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Sample records for liquefaction fischer-tropsch synthesis

  1. Tailored fischer-tropsch synthesis product distribution

    DOEpatents

    Wang, Yong [Richland, WA; Cao, Chunshe [Kennewick, WA; Li, Xiaohong Shari [Richland, WA; Elliott, Douglas C [Richland, WA

    2012-06-19

    Novel methods of Fischer-Tropsch synthesis are described. It has been discovered that conducting the Fischer-Tropsch synthesis over a catalyst with a catalytically active surface layer of 35 microns or less results in a liquid hydrocarbon product with a high ratio of C.sub.5-C.sub.20:C.sub.20+. Descriptions of novel Fischer-Tropsch catalysts and reactors are also provided. Novel hydrocarbon compositions with a high ratio of C.sub.5-C.sub.20:C.sub.20+ are also described.

  2. Public health hazards of Lurgi/Fischer-Tropsch coal liquefaction

    SciTech Connect

    Gasper, J.R.; Rosenberg, S.E.

    1981-01-01

    This analysis identifies the public hazards of wastes from Lurgi/Fischer-Tropsch coal liquefaction. Because data on dose-response and synergism are not available for many of the waste chemicals from this process, we evaluated hazards with a relative risk approach. This approach employs two measures of hazards. First, body burdens that result from exposure to Lurgi/Fischer-Tropsch wastes are compared to body burdens from other sources of the same chemicals. Second ambient concentrations of pollutants from Lurgi/Fischer-Tropsch operations are projected and compared to various air and water quality standards.

  3. Moderated ruthenium fischer-tropsch synthesis catalyst

    DOEpatents

    Abrevaya, Hayim

    1991-01-01

    The subject Fischer-Tropsch catalyst comprises moderated ruthenium on an inorganic oxide support. The preferred moderator is silicon. Preferably the moderator is effectively positioned in relationship to ruthenium particles through simultaneous placement on the support using reverse micelle impregnation.

  4. Alternative Fuel Research in Fischer-Tropsch Synthesis

    NASA Technical Reports Server (NTRS)

    Surgenor, Angela D.; Klettlinger, Jennifer L.; Yen, Chia H.; Nakley, Leah M.

    2011-01-01

    NASA Glenn Research Center has recently constructed an Alternative Fuels Laboratory which is solely being used to perform Fischer-Tropsch (F-T) reactor studies, novel catalyst development and thermal stability experiments. Facility systems have demonstrated reliability and consistency for continuous and safe operations in Fischer-Tropsch synthesis. The purpose of this test facility is to conduct bench scale Fischer-Tropsch (F-T) catalyst screening experiments while focusing on reducing energy inputs, reducing CO2 emissions and increasing product yields within the F-T process. Fischer-Tropsch synthesis is considered a gas to liquid process which reacts syn-gas (a gaseous mixture of hydrogen and carbon monoxide), over the surface of a catalyst material which is then converted into liquids of various hydrocarbon chain length and product distributions1. These hydrocarbons can then be further processed into higher quality liquid fuels such as gasoline and diesel. The experiments performed in this laboratory will enable the investigation of F-T reaction kinetics to focus on newly formulated catalysts, improved process conditions and enhanced catalyst activation methods. Currently the facility has the capability of performing three simultaneous reactor screening tests, along with a fourth fixed-bed reactor used solely for cobalt catalyst activation.

  5. Improved Fischer-Tropsch catalysts for indirect coal liquefaction

    SciTech Connect

    Wilson, R.B. Jr.; Tong, G.T.; Chan, Y.W.; Huang, H.W.; McCarty, J.G.

    1989-02-01

    The Fischer-Tropsch synthesis (FTS)reaction is the established technology for the production of liquid fuels from coal by an indirect route using coal-derived syngas (CO + H{sub 2}). Modern FTS catalysts are potassium- and copper-promoted iron preparations. These catalysts exhibit moderate activity with carbon monoxide-rich feedstocks such as the syngas produced by advanced coal gasification processes. However, the relatively large yields of by-product methane and high-molecular-weight hydrocarbon waxes detract from the production of desired liquid products in the C{sub 5}-C{sub 16} range needed for motor and aviation fuel. The goal of this program is to decrease undesirable portions of the FTS hydrocarbon yield by altering the Schultz-Flory polymerization product distribution through design and formulation of improved catalysts. Two approaches were taken: (1) reducing the yield of high-molecular-weight hydrocarbon waxes by using highly dispersed catalysts produced from surface-confined multiatomic clusters on acid supports and (2) suppressing methane production by uniformly pretreating active, selective conventional FTS catalysts with submonolayer levels of sulfur.

  6. The role of zeolite in the Fischer-Tropsch synthesis over cobalt-zeolite catalysts

    NASA Astrophysics Data System (ADS)

    Sineva, L. V.; Asalieva, E. Yu; Mordkovich, V. Z.

    2015-11-01

    The review deals with the specifics of the Fischer-Tropsch synthesis for the one-stage syncrude production from CO and H2 in the presence of cobalt-zeolite catalytic systems. Different types of bifunctional catalysts (hybrid, composite) combining a Fischer-Tropsch catalyst and zeolite are reviewed. Special attention focuses on the mechanisms of transformations of hydrocarbons produced in the Fischer-Tropsch process on zeolite acid sites under the synthesis conditions. The bibliography includes 142 references.

  7. New developments in the field of Fischer-Tropsch synthesis

    SciTech Connect

    Brink, A.

    1985-01-01

    The Fischer-Tropsch synthesis for the production of transport fuels from syngas has been a commercial success in South Africa for nearly thirty years. It cannot be regarded as an entirely mature technology, though, and exciting prospects remain for improvements. The characteristics of the newer gasifiers such as Texaco, slagging BGC-Lurgi, Koppers-Totzek, Winkler and U-gas have to be carefully studied to determine their impact on the F T-synthesis. The wide carbon number selectivity of the F T-synthesis is not the drawback it is often assumbed to be since this can be easily rectified in the downstream refining section. Nevertheless, improved selectivity as regards the production of less methane and carbon, more ..cap alpha..-olefins and greater control over oxygenate production remain challenging possibilities.

  8. Fischer-Tropsch synthesis in supercritical reaction media

    SciTech Connect

    Subramaniam, B.

    1995-05-01

    The goal of the proposed research is to develop novel reactor operating strategies for the catalytic conversion of syngas to transportation grade fuels and oxygenates using near-critical (nc) fluids as reaction media. This will be achieved through systematic investigations aimed at a better fundamental understanding of the physical and chemical rate processes underlying catalytic syngas conversion in nc reaction media. Syngas conversion to fuels and fuel additives on Fe catalysts (Fischer-Tropsch synthesis) was investigated. Specific objectives are to investigate the effects of various nc media, their flow rates and operating pressure on syngas conversion, reactor temperature profiles, product selectivity and catalyst activity in trickle-bed reactors. Solvents that exhibit gas to liquid-like densities with relatively moderate pressure changes (from 25 to 60 bars) at typical syngas conversion temperatures (in the 220-280{degree}C range) will be chosen as reaction media.

  9. Intensified Fischer-Tropsch Synthesis Process with Microchannel Catalytic Reactors

    SciTech Connect

    Cao, Chunshe; Hu, Jianli; Li, Shari; Wilcox, Wayne A.; Wang, Yong

    2009-02-28

    A microchannel catalytic reactor with improved heat and mass transport has been used for Fischer-Tropsch synthesis to produce fuels and chemicals. This type of novel reactor takes advantages of highly active and selective catalysts with increased site density so that the FT synthesis process can be intensified. It was demonstrated that this microchannel reactor based process can be carried out at gas hourly space velocity (GHSV) as high as 60,000 hr-1 to achieve greater than 60% of one-pass CO conversion while maintaining low methane selectivity (<10%) and high chain growth probability(>0.9). Such superior FT synthesis performance has not ever been reported in the prior open literatures. The overall productivity to heavy hydrocarbons has been significantly improved over the conventional reactor technology. In this study, performance data were obtained in a wide range of pressure (10atm-35atm) and hydrogen to carbon monoxide ratio (1-2.5). The catalytic system was characterized by BET, scanning electron microcopy (SEM), transmission electron microcopy(TEM), and H2 chemisorption. A three dimensional pseudo-homogeneous model were used to simulate temperature profiles in the exothermic reaction system in order to optimize the reactor design and intensify the synthesis process. Intraparticle non-isothermal characteristics are also analyzed for the FT synthesis catalyst.

  10. Fischer-Tropsch synthesis in supercritical reaction media

    SciTech Connect

    Subramaniam, B.

    1992-10-01

    The goal of this research is to thoroughly investigate the feasibility of using supercritical fluid (SCF) solvent medium for carrying out Fischer-Tropsch (FT) synthesis. Research will address the systematic experimental investigations of FT synthesis over supported Fe and Co catalysts in a CSTR and in a fixed-bed reactor at typical synthesis temperatures (240-260[degrees]C). The SCF medium to be employed is n-Hexane (P[sub c] = 29.7 bar; [Tc] = 233.7[degrees]C), while n-Hexadecane will be employed as the liquid reaction medium. Overall conversion, product distribution and catalyst deactivation will be measured in each case for various feed H[sub 2]/CO ratios ranging from 0.5 to 2. Product analyses will be carried out using GC/TCD, GC/FID and GC/MS systems. The fresh and used catalysts will be characterized with respect to active metal dispersion, surface area and pore size distribution.

  11. KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYNTHESIS

    SciTech Connect

    Dragomir B. Bukur; Gilbert F. Froment; Lech Nowicki; Jiang Wang; Wen-Ping Ma

    2003-09-29

    This report covers the first year of this three-year research grant under the University Coal Research program. The overall objective of this project is to develop a comprehensive kinetic model for slurry phase Fischer-Tropsch synthesis on iron catalysts. This model will be validated with experimental data obtained in a stirred tank slurry reactor (STSR) over a wide range of process conditions. The model will be able to predict concentrations of all reactants and major product species (H{sup 2}O, CO{sub 2}, linear 1- and 2-olefins, and linear paraffins) as a function of reaction conditions in the STSR. During the reporting period we have completed one STSR test with precipitated iron catalyst obtained from Ruhrchemie AG (Oberhausen-Holten, Germany). This catalyst was initially in commercial fixed bed reactors at Sasol in South Africa. The catalyst was tested at 13 different sets of process conditions, and had experienced a moderate deactivation during the first 500 h of testing (decrease in conversion from 56% to 50% at baseline process conditions). The second STSR test has been initiated and after 270 h on stream, the catalyst was tested at 6 different sets of process conditions.

  12. KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYNTHESIS

    SciTech Connect

    Dragomir B. Bukur

    2004-09-29

    This report covers the second year of this three-year research grant under the University Coal Research program. The overall objective of this project is to develop a comprehensive kinetic model for slurry phase Fischer-Tropsch synthesis on iron catalysts. This model will be validated with experimental data obtained in a stirred tank slurry reactor (STSR) over a wide range of process conditions. The model will be able to predict concentrations of all reactants and major product species (H{sub 2}O, CO{sub 2}, linear 1- and 2-olefins, and linear paraffins) as a function of reaction conditions in the STSR. During the second year of the project we completed the STSR test SB-26203 (275-343 h on stream), which was initiated during the first year of the project, and another STSR test (SB-28603 lasting 341 h). Since the inception of the project we completed 3 STSR tests, and evaluated catalyst under 25 different sets of process conditions. A precipitated iron catalyst obtained from Ruhrchemie AG (Oberhausen-Holten, Germany) was used in all tests. This catalyst was used initially in commercial fixed bed reactors at Sasol in South Africa. Also, during the second year we performed a qualitative analysis of experimental data from all three STSR tests. Effects of process conditions (reaction temperature, pressure, feed composition and gas space velocity) on water-gas-shift (WGS) activity and hydrocarbon product distribution have been determined.

  13. Process for upgrading wax from Fischer-Tropsch synthesis

    DOEpatents

    Derr, Jr., W. Rodman; Garwood, William E.; Kuo, James C.; Leib, Tiberiu M.; Nace, Donald M.; Tabak, Samuel A.

    1987-01-01

    The waxy liquid phase of an oil suspension of Fischer-Tropsch catalyst containing dissolved wax is separated out and the wax is converted by hydrocracking, dewaxing or by catalytic cracking with a low activity catalyst to provide a highly olefinic product which may be further converted to premium quality gasoline and/or distillate fuel.

  14. Process for upgrading wax from Fischer-Tropsch synthesis

    DOEpatents

    Derr, W.R. Jr.; Garwood, W.E.; Kuo, J.C.; Leib, T.M.; Nace, D.M.; Tabak, S.A.

    1987-08-04

    The waxy liquid phase of an oil suspension of Fischer-Tropsch catalyst containing dissolved wax is separated out and the wax is converted by hydrocracking, dewaxing or by catalytic cracking with a low activity catalyst to provide a highly olefinic product which may be further converted to premium quality gasoline and/or distillate fuel. 2 figs.

  15. Fischer-Tropsch synthesis process employing a moderated ruthenium catalyst

    DOEpatents

    Abrevaya, H.

    1990-07-31

    A Fischer-Tropsch type process produces hydrocarbons from carbon monoxide and hydrogen using a novel catalyst comprising moderated ruthenium on an inorganic oxide support. The preferred moderator is silicon. Preferably the moderator is effectively positioned in relationship to ruthenium particles through simultaneous placement on the support using reverse micelle impregnation. 1 fig.

  16. Fischer-Tropsch synthesis process employing a moderated ruthenium catalyst

    DOEpatents

    Abrevaya, Hayim

    1990-01-01

    A Fischer-Tropsch type process produces hydrocarbons from carbon monoxide and hydrogen using a novel catalyst comprising moderated ruthenium on an inorganic oxide support. The preferred moderator is silicon. Preferably the moderator is effectively positioned in relationship to ruthenium particles through simultaneous placement on the support using reverse micelle impregnation.

  17. Fischer-Tropsch synthesis in supercritical fluids. Final report

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1998-12-31

    The objective of this study was to investigate Fischer-Tropsch Synthesis (FTS) in the supercritical phase employing a commercial precipitated iron catalysts. As the supercritical fluid the authors used propane and n-hexane. The catalyst had a nominal composition of 100 Fe/5 Cu/4.2 K/25 SiO{sub 2} on mass basis and was used in a fixed bed reactor under both normal (conventional) and supercritical conditions. Experimental data were obtained at different temperatures (235 C, 250 C, and 260 C) and synthesis gas feed compositions (H{sub 2}/CO molar feed ratio of 0.67, 1.0 and 2.0) in both modes of operation under steady state conditions. The authors compared the performance of the precipitated iron catalyst in the supercritical phase, with the data obtained in gas phase (fixed bed reactor) and slurry phase (STS reactor). Comparisons were made in terms of bulk catalyst activity and various aspects of product selectivity (e.g. lumped hydrocarbon distribution and olefin content as a function of carbon number). In order to gain better understanding of the role of intraparticle mass transfer during FTS under conventional or supercritical conditions, the authors have measured diffusivities of representative hydrocarbon products in supercritical fluids, as well as their effective diffusion rates into the pores of catalyst at the reaction conditions. They constructed a Taylor dispersion apparatus to measure diffusion coefficients of hydrocarbon products of FTS in sub and supercritical ethane, propane, and hexane. In addition, they developed a tracer response technique to measure the effective diffusivities in the catalyst pores at the same conditions. Based on these results they have developed an equation for prediction of diffusion in supercritical fluids, which is based on the rough hard sphere theory.

  18. Fischer-Tropsch synthesis. Evaluation of an aluminum small channel reactor.

    PubMed

    Sparks, D E; Vallee, S; Jia, Zhijun; Shafer, W D; Davis, B H

    2017-02-10

    Fischer-Tropsch synthesis was conducted in a small channel compact heat exchange reactor that was constructed of aluminum. While limited to lower temperature-pressure regions of the Fischer-Tropsch synthesis, the reactor could be operated in an isothermal mode with nearly a constant temperature along the length of the channel. The results obtained with the compact heat exchange reactor were similar to those obtained in the isothermal continuous stirred tank reactor, with respect to both activity and selectivity. Following a planned or unplanned shutdown, the reactor could be restarted to produce essentially the same catalytic activity and selectivity as before the shutdown.

  19. KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYNTHESIS

    SciTech Connect

    Dragomir B. Bukur; Gilbert F. Froment; Tomasz Olewski

    2006-09-29

    This report covers the fourth year of a research project conducted under the University Coal Research Program. The overall objective of this project is to develop a comprehensive kinetic model for slurry-phase Fischer-Tropsch synthesis (FTS) employing iron-based catalysts. This model will be validated with experimental data obtained in a stirred-tank slurry reactor (STSR) over a wide range of process conditions. The model will be able to predict molar flow rates and concentrations of all reactants and major product species (water, carbon dioxide, linear 1- and 2-olefins, and linear paraffins) as a function of reaction conditions in the STSR. During the fourth year of the project, an analysis of experimental data collected during the second year of this project was performed. Kinetic parameters were estimated utilizing product distributions from 27 mass balances. During the reporting period two kinetic models were employed: a comprehensive kinetic model of Dr. Li and co-workers (Yang et al., 2003) and a hydrocarbon selectivity model of Van der Laan and Beenackers (1998, 1999) The kinetic model of Yang et al. (2003) has 24 parameters (20 parameters for hydrocarbon formation, and 4 parameters for the water-gas-shift (WGS) reaction). Kinetic parameters for the WGS reaction and FTS synthesis were estimated first separately, and then simultaneously. The estimation of these kinetic parameters employed the Levenberg-Marquardt (LM) method and the trust-region reflective Newton large-scale (LS) method. A genetic algorithm (GA) was incorporated into estimation of parameters for FTS reaction to provide initial estimates of model parameters. All reaction rate constants and activation energies were found to be positive, but at the 95% confidence level the intervals were large. Agreement between predicted and experimental reaction rates has been fair to good. Light hydrocarbons are predicted fairly accurately, whereas the model underpredicts values of higher molecular weight

  20. Fly ash zeolite catalyst support for Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Campen, Adam

    This dissertation research aimed at evaluating a fly ash zeolite (FAZ) catalyst support for use in heterogeneous catalytic processes. Gas phase Fischer-Tropsch Synthesis (FTS) over a fixed-bed of the prepared catalyst/FAZ support was identified as an appropriate process for evaluation, by comparison with commercial catalyst supports (silica, alumina, and 13X). Fly ash, obtained from the Wabash River Generating Station, was first characterized using XRD, SEM/EDS, particle size, and nitrogen sorption techniques. Then, a parametric study of a two-step alkali fusion/hydrothermal treatment process for converting fly ash to zeolite frameworks was performed by varying the alkali fusion agent, agent:flyash ratio, fusion temperature, fused ash/water solution, aging time, and crystallization time. The optimal conditions for each were determined to be NaOH, 1.4 g NaOH: 1 g fly ash, 550 °C, 200 g/L, 12 hours, and 48 hours. This robust process was applied to the fly ash to obtain a faujasitic zeolite structure with increased crystallinity (40 %) and surface area (434 m2/g). Following the modification of fly ash to FAZ, ion exchange of H+ for Na+ and cobalt incipient wetness impregnation were used to prepare a FTS catalyst. FTS was performed on the catalysts at 250--300 °C, 300 psi, and with a syngas ratio H2:CO = 2. The HFAZ catalyst support loaded with 11 wt% cobalt resulted in a 75 % carbon selectivity for C5 -- C18 hydrocarbons, while methane and carbon dioxide were limited to 13 and 1 %, respectively. Catalyst characterization was performed by XRD, N2 sorption, TPR, and oxygen pulse titration to provide insight to the behavior of each catalyst. Overall, the HFAZ compared well with silica and 13X supports, and far exceeded the performance of the alumina support under the tested conditions. The successful completion of this research could add value to an underutilized waste product of coal combustion, in the form of catalyst supports in heterogeneous catalytic processes.

  1. Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, January 1, 1994--March 31, 1994

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1994-06-01

    We have successfully completed our first Fischer-Tropsch synthesis test with propane as the supercritical fluid. The catalyst activity and hydrocarbon product distribution under the SFT conditions were similar to those obtained during the normal Fischer-Tropsch synthesis, however, the use of supercritical fluid resulted in higher selectivity of the primary products. The use of a new trap with larger inside surface area, improved the collection of liquid products and thus enabling us to achieve better atomic and overall mass balance closures. This has also improved results from on-line GC analysis. However, further improvement are needed to achieve more stable and reproducible gas phase analysis, including the capability of the on-line analysis of the feed gas (mixture of hydrogen, carbon monoxide and propane).

  2. Incorporation of catalytic dehydrogenation into fischer-tropsch synthesis to significantly reduce carbon dioxide emissions

    DOEpatents

    Huffman, Gerald P.

    2012-11-13

    A new method of producing liquid transportation fuels from coal and other hydrocarbons that significantly reduces carbon dioxide emissions by combining Fischer-Tropsch synthesis with catalytic dehydrogenation is claimed. Catalytic dehydrogenation (CDH) of the gaseous products (C1-C4) of Fischer-Tropsch synthesis (FTS) can produce large quantities of hydrogen while converting the carbon to multi-walled carbon nanotubes (MWCNT). Incorporation of CDH into a FTS-CDH plant converting coal to liquid fuels can eliminate all or most of the CO.sub.2 emissions from the water-gas shift (WGS) reaction that is currently used to elevate the H.sub.2 level of coal-derived syngas for FTS. Additionally, the FTS-CDH process saves large amounts of water used by the WGS reaction and produces a valuable by-product, MWCNT.

  3. Fischer-Tropsch process

    DOEpatents

    Dyer, Paul N.; Pierantozzi, Ronald; Withers, Howard P.

    1987-01-01

    A Fischer-Tropsch process utilizing a product selective and stable catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas is selectively converted to higher hydrocarbons of relatively narrow carbon number range is disclosed. In general, the selective and notably stable catalyst, consist 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 a Fischer-Tropsch metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

  4. Kinetics of Slurry Phase Fischer-Tropsch Synthesis

    SciTech Connect

    Dragomir B. Bukur; Gilbert F. Froment; Tomasz Olewski; Lech Nowicki; Madhav Nayapati

    2006-12-31

    The overall objective of this project is to develop a comprehensive kinetic model for slurry-phase Fischer-Tropsch synthesis (FTS) employing iron-based catalysts. This model will be validated with experimental data obtained in a stirred-tank slurry reactor (STSR) over a wide range of process conditions. Three STSR tests of the Ruhrchemie LP 33/81 catalyst were conducted to collect data on catalyst activity and selectivity under 25 different sets of process conditions. The observed decrease in 1-olefin content and increase in 2-olefin and n-paraffin contents with the increase in conversion are consistent with a concept that 1-olefins participate in secondary reactions (e.g. 1-olefin hydrogenation, isomerization and readsorption), whereas 2-olefins and n-paraffins are formed in these reactions. Carbon number product distribution showed an increase in chain growth probability with increase in chain length. Vapor-liquid equilibrium calculations were made to check validity of the assumption that the gas and liquid phases are in equilibrium during FTS in the STSR. Calculated vapor phase compositions were in excellent agreement with experimental values from the STSR under reaction conditions. Discrepancies between the calculated and experimental values for the liquid-phase composition (for some of the experimental data) are ascribed to experimental errors in the amount of wax collected from the reactor, and the relative amounts of hydrocarbon wax and Durasyn 164 oil (start-up fluid) in the liquid samples. Kinetic parameters of four kinetic models (Lox and Froment, 1993b; Yang et al., 2003; Van der Laan and Beenackers, 1998, 1999; and an extended kinetic model of Van der Laan and Beenackers) were estimated from experimental data in the STSR tests. Two of these kinetic models (Lox and Froment, 1993b; Yang et al., 2003) can predict a complete product distribution (inorganic species and hydrocarbons), whereas the kinetic model of Van der Laan and Beenackers (1998, 1999) can

  5. Processes and catalysts for conducting fischer-tropsch synthesis in a slurry bubble column reactor

    DOEpatents

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    1999-01-01

    Processes and catalysts for conducting Fischer-Tropsch synthesis in a slurry bubble column reactor (SBCR). One aspect of the invention involves the use of cobalt catalysts without noble metal promotion in an SBCR. Another aspect involves using palladium promoted cobalt catalysts in an SBCR. Methods for preparing noble metal promoted catalysts via totally aqueous impregnation and procedures for producing attrition resistant catalysts are also provided.

  6. Processes and catalysts for conducting Fischer-Tropsch synthesis in a slurry bubble column reactor

    DOEpatents

    Singleton, A.H.; Oukaci, R.; Goodwin, J.G.

    1999-08-17

    Processes and catalysts are disclosed for conducting Fischer-Tropsch synthesis in a slurry bubble column reactor (SBCR). One aspect of the invention involves the use of cobalt catalysts without noble metal promotion in an SBCR. Another aspect involves using palladium promoted cobalt catalysts in an SBCR. Methods for preparing noble metal promoted catalysts via totally aqueous impregnation and procedures for producing attrition resistant catalysts are also provided. 1 fig.

  7. Improved Fischer-Tropsch catalysts for indirect coal liquefaction. Final report

    SciTech Connect

    Wilson, R.B. Jr.; Tong, G.T.; Chan, Y.W.; Huang, H.W.; McCarty, J.G.

    1989-02-01

    The Fischer-Tropsch synthesis (FTS)reaction is the established technology for the production of liquid fuels from coal by an indirect route using coal-derived syngas (CO + H{sub 2}). Modern FTS catalysts are potassium- and copper-promoted iron preparations. These catalysts exhibit moderate activity with carbon monoxide-rich feedstocks such as the syngas produced by advanced coal gasification processes. However, the relatively large yields of by-product methane and high-molecular-weight hydrocarbon waxes detract from the production of desired liquid products in the C{sub 5}-C{sub 16} range needed for motor and aviation fuel. The goal of this program is to decrease undesirable portions of the FTS hydrocarbon yield by altering the Schultz-Flory polymerization product distribution through design and formulation of improved catalysts. Two approaches were taken: (1) reducing the yield of high-molecular-weight hydrocarbon waxes by using highly dispersed catalysts produced from surface-confined multiatomic clusters on acid supports and (2) suppressing methane production by uniformly pretreating active, selective conventional FTS catalysts with submonolayer levels of sulfur.

  8. Effect of process conditions on olefin selectivity during conventional and supercritical Fischer-Tropsch synthesis

    SciTech Connect

    Bukur, D.B.; Lang, X.; Akgerman, A.; Feng, Z.

    1997-07-01

    A precipitated iron catalyst (100 Fe/5 Cu/4.2 K/25 SiO{sub 2} on mass basis) was tested in a fixed-bed reactor under a variety of process conditions during conventional Fischer-Tropsch synthesis (FTS) and supercritical Fischer-Tropsch synthesis (SFTS). In both modes of operation it was found that: total olefin content decreases whereas 2-olefin content increases with either increase in conversion or H{sub 2}/CO molar feed ratio. Total olefin and 2-olefin selectivities were essentially independent of reaction temperature. The effect of conversion was more pronounced during conventional FTS. Comparison of olefin selectivities in the two modes of operation reveals that total olefin content is greater while the 2-olefin content is smaller during SFTS. Also, both the decrease in total olefin content and the increase in 2-olefin content with increase in carbon number (i.e., molecular weight of hydrocarbon products) was significantly less pronounced during SFTS in comparison to the conventional FTS. The obtained results suggest that 1-olefins, and to a smaller extent n-paraffins, are the primary products of FTS. Secondary reactions (isomerization, hydrogenation, and readsorption) of high molecular weight {alpha}-olefins occur to a smaller extent during SFTS, due to higher diffusivities and desorption rates of {alpha}-olefins in the supercritical propane than in the liquid-filled catalyst pores (conventional FTS).

  9. Assessment of trace contaminants from a model indirect liquefaction facility. Volume V. Occupational chemical hazards of Lurgi/Fischer-Tropsch coal liquefaction

    SciTech Connect

    Walsh, P.J.; Gasper, J.R.

    1982-01-01

    This analysis investigates the potential for occupational exposure to toxic chemicals during Lurgi/Fischer-Tropsch coal liquefaction. The reference plant is a commercial-scale facility that processes 28,000 tons of coal per day. Because no such facility currently operates in the United States, much of our data is from foreign commercial-scale facilities and US pilot plants. No definitive assessment of occupational hazards can be made until US commercial-scale data is available. However, by extrapolating available data, we identify major chemical hazards of specific Lurgi/Fischer-Tropsch process streams through inhalation and dermal exposure routes. We also identify which workers are at risk and summarize procedures for mitigating potential exposures. Chemicals of interest are carbon monoxide, methane, hydrogen sulfides, tars, and oils. 11 references, 1 figure, 8 tables.

  10. Silicon carbide coated with TiO2 with enhanced cobalt active phase dispersion for Fischer-Tropsch synthesis.

    PubMed

    Liu, Yuefeng; Florea, Ileana; Ersen, Ovidiu; Pham-Huu, Cuong; Meny, Christian

    2015-01-04

    The introduction of a thin layer of TiO2 on β-SiC allows a significant improvement of the cobalt dispersion. This catalyst exhibits an excellent and stable catalytic activity for the Fischer-Tropsch synthesis (FTS) with high C5+ selectivity, which contributes to the development of a new active catalyst family in the gas-to-liquid process.

  11. Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts.

    PubMed

    Santos, Vera P; Wezendonk, Tim A; Jaén, Juan José Delgado; Dugulan, A Iulian; Nasalevich, Maxim A; Islam, Husn-Ubayda; Chojecki, Adam; Sartipi, Sina; Sun, Xiaohui; Hakeem, Abrar A; Koeken, Ard C J; Ruitenbeek, Matthijs; Davidian, Thomas; Meima, Garry R; Sankar, Gopinathan; Kapteijn, Freek; Makkee, Michiel; Gascon, Jorge

    2015-03-05

    Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

  12. Platinum-Modulated Cobalt Nanocatalysts for Low-Temperature Aqueous-Phase Fischer Tropsch Synthesis

    SciTech Connect

    Wang, Hang; Zhou, Wu; Liu, JinXun; Si, Rui; Sun, Geng; Zhong, Mengqi; Su, Haiyan; Zhao, Huabo; Rodrigues, Jose; Pennycook, Stephen J; Idrobo Tapia, Juan C; Li, Weixue; Kou, Yuan; Ma, Ding

    2013-01-01

    Fischer Tropsch synthesis (FTS) is an important catalytic process for liquid fuel generation, which converts coal/shale gas/biomass-derived syngas (a mixture of CO and H2) to oil. While FTS is thermodynamically favored at low temperature, it is desirable to develop a new catalytic system that could allow working at a relatively low reaction temperature. In this article, we present a one-step hydrogenation reduction route for the synthesis of Pt Co nanoparticles (NPs) which were found to be excellent catalysts for aqueous-phase FTS at 433 K. Coupling with atomic-resolution scanning transmission electron microscopy (STEM) and theoretical calculations, the outstanding activity is rationalized by the formation of Co overlayer structures on Pt NPs or Pt Co alloy NPs. The improved energetics and kinetics from the change of the transition states imposed by the lattice mismatch between the two metals are concluded to be the key factors responsible for the dramatically improved FTS performance.

  13. Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts

    NASA Astrophysics Data System (ADS)

    Santos, Vera P.; Wezendonk, Tim A.; Jaén, Juan José Delgado; Dugulan, A. Iulian; Nasalevich, Maxim A.; Islam, Husn-Ubayda; Chojecki, Adam; Sartipi, Sina; Sun, Xiaohui; Hakeem, Abrar A.; Koeken, Ard C. J.; Ruitenbeek, Matthijs; Davidian, Thomas; Meima, Garry R.; Sankar, Gopinathan; Kapteijn, Freek; Makkee, Michiel; Gascon, Jorge

    2015-03-01

    Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

  14. Isotopic tracer studies of Fischer-Tropsch Synthesis over Ru/TiO sub 2 catalysts

    SciTech Connect

    Krishna, K.R.

    1992-01-01

    Fischer-Tropsch synthesis is a process in which CO and H{sub 2} react to give predominantly liquid hydrocarbons. The reaction can be considered a special type of polymerization in which the monomer is produced in situ, and chain growth occurs by a sequence of independently repeated additions of the monomer to the growing chain. A investigation has been conducted to study the CO hydrogenation reaction in order to better understand catalyst deactivation and the elementary surface processes involved in chain growth. Isotopic tracers are used in conjunction with transient-response techniques in this study of Fischer-Tropsch synthesis over Ru/TiO{sub 2} catalysts. Experiments are conducted at a total pressure of 1 atmosphere, reaction temperatures of 453--498 K and D{sub 2}/CO (or H{sub 2}/CO) ratios of 2--5. Synthesis products are analyzed by gas chromatography or isotope-ratio gas chromatography-mass spectrometry. Rate constants for chain initiation, propagation and termination are evaluated under steady-state reaction conditions by using transients in isotopic composition. The activation energy for chain termination is much higher than that for propagation, accounting for the observed decrease in the chain growth parameter are also estimated. Coverages by reaction intermediates are also estimated. When small amounts of {sup 12}C-labelled ethylene are added to {sup 13}CO/H{sub 2} synthesis gas, ethylene acts as the sole chain initiator. Ethylene-derived carbon also accounts for 45% of the C{sub 1} monomer pool. 102 refs., 29 figs., 11 tabs.

  15. Isotopic tracer studies of Fischer-Tropsch Synthesis over Ru/TiO{sub 2} catalysts

    SciTech Connect

    Krishna, K.R.

    1992-01-01

    Fischer-Tropsch synthesis is a process in which CO and H{sub 2} react to give predominantly liquid hydrocarbons. The reaction can be considered a special type of polymerization in which the monomer is produced in situ, and chain growth occurs by a sequence of independently repeated additions of the monomer to the growing chain. A investigation has been conducted to study the CO hydrogenation reaction in order to better understand catalyst deactivation and the elementary surface processes involved in chain growth. Isotopic tracers are used in conjunction with transient-response techniques in this study of Fischer-Tropsch synthesis over Ru/TiO{sub 2} catalysts. Experiments are conducted at a total pressure of 1 atmosphere, reaction temperatures of 453--498 K and D{sub 2}/CO (or H{sub 2}/CO) ratios of 2--5. Synthesis products are analyzed by gas chromatography or isotope-ratio gas chromatography-mass spectrometry. Rate constants for chain initiation, propagation and termination are evaluated under steady-state reaction conditions by using transients in isotopic composition. The activation energy for chain termination is much higher than that for propagation, accounting for the observed decrease in the chain growth parameter are also estimated. Coverages by reaction intermediates are also estimated. When small amounts of {sup 12}C-labelled ethylene are added to {sup 13}CO/H{sub 2} synthesis gas, ethylene acts as the sole chain initiator. Ethylene-derived carbon also accounts for 45% of the C{sub 1} monomer pool. 102 refs., 29 figs., 11 tabs.

  16. ε-Iron carbide as a low-temperature Fischer-Tropsch synthesis catalyst.

    PubMed

    Xu, Ke; Sun, Bo; Lin, Jun; Wen, Wen; Pei, Yan; Yan, Shirun; Qiao, Minghua; Zhang, Xiaoxin; Zong, Baoning

    2014-12-12

    ε-Iron carbide has been predicted to be promising for low-temperature Fischer-Tropsch synthesis (LTFTS) targeting liquid fuel production. However, directional carbidation of metallic iron to ε-iron carbide is challenging due to kinetic hindrance. Here we show how rapidly quenched skeletal iron featuring nanocrystalline dimensions, low coordination number and an expanded lattice may solve this problem. We find that the carbidation of rapidly quenched skeletal iron occurs readily in situ during LTFTS at 423-473 K, giving an ε-iron carbide-dominant catalyst that exhibits superior activity to literature iron and cobalt catalysts, and comparable to more expensive noble ruthenium catalyst, coupled with high selectivity to liquid fuels and robustness without the aid of electronic or structural promoters. This finding may permit the development of an advanced energy-efficient and clean fuel-oriented FTS process on the basis of a cost-effective iron catalyst.

  17. Techno-economic assessment of integrating methanol or Fischer-Tropsch synthesis in a South African sugar mill.

    PubMed

    Petersen, Abdul M; Farzad, Somayeh; Görgens, Johann F

    2015-05-01

    This study considered an average-sized sugar mill in South Africa that crushes 300 wet tonnes per hour of cane, as a host for integrating methanol and Fischer-Tropsch synthesis, through gasification of a combined flow of sugarcane trash and bagasse. Initially, it was shown that the conversion of biomass to syngas is preferably done by catalytic allothermal gasification instead of catalytic autothermal gasification. Thereafter, conventional and advanced synthesis routes for both Methanol and Fischer-Tropsch products were simulated with Aspen Plus® software and compared by technical and economic feasibility. Advanced FT synthesis satisfied the overall energy demands, but was not economically viable for a private investment. Advanced methanol synthesis is also not viable for private investment since the internal rate of return was 21.1%, because it could not provide the steam that the sugar mill required. The conventional synthesis routes had less viability than the corresponding advanced synthesis routes.

  18. Hydrodynamics of Fischer-Tropsch synthesis in slurry bubble column reactors: Final report

    SciTech Connect

    Bukur, D.B.; Daly, J.G.; Patel, S.A.; Raphael, M.L.; Tatterson, G.B.

    1987-06-01

    This report describes studies on hydrodynamics of bubble columns for Fischer-Tropsch synthesis. These studies were carried out in columns of 0.051 m and 0.229 m in diameter and 3 m tall to determine effects of operating conditions (temperature and gas flow rate), distributor type (sintered metal plate and single and multi-hole perforated plates) and liquid media (paraffin and reactor waxes) on gas hold-up and bubble size distribution. In experiments with the Fischer-Tropsch (F-T) derived paraffin wax (FT-300) for temperatures between 230 and 280/sup 0/C there is a range of gas velocities (transition region) where two values of gas hold-up (i.e., two flow regimes) are possible. Higher hold-ups were accompanied by the presence of foam (''foamy'' regime) whereas lower values were obtained in the absence of foam (''slug flow'' in the 0.051 m column, or ''churn-turbulent'' flow regime in the 0.229 m column). This type of behavior has been observed for the first time in a system with molten paraffin wax as the liquid medium. Several factors which have significant effect on foaming characteristics of this system were identified. Reactor waxes have much smaller tendency to foam and produce lower hold-ups due to the presence of larger bubbles. Finally, new correlations for prediction of the gas hold-up and the specific gas-liquid interfacial area were developed on the basis of results obtained in the present study. 49 refs., 99 figs., 19 tabs.

