cyclic organic structures and highlight the crucial role played by minerals in this process.

Produced water re-injection in a non-fresh water aquifer with geochemical reaction, hydrodynamic molecular dispersion and adsorption kinetics controlling: model development and numerical simulation

NASA Astrophysics Data System (ADS)

Obe, Ibidapo; Fashanu, T. A.; Idialu, Peter O.; Akintola, Tope O.; Abhulimen, Kingsley E.

2017-06-01

An improved produced water reinjection (PWRI) model that incorporates filtration, geochemical reaction, molecular transport, and mass adsorption kinetics was developed to predict cake deposition and injectivity performance in hydrocarbon aquifers in Nigeria oil fields. Thus, the improved PWRI model considered contributions of geochemical reaction, adsorption kinetics, and hydrodynamic molecular dispersion mechanism to alter the injectivity and deposition of suspended solids on aquifer wall resulting in cake formation in pores during PWRI and transport of active constituents in hydrocarbon reservoirs. The injectivity decline and cake deposition for specific case studies of hydrocarbon aquifers in Nigeria oil fields were characterized with respect to its well geometry, lithology, and calibrations data and simulated in COMSOL multiphysics software environment. The PWRI model was validated by comparisons to assessments of previous field studies based on data and results supplied by operator and regulator. The results of simulation showed that PWRI performance was altered because of temporal variations and declinations of permeability, injectivity, and cake precipitation, which were observed to be dependent on active adsorption and geochemical reaction kinetics coupled with filtration scheme and molecular dispersion. From the observed results and findings, transition time t r to cake nucleation and growth were dependent on aquifer constituents, well capacity, filtration coefficients, particle-to-grain size ratio, water quality, and more importantly, particle-to-grain adsorption kinetics. Thus, the results showed that injectivity decline and permeability damage were direct contributions of geochemical reaction, hydrodynamic molecular diffusion, and adsorption kinetics to the internal filtration mechanism, which are largely dependent on the initial conditions of concentration of active constituents of produced water and aquifer capacity.

A novel headspace gas chromatographic method for in situ monitoring of monomer conversion during polymerization in an emulsion environment.

PubMed

Chai, Xin-Sheng; Zhong, Jin-Feng; Hu, Hui-Chao

2012-05-18

This paper describes a novel multiple-headspace extraction/gas chromatographic (MHE-GC) technique for monitoring monomer conversion during a polymerization reaction in a water-based emulsion environment. The polymerization reaction of methyl methacrylate (MMA) in an aqueous emulsion is used as an example. The reaction was performed in a closed headspace sample vial (as a mini-reactor), with pentane as a tracer. In situ monitoring of the vapor concentration of the tracer, employing a multiple headspace extraction (sampling) scheme, coupled to a GC, makes it possible to quantitatively follow the conversion of MMA during the early stages of polymerization. Data on the integrated amount of the tracer vapor released from the monomer droplet phase during the polymerization is described by a mathematic equation from which the monomer conversion can be calculated. The present method is simple, automated and economical, and provides an efficient tool in the investigation of the reaction kinetics and effects of the reaction conditions on the early stage of polymerization. Copyright © 2012 Elsevier B.V. All rights reserved.

Problems Caused by Microbes and Treatment Strategies Anaerobic Hydrocarbon Biodegradation and Biocorrosion: A Case Study

NASA Astrophysics Data System (ADS)

Suflita, Joseph M.; Duncan, Kathleen E.

The anaerobic biodegradation of petroleum hydrocarbons is important for the intrinsic remediation of spilt fuels (Gieg and Suflita, 2005), for the conversion of hydrocarbons to clean burning natural gas (Gieg et al., 2008; Jones et al., 2008) and for the fundamental cycling of carbon on the planet (Caldwell et al., 2008). However, the same process has also been implicated in a host of difficult problems including reservoir souring (Jack and Westlake, 1995), oil viscosity alteration (Head et al., 2003), compromised equipment performance and microbiologically influenced corrosion (Duncan et al., 2009). Herein, we will focus on the role of anaerobic microbial communities in catalysing biocorrosion activities in oilfield facilities. Biocorrosion is a costly problem that remains relatively poorly understood. Understanding of the underlying mechanisms requires reliable information on the carbon and energy sources supporting biofilm microorganisms capable of catalysing such activities.

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

McAlexander, Benjamin L., E-mail: bmcalexander@trihydro.com

Petroleum-contaminated site management typically counts destruction of hydrocarbons by either natural or engineered processes as a beneficial component of remediation. While such oxidation of spilled hydrocarbons is often necessary for achieving risk reduction for nearby human and ecological receptors, site assessments tend to neglect that this also means that the pollutants are converted to greenhouse gases and emitted to the atmosphere. This article presents a suggestion that the current and long term greenhouse gas emissions from spilled hydrocarbons be incorporated to petroleum site assessments. This would provide a more complete picture of pollutant effects that could then be incorporated tomore » remedial objectives. At some sites, this additional information may affect remedy selection. Possible examples include a shift in emphasis to remedial technologies that reduce pollutant greenhouse gas effects (e.g., by conversion of methane to carbon dioxide in the subsurface), and a more holistic context for considering remedial technologies with low emission footprints.« less

Specific biases for identifying facial expression of emotion in children and adolescents with conversion disorders.