  19. Metal-carbon nanosystem IR-PVA/Fe-Co for catalysis in the Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Vasilev, A. A.; Dzidziguri, E. L.; Ivantsov, M. I.; Efimov, M. N.

    2016-08-01

    Metal-carbon nanosystems consisting of nanodimensional bimetallic particles of Fe- Co dispersed in a carbon matrix for the Fischer-Tropsch synthesis were studied. Prepared metal-carbon nanopowders samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). It was shown formation of FeCo nanoparticles with body-centered cubic structures started at 400 °C. FeCo nanoparticles have spherical form, the mean size is 7 - 12 nm and uniform distribution in a carbon matrix. The metal-carbon nanosystem demonstrates a catalytic activity in the Fischer- Tropsch synthesis. The maximum yield of liquid hydrocabons C5+ was 92 g/m3 while the selectivity for the target product - 35%.

  20. Mechanistic role of water on the rate and selectivity of Fischer-Tropsch synthesis on ruthenium catalysts.

    PubMed

    Hibbitts, David D; Loveless, Brett T; Neurock, Matthew; Iglesia, Enrique

    2013-11-18

    Water increases Fischer-Tropsch synthesis (FTS) rates on Ru through H-shuttling processes. Chemisorbed hydrogen (H*) transfers its electron to the metal and protonates the O-atom of CO* to form COH*, which subsequently hydrogenates to *HCOH* in the kinetically relevant step. H2 O also increases the chain length of FTS products by mediating the H-transfer steps during reactions of alkyl groups with CO* to form longer-chain alkylidynes and OH*.

  1. Lipid synthesis under hydrothermal conditions by Fischer-Tropsch-type reactions

    NASA Technical Reports Server (NTRS)

    McCollom, T. M.; Ritter, G.; Simoneit, B. R.

    1999-01-01

    Ever since their discovery in the late 1970's, mid-ocean-ridge hydrothermal systems have received a great deal of attention as a possible site for the origin of life on Earth (and environments analogous to mid-ocean-ridge hydrothermal systems are postulated to have been sites where life could have originated or Mars and elsewhere as well). Because no modern-day terrestrial hydrothermal systems are free from the influence of organic compounds derived from biologic processes, laboratory experiments provide the best opportunity for confirmation of the potential for organic synthesis in hydrothermal systems. Here we report on the formation of lipid compounds during Fischer-Tropsch-type synthesis from aqueous solutions of formic acid or oxalic acid. Optimum synthesis occurs in stainless steel vessels by heating at 175 degrees C for 2-3 days and produces lipid compounds ranging from C2 to > C35 which consist of n-alkanols, n-alkanoic acids, n-alkenes, n-alkanes and alkanones. The precursor carbon sources used are either formic acid or oxalic acid, which disproportionate to H2, CO2 and probably CO. Both carbon sources yield the same lipid classes with essentially the same ranges of compounds. The synthesis reactions were confirmed by using 13C labeled precursor acids.

  2. Fischer-Tropsch synthesis in supercritical reaction media. Progress report, July 10, 1992--September 30, 1992

    SciTech Connect

    Subramaniam, B.

    1992-10-01

    The goal of this research is to thoroughly investigate the feasibility of using supercritical fluid (SCF) solvent medium for carrying out Fischer-Tropsch (FT) synthesis. Research will address the systematic experimental investigations of FT synthesis over supported Fe and Co catalysts in a CSTR and in a fixed-bed reactor at typical synthesis temperatures (240-260{degrees}C). The SCF medium to be employed is n-Hexane (P{sub c} = 29.7 bar; {Tc} = 233.7{degrees}C), while n-Hexadecane will be employed as the liquid reaction medium. Overall conversion, product distribution and catalyst deactivation will be measured in each case for various feed H{sub 2}/CO ratios ranging from 0.5 to 2. Product analyses will be carried out using GC/TCD, GC/FID and GC/MS systems. The fresh and used catalysts will be characterized with respect to active metal dispersion, surface area and pore size distribution.

  3. Pyrolysis-GCMS Analysis of Solid Organic Products from Catalytic Fischer-Tropsch Synthesis Experiments

    NASA Technical Reports Server (NTRS)

    Locke, Darren R.; Yazzie, Cyriah A.; Burton, Aaron S.; Niles, Paul B.; Johnson, Natasha M.

    2015-01-01

    Abiotic synthesis of complex organic compounds in the early solar nebula that formed our solar system is hypothesized to occur via a Fischer-Tropsch type (FTT) synthesis involving the reaction of hydrogen and carbon monoxide gases over metal and metal oxide catalysts. In general, at low temperatures (less than 200 C), FTT synthesis is expected to form abundant alkane compounds while at higher temperatures (greater than 200 C) it is expected to product lesser amounts of n-alkanes and greater amounts of alkene, alcohol, and polycyclic aromatic hydrocarbons (PAHs). Experiments utilizing a closed-gas circulation system to study the effects of FTT reaction temperature, catalysts, and number of experimental cycles on the resulting solid insoluble organic products are being performed in the laboratory at NASA Goddard Space Flight Center. These experiments aim to determine whether or not FTT reactions on grain surfaces in the protosolar nebula could be the source of the insoluble organic matter observed in meteorites. The resulting solid organic products are being analyzed at NASA Johnson Space Center by pyrolysis gas chromatography mass spectrometry (PY-GCMS). PY-GCMS yields the types and distribution of organic compounds released from the insoluble organic matter generated from the FTT reactions. Previously, exploratory work utilizing PY-GCMS to characterize the deposited organic materials from these reactions has been reported. Presented here are new organic analyses using magnetite catalyst to produce solid insoluble organic FTT products with varying reaction temperatures and number of experimental cycles.

  4. Highly active and stable iron Fischer-Tropsch catalyst for synthesis gas conversion to liquid fuels

    SciTech Connect

    Bukur, D.B.; Lang, X.

    1999-09-01

    A precipitated iron Fischer-Tropsch (F-T) catalyst (100 Fe/3 Cu/4 K/16 SiO{sub 2} on mass basis) was tested in a stirred tank slurry reactor under reaction conditions representative of industrial practice using CO-rich synthesis gas (260 C, 1.5--2.2 MPa, H{sub 2}/CO = 2/3). Repeatability of performance and reproducibility of catalyst preparation procedure were successfully demonstrated on a laboratory scale. Catalyst productivity was increased by operating at higher synthesis pressure while maintaining a constant contact time in the reactor and through the use of different catalyst pretreatment procedures. In one of the tests (run SA-2186), the catalyst productivity was 0.86 (g hydrocarbons/g Fe/h) at syngas conversion of 79%, methane selectivity of 3% (weight percent of total hydrocarbons produced), and C{sub 5}+ hydrocarbon selectivity of 83 wt %. This represents a substantial improvement in productivity in comparison to state-of-the-art iron F-T catalysts. This catalyst is ideally suited for production of high-quality diesel fuels and C{sub 2}-c{sub 4} olefins from a coal-derived synthesis gas.

  5. Fischer-Tropsch synthesis in supercritical phase carbon dioxide: Recycle rates

    NASA Astrophysics Data System (ADS)

    Soti, Madhav

    With increasing oil prices and attention towards the reduction of anthropogenic CO2, the use of supercritical carbon dioxide for Fischer Tropsch Synthesis (FTS) is showing promise in fulfilling the demand of clean liquid fuels. The evidence of consumption of carbon dioxide means that it need not to be removed from the syngas feed to the Fischer Tropsch reactor after the gasification process. Over the last five years, research at SIUC have shown that FTS in supercritical CO2reduces the selectivities for methane, enhances conversion, reduces the net CO2produces in the coal to liquid fuels process and increase the life of the catalyst. The research has already evaluated the impact of various operating and feed conditions on the FTS for the once through process. We believe that the integration of unreacted feed recycle would enhance conversion, increase the yield and throughput of liquid fuels for the same reactor size. The proposed research aims at evaluating the impact of recycle of the unreacted feed gas along with associated product gases on the performance of supercritical CO2FTS. The previously identified conditions will be utilized and various recycle ratios will be evaluated in this research once the recycle pump and associated fittings have been integrated to the supercritical CO2FTS. In this research two different catalysts (Fe-Zn-K, Fe-Co-Zn-K) were analyzed under SC-FTS in different recycle rate at 350oC and 1200 psi. The use of recycle was found to improve conversion from 80% to close to 100% with both catalysts. The experiment recycle rate at 4.32 and 4.91 was clearly surpassing theoretical recycle curve. The steady state reaction rate constant was increased to 0.65 and 0.8 min-1 for recycle rate of 4.32 and 4.91 respectively. Carbon dioxide selectivity was decreased for both catalyst as it was converting to carbon monoxide. Carbon dioxide consumption was increased from 0.014 to 0.034 mole fraction. This concluded that CO2is being used in the system and

  6. Platinum-modulated cobalt nanocatalysts for low-temperature aqueous-phase Fischer-Tropsch synthesis.

    PubMed

    Wang, Hang; Zhou, Wu; Liu, Jin-Xun; Si, Rui; Sun, Geng; Zhong, Meng-Qi; Su, Hai-Yan; Zhao, Hua-Bo; Rodriguez, Jose A; Pennycook, Stephen J; Idrobo, Juan-Carlos; Li, Wei-Xue; Kou, Yuan; Ma, Ding

    2013-03-13

    Fischer-Tropsch synthesis (FTS) is an important catalytic process for liquid fuel generation, which converts coal/shale gas/biomass-derived syngas (a mixture of CO and H2) to oil. While FTS is thermodynamically favored at low temperature, it is desirable to develop a new catalytic system that could allow working at a relatively low reaction temperature. In this article, we present a one-step hydrogenation-reduction route for the synthesis of Pt-Co nanoparticles (NPs) which were found to be excellent catalysts for aqueous-phase FTS at 433 K. Coupling with atomic-resolution scanning transmission electron microscopy (STEM) and theoretical calculations, the outstanding activity is rationalized by the formation of Co overlayer structures on Pt NPs or Pt-Co alloy NPs. The improved energetics and kinetics from the change of the transition states imposed by the lattice mismatch between the two metals are concluded to be the key factors responsible for the dramatically improved FTS performance.

  7. Incorporation of catalytic dehydrogenation into Fischer-Tropsch synthesis to lower carbon dioxide emissions

    DOEpatents

    Huffman, Gerald P

    2012-09-18

    A method for producing liquid fuels includes the steps of gasifying a starting material selected from a group consisting of coal, biomass, carbon nanotubes and mixtures thereof to produce a syngas, subjecting that syngas to Fischer-Tropsch synthesis (FTS) to produce a hyrdrocarbon product stream, separating that hydrocarbon product stream into C1-C4 hydrocarbons and C5+ hydrocarbons to be used as liquid fuels and subjecting the C1-C4 hydrocarbons to catalytic dehydrogenation (CDH) to produce hydrogen and carbon nanotubes. The hydrogen produced by CDH is recycled to be mixed with the syngas incident to the FTS reactor in order to raise the hydrogen to carbon monoxide ratio of the syngas to values of 2 or higher, which is required to produce liquid hydrocarbon fuels. This is accomplished with little or no production of carbon dioxide, a greenhouse gas. The carbon is captured in the form of a potentially valuable by-product, multi-walled carbon nanotubes (MWNT), while huge emissions of carbon dioxide are avoided and very large quantities of water employed for the water-gas shift in traditional FTS systems are saved.

  8. Silylated Co/SBA-15 catalysts for Fischer-Tropsch synthesis

    SciTech Connect

    Jia Lihong; Jia Litao; Li Debao; Hou Bo; Wang Jungang; Sun Yuhan

    2011-03-15

    A series of silylated Co/SBA-15 catalysts were prepared via the reaction of surface Si-OH of SBA-15 with hexamethyldisilazane (HMDS) under anhydrous, vapor-phase conditions, and then characterized by FT-IR, N{sub 2} physisorption, TG, XRD, and TPR-MS. The results showed that organic modification led to a silylated SBA-15 surface composed of stable hydrophobic Si-(CH{sub 3}){sub 3} species even after calcinations and H{sub 2} reduction at 673 K. Furthermore, the hydrophobic surface strongly influenced both metal dispersion and reducibility. Compared with non-silylated Co/SBA, Co/S-SBA (impregnation after silylation) showed a high activity, due to the better cobalt reducibility on the hydrophobic support. However, S-Co/SBA (silylation after impregnation) had the lowest FT activity among all the catalysts, due to the lower cobalt reducibility along with the steric hindrance of grafted -Si(CH{sub 3}){sub 3} for the re-adsorption of {alpha}-olefins. -- Graphical abstract: The silylation of an SBA-15 before cobalt impregnation enhanced the reducibility of cobalt oxides on an SBA-15-supported cobalt catalyst and consequently increased the catalytic activity for Fischer-Tropsch synthesis. Display Omitted

  9. Nanocrystalline Iron-Ore-Based Catalysts for Fischer-Tropsch Synthesis.

    PubMed

    Yong, Seok; Park, Ji Chan; Lee, Ho-Tae; Yang, Jung-Il; Hong, SungJun; Jung, Heon; Chun, Dong Hyun

    2016-02-01

    Nanocrystalline iron ore particles were fabricated by a wet-milling process using an Ultra Apex Mill, after which they were used as raw materials of iron-based catalysts for low-temperature Fischer-Tropsch synthesis (FTS) below 280 degrees C, which usually requires catalysts with a high surface area, a large pore volume, and a small crystallite size. The wet-milling process using the Ultra Apex Mill effectively destroyed the initial crystallite structure of the natural iron ores of several tens to hundreds of nanometers in size, resulting in the generation of nanocrystalline iron ore particles with a high surface area and a large pore volume. The iron-ore-based catalysts prepared from the nanocrystalline iron ore particles effectively catalyzed the low-temperature FTS, displaying a high CO conversion (about 90%) and good C5+ hydrocarbon productivity (about 0.22 g/g(cat)(-h)). This demonstrates the feasibility of using the iron-ore-based catalysts as inexpensive and disposable catalysts for the low-temperature FTS.

  10. Effect of the Polymeric Stabilizer in the Aqueous Phase Fischer-Tropsch Synthesis Catalyzed by Colloidal Cobalt Nanocatalysts.

    PubMed

    Delgado, Jorge A; Claver, Carmen; Castillón, Sergio; Curulla-Ferré, Daniel; Godard, Cyril

    2017-03-06

    A series of small and well defined cobalt nanoparticles were synthesized by the chemical reduction of cobalt salts in water using NaBH4 as a reducing agent and using various polymeric stabilizers. The obtained nanocatalysts of similar mean diameters (ca. 2.6 nm) were fully characterized and tested in the aqueous phase Fischer-Tropsch Synthesis (AFTS). Interestingly, the nature and structure of the stabilizers used during the synthesis of the CoNPs affected the reduction degree of cobalt and the B-doping of these NPs and consequently, influenced the performance of these nanocatalysts in AFTS.

  11. Effect of the Polymeric Stabilizer in the Aqueous Phase Fischer-Tropsch Synthesis Catalyzed by Colloidal Cobalt Nanocatalysts

    PubMed Central

    Delgado, Jorge A.; Claver, Carmen; Castillón, Sergio; Curulla-Ferré, Daniel; Godard, Cyril

    2017-01-01

    A series of small and well defined cobalt nanoparticles were synthesized by the chemical reduction of cobalt salts in water using NaBH4 as a reducing agent and using various polymeric stabilizers. The obtained nanocatalysts of similar mean diameters (ca. 2.6 nm) were fully characterized and tested in the aqueous phase Fischer-Tropsch Synthesis (AFTS). Interestingly, the nature and structure of the stabilizers used during the synthesis of the CoNPs affected the reduction degree of cobalt and the B-doping of these NPs and consequently, influenced the performance of these nanocatalysts in AFTS. PMID:28336892

  12. Exploring iron-based multifunctional catalysts for Fischer-Tropsch synthesis: a review.

    PubMed

    Abelló, Sònia; Montané, Daniel

    2011-11-18

    The continuous increase in oil prices together with an increase in carbon dioxide concentration in the atmosphere has prompted an increased interest in the production of liquid fuels from non-petroleum sources to ensure the continuation of our worldwide demands while maximizing CO(2) utilization. In this sense, the Fischer-Tropsch (FT) technology provides a feasible option to render high value-added hydrocarbons. Alternative sources, such as biomass or coal, offer a real possibility to realize these purposes by making use of H(2)-deficient or CO(2)-rich syngas feeds. The management of such feeds ideally relies on the use of iron catalysts, which exhibit the unique ability to adjust the H(2)/CO molar ratio to an optimum value for hydrocarbon synthesis through the water-gas-shift reaction. Taking advantage of the emerging attention to hybrid FT-synthesis catalysts based on cobalt and their associated benefits, an overview of the current state of literature in the field of iron-based multifunctional catalysts is presented. Of particular interest is the use of zeolites in combination with a FT catalyst in a one-stage operation, herein named multifunctional, which offer key opportunities in the modification of desired product distributions and selectivity, to eventually overcome the quality limitations of the fuels prepared under intrinsic FT conditions. This review focuses on promising research activities addressing the conversion of syngas to liquid fuels mediated by iron-based multifunctional materials, highlights their preparation and properties, and discusses their implication and challenges in the area of carbon utilization through H(2)/CO(+CO(2)) mixtures.

  13. Mechanism and kinetics of Fischer-Tropsch synthesis over supported ruthenium catalysts

    SciTech Connect

    Kellner, C.S.

    1981-06-01

    A detailed study of the kinetics of the Fischer-Tropsch synthesis of hydrocarbons, methanol, and acetaldehyde, over alumina- and silica-supported ruthenium catalysts has been carried out over a broad range of reaction conditions. Based on these results and information taken from the literature, mechanisms for the formation of normal paraffins, ..cap alpha..-olefins, methanol, and acetaldehyde have been proposed. Rate data were obtained between 448 and 548K, 1 and 10 atm, and H/sub 2//CO ratios between 1 and 3, utilizing a micro flow reactor operated at very low conversions. In addition to the studies performed with H/sub 2//CO mixtures, a series of experiments were carried out utilizing D/sub 2//CO mixtures. These studies were used to help identify rate limited steps and steps that were at equilibrium. A complementary investigation, carried out by in situ infrared spectroscopy, was performed using a Fourier Transform spectrometer. The spectra obtained were used to identify the modes of CO adsorption, the CO coverage, and the relative reactivity of different forms of adsorbed CO. It was established that CO adsorbs on alumina-supported Ru in, at least, two forms: (i) Ru-CO and (ii) OC-Ru-CO. Only the first of these forms participates in CO hydrogenation. The coverage of this species is described by a simple Langmuir isotherm. A reaction mechanism is presented for interpreting the kinetics of hydrocarbon synthesis, the olefin to paraffin ratio for each product, and the probability of chain propagation. Rate expressions based on this mechanism are reasonably consistent with the experimental data. Acetaldehyde, obtained mainly over silica-supported Ru, appears to be formed by a mechanism related to that for hydroformulation of olefins. The effect of the dispersion of Ru/Al/sub 2/O/sub 3/ catalysts on their specific activity and selectivity was also investigated. The specific activity for all products decreased rapidly with increasing dispersions.

  14. 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.

  15. Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, October 1, 1993--December 31, 1993

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1993-12-31

    Objectives for the first quarter for Task A, Diffusion Coefficients of F-T Products in Supercritical Fluids, were to measure diffusion coefficients of 1-tetradecene in subcritical propane and the diffusion coefficients of 1-octene and 1-tetradecene in subcritical propane and the diffusion coefficients of 1-octene and 1-tetradecene in subcritical and supercritical ethane. We planned to use ethane as a solvent because its lower critical temperature enabled measurements without modification of the existing unit. Our objective was to investigate the behavior of the diffusion coefficients in crossing from subcritical to supercritical conditions. Objectives for Task B, Fischer Tropsch reaction related studies, were: (1) to install and test the temperature probe and the flammable gas detector: (2) to conduct Fischer-Tropsch experiments at baseline conditions and at a high pressure in order to test the newly constructed fixed bed reactor assembly. Accomplishments and problems, are presented.

  16. Nitrogen isotope fractionations in the Fischer-Tropsch synthesis and in the Miller-Urey reaction

    NASA Technical Reports Server (NTRS)

    King, C.-C.; Clayton, R. N.; Hayatsu, R.; Studier, M. H.

    1979-01-01

    Nitrogen isotope fractionations have been measured in Fischer-Tropsch and Miller-Urey reactions in order to determine whether these processes can account for the large N-15/N-14 ratios found in organic matter in carbonaceous chondrites. Polymeric material formed in the Fischer-Tropsch reaction was enriched in N-15 by only 3 per mil relative to the starting material (NH3). The N-15 enrichment in polymers from the Miller-Urey reaction was 10-12 per mil. Both of these fractionations are small compared to the 80-90 per mil differences observed between enstatite chondrites and carbonaceous chondrites. These large differences are apparently due to temporal or spatial variations in the isotopic composition of nitrogen in the solar nebula, rather than to fractionation during the production of organic compounds.

  17. Phase transformation of iron-based catalysts for Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Jin, Yaming

    Fischer-Tropsch (F-T) synthesis is used to convert syngas to liquid hydrocarbons using iron-based catalysts. However, the nature of the active phase and phase transformations during F-T synthesis are not well understood. In this work, the phase transformations of Fe catalysts both during F-T synthesis and controlled treatment conditions have been studied using cross-section transmission electron microscopy, x-ray diffraction and Mossbauer spectroscopy. Catalyst samples were obtained from F-T synthesis runs at medium pressure (1.48 MPa) with a H2:CO ratio of 0.7. Samples were analyzed without removal of the wax to preserve the catalyst microstructure intact and prevent oxidation due to air exposure. In all active Fe catalysts, a highly dispersed chi-carbide (Fe5C2) phase with an average particle size <10 nm was seen to be present along with larger sized particles of hexagonal Fe 7C3. On the other hand, the carbide phase whose XRD pattern resembles that obtained by the Barton and Gale was found to be associated with catalysts of low activity. All carbide particles are covered with amorphous carbonaceous layers as seen by electron energy loss spectroscopy (EELS). In a series of separate experiments, phase transformations that occur during catalyst activation at atmospheric pressure were studied. During direct CO carburization of iron oxide at 250°C, multiple nucleation sites lead to formation of smaller Fe carbide particles predominantly of the Barton-Gale carbide. However, starting from metallic Fe we obtain a chi-carbide phase without significant change in particle size. Treatment in syngas (H 2:CO = 0.7) results in less complete carburization and larger particle sizes for both the carbide and the magnetite phases. The presence of trace amounts of water vapor during reduction appears to cause formation of large faceted magnetite crystals, which are difficult to further transform to the active carbide phase. The silica support is effective at keeping the Fe phases

  18. Selective synthesis and chain growth of linear hydrocarbons in the Fischer-Tropsch synthesis over zeolite-entrapped cobalt catalysts

    SciTech Connect

    Koh, D.J.; Chung, J.S.; Kim, Y.G.

    1995-06-01

    The impregnation of NaOH solution into the pores of cobalt-exchanged zeolite promoted the conventional reduction of cobalt ions with hydrogen gas. The method yielded catalysts that had high degrees of reduction and small cobalt clusters located inside zeolite pores. In the Fischer-Tropsch synthesis these catalysts showed a chain-extension effect, producing hydrocarbons higher than C{sub 10} in appreciable amounts, and an enhanced production of linear hydrocarbons such as 1-olefins and n-paraffins. The formation of long-chain hydrocarbons is attributed to an increased chance of the chain growth owing to a hold-up effect of reaction intermediates, especially 1-olefins, which are accumulated inside zeolite pores during the reaction. Hydrocarbon isomers are produced over acidic sites of zeolite by secondary reactions (isomerization and cracking), which result in a chain shortening of the long-chain hydrocarbons.

  19. Potassium effects on activated-carbon-supported iron catalysts for Fischer-Tropsch synthesis

    SciTech Connect

    Wenping Ma; Edwin L. Kugler; Dady B. Dadyburjor

    2007-08-15

    The effect of potassium on the activity, selectivity, and distribution of products (hydrocarbons and oxygenates) was studied over iron catalysts supported on activated carbon (AC) for Fischer-Tropsch synthesis (FTS). This is part of a wider study on the incremental effects of components (including the support) of a multicomponent (Fe-Cu-Mo-K/AC) FTS catalyst. The range of potassium loading used was 0-2 wt%. A fixed-bed reactor was used under the conditions of 260-300{sup o}C, 300 psig, and 3 Nl/g cat/h, using syngas with a H{sub 2}/CO molar feed ratio of 0.9. Both FTS and water-gas shift activities increase after the addition of 0.9 wt % potassium, whereas an opposite trend is observed with the addition of 2 wt % potassium. This is shown to be the result of interaction between the decrease of both the activation energy (E{sub a}) and the pre-exponental factor (k{sub 0}) with the amount of potassium promoter added. Detectable hydrocarbons up to C{sub 34} and oxygenates up to C{sub 5} are formed on the Fe/AC catalysts with or without potassium. The potassium promoter significantly suppresses formation of methane and methanol and shifts selectivities to higher-molecular-weight hydrocarbons (C{sub 5+}) and alcohols (C{sub 2}-C{sub 5}). Meanwhile, the potassium promoter changes paraffin and olefin distributions. At least for carbon numbers of 25 or less, increasing the K level to 0.9 wt % greatly decreases the amount of n-paraffins and internal olefins (i.e., those with the double bond in other than the terminal positions) and dramatically increases branched paraffins and 1-olefins, but a further increase in the K level shows little additional improvement. The addition of potassium changes the effect of temperature on the selectivity to oxygenates. In the absence of K, oxygenate selectivity decreases with temperature. However, when K is present, the selectivity is almost independent of the temperature. 71 refs., 13 figs., 3 tabs.

  20. PROGRESS TOWARDS MODELING OF FISCHER TROPSCH SYNTHESIS IN A SLURRY BUBBLE COLUMN REACTOR

    SciTech Connect

    Donna Post Guillen; Tami Grimmett; Anastasia M. Gandrik; Steven P. Antal

    2010-11-01

    The Hybrid Energy Systems Testing (HYTEST) Laboratory is being established at the Idaho National Laboratory to develop and test hybrid energy systems with the principal objective to safeguard U.S. Energy Security by reducing dependence on foreign petroleum. A central component of the HYTEST is the slurry bubble column reactor (SBCR) in which the gas-to-liquid reactions will be performed to synthesize transportation fuels using the Fischer Tropsch (FT) process. SBCRs are cylindrical vessels in which gaseous reactants (for example, synthesis gas or syngas) is sparged into a slurry of liquid reaction products and finely dispersed catalyst particles. The catalyst particles are suspended in the slurry by the rising gas bubbles and serve to promote the chemical reaction that converts syngas to a spectrum of longer chain hydrocarbon products, which can be upgraded to gasoline, diesel or jet fuel. These SBCRs operate in the churn-turbulent flow regime which is characterized by complex hydrodynamics, coupled with reacting flow chemistry and heat transfer, that effect reactor performance. The purpose of this work is to develop a computational multiphase fluid dynamic (CMFD) model to aid in understanding the physico-chemical processes occurring in the SBCR. Our team is developing a robust methodology to couple reaction kinetics and mass transfer into a four-field model (consisting of the bulk liquid, small bubbles, large bubbles and solid catalyst particles) that includes twelve species: (1) CO reactant, (2) H2 reactant, (3) hydrocarbon product, and (4) H2O product in small bubbles, large bubbles, and the bulk fluid. Properties of the hydrocarbon product were specified by vapor liquid equilibrium calculations. The absorption and kinetic models, specifically changes in species concentrations, have been incorporated into the mass continuity equation. The reaction rate is determined based on the macrokinetic model for a cobalt catalyst developed by Yates and Satterfield [1]. The

  1. The synthesis of Fe-Cu-Si oxide as a potential catalyst material for Fischer Tropsch reaction

    NASA Astrophysics Data System (ADS)

    Tjahjanto, Rachmat Triandi; Mustaqimah, Aili Millatul; Ayun, Qurratu

    2017-03-01

    Variations of iron(III) concentration were made during the synthesis of iron-copper-silicon oxide with sol-gel technique. The material was synthesized as a potential catalyst material for Fischer Tropsch reaction. A solution of sodium metasilicate was added dropwise onto solutions of iron(III) and copper(II) nitrate in diluted nitric acid. At pH 5 gels were obtained, followed with drying, calcination, and grinding to obtain fine powders. At concentration of iron(III) nitrate of 22.99% and 23.81% the process provided pale yellow colored powders, while those with 24.20%, 26.93%, and 27.58% of iron(III) nitrates gave brown powders. One of the brown powders showed crystalline phase in its diffractograms, while the yellow one was completely amorphous.

  2. Synthesis of adenine, guanine, cytosine, and other nitrogen organic compounds by a Fischer-Tropsch-like process.

    NASA Technical Reports Server (NTRS)

    Yang, C. C.; Oro, J.

    1971-01-01

    Study of the formation of purines, pyrimidines, and other bases from CO, H2, and NH3 under conditions similar to those used in the Fischer-Tropsch process. It is found that industrial nickel/iron alloy catalyzes the synthesis of adenine, guanine, cytosine, and other nitrogenous compounds from mixtures of CO, H2, and NH3 at temperatures of about 600 C. Sufficient sample was accumulated to isolate as solid products adenine, guanine, and cytosine, which were identified by infrared spectrophotometry. In the absence of nickel/iron catalyst, at 650 C, or in the presence of this catalyst, at 450 C, no purines or pyrimidines were synthesized. These results confirm and extend some of the work reported by Kayatsu et al. (1968).

  3. Trapping Planetary Noble Gases During the Fischer-Tropsch-Type Synthesis of Organic Materials

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A.; Johnson, N. M.; Meshik, A.

    2010-01-01

    When hydrogen, nitrogen and CO arc exposed to amorphous iron silicate surfaces at temperatures between 500 - 900K, a carbonaceous coating forms via Fischer-Tropsch type reactions!, Under normal circumstances such a catalytic coating would impede or stop further reaction. However, we find that this coating is a better catalyst than the amorphous iron silicates that initiate these rcactions:u . The formation of a self-perpetuating catalytic coating on grain surfaces could explain the rich deposits of macromolecular carbon found in primitive meteorites and would imply that protostellar nebulae should be rich in organic materiaL Many more experiments are needed to understand this chemical system and its application to protostellar nebulae.

  4. Synthesis and catalysis of location-specific cobalt nanoparticles supported by multiwall carbon nanotubes for Fischer-Tropsch synthesis.

    PubMed

    Zhu, Yuan; Ye, Yingchun; Zhang, Shiran; Leong, Mark E; Tao, Franklin Feng

    2012-05-29

    Cobalt nanoparticles located on the concave internal surface of multiwalled carbon nanotubes (Co-in-MW-CNTs) and the convex external surface of MW-CNTs (Co-on-MW-CNTs) were synthesized. Their catalytic performances in Fischer-Tropsch synthesis (FTS) were investigated. A correlation between the location, pretreatment, and surface chemistry of the cobalt nanoparticles and the catalytic selectivity in FTS was built. It is found that the selectivity in production of C(5+) molecules through FTS on cobalt catalysts supported by MW-CNTs depends on activation temperatures and surface chemistry of the cobalt nanoparticles. A pretreatment at 300 °C in H(2) flow results in a different surface chemistry for Co-in-MW-CNTs than for Co-on-MW-CNTs, which leads to a difference in selectvity to the production of C(5+) molecules. Pretreatment at a relatively high temperature, 400 °C, in H(2) flow produces completely reduced Co nanoparticles in Co-in-MW-CNTs and Co-on-MW-CNTs. There is no signifcant difference in catalytic selectivity between the two catalysts upon pretreatment at 400 °C. The absence of a significant difference in catalytic selectivity of metallic Co-on-MW-CNTs and metallic Co-in-MW-CNTs suggests that the electronic effect of the MW-CNT support does not significantly affect the C(5+) selectivity of cobalt catalysts in FTS.

  5. Small-Scale Coal-Biomass to Liquids Production Using Highly Selective Fischer-Tropsch Synthesis

    SciTech Connect

    Gangwal, Santosh K.; McCabe, Kevin

    2015-04-30

    The research project advanced coal-to-liquids (CTL) and coal-biomass to liquids (CBTL) processes by testing and validating Chevron’s highly selective and active cobalt-zeolite hybrid Fischer-Tropsch (FT) catalyst to convert gasifier syngas predominantly to gasoline, jet fuel and diesel range hydrocarbon liquids, thereby eliminating expensive wax upgrading operations The National Carbon Capture Center (NCCC) operated by Southern Company (SC) at Wilsonville, Alabama served as the host site for the gasifier slip-stream testing/demonstration. Southern Research designed, installed and commissioned a bench scale skid mounted FT reactor system (SR-CBTL test rig) that was fully integrated with a slip stream from SC/NCCC’s transport integrated gasifier (TRIGTM). The test-rig was designed to receive up to 5 lb/h raw syngas augmented with bottled syngas to adjust the H2/CO molar ratio to 2, clean it to cobalt FT catalyst specifications, and produce liquid FT products at the design capacity of 2 to 4 L/day. It employed a 2-inch diameter boiling water jacketed fixed-bed heat-exchange FT reactor incorporating Chevron’s catalyst in Intramicron’s high thermal conductivity micro-fibrous entrapped catalyst (MFEC) packing to efficiently remove heat produced by the highly exothermic FT reaction.

  6. Organic Analysis of Catalytic Fischer-Tropsch Type Synthesis Products: Are they Similar to Organics in Chondritic Meteorites?

    NASA Technical Reports Server (NTRS)

    Yazzie, Cyriah A.; Locke, Darren R.; Johnson, Natasha M.

    2014-01-01

    Fischer-Tropsch Type (FTT) synthesis of organic compounds has been hypothesized to occur in the early solar nebula that formed our Solar System. FTT is a collection of abiotic chemical reactions that convert a mixture of carbon monoxide and hydrogen over nano-catalysts into hydrocarbons and other more complex aromatic compounds. We hypothesized that FTT can generate similar organic compounds as those seen in chondritic meteorites; fragments of asteroids that are characteristic of the early solar system. Specific goals for this project included: 1) determining the effects of different FTT catalyst, reaction temperature, and cycles on organic compounds produced, 2) imaging of organic coatings found on the catalyst, and 3) comparison of organic compounds produced experimentally by FTT synthesis and those found in the ordinary chondrite LL5 Chelyabinsk meteorite. We used Pyrolysis Gas Chromatography Mass Spectrometry (PY-GCMS) to release organic compounds present in experimental FTT and meteorite samples, and Scanning Electron Microscopy (SEM) to take images of organic films on catalyst grains.

  7. Segregation of Fischer-Tropsch reactants on cobalt nanoparticle surfaces.

    PubMed

    Lewis, E A; Le, D; Jewell, A D; Murphy, C J; Rahman, T S; Sykes, E C H

    2014-06-21

    Using scanning tunnelling microscopy, we have visualized the segregation of carbon monoxide and hydrogen, the two reactants in Fischer-Tropsch synthesis, on cobalt nanoparticles at catalytically relevant coverages. Density functional theory was used to interrogate the relevant energetics.

  8. Fischer-Tropsch Wastewater Utilization

    DOEpatents

    Shah, Lalit S.

    2003-03-18

    The present invention is generally directed to handling the wastewater, or condensate, from a hydrocarbon synthesis reactor. More particularly, the present invention provides a process wherein the wastewater of a hydrocarbon synthesis reactor, such as a Fischer-Tropsch reactor, is sent to a gasifier and subsequently reacted with steam and oxygen at high temperatures and pressures so as to produce synthesis gas. The wastewater may also be recycled back to a slurry preparation stage, where solid combustible organic materials are pulverized and mixed with process water and the wastewater to form a slurry, after which the slurry fed to a gasifier where it is reacted with steam and oxygen at high temperatures and pressures so as to produce synthesis gas.

  9. Novel Attrition-Resistant Fischer Tropsch Catalyst

    SciTech Connect

    Weast, Logan, E.; Staats, William, R.

    2009-05-01

    There is a strong national interest in the Fischer-Tropsch synthesis process because it offers the possibility of making liquid hydrocarbon fuels from reformed natural gas or coal and biomass gasification products. This project explored a new approach that had been developed to produce active, attrition-resistant Fischer-Tropsch catalysts that are based on glass-ceramic materials and technology. This novel approach represented a promising solution to the problem of reducing or eliminating catalyst attrition and maximizing catalytic activity, thus reducing costs. The technical objective of the Phase I work was to demonstrate that glass-ceramic based catalytic materials for Fischer-Tropsch synthesis have resistance to catalytic deactivation and reduction of particle size superior to traditional supported Fischer-Tropsch catalyst materials. Additionally, these novel glass-ceramic-based materials were expected to exhibit catalytic activity similar to the traditional materials. If successfully developed, the attrition-resistant Fischer-Tropsch catalyst materials would be expected to result in significant technical, economic, and social benefits for both producers and public consumers of Fischer-Tropsch products such as liquid fuels from coal or biomass gasification. This program demonstrated the anticipated high attrition resistance of the glass-ceramic materials. However, the observed catalytic activity of the materials was not sufficient to justify further development at this time. Additional testing documented that a lack of pore volume in the glass-ceramic materials limited the amount of surface area available for catalysis and consequently limited catalytic activity. However, previous work on glass-ceramic catalysts to promote other reactions demonstrated that commercial levels of activity can be achieved, at least for those reactions. Therefore, we recommend that glass-ceramic materials be considered again as potential Fischer-Tropsch catalysts if it can be

  10. Evaluation of Reoxidation Thresholds for γ-Al2O3-Supported Cobalt Catalysts under Fischer-Tropsch Synthesis Conditions.

    PubMed

    Tsakoumis, Nikolaos E; Walmsley, John C; Rønning, Magnus; van Beek, Wouter; Rytter, Erling; Holmen, Anders

    2017-02-28

    Size-dependent phenomena at the nanoscale influence many applications, notably in the science of heterogeneous catalysis. In cobalt-based Fischer-Tropsch synthesis (FTS), the size of Co nanoparticles (NPs) dictates to a high degree catalyst's performance in terms of activity, selectivity, and stability. Here, a highly dispersed Re/Co/γ-Al2O3 catalyst with high Co surface area per gram of catalyst was exposed to industrially relevant FTS conditions and monitored in situ by synchrotron X-ray radiation. X-ray absorption near-edge structure spectra were obtained on the cobalt K edge and Re L3 edge of the working catalyst. The experimental results demonstrate development of tetrahedrally coordinated Co(2+) forming at the expense of metallic Co((0)). The structure of the oxide resembles CoAl2O4 and appears at the onset (first 5-10 h) of the reaction. Reoxidation of Co((0)) is more pronounced close to the outlet of the reactor, where higher pH2O is anticipated. The state of the Re promoter does not change during the FT process. We propose that reoxidation of small Co NPs is followed by spreading of Co oxide that leads to the formation of CoxAlyOz phases. Hence, in order to avoid an irreversible loss of the active phase during process start-up, catalyst design should be restricted to Co NPs larger than 5.3 nm.

  11. On-line gas chromatographic analysis of Fischer-Tropsch synthesis products formed in a supercritical reaction medium

    SciTech Connect

    Snavely, K.; Subramaniam, B.

    1997-10-01

    C{sub 1}-C{sub 30} products from Fischer-Tropsch synthesis, conducted in a supercritical n-hexane medium over an Fe catalyst in a fixed-bed reactor, are analyzed using on-line gas chromatography. A Hewlett-Packard 5890 Series II gas chromatograph (GC) is modified to minimize the effects of condensation of the on-line sample in the transfer lines. The GC is configured with a Supelco Petrocol DH capillary column connected to a flame ionization detector (FID) and two 1.83 m {times} 3.18 mm stainless steel columns placed in series, packed with 80/100 mesh HayeSep D, connected to a thermal conductivity detector (TCD). It is shown that pressure and temperature affect the elution order of oxygenates relative to hydrocarbons in the nonpolar capillary column. This phenomenon is exploited for obtaining improved resolution; several distinct methods produce similar elution orders. Ar, added to the syngas feed, is used to calculate syngas conversion. All compounds eluting before hexane (C{sub 1}-C{sub 5}, other than 2-methylpropene/1-butene and propanal/propanone) and nearly all the major peaks eluting after hexane are resolved in the capillary column. H{sub 2}, Ar, CO, CH{sub 4}, CO{sub 2}, and H{sub 2}O are resolved in the packed columns. The method provides excellent quantitative measurement of component mole fractions that are within the range of calibration.

  12. Effect of Potassium Addition on Coprecipitated Iron Catalysts for Fischer-Tropsch Synthesis Using Bio-oil-syngas

    NASA Astrophysics Data System (ADS)

    Wang, Zhao-xiang; Dong, Ting; Kan, Tao; Li, Quan-xin

    2008-04-01

    The effects of potassium addition and the potassium content on the activity and selectivity of coprecipitated iron catalyst for Fischer-Tropsch synthesis (FTS) were studied in a fixed bed reactor at 1.5 MPa, 300°C, and contact time (W/F) of 12.5 gcath/mol using the model bio-oil-syngas of H2/CO/CO2/N2 (62/8/25/5, vol%). It was found that potassium addition increases the catalyst activity for FTS and the reverse water gas shift reaction. Moreover, potassium increases the average molecular weight (chain length) of the hydrocarbon products. With the increase of potassium content, it was found that CH4 selectivity decreases and the selectivity of liquid phase products (C5+) increases. The characteristics of FTS catalysts with different potassium content were also investigated by various characterization measurements including X-ray diffraction, X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller surface area. Based on experimental results, 100Fe/6Cu/16Al/6K (weight ratio) was selected as the optimal catalyst for FTS from bio-oil-syngas. The results indicate that the 100Fe/6Cu/16Al/6K catalyst is one of the most promising candidates to directly synthesize liquid bio-fuel using bio-oil-syngas.

  13. Nanocrystalline Ferrihydrite-Based Catalysts for Fischer-Tropsch Synthesis: Part II. Effects of Activation Gases on the Catalytic Performance.

    PubMed

    Rhim, Geun Bae; Hong, Seok Yong; Park, Ji Chan; Jung, Heon; Rhee, Young Woo; Chun, Dong Hyun

    2016-02-01

    Fischer-Tropsch synthesis (FTS) was carried out over nanocrystalline ferrihydrite-based (Fe9O2(OH)23) catalysts activated by different reducing agents: syngas (H2+CO), CO, and H2. The syngas activation successfully changed the ferrihydrite-based catalysts into an active and stable catalytic structure with chi-carbide (Fe2.5 C) and epsilon'-carbide (Fe2.2 C). The crystal structure of the catalysts obtained by syngas activation was similar to the structure obtained by CO activation; this similarity was probably due to the peculiar reduction behavior of the ferrihydrite-based catalysts, which exhibit much greater reducibility in CO atmosphere than in H2 atmosphere. The performance of the catalysts activated by syngas was much higher than the performance of the catalysts activated by H2 and was comparable to the performance of the catalysts activated by CO. This strongly demonstrates that the ferrihydrite-based catalysts are advantageous for industrial FTS processes because syngas can be commonly used for both activation pre-treatment and subsequent reaction.

  14. Sulfated zirconia as a CO-catalyst for the production of branched hydrocarbons via Fischer-Tropsch synthesis

    SciTech Connect

    Song, S.; Savari, A.

    1995-12-01

    This communication deals with the direct synthesis of branched hydrocarbons from synthesis gas using a two-component catalyst: a sulfated zirconia (SO{sub 4}{sup 2-}/ZrO{sub 2}) superacid and a Fischer-Tropsch synthesis catalyst (2% RuKY). The composition of C{sub 7} hydrocarbons was used to monitor the effect of SO{sub 4} {sup 2-}/ZrO{sub 2} on product selectivity. Over pure 2% RuKY, at P = 10 atm. and T = 250{degrees}C, the content of branched C{sub 7} in total C{sub 7} hydrocarbons (iC{sub 7}%) was below 10 wt.%, while that of C{sub 7} olefins was very high (C{sub 7}{sup =}% = 67 wt.%). When SO{sub 4}{sup 2-} was loaded downstream of the 2% RuKY catalyst, the production amounts of olefins were of iC{sub 7} hydrocarbons increased significantly (67 wt.%), while only negligible amounts of olefins were produced in the early stages of the reaction. However, during the subsequent deactivation of SO{sub 4}{sup 2-}/ZrO{sub 2} catalyst, the production of iC{sub 7} decreased and that of C{sub 7}{sup =} increased. Addition of ca. 1 wt.% of platinum to SO{sub 4}{sup 2-}/ZrO{sub 2} improved its stability. Under steady state, the iC{sub 7}% and C{sub 7}{sup =}% fractions reached 50% and 20%, respectively. The deactivation of sulfated zirconia was interpreted in terms of coking and effect of CO on the catalyst acidity. In addition, the effects of operational conditions (pressure, H{sub 2}/CO ratio, ratio of catalyst components, and Pt content) will be discussed.

  15. Chemical Insights into the Design and Development of Face-Centered Cubic Ruthenium Catalysts for Fischer-Tropsch Synthesis.

    PubMed

    Li, Wei-Zhen; Liu, Jin-Xun; Gu, Jun; Zhou, Wu; Yao, Si-Yu; Si, Rui; Guo, Yu; Su, Hai-Yan; Yan, Chun-Hua; Li, Wei-Xue; Zhang, Ya-Wen; Ma, Ding

    2017-02-15

    Ruthenium is a promising low-temperature catalyst for Fischer-Tropsch synthesis (FTS). However, its scarcity and modest specific activity limit its widespread industrialization. We demonstrate here a strategy for tuning the crystal phase of catalysts to expose denser and active sites for a higher mass-specific activity. Density functional theory calculations show that upon CO dissociation there are a number of open facets with modest barrier available on the face-centered cubic (fcc) Ru but only a few step edges with a lower barrier on conventional hexagonal-closest packed (hcp) Ru. Guided by theoretical calculations, water-dispersible fcc Ru catalysts containing abundant open facets were synthesized and showed an unprecedented mass-specific activity in the aqueous-phase FTS, 37.8 molCO·molRu(-1)·h(-1) at 433 K. The mass-specific activity of the fcc Ru catalysts with an average size of 6.8 nm is about three times larger than the previous best hcp catalyst with a smaller size of 1.9 nm and a higher specific surface area. The origin of the higher mass-specific activity of the fcc Ru catalysts is identified experimentally from the 2 orders of magnitude higher density of the active sites, despite its slightly higher apparent barrier. Experimental results are in excellent agreement with prediction of theory. The great influence of the crystal phases on site distribution and their intrinsic activities revealed here provides a rationale design of catalysts for higher mass-specific activity without decrease of the particle size.

  16. Structural and elemental influence from various MOFs on the performance of Fe@C catalysts for Fischer-Tropsch synthesis.

    PubMed

    Wezendonk, Tim A; Warringa, Quirinus S E; Santos, Vera P; Chojecki, Adam; Ruitenbeek, Matthijs; Meima, Garry; Makkee, Michiel; Kapteijn, Freek; Gascon, Jorge

    2017-02-14

    The structure and elementary composition of various commercial Fe-based MOFs used as precursors for Fischer-Tropsch synthesis (FTS) catalysts have a large influence on the high-temperature FTS activity and selectivity of the resulting Fe on carbon composites. The selected Fe-MOF topologies (MIL-68, MIL-88A, MIL-100, MIL-101, MIL-127, and Fe-BTC) differ from each other in terms of porosity, surface area, Fe and heteroatom content, crystal density and thermal stability. They are re-engineered towards FTS catalysts by means of simple pyrolysis at 500 °C under a N2 atmosphere and afterwards characterized in terms of porosity, crystallite phase, bulk and surface Fe content, Fe nanoparticle size and oxidation state. We discovered that the Fe loading (36-46 wt%) and nanoparticle size (3.6-6.8 nm) of the obtained catalysts are directly related to the elementary composition and porosity of the initial MOFs. Furthermore, the carbonization leads to similar surface areas for the C matrix (SBET between 570 and 670 m(2) g(-1)), whereas the pore width distribution is completely different for the various MOFs. The high catalytic performance (FTY in the range of 1.9-4.6 × 10(-4) molCO gFe(-1) s(-1)) of the resulting materials could be correlated to the Fe particle size and corresponding surface area, and only minor deactivation was found for the N-containing catalysts. Elemental analysis of the catalysts containing deliberately added promoters and inherent impurities from the commercial MOFs revealed the subtle interplay between Fe particle size and complex catalyst composition in order to obtain high activity and stability next to a low CH4 selectivity.

  17. DEVELOPMENT OF A COMPUTATIONAL MULTIPHASE FLOW MODEL FOR FISCHER TROPSCH SYNTHESIS IN A SLURRY BUBBLE COLUMN REACTOR

    SciTech Connect

    Donna Post Guillen; Tami Grimmett; Anastasia M. Gribik; Steven P. Antal

    2010-09-01

    The Hybrid Energy Systems Testing (HYTEST) Laboratory is being established at the Idaho National Laboratory to develop and test hybrid energy systems with the principal objective to safeguard U.S. Energy Security by reducing dependence on foreign petroleum. A central component of the HYTEST is the slurry bubble column reactor (SBCR) in which the gas-to-liquid reactions will be performed to synthesize transportation fuels using the Fischer Tropsch (FT) process. SBCRs are cylindrical vessels in which gaseous reactants (for example, synthesis gas or syngas) is sparged into a slurry of liquid reaction products and finely dispersed catalyst particles. The catalyst particles are suspended in the slurry by the rising gas bubbles and serve to promote the chemical reaction that converts syngas to a spectrum of longer chain hydrocarbon products, which can be upgraded to gasoline, diesel or jet fuel. These SBCRs operate in the churn-turbulent flow regime which is characterized by complex hydrodynamics, coupled with reacting flow chemistry and heat transfer, that effect reactor performance. The purpose of this work is to develop a computational multiphase fluid dynamic (CMFD) model to aid in understanding the physico-chemical processes occurring in the SBCR. Our team is developing a robust methodology to couple reaction kinetics and mass transfer into a four-field model (consisting of the bulk liquid, small bubbles, large bubbles and solid catalyst particles) that includes twelve species: (1) CO reactant, (2) H2 reactant, (3) hydrocarbon product, and (4) H2O product in small bubbles, large bubbles, and the bulk fluid. Properties of the hydrocarbon product were specified by vapor liquid equilibrium calculations. The absorption and kinetic models, specifically changes in species concentrations, have been incorporated into the mass continuity equation. The reaction rate is determined based on the macrokinetic model for a cobalt catalyst developed by Yates and Satterfield [1]. The

  18. The effect of the nanofibrous Al2O3 aspect ratio on Fischer-Tropsch synthesis over cobalt catalysts.

    PubMed

    Liu, Chengchao; Zhang, Yuhua; Zhao, Yanxi; Wei, Liang; Hong, Jingping; Wang, Li; Chen, Sufang; Wang, Guanghui; Li, Jinlin

    2017-01-05

    A series of nanofibrous alumina materials with diameters of 4-6 nm and with different aspect ratios ranging from 3 to 16 were prepared. Cobalt impregnated catalysts were prepared by means of incipient wetness impregnation on alumina nanofibers while the 'rearranged' catalysts were prepared by using ultrasonication assistance to mix the fibers with the Co3O4 nanoparticles. The effects of the alumina nanofiber aspect ratios on the Co catalyst structure and performance for Fischer-Tropsch synthesis were studied. The pore size of the two series of catalysts increased as the aspect ratio of the alumina nanofiber increased. For impregnated catalysts, large Co3O4 particles were formed on the external surface of the alumina support when the aspect ratio was 3 and 5, while the crystallite sizes of Co3O4 increased from 13.3 nm to 15.6 nm with the increase of the aspect ratio from 7 to 16. The four 'rearranged' catalysts possessed similar and homogeneously dispersed Co3O4 crystallites of 9.5 nm. As expected the reduction behavior of the two series of catalysts was primarily influenced by the Co3O4 crystallite size and structure. The FT data of the two series of catalysts indicate that dispersed Co catalysts on alumina nanofibers with large aspect ratios having large inter-crystallite pores significantly improve the catalyst activity and C5+ selectivity. The FT data of the 'rearranged' catalysts strongly demonstrated that the internal mass transfer of reactants and products increased with a decrease in inter-crystallite pore size, resulting in a decrease of C5+ selectivity and C3 olefin/paraffin ratio, and an increase of CH4 selectively, while the CO consumption rate was little altered. Furthermore, catalytic stability tests showed that the alumina nanofibers with larger aspect ratios inhibited Co migration and coalescence in the matrices of the nanofibrous alumina, and this significantly enhanced the stability of the catalyst. The Cop/Al2O3-16 catalyst possessing uniformly

  19. Indirect liquefaction of coal. [Coal gasification plus Fischer-Tropsch, methanol or Mobil M-gasoline process

    SciTech Connect

    1980-06-30

    The most important potential environmental problems uniquely associated with indirect liquefaction appear to be related to the protection of occupational personnel from the toxic and carcinogenic properties of process and waste stream constituents, the potential public health risks from process products, by-products and emissions and the management of potentially hazardous solid wastes. The seriousness of these potential problems is related partially to the severity of potential effects (i.e., human mortality and morbidity), but even more to the uncertainty regarding: (1) the probable chemical characteristics and quantities of process and waste streams; and (2) the effectiveness and efficiencies of control technologies not yet tested on a commercial scale. Based upon current information, it is highly improbable that these potential problems will actually be manifested or pose serious constraints to the development of indirect liquefaction technologies, although their potential severity warrants continued research and evaluation. The siting of indirect liquefaction facilities may be significantly affected by existing federal, state and local regulatory requirements. The possibility of future changes in environmental regulations also represents an area of uncertainty that may develop into constraints for the deployment of indirect liquefaction processes. Out of 20 environmental issues identified as likely candidates for future regulatory action, 13 were reported to have the potential to impact significantly the commercialization of coal synfuel technologies. These issues are listed.

  20. Simulation models and designs for advanced Fischer-Tropsch technology

    SciTech Connect

    Choi, G.N.; Kramer, S.J.; Tam, S.S.

    1995-12-31

    Process designs and economics were developed for three grass-roots indirect Fischer-Tropsch coal liquefaction facilities. A baseline and an alternate upgrading design were developed for a mine-mouth plant located in southern Illinois using Illinois No. 6 coal, and one for a mine-mouth plane located in Wyoming using Power River Basin coal. The alternate design used close-coupled ZSM-5 reactors to upgrade the vapor stream leaving the Fischer-Tropsch reactor. ASPEN process simulation models were developed for all three designs. These results have been reported previously. In this study, the ASPEN process simulation model was enhanced to improve the vapor/liquid equilibrium calculations for the products leaving the slurry bed Fischer-Tropsch reactors. This significantly improved the predictions for the alternate ZSM-5 upgrading design. Another model was developed for the Wyoming coal case using ZSM-5 upgrading of the Fischer-Tropsch reactor vapors. To date, this is the best indirect coal liquefaction case. Sensitivity studies showed that additional cost reductions are possible.

  1. Monodisperse and size-tunable CoO nanocrystals synthesized by thermal decomposition and as an active precursor for Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Lv, Shuai; Zhao, Xin; Xia, Guofu; Jin, Chao; Wang, Li; Yang, Weimin; Zhang, Yuhua; Li, Jinlin

    2017-01-01

    CoO nanocrystals with tunable particle sizes were prepared by thermal decomposition of cobalt(II) acetate in different long-chain alkyl amines. These alkyl amines strongly affect the coordination of the amine group to the metal atoms and the metal-amine interaction, thereby mediating the eventual particle sizes in the condensation process. Moreover, CoO nanocrystals were applied for synthesis of supported catalyst, and exhibited higher catalytic activity in Fischer-Tropsch reaction, demonstrating that nanocrystals are active precursor. The TOF of CO on CoAl-n catalyst obtained from CoO nanocrystals is ∼1.5 times higher than that on conventional catalyst with the same particle size.

  2. Experimental evidence of {alpha}-olefin readsorption in Fischer-Tropsch synthesis on ruthenium-supported ETS-10 titanium silicate catalysts

    SciTech Connect

    Bianchi, C.L.; Ragaini, V.

    1997-05-01

    Fischer-Tropsch synthesis seems to develop the following two consecutive paths: a primary process that involves the formation of {alpha}-olefin products and a secondary process leading to the production of branched isomers and paraffins and requiring the readsorption of primary {alpha}-olefin products. It was already shown by Iglesia et al. that such readsorption steps are of fundamental importance for Ru catalysts and that they occur due to the slow diffusive removal of {alpha}-olefins when the molecular size increases, this resulting in a long intraparticle residence time. In the present paper {alpha}-olefins readsorption was enhanced by changing the metal distribution inside the pores of a titanium silicate (ETS-10), modified by ion exchange with alkali metal ions, used as a support for Ru-based catalysts. 24 refs., 5 figs., 3 tabs.

  3. Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

    SciTech Connect

    Alptekin, Gokhan

    2013-02-15

    Co-gasification of biomass and coal in large-scale, Integrated Gasification Combined Cycle (IGCC) plants increases the efficiency and reduces the environmental impact of making synthesis gas ("syngas") that can be used in Coal-Biomass-to-Liquids (CBTL) processes for producing transportation fuels. However, the water-gas shift (WGS) and Fischer-Tropsch synthesis (FTS) catalysts used in these processes may be poisoned by multiple contaminants found in coal-biomass derived syngas; sulfur species, trace toxic metals, halides, nitrogen species, the vapors of alkali metals and their salts (e.g., KCl and NaCl), ammonia, and phosphorous. Thus, it is essential to develop a fundamental understanding of poisoning/inhibition mechanisms before investing in the development of any costly mitigation technologies. We therefore investigated the impact of potential contaminants (H2S, NH3, HCN, AsH3, PH3, HCl, NaCl, KCl, AS3, NH4NO3, NH4OH, KNO3, HBr, HF, and HNO3) on the performance and lifetime of commercially available and generic (prepared in-house) WGS and FT catalysts.

  4. Supported fischer-tropsch catalyst and method of making the catalyst

    DOEpatents

    Dyer, Paul N.; Pierantozzi, Ronald; Withers, Howard P.

    1987-01-01

    A Fischer-Tropsch catalyst and a method of making the catalyst for a Fischer-Tropsch 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 is disclosed. In general, the selective and notably stable catalyst, consist 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 a Fischer-Tropsch metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

  5. Improved Sasol Fischer-Tropsch processes

    SciTech Connect

    Jager, B.

    1995-12-31

    Fischer-Tropsch (FT) processes can be used to produce either a light syncrude and light olefins or to produce heavy waxy hydrocarbons. The syncrude can be refined to environmentally friendly gasoline and diesel and the heavy hydrocarbons to specialty waxes or if hydrocracked, and/or isomerized, to produce excellent diesel, lube oils and a naphtha which is ideal feedstock for cracking. Over the last few years much better reactor systems have been developed for both high temperature FT (HTFT) and low temperature FT (LTFT). For HTFT the Sasol Advanced Synthol (SAS) reactor with solid-gas fluidization was developed. This gives very much the same product spectra as the CFB reactors, but does it much more effectively and cheaply. For LTFT, the Sasol Slurry Phase Distillate (SSPD) reactor, of the bubble column type, was developed which is a significant improvement on the tubular fixed bed (TFB) reactor used in the Arge process. The SSPD reactor can make products with the same carbon distribution as the TFB reactor with Schulz-Flory distribution alpha values 0,95 and higher. It has greater flexibility with respect to product distribution. The paper describes both reactors, and the integration of Fischer-Tropsch synthesis with coal gasification.

  6. Impact of Hydrogenolysis on the Selectivity of the Fischer-Tropsch Synthesis: Diesel Fuel Production over Mesoporous Zeolite-Y-Supported Cobalt Nanoparticles.

    PubMed

    Peng, Xiaobo; Cheng, Kang; Kang, Jincan; Gu, Bang; Yu, Xiang; Zhang, Qinghong; Wang, Ye

    2015-04-07

    Selectivity control is a challenging goal in Fischer-Tropsch (FT) synthesis. Hydrogenolysis is known to occur during FT synthesis, but its impact on product selectivity has been overlooked. Demonstrated herein is that effective control of hydrogenolysis by using mesoporous zeolite Y-supported cobalt nanoparticles can enhance the diesel fuel selectivity while keeping methane selectivity low. The sizes of the cobalt particles and mesopores are key factors which determine the selectivity both in FT synthesis and in hydrogenolysis of n-hexadecane, a model compound of heavier hydrocarbons. The diesel fuel selectivity in FT synthesis can reach 60 % with a CH4 selectivity of 5 % over a Na-type mesoporous Y-supported cobalt catalyst with medium mean sizes of 8.4 nm (Co particles) and 15 nm (mesopores). These findings offer a new strategy to tune the product selectivity and possible interpretations of the effect of cobalt particle size and the effect of support pore size in FT synthesis.

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

    PubMed

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

    2014-07-15

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

  8. Fischer-Tropsch Catalyst for Aviation Fuel Production

    NASA Technical Reports Server (NTRS)

    deLaRee, Ana B.; Best, Lauren M.; Hepp, Aloysius F.

    2011-01-01

    As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

  9. Fischer-Tropsch Catalyst for Aviation Fuel Production

    NASA Technical Reports Server (NTRS)

    DeLaRee, Ana B.; Best, Lauren M.; Bradford, Robyn L.; Gonzalez-Arroyo, Richard; Hepp, Aloysius F.

    2012-01-01

    As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to nonpetroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

  10. Fischer Tropsch synthesis : influence of Mn on the carburization rates and activities of Fe-based catalysts by TPR-EXAFS/XANES and catalyst testing.

    SciTech Connect

    Ribeiro, M. C.; Jacobs, G.; Pendyala, R.; Davis, B. H.; Cronauer, D. C.; Kropf, A. J.; Marshall, C. L.

    2011-03-24

    Fe-based catalysts containing different amounts of Mn were tested for Fischer-Tropsch synthesis using a stirred tank reactor at 270 C, 1.21 MPa, and H{sub 2}:CO = 0.7. Catalyst activation by carburization with 10% CO/He was followed by Temperature Programmed Reduction/X-ray Absorption Spectroscopy (TPR-EXAFS/XANES) from room temperature to 300 C. {gamma}-Fe{sub 2}O{sub 3} was converted into iron carbides, whereas MnO{sub x} was reduced to oxygen deficient MnO. Mn hindered Fe carburization, such that the carburized catalyst displayed higher Fe{sub 3}O{sub 4} content than the catalyst without Mn. EXAFS fitting indicates that the carburized catalyst contained a mixture of Hgg carbide, Fe{sub 3}O{sub 4}, and Mn oxides. Increasing Mn content led to higher CH{sub 4} and light product selectivities, and lower light olefin selectivities. Higher and stable conversions were obtained with a catalyst containing an almost equimolar Fe/Mn ratio relative to the catalyst without Mn. Selectivity trends are attributed to the higher WGS rates observed on the FeMn catalysts, consistent with the structural differences observed.

  11. Synthesis, characterization, and Fischer-Tropsch performance of cobalt/zinc aluminate nanocomposites via a facile and corrosion-free coprecipitation route

    NASA Astrophysics Data System (ADS)

    Liu, Zhenxin; Xing, Yu; Xue, Yingying; Wu, Depeng; Fang, Shaoming

    2015-02-01

    Literature about ZnAl2O4-supported cobalt Fischer-Tropsch synthesis (FTS) catalytic materials is sparse. A series of cobalt-containing nanocomposites, supported by nanosized ZnAl2O4 spinel (i.e., a complex oxide of about 6.4 nm) or alumina (i.e., a simple oxide of about 6.2 nm), were prepared via urea-gelation, coprecipitation, or impregnation methods followed by stepwise reduction. These materials were examined by XRD, TGA, nitrogen sorption, FESEM, and EDS. Effects of corrosion and pore size distributions on materials preparation were also investigated. The "coprecipitation/stepwise reduction" route is facile and suitable to prepare nanosized ZnAl2O4-supported Co0 nanocomposites. At similar CO conversions, the coprecipitated Co/ZnAl2O4 exhibits significantly lower C1 hydrocarbon distribution, slightly lower C5+ hydrocarbon distribution, significantly higher C2-C4 hydrocarbon distribution, and significantly higher olefin/paraffin ratio of C2-C4 than Co/γ-Al2O3.

  12. Fischer-Tropsch Catalysts

    NASA Technical Reports Server (NTRS)

    White, James H. (Inventor); Taylor, Jesse W. (Inventor)

    2008-01-01

    Catalyst compositions and methods for F-T synthesis which exhibit high CO conversion with minor levels (preferably less than 35% and more preferably less than 5%) or no measurable carbon dioxide generation. F-T active catalysts are prepared by reduction of certain oxygen deficient mixed metal oxides.

  13. Organic Analysis of Catalytic Fischer-Tropsch Synthesis Products and Ordinary Chondrite Meteorites by Stepwise Pyrolysis-GCMS: Organics in the Early Solar Nebula

    NASA Technical Reports Server (NTRS)

    Locke, Darren R.; Yazzie, Cyriah A.; Burton, Aaron S.; Niles, Paul B.; Johnson, Natasha M.

    2014-01-01

    Abiotic generation of complex organic compounds, in the early solar nebula that formed our solar system, is hypothesized by some to occur via Fischer-Tropsch (FT) synthesis. In its simplest form, FT synthesis involves the low temperature (<300degC) catalytic reaction of hydrogen and carbon monoxide gases to form more complex hydrocarbon compounds, primarily n-alkanes, via reactive nano-particulate iron, nickel, or cobalt, for example. Industrially, this type of synthesis has been utilized in the gas-to-liquid process to convert syngas, produced from coal, natural gas, or biomass, into paraffin waxes that can be cracked to produce liquid diesel fuels. In general, the effect of increasing reaction temperature (>300degC) produces FT products that include lesser amounts of n-alkanes and greater alkene, alcohol, and polycyclic aromatic hydrocarbon (PAH) compounds. We have begun to experimentally investigate FT synthesis in the context of abiotic generation of organic compounds in the early solar nebula. It is generally thought that the early solar nebula included abundant hydrogen and carbon monoxide gases and nano-particulate matter such as iron and metal silicates that could have catalyzed the FT reaction. The effect of FT reaction temperature, catalyst type, and experiment duration on the resulting products is being investigated. These solid organic products are analyzed by thermal-stepwise pyrolysis-GCMS and yield the types and distribution of hydrocarbon compounds released as a function of temperature. We show how the FT products vary by reaction temperature, catalyst type, and experimental duration and compare these products to organic compounds found to be indigenous to ordinary chondrite meteorites. We hypothesize that the origin of organics in some chondritic meteorites, that represent an aggregation of materials from the early solar system, may at least in part be from FT synthesis that occurred in the early solar nebula.

  14. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalysts to Poisons from High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burtron Davis; Gary Jacobs; Wenping Ma; Khalid Azzam; Dennis Sparks; Wilson Shafer

    2010-09-30

    The successful adaptation of conventional cobalt and iron-based Fischer-Tropsch synthesis catalysts for use in converting biomass-derived syngas hinges in part on understanding their susceptibility to byproducts produced during the biomass gasification process. With the possibility that oil production will peak in the near future, and due to concerns in maintaining energy security, the conversion of biomass-derived syngas and syngas derived from coal/biomass blends to Fischer-Tropsch synthesis products to liquid fuels may provide a sustainable path forward, especially considering if carbon sequestration can be successfully demonstrated. However, one current drawback is that it is unknown whether conventional catalysts based on iron and cobalt will be suitable without proper development because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using an entrained-flow oxygen-blown gasifier) than solely from coal, other byproducts may be present in higher concentrations. The current project examines the impact of a number of potential byproducts of concern from the gasification of biomass process, including compounds containing alkali chemicals like the chlorides of sodium and potassium. In the second year, researchers from the University of Kentucky Center for Applied Energy Research (UK-CAER) continued the project by evaluating the sensitivity of a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to a number of different compounds, including KHCO{sub 3}, NaHCO{sub 3}, HCl, HBr, HF, H{sub 2}S, NH{sub 3}, and a combination of H{sub 2}S and NH{sub 3}. Cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts were also subjected to a number of the same compounds in order to evaluate their sensitivities.

  15. 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.

  16. Gaseous product mixture from Fischer-Tropsch synthesis as an efficient carbon feedstock for low temperature CVD growth of carbon nanotube carpets

    NASA Astrophysics Data System (ADS)

    Almkhelfe, Haider; Carpena-Núñez, Jennifer; Back, Tyson C.; Amama, Placidus B.

    2016-07-01

    Low-temperature chemical vapor deposition (CVD) growth of carbon nanotube (CNT) carpets from Fe and Fe-Cu catalysts using a gaseous product mixture from Fischer-Tropsch synthesis (FTS-GP) as a superior carbon feedstock is demonstrated. This growth approach addresses a persistent issue of obtaining thick CNT carpets on temperature-sensitive substrates at low temperatures using a non-plasma CVD approach without catalyst pretreatment and/or preheating of the carbon feedstock. The efficiency of the process is evidenced by the highly dense, vertically aligned CNT structures from both Fe and Fe-Cu catalysts even at temperatures as low as 400 °C - a record low growth temperature for CNT carpets obtained via conventional thermal CVD. The grown CNTs exhibit a straight morphology with hollow interior and parallel graphitic planes along the tube walls. The apparent activation energies for CNT carpet growth on Fe and Fe-Cu catalysts are 0.71 and 0.54 eV, respectively. The synergistic effect of Fe and Cu show a strong dependence on the growth temperature, with Cu being more influential at temperatures higher than 450 °C. The low activation energies and long catalyst lifetimes observed are rationalized based on the unique composition of FTS-GP and Gibbs free energies for the decomposition reactions of the hydrocarbon components. The use of FTS-GP facilitates low-temperature growth of CNT carpets on traditional (alumina film) and nontraditional substrates (aluminum foil) and has the potential of enhancing CNT quality, catalyst lifetime, and scalability.Low-temperature chemical vapor deposition (CVD) growth of carbon nanotube (CNT) carpets from Fe and Fe-Cu catalysts using a gaseous product mixture from Fischer-Tropsch synthesis (FTS-GP) as a superior carbon feedstock is demonstrated. This growth approach addresses a persistent issue of obtaining thick CNT carpets on temperature-sensitive substrates at low temperatures using a non-plasma CVD approach without catalyst

  17. 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.

  18. 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.

  19. Heat transfer and bubble dynamics in bubble and slurry bubble columns with internals for Fischer-Tropsch synthesis of clean alternative fuels and chemicals

    NASA Astrophysics Data System (ADS)

    Kagumba, Moses Odongo O.

    Synthesis gas, a mixture of CO and H2 obtained from coal, natural gas and biomass are increasingly becoming reliable sources of clean synthetic fuels and chemicals and via Fischer-Tropsch (F-T) synthesis process. Slurry bubble column reactor is the reactor of choice for the commercialization of the F-T synthesis. Even though the slurry bubble column reactors and contactors are simple in structures, their design, scale-up, operation, and performance prediction are still challenging and not well understood due to complex interaction of phases. All the studies of heat transfer have been performed without simultaneously investigating the bubble dynamics adjacent to the heat transfer surfaces, particularly in slurry with dense internals. This dissertation focuses on enhancing the understanding of the role of local and overall gas holdup, bubble passage frequency, bubble sizes and bubble velocity on the heat transfer characteristics by means of a hybrid measurement technique comprising an advanced four-point optical probe and a fast response heat transfer probe used simultaneously, in the presence and absence of dense internals. It also seeks to advance a mechanistic approach for estimating the needed parameters for predicting the heat transfer rate in two phase and three phase systems. The results obtained suggest that the smaller diameter internals gives higher heat transfer coefficient, higher local and overall gas holdup, bubble passage frequency and specific interfacial area but smaller bubble sizes and lower axial bubble velocities. The presence of dense internals enhances the heat transfer coefficient in both the large and smaller columns, while increased column diameter increases the heat transfer coefficient, axial bubble velocity, local and overall gas holdup, bubble chord lengths and specific interfacial area. Addition of solids (glass beads) leads to increased bubble chord lengths and increase in axial bubble velocity, but a decrease in local and overall gas

  20. Development of precipitated iron Fischer-Tropsch catalysts. Quarterly technical progress report, April 1, 1995--June 30, 1995

    SciTech Connect

    Bukur, D.B.; Lang, X.; Wei, G.; Xiao, S.

    1995-08-17

    Work continued on the development of catalysts for Fischer-Tropsch synthesis. Six catalysts were synthesised. The effects of a calcium oxide promoter were evaluated. Catalysts were characterized for pore size and BET surface area.

  1. Poisoning of a silica supported cobalt catalyst due to the presence of sulfur impurities in syngas during Fischer-Tropsch synthesis: Effect of chelating agent

    SciTech Connect

    Bambal, A.S.; Gardner, T.H.; Kugler, E.L.; Dadyburjor, D.B.

    2012-01-01

    Sulfur compounds that are generally found in syngas derived from coal and biomass are a poison to Fischer-Tropsch (FT) catalysts. The presence of sulfur impurities in the ppm range can limit the life of a FT catalyst to a few hours or a few days. In this study, FT synthesis was carried out in a fixed-bed reactor at 230 °C, 20 bar, and 13,500 Ncm3/h/gcat for 72 h using syngas with H2/CO = 2.0. Cobalt-based catalysts were subjected to poisoning by 10 and 50 ppm sulfur in the syngas. The performance of FT catalyst was compared in context of syngas conversion, product selectivities and yields, during the poisoning as well as post-poisoning stages. At both the impurity concentrations, the sulfur was noted to cause permanent loss in the activity, possibly by adsorbing irreversibly on the surface. The sulfur poison affects the hydrogenation and the chain-propagation ability of the catalysts, and shifts the product selectivity towards short-chain hydrocarbons with higher percentages of olefins. Additional diffusion limitations caused due to sulfur poisoning are thought to alter the product selectivity. The shifts in product selectivities suggest that the sulfur decreases the ability of the catalyst to form C-C bonds to produce longer-chain hydrocarbons. The selective blocking of sulfur is thought to affect the hydrogenation ability on the catalyst, resulting in more olefins in the product after sulfur poisoning. The sulfur poisoning on the cobalt catalyst is expected to cause an increase in the number of sites responsible for WGS or to influence the Boudouard reaction, resulting in a higher CO2 selectivity. Both the sites responsible for CO adsorptions as well as the sites for chain growth are poisoned during the poisoning. Additionally, the performance of a base-case cobalt catalyst is compared with that of catalysts modified by chelating agents (CAs). The superior performance of CA-modified catalysts during sulfur poisoning is attributed to the presence of smaller

  2. Fischer-Tropsch synthesis of hydrocarbons during sub-solidus alteration of the Strange Lake peralkaline granite, Quebec/Labrador, Canada

    SciTech Connect

    Salvi, S.; Williams-Jones, A.E.

    1997-01-01

    The composition of the carbonic phase(s) of fluid inclusions in pegmatite quartz from the Strange Lake peralkaline complex has been analysed by gas chromatography using online extraction of inclusion contents and a PoraPLOT{reg_sign} Q capillary column. The measured gas species are, in order of abundance, CH{sub 4} H{sub 2}, C{sub 2}H{sub 6}, CO{sub 2}, N{sub 2}, C{sub 3}H{sub 8}, n-C{sub 4}H{sub 10}, n-C{sub 5}H{sub 12}, C{sub 2}H{sub 2}-i-C{sub 4}H{sub 10}, and C{sub 2}H{sub 4}. Minor amounts of i-C{sub 5}H{sub 12}, n-C{sub 6}H{sub 14}, i-C{sub 6}H{sub 14}, and neo-C{sub 6}H{sub 14}, were also detected (but not quantified) in some samples. A suite of quartz samples from Ca-metasomatised pegmatites contains fluid inclusions with a similar distribution of hydrocarbons but much higher proportions of CO{sub 2}. The carbonic fluid coexisted immiscibly with a brine, which on the basis of field and petrographic evidence, was interpreted to have originated from the magma. However, thermodynamic calculations indicate that the above gas species, specifically the hydrocarbons, could not have coexisted at equilibrium in the proportions measured, at any geologically reasonable conditions either prior to or post entrapment. We propose, instead, that the gas compositions measured in the Strange Lake inclusions, and in inclusions from other alkalic complexes, resulted from the production of H{sub 2} during the alteration of arfvedsonite to aegirine, and the subsequent reaction of this H{sub 2} with orthomagmatic CO{sub 2} and CO to form hydrocarbons in a magnetite-catalysed Fischer-Tropsch synthesis. Locally, influx of an oxidised calcic brine, derived externally from the pluton, altered the original composition of the fluid by converting hydrocarbons to CO{sub 2}. 70 refs., 7 figs., 5 tabs.

  3. 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.

  4. 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.

  5. 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.