PubMed

Kozlowska, Kasia; Brown, Kerri J; Palmer, Donna M; Williams, Lea M

2013-04-01

This study aimed to assess how children and adolescents with conversion disorders identify universal facial expressions of emotion and to determine whether identification of emotion in faces relates to subjective emotional distress. Fifty-seven participants (41 girls and 16 boys) aged 8.5 to 18 years with conversion disorders and 57 age- and sex-matched healthy controls completed a computerized task in which their accuracy and reaction times for identifying facial expressions were recorded. To isolate the effect of individual emotional expressions, participants' reaction times for each emotion (fear, anger, sadness, disgust, and happiness) were subtracted from their reaction times for the neutral control face. Participants also completed self-report measures of subjective emotional distress. Children/Adolescents with conversion disorders showed faster reaction times for identifying expressions of sadness (t(112) = -2.2, p = .03; 444 [609] versus 713 [695], p = .03) and slower reactions times for happy expressions (t(99.3) = 2.28, p ≤ .024; -33 [35] versus 174 [51], p = .024), compared with controls (F(33.75, 419.81) = 3.76, p < .001). There were no significant correlations (at the corrected p value of .01) between reaction times and subjective reports of perceived distress (r values ranged from 092 to 0.221; p > .018). There were also no differences in identification accuracy for any emotion (p > .82). The observation of faster reaction times to sad faces in children and adolescents with conversion disorders suggests increased vigilance and motor readiness to emotional signals that are potential threats to self or to close others. These effects may occur before conscious processing.

Thermic conversion of benzene into 6-phenylfulvene with high yield mediated by GaP nanocrystals.

PubMed

Gao, Shanmin; Lu, Jun; Zhao, Yan; Chen, Nan; Xie, Yi

2002-12-07

With GaP nanocrystals being used in a close reaction system, 6-phenylfulvene is successfully obtained via a high yield thermic conversion from benzene, which provides the possibility of applying nanocrystals to mediate organic reactions.

Octahedral molecular sieve sorbents and catalysts

DOEpatents

Li, Liyu [Richland, WA; King, David L [Richland, WA

2010-04-20

Octahedral molecular sieve sorbents and catalysts are disclosed, including silver hollandite and cryptomelane. These materials can be used, for example, to catalyze the oxidation of CO.sub.x (e.g., CO), NO.sub.x (e.g., NO), hydrocarbons (e.g., C.sub.3H.sub.6) and/or sulfur-containing compounds. The disclosed materials also may be used to catalyze other reactions, such as the reduction of NO.sub.2. In some cases, the disclosed materials are capable of sorbing certain products from the reactions they catalyze. Silver hollandite, in particular, can be used to remove a substantial portion of certain sulfur-containing compounds from a gas or liquid by catalysis and/or sorption. The gas or liquid can be, for example, natural gas or a liquid hydrocarbon.

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

NASA Technical Reports Server (NTRS)

Chinitz, W.

1986-01-01

A computationally-viable model describing the interaction between fluid-mechanical turbulence and finite-rate combustion reactions, principally in high-speed flows was developed. Chemical kinetic mechanisms, complete and global, were developed describing the finite rate reaction of fuels of interest to NASA. These fuels included principally hydrogen and silane, although a limited amount of work involved hydrocarbon fuels as well.

Validation Testing a Contaminant Transport and Natural Attenuation Simulation Model Using Field Data.

DTIC Science & Technology

1995-12-01

reactions . The following figure shows the relationship of common electron acceptors with regard to their redox potential. Redox Potential (pH = 7) in...Model 8 Fuel-Spill Plume Profile 8 Hydrocarbon Biodegradation 1° Oxygen 11 Anaerobic Electron Acceptors 12 Redox Potential *4 Contaminants of...Biodegradation Reactions 21 Oxygen Reactions 21 Nitrate 22 Manganese (IV) 22 Iron (III) 23 Sulfate 24 in Page Intrinsic Bioremediation Model

The direct aromatization of methane

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

Marcelin, G.; Oukaci, R.; Migone, R.A.

1995-12-31

The thermal decomposition of methane shows significant potential as a process for the production of higher unsaturated and aromatic hydrocarbons when the extent of the reaction is limited. Thermodynamic calculations have shown that when the reaction is limited to the formation of C{sub 2} to C{sub 10} products, yields of aromatics can exceed 40% at temperatures of 1200{degrees}C. Preliminary experiments have shown that when the reaction is limited to the formation of C{sub 2} to C{sub 10} products, yields of aromatics can exceed 40% at temperatures of 1200{degrees}C. Preliminary experiments have shown that cooling the product and reacting gases asmore » the reaction proceeds can significantly reduce or eliminate the formation of solid carbon and heavier (C{sub 10+}) materials. Much work remains to be done in optimizing the quenching process and this is one of the goals of this program. Means to lower the temperature of the reaction are being studied as this result in a more feasible commercial process due to savings realized in energy and material of construction costs. The use of free-radical generators and catalysts will be investigated as a means of lowering the reaction temperature thus allowing faster quenching. It is highly likely that such studies will lead to a successful direct methane to higher hydrocarbon process.« less