  6. Combinatorial computational chemistry approach for materials design: applications in deNOx catalysis, Fischer-Tropsch synthesis, lanthanoid complex, and lithium ion secondary battery.

    PubMed

    Koyama, Michihisa; Tsuboi, Hideyuki; Endou, Akira; Takaba, Hiromitsu; Kubo, Momoji; Del Carpio, Carlos A; Miyamoto, Akira

    2007-02-01

    Computational chemistry can provide fundamental knowledge regarding various aspects of materials. While its impact in scientific research is greatly increasing, its contributions to industrially important issues are far from satisfactory. In order to realize industrial innovation by computational chemistry, a new concept "combinatorial computational chemistry" has been proposed by introducing the concept of combinatorial chemistry to computational chemistry. This combinatorial computational chemistry approach enables theoretical high-throughput screening for materials design. In this manuscript, we review the successful applications of combinatorial computational chemistry to deNO(x) catalysts, Fischer-Tropsch catalysts, lanthanoid complex catalysts, and cathodes of the lithium ion secondary battery.

  7. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalysts to Poisons from High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burton Davis; Gary Jacobs; Wenping Ma; Dennis Sparks; Khalid Azzam; Janet Chakkamadathil Mohandas; Wilson Shafer; Venkat Ramana Rao Pendyala

    2011-09-30

    There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased. Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations. In the second and third years, researchers from the University of Kentucky Center for Applied Energy Research (UK-CAER) continued the project by evaluating the sensitivity of a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to a number of different compounds, including KHCO{sub 3}, NaHCO{sub 3}, HCl, HBr, HF, H{sub 2}S, NH{sub 3}, and a combination of H

  8. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalystes to Poisons form High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burton Davis; Gary Jacobs; Wenping Ma; Khalid Azzam; Janet ChakkamadathilMohandas; Wilson Shafer

    2009-09-30

    There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased. Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations.

  9. Which route to coal liquefaction

    SciTech Connect

    Nene, R.G.

    1981-11-01

    The author compares the SRC-II process with three indirect liquefaction processes: Lurgi gasification and Mobil's methanol to gasoline (MTG) process; Shell-Koppers gasification and the Mobil MTG process; and Lurgi gasification and SASOL Fischer-Tropsch synthesis. Yields, thermal efficiencies, costs, state of development, and complexity of the processes are examined. Direct liquefaction is more thermally efficient. Investment costs are so close that the relative ranking of the process may change.

  10. Cobalt Fischer-Tropsch catalysts having improved selectivity

    DOEpatents

    Miller, James G.; Rabo, Jule A.

    1989-01-01

    A cobalt Fischer-Tropsch catalyst having an improved steam treated, acid extracted LZ-210 support is taught. The new catalyst system demonstrates improved product selectivity at Fischer-Tropsch reaction conditions evidenced by lower methane production, higher C.sub.5.sup.+ yield and increased olefin production.

  11. TECHNOLOGY DEVELOPMENT FOR IRON FISCHER-TROPSCH CATALYSTS

    SciTech Connect

    Davis, B.H.

    1998-07-22

    The goal of the proposed work described in this Final Report was the development of iron-based Fischer-Tropsch catalysts that combined high activity, selectivity and life with physical robustness for slurry phase reactors that will produce either low-alpha or high-alpha products. The work described here has optimized the catalyst composition and pretreatment operation for a low-alpha catalyst. In parallel, work has been conducted to design a high-alpha iron catalyst that is suitable for slurry phase synthesis. Studies have been conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors have been studied at the laboratory scale. Catalyst performance has been determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.

  12. Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co

    DOE PAGES

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Ma, Wenping; ...

    2016-07-23

    The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer-Tropsch (FT) catalysts was investigated in our earlier studies [ACS Catal. 5 (2015) 3124-3136 and DOE final report 2011; Catal. Lett. 144 (2014) 1127-1133]. For an iron catalyst, lower HCl concentrations (< 2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts ismore » explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate HCl poisoning mechanism on the iron and cobalt catalysts. Cl K-edge normalized XANES results indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observed to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g.,cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.« less

  13. Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co

    SciTech Connect

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Ma, Wenping; Sparks, Dennis E.; Shafer, Wilson D.; Khalid, Syed; Xiao, Qunfeng; Hu, Yongfeng; Davis, Burtron H.

    2016-07-23

    The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer-Tropsch (FT) catalysts was investigated in our earlier studies [ACS Catal. 5 (2015) 3124-3136 and DOE final report 2011; Catal. Lett. 144 (2014) 1127-1133]. For an iron catalyst, lower HCl concentrations (< 2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts is explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate HCl poisoning mechanism on the iron and cobalt catalysts. Cl K-edge normalized XANES results indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observed to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g.,cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.

  14. Technology development for iron Fischer-Tropsch catalysts

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1992-12-22

    Objective is to develop producing active, stable iron Fischer-Tropsch catalysts for use in slurry-phase synthesis reactors and to synthesize such catalysts on a large scale for process development and long-term testing in slurry bubble-column reactors. A mixed oxalate of Fe, Cu, and K was prepared; a catalyst will be prepared from this material. An evaluation run was performed on an Fe-based UCI catalyst, which was shown to produce low levels of C[sub 1] and C[sub 2] paraffins; e.g., at the end of the run, when the catalyst was converting 60% of the CO, the C[sub 1] and C[sub 2] paraffin selectivities were 4.2 and 1.0, respectively.

  15. Fischer-Tropsch catalysts for the production of hydrocarbon fuels with high selectivity.

    PubMed

    Zhang, Qinghong; Cheng, Kang; Kang, Jincan; Deng, Weiping; Wang, Ye

    2014-05-01

    Fischer-Tropsch synthesis is a key reaction in the utilization of non-petroleum carbon resources, such as methane (natural gas, shale gas, and biogas), coal, and biomass, for the sustainable production of clean liquid fuels from synthesis gas. Selectivity control is one of the biggest challenges in Fischer-Tropsch synthesis. This Minireview focuses on the development of new catalysts with controllable product selectivities. Recent attempts to increase the selectivity to C5+ hydrocarbons by preparing catalysts with well-defined active phases or with new supports or by optimizing the interaction between the promoter and the active phase are briefly highlighted. Advances in developing bifunctional catalysts capable of catalyzing both CO hydrogenation to heavier hydrocarbons and hydrocracking/isomerization of heavier hydrocarbons are critically reviewed. It is demonstrated that the control of the secondary hydrocracking reactions by using core-shell nanostructures or solid-acid materials, such as mesoporous zeolites and carbon nanotubes with acid functional groups, is an effective strategy to tune the product selectivity of Fischer-Tropsch synthesis. Very promising selectivities to gasoline- and diesel-range hydrocarbons have been attained over some bifunctional catalysts.

  16. Development and process evaluation of improved Fischer-Tropsch slurry catalysts

    SciTech Connect

    Withers, H.P. ); Bukur, D.B.; Rosynek, M.P. )

    1988-01-01

    The objective of this contract is to develop a consistent technical data base on the use of iron-based catalysts in Fischer-Tropsch (FT) synthesis reactions. This data base will be developed to allow the unambiguous comparison of the performance of these catalysts with each other and with state-of-the-art iron catalyst compositions. Particular attention will be devoted to generating reproducible kinetic and selectivity data and to developing reproducible improved catalyst compositions.

  17. Development and process evaluation of improved Fischer-Tropsch slurry catalysts

    SciTech Connect

    Withers, H.P. ); Bukur, D.B.; Rosynek, M.P. )

    1988-01-01

    The objective of this contract is to develop a consistent technical data base on the use of iron-based catalysts in Fischer-Tropsch (F-T) synthesis reactions. This data base will be developed to allow the unambiguous comparison of the performance of these catalysts with each other and with state-of-the-art iron catalyst compositions. Particular attention will be devoted to generating reproducible kinetic and selectivity data and to developing reproducible improved catalyst compositions.

  18. An Ab Initio Approach Towards Engineering Fischer-Tropsch Surface Chemistry

    SciTech Connect

    Matthew Neurock

    2005-06-13

    As petroleum prices continue to rise and the United States seeks to reduce its dependency on foreign oil, there is a renewed interest in the research and development of more efficient and alternative energy sources, such as fuel cells. One approach is to utilize processes that can produce long-chain hydrocarbons from other sources. One such reaction is Fischer-Tropsch synthesis. Fischer-Tropsch synthesis is a process by which syngas (CO and H{sub 2}) is converted to higher molecular weight hydrocarbons. The reaction involves a complex set of bond-breaking and bond-making reactions, such as CO and H{sub 2} activation, hydrocarbon hydrogenation reactions, and hydrocarbon coupling reactions. This report details our initial construction of an ab initio based kinetic Monte Carlo code that can be used to begin to simulate Fischer-Tropsch synthesis over model Co(0001) surfaces. The code is based on a stochastic kinetic formalism that allows us to explicitly track the transformation of all reactants, intermediates and products. The intrinsic kinetics for the simulations were derived from the ab initio results that we reported in previous year summaries.

  19. Fischer-Tropsch synthesis: study of the promotion of Pt on the reduction property of Co/Al2O3 catalysts by in situ EXAFS of Co K and Pt LIII edges and XPS.

    PubMed

    Jacobs, Gary; Chaney, John A; Patterson, Patricia M; Das, Tapan K; Maillot, Julie C; Davis, Burtron H

    2004-09-01

    The addition of platinum metal to cobalt/alumina-based Fischer-Tropsch synthesis (FTS) catalysts increases both the reduction rate and, consequently, the density of active cobalt sites. Platinum also lowers the temperature of the two-step conversion of cobalt oxide to cobalt metal observed in temperature programmed reduction (TPR) as Co3O4 to CoO and CoO to Co0. The interaction of the alumina support with cobalt oxide ultimately determines the active site density of the catalyst surface. This interaction can be controlled by varying the cobalt loading and dispersion, selecting supports with differing surface areas or pore sizes, or changing the noble metal promoter. However, the active site density is observed to depend primarily on the cluster size and extent of reduction, and there is a direct relationship between site density and FTS rate. In this work, in situ extended X-ray absorption fine structure (EXAFS) at the LIII edge of Pt was used to show that isolated Pt atoms interact with supported cobalt clusters without forming observable Pt--Pt bonds. K-edge EXAFS was also used to verify that the cobalt cluster size increases slightly for those systems with Pt promotion. X-ray absorption near-edge spectroscopy (XANES) was used to examine the remaining cobalt clusters after the first stage of TPR, and it revealed that the species were almost entirely cobalt (II) oxide. After the second stage of TPR to form cobalt metal, a residual oxide persists in the sample, and this oxide has been identified as cobalt (II) aluminate using X-ray photoelectron spectroscopy (XPS). Sequential in situ reduction of promoted and unpromoted systems was also monitored through XPS, and Pt was seen to increase the extent of cobalt reduction by a factor of two.

  20. Mo-Fe catalysts supported on activated carbon for synthesis of liquid fuels by the Fischer-Tropsch process: effect of Mo addition on reducibility, activity, and hydrocarbon selectivity

    SciTech Connect

    Wenping Ma; Edwin L. Kugler; James Wright; Dady B. Dadyburjor

    2006-12-15

    The effects of Mo loading (0-12 wt %) on the properties of activated-carbon- (AC-) supported Fe-Cu-K catalysts and their performance for Fischer-Tropsch synthesis are studied. Physicochemical properties studied include particle size, reducibility, and dispersion, and catalytic properties include activity, selectivity, and stability. Catalysts were characterized by N{sub 2} adsorption, energy-dispersive spectroscopy, X-ray diffraction (XRD), H{sub 2} temperature-programmed reduction (TPR), and CO chemisorption. Catalyst performance was studied at 310-320{sup o}C, 2.2 MPa, 3 Nl/g-cat/h, and H{sub 2}/CO = 0.9. Reaction results in a fixed-bed reactor show that addition of 6% Mo into the Fe-Cu-K/AC catalyst improves catalyst stability without sacrificing activity, but activity is suppressed dramatically on a 12% Mo-loaded catalyst. Detectable hydrocarbons of C{sub 1} to C{sub 34} are produced on the Fe-Cu-K/AC catalysts with or without Mo. However, the addition of Mo results in the production of more CH{sub 4} and less C{sub 5+} hydrocarbons. The Mo promoter greatly enhances secondary reactions of olefins, leading to a large amount of internal olefins (i.e., other than 1-olefins) in the product. TPR shows that a strong interaction between Fe and Mo oxides is present, and the extent of reduction of Fe is suppressed after addition of Mo to the Fe-Cu-K catalyst. CO-chemisorption and XRD studies show increased iron dispersion and decreased particle size of the iron carbide and iron oxide after the addition of Mo. Segregation of iron active sites, thereby preventing them from agglomerating, and a larger number of active sites on the 6% Mo catalyst are possible reasons for the improved stability and higher activity of Mo-promoted catalysts. 54 refs., 5 figs., 6 tabs.

  1. Technology development for iron Fischer-Tropsch catalysts

    SciTech Connect

    O`Brien, R.J.; Raje, A.; Keogh, R.A.

    1995-12-31

    The objective of this research project is to develop the technology for the production of physically robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry phase synthesis reactor development. The catalysts that are developed shall be suitable for testing in the Advanced Fuels Development Facility at LaPorte, Texas, to produce either low-or high-alpha product distributions. Previous work by the offeror has produced a catalyst formulation that is 1.5 times as active as the {open_quotes}standard-catalyst{close_quotes} developed by German workers for slurry phase synthesis. In parallel, work will be conducted to design a high-alpha iron catalyst this is suitable for slurry phase synthesis. Studies will be conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors will be studied at the laboratory scale. Catalyst performance will be determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.

  2. Size dependent stability of cobalt nanoparticles on silica under high conversion Fischer-Tropsch environment.

    PubMed

    Wolf, Moritz; Kotzé, Hendrik; Fischer, Nico; Claeys, Michael

    2017-02-15

    Highly monodisperse cobalt crystallites, supported on Stöber silica spheres, as model catalysts for the Fischer-Tropsch synthesis were exposed to simulated high conversion environments in the presence and absence of CO utilising an in house developed in situ magnetometer. The catalyst comprising the smallest crystallites in the metallic state (average diameter of 3.2 nm) experienced pronounced oxidation whilst the ratio of H2O to H2 was increased stepwise to simulate CO conversions from 26% up to complete conversion. Direct exposure of this freshly reduced catalyst to a high conversion Fischer-Tropsch environment resulted in almost spontaneous oxidation of 40% of the metallic cobalt. In contrast, a model catalyst with cobalt crystallites of 5.3 nm only oxidised to a small extent even when exposed to a simulated conversion of over 99%. The largest cobalt crystallites were rather stable and only experienced measurable oxidation when subjected to H2O in the absence of H2. This size dependency of the stability is in qualitative accordance with reported thermodynamic calculations. However, the cobalt crystallites showed an unexpected low susceptibility to oxidation, i.e. only relatively high ratios of H2O to H2 partial pressure caused oxidation. Similar experiments in the presence of CO revealed the significance of the actual Fischer-Tropsch synthesis on the metallic surface as the dissociation of CO, an elementary step in the Fischer-Tropsch mechanism, was shown to be a prerequisite for oxidation. Direct oxidation of cobalt to CoO by H2O seems to be kinetically hindered. Thus, H2O may only be capable of indirect oxidation, i.e. high concentrations prevent the removal of adsorbed oxygen species on the cobalt surface leading to oxidation. However, a spontaneous direct oxidation of cobalt at the interface between the support and the crystallites by H2O forming presumably cobalt silicate type species was observed in the presence and absence of CO. The formation of these

  3. TECHNOLOGY DEVELOPMENT FOR IRON FISCHER-TROPSCH CATALYSIS

    SciTech Connect

    Burtron H. Davis

    1998-04-01

    The goal of the proposed work is the development of iron-based Fischer-Tropsch catalysts that combined high activity, selectivity and life with physical robustness for slurry phase reactors that will produce either low-alpha or high-alpha products. The catalyst that is developed will be suitable for testing at the Advanced Fuels Development Facility at LaPorte, Texas or similar sized plant. Previous work by the offeror has produced a catalyst formulation that is 1.5 times as active as the ''standard-catalyst'' developed by German workers for slurry phase synthesis. The proposed work will optimize the catalyst composition and pretreatment operation for this low-alpha catalyst. In parallel, work will be conducted to design a high-alpha iron catalyst that is suitable for slurry phase synthesis. Studies will be conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors will be studied at the laboratory scale. Catalyst performance will be determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.

  4. Technology Development for Iron Fischer-Tropsch Catalysis.

    SciTech Connect

    Davis, B.H.

    1997-12-16

    The goal of the proposed work is the development of iron-based Fischer-Tropsch catalysts that combined high activity, selectivity and life with physical robustness for slurry phase reactors that will produce either low-alpha or high-alpha products. The catalyst that is developed will be suitable for testing at the Advanced Fuels Development Facility at LaPorte, Texas or similar sized plant. Previous work by the offeror has produced a catalyst formulation that is 1.5 times as active as the `standard-catalyst` developed by German workers for slurry phase synthesis. The proposed work will optimize the catalyst composition and pretreatment operation for this low-alpha catalyst. In parallel, work will be conducted to design a high-alpha iron catalyst that is suitable for slurry phase synthesis. Studies will be conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors will be studied at the laboratory scale. Catalyst performance will be determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.

  5. Chemical imaging of Fischer-Tropsch catalysts under operating conditions

    PubMed Central

    Price, Stephen W. T.; Martin, David J.; Parsons, Aaron D.; Sławiński, Wojciech A.; Vamvakeros, Antonios; Keylock, Stephen J.; Beale, Andrew M.; Mosselmans, J. Frederick W.

    2017-01-01

    Although we often understand empirically what constitutes an active catalyst, there is still much to be understood fundamentally about how catalytic performance is influenced by formulation. Catalysts are often designed to have a microstructure and nanostructure that can influence performance but that is rarely considered when correlating structure with function. Fischer-Tropsch synthesis (FTS) is a well-known and potentially sustainable technology for converting synthetic natural gas (“syngas”: CO + H2) into functional hydrocarbons, such as sulfur- and aromatic-free fuel and high-value wax products. FTS catalysts typically contain Co or Fe nanoparticles, which are often optimized in terms of size/composition for a particular catalytic performance. We use a novel, “multimodal” tomographic approach to studying active Co-based catalysts under operando conditions, revealing how a simple parameter, such as the order of addition of metal precursors and promoters, affects the spatial distribution of the elements as well as their physicochemical properties, that is, crystalline phase and crystallite size during catalyst activation and operation. We show in particular how the order of addition affects the crystallinity of the TiO2 anatase phase, which in turn leads to the formation of highly intergrown cubic close-packed/hexagonal close-packed Co nanoparticles that are very reactive, exhibiting high CO conversion. This work highlights the importance of operando microtomography to understand the evolution of chemical species and their spatial distribution before any concrete understanding of impact on catalytic performance can be realized. PMID:28345057

  6. Chemical imaging of Fischer-Tropsch catalysts under operating conditions.

    PubMed

    Price, Stephen W T; Martin, David J; Parsons, Aaron D; Sławiński, Wojciech A; Vamvakeros, Antonios; Keylock, Stephen J; Beale, Andrew M; Mosselmans, J Frederick W

    2017-03-01

    Although we often understand empirically what constitutes an active catalyst, there is still much to be understood fundamentally about how catalytic performance is influenced by formulation. Catalysts are often designed to have a microstructure and nanostructure that can influence performance but that is rarely considered when correlating structure with function. Fischer-Tropsch synthesis (FTS) is a well-known and potentially sustainable technology for converting synthetic natural gas ("syngas": CO + H2) into functional hydrocarbons, such as sulfur- and aromatic-free fuel and high-value wax products. FTS catalysts typically contain Co or Fe nanoparticles, which are often optimized in terms of size/composition for a particular catalytic performance. We use a novel, "multimodal" tomographic approach to studying active Co-based catalysts under operando conditions, revealing how a simple parameter, such as the order of addition of metal precursors and promoters, affects the spatial distribution of the elements as well as their physicochemical properties, that is, crystalline phase and crystallite size during catalyst activation and operation. We show in particular how the order of addition affects the crystallinity of the TiO2 anatase phase, which in turn leads to the formation of highly intergrown cubic close-packed/hexagonal close-packed Co nanoparticles that are very reactive, exhibiting high CO conversion. This work highlights the importance of operando microtomography to understand the evolution of chemical species and their spatial distribution before any concrete understanding of impact on catalytic performance can be realized.

  7. ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

    SciTech Connect

    K. Jothimurugesan; James G. Goodwin, Jr.; Santosh K. Gangwal

    1999-10-01

    Fischer-Tropsch (FT) synthesis to convert syngas (CO + H{sub 2}) derived from natural gas or coal to liquid fuels and wax is a well-established technology. For low H{sub 2} to CO ratio syngas produced from CO{sub 2} reforming of natural gas or from gasification of coal, the use of Fe catalysts is attractive because of their high water gas shift activity in addition to their high FT activity. Fe catalysts are also attractive due to their low cost and low methane selectivity. Because of the highly exothermic nature of the FT reaction, there has been a recent move away from fixed-bed reactors toward the development of slurry bubble column reactors (SBCRs) that employ 30 to 90 {micro}m catalyst particles suspended in a waxy liquid for efficient heat removal. However, the use of FeFT catalysts in an SBCR has been problematic due to severe catalyst attrition resulting in fines that plug the filter employed to separate the catalyst from the waxy product. Fe catalysts can undergo attrition in SBCRs not only due to vigorous movement and collisions but also due to phase changes that occur during activation and reaction.

  8. An Investigation into the Effects of Mn Promotion on the Activity and Selectivity of Co/SiO2 for Fischer - Tropsch Synthesis: Evidence for Enhanced CO Adsorption and Dissociation

    SciTech Connect

    Johnson, Gregory R.; Werner, Sebastian; Bell, Alexis T.

    2016-03-04

    Mn is an effective promoter for improving the activity and selectivity of Co-based Fischer-Tropsch synthesis (FTS) catalysts, but the mechanism by which this promoter functions is poorly understood. The work reported here was aimed at defining the manner in which Mn interacts with Co and determining how these interactions affect the activity and selectivity of Co. Detailed measurements are reported for the kinetics of FTS as a function of Mn/Co ratio, temperature, and reactant partial pressure. These data are described by a single, two-parameter rate expression. Mn promotion was found to increase both the apparent rate constant for CO consumption and the CO adsorption constant. Further evidence for enhanced CO adsorption and dissociation was obtained from measurements of temperature-programmed desorption of CO and CO disproportionation rates, respectively. Our quantitative analysis of elemental maps obtained by STEM-EDS revealed that the promoter accumulates preferentially on the surface of Co nanoparticles at low Mn loadings, resulting in a rapid onset of improvements in the product selectivity as the Mn loading increases. For catalysts prepared with loadings higher than Mn/Co = 0.1, the additional Mn accumulates in the form of nanometer-scale particles of MnO on the support. In situ IR spectra of adsorbed CO show that Mn promotion increases the abundance of adsorbed CO with weakened C-O bonds. Furthermore, it is proposed that the cleavage of the C-O bond is promoted through Lewis acid-base interactions between the Mn2+ cations located at the edges of MnO islands covering the Co nanoparticles and the O atom of CO adsorbates adjacent to the MnO islands. The observed decrease in selectivity to CH4 and the increased selectivity to C5+ products with increasing Mn/Co ratio are attributed to a decrease in the ratio of adsorbed H to CO on the surface of the supported Co nanoparticles.

  9. An Ab Initio Approach Towards Engineering Fischer-Tropsch Surface Chemistry

    SciTech Connect

    Matthew Neurock; David A. Walthall

    2006-05-07

    One of the greatest societal challenges over the next decade is the production of cheap, renewable energy for the 10 billion people that inhabit the earth. This will require the development of various different energy sources potentially including fuels derived from methane, coal, and biomass and alternatives sources such as solar, wind and nuclear energy. One approach will be to synthesize gasoline and other fuels from simpler hydrocarbons such as CO derived from methane or other U.S. based sources such as coal. Syngas (CO and H{sub 2}) can be readily converted into higher molecular weight hydrocarbons through Fischer-Tropsch synthesis. Fischer-Tropsch synthesis involves the initiation or activation of CO and H{sub 2} bonds, the subsequent propagation steps including hydrogenation and carbon-carbon coupling, followed by chain termination reactions. Commercially viable catalysts include supported Co and Co-alloys. Over the first two years of this project we have used ab initio methods to determine the adsorption energies for all reactants, intermediates, and products along with the overall reaction energies and their corresponding activation barriers over the Co(0001) surface. Over the third year of the project we developed and advanced an ab initio-based kinetic Monte Carlo simulation code to simulate Fischer Tropsch synthesis. This report details our work over the last year which has focused on the derivation of kinetic parameters for the elementary steps involved in FT synthesis from ab initio density functional theoretical calculations and the application of the kinetic Monte Carlo algorithm to simulate the initial rates of reaction for FT over the ideal Co(0001) surface. The results from our simulations over Co(0001) indicate the importance of stepped surfaces for the activation of adsorbed CO. In addition, they demonstrate that the dominant CH{sub x}* surface intermediate under steady state conditions is CH*. This strongly suggests that hydrocarbon coupling

  10. Slurry Phase Iron Catalysts for Indirect Coal Liquefaction

    SciTech Connect

    Abhaya K. Datye

    1998-09-10

    This report describes research conducted to support the DOE program in indirect coal liquefaction. Specifically, we have studied the attrition behavior of Iron Fischer-Tropsch catalysts, their interaction with the silica binder and the evolution of iron phases in a synthesis gas conversion process. The results provide significant insight into factors that should be considered in the design of catalysts for the conversion of coal-derived synthesis gas into liquid fuels.

  11. Cobalt Fischer-Tropsch catalysts having improved selectivity

    DOEpatents

    Miller, James G.; Rabo, Jule A.

    1989-01-01

    The promoter(s) Mn oxide or Mn oxide and Zr oxide are added to a cobalt Fischer-Tropsch catalyst combined with the molecular sieve TC-103 or TC-123 such that the resultant catalyst demonstrates improved product selectivity, stability and catalyst life. The improved selectivity is evidenced by lower methane production, higher C5+ yield and increased olefin production.

  12. Development of precipitated iron Fischer-Tropsch catalysts. Quarterly report, October 1, 1996--December 31, 1996

    SciTech Connect

    Bukur, D.B.

    1997-03-07

    The overall contract objectives are to: (1) demonstrate repeatability of performance and preparation procedure of two high activity, high alpha iron Fischer-Tropsch catalysts synthesized at Texas A&M University, (2) seek potential improvements in the catalyst performance through variations in process condition, pretreatment procedures and/or modification in catalyst synthesis, (3) investigate performance of catalysts in a small scale bubble column slurry reactor, and (4) investigate feasibility of producing catalysts on a large scale in collaboration with a catalyst manufacturer. Work during this period included pretreatment effect research and catalyst characterization.

  13. 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.

  14. Development and process evaluation of improved Fischer-Tropsch slurry catalysts. Quarterly technical progress report, 1 July--30 September 1988

    SciTech Connect

    Withers, H.P.; Bukur, D.B.; Rosynek, M.P.

    1988-12-31

    The objective of this contract is to develop a consistent technical data base on the use of iron-based catalysts in Fischer-Tropsch (F-T) synthesis reactions. This data base will be developed to allow the unambiguous comparison of the performance of these catalysts with each other and with state-of-the-art iron catalyst compositions. Particular attention will be devoted to generating reproducible kinetic and selectivity data and to developing reproducible improved catalyst compositions.

  15. Development and process evaluation of improved Fischer-Tropsch slurry catalysts. Quarterly technical progress report, 1 October--31 December 1988

    SciTech Connect

    Withers, H.P.; Bukur, D.B.; Rosynek, M.P.

    1988-12-31

    The objective of this contract is to develop a consistent technical data base on the use of iron-based catalysts in Fischer-Tropsch (FT) synthesis reactions. This data base will be developed to allow the unambiguous comparison of the performance of these catalysts with each other and with state-of-the-art iron catalyst compositions. Particular attention will be devoted to generating reproducible kinetic and selectivity data and to developing reproducible improved catalyst compositions.

  16. SLURRY PHASE IRON CATALYSTS FOR INDIRECT COAL LIQUEFACTION

    SciTech Connect

    Abhaya K. Datye

    1998-11-19

    This report describes research conducted to support the DOE program in indirect coal liquefaction. Specifically, they have studied the attrition behavior of iron Fischer-Tropsch catalysts, their interaction with the silica binder and the evolution of iron phases in a synthesis gas conversion process. The results provide significant insight into factors that should be considered in the design of catalysts for converting coal based syngas into liquid fuels.

  17. Development and process evaluation of improved Fischer-Tropsch slurry catalysts. Final report

    SciTech Connect

    Bukur, D.B.; Mukesh, D.; Patel, S.A.; Zimmerman, W.H.; Rosynek, M.P.; Kellogg, L.J.

    1990-04-01

    This report describes results of a study aimed at developing and evaluating improved catalysts for a slurry Fischer-Tropsch (FT) process for converting synthesis gas to high quality transportation fuels (gasoline and distillate). The improvements in catalyst performance were sought by studying effects of pretreatment conditions, promoters and binders/supports. A total of 20 different, iron based, catalysts were evaluated in 58 fixed bed reactor tests and 10 slurry reactor tests. The major accomplishments and conclusions are summarized below. The pretreatment conditions (temperature, duration and the nature of reducing gas) have significant effect on catalyst performance (activity, selectivity and stability) during Fischer-Tropsch synthesis. One of precipitated unsupported catalysts had hydrocarbon selectivity similar to Mobil`s I-B catalyst in high wax mode operation, and had not experienced any loss in activity during 460 hours of testing under variable process conditions in a slurry reactor. The effect of promoters (copper and potassium) on catalyst performance during FT synthesis has been studied in a systematic way. It was found that potassium promotion increases activities of the FT and water-gas-shift (WGS) reactions, the average molecular weight of hydrocarbon products, and suppresses the olefin hydrogenation and isomerization reactions. The addition of binders/supports (silica or alumina) to precipitated Fe/Cu/K catalysts, decreased their activity but improved their stability and hydrocarbon selectivity. The performance of catalysts of this type was very promising and additional studies are recommended to evaluate their potential for use in commercial slurry reactors.

  18. Subtask 3.4 - Fischer - Tropsch Fuels Development

    SciTech Connect

    Strege, Joshua; Snyder, Anthony; Laumb, Jason; Stanislowski, Joshua; Swanson, Michael

    2012-05-01

    Under Subtask 3.4, the Energy & Environmental Research Center (EERC) examined the opportunities and challenges facing FischerTropsch (FT) technology in the United States today. Work was completed in two distinct budget periods (BPs). In BP1, the EERC examined the technical feasibility of using modern warm-gas cleanup techniques for FT synthesis. FT synthesis is typically done using more expensive and complex cold-gas sweetening. Warm-gas cleanup could greatly reduce capital and operating costs, making FT synthesis more attractive for domestic fuel production. Syngas was generated from a variety of coal and biomass types; cleaned of sulfur, moisture, and condensables; and then passed over a pilot-scale FT catalyst bed. Laboratory and modeling work done in support of the pilot-scale effort suggested that the catalyst was performing suboptimally with warm-gas cleanup. Long-term trends showed that the catalyst was also quickly deactivating. In BP3, the EERC compared FT catalyst results using warm-gas cleanup to results using cold-gas sweetening. A gas-sweetening absorption system (GSAS) was designed, modeled, and constructed to sweeten syngas between the gasifier and the pilot-scale FT reactor. Results verified that the catalyst performed much better with gas sweetening than it had with warm-gas cleanup. The catalyst also showed no signs of rapid deactivation when the GSAS was running. Laboratory tests in support of this effort verified that the catalyst had deactivated quickly in BP1 because of exposure to syngas, not because of any design flaw with the pilot-scale FT reactor itself. Based on these results, the EERC concludes that the two biggest issues with using syngas treated with warm-gas cleanup for FT synthesis are high concentrations of CO{sub 2} and volatile organic matter. Other catalysts tested by the EERC may be more tolerant of CO{sub 2}, but volatile matter removal is critical to ensuring long-term FT catalyst operation. This subtask was funded through

  19. KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYSTHESIS

    SciTech Connect

    Dragomir B. Bukur; Gilbert F. Froment; Tomasz Olewski

    2005-09-29

    This report covers the third year of this research grant under the University Coal Research program. The overall objective of this project is to develop a comprehensive kinetic model for slurry phase Fischer-Tropsch synthesis (FTS) on iron catalysts. This model will be validated with experimental data obtained in a stirred tank slurry reactor (STSR) over a wide range of process conditions. The model will be able to predict molar flow rates and concentrations of all reactants and major product species (H{sub 2}O, CO{sub 2}, linear 1- and 2-olefins, and linear paraffins) as a function of reaction conditions in the STSR. During the reporting period we utilized experimental data from the STSR, that were obtained during the first two years of the project, to perform vapor-liquid equilibrium (VLE) calculations and estimate kinetic parameters. We used a modified Peng-Robinson (PR) equation of state (EOS) with estimated values of binary interaction coefficients for the VLE calculations. Calculated vapor phase compositions were in excellent agreement with experimental values from the STSR under reaction conditions. Occasional discrepancies (for some of the experimental data) between calculated and experimental values of the liquid phase composition were ascribed to experimental errors. The VLE calculations show that the vapor and the liquid are in thermodynamic equilibrium under reaction conditions. Also, we have successfully applied the Levenberg-Marquardt method (Marquardt, 1963) to estimate parameters of a kinetic model proposed earlier by Lox and Froment (1993b) for FTS on an iron catalyst. This kinetic model is well suited for initial studies where the main goal is to learn techniques for parameter estimation and statistical analysis of estimated values of model parameters. It predicts that the chain growth parameter ({alpha}) and olefin to paraffin ratio are independent of carbon number, whereas our experimental data show that they vary with the carbon number

  20. Coal liquefaction and gas conversion: Proceedings. Volume 2

    SciTech Connect

    Not Available

    1993-12-31

    Volume II contains papers presented at the following sessions: Indirect Liquefaction (oxygenated fuels); and Indirect Liquefaction (Fischer-Tropsch technology). Selected papers have been processed separately for inclusion in the Energy Science and Technology Database.

  1. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  2. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  3. 40 CFR 721.10178 - Distillates (Fischer-Tropsch), hydroisomerized middle, C10-13-branched alkane fraction.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Distillates (Fischer-Tropsch... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10178 Distillates (Fischer-Tropsch... to reporting. (1) The chemical substance identified as distillates (Fischer-Tropsch),...

  4. Quantification of progress in indirect coal liquefaction

    SciTech Connect

    Gray, D.; ElSawy, A.; Tomlinson, G.

    1991-01-01

    The objective of this study is to quantify the economic and technical impact of incorporating various advanced technologies into the indirect coal liquefaction system. These advanced technologies include entrained flow Shell gasification and slurry-phase Fischer-Tropsch (F-T) synthesis. This objective was accomplished by substituting the Shell entrained goal gasifier system for the Lurgi and the advanced slurry F-T reactor for the Synthol and ARGE F-T systems in a SASOL-type indirect liquefaction facility. 4 refs., 3 figs., 2 tabs.

  5. The role of electrophilic species in the Fischer-Tropsch reaction.

    PubMed

    Maitlis, Peter M; Zanotti, Valerio

    2009-04-07

    The heterogeneously catalysed Fischer-Tropsch (FT) synthesis converts syngas (CO+H2) into long chain hydrocarbons and is a key step in the economically important transformation of natural gas, coal, or biomass into liquid fuels, such as diesel. Catalyst surface studies indicate that the FT reaction starts when CO is activated at imperfections on the surfaces of late transition metals (Fe, Ru, Co, or Rh) and at interfaces with "islands" of promoters (Lewis acid oxides such as alumina or titania). Activation involves CO cleavage to generate a surface carbide, C(ad), which is sequentially hydrogenated to CHx(ad) species (x=1-4). An overview of practical aspects of the FT synthesis is followed by a discussion of the chief mechanisms that have been proposed for the formation of 1-alkenes by polymerisation of surface C1 species. These mechanisms have traditionally postulated rather non-polar intermediates, such as CH2(ad) and CH3(ad). However, electrophiles and nucleophiles are well-known to play key roles in the reactions of organic and organometallic compounds, and also in many reactions homogeneously catalysed by soluble metal complexes, including olefin polymerisation. We have now extended these concepts to the Fischer-Tropsch reaction, and show that the polymerisation reactions at polarising surfaces, such as oxide-metal interfaces, can be understood if the reactive chain carrier is an electrophilic species, such as the cationic methylidyne, CH(delta+)(ad). It is proposed that the key coupling step in C-C bond formation involves the interaction of the electrophilic methylidyne with an alkylidene (RCH(ad), R=H, alkyl), followed by an H-transfer to generate the homologous alkylidene: CHdelta+(ad)+RCH(ad)-->RCHCH(ad) and RCHCH(ad)+H(ad)-->RCH2CH(ad). If the reactions occur on non-polarising surfaces, an alternative C-C bond forming reaction such as the alkenyl+methylene, RCH=CH(ad)+CH2(ad)-->RCH=CHCH2(ad), can take place. This approach explains important aspects of the

  6. Separation of Fischer-Tropsch Wax Products from Ultrafine Iron Catalyst Particles

    SciTech Connect

    Amitava Sarkar; James K. Neathery; Burtron H. Davis

    2006-12-31

    A fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of operation since the reaction is highly exothermic. Consequently, heavy wax products in one approach may be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase iron-based FTS and is a key factor for optimizing operating costs. The separation problem is further compounded by attrition of iron catalyst particles and the formation of ultra-fine particles.

  7. Effects of vanadium and zinc promotion on the olefin selectivity of iron Fischer-Tropsch catalysts

    SciTech Connect

    Saglam, M.

    1989-02-01

    The aim in most of the studies on Fischer-Tropsch synthesis has been the selective production of olefins, which are the raw materials of petrochemical industry. In this study, the effects of V and Zn addition, separately or together in the form of their oxides, to Fe catalysts obtained through precipitation on the olefin selectivity of the catalysts have been investigated. The experiments have been done in a fixed-bed reactor at different temperatures and pressures with various ratios of H/sub 2//CO. The addition of V separately (catalyst 2) or together with Zn (catalyst 1) has greatly increased the olefin selectivity of Fe catalyst. So the amount of olefin in hydrocarbon fractions has reached over 80%. Besides, the ..cap alpha..-olefin parts in olefin fractions have gone over 90%. But the addition of Zn separately has been less effective on the olefin selectivity of the catalyst.

  8. Improved Fischer-Tropsch Slurry Reactors

    SciTech Connect

    Andrew Lucero

    2009-03-20

    The conversion of synthesis gas to hydrocarbons or alcohols involves highly exothermic reactions. Temperature control is a critical issue in these reactors for a number of reasons. Runaway reactions can be a serious safety issue, even raising the possibility of an explosion. Catalyst deactivation rates tend to increase with temperature, particularly of there are hot spots in the reactor. For alcohol synthesis, temperature control is essential because it has a large effect on the selectivity of the catalysts toward desired products. For example, for molybdenum disulfide catalysts unwanted side products such as methane, ethane, and propane are produced in much greater quantities if the temperature increases outside an ideal range. Slurry reactors are widely regarded as an efficient design for these reactions. In a slurry reactor a solid catalyst is suspended in an inert hydrocarbon liquid, synthesis gas is sparged into the bottom of the reactor, un-reacted synthesis gas and light boiling range products are removed as a gas stream, and heavy boiling range products are removed as a liquid stream. This configuration has several positive effects for synthesis gas reactions including: essentially isothermal operation, small catalyst particles to reduce heat and mass transfer effects, capability to remove heat rapidly through liquid vaporization, and improved flexibility on catalyst design through physical mixtures in addition to use of compositions that cannot be pelletized. Disadvantages include additional mass transfer resistance, potential for significant back-mixing on both the liquid and gas phases, and bubble coalescence. In 2001 a multiyear project was proposed to develop improved FT slurry reactors. The planned focus of the work was to improve the reactors by improving mass transfer while considering heat transfer issues. During the first year of the project the work was started and several concepts were developed to prepare for bench-scale testing. Power

  9. Development of precipitated iron Fischer-Tropsch catalysts. Quarterly technical progress report, 1 January 1996--31 March 1996

    SciTech Connect

    Bukur, D.B.

    1996-06-03

    The overall contract objectives are to: (1) demonstrate repeatability of performance and preparation procedure of two high activity, high alpha iron Fischer-Tropsch catalysts synthesized at Texas A&M University (TAMU); (2) seek potential improvements in the catalyst performance through variations in process conditions, pretreatment procedures and/or modifications in catalyst synthesis; (3) investigate performance of catalysts in a small scale bubble column slurry reactor, and (4) investigate feasibility of producing catalysts on a large scale in collaboration with a catalyst manufacturer. In order to achieve these objectives the work is divided into ten tasks, which are described and their accomplishments are reported.

  10. Development of precipitated iron Fischer-Tropsch catalysts. Quarterly technical progress report, 1 April 1996--30 June 1996

    SciTech Connect

    Bukur, D.B.; Lang, X.; Ding, Y.; Chokkaram, S.

    1996-09-02

    The overall contract objectives are to: (1) demonstrate repeatability of performance and preparation procedure of two high activity, high alpha iron Fischer-Tropsch catalysts synthesized at Texas A&M University (TAMU) during the DOE Contract DE-AC22-89PC89868; (2) seek potential improvements in the catalyst performance through variations in process conditions, pretreatment procedures and/or modifications in catalyst synthesis; (3) investigate performance of catalysts in a small scale bubble column slurry reactor, and (4) investigate feasibility of producing catalysts on a large scale in collaboration with a catalyst manufacturer. The performance of an iron, and iron-copper-silica catalyst are described.

  11. Iron on mixed zirconia-titania substrate Fischer-Tropsch catalyst and method of making same

    DOEpatents

    Dyer, Paul N.; Nordquist, Andrew F.; Pierantozzi, Ronald

    1986-01-01

    A Fischer-Tropsch catalyst comprising iron co-deposited with or deposited on particles comprising a mixture of zirconia and titania, preferably formed by co-precipitation of compounds convertible to zirconia and titania, such as zirconium and titanium alkoxide. The invention also comprises the method of making this catalyst and an improved Fischer-Tropsch reaction process in which the catalyst is utilized.

  12. CHAIN-LIMITING OPERATION OF FISCHER-TROPSCH REACTOR

    SciTech Connect

    Apostolos A. Nikolopoulos; Santosh K. Gangwal

    2003-06-01

    The use of pulsing in Fischer-Tropsch (FT) synthesis to limit the hydrocarbon chain growth and maximize the yield of diesel-range (C{sub 10}-C{sub 20}) products was examined on high-chain-growth-probability ({alpha} {ge} 0.9) FT catalysts. Pulsing experiments were conducted using a stainless-steel fixed-bed micro-reactor, equipped with both on-line (for the permanent gases and light hydrocarbons, C{sub 1}-C{sub 15}) and off-line (for the heavier hydrocarbons, C{sub 10}-C{sub 65}) gas chromatography analysis. Additional experiments were performed using a highly active attrition-resistant iron-based FT synthesis catalyst in a 1-liter continuous stirred-tank rector (CSTR). On both a Co-ZrO{sub 2}/SiO{sub 2} and a Co/Al{sub 2}O{sub 3} FT synthesis catalyst application of H{sub 2} pulsing causes significant increase in CO conversion, and only an instantaneous increase in undesirable selectivity to CH{sub 4}. Increasing the frequency of H{sub 2} pulsing enhances the selectivity to C{sub 10}-C{sub 20} compounds but the chain-growth probability {alpha} remains essentially unaffected. Increasing the duration of H{sub 2} pulsing results in enhancing the maximum obtained CO conversion and an instantaneous selectivity to CH{sub 4}. An optimum set of H{sub 2} pulse parameters (pulse frequency, pulse duration) is required for maximizing the yield of desirable diesel-range C{sub 10}-C{sub 20} products. Application of a suitable H{sub 2} pulse in the presence of added steam in the feed is a simple method to overcome the loss in activity and the shift in paraffin vs. olefin selectivity (increase in the olefin/paraffin ratio) caused by the excess steam. A decrease in syngas concentration has a strong suppressing effect on the olefin/paraffin ratio of the light hydrocarbon products. Higher syngas concentration can increase the chain growth probability {alpha} and thus allow for better evaluation of the effect of pulsing on FT synthesis. On a high-{alpha} Fe/K/Cu/SiO{sub 2} FT

  13. Techno-economic assessment of the Mobil Two-Stage Slurry Fischer-Tropsch/ZSM-5 process

    SciTech Connect

    El Sawy, A.; Gray, D.; Neuworth, M.; Tomlinson, G.

    1984-11-01

    A techno-economic assessment of the Mobil Two-Stage Slurry Fischer-Tropsch reactor system was carried out. Mobil bench-scale data were evaluated and scaled to a commercial plant design that produced specification high-octane gasoline and high-cetane diesel fuel. Comparisons were made with three reference plants - a SASOL (US) plant using dry ash Lurgi gasifiers and Synthol synthesis units, a modified SASOL plant with a British Gas Corporation slagging Lurgi gasifier (BGC/Synthol) and a BGC/slurry-phase process based on scaled data from the Koelbel Rheinpreussen-Koppers plant. A conceptual commercial version of the Mobil two-stage process shows a higher process efficiency than a SASOL (US) and a BGC/Synthol plant. The Mobil plant gave lower gasoline costs than obtained from the SASOL (US) and BGC/Synthol versions. Comparison with published data from a slurry-phase Fischer-Tropsch (Koelbel) unit indicated that product costs from the Mobil process were within 6% of the Koelbel values. A high-wax version of the Mobil process combined with wax hydrocracking could produce gasoline and diesel fuel at comparable cost to the lowest values achieved from prior published slurry-phase results. 27 references, 18 figures, 49 tables.

  14. An Ab Initio Approach Towards Engineering Fischer-Tropsch Surface Chemistry

    SciTech Connect

    Matthew Neurock

    2006-09-11

    One of the greatest societal challenges over the next decade is the production of cheap, renewable energy for the 10 billion people that inhabit the earth. This will require the development of various energy sources which will likely include fuels derived from methane, coal, and biomass and alternatives sources such as solar, wind and nuclear energy. One approach will be to synthesize gasoline and other fuels from simpler hydrocarbons such as CO derived from methane or other U.S. based sources such as coal. Syngas (CO and H{sub 2}) can be readily converted into higher molecular weight hydrocarbons through Fischer-Tropsch synthesis. Fischer-Tropsch (FT) synthesis involves the adsorption and the activation of CO and H{sub 2}, the subsequent propagation steps including hydrogenation and carbon-carbon coupling, followed by chain termination reactions. The current commercial catalysts are supported Co and Co-alloys particles. This project set out with the following objectives in mind: (1) understand the reaction mechanisms that control FT kinetics, (2) predict how the intrinsic metal-adsorbate bond affects the sequence of elementary steps in FT, (3) establish the effects of the reaction environment on catalytic activity and selectivity, (4) construct a first-principles based algorithm that can incorporate the detailed atomic surface structure and simulate the kinetics for the myriad of elementary pathways that make up FT chemistry, and (5) suggest a set of optimal features such as alloy composition and spatial configuration, oxide support, distribution of defect sites. As part of this effort we devoted a significant portion of time to develop an ab initio based kinetic Monte Carlo simulation which can be used to follow FT surface chemistry over different transition metal and alloy surfaces defined by the user. Over the life of this program, we have used theory and have developed and applied stochastic Monte Carlo simulations in order to establish the fundamental

  15. Attrition resistant catalysts for slurry-phase Fischer-Tropsch process

    SciTech Connect

    K. Jothimurugesan

    1999-11-01

    The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T because they are relatively inexpensive and possess reasonable activity for F-T synthesis (FTS). Their most advantages trait is their high water-gas shift (WGS) activity compared to their competitor, namely cobalt. This enables Fe F-T catalysts to process low H{sub 2}/CO ratio synthesis gas without an external shift reaction step. However, a serious problem with the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, make the separation of catalyst from the oil/wax product very difficult if not impossible, an d result in a steady loss of catalyst from the reactor. The objectives of this research were to develop a better understanding of the parameters affecting attrition of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance.

  16. In situ observation of self-assembled hydrocarbon Fischer-Tropsch products on a cobalt catalyst

    NASA Astrophysics Data System (ADS)

    Navarro, Violeta; van Spronsen, Matthijs A.; Frenken, Joost W. M.

    2016-10-01

    Fischer-Tropsch synthesis is a heterogeneous catalytic reaction that creates approximately 2% of the world's fuel. It involves the synthesis of linear hydrocarbon molecules from a gaseous mixture of carbon monoxide and hydrogen at high pressures (from a few to tens of bars) and high temperatures (200-350 °C). To gain further insight into the fundamental mechanisms of this industrial process, we have used a purpose-built scanning tunnelling microscope to monitor a cobalt model catalyst under reaction conditions. We show that, after 30 minutes of reaction, the terraces of the cobalt catalyst are covered by parallel arrays of stripes. We propose that the stripes are formed by the self-assembly of linear hydrocarbon product molecules. Surprisingly, the width of the stripes corresponds to molecules that are 14 or 15 carbon atoms long. We introduce a simple model that explains the accumulation of such long molecules by describing their monomer-by-monomer synthesis and explicitly accounting for their thermal desorption.

  17. Fischer-Tropsch Cobalt Catalyst Activation and Handling Through Wax Enclosure Methods

    NASA Technical Reports Server (NTRS)

    Klettlinger, Jennifer L. S.; Yen, Chia H.; Nakley, Leah M.; Surgenor, Angela D.

    2016-01-01

    Fischer-Tropsch (F-T) synthesis is considered a gas to liquid process which converts syn-gas, a gaseous mixture of hydrogen and carbon monoxide, into liquids of various hydrocarbon chain length and product distributions. Cobalt based catalysts are used in F-T synthesis and are the focus of this paper. One key concern with handling cobalt based catalysts is that the active form of catalyst is in a reduced state, metallic cobalt, which oxidizes readily in air. In laboratory experiments, the precursor cobalt oxide catalyst is activated in a fixed bed at 350 ?C then transferred into a continuous stirred tank reactor (CSTR) with inert gas. NASA has developed a process which involves the enclosure of active cobalt catalyst in a wax mold to prevent oxidation during storage and handling. This improved method allows for precise catalyst loading and delivery into a CSTR. Preliminary results indicate similar activity levels in the F-T reaction in comparison to the direct injection method. The work in this paper was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.

  18. Impact of developing technology on indirect liquefaction

    SciTech Connect

    Gray, D.; Lytton, M.; Neuworth, M.; Tomlinson, G.

    1980-11-01

    The status of commercial technology for indirect liquefaction, as exemplified by SASOL facilities in South Africa, is reviewed. The impact of substituting more advanced gasifiers and synthesis systems is then investigated. Slagging BGC/Lurgi, Texaco and Shell-Koppers gasifiers were substituted for the Dry Ash Lurgi units used at SASOL. SASOL SYNTHOL synthesis units were replaced by slurry phase Fischer-Tropsch units employing technology pioneered by Kolbel. The advanced systems were found to have a highly favorable impact on plant efficiency, product distribution and gasoline cost. If all the projected technical improvements can be realized for indirect liquefaction, the yields of refined transportation fuels per ton of coal will approach those anticipated for direct liquefaction processes.

  19. Carbon induced selective regulation of cobalt-based Fischer-Tropsch catalysts by ethylene treatment.

    PubMed

    Zhai, Peng; Chen, Pei-Pei; Xie, Jinglin; Liu, Jin-Xun; Zhao, Huabo; Lin, Lili; Zhao, Bo; Su, Hai-Yan; Zhu, Qingjun; Li, Wei-Xue; Ma, Ding

    2017-02-10

    Various carbonaceous species were controllably deposited on Co/Al2O3 catalysts using ethylene as carbon source during the activation process for Fischer-Tropsch synthesis (FTS). Atomic, polymeric and graphitic carbon were distinguished by Raman spectroscopy, thermoanalysis and temperature programmed hydrogenation. Significant changes occurred in both the catalytic activity and selectivity toward hydrocarbon products after ethylene treatment. The activity decreased along with an increase in CH4 selectivity, at the expense of a remarkable decrease of heavy hydrocarbon production, resulting in enhanced selectivity for the gasoline fraction. In situ XPS experiments show the possible electron transfer from cobalt to carbon and the blockage of metallic cobalt sites, which is responsible for the deactivation of the catalyst. DFT calculations reveal that the activation barrier (Ea) of methane formation decreases by 0.61 eV on the carbon-absorbed Co(111) surface, whereas the Ea of the CH + CH coupling reaction changes unnoticeably. Hydrogenation of CHx to methane becomes the preferable route among the elementary reactions on the Co(111) surface, leading to dramatic changes in the product distribution. Detailed coke-induced deactivation mechanisms of Co-based catalysts during FTS are discussed.

  20. The selective catalytic cracking of Fischer-Tropsch liquids to high value transportation fuels. Final report

    SciTech Connect

    Schwartz, M.M.; Reagon, W.J.; Nicholas, J.J.; Hughes, R.D.

    1994-11-01

    Amoco Oil Company, investigated a selective catalytic cracking process (FCC) to convert the Fischer-Tropsch (F-T) gasoline and wax fractions to high value transportation fuels. The primary tasks of this contract were to (1) optimize the catalyst and process conditions of the FCC process for maximum conversion of F-T wax into reactive olefins for later production of C{sub 4}{minus}C{sub 8} ethers, and (2) use the olefin-containing light naphtha obtained from FCC processing of the F-T wax as feedstock for the synthesis of ethers. The catalytic cracking of F-T wax feedstocks gave high conversions with low activity catalysts and low process severities. HZSM-5 and beta zeolite catalysts gave higher yields of propylene, isobutylene, and isoamylenes but a lower gasoline yield than Y zeolite catalysts. Catalyst selection and process optimization will depend on product valuation. For a given catalyst and process condition, Sasol and LaPorte waxes gave similar conversions and product selectivities. The contaminant iron F-T catalyst fines in the LaPorte wax caused higher coke and hydrogen yields.

  1. Fischer-Tropsch reaction on a thermally conductive and reusable silicon carbide support.

    PubMed

    Liu, Yuefeng; Ersen, Ovidiu; Meny, Christian; Luck, Francis; Pham-Huu, Cuong

    2014-05-01

    The Fischer-Tropsch (FT) process, in which synthesis gas (syngas) derived from coal, natural gas, and biomass is converted into synthetic liquid fuels and chemicals, is a strongly exothermic reaction, and thus, a large amount of heat is generated during the reaction that could severely modify the overall selectivity of the process. In this Review, we report the advantages that can be offered by different thermally conductive supports, that is, carbon nanomaterials and silicon carbide, pure or doped with different promoters, for the development of more active and selective FT catalysts. This Review follows a discussion regarding the clear trend in the advantages and drawbacks of these systems in terms of energy efficiency and catalytic performance for this most-demanded catalytic process. It is demonstrated that the use of a support with an appropriate pore size and thermal conductivity is an effective strategy to tune and improve the activity of the catalyst and to improve product selectivity in the FT process. The active phase and the recovery of the support, which also represents a main concern in terms of the large amount of FT catalyst used and the cost of the active cobalt phase, is also discussed within the framework of this Review. It is expected that a thermally conductive support such as β-SiC will not only improve the development of the FT process, but that it will also be part of a new support for different catalytic processes for which high catalytic performance and selectivity are strongly needed.

  2. Meteorites, Organics and Fischer-Tropsch Type Reaction: Production and Destruction

    NASA Technical Reports Server (NTRS)

    Johnson, Natasha M.; Burton, A. S.; Nurth, J. A., III

    2011-01-01

    There has been an ongoing debate about the relative importance about the various chemical reactions that fonned organics in the early solar system. One proposed method that has long been recognized as a potential source of organics is Fischer-Tropsch type (FTT) synthesis. This process is commonly used in industry to produce fuels (i.e., complex hydrocarbons) by catalytic hydrogenation of carbon monoxide. Hill and Nuth were the first to publish results of FTT experiments that also included Haber-Bosch (HB) processes (hydrogenation of nitrogen. Their findings included the production of nitrilebearing compounds as well as trace amounts of methyl amine. Previous experience with these reactions revealed that the organic coating deposited on the grains is also an efficient catalyst and that the coating is composed of insoluble organic matter (10M) and could be reminiscent of the organic matrix found in some meteorites. This current set of FTT-styled experiments tracks the evolution of a set of organics, amino acids, in detail.

  3. SEPARATION OF FISCHER-TROPSCH WAX PRODUCTS FROM ULTRAFINE IRON CATALYST PARTICLES

    SciTech Connect

    James K. Neathery; Gary Jacobs; Burtron H. Davis

    2004-03-31

    In this reporting period, a fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of production since the reaction is highly exothermic. Consequently, heavy wax products must be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase FTS. The separation problem is further compounded by catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbon particles. Existing pilot-scale equipment was modified to include a filtration test apparatus. After undergoing an extensive plant shakedown period, filtration tests with cross-flow filter modules using simulant FTS wax slurry were conducted. The focus of these early tests was to find adequate mixtures of polyethylene wax to simulate FTS wax. Catalyst particle size analysis techniques were also developed. Initial analyses of the slurry and filter permeate particles will be used by the research team to design improved filter media and cleaning strategies.

  4. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 11, March 26, 1993--June 26, 1993

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1994-05-01

    The objectives of this contract are to develop a technology for the production of active and stable iron (Fe) Fischer-Tropsch catalysts for use in slurry-phase synthesis reactors and to develop a scaleup procedure for large-scale synthesis of such catalysts for process development and long-term testing in slurry bubble-column reactors. With a feed containing hydrogen (H{sub 2}) and carbon monoxide (CO) in the molar ratio of 0.5 to 1.0 to the slurry bubble-column reactor, the catalyst performance target is 88% CO+H{sub 2} conversion at a minimum space velocity of 2.4 NL/hr/g Fe. The desired sum of methane and ethane selectivities is no more than 4%, and the conversion loss per week is not to exceed 1%.

  5. Thermal Stability Testing of a Fischer-Tropsch Fuel and Various Blends with Jet A

    NASA Technical Reports Server (NTRS)

    Klettlinger, Jennifer Suder; Surgenor, Angela; Yen, Chia

    2010-01-01

    Fischer-Tropsch (F-T) jet fuel composition differs from petroleum-based, conventional commercial jet fuel because of differences in feedstock and production methodology. Fischer-Tropsch fuel typically has a lower aromatic and sulfur content and consists primarily of iso and normal parafins. The ASTM D3241 specification for Jet Fuel Thermal Oxidation Test (JFTOT) break point testing method was used to test the breakpoint of a baseline conventional Jet A, a commercial grade F-T jet fuel, and various blends of this F-T fuel in Jet A. The testing completed in this report was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.

  6. Moessbauer study of iron-carbide growth and Fischer-Tropsch activity

    SciTech Connect

    Rao, K.R.P.M.; Huggins, F.E.; Huffman, G.P.

    1995-12-31

    There is a need to establish a correlation between the Fischer-Tropsch (FT) activity of an iron-based catalyst and the catalyst phase during FT synthesis. The nature of iron phases formed during activation and FT synthesis is influenced by the gas used for activation. Moessbauer investigations of iron-based catalysts subjected to pretreatment in gas atmospheres containing mixtures of CO, H{sub 2}, and He have been carried out. Studies on UCI 1185-57 catalyst indicate that activation of the catalyst in CO leads to the formation of 100% magnetite and the magnetite formed gets rapidly converted to at least 90% of x-Fe{sub 5}C{sub 2} during activation. The x-Fe{sub 5}C{sub 2} formed during activation gets partly (= 25%) converted back to Fe{sub 3}O{sub 4} during FT synthesis and both x-Fe{sub 5}C{sub 2} and Fe{sub 3}O{sub 4} reach constant values. On the other hand, activation of the catalyst in synthesis gas leads to formation of Fe{sub 3}O{sub 4} and which is slowly converted to x-Fe{sub 5}C{sub 2} and e-Fe{sub 2.2}C during activation, and both carbide phases increase slowly during FT synthesis. FT synthesis activity is found to give rise to {approx} 70% (H2+CO) conversion in the case of CO activated catalyst as compared to {approx} 20% (H2+CO) conversion in the case of synthesis gas-activated catalyst.

  7. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 5, September 26, 1991--December 26, 1991

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1992-12-22

    Objective is to develop producing active, stable iron Fischer-Tropsch catalysts for use in slurry-phase synthesis reactors and to synthesize such catalysts on a large scale for process development and long-term testing in slurry bubble-column reactors. A mixed oxalate of Fe, Cu, and K was prepared; a catalyst will be prepared from this material. An evaluation run was performed on an Fe-based UCI catalyst, which was shown to produce low levels of C{sub 1} and C{sub 2} paraffins; e.g., at the end of the run, when the catalyst was converting 60% of the CO, the C{sub 1} and C{sub 2} paraffin selectivities were 4.2 and 1.0, respectively.

  8. Effect of Surface Modification by Chelating Agents on Fischer- Tropsch Performance of Co/SiO{sub 2} Catalysts

    SciTech Connect

    Bambal, Ashish S.; Kugler, Edwin L.; Gardner, Todd H.; Dadyburjor, Dady B.

    2013-11-14

    The silica support of a Co-based catalyst for Fischer-Tropsch (FT) synthesis was modified by the chelating agents (CAs) nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA). After the modification, characterization of the fresh and spent catalysts show reduced crystallite sizes, a better-dispersed Co₃O₄ phase on the calcined samples, and increased metal dispersions for the reduced samples. The CA-modified catalysts display higher CO conversions, product yields, reaction rates and rate constants. The improved FT performance of CA-modified catalysts is attributed to the formation of stable complexes with Co. The superior performance of the EDTA-modified catalyst in comparison to the NTA-modified catalyst is due to the higher affinity of the former for complex formation with Co ions.

  9. FISCHER-TROPSCH FUELS PRODUCTION AND DEMONSTRATION PROJECT

    SciTech Connect

    Stephen P. Bergin

    2003-04-23

    This project has two primary purposes: (1) Build a small-footprint (SFP) fuel production plant to prove the feasibility of this relatively transportable technology on an intermediate scale (i.e. between laboratory-bench and commercial capacity) and produce as much as 150,000 gallons of hydrogen-saturated Fischer-Tropsch (FT) diesel fuel; and (2) Use the virtually sulfur-free fuel produced to demonstrate (over a period of at least six months) that it can not only be used in existing diesel engines, but that it also can enable significantly increased effectiveness and life of the next-generation exhaust-after-treatment emission control systems that are currently under development and that will be required for future diesel engines. Furthermore, a well-to-wheels economic analysis will be performed to characterize the overall costs and benefits that would be associated with the actual commercial production, distribution and use of such FT diesel fuel made by the process under consideration, from the currently underutilized (or entirely un-used) energy resources targeted, primarily natural gas that is stranded, sub-quality, off-shore, etc. During the first year of the project, which is the subject of this report, there have been two significant areas of progress: (1) Most of the preparatory work required to build the SFP fuel-production plant has been completed, and (2) Relationships have been established, and necessary project coordination has been started, with the half dozen project-partner organizations that will have a role in the fuel demonstration and evaluation phase of the project. Additional project tasks directly related to the State of Alaska have also been added to the project. These include: A study of underutilized potential Alaska energy resources that could contribute to domestic diesel and distillate fuel production by providing input energy for future commercial-size SFP fuel production plants; Demonstration of the use of the product fuel in a heavy

  10. Separation of Fischer-Tropsch Wax Products from Ultrafine Iron Catalyst Particles

    SciTech Connect

    James K. Neathery; Gary Jacobs; Amitava Sarkar; Burtron H. Davis

    2005-09-30

    In this reporting period, a study of ultra-fine iron catalyst filtration was initiated to study the behavior of ultra-fine particles during the separation of Fischer-Tropsch Synthesis (FTS) liquids filtration. The overall focus of the program is with slurry-phase FTS in slurry bubble column reactor systems. Hydrocarbon products must be separated from catalyst particles before being removed from the reactor system. An efficient wax product/catalyst separation system is a key factor for optimizing operating costs for iron-based slurry-phase FTS. Previous work has focused on catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbon particles. With the current study, we are investigating how the filtration properties are affected by these chemical and physical changes of the catalyst slurry during activation/synthesis. The change of particle size during the slurry-phase FTS has monitored by withdrawing catalyst sample at different TOS. The measurement of dimension of the HRTEM images of samples showed a tremendous growth of the particles. Carbon rims of thickness 3-6 nm around the particles were observed. This growth in particle size was not due to carbon deposition on the catalyst. A conceptual design and operating philosophy was developed for an integrated wax filtration system for a 4 liter slurry bubble column reactor to be used in Phase II of this research program. The system will utilize a primary inertial hydroclone followed by a Pall Accusep cross-flow membrane. Provisions for cleaned permeate back-pulsing will be included to as a flux maintenance measure.

  11. SEPARATION OF FISCHER-TROPSCH WAX PRODUCTS FROM ULTRAFINE IRON CATALYST PARTICLES

    SciTech Connect

    James K. Neathery; Gary Jacobs; Burtron H. Davis

    2005-03-31

    In this reporting period, a fundamental filtration study was continued to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. The overall focus of the program is with slurry-phase FTS in slurry bubble column reactor systems. Hydrocarbon products must be separated from catalyst particles before being removed from the reactor system. An efficient wax product/catalyst separation system is a key factor for optimizing operating costs for iron-based slurry-phase FTS. Previous work has focused on catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbon particles. With the current study, we are investigating how the filtration properties are affected by these chemical and physical changes of the catalyst slurry during activation/synthesis. In this reporting period, a series of crossflow filtration experiments were initiated to study the effect of olefins and oxygenates on the filtration flux and membrane performance. Iron-based FTS reactor waxes contain a significant amount of oxygenates, depending on the catalyst formulation and operating conditions. Mono-olefins and aliphatic alcohols were doped into an activated iron catalyst slurry (with Polywax) to test their influence on filtration properties. The olefins were varied from 5 to 25 wt% and oxygenates from 6 to 17 wt% to simulate a range of reactor slurries reported in the literature. The addition of an alcohol (1-dodecanol) was found to decrease the permeation rate while the olefin added (1-hexadecene) had no effect on the permeation rate. A passive flux maintenance technique was tested that can temporarily increase the permeate rate for 24 hours.

  12. Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

    PubMed Central

    2011-01-01

    This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), CO-chemisorption, transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM-EDX) and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions. H2-TPR analysis of cobalt catalyst indicated three temperature regions at 506°C (low), 650°C (medium) and 731°C (high). The incorporation of iron up to 30% into cobalt catalysts increased the reduction, CO chemisorption and number of cobalt active sites of the catalyst while an opposite trend was observed for the iron-riched bimetallic catalysts. The CO conversion was 6.3% and 4.6%, over the monometallic cobalt and iron catalysts, respectively. Bimetallic catalysts enhanced the CO conversion. Amongst the catalysts studied, bimetallic catalyst with the composition of 70Co30Fe showed the highest CO conversion (8.1%) while exhibiting the same product selectivity as that of monometallic Co catalyst. Monometallic iron catalyst showed the lowest selectivity for C5+ hydrocarbons (1.6%). PMID:22047220

  13. SEPARATION OF FISCHER-TROPSCH WAX PRODUCTS FROM ULTRAFINE IRON CATALYST PARTICLES

    SciTech Connect

    James K. Neathery; Gary Jacobs; Burtron H. Davis

    2004-09-30

    In this reporting period, a fundamental filtration study was continued to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. The overall focus of the program is with slurry-phase FTS in slurry bubble column reactor systems. Hydrocarbon products must be separated from catalyst particles before being removed from the reactor system. An efficient wax product/catalyst separation system is a key factor for optimizing operating costs for iron-based slurry-phase FTS. Previous work has focused on catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbon particles. With the current study, we are investigating how the filtration properties are affected by these chemical and physical changes of the catalyst slurry during activation/synthesis. The shakedown phase of the pilot-scale filtration platform was completed at the end of the last reporting period. A study of various molecular weight waxes was initiated to determine the effect of wax physical properties on the permeation rate without catalyst present. As expected, the permeation flux was inversely proportional to the nominal average molecular weight of the polyethylene wax. Even without catalyst particles present in the filtrate, the filtration membranes experience fouling during an induction period on the order of days on-line. Another long-term filtration test was initiated using a batch of iron catalyst that was previously activated with CO to form iron carbide in a separate continuous stirred tank reactor (CSTR) system. The permeation flux stabilized more rapidly than that experienced with unactivated catalyst tests.

  14. Effect of Thermal Treatment on Structure and Catalytic Activity of Supported Fischer-Tropsch Nano-Cobalt Catalysts for Clean Fuels

    NASA Astrophysics Data System (ADS)

    Chu, Wei; Hong, J. P.; Payen, E.; Dai, X. Y.

    2007-12-01

    A series of 15%Co/Al2O3 catalysts were prepared by incipient wetness impregnation under various calcination conditions (90-500°C), and were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy experiments (XPS), temperature programmed reduction, and catalytic measurements of hydrogenation of carbon monoxide to long-chained hydrocarbons leading to clean fuels (Fischer-Tropsch synthesis). The results of XPS show the presence of incompletely decomposed cobalt nitrate for catalysts calcined at 90-200°C, and the presence of Co3O4 for catalysts calcined at 200-500°C. For the four alumina-supported nano-cobalt catalysts with different thermal treatment (200-500°C), XRD and XPS results illustrated that there were mainly nano Co3O4 crystalite phases of 9-10 nm and the size of cobalt nano-particles did almost not change with the different temperature of thermal treatment. This was different from that of silica-supported cobalt catalysts. The supported cobalt catalyst (CoAp340 sample) calcinated at 340°C presented a better activity for Fischer Tropsch synthesis to clean fuels, at mild conditions like atmospheric pressure (100 kPa), 1800 mL/g/h and 190°C rather than high pressure (2 MPa or more).

  15. Effect of Aromatic Concentration of a Fischer-Tropsch Fuel on Thermal Stability

    NASA Technical Reports Server (NTRS)

    Klettlinger, Jennifer Lindsey Suder

    2012-01-01

    Fischer-Tropsch (F-T) jet fuel composition differs from petroleum-based, conventional commercial jet fuel because of differences in feedstock and production methodology. Fischer­ Tropsch fuel typically has a lower aromatic and sulfur content and consists primarily of iso and normal parafins. The ASTM D3241 specification for Jet Fuel Thermal Oxidation Test (JFTOT) break point testing method was used to test the breakpoint of a baseline commercial grade F-T jet fuel, and various blends of this F-T fuel with an aromatic solution. The goal of this research is to determine the effect of aromatic content on the thermal stability of Fischer-Tropsch fuel. The testing completed in this report was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.

  16. Fischer-Tropsch Synthesis on Ceramic Monolith-Structured Catalysts

    SciTech Connect

    Wang, Yong; Liu, Wei

    2009-04-19

    This paper reports recent research results about impact of different catalyst bed configurations on FT reaction product distribution. A CoRe/γ-alumina catalyst is prepared in bulk particle form and tested in the packed bed reactor at a size of 60 to 100 mesh. The same catalyst is ball milled and coated on a ceramic monolith support structure of channel size about 1mm. The monolith catalyst module is tested in two different ways, as a whole piece and as well-defined channels. Steady-state reaction conversion is measured at various temperatures under constant H2/CO feed ratio of 2 and reactor pressure of 25 bar. Detailed product analysis is performed. Significant formation of wax is evident with the packed particle bed and with the monolith catalyst that is improperly packed. By contrast, the wax formation is not detected in the liquid product by confining the reactions inside the monolith channel. This study presents an important finding about the structured catalyst/reactor system that the product distribution highly depends on the way how the structured reactor is set up. Even if the same catalyst and same reaction conditions (T, P, H2/oil ratio) are used, hydrodynamics (or flow conditions) inside a structured channel can have a significant impact on the product distribution.

  17. Microscopic Understanding of Fischer-Tropsch Synthesis on Ruthenium

    SciTech Connect

    Chavez, Donna L.

    2014-10-01

    Total energy calculations and scanning tunneling microscope (STM) image simulations were conducted in an effort to interpret new experimental images of CO and H adsorbed on the closepacked surface of ruthenium metal. The images are remarkable in suggesting that the adsorbed species are intermixed, plausibly accounting for the superior catalytic activity of this metal in forming hydrocarbons. Insight was gained over the short duration of the project, but a more accurate method of simulating images will be required before contact between theory and experiment points to a final result.

  18. IMPROVED IRON CATALYSTS FOR SLURRY PHASE FISCHER-TROPSCH SYNTHESIS

    SciTech Connect

    Dr. Dragomir B. Bukur; Dr. Lech Nowicki; Victor Carreto-Vazquez; Dr. Wen-Ping Ma

    2001-11-28

    PureVision Technology, Inc. (PureVision) of Fort Lupton, Colorado is developing a process for the conversion of lignocellulosic biomass into fuel-grade ethanol and specialty chemicals in order to enhance national energy security, rural economies, and environmental quality. Lignocellulosic-containing plants are those types of biomass that include wood, agricultural residues, and paper wastes. Lignocellulose is composed of the biopolymers cellulose, hemicellulose, and lignin. Cellulose, a polymer of glucose, is the component in lignocellulose that has potential for the production of fuel-grade ethanol by direct fermentation of the glucose. However, enzymatic hydrolysis of lignocellulose and raw cellulose into glucose is hindered by the presence of lignin. The cellulase enzyme, which hydrolyzes cellulose to glucose, becomes irreversibly bound to lignin. This requires using the enzyme in reagent quantities rather than in catalytic concentration. The extensive use of this enzyme is expensive and adversely affects the economics of ethanol production. PureVision has approached this problem by developing a biomass fractionator to pretreat the lignocellulose to yield a highly pure cellulose fraction. The biomass fractionator is based on sequentially treating the biomass with hot water, hot alkaline solutions, and polishing the cellulose fraction with a wet alkaline oxidation step. In September 2001 PureVision and Western Research Institute (WRI) initiated a jointly sponsored research project with the U.S. Department of Energy (DOE) to evaluate their pretreatment technology, develop an understanding of the chemistry, and provide the data required to design and fabricate a one- to two-ton/day pilot-scale unit. The efforts during the first year of this program completed the design, fabrication, and shakedown of a bench-scale reactor system and evaluated the fractionation of corn stover. The results from the evaluation of corn stover have shown that water hydrolysis prior to alkaline hydrolysis may be beneficial in removing hemicellulose and lignin from the feedstock. In addition, alkaline hydrolysis has been shown to remove a significant portion of the hemicellulose and lignin. The resulting cellulose can be exposed to a finishing step with wet alkaline oxidation to remove the remaining lignin. The final product is a highly pure cellulose fraction containing less than 1% of the native lignin with an overall yield in excess of 85% of the native cellulose. This report summarizes the results from the first year's effort to move the technology to commercialization.

  19. Moessbauer study of iron-carbide growth and Fischer-Tropsch activity

    SciTech Connect

    Rao, K.R.P.M.; Huggins, F.E.; Huffman, G.P.

    1995-12-31

    There is a need to establish a correlation between the Fischer-Tropsch (FT) activity of an iron-based catalyst and the catalyst phase during FT synthesis. The nature of iron phases formed during activation and FT synthesis is influenced by the nature of the gas and pressure apart from other parameters like temperature, flow rate etc., used for activation. Moessbauer investigations of iron-based catalysts subjected to pretreatment at two different pressures in gas atmospheres containing mixtures of CO, H{sub 2}, and He have been carried out. Studies on UCI 1185-57 (64%Fe{sub 2}O{sub 3}/5%CuO/1%K{sub 2}O/30% Kaolin) catalyst indicate that activation of the catalyst in CO at 12 atms. leads to the formation of 100% magnetite and the magnetite formed gets rapidly converted to at least 90% of {chi}-Fe{sub 5}C{sub 2} during activation. The FT activity was found to be good at 70-80% of (H{sub 2}+CO) conversion. On the other hand, activation. The FT activity was found to be good at 70-80% of (H{sub 2}+CO) conversion. On the other hand, activation of the catalyst in synthesis gas at 12 atms. leads to formation of Fe{sub 3}O{sub 4} and it gets sluggishly converted to {chi}-Fe{sub 5}C{sub 2} and {epsilon}-Fe{sub 2.2}C during activation and both continue to grow slowly during FT synthesis. FT activity is found to be poor. Pretreatment of the catalyst, 100fe/3.6Si/0.71K at a low pressure of 1 atms. in syngas gave rise to the formation of {chi}-Fe{sub 5}C{sub 2} and good FT activity. On the other hand, pretreatment of the catalyst, 100Fe/3.6Si/0.71K at a relatively high pressure of 12 atms. in syngas did not give rise to the formation any carbide and FT activity was poor.

  20. Heat transfer and bubble dynamics in slurry bubble columns for Fischer-Tropsch clean alternative energy

    NASA Astrophysics Data System (ADS)

    Wu, Chengtian

    With the increasing demand for alternative energy resources, the Fischer-Tropsch (FT) process that converts synthesis gas into clean liquid fuels has attracted more interest from the industry. Slurry bubble columns are the most promising reactors for FT synthesis due to their advantages over other reactors. Successful operation, design, and scale-up of such reactors require detailed knowledge of hydrodynamics, bubble dynamics, and transport characteristics. However, most previous studies have been conducted at ambient pressure or covered only low superficial gas velocities. The objectives of this study were to experimentally investigate the heat transfer coefficient and bubble dynamics in slurry bubble columns at conditions that can mimic FT conditions. The air-C9C 11-FT catalysts/glass beads systems were selected to mimic the physical properties of the gas, liquid, and solid phases at commercial FT operating conditions. A heat transfer coefficient measurement technique was developed, and for the first time, this technique was applied in a pilot scale (6-inch diameter) high pressure slurry bubble column. The effects of superficial gas velocity, pressure, solids loading, and liquid properties on the heat transfer coefficients were investigated. Since the heat transfer coefficient can be affected by the bubble properties (Kumar et al., 1992), in this work bubble dynamics (local gas holdup, bubble chord length, apparent bubble frequency, specific interfacial area, and bubble velocity) were studied using the improved four-point optical probe technique (Xue et al., 2003; Xue, 2004). Because the four-point optical technique had only been successfully applied in a churn turbulent flow bubble column (Xue, 2004), this technique was first assessed in a small scale slurry bubble column in this study. Then the bubble dynamics were studied at the same conditions as the heat transfer coefficient investigation in the same pilot scale column. The results from four-point probe

  1. A chemical route to the formation of water in circumstellar envelopes around carbon-rich asymptotic branch stars: Fischer-Tropsch catalysis

    NASA Technical Reports Server (NTRS)

    Willacy, K.

    2004-01-01

    Fischer-Tropsch catalysis has been suggested as a means of driving hydrocarbon chemistry in oxygen rich regions such as the protosolar nebula. In addition to producing hydrocarbons, Fischer-Tropsch catalysis also produces water, and it is therefore possible that such processes could account for the recent observations of water in the circumstellar envelope of asymptotic giant branch star IRC +10216.

  2. The role of catalyst activation on the activity and attrition of precipitated iron Fischer-Tropsch catalysts

    SciTech Connect

    Datye, A.K.; Shroff, M.D.; Harrington, M.S.; Coulter, K.E.; Sault, A.G.; Jackson, N.B.

    1995-12-31

    The results of this work indicate that magnetite is not catalytically active for Fischer-Tropsch Synthesis (FTS) in precipitated, unsupported iron catalysts, but the formation of the carbide phase is necessary to obtain FTS activity. The transformation of magnetite to carbide, though essential to obtain FTS activity, also causes the catalyst to break down. This can lead to severe problems during operation in a commercial slurry phase reactor. The results presented here imply that activation and attrition are simultaneous and complementary processes. In another study, we show that the catalyst can also under go attrition on a micron scale which is caused by lack of strength of the forces binding the catalyst primary particles in the agglomerates. Both these processes can make wax separation and product recovery extremely difficult. In this study, we have also shown that H{sub 2} reduction of this catalyst to metallic iron is detrimental to subsequent catalyst activity and causes a loss of surface area due to sintering of the iron crystallites. Reduction to metallic Fe also causes impurities such as S to segregate to the surface causing a complete loss of FTS activity. It has been shown that even submonolayer amounts of S can cause a dramatic decrease in FTS activity, hence reduction to metallic Fe should be avoided during activation of these catalysts. We have shown, however, that a mild H{sub 2} reduction to magnetite does not lead to S segregation to the surface, and is therefore acceptable.

  3. Thermal Stability Testing of Fischer-Tropsch Fuel and Various Blends with Jet A, as Well as Aromatic Blend Additives

    NASA Technical Reports Server (NTRS)

    Klettlinger, J.; Rich, R.; Yen, C.; Surgenor, A.

    2011-01-01

    Fischer-Tropsch (F-T) jet fuel composition differs from petroleum-based, conventional commercial jet fuel because of differences in feedstock and production methodology. Fischer-Tropsch fuel typically has a lower aromatic and sulfur content and consists primarily of iso and normal parafins. The ASTM D3241 specification for Jet Fuel Thermal Oxidation Test (JFTOT) break point testing method was used to test the breakpoint of a baseline conventional Jet A, a commercial grade F-T jet fuel, and various blends of this F-T fuel in Jet A. The testing completed in this report was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.

  4. Liquid phase Fischer-Tropsch (II) demonstration in the Laporte Alternative Fuels Development Unit. Final topical report. Volume 7, Appendix. Task 1, Engineering modifications (Fischer-Tropsch II demonstration) and Task 2, AFDU shakedown, operations, deactivation and disposal (Fischer-Tropsch II demonstration)

    SciTech Connect

    Bhatt, B.L.

    1995-09-01

    This report presents results from a demonstration of Liquid Phase Fischer-Tropsch (LPFT) technology in DOE`s Alternative Fuels Development Unit (AFDU) at LaPorte, Texas. The run was conducted in a bubble column at the AFDU in May--June 1994. The 10-day run demonstrated a very high level of reactor productivity for LPFT, more than five times the previously demonstrated productivity (1). The productivity was constrained by mass transfer limitations, perhaps due to slurry thickening as a result of carbon formation on the catalyst. With a cobalt catalyst or an improved iron catalyst, if the carbon formation can be avoided, there is significant room for further improvements. This volume contains appendices for: reactor temperature stability; Mott Cross-flow filter test for F-T II; Fischer-Tropsch II run authorizations; Fischer-Tropsch II run chronology; liquid compositions; and F-T II / IIA Demonstration Mass Balances.

  5. Design of slurry reactor for indirect liquefaction applications

    SciTech Connect

    Prakash, A.; Bendale, P.G.

    1991-01-01

    The objective of this project is to design and model a conceptual slurry reactor for two indirect liquefaction applications; (1) production of methanol and (2) production of hydrocarbon fuels via Fischer-Tropsch route. A slurry reactor is defined here as a three-phase bubble column reactor using a fine catalyst particle suspension in a high molecular weight liquid. The feed gas is introduced through spargers. It then bubbles through the column providing the agitation necessary for catalyst suspension and mass transfer. The reactor models for the two processes have been formulated using computer simulation. Process data, kinetic and thermodynamic data, heat and mass transfer data and hydrodynamic data have been used in the mathematical models to describe the slurry reactor for each of the two processes. Available data from process development units and demonstration units were used to test and validate the models. Commercial size slurry reactors for methanol and Fischer-Tropsch synthesis were sized using reactor models developed in this report.

  6. Design of slurry reactor for indirect liquefaction applications. Final report

    SciTech Connect

    Prakash, A.; Bendale, P.G.

    1991-12-31

    The objective of this project is to design and model a conceptual slurry reactor for two indirect liquefaction applications; (1) production of methanol and (2) production of hydrocarbon fuels via Fischer-Tropsch route. A slurry reactor is defined here as a three-phase bubble column reactor using a fine catalyst particle suspension in a high molecular weight liquid. The feed gas is introduced through spargers. It then bubbles through the column providing the agitation necessary for catalyst suspension and mass transfer. The reactor models for the two processes have been formulated using computer simulation. Process data, kinetic and thermodynamic data, heat and mass transfer data and hydrodynamic data have been used in the mathematical models to describe the slurry reactor for each of the two processes. Available data from process development units and demonstration units were used to test and validate the models. Commercial size slurry reactors for methanol and Fischer-Tropsch synthesis were sized using reactor models developed in this report.

  7. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-alkane, branched and linear. 721.10103 Section 721.10103 Protection of Environment ENVIRONMENTAL..., branched and linear. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  8. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-alkane, branched and linear. 721.10103 Section 721.10103 Protection of Environment ENVIRONMENTAL..., branched and linear. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  9. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-alkane, branched and linear. 721.10103 Section 721.10103 Protection of Environment ENVIRONMENTAL..., branched and linear. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  10. Enhancing the properties of Fischer-Tropsch fuel produced from syngas over Co/SiO2 catalyst: Lubricity and Calorific Value

    NASA Astrophysics Data System (ADS)

    Doustdar, O.; Wyszynski, M. L.; Mahmoudi, H.; Tsolakis, A.

    2016-09-01

    Bio-fuel produced from renewable sources is considered the most viable alternatives for the replacement of mineral diesel fuel in compression ignition engines. There are several options for biomass derived fuels production involving chemical, biological and thermochemical processes. One of the best options is Fischer Tropsch Synthesis, which has an extensive history of gasoline and diesel production from coal and natural gas. FTS fuel could be one of the best solutions to the fuel emission due to its high quality. FTS experiments were carried out in 16 different operation conditions. Mini structured vertical downdraft fixed bed reactor was used for the FTS. Instead of Biomass gasification, a simulated N2 -rich syngas cylinder of, 33% H2 and 50% N2 was used. FT fuels products were analyzed in GCMS to find the hydrocarbon distributions of FT fuel. Calorific value and lubricity of liquid FT product were measured and compared with commercial diesel fuel. Lubricity has become an important quality, particularly for biodiesel, due to higher pressures in new diesel fuel injection (DFI) technology which demands better lubrication from the fuel and calorific value which is amount of energy released in combustion paly very important role in CI engines. Results show that prepared FT fuel has desirable properties and it complies with standard values. FT samples lubricities as measured by ASTM D6079 standard vary from 286μm (HFRR scar diameter) to 417μm which are less than limit of 520μm. Net Calorific value for FT fuels vary from 9.89 MJ/kg to 43.29 MJ/kg, with six of the samples less than EN 14213 limit of 35MJ/kg. Effect of reaction condition on FT fuel properties was investigated which illustrates that in higher pressure Fischer-Tropsch reaction condition liquid product has better properties.

  11. Size and Promoter Effects on Stability of Carbon-Nanofiber-Supported Iron-Based Fischer-Tropsch Catalysts.

    PubMed

    Xie, Jingxiu; Torres Galvis, Hirsa M; Koeken, Ard C J; Kirilin, Alexey; Dugulan, A Iulian; Ruitenbeek, Matthijs; de Jong, Krijn P

    2016-06-03

    The Fischer-Tropsch Synthesis converts synthesis gas from alternative carbon resources, including natural gas, coal, and biomass, to hydrocarbons used as fuels or chemicals. In particular, iron-based catalysts at elevated temperatures favor the selective production of C2-C4 olefins, which are important building blocks for the chemical industry. Bulk iron catalysts (with promoters) were conventionally used, but these deactivate due to either phase transformation or carbon deposition resulting in disintegration of the catalyst particles. For supported iron catalysts, iron particle growth may result in loss of catalytic activity over time. In this work, the effects of promoters and particle size on the stability of supported iron nanoparticles (initial sizes of 3-9 nm) were investigated at industrially relevant conditions (340 °C, 20 bar, H2/CO = 1). Upon addition of sodium and sulfur promoters to iron nanoparticles supported on carbon nanofibers, initial catalytic activities were high, but substantial deactivation was observed over a period of 100 h. In situ Mössbauer spectroscopy revealed that after 20 h time-on-stream, promoted catalysts attained 100% carbidization, whereas for unpromoted catalysts, this was around 25%. In situ carbon deposition studies were carried out using a tapered element oscillating microbalance (TEOM). No carbon laydown was detected for the unpromoted catalysts, whereas for promoted catalysts, carbon deposition occurred mainly over the first 4 h and thus did not play a pivotal role in deactivation over 100 h. Instead, the loss of catalytic activity coincided with the increase in Fe particle size to 20-50 nm, thereby supporting the proposal that the loss of active Fe surface area was the main cause of deactivation.

  12. Optimisation of the Fischer-Tropsch process using zeolites for tail gas separation.

    PubMed

    Perez-Carbajo, J; Gómez-Álvarez, P; Bueno-Perez, R; Merkling, P J; Calero, S

    2014-03-28

    This work is aimed at optimizing a Fischer-Tropsch Gas To Liquid (GTL) process by recycling compounds of the expelled gas mixture using zeolites for the separation. To that end, we have performed a computational study on four structures widely used in industry. A range of Si/Al ratios have been explored and the effects of their distribution assessed. The ability of the considered force fields and molecular models to reproduce experimental results has been widely proved in previously reported studies. Since this tail gas is formed by a five-component mixture, namely carbon dioxide, methane, carbon monoxide, nitrogen and hydrogen, molecular simulations present clear advantages over experiments. In addition, the viability of the Ideal Adsorption Solution Theory (IAST) has been evaluated to easily handle further separation steps. On the basis of the obtained results, we provide a separation scheme to perform sequentially the separation of CO2, CH4, CO, N2 and H2.

  13. Separation of Fischer-Tropsch Wax from Catalyst by Supercritical Extraction

    SciTech Connect

    Joyce, P.C.; Thies, M.C.

    1997-01-31

    The proposed process of using supercritical fluid extraction in conjunction with the Fischer-Tropsch slurry bubble column reactor has been examined using the ASPEN Plus simulator by the research group at North Carolina State University. Qualitative results have been obtained for varying the following process parameters: solvent-to-wax ratio, solvent type (pentane or hexane), extraction temperature and pressure, and recovery unit temperature and pressure. The region of retrograde behavior was determined for pentane and hexane. Initial results show hexane to be the superior solvent; compared to pentane, hexane requires lower quantities of solvent makeup (the amount of solvent which needs to be added to account for solvent that cannot be recycled), and also results in a lower average molecular weight of slurry in the reactor. Studies indicate that increasing the extraction temperature, extraction pressure, recovery temperature, or solvent to wax ratio decreases the amount solvent makeup required. Decreasing the recovery pressure was found to decrease the makeup flowrate.

  14. Preparation of Fischer-Tropsch catalysts from cobalt/iron hydrotalcites

    SciTech Connect

    Howard, B.H.; Boff, J.J.; Zarochak, M.F.

    1995-12-31

    Compounds with the (hydrotalcites) have properties that make them attractive as precursors for Fischer-Tropsch catalysts. A series of single-phase hydrotalcites with cobalt/iron atom ratios ranging from 75/25 to 25/75 has been synthesized. Mixed cobalt/iron oxides have been prepared from these hydrotalcites by controlled thermal decomposition. Thermal decomposition at temperatures below 600 {degrees}C typically produced a single-phase mixed metal oxide with a spinel structure. The BET surface areas of the spinal samples have been found to be as high as about 150 m{sup 2}/g. Appropriate reducing pretreatments have been developed for several of these spinels and their activity, selectivity, and activity and selectivity maintenance have been examined at 13 MPa in a fixed-bed microreactor.

  15. Morphological transformation during activation and reaction of an iron Fischer-Tropsch catalyst

    SciTech Connect

    Jackson, N.B.; Kohler, S.; Harrington, M.

    1995-12-31

    The purpose of this project is to support the development of slurry-phase bubble column processes being studied at the La Porte Alternative Fuel Development Unit. This paper describes the aspects of Sandia`s recent work regarding the advancement and understanding of the iron catalyst used in the slurry phase process. A number of techniques were used to understand the chemical and physical effects of pretreatment and reaction on the attrition and carbon deposition characteristics of iron catalysts. Unless otherwise stated, the data discussed was derived form experiments carried out on the catalyst chosen for the summer 1994 Fischer-Tropsch run at LaPorte, UCI 1185-78-370, (an L 3950 type) that is 88% Fe{sub 2}O{sub 3}, 11% CuO, and 0.052%K{sub 2}O.

  16. Carbon Isotopic Fractionation in Fischer-Tropsch Type Reactions and Relevance to Meteorite Organics

    NASA Technical Reports Server (NTRS)

    Johnson, Natasha M; Elsila, Jamie E.; Kopstein, Mickey; Nuth, Joseph A., III

    2012-01-01

    Fischer-Tropsch-Type (FTT) reactions have been hypothesized to contribute to the formation of organic compounds in the early solar system, but it has been difficult to identify a signature of such reactions in meteoritic organics. The work reported here examined whether temperature-dependent carbon isotopic fractionation of FTT reactions might provide such a signature. Analyses of bulk organic deposits resulting from FTT experiments show a slight trend towards lighter carbon isotopic ratios with increasing temperature. It is unlikely, however, that these carbon isotopic signatures could provide definitive provenance for organic compounds in solar system materials produced through FTT reactions, because of the small scale of the observed fractionations and the possibility that signatures from many different temperatures may be present in any specific grain.

  17. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts: A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    SciTech Connect

    Manos Mavrikakis; James A. Dumesic; Rahul P. Nabar

    2006-09-29

    Work continued on the development of a microkinetic model of Fischer-Tropsch synthesis (FTS) on supported and unsupported Fe catalysts. The following aspects of the FT mechanism on unsupported iron catalysts were investigated on during this third year: (1) the collection of rate data in a Berty CSTR reactor based on sequential design of experiments; (2) CO adsorption and CO-TPD for obtaining the heat of adsorption of CO on polycrystalline iron; and (3) isothermal hydrogenation (IH) after Fischer Tropsch reaction to identify and quantify surface carbonaceous species. Rates of C{sub 2+} formation on unsupported iron catalysts at 220 C and 20 atm correlated well to a Langmuir-Hinshelwood type expression, derived assuming carbon hydrogenation to CH and OH recombination to water to be rate-determining steps. From desorption of molecularly adsorbed CO at different temperatures the heat of adsorption of CO on polycrystalline iron was determined to be 100 kJ/mol. Amounts and types of carbonaceous species formed after FT reaction for 5-10 minutes at 150, 175, 200 and 285 C vary significantly with temperature. Mr. Brian Critchfield completed his M.S. thesis work on a statistically designed study of the kinetics of FTS on 20% Fe/alumina. Preparation of a paper describing this work is in progress. Results of these studies were reported at the Annual Meeting of the Western States Catalysis and at the San Francisco AIChE meeting. In the coming period, studies will focus on quantitative determination of the rates of kinetically-relevant elementary steps on unsupported Fe catalysts with/without K and Pt promoters by SSITKA method. This study will help us to (1) understand effects of promoter and support on elementary kinetic parameters and (2) build a microkinetics model for FTS on iron. Calculations using periodic, self-consistent Density Functional Theory (DFT) methods were performed on models of defected Fe surfaces, most significantly the stepped Fe(211) surface. Binding

  18. Metal (Fe, Co, Ni) supported on different aluminas as Fischer-Tropsch catalyst

    SciTech Connect

    Dahlan; Marsih, I. Nyoman Ismunandar; Makertihartha, I. G. B. N.; Praserthdam, Piyasan; Panpranot, Joongjai

    2015-09-30

    This research aimed to compare the physico-chemical properties of the same metal M (M = iron, cobalt, nickel) supported on aluminas with different morphology and pore size as Fischer-Tropsch catalyst. The aluminas applied as support were alumina synthesized through hydrothermal process, alumina formed by pretreatment of catapal and commercial alumina which named as Ahy, Aca, and Aco respectively. Ahy has uniform morphology of nanotubes while Aca and Aco showed non-uniform morphology of particle lumps. The particle lumps of Aca were larger than those of Aco. Ahy, Aca, and Aco respectively has average pore diameter of 2.75, 2.86 and 2.9 nm. Metals were deposited on the supports by incipient-wetness impregnation method. The catalysts were characterized by XRD, H{sub 2}-TPR, and H{sub 2} chemisorption. Catalyst acitivity test for Fischer-Tropsch reaction was carried out in a micro reactor at 200 °C and 1 atm, and molar ratio of H{sub 2}/CO = 2:1. The metal oxide particle size increased in the order M/Aco < M/Aca < M/Ahy. The catalysts reducibility also increased according to the order M/Aco < M/Aca < M/Ahy suggesting that the larger metal oxide particles are more reducible. The number of active site was not proportional to the reducibility because during the reduction, larger metal oxide particles were converted into larger metal particles. On the other hand, the number of active sites was inversely proportional to the particle sizes. The number of active site increased in the order M/Ahy < M/Aco < M/Aca. The catalytic activity also increased in the following order M/Ahy < M/Aco < M/Aca. The activity per active site increased according to the order M/Aca < M/Aco < M/Ahy meaning that for M/Ahy, a little increase in active site will lead to a significance increase in catalytic activity. It showed that Ahy has potential for the better support.

  19. Laboratory Studies of Fischer-Tropsch-Type Reactions and Their Implications for Organics in Asteroids and Comets

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph

    2011-01-01

    We have been studying Fischer-Tropsch type (FTT) reactions as a source for organic materials both in the gas phase of the solar nebula and incorporated into primitive comets and asteroids for almost 10 years, and over this time our concept has evolved greatly from the standard "catalytic" model to a much more robust chemical scenario. Our simulations have been conducted at temperatures that are much higher than we like, primarily for practical reasons such as the timescale of individual reactions, and we are just starting a series of measurements to allow us to measure reaction rates at temperatures from 873K down to as low as 373K. We have preliminary data on the carbon (d13C = -50) & nitrogen (d15N = +9.5) isotopic fractionation at 873K, but not on materials produced at lower temperature. Isotope values are on the VPDB scale for carbon and vs. Air for nitrogen. We have also investigated the noble gas trapping efficiency of the FTT process by adding a small amount of a noble gas mix to our standard synthesis mix. The noble gas ratio is 49:49:1:1::Ne:Ar:Kr:Xe. Xe and Kr are trapped at 873K and are more efficiently trapped at 673K with no isotopic fractionation at either temperature. Ar trapping is detected at 673K, but not at 873K. Ne has not yet been observed in our samples. The solar nebula was an extremely complex system, mixing materials from the innermost regions out to well into the zones where comets formed and thus mixing highly processed nebular materials with grains and coatings formed before the nebula began to collapse. Laboratory studies may provide the means to separate such diverse components based on carbon or nitrogen isotopic fractionation or the quantities of noble gases trapped in grain coatings and their thermal release patterns, among other observables. The ultimate goal of laboratory synthesis of nebular analogs is to provide the means to identifY the conditions under which natural samples were formed and the signatures of subsequent

  20. Fischer-Tropsch Cobalt Catalyst Improvements with the Presence of TiO2, La2O3, and ZrO2 on an Alumina Support

    NASA Technical Reports Server (NTRS)

    Klettlinger, Jennifer Lindsey Suder

    2012-01-01

    The objective of this study was to evaluate the effect of titanium oxide, lanthanum oxide, and zirconium oxide on alumina supported cobalt catalysts. The hypothesis was that the presence of lanthanum oxide, titanium oxide, and zirconium oxide would reduce the interaction between cobalt and the alumina support. This was of interest because an optimized weakened interaction could lead to the most advantageous cobalt dispersion, particle size, and reducibility. The presence of these oxides on the support were investigated using a wide range of characterization techniques such as SEM, nitrogen adsorption, x-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed reduction after reduction (TPR-AR), and hydrogen chemisorptions/pulse reoxidation. Results indicated that both La2O3 and TiO2 doped supports facilitated the reduction of cobalt oxide species in reference to pure alumina supported cobalt catalysts, however further investigation is needed to determine the effect of ZrO2 on the reduction profile. Results showed an increased corrected cluster size for all three doped supported catalysts in comparison to their reference catalysts. The increase in reduction and an increase in the cluster size led to the conclusion that the support-metal interaction weakened by the addition of TiO2 and La2O3. It is also likely that the interaction decreased upon presence of ZrO2 on the alumina, but further research is necessary. Preliminary results have indicated that the alumina-supported catalysts with titanium oxide and lanthanum oxide present are of interest because of the weakened cobalt support interaction. These catalysts showed an increased extent of reduction, therefore more metallic cobalt is present on the support. However, whether or not there is more cobalt available to participate in the Fischer-Tropsch synthesis reaction (cobalt surface atoms) depends also on the cluster size. On one hand, increasing cluster size alone tends to decrease the

  1. New approach to the generation of metal-bearing, medium-pore, shape-selective zeolites for Fischer-Tropsch catalysis. Spectroscopic studies of zeolites

    SciTech Connect

    Iton, L.E.; Beal, R.B.; Hodul, D.T.

    1983-01-01

    Two recent developments in zeolite synthesis and modification were successfully combined to demonstrate a new approach to the generation of metal-bearing, medium-pore, shape-selective zeolites for use as catalysts in Fischer-Tropsch conversions. The steps are: (1) synthesis of an aluminoferrisilicate zeolite having the ZSM-5-type structure; (2) removal of the organic base template incorporated in the channel system during synthesis; (3) formation of a polycyano inclusion compound in the AFS zeolite; and (4) reduction of the inclusion compound by hydrogen at approx. 400/sup 0/C. PAS and EPR spectroscopy have been used to establish that the as-synthesized AFS zeolite contains Fe/sup 3 +/ ions in both framework and non-framework sites. FMR spectroscopy has been used to confirm the formation of the metallic (Fe) and bimetallic (Fe/Ru and Fe/Co) particles as products of the reduction of the inclusion compounds by hydrogen. The application of other spectroscopic techniques in recent studies of cations, complexes, and metal particles in zeolites is reviewed: high-resolution solid-state NMR, nuclear-spin-relaxation studies, FMR, EXAFS, and XANES.

  2. ULTRA-CLEAN FISCHER-TROPSCH FUELS PRODUCTION AND DEMONSTRATION PROJECT

    SciTech Connect

    Steve Bergin

    2003-10-17

    The Syntroleum plant is mechanically complete and currently undergoing start-up. The fuel production and demonstration plan is near completion. The study on the impact of small footprint plant (SFP) fuel on engine performance is about half-completed. Cold start testing has been completed. Preparations have been completed for testing the fuel in diesel electric generators in Alaska. Preparations are in progress for testing the fuel in bus fleets at Denali National Park and the Washington Metropolitan Transit Authority. The experiments and analyses conducted during this project show that Fischer-Tropsch (FT) gas-to-liquid diesel fuel can easily be used in a diesel engine with little to no modifications. Additionally, based on the results and discussion presented, further improvements in performance and emissions can be realized by configuring the engine to take advantage of FT diesel fuel's properties. The FT fuel also shows excellent cold start properties and enabled the engine tested to start at more the ten degrees than traditional fuels would allow. This plant produced through this project will produce large amounts of FT fuel. This will allow the fuel to be tested extensively, in current, prototype, and advanced diesel engines. The fuel may also contribute to the nation's energy security. The military has expressed interest in testing the fuel in aircraft and ground vehicles.

  3. Influence of liquid medium on the activity of a low-alpha Fischer-Tropsch catalyst

    SciTech Connect

    Gormley, R.J.; Zarochak, M.F.; Deffenbaugh, P.W.; Rao, K.R.P.M.

    1995-12-31

    The purpose of this research was to measure activity, selectivity, and the maintenance of these properties in slurry autoclave experiments with a Fischer-Tropsch (FT) catalyst that was used in the {open_quotes}FT II{close_quotes} bubble-column test, conducted at the Alternative Fuels Development Unit (AFDU) at LaPorte, Texas during May 1994. The catalyst contained iron, copper, and potassium and was formulated to produce mainly hydrocarbons in the gasoline range with lesser production of diesel-range products and wax. The probability of chain growth was thus deliberately kept low. Principal goals of the autoclave work have been to find the true activity of this catalyst in a stirred tank reactor, unhindered by heat or mass transfer effects, and to obtain a steady conversion and selectivity over the approximately 15 days of each test. Slurry autoclave testing of the catalyst in heavier waxes also allows insight into operation of larger slurry bubble column reactors. The stability of reactor operation in these experiments, particularly at loadings exceeding 20 weight %, suggests the likely stability of operations on a larger scale.

  4. On the origin of the cobalt particle size effects in Fischer-Tropsch catalysis.

    PubMed

    den Breejen, J P; Radstake, P B; Bezemer, G L; Bitter, J H; Frøseth, V; Holmen, A; de Jong, K P

    2009-05-27

    The effects of metal particle size in catalysis are of prime scientific and industrial importance and call for a better understanding. In this paper the origin of the cobalt particle size effects in Fischer-Tropsch (FT) catalysis was studied. Steady-State Isotopic Transient Kinetic Analysis (SSITKA) was applied to provide surface residence times and coverages of reaction intermediates as a function of Co particle size (2.6-16 nm). For carbon nanofiber supported cobalt catalysts at 210 degrees C and H(2)/CO = 10 v/v, it appeared that the surface residence times of reversibly bonded CH(x) and OH(x) intermediates increased, whereas that of CO decreased for small (<6 nm) Co particles. A higher coverage of irreversibly bonded CO was found for small Co particles that was ascribed to a larger fraction of low-coordinated surface sites. The coverages and residence times obtained from SSITKA were used to describe the surface-specific activity (TOF) quantitatively and the CH(4) selectivity qualitatively as a function of Co particle size for the FT reaction (220 degrees C, H(2)/CO = 2). The lower TOF of Co particles <6 nm is caused by both blocking of edge/corner sites and a lower intrinsic activity at the small terraces. The higher methane selectivity of small Co particles is mainly brought about by their higher hydrogen coverages.

  5. Thermal Stability Results of a Fischer-Tropsch Fuel With Various Blends of Aromatic Solution

    NASA Technical Reports Server (NTRS)

    Lindsey, Jennifer; Klettlinger, Suder

    2013-01-01

    Fischer-Tropsch (F-T) jet fuel composition differs from petroleum-based, conventional commercial jet fuel because of differences in feedstock and production methodology. F-T fuel typically has a lower aromatic and sulfur content and consists primarily of iso and normal paraffins. The ASTM D3241 specification for Jet Fuel Thermal Oxidation Test (JFTOT) break point testing method was used to test the breakpoint of a baseline commercial grade F-T jet fuel, and various blends of this F-T fuel with an aromatic solution. The goal of this research is to determine the effect of aromatic content on the thermal stability of F-T fuel. The testing completed in this report was supported by the NASA Fundamental Aeronautics Subsonic Fixed Wing Project. Two different aromatic content fuels from Rentech, as well as these fuels with added aromatic blend were analyzed for thermal stability using the JFTOT method. Preliminary results indicate a reduction in thermal stability occurs upon increasing the aromatic content to 10% by adding an aromatic blend to the neat fuel. These results do not specify a failure based on pressure drop, but only on tube color. It is unclear whether tube color correlates to more deposition on the tube surface or not. Further research is necessary in order to determine if these failures are true failures based on tube color. Research using ellipsometry to determine tube deposit thickness rather than color will be continued in follow-up of this study.

  6. ATOMIC-SCALE DESIGN OF IRON FISCHER-TROPSCH CATALYSTS: A COMBINED COMPUTATIONAL CHEMISTRY, EXPERIMENTAL, AND MICROKINETIC MODELING APPROACH

    SciTech Connect

    Manos Mavrikakis; James A. Dumesic; Amit A. Gokhale; Rahul P. Nabar; Calvin H. Bartholomew; Hu Zou; Brian Critchfield

    2005-03-22

    Efforts during this first year focused on four areas: (1) searching/summarizing published FTS mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) construction of mass spectrometer-TPD and Berty CSTR reactor systems; (3) preparation and characterization of unsupported iron and alumina-supported iron catalysts at various iron loadings (4) Determination of thermochemical parameters such as binding energies of reactive intermediates, heat of FTS elementary reaction steps, and kinetic parameters such as activation energies, and frequency factors of FTS elementary reaction steps on a number of model surfaces. Literature describing mechanistic and kinetic studies of Fischer-Tropsch synthesis on iron catalysts was compiled in a draft review. Construction of the mass spectrometer-TPD system is 90% complete and of a Berty CSTR reactor system 98% complete. Three unsupported iron catalysts and three alumina-supported iron catalysts were prepared by nonaqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2}, thus ideal for kinetic and mechanistic studies. The alumina-supported iron catalysts will be used for kinetic and mechanistic studies. In the coming year, adsorption/desorption properties, rates of elementary steps, and global reaction rates will be measured for these catalysts, with and without promoters, providing a database for understanding effects of dispersion, metal loading, and support on elementary kinetic parameters and for validation of computational models that incorporate effects of surface structure and promoters. Furthermore, using state-of-the-art self-consistent Density Functional Theory (DFT) methods, we have extensively studied the thermochemistry and kinetics of various elementary steps on

  7. Development of precipitated iron Fischer-Tropsch catalysts. Quarterly technical progress report for the period July 1, 1996--September 30, 1996

    SciTech Connect

    Bukur, D.B.

    1996-12-02

    Two slurry reactor tests were completed in continuation of our studies on the effect of pretreatment conditions on catalyst reactivity and selectivity. Exceptionally good performance was obtained in run SA-2186, using the new pretreatment developed at Texas A&M University. The work on catalyst characterization by temperature programmed and isothermal reduction on a variety of iron catalysts, with different amounts of promoters, has been continued. These studies are complementing our work on pretreatment effect research, and provide additional insights into the effect of pretreatment procedures on the reduction behavior of iron catalysts. The overall objectives are to: (1) demonstrate repeatability of performance and preparation procedure of two high activity, high alpha iron Fischer-Tropsch catalysts synthesized at Texas A&M University; (2) seek potential improvements in the catalysts performance through variation in process condition, pretreatment procedures and/or modifications in catalyst synthesis; (3) investigate performance of catalysts in a small bubble column slurry reactor; and (4) investigate feasibility of producing catalysts on a large scale in collaboration with a catalyst manufacturer.

  8. The application of inelastic neutron scattering to explore the significance of a magnetic transition in an iron based Fischer-Tropsch catalyst that is active for the hydrogenation of CO.

    PubMed

    Warringham, Robbie; McFarlane, Andrew R; MacLaren, Donald A; Webb, Paul B; Tooze, Robert P; Taylor, Jon; Ewings, Russell A; Parker, Stewart F; Lennon, David

    2015-11-07

    An iron based Fischer-Tropsch synthesis catalyst is evaluated using CO hydrogenation at ambient pressure as a test reaction and is characterised by a combination of inelastic neutron scattering (INS), powder X-ray diffraction, temperature-programmed oxidation, Raman scattering, and transmission electron microscopy. The INS spectrum of the as-prepared bulk iron oxide pre-catalyst (hematite, α-Fe2O3) is distinguished by a relatively intense band at 810 cm(-1), which has previously been tentatively assigned as a magnon (spinon) feature. An analysis of the neutron scattering intensity of this band as a function of momentum transfer unambiguously confirms this assignment. Post-reaction, the spinon feature disappears and the INS spectrum is characterised by the presence of a hydrocarbonaceous overlayer. A role for the application of INS in magnetic characterisation of iron based FTS catalysts is briefly considered.

  9. The application of inelastic neutron scattering to explore the significance of a magnetic transition in an iron based Fischer-Tropsch catalyst that is active for the hydrogenation of CO

    SciTech Connect

    Warringham, Robbie; McFarlane, Andrew R.; Lennon, David; MacLaren, Donald A.; Webb, Paul B.; Tooze, Robert P.; Taylor, Jon; Ewings, Russell A.; Parker, Stewart F.

    2015-11-07

    An iron based Fischer-Tropsch synthesis catalyst is evaluated using CO hydrogenation at ambient pressure as a test reaction and is characterised by a combination of inelastic neutron scattering (INS), powder X-ray diffraction, temperature-programmed oxidation, Raman scattering, and transmission electron microscopy. The INS spectrum of the as-prepared bulk iron oxide pre-catalyst (hematite, α-Fe{sub 2}O{sub 3}) is distinguished by a relatively intense band at 810 cm{sup −1}, which has previously been tentatively assigned as a magnon (spinon) feature. An analysis of the neutron scattering intensity of this band as a function of momentum transfer unambiguously confirms this assignment. Post-reaction, the spinon feature disappears and the INS spectrum is characterised by the presence of a hydrocarbonaceous overlayer. A role for the application of INS in magnetic characterisation of iron based FTS catalysts is briefly considered.

  10. Ab initio study of key branching reactions in biodiesel and Fischer-Tropsch fuels.

    PubMed

    Davis, Alexander C; Francisco, Joseph S

    2011-11-30

    Many biologically and Fischer-Tropsch synthesized fuels contain branched alkanes which, during their combustion and atmospheric oxidation mechanism, produce methylalkyl radicals. As a result, an accurate description of the chemistry of these species is essential to integrating these fuels into our energy systems. Even though branched alkanes make up roughly one-third of the compounds in gasoline and diesel fuels, both experimental and theoretical data on methylalkyl radicals and their reactions are scarce, especially for larger chain systems and combustion conditions. The present work investigates all the hydrogen migration reactions available to the n-methylprop-1-yl through n-methylhept-1-yl radicals, for n = 2-6, using the CBS-Q, G2, and G4 composite computational methods, over a wide temperature range. The resulting thermodynamic and kinetic parameters are used to determine the effect that the presence of the methyl group has on these important unimolecular, chain branching reactions, for the reactions involving not only a tertiary abstraction site but also all the primary and secondary sites. The activation energies of hydrogen migration reactions with the methyl group, either within or immediately outside the ring, are found to be roughly 0.8-1.6 kcal mol(-1) lower in energy than expected on the basis of analogous reactions in n-alkyl radicals. An important implication of this result is that the current method of using rate parameters derived from n-alkyl radicals to predict the chain branching characteristics of methylated alkyl radicals significantly underpredicts the importance of these reactions in atmospheric and combustion processes. Discussion of a possible cause for this phenomenon and its effect on the overall combustion mechanism of branched hydrocarbons is presented. Of particular concern is that 2,2,4,4,6,8,8-heptamethylnonane, which is currently used to model branched alkanes in diesel fuel surrogates, is predicted to have a much lower activation

  11. LIQUID PHASE FISCHER-TROPSCH (III & IV) DEMONSTRATION IN THE LAPORTE ALTERNATIVE FUELS DEVELOPMENT UNIT. Final Topical Report. Volume I/II: Main Report. Task 1: Engineering Modifications (Fischer-Tropsch III & IV Demonstration) and Task 2: AFDU Shakedown, Operations, Deactivation (Shut-Down) and Disposal (Fischer-Tropsch III & IV Demonstration).

    SciTech Connect

    Bharat L. Bhatt

    1999-06-01

    Slurry phase Fischer-Tropsch technology was successfully demonstrated in DOE's Alternative Fuels Development Unit (AFDU) at LaPorte, Texas. Earlier work at LaPorte, with iron catalysts in 1992 and 1994, had established proof-of-concept status for the slurry phase process. The third campaign (Fischer-Tropsch III), in 1996, aimed at aggressively extending the operability of the slurry reactor using a proprietary cobalt catalyst. Due to an irreversible plugging of catalyst-wax separation filters as a result of unexpected catalyst fines generation, the operations had to be terminated after seven days on-stream. Following an extensive post-run investigation by the participants, the campaign was successfully completed in March-April 1998, with an improved proprietary cobalt catalyst. These runs were sponsored by the U. S. Department of Energy (DOE), Air Products & Chemicals, Inc., and Shell Synthetic Fuels, Inc. (SSFI). A productivity of approximately 140 grams (gm) of hydrocarbons (HC)/ hour (hr)-liter (lit) of expanded slurry volume was achieved at reasonable system stability during the second trial (Fischer-Tropsch IV). The productivity ranged from 110-140 at various conditions during the 18 days of operations. The catalyst/wax filters performed well throughout the demonstration, producing a clean wax product. For the most part, only one of the four filter housings was needed for catalyst/wax filtration. The filter flux appeared to exceed the design flux. A combination of use of a stronger catalyst and some innovative filtration techniques were responsible for this success. There was no sign of catalyst particle attrition and very little erosion of the slurry pump was observed, in contrast to the Fischer-Tropsch III operations. The reactor operated hydrodynamically stable with uniform temperature profile and gas hold-ups. Nuclear density and differential pressure measurements indicated somewhat higher than expected gas hold-up (45 - 50 vol%) during Fischer-Tropsch IV

  12. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts; A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    SciTech Connect

    Manos Mavrikakis; James Dumesic; Rahul Nabar; Calvin Bartholonew; Hu Zou; Uchenna Paul

    2008-09-29

    This work focuses on (1) searching/summarizing published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) preparation and characterization of unsupported iron catalysts with/without potassium/platinum promoters; (3) measurement of H{sub 2} and CO adsorption/dissociation kinetics on iron catalysts using transient methods; (3) analysis of the transient rate data to calculate kinetic parameters of early elementary steps in FTS; (4) construction of a microkinetic model of FTS on iron, and (5) validation of the model from collection of steady-state rate data for FTS on iron catalysts. Three unsupported iron catalysts and three alumina-supported iron catalysts were prepared by non-aqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, temperature-programmed reduction (TPR), extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2} and thus ideal for kinetic and mechanistic studies. Kinetic parameters for CO adsorption, CO dissociation, and surface carbon hydrogenation on these catalysts were determined from temperature-programmed desorption (TPD) of CO and temperature programmed surface hydrogenation (TPSR), temperature-programmed hydrogenation (TPH), and isothermal, transient hydrogenation (ITH). A microkinetic model was constructed for the early steps in FTS on polycrystalline iron from the kinetic parameters of elementary steps determined experimentally in this work and from literature values. Steady-state rate data were collected in a Berty reactor and used for validation of the microkinetic model. These rate data were fitted to 'smart' Langmuir-Hinshelwood rate expressions derived from a sequence of elementary steps and using a combination of fitted steady-state parameters and parameters specified from the transient

  13. Reductions in aircraft particulate emissions due to the use of Fischer-Tropsch fuels

    NASA Astrophysics Data System (ADS)

    Beyersdorf, A. J.; Timko, M. T.; Ziemba, L. D.; Bulzan, D.; Corporan, E.; Herndon, S. C.; Howard, R.; Miake-Lye, R.; Thornhill, K. L.; Winstead, E.; Wey, C.; Yu, Z.; Anderson, B. E.

    2013-06-01

    The use of alternative fuels for aviation is likely to increase due to concerns over fuel security, price stability and the sustainability of fuel sources. Concurrent reductions in particulate emissions from these alternative fuels are expected because of changes in fuel composition including reduced sulfur and aromatic content. The NASA Alternative Aviation Fuel Experiment (AAFEX) was conducted in January-February 2009 to investigate the effects of synthetic fuels on gas-phase and particulate emissions. Standard petroleum JP-8 fuel, pure synthetic fuels produced from natural gas and coal feedstocks using the Fischer-Tropsch (FT) process, and 50% blends of both fuels were tested in the CFM-56 engines on a DC-8 aircraft. To examine plume chemistry and particle evolution with time, samples were drawn from inlet probes positioned 1, 30, and 145 m downstream of the aircraft engines. No significant alteration to engine performance was measured when burning the alternative fuels. However, leaks in the aircraft fuel system were detected when operated with the pure FT fuels as a result of the absence of aromatic compounds in the fuel. Dramatic reductions in soot emissions were measured for both the pure FT fuels (reductions of 84% averaged over all powers) and blended fuels (64%) relative to the JP-8 baseline with the largest reductions at idle conditions. The alternative fuels also produced smaller soot (e.g. at 85% power, volume mean diameters were reduced from 78 nm for JP-8 to 51 nm for the FT fuel), which may reduce their ability to act as cloud condensation nuclei (CCN). The reductions in particulate emissions are expected for all alternative fuels with similar reductions in fuel sulfur and aromatic content regardless of the feedstock. As the plume cools downwind of the engine, nucleation-mode aerosols form. For the pure FT fuels, reductions (94% averaged over all powers) in downwind particle number emissions were similar to those measured at the exhaust plane (84

  14. Ultra-clean Fischer-Tropsch (F-T) Fuels Production and Demonstration Project

    SciTech Connect

    Stephen P. Bergin

    2006-06-30

    The objective of the DOE-NETL Fischer-Tropsch (F-T) Production and Demonstration Program was to produce and evaluate F-T fuel derived from domestic natural gas. The project had two primary phases: (1) fuel production of ultra-clean diesel transportation fuels from domestic fossil resources; and (2) demonstration and performance testing of these fuels in engines. The project also included a well-to-wheels economic analysis and a feasibility study of small-footprint F-T plants (SFPs) for remote locations such as rural Alaska. During the fuel production phase, ICRC partnered and cost-shared with Syntroleum Corporation to complete the mechanical design, construction, and operation of a modular SFP that converts natural gas, via F-T and hydro-processing reactions, into hydrogensaturated diesel fuel. Construction of the Tulsa, Oklahoma plant started in August 2002 and culminated in the production of over 100,000 gallons of F-T diesel fuel (S-2) through 2004, specifically for this project. That fuel formed the basis of extensive demonstrations and evaluations that followed. The ultra-clean F-T fuels produced had virtually no sulfur (less than 1 ppm) and were of the highest quality in terms of ignition quality, saturation content, backend volatility, etc. Lubricity concerns were investigated to verify that commercially available lubricity additive treatment would be adequate to protect fuel injection system components. In the fuel demonstration and testing phase, two separate bus fleets were utilized. The Washington DC Metropolitan Area Transit Authority (WMATA) and Denali National Park bus fleets were used because they represented nearly opposite ends of several spectra, including: climate, topography, engine load factor, mean distance between stops, and composition of normally used conventional diesel fuel. Fuel evaluations in addition to bus fleet demonstrations included: bus fleet emission measurements; F-T fuel cold weather performance; controlled engine dynamometer

  15. Wabash Valley Integrated Gasification Combined Cycle, Coal to Fischer Tropsch Jet Fuel Conversion Study

    SciTech Connect

    Shah, Jayesh; Hess, Fernando; Horzen, Wessel van; Williams, Daniel; Peevor, Andy; Dyer, Andy; Frankel, Louis

    2016-06-01

    This reports examines the feasibility of converting the existing Wabash Integrated Gasification Combined Cycle (IGCC) plant into a liquid fuel facility, with the goal of maximizing jet fuel production. The fuels produced are required to be in compliance with Section 526 of the Energy Independence and Security Act of 2007 (EISA 2007 §526) lifecycle greenhouse gas (GHG) emissions requirements, so lifecycle GHG emissions from the fuel must be equal to or better than conventional fuels. Retrofitting an existing gasification facility reduces the technical risk and capital costs associated with a coal to liquids project, leading to a higher probability of implementation and more competitive liquid fuel prices. The existing combustion turbine will continue to operate on low cost natural gas and low carbon fuel gas from the gasification facility. The gasification technology utilized at Wabash is the E-Gas™ Technology and has been in commercial operation since 1995. In order to minimize capital costs, the study maximizes reuse of existing equipment with minimal modifications. Plant data and process models were used to develop process data for downstream units. Process modeling was utilized for the syngas conditioning, acid gas removal, CO2 compression and utility units. Syngas conversion to Fischer Tropsch (FT) liquids and upgrading of the liquids was modeled and designed by Johnson Matthey Davy Technologies (JM Davy). In order to maintain the GHG emission profile below that of conventional fuels, the CO2 from the process must be captured and exported for sequestration or enhanced oil recovery. In addition the power utilized for the plant’s auxiliary loads had to be supplied by a low carbon fuel source. Since the process produces a fuel gas with sufficient energy content to power the plant’s loads, this fuel gas was converted to hydrogen and exported to the existing gas turbine for low carbon power production. Utilizing low carbon fuel gas and

  16. Reductions in aircraft particulate emissions due to the use of Fischer-Tropsch fuels

    NASA Astrophysics Data System (ADS)

    Beyersdorf, A. J.; Timko, M. T.; Ziemba, L. D.; Bulzan, D.; Corporan, E.; Herndon, S. C.; Howard, R.; Miake-Lye, R.; Thornhill, K. L.; Winstead, E.; Wey, C.; Yu, Z.; Anderson, B. E.

    2014-01-01

    The use of alternative fuels for aviation is likely to increase due to concerns over fuel security, price stability, and the sustainability of fuel sources. Concurrent reductions in particulate emissions from these alternative fuels are expected because of changes in fuel composition including reduced sulfur and aromatic content. The NASA Alternative Aviation Fuel Experiment (AAFEX) was conducted in January-February 2009 to investigate the effects of synthetic fuels on gas-phase and particulate emissions. Standard petroleum JP-8 fuel, pure synthetic fuels produced from natural gas and coal feedstocks using the Fischer-Tropsch (FT) process, and 50% blends of both fuels were tested in the CFM-56 engines on a DC-8 aircraft. To examine plume chemistry and particle evolution with time, samples were drawn from inlet probes positioned 1, 30, and 145 m downstream of the aircraft engines. No significant alteration to engine performance was measured when burning the alternative fuels. However, leaks in the aircraft fuel system were detected when operated with the pure FT fuels as a result of the absence of aromatic compounds in the fuel. Dramatic reductions in soot emissions were measured for both the pure FT fuels (reductions in mass of 86% averaged over all powers) and blended fuels (66%) relative to the JP-8 baseline with the largest reductions at idle conditions. At 7% power, this corresponds to a reduction from 7.6 mg kg-1 for JP-8 to 1.2 mg kg-1 for the natural gas FT fuel. At full power, soot emissions were reduced from 103 to 24 mg kg-1 (JP-8 and natural gas FT, respectively). The alternative fuels also produced smaller soot (e.g., at 85% power, volume mean diameters were reduced from 78 nm for JP-8 to 51 nm for the natural gas FT fuel), which may reduce their ability to act as cloud condensation nuclei (CCN). The reductions in particulate emissions are expected for all alternative fuels with similar reductions in fuel sulfur and aromatic content regardless of the

  17. Indirect thermal liquefaction process for producing liquid fuels from biomass

    SciTech Connect

    Kuester, J.L.

    1980-01-01

    A progress report on an indirect liquefaction process to convert biomass type materials to quality liquid hydrocarbon fuels by gasification followed by catalytic liquid fuels synthesis has been presented. A wide variety of feedstocks can be processed through the gasification system to a gas with a heating value of 500 + Btu/SCF. Some feedstocks are more attractive than others with regard to producing a high olefin content. This appears to be related to hydrocarbon content of the material. The H/sub 2//CO ratio can be manipulated over a wide range in the gasification system with steam addition. Some feedstocks require the aid of a water-gas shift catalyst while others appear to exhibit an auto-catalytic effect to achieve the conversion. H/sub 2/S content (beyond the gasification system wet scrubber) is negligible for the feedstocks surveyed. The water gas shift reaction appears to be enhanced with an increase in pyrolysis reactor temperature over the range of 1300 to 1700/sup 0/F. Reactor temperature in the Fischer-Tropsch step is a significant factor with regard to manipulating product composition analysis. The optimum temperature however will probably correspond to maximum conversion to liquid hydrocarbons in the C/sub 5/ - C/sub 17/ range. Continuing research includes integrated system performance assessment, alternative feedstock characterization (through gasification) and factor studies for gasification (e.g., catalyst usage, alternate heat transfer media, steam usage, recycle effects, residence time study) and liquefaction (e.g., improved catalysts, catalyst activity characterization).

  18. Environmental risk analysis for indirect coal liquefaction

    SciTech Connect

    Barnthouse, L.W.; Suter, G.W. II; Baes, C.F. III; Bartell, S.M.; Cavendish, M.G.; Gardner, R.H.; O'Neill, R.V.; Rosen, A.E.

    1985-01-01

    This report presents an analysis of the risks to fish, water quality (due to noxious algal blooms), crops, forests, and wildlife of two technologies for the indirect liquefaction of coal: Lurgi and Koppers-Totzek gasification of coal for Fischer-Tropsch synthesis. A variety of analytical techniques were used to make maximum use of the available data to consider effects of effluents on different levels of ecological organization. The most significant toxicants to fish were found to be ammonia, cadmium, and acid gases. An analysis of whole-effluent toxicity indicated that the Lurgi effluent is more acutely toxic than the Koppers-Totzek effluent. Six effluent components appear to pose a potential threat of blue-green algal blooms, primarily because of their effects on higher trophic levels. The most important atmospheric emissions with respect to crops, forests, and wildlife were found to be the conventional combustion products SO/sub 2/ and NO/sub 2/. Of the materials deposited on the soil, arsenic, cadmium, and nickel appear of greatest concern for phytotoxicity. 147 references, 5 figures, 41 tables.

  19. Determination of the Effect of Coal/Biomass-Derived Syngas Contaminants on the Performance of Fischer-Tropsch and Water-Gas-Shift Catalysts

    SciTech Connect

    Trembly, Jason; Cooper, Matthew; Farmer, Justin; Turk, Brian; Gupta, Raghubir

    2010-12-31

    Today, nearly all liquid fuels and commodity chemicals are produced from non-renewable resources such as crude oil and natural gas. Because of increasing scrutiny of carbon dioxide (CO{sub 2}) emissions produced using traditional fossil-fuel resources, the utilization of alternative feedstocks for the production of power, hydrogen, value-added chemicals, and high-quality hydrocarbon fuels such as diesel and substitute natural gas (SNG) is critical to meeting the rapidly growing energy needs of modern society. Coal and biomass are particularly attractive as alternative feedstocks because of the abundant reserves of these resources worldwide. The strategy of co-gasification of coal/biomass (CB) mixtures to produce syngas for synthesis of Fischer-Tropsch (FT) fuels offers distinct advantages over gasification of either coal or biomass alone. Co-feeding coal with biomass offers the opportunity to exploit economies of scale that are difficult to achieve in biomass gasification, while the addition of biomass to the coal gasifier feed leverages proven coal gasification technology and allows CO{sub 2} credit benefits. Syngas generated from CB mixtures will have a unique contaminant composition because coal and biomass possess different concentrations and types of contaminants, and the final syngas composition is also strongly influenced by the gasification technology used. Syngas cleanup for gasification of CB mixtures will need to address this unique contaminant composition to support downstream processing and equipment. To investigate the impact of CB gasification on the production of transportation fuels by FT synthesis, RTI International conducted thermodynamic studies to identify trace contaminants that will react with water-gas-shift and FT catalysts and built several automated microreactor systems to investigate the effect of single components and the synergistic effects of multiple contaminants on water-gas-shift and FT catalyst performance. The contaminants

  20. Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, July 1, 1995--September 30, 1995

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1996-05-01

    Our objective for this quarter was to compare performance of the Ruhrchemie catalyst in different modes of operation: fixed bed reactor (conventional and supercritical mode of operation), and stirred tank slurry reactor. Diffusion coefficients are discussed.

  1. Stability and effects of carbon-induced surface reconstructions in cobalt Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Ciobîcă, I. M.; van Helden, P.; van Santen, R. A.

    2016-11-01

    This computational study of carbon induced reconstruction of Co surfaces demonstrates that surface reconstruction is stable in the presence of a hydrogen at low coverage. These reconstructions can create new sites that allow for low activation energy CO dissociation. Carbon induced surface reconstruction of the edge of the FCC-Co(221) step surface will result in highly reactive step-edge sites. Such sites also provide a low activation energy for carbon to diffuse into the subsurface layer of cobalt.

  2. 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.

  3. Incorporation of Reaction Kinetics into a Multiphase, Hydrodynamic Model of a Fischer Tropsch Slurry Bubble Column Reactor

    SciTech Connect

    Donna Guillen, PhD; Anastasia Gribik; Daniel Ginosar, PhD; Steven P. Antal, PhD

    2008-11-01

    This paper describes the development of a computational multiphase fluid dynamics (CMFD) model of the Fischer Tropsch (FT) process in a Slurry Bubble Column Reactor (SBCR). The CMFD model is fundamentally based which allows it to be applied to different industrial processes and reactor geometries. The NPHASE CMFD solver [1] is used as the robust computational platform. Results from the CMFD model include gas distribution, species concentration profiles, and local temperatures within the SBCR. This type of model can provide valuable information for process design, operations and troubleshooting of FT plants. An ensemble-averaged, turbulent, multi-fluid solution algorithm for the multiphase, reacting flow with heat transfer was employed. Mechanistic models applicable to churn turbulent flow have been developed to provide a fundamentally based closure set for the equations. In this four-field model formulation, two of the fields are used to track the gas phase (i.e., small spherical and large slug/cap bubbles), and the other two fields are used for the liquid and catalyst particles. Reaction kinetics for a cobalt catalyst is based upon values reported in the published literature. An initial, reaction kinetics model has been developed and exercised to demonstrate viability of the overall solution scheme. The model will continue to be developed with improved physics added in stages.

  4. Comparison of PM emissions from a commercial jet engine burning conventional, biomass, and Fischer-Tropsch fuels.

    PubMed

    Lobo, Prem; Hagen, Donald E; Whitefield, Philip D

    2011-12-15

    Rising fuel costs, an increasing desire to enhance security of energy supply, and potential environmental benefits have driven research into alternative renewable fuels for commercial aviation applications. This paper reports the results of the first measurements of particulate matter (PM) emissions from a CFM56-7B commercial jet engine burning conventional and alternative biomass- and, Fischer-Tropsch (F-T)-based fuels. PM emissions reductions are observed with all fuels and blends when compared to the emissions from a reference conventional fuel, Jet A1, and are attributed to fuel properties associated with the fuels and blends studied. Although the alternative fuel candidates studied in this campaign offer the potential for large PM emissions reductions, with the exception of the 50% blend of F-T fuel, they do not meet current standards for aviation fuel and thus cannot be considered as certified replacement fuels. Over the ICAO Landing Takeoff Cycle, which is intended to simulate aircraft engine operations that affect local air quality, the overall PM number-based emissions for the 50% blend of F-T fuel were reduced by 34 ± 7%, and the mass-based emissions were reduced by 39 ± 7%.

  5. Fuel-blending stocks from the hydrotreatment of a distillate formed by direct coal liquefaction

    SciTech Connect

    Andile B. Mzinyati

    2007-09-15

    The direct liquefaction of coal in the iron-catalyzed Suplex process was evaluated as a technology complementary to Fischer-Tropsch synthesis. A distinguishing feature of the Suplex process, from other direct liquefaction processes, is the use of a combination of light- and heavy-oil fractions as the slurrying solvent. This results in a product slate with a small residue fraction, a distillate/naphtha mass ratio of 6, and a 65.8 mass % yield of liquid fuel product on a dry, ash-free coal basis. The densities of the resulting naphtha (C{sub 5}-200{sup o}C) and distillate (200-400{sup o}C) fractions from the hydroprocessing of the straight-run Suplex distillate fraction were high (0.86 and 1.04 kg/L, respectively). The aromaticity of the distillate fraction was found to be typical of coal liquefaction liquids, at 60-65%, with a Ramsbottom carbon residue content of 0.38 mass %. Hydrotreatment of the distillate fraction under severe conditions (200{sup o}C, 20.3 MPa, and 0.41 g{sub feed} h{sup -1} g{sub catalyst}{sup -1}) with a NiMo/Al{sub 2}O{sub 3} catalyst gave a product with a phenol content of {lt}1 ppm, a nitrogen content {lt}200 ppm, and a sulfur content {lt}25 ppm. The temperature was found to be the main factor affecting diesel fraction selectivity when operating at conditions of WHSV = 0.41 g{sub feed} h{sup -1} g{sub catalyst}{sup -1} and PH{sub 2} = 20.3 MPa, with excessively high temperatures (T {gt} 420{sup o}C) leading to a decrease in diesel selectivity. The fuels produced by the hydroprocessing of the straight-run Suplex distillate fraction have properties that make them desirable as blending components, with the diesel fraction having a cetane number of 48 and a density of 0.90 kg/L. The gasoline fraction was found to have a research octane number (RON) of 66 and (N + 2A) value of 100, making it ideal as a feedstock for catalytic reforming and further blending with Fischer-Tropsch liquids. 44 refs., 9 figs., 12 tabs.

  6. Fischer-Tropsch activity for non-promoted cobalt-on-alumina catalysts

    DOEpatents

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    2001-01-01

    Cobalt catalysts, and processes employing these inventive catalysts, for hydrocarbon synthesis. The inventive catalyst comprises cobalt on an alumina support and is not promoted with any noble or near noble metals. In one aspect of the invention, the alumina support preferably includes a dopant in an amount effective for increasing the activity of the inventive catalyst. The dopant is preferably a titanium dopant. In another aspect of the invention, the cobalt catalyst is preferably reduced in the presence of hydrogen at a water vapor partial pressure effective to increase the activity of the cobalt catalyst for hydrocarbon synthesis. The water vapor partial pressure is preferably in the range of from 0 to about 0.1 atmospheres.

  7. Technology development for iron Fischer-Tropsch catalysts, September 30, 1991

    SciTech Connect

    Davis, B.H.

    1991-01-01

    Although the oxidation process of Fe(OH){sub 2} and the mechanism of formation of {gamma}-FeOOH have been studied by several groups, many questions still need to be answered. In addition, the procedure for the synthesis of pure {gamma}-FeOOH has not been well defined. This study is to an attempt to define better the chemistry associated with oxidizing Fe{sup 2+} to {gamma}-FeOOH, and to provide a rationale for scaling this method up to produce kg/hr amounts of {gamma}-FeOOH.

  8. Reducing fischer-tropsch catalyst attrition losses in high agitation reaction systems

    DOEpatents

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    2001-01-01

    A method for reducing catalyst attrition losses in hydrocarbon synthesis processes conducted in high agitation reaction systems; a method of producing an attrition-resistant catalyst; a catalyst produced by such method; a method of producing an attrition-resistant catalyst support; and a catalyst support produced by such method. The inventive method of reducing catalyst attrition losses comprises the step of reacting a synthesis gas in a high agitation reaction system in the presence of a catalyst. In one aspect, the catalyst preferably comprises a .gamma.-alumina support including an amount of titanium effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support which has been treated, after calcination, with an acidic, aqueous solution. The acidic aqueous solution preferably has a pH of not more than about 5. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support wherein the cobalt has been applied to the .gamma.-alumina support by totally aqueous, incipient wetness-type impregnation. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support with an amount of a lanthana promoter effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support produced from boehmite having a crystallite size, in the 021 plane, in the range of from about 30 to about 55 .ANG.ngstrons. In another aspect, the inventive method of producing an attrition-resistant catalyst comprises the step of treating a .gamma.-alumina support, after calcination of and before adding catalytic material to the support, with an acidic solution effective for increasing the attrition resistance of the catalyst. In another aspect, the inventive method of producing an attrition-resistant catalyst support comprises the step of treating calcined .gamma.-alumina with an acidic, aqueous

  9. Chemistry and morphology of coal liquefaction. Quarterly report, October 1-December 31, 1981

    SciTech Connect

    Heinemann, H.

    1981-12-01

    Progress reports are presented for the following six tasks: (1) selective synthesis of gasoline range components from synthesis gas; (2) electron microscopy studies of coal during hydrogenation; (3) catalysed low temperature hydrogenation of coal; (4) selctive hydrogenation, hydrogenolysis and alkylation of coal and coal liquids by organo-metallic systems; (5) chemistry of coal solubilization and liquefaction; (6) coal conversion catalysts-deactivation studies. Highlights are as follows: (1) In the presence of hydrogen and the absence of base, using the catalyst RuCl/sub 2/ (CO)/sub 2/ (phi/sub 3/ P)/sub 2/ excellent yields of reduced polynuclear heteroaromatic nitrogen compound were produced with 100% selectivity for the N-containing ring. (2) A careful gas chromatographic analysis of Fischer-Tropsch products has shown that major peaks, previously thought to be single compounds are composites of two or more compounds. Resolution of these peaks will enable one to establish a rational grouping of n/i and paraffin/olefin ratios. (3) Addition of iron or rhodium to potassium impregnated graphite did not result in the production of heavier hydrocarbons than methane from the graphite-steam reaction at low temperature. However, small amounts of iron enhanced the methane production. (ATT)

  10. Environmental and economic aspects of indirect coal liquefaction processes: a report emphasizing the relationship between product mix and efficiency

    SciTech Connect

    Hoffman, L.

    1981-09-01

    This report covers environmental and economic aspects of three indirect liquefaction processes. Specifically, the following are addressed: U.S. coal resources; the Lurgi/Methanol, Lurgi/Methanol/Mobil M, and the Lurgi/Fischer-Tropsch indirect coal liquefaction processes; and environmental and economic aspects associated with the considered processes. Even though our coal resources are considered very large, the life expectancy of currently defined reserves would be quite limited if we were to derive an appreciable part of our fossil-fuel-derived energy from coal. The conservation of coal resources would be affected by conversion efficiencies, which vary with process and product mix. For the processes considered, for similar liquid-to-gas ratio values (product mix), the coal-to-methanol is the most efficient while the Fischer-Tropsch is the least efficient. For these processes, the cost per Btu of product at reasonable equivalent liquid/gas ratios is greatest for Fischer-Tropsch and the least for the coal-to-methanol process.

  11. Process for producing dimethyl ether form synthesis gas

    DOEpatents

    Pierantozzi, Ronald

    1985-01-01

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  12. Process for producing dimethyl ether from synthesis gas

    DOEpatents

    Pierantozzi, R.

    1985-06-04

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  13. Propulsion and Power Rapid Response Research and Development Support. Delivery Order 0042: Demonstration and Evaluation of Fischer-Tropsch Research Fuels for the DoD Assured Fuels Program

    DTIC Science & Technology

    2006-12-01

    constructed in cooperation with the Department of Energy (DOE) via funding provided by the Department’s Ultra-Clean Fuels Program. As part of this DOE...of Analysis cSt centistokes CU Conductivity Units deg Degrees DESC Defense Energy Support Center DoD Department of Defense DOE Department...of Energy EAFB Edwards Air Force Base FBP Final Boiling Point FSII Fuel System Icing Inhibitor FT Fischer-Tropsch ISO International

  14. Shape-selective catalysts for Fischer-Tropsch chemistry. Final report : January 1, 2001 - December 31, 2008.

    SciTech Connect

    Cronauer, D. C.

    2011-04-11

    Argonne National Laboratory carried out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry-specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it was desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. It was desired that selectivity be directed toward producing diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. The original goal was to produce shape-selective catalysts that had the potential to limit the formation of long-chain products and yet retain the active metal sites in a protected 'cage.' This cage would also restrict their loss by attrition during use in slurry-bed reactors. The first stage of this program was to prepare and evaluate iron-containing particulate catalysts. Such catalysts were prepared with silica-containing fractal cages. The activity and strength was essentially the same as that of catalysts without the cages. Since there was no improvement, the program plan was modified as discussed below. A second experimental stage was undertaken to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes and particulate supports. The concept was that of depositing active metals (i.e. ruthenium, iron or cobalt) upon membranes with well defined flow channels of small diameter and length such that the catalytic activity and product molecular weight distribution could be controlled. In order to rapidly evaluate the catalytic membranes, the ALD coating processes were performed in an 'exploratory mode' in which ALD procedures from the literature appropriate for coating flat surfaces were applied to the high surface area membranes. Consequently, the Fe and Ru loadings in the membranes were likely to be smaller than those expected for

  15. Experimental reactor system for investigation of indirect liquefaction catalysts in slurry phase operation

    SciTech Connect

    Zarochak, M.F.; Pennline, H.W.; Schehl, R.R.

    1984-02-01

    A detailed description of the slurry (three-phase) reactor scheme employed at the Pittsburgh Energy Technology Center for Fischer-Tropsch synthesis is reported. Emphasis is placed on materials of construction, equipment operation, and product collection and analysis. The unit's functional limits and safety features are also provided. Operational problems and the resolving remedial action are discussed. The reactor scheme now operates such that near isothermal conditions exist over the reactor internal length. Thus, with excellent temperature control assured, reliable information for evaluation of potential catalyst candidates for slurry phase Fischer-Tropsch synthesis is possible within a wide range of operating conditions. Test results with a fused-iron catalyst suspended in a paraffinic liquid medium are given as an example.

  16. Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

    SciTech Connect

    Enrique Iglesia

    2004-09-30

    This project explores the extension of previously discovered Fe-based catalysts with unprecedented Fischer-Tropsch synthesis rate, selectivity, and ability to convert hydrogen-poor synthesis gas streams typical of those produced from coal and biomass sources. Contract negotiations were completed on December 9, 2004. During the first reporting period, we certified a microreactor, installed required analytical equipment, and reproduced synthetic protocols and catalytic performance previously reported. During this second reporting period, we have prepared and tested several Fe-based compositions for Fischer-Tropsch synthesis and tested the effects of product recycle under both subcritical and supercritical conditions. These studies established modest improvements in rates and selectivities with light hydrocarbon recycle without any observed deleterious effects, opening up the opportunities for using of recycle strategies to control temperature profiles in fixed-bed Fe-based Fischer-Tropsch synthesis reactors without any detectable kinetic detriment. In a parallel study, we examined similar effects of recycle for cobalt-based catalysts; marked selectivity improvements were observed as a result of the removal of significant transport restrictions on these catalysts. Finally, we have re-examined some previously unanalyzed data dealing with the mechanism of the Fischer-Tropsch synthesis, specifically kinetic isotope effects on the rate and selectivity of chain growth reactions on Fe-based catalysts.

  17. Fischer-Tropsch-Type Production of Organic Materials in the Solar Nebula: Studies Using Graphite Catalysts and Measuring the Trapping of Noble Gases

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A., III; Ferguson, Frank T.; Lucas, Christopher; Kimura, Yuki; Hohenberg, Charles

    2009-01-01

    The formation of abundant carbonaceous material in meteorites is a long standing problem and an important factor in the debate on the potential for the origin of life in other stellar systems. The Fischer-Tropsch-type (FTT) catalytic reduction of CO by hydrogen was once the preferred model for production of organic materials in the primitive solar nebula. We have demonstrated that many grain surfaces can catalyze both FTT and HB-type reactions, including amorphous iron and magnesium silicates, pure silica smokes as well as several minerals. Graphite is not a particularly good FTT catalyst, especially compared to iron powder or to amorphous iron silicate. However, like other silicates that we have studied, it gets better with exposure to CO. N2 and H2 over time: e.g., after formation of a macromolecular carbonaceous layer on the surfaces of the underlying gains. While amorphous iron silicates required only 1 or 2 experimental runs to achieve steady state reaction rates, graphite only achieved steady state after 6 or more experiments. We will present results showing the catalytic action of graphite grains increasing with increasing number of experiments and will also discuss the nature of the final "graphite" grains aster completion of our experiments.

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

    SciTech Connect

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

    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 and 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}.

  19. Enhanced treatment of Fischer-Tropsch (F-T) wastewater using the up-flow anaerobic sludge blanket coupled with bioelectrochemical system: Effect of electric field.

    PubMed

    Wang, Dexin; Han, Hongjun; Han, Yuxing; Li, Kun; Zhu, Hao

    2017-02-07

    The coupling of bioelectrochemical system (BES) with an up-flow anaerobic sludge blanket (UASB) was established for enhanced Fischer-Tropsch (F-T) wastewater treatment while the UASB (control group) was operated in parallel. The presence of electric field could offer system a more reductive micro-environment that lower the ORP values and maintain the appropriate pH range, resulting in the higher chemical oxygen demand (COD) removal efficiency and methane production for BES-UASB (86.8% and 2.31±0.1L/(L·d)) while those values in control group were 72.1% and 1.77±0.08L/(L·d). In addition, the coupled system could promote sludge granulation to perform a positive effect on maintaining stability of pollutants removal. The high-throughput 16S rRNA gene pyrosequencing in this study further confirmed that the promoting direct interspecies electron transfer (DIET) between Geobacter and Methanosarcina might be established in BES-UASB to improve the syntrophic degradation of propionate and butyrate, finally facilitated completely methane production.

  20. Comparing a Fischer-Tropsch Alternate Fuel to JP-8 and Their 50-50 Blend: Flow and Flame Visualization Results

    NASA Technical Reports Server (NTRS)

    Hicks, Yolanda R.; Tacina, M.

    2013-01-01

    Combustion performance of a Fischer-Tropsch (FT) jet fuel manufactured by Sasol was compared to JP-8 and a 50-50 blend of the two fuels, using the NASA/Woodward 9 point Lean Direct Injector (LDI) in its baseline configuration. The baseline LDI configuration uses 60deg axial air-swirlers, whose vanes generate clockwise swirl, in the streamwise sense. For all cases, the fuel-air equivalence ratio was 0.455, and the combustor inlet pressure and pressure drop were 10-bar and 4 percent. The three inlet temperatures used were 828, 728, and 617 K. The objectives of this experiment were to visually compare JP-8 flames with FT flames for gross features. Specifically, we sought to ascertain in a simple way visible luminosity, sooting, and primary flame length of the FT compared to a standard JP grade fuel. We used color video imaging and high-speed imaging to achieve these goals. The flame color provided a way to qualitatively compare soot formation. The length of the luminous signal measured using the high speed camera allowed an assessment of primary flame length. It was determined that the shortest flames resulted from the FT fuel.

  1. Assessment of fuel-cycle energy use and greenhouse gas emissions for Fischer-Tropsch diesel from coal and cellulosic biomass.

    SciTech Connect

    Xie, X.; Wang, M.; Han, J.

    2011-04-01

    This study expands and uses the GREET (Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation) model to assess the effects of carbon capture and storage (CCS) technology and cellulosic biomass and coal cofeeding in Fischer-Tropsch (FT) plants on energy use and greenhouse gas (GHG) emissions of FT diesel (FTD). To demonstrate the influence of the coproduct credit methods on FTD life-cycle analysis (LCA) results, two allocation methods based on the energy value and the market revenue of different products and a hybrid method are employed. With the energy-based allocation method, fossil energy use of FTD is less than that of petroleum diesel, and GHG emissions of FTD could be close to zero or even less than zero with CCS when forest residue accounts for 55% or more of the total dry mass input to FTD plants. Without CCS, GHG emissions are reduced to a level equivalent to that from petroleum diesel plants when forest residue accounts for 61% of the total dry mass input. Moreover, we show that coproduct method selection is crucial for LCA results of FTD when a large amount of coproducts is produced.

  2. Toward a more comprehensive greenhouse gas emissions assessment of biofuels: the case of forest-based fischer-tropsch diesel production in Finland.

    PubMed

    Soimakallio, Sampo

    2014-01-01

    Increasing the use of biofuels influences atmospheric greenhouse gas concentrations. Although widely recognized, uncertainties related to the particular impacts are typically ignored or only partly considered. In this paper, various sources of uncertainty related to the GHG emission savings of biofuels are considered comprehensively and transparently through scenario analysis and stochastic simulation. Technology and feedstock production chain-specific factors, market-mediated factors and climate policy time frame issues are reflected using as a case study Fischer-Tropsch diesel derived from boreal forest biomass in Finland. This case study shows that the GHG emission savings may be positive or negative in many of the cases studied, and are subject to significant uncertainties, which are mainly determined by market-mediated factors related to fossil diesel substitution. Regardless of the considerable uncertainties, some robust conclusions could be drawn; it was likely of achieving some sort of but unlikely of achieving significant savings in the GHG emissions within the 100 year time frame in many cases. Logging residues (branches) performed better than stumps and living stem wood in terms of the GHG emission savings, which could be increased mainly by blocking carbon leakage. Forest carbon stock changes also significantly contributed to the GHG emission savings.

  3. On the Use of Fourier Transform Infrared (FT-IR) Spectroscopy and Synthetic Calibration Spectra to Quantify Gas Concentrations in a Fischer-Tropsch Catalyst System

    NASA Technical Reports Server (NTRS)

    Ferguson, Frank T.; Johnson, Natasha M.; Nuth, Joseph A., III

    2015-01-01

    One possible origin of prebiotic organic material is that these compounds were formed via Fischer-Tropsch-type (FTT) reactions of carbon monoxide and hydrogen on silicate and oxide grains in the warm, inner-solar nebula. To investigate this possibility, an experimental system has been built in which the catalytic efficiency of different grain-analog materials can be tested. During such runs, the gas phase above these grain analogs is sampled using Fourier transform infrared (FT-IR) spectroscopy. To provide quantitative estimates of the concentration of these gases, a technique in which high-resolution spectra of the gases are calculated using the high-resolution transmission molecular absorption (HITRAN) database is used. Next, these spectra are processed via a method that mimics the processes giving rise to the instrumental line shape of the FT-IR spectrometer, including apodization, self-apodization, and broadening due to the finite resolution. The result is a very close match between the measured and computed spectra. This technique was tested using four major gases found in the FTT reactions: carbon monoxide, methane, carbon dioxide, and water. For the ranges typical of the FTT reactions, the carbon monoxide results were found to be accurate to within 5% and the remaining gases accurate to within 10%. These spectra can then be used to generate synthetic calibration data, allowing the rapid computation of the gas concentrations in the FTT experiments.

  4. Shell's Middle Distillate Synthesis process

    SciTech Connect

    Voetter, H.; VanDerBurgt, M.J. B.V., The Hague )

    1988-01-01

    The basis of the Shell Middle Distillate Synthesis (SMDS) process is the classic Fischer-Tropsch synthesis. For the case of middle distillate production from natural gas the procedure has been developed to commercial maturity, making use of tailored line-up for synthesis gas production and of proprietary modern catalysts in synthesis. Development work over the last years has in particular lead to improvement of the economy of the process altogether via catalyst performance, reactor sizing and syngas manufacturing line-up.

  5. Fischer-Tropsch synthesis in supercritical fluids. Quarterly technical progress report, April 1, 1996--June 30, 1996

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1996-12-31

    For the task on diffusion coefficients of F-T products in supercritical fluids, we attempted to find a model for the {beta} parameter to predict the molecular diffusion coefficients to a high degree of accuracy so we may be able to predict both the molecular diffusion coefficient and thus the effective diffusivity a priori. The dependency of solvent/solute interactions on the {beta} parameter was analyzed and a correlation developed to predict the functionality. This allowed us to develop an empirical formula to correlate the molecular diffusion coefficient to ratios of mass, size, and density. Thus finally allowing for supercritical fluid diffusion predictions a priori. Figure 6 shows our predictions of the data available on the self diffusion coefficient of carbon dioxide (Chen, 1983; Takahashi and Iwasaki, 1966) ethylene (Arends et al., 1981; Baker et al., 1984), toluene (Baker et al., 1985) and chlorotrifuoromethane (Harris, 1978). The predictions, with no parameters adjusted from the data, are excellent with an average absolute error of 3.64%.

  6. Fischer-tropsch synthesis in supercritical fluids. Quarterly technical progress report, April 1, 1993--June 30, 1993

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1993-07-29

    We have completed modifications of the Taylor Dispersion Apparatus so that propane can be used as a solvent. Problems were encountered initially compressing propane to the necessary pressures because of cavitation in the liquid pump. This problem was overcome by placing a check valve in the line after the pump and pressures of 2500 psi have been achieved. The system has been pressure tested by using a soap solution on exposed joints and performing a mass balance (leak test). The mass balance was made by reading the volumetric flow rate of liquid in the syringe pump and converting this to expected gas flow rate. The liquid was then vaporized and a dry gas meter measured the amount of gas at the exit of the apparatus. The expected and measured gas flow rates were in excellent agreement, indicating that there are no significant leaks in the system. Presently, we are having problems with the use of UV detection for the dim using compounds. The detector is successfully auto-zeroing with a blank cell and with Co{sub 2}. With the use of instrument grade propane, however, the detector is unable to auto-zero because of absorption of unknown impurity. We believe this problem is caused by a sulfur compound in the propane gas cylinder and we plan to install an active carbon guard bed to remove a sulfur containing compounds.

  7. Microemulsion impregnated catalyst composite and use thereof in a synthesis gas conversion process

    DOEpatents

    Abrevaya, Hayim; Targos, William M.

    1987-01-01

    A catalyst composition for synthesis gas conversion comprising a ruthenium metal component deposited on a support carrier wherein the average metal particle size is less than about 100 A. The method of manufacture of the composition via a reverse micelle impregnation technique and the use of the composition in a Fischer-Tropsch conversion process is also disclosed.

  8. Microemulsion impregnated catalyst composite and use thereof in a synthesis gas conversion process

    DOEpatents

    Abrevaya, H.; Targos, W.M.

    1987-12-22

    A catalyst composition is described for synthesis gas conversion comprising a ruthenium metal component deposited on a support carrier wherein the average metal particle size is less than about 100 A. The method of manufacture of the composition via a reverse micelle impregnation technique and the use of the composition in a Fischer-Tropsch conversion process is also disclosed.

  9. Quantification of trace O-containing compounds in GTL process samples via Fischer-Tropsch reaction by comprehensive two-dimensional gas chromatography/mass spectrometry.

    PubMed

    Fernandes, Daniella R; Pereira, Vinícius B; Stelzer, Karen T; Gomes, Alexandre O; Neto, Francisco R Aquino; Azevedo, Débora A

    2015-11-01

    Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS) was successfully applied to eight real Brazilian Fischer-Tropsch (FT) product samples for the quantitative analysis of O-containing compounds. It not only allowed identifying and quantifying simultaneously a large number of O-containing compounds but also resolved many co-eluting components, such as carboxylic acids, which co-elute in one-dimensional gas chromatography. The homologous series of alcohols and carboxylic acids as trimethylsilyl derivatives were detected and identified at trace levels. The absolute quantification of each compound was accomplished with reliability using analytical curves. Linear alcohols (from C5 to C19), branched alcohols (C6-C13) and carboxylic acids (C4 to C12) were obtained in the range of 1.58 mg g(-1) to 14.75 mg g(-1), 0.51 mg g(-1) to 1.12 mg g(-1) and 0.21 mg g(-1) to 1.63 mg g(-1) of FT product samples, respectively. GC×GC-TOFMS provided a linear range (from 0.3 ng µL(-1) to 10 ng µL(-1)), good precision (<8%), and excellent accuracy (recovery range of 77% to 118%) for quantification of individual O-containing compounds in FT product samples. The results can benefit the development of gas-to-liquid technologies from natural gas and guide the choice of an FT conversion process that generates clean products with higher added value.

  10. Development of precipitated iron Fischer-Tropsch catalysts. Quarterly technical progress report, 1 January 1995--31 March 1995

    SciTech Connect

    Bukur, D.B.; Lang, X.; Reddy, B.

    1995-05-23

    During the reporting period we completed synthesis of about 100 g of catalyst with nominal composition 100 Fe/3 Cu/4 K/16 SiO{sub 2} (S-3416-2), and of another batch (173 g) of the same catalyst (S-3416-3). Also, we synthesized two additional batches of catalyst with nominal composition 100 Fe/5 Cu/6 K/24 SiO{sub 2}, in the amounts of 240 g (S-5624-3) and 200 g (S-5624-4). These amounts are sufficient for all planned tests with these two catalysts for the entire duration of this contract. The synthesized catalysts were characterized by atomic absorption, and BET surface area and pore size distribution measurements.

  11. Synthesis gas production by mixed conducting membranes with integrated conversion into liquid products

    DOEpatents

    Nataraj, Shankar; Russek, Steven Lee; Dyer, Paul Nigel

    2000-01-01

    Natural gas or other methane-containing feed gas is converted to a C.sub.5 -C.sub.19 hydrocarbon liquid in an integrated system comprising an oxygenative synthesis gas generator, a non-oxygenative synthesis gas generator, and a hydrocarbon synthesis process such as the Fischer-Tropsch process. The oxygenative synthesis gas generator is a mixed conducting membrane reactor system and the non-oxygenative synthesis gas generator is preferably a heat exchange reformer wherein heat is provided by hot synthesis gas product from the mixed conducting membrane reactor system. Offgas and water from the Fischer-Tropsch process can be recycled to the synthesis gas generation system individually or in combination.

  12. Shape-selective catalysts for Fischer-Tropsch chemistry : iron-containing particulate catalysts. Activity report : January 1, 2001 - December 31, 2004.

    SciTech Connect

    Cronauer, D.; Chemical Engineering

    2006-05-12

    Argonne National Laboratory is carrying out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry--specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it is desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. It is desired that selectivity be directed toward producing diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. The goal is to produce shape-selective catalysts that have the potential to limit the formation of longchain products and yet retain the active metal sites in a protected 'cage'. This cage also restricts their loss by attrition during use in slurry-bed reactors. The first stage of this program was to prepare and evaluate iron-containing particulate catalysts. This activity report centers upon this first stage of experimentation with particulate FT catalysts. (For reference, a second experimental stage is under way to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes.) To date, experimentation has centered upon the evaluation of a sample of iron-based, spray-dried catalyst prepared by B.H. Davis of the Center of Applied Energy Research (CAER) and samples of his catalyst onto which inorganic 'shells' were deposited. The reference CAER catalyst contained a high level of dispersed fine particles, a portion of which was removed by differential settling. Reaction conditions have been established using a FT laboratory unit such that reasonable levels of CO conversion can be achieved, where therefore a valid catalyst comparison can be made. A wide range of catalytic activities was observed with SiO{sub 2}-coated FT catalysts. Two techniques were used for SiO{sub 2}coating. The first involved a caustic precipitation of SiO{sub 2} from an

  13. Shape-selective catalysts for Fischer-Tropsch chemistry : atomic layer deposition of active catalytic metals. Activity report : January 1, 2005 - September 30, 2005.

    SciTech Connect

    Cronauer, D. C.

    2011-04-15

    Argonne National Laboratory is carrying out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry - specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it is desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. The broad goal is to produce diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. Originally the goal was to prepare shape-selective catalysts that would limit the formation of long-chain products and yet retain the active metal sites in a protected 'cage.' Such catalysts were prepared with silica-containing fractal cages. The activity was essentially the same as that of catalysts without the cages. We are currently awaiting follow-up experiments to determine the attrition strength of these catalysts. A second experimental stage was undertaken to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes and particulate supports. The concept was that of depositing active metals (i.e. ruthenium, iron or cobalt) upon membranes with well defined flow channels of small diameter and length such that the catalytic activity and product molecular weight distribution could be controlled. In order to rapidly evaluate the catalytic membranes, the ALD coating processes were performed in an 'exploratory mode' in which ALD procedures from the literature appropriate for coating flat surfaces were applied to the high surface area membranes. Consequently, the Fe and Ru loadings in the membranes were likely to be smaller than those expected for complete monolayer coverage. In addition, there was likely to be significant variation in the Fe and Ru loading among the membranes due to difficulties in nucleating these materials on the aluminum oxide surfaces. The first

  14. Pollution Control Technical Manual for Lurgi-based indirect coal liquefaction and SNG (substitute natural gas). Final report Jun 82-Feb 83

    SciTech Connect

    Not Available

    1983-04-01

    The Environmental Protection Agency (EPA), Office of Research and Development has undertaken an extensive study to determine synthetic fuel plant waste stream characteristics and to evaluate potentially applicable pollution control systems. The purpose of this and all other PCTMs is to convey this information in a manner that is readily useful to designers, permit writers, and the public. This specific PCTM addresses coal-based synthetic fuels facilities using dry ash Lurgi gasifiers to generate a synthesis process feed gas. Product synthesis technologies examined in this PCTM include: methanation to produce substitute natural gas (SNG), methanol synthesis, Mobil M-gasoline synthesis from methanol, and Fischer-Tropsch synthesis.

  15. Catalyst for converting synthesis gas to liquid motor fuels

    DOEpatents

    Coughlin, Peter K.

    1986-01-01

    The addition of an inert metal component, such as gold, silver or copper, to a Fischer-Tropsch catalyst comprising cobalt enables said catalyst to convert synthesis gas to liquid motor fuels at about 240.degree.-370.degree. C. with advantageously reduced selectivity of said cobalt for methane in said conversion. The catalyst composition can advantageously include a support component, such as a molecular sieve, co-catalyst/support component or a combination of such support components.

  16. Synthesis of model compounds for coal liquefaction research

    SciTech Connect

    Not Available

    1991-11-01

    Coal liquefaction investigations required the availability of model compounds for mechanistic investigations. Towards this end, IITRI was funded to develop an approach for the synthesis of one of the target compound. This study was carried out in several phases as outlined here. Initial synthetic investigations on obtaining 2-tetrolol was carried out using high pressure and temperature reduction with Raney nickel catalyst. The next step consisted in incorporation of a hydroxymethyelene group at the C-3 position. This was successfully carried out utilizing 2-tetrolol, formaldehyde, and calcium oxide. An alternate improved method was developed using 3-carboxyl-2-naphthol. This required less time, gave a cheer product in higher yield. Efforts at the introduction of a chloromethylene group only yielded polymeric material or starting material in spite of protection the phenolic group by various groups. They synthesis of 3, 5-dimethyl-6- bromobenzyl chloride was successfully carried out by performing the Blank reaction of 2, 4-dimethyl bromobenzene. The product was characterized by GC/MS. Purification was not possible, as it was a complex mixture. Efforts at converting it to the acetate followed by separation to was not feasible. Unlike in the case of 2- hydroxyteralol, hydroxymetylation by established procedure yielded only the starting materials. Commercially available 4-methoxy-1- maphthaldehyde was protected as the ethylene acetal. The Wittig reagent 3-chlorobenzyl phosphonium bromide was prepared and condensed with 4-methoxy-1-napthaldehyde successfully and proved that the overall synthetic approach was proceeding in the desired direction. All the necessary intermediates have been synthesized,and we have demonstrated using model compounds, that the synthetic objective can be attained.

  17. Catalyst and process for converting synthesis gas to liquid motor fuels

    DOEpatents

    Coughlin, Peter K.

    1987-01-01

    The addition of an inert metal component, such as gold, silver or copper, to a Fischer-Tropsch catalyst comprising cobalt enables said catalyst to convert synthesis gas to liquid motor fuels at about 240.degree.-370.degree. C. with advantageously reduced selectivity of said cobalt for methane in said conversion. The catalyst composition can advantageously include a support component, such as a molecular sieve, co-catalyst/support component or a combination of such support components.

  18. (Pittsburgh Energy Technology Center): Quarterly technical progress report for the period ending June 30, 1987. [Advanced Coal Research and Technology Development Programs

    SciTech Connect

    1988-02-01

    Research programs on coal and coal liquefaction are presented. Topics discussed are: coal science, combustion, kinetics, surface science; advanced technology projects in liquefaction; two stage liquefaction and direct liquefaction; catalysts of liquefaction; Fischer-Tropsch synthesis and thermodynamics; alternative fuels utilization; coal preparation; biodegradation; advanced combustion technology; flue gas cleanup; environmental coordination, and technology transfer. Individual projects are processed separately for the data base. (CBS)

  19. Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

    SciTech Connect

    Akio; Ishikawa; Manuel Ojeda; Nan Yao; Enrique Iglesia

    2006-09-30

    This project extends previously discovered Fe-based catalysts to hydrogen-poor synthesis gas streams derived from coal and biomass sources. These catalysts have shown unprecedented Fischer-Tropsch synthesis rates and selectivities for feedstocks consisting of synthesis gas derived from methane. During the first reporting period, we certified a microreactor, installed required analytical equipment, and reproduced synthetic protocols and catalytic results previously reported. During the second reporting period, we prepared several Fe-based compositions for Fischer-Tropsch Synthesis and tested the effects of product recycle under both subcritical and supercritical conditions. During the third and fourth reporting periods, we improved the catalysts preparation method, which led to Fe-based FT catalysts with the highest FTS reaction rates and selectivities so far reported, a finding that allowed their operation at lower temperatures and pressures with high selectivity to desired products (C{sub 5+}, olefins). During the fifth reporting period, we studied the effects of different promoters on catalytic performance, specifically how their sequence of addition dramatically influenced the performance of these materials in the Fischer-Tropsch synthesis. We also continued our studies of the kinetic behavior of these materials. Specifically, the effects of H{sub 2}, CO, and CO{sub 2} on the rates and selectivities of Fischer-Tropsch Synthesis reactions led us to propose a new sequence of elementary steps on Fe and Co Fischer-Tropsch catalysts. More specifically, we were focused on the roles of hydrogen-assisted and alkali-assisted dissociation of CO in determining rates and CO{sub 2} selectivities. During this sixth reporting period, 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

  20. Understanding the effect of cobalt particle size on Fischer-Tropsch synthesis: surface species and mechanistic studies by SSITKA and kinetic isotope effect.

    PubMed

    Yang, Jia; Tveten, Erik Z; Chen, De; Holmen, Anders

    2010-11-02

    Co/γ-Al(2)O(3) catalysts with particle sizes in the range of 4-15 nm were investigated by isothermal hydrogenation (IH), temperature programmed hydrogenation (TPH), and steady-state isotopic transient kinetic analysis (SSITKA). Kinetic isotope effect experiments were used to probe possible mechanisms on Co/γ-Al(2)O(3) with different particle size. It was found that CO dissociated on Co/γ-Al(2)O(3) catalysts at 210 °C. The total amount of CO(2) formed following the dissociation depends on the cobalt crystal size. O-Co binding energy was found to be highly dependent on the Co metal particle size, whereas similar C-Co binding energy was found on catalysts with different Co particle size. Very strongly bonded carbon and oxygen surface species increased with decreasing particle size and acted as site blocking species in the methanation reaction. SSITKA experiments showed that the intrinsic activity (1/τ(CH(x))) remained constant as the particle size increased from 4 to 15 nm. The number of surface intermediates (N(CH(x))) increased with increasing particle size. The apparent activation energies were found similar for these catalysts, about 85 kJ/mol. D(2)-H(2) switches further confirmed that the particle size did not change the kinetically relevant steps in the reaction. The reactivity of the active sites on the 4 nm particles was the same as those on the 8, 11, and 15 nm particles, and only the number of total available surface active sites was less on the 4 nm particles than on the others.

  1. Design and synthesis of catalysts for coal liquefaction

    SciTech Connect

    Dadyburjor, D.B.; Stinespring, C.D.; Stiller, A.H.; Zondio, J.W.

    1996-10-01

    Ferric-sulfide-based materials satisfy many of the requirements of catalysts for coal liquefaction - they are cheap enough and environmentally-benign enough to be considered {open_quotes}disposable,{close_quotes} and they can be made small enough and active enough to be considered economical. The talk will focus on the different ways in which these catalysts can be made, including hydrothermal disproportionation, in situ impregnation, and aerosol, as well as their characterization and performance.

  2. Transportation fuels from wood

    SciTech Connect

    Baker, E.G.; Elliott, D.C.; Stevens, D.J.

    1980-01-01

    The various methods of producing transportation fuels from wood are evaluated in this paper. These methods include direct liquefaction schemes such as hydrolysis/fermentation, pyrolysis, and thermochemical liquefaction. Indirect liquefaction techniques involve gasification followed by liquid fuels synthesis such as methanol synthesis or the Fischer-Tropsch synthesis. The cost of transportation fuels produced by the various methods are compared. In addition, three ongoing programs at Pacific Northwest Laboratory dealing with liquid fuels from wood are described.

  3. Process for the liquefaction of solid carbonaceous materials wherein nitrogen is separated from hydrogen via ammonia synthesis

    DOEpatents

    Stetka, Steven S.; Nazario, Francisco N.

    1982-01-01

    In a process for the liquefaction of solid carbonaceous materials wherein bottoms residues are upgraded with a process wherein air is employed, the improvement wherein nitrogen buildup in the system is avoided by ammonia synthesis. In a preferred embodiment hydrogen from other portions of the liquefaction process will be combined with hydrogen produced as a result of the bottoms upgrading to increase the H.sub.2 :N.sub.2 ratio in the ammonia reactor.

  4. Technology development for iron Fischer-Tropsch catalysts, September 30, 1991. Technical progress report for quarterly period ending September 30, 1991

    SciTech Connect

    Davis, B.H.

    1991-12-31

    Although the oxidation process of Fe(OH){sub 2} and the mechanism of formation of {gamma}-FeOOH have been studied by several groups, many questions still need to be answered. In addition, the procedure for the synthesis of pure {gamma}-FeOOH has not been well defined. This study is to an attempt to define better the chemistry associated with oxidizing Fe{sup 2+} to {gamma}-FeOOH, and to provide a rationale for scaling this method up to produce kg/hr amounts of {gamma}-FeOOH.

  5. DESIGN, SYNTHESIS, AND MECHANISTIC EVALUATION OF IRON-BASED CATALYSIS FOR SYNTHESIS GAS CONVERSION TO FUELS AND CHEMICALS

    SciTech Connect

    Akio Ishikawa; Manuel Ojeda; Enrique Iglesia

    2005-03-31

    This project explores the extension of previously discovered Fe-based catalysts to hydrogen-poor synthesis gas streams derived from coal and biomass sources. These catalysts have previously shown unprecedented Fischer-Tropsch synthesis rate, selectivity with synthesis gas derived from methane. During the first reporting period, we certified a microreactor, installed required analytical equipment, and reproduced synthetic protocols and catalytic performance previously reported. During the second reporting period, we prepared several Fe-based compositions for Fischer-Tropsch synthesis and tested the effects of product recycle under both subcritical and supercritical conditions. During this third reporting period, we have prepared a large number of Fe-based catalyst compositions using precipitation and impregnations methods with both supercritical and subcritical drying and with the systematic use of surface active agents to prevent pore collapse during drying steps required in synthetic protocols. These samples were characterized during this period using X-ray diffraction, surface area, and temperature-programmed reduction measurements. These studies have shown that these synthesis methods lead to even higher surface areas than in our previous studies and confirm the crystalline structures of these materials and their reactivity in both oxide-carbide interconversions and in Fischer-Tropsch synthesis catalysis. Fischer-Tropsch synthesis reaction rates and selectivities with low H{sub 2}/CO ratio feeds (H{sub 2}/CO = 1) were the highest reported in the literature at the low-temperature and relatively low pressure in our measurements. Current studies are exploring the optimization of the sequence of impregnation of Cu, K, and Ru promoters, of the activation and reaction conditions, and of the co-addition of light hydrocarbons to increase diffusion rates of primary olefin products so as to increase the selectivity to unsaturated products. Finally, we are also addressing

  6. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis

    SciTech Connect

    Osseo-Asare, K.; Radovic, L.R.

    1991-07-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. (VC)

  7. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis

    SciTech Connect

    Osseo-Asare, K.; Radovic, L.R.

    1991-02-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effects that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable.

  8. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis

    SciTech Connect

    Osseo-Asare, K.; Boakye, E.; Vaidyanathan, N.; Radovic, L.R.

    1992-04-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. (VC)

  9. Fischer-Tropsch Slurry Reactor modeling

    SciTech Connect

    Soong, Y.; Gamwo, I.K.; Harke, F.W.

    1995-12-31

    This paper reports experimental and theoretical results on hydrodynamic studies. The experiments were conducted in a hot-pressurized Slurry-Bubble Column Reactor (SBCR). It includes experimental results of Drakeol-10 oil/nitrogen/glass beads hydrodynamic study and the development of an ultrasonic technique for measuring solids concentration. A model to describe the flow behavior in reactors was developed. The hydrodynamic properties in a 10.16 cm diameter bubble column with a perforated-plate gas distributor were studied at pressures ranging from 0.1 to 1.36 MPa, and at temperatures from 20 to 200{degrees}C, using a dual hot-wire probe with nitrogen, glass beads, and Drakeol-10 oil as the gas, solid, and liquid phase, respectively. It was found that the addition of 20 oil wt% glass beads in the system has a slight effect on the average gas holdup and bubble size. A well-posed three-dimensional model for bed dynamics was developed from an ill-posed model. The new model has computed solid holdup distributions consistent with experimental observations with no artificial {open_quotes}fountain{close_quotes} as predicted by the earlier model. The model can be applied to a variety of multiphase flows of practical interest. An ultrasonic technique is being developed to measure solids concentration in a three-phase slurry reactor. Preliminary measurements have been made on slurries consisting of molten paraffin wax, glass beads, and nitrogen bubbles at 180 {degrees}C and 0.1 MPa. The data show that both the sound speed and attenuation are well-defined functions of both the solid and gas concentrations in the slurries. The results suggest possibilities to directly measure solids concentration during the operation of an autoclave reactor containing molten wax.

  10. Mixed Alcohol Synthesis Catalyst Screening

    SciTech Connect

    Gerber, Mark A.; White, James F.; Stevens, Don J.

    2007-09-03

    National Renewable Energy Laboratory (NREL) and Pacific Northwest National Laboratory (PNNL) are conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). PNNL is tasked with obtaining commercially available or preparing promising mixed-alcohol catalysts and screening them in a laboratory-scale reactor system. Commercially available catalysts and the most promising experimental catalysts are provided to NREL for testing using a slipstream from a pilot-scale biomass gasifier. From the standpoint of producing C2+ alcohols as the major product, it appears that the rhodium catalyst is the best choice in terms of both selectivity and space-time yield (STY). However, unless the rhodium catalyst can be improved to provide minimally acceptable STYs for commercial operation, mixed alcohol synthesis will involve significant production of other liquid coproducts. The modified Fischer-Tropsch catalyst shows the most promise for providing both an acceptable selectivity to C2+ alcohols and total liquid STY. However, further optimization of the Fischer-Tropsch catalysts to improve selectivity to higher alcohols is highly desired. Selection of a preferred catalyst will likely entail a decision on the preferred coproduct slate. No other catalysts tested appear amenable to the significant improvements needed for acceptable STYs.

  11. [Progress in synthesis technologies and application of aviation biofuels].

    PubMed

    Sun, Xiaoying; Liu, Xiang; Zhao, Xuebing; Yang, Ming; Liu, Dehua

    2013-03-01

    Development of aviation biofuels has attracted great attention worldwide because that the shortage of fossil resources has become more and more serious. In the present paper, the development background, synthesis technologies, current application status and existing problems of aviation biofuels were reviewed. Several preparation routes of aviation biofuels were described, including Fischer-Tropsch process, catalytic hydrogenation and catalytic cracking of bio-oil. The status of flight tests and commercial operation were also introduced. Finally the problems for development and application of aviation biofuels were stated, and some accommodation were proposed.

  12. 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.

  13. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Final technical report, October 1990--December 1994

    SciTech Connect

    Osseo-Asare, K.; Boakye, E.; Vittal, M.

    1995-04-01

    This report described the synthesis of Molybdenum Sulfides in microemulsions by acidification of ammonium tetrathiomolybdate. Molybdenum Sulfides have been shown to be potential coal liquefaction catalysts. The importance of particle size, temperature effects, and coal surface chemistry to impregnation are discussed.

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

    SciTech Connect

    Tan, Eric C. D.; Snowden-Swan, Lesley J.; Talmadge, Michael; Dutta, Abhijit; Jones, Susanne; Ramasamy, Karthikeyan K.; Gray, Michel; Dagle, Robert; Padmaperuma, Asanga; Gerber, Mark; Sahir, Asad H.; Tao, Ling; Zhang, Yanan

    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) mixed alcohols over a MoS2 catalyst, (ii) mixed oxygenates (a mixture of C2+ 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.

  15. 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 MoS2 catalyst, (ii) mixed oxygenates (a mixture of C2+ 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

  16. Deactivation by carbon of iron catalysts for indirect liquefaction

    SciTech Connect

    Bartholomew, C.H.

    1991-01-10

    Although promoted cobalt and iron catalysts for Fischer-Tropsch (FT) synthesis of gasoline feedstock were first developed more than three decades ago, a major technical problem still limiting the commercial use of these catalysts today is carbon deactivation. This report describes recent progress in a fundamental, three-year investigation of carbon formation and its effects on the activity and selectivity of promoted iron catalysts for FT synthesis, the objectives of which are to: determine rates and mechanisms of carbon deactivation of unsupported Fe and Fe/K catalysts during CO hydrogenation over a range of CO concentrations, CO:H{sub 2} ratios, and temperatures; and model the rates of deactivation of the same catalysts in fixed-bed reactors. To accomplish the above objectives, the project is divided into the following tasks: (1) determine the kinetics of reaction and of carbon deactivation during CO hydrogenation on Fe and Fe/K catalysts coated on monolith bodies. (2) Determine the reactivities and types of carbon deposited during reaction on the same catalysts from temperature-programmed-surface-reaction spectroscopy (TPSR) and transmission electron microscopy (TEM). Determine the types of iron carbides formed at various temperatures and H{sub 2}/CO ratios using x-ray diffraction and Moessbauer spectroscopy. (3) Develop mathematical deactivation models which include heat and mass transport contributions for FT synthesis is packed-bed reactors. Progress to date is described. 48 refs., 3 figs., 1 tab.

  17. Design, Synthesis and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

    SciTech Connect

    Akio Ishikawa; Manuel Ojeda; Nan Yao; Enrique Iglesia

    2007-03-31

    This project extends previously discovered Fe-based catalysts to hydrogen-poor synthesis gas streams derived from coal and biomass sources. These catalysts have shown unprecedented Fischer-Tropsch synthesis rates and selectivities for synthesis gas derived from methane. During the first reporting period, we certified a microreactor, installed required analytical equipment, and reproduced synthetic protocols and catalytic results previously reported. During the second reporting period, we prepared several Fe-based compositions for Fischer-Tropsch Synthesis and tested the effects of product recycle under both subcritical and supercritical conditions. During the third and fourth reporting periods, we improved the catalysts preparation method, which led to Fe-based materials with the highest FTS reaction rates and selectivities so far reported, a finding that allowed their operation at lower temperatures and pressures with high selectivity to desired products (C{sub 5+}, olefins). During the fifth and sixth reporting period, we studied the effects of different promoters on catalytic performance, specifically how their sequence of addition dramatically influenced the performance of these materials in the Fischer-Tropsch synthesis. We also continued our studies of the kinetic behavior of these materials during the sixth reporting period. Specifically, the effects of H{sub 2}, CO, and CO{sub 2} on the rates and selectivities of Fischer-Tropsch Synthesis reactions led us to propose a new sequence of elementary steps on Fe and Co Fischer-Tropsch catalysts. Finally, we also started a study of the use of colloidal precipitation methods for the synthesis small Co clusters using recently developed methods to explore possible further improvements in FTS rates and selectivities. We found that colloidal synthesis makes possible the preparation of small cobalt particles, although large amount of cobalt silicate species, which are difficult to reduce, were formed. During this

  18. Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

    SciTech Connect

    Akio Ishikawa; Manuel Ojeda; Nan Yao; Enrique Iglesia

    2006-03-31

    This project extends previously discovered Fe-based catalysts to hydrogen-poor synthesis gas streams derived from coal and biomass sources. These catalysts have shown unprecedented Fischer-Tropsch synthesis rate, selectivity for feedstocks consisting of synthesis gas derived from methane. During the first reporting period, we certified a microreactor, installed required analytical equipment, and reproduced synthetic protocols and catalytic results previously reported. During the second reporting period, we prepared several Fe-based compositions for Fischer-Tropsch synthesis and tested the effects of product recycle under both subcritical and supercritical conditions. During the third and fourth reporting periods, we improved the catalysts preparation method, which led to Fe-based FT catalysts with the highest FTS reaction rates and selectivities so far reported, a finding that allowed their operation at lower temperatures and pressures with high selectivity to desired products (C{sub 5+}, olefins). During this fifth reporting period, we have studied the effects of different promoters on catalytic performance, specifically 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. During this fifth reporting period, we have also continued our studies of optimal activation procedures, involving reduction and carburization of oxide precursors during the early stages of contact with synthesis gas. We have completed the analysis of the evolution of oxide, carbide, and metal phases of the active iron components during initial contact with synthesis gas using advanced synchrotron techniques based on X-ray absorption spectroscopy. We have confirmed that the Cu or Ru compensates for inhibitory effects of Zn, a

  19. 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

    SciTech Connect

    Tan, Eric C. D.; Snowden-Swan, Lesley J.; Talmadge, Michael; Dutta, Abhijit; Jones, Susanne; Ramasamy, Karthikeyan K.; Gray, Michel; Dagle, Robert; Padmaperuma, Asanga; Gerber, Mark; Sahir, Asad H.; Tao, Ling; Zhang, Yanan

    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 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) 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.

  20. Coal liquefaction

    DOEpatents

    Schindler, Harvey D.

    1985-01-01

    In a two-stage liquefaction wherein coal, hydrogen and liquefaction solvent are contacted in a first thermal liquefaction zone, followed by recovery of an essentially ash free liquid and a pumpable stream of insoluble material, which includes 850.degree. F.+ liquid, with the essentially ash free liquid then being further upgraded in a second liquefaction zone, the liquefaction solvent for the first stage includes the pumpable stream of insoluble material from the first liquefaction stage, and 850.degree. F.+ liquid from the second liquefaction stage.

  1. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis

    SciTech Connect

    Osseo-Asare, K.; Boakye, E.; Vaidyanathan, N.; Radovic, L.R.

    1991-10-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metalbearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. The size of these very small and monodispersed particles will be accurately determined both separately and after in situ and ex situ coal impregnation. The as-prepared nanoparticles as well as the catalyst-impregnated coal or char matrix will be characterized using the following techniques: dynamic light scattering, x-ray diffraction, x-ray photoelectron spectroscopy, scanning and/or transmission electron microscopy, and selective chemisorption.

  2. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis

    SciTech Connect

    Osseo-Asare, K.; Radovic, L.R.

    1991-04-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. The size of these very small and monodispersed particles will be accurately determined both separately and after in situ and ex situ coal impregnation. The as-prepared nanoparticles as well as the catalyst-impregnated coal or char matrix will be characterized using the following techniques: dynamic light scattering, x-ray diffraction, x-ray photoelectron spectroscopy, scanning and/or transmission electron microscopy, and selective chemisorption.

  3. Deactivation by carbon of iron catalysts for indirect liquefaction

    SciTech Connect

    Bartholomew, C.H.

    1990-10-11

    This report describes recent progress in a fundamental, three-year investigation of carbon formation and its effects on the activity and selectivity of promoted iron catalysts for Fischer-Tropsch (FT) synthesis, the objectives of which are: determine rates and mechanisms of carbon deactivation of unsupported Fe and Fe/K catalysts during CO hydrogenation over a range of CO concentrations, CO:H{sub 2} ratios, and temperatures; model the rates of deactivation of the same catalysts in fixed-bed reactors. During the thirteenth quarter design of software for a computer-automated reactor system to be used in the kinetic and deactivation studies was continued. Further progress was made toward the completion of the control language, control routines, and software for operating this system. Progress was also made on the testing of the system hardware and software. H{sub 2} chemisorption capacities and activity selectivity data were also measured for three iron catalysts promoted with 1% alumina. 47 refs., 8 figs., 1 tab.

  4. Synthesis of model compounds for coal liquefaction research. Final report, April 15, 1990--April 14, 1991

    SciTech Connect

    Not Available

    1991-11-01

    Coal liquefaction investigations required the availability of model compounds for mechanistic investigations. Towards this end, IITRI was funded to develop an approach for the synthesis of one of the target compound. This study was carried out in several phases as outlined here. Initial synthetic investigations on obtaining 2-tetrolol was carried out using high pressure and temperature reduction with Raney nickel catalyst. The next step consisted in incorporation of a hydroxymethyelene group at the C-3 position. This was successfully carried out utilizing 2-tetrolol, formaldehyde, and calcium oxide. An alternate improved method was developed using 3-carboxyl-2-naphthol. This required less time, gave a cheer product in higher yield. Efforts at the introduction of a chloromethylene group only yielded polymeric material or starting material in spite of protection the phenolic group by various groups. They synthesis of 3, 5-dimethyl-6- bromobenzyl chloride was successfully carried out by performing the Blank reaction of 2, 4-dimethyl bromobenzene. The product was characterized by GC/MS. Purification was not possible, as it was a complex mixture. Efforts at converting it to the acetate followed by separation to was not feasible. Unlike in the case of 2- hydroxyteralol, hydroxymetylation by established procedure yielded only the starting materials. Commercially available 4-methoxy-1- maphthaldehyde was protected as the ethylene acetal. The Wittig reagent 3-chlorobenzyl phosphonium bromide was prepared and condensed with 4-methoxy-1-napthaldehyde successfully and proved that the overall synthetic approach was proceeding in the desired direction. All the necessary intermediates have been synthesized,and we have demonstrated using model compounds, that the synthetic objective can be attained.

  5. Integrated coal liquefaction process

    DOEpatents

    Effron, Edward

    1978-01-01

    In a process for the liquefaction of coal in which coal liquids containing phenols and other oxygenated compounds are produced during the liquefaction step and later hydrogenated, oxygenated compounds are removed from at least part of the coal liquids in the naphtha and gas oil boiling range prior to the hydrogenation step and employed as a feed stream for the manufacture of a synthesis gas or for other purposes.

  6. Synthesis, Decomposition and Characterization of Fe and Ni Sulfides and Fe and CO Nanoparticles for Aerospace Applications

    NASA Technical Reports Server (NTRS)

    Cowen, Jonathan E.; Hepp, Aloysius F.; Duffy, Norman V.; Jose, Melanie J.; Choi, D. B.; Brothers, Scott M.; Baird, Michael F.; Tomsik, Thomas M.; Duraj, Stan A.; Williams, Jennifer N.; Kulis, Michael J.; Gaier, James R.

    2009-01-01

    We describe several related studies where simple iron, nickel, and cobalt complexes were prepared, decomposed, and characterized for aeronautics (Fischer-Tropsch catalysts) and space (high-fidelity lunar regolith simulant additives) applications. We describe the synthesis and decomposition of several new nickel dithiocarbamate complexes. Decomposition resulted in a somewhat complicated product mix with NiS predominating. The thermogravimetric analysis of fifteen tris(diorganodithiocarbamato)iron(III) has been investigated. Each undergoes substantial mass loss upon pyrolysis in a nitrogen atmosphere between 195 and 370 C, with major mass losses occurring between 279 and 324 C. Steric repulsion between organic substituents generally decreased the decomposition temperature. The product of the pyrolysis was not well defined, but usually consistent with being either FeS or Fe2S3 or a combination of these. Iron nanoparticles were grown in a silica matrix with a long-term goal of introducing native iron into a commercial lunar dust simulant in order to more closely simulate actual lunar regolith. This was also one goal of the iron and nickel sulfide studies. Finally, cobalt nanoparticle synthesis is being studied in order to develop alternatives to crude processing of cobalt salts with ceramic supports for Fischer-Tropsch synthesis.

  7. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Technical progress report, April--June 1991

    SciTech Connect

    Osseo-Asare, K.; Radovic, L.R.

    1991-07-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. (VC)

  8. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Technical progress report, October--December 1991

    SciTech Connect

    Osseo-Asare, K.; Boakye, E.; Vaidyanathan, N.; Radovic, L.R.

    1992-04-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. (VC)

  9. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Technical progress report, October--December 1990

    SciTech Connect

    Osseo-Asare, K.; Radovic, L.R.

    1991-02-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effects that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable.

  10. Abiotic synthesis of fatty acids

    NASA Technical Reports Server (NTRS)

    Leach, W. W.; Nooner, D. W.; Oro, J.

    1978-01-01

    The formation of fatty acids by Fischer-Tropsch-type synthesis was investigated with ferric oxide, ammonium carbonate, potassium carbonate, powdered Pueblito de Allende carbonaceous chondrite, and filings from the Canyon Diablo meteorite used as catalysts. Products were separated and identified by gas chromatography and mass spectrometry. Iron oxide, Pueblito de Allende chondrite, and Canyon Diablo filings in an oxidized catalyst form yielded no fatty acids. Canyon Diablo filings heated overnight at 500 C while undergoing slow purging by deuterium produced fatty acids only when potassium carbonate was admixed; potassium carbonate alone also produced these compounds. The active catalytic combinations gave relatively high yields of aliphatic and aromatic hydrocarbons; substantial amounts of n-alkenes were almost invariably observed when fatty acids were produced; the latter were in the range C6 to C18, with maximum yield in C9 or 10.

  11. The influence of the potassium promoter on the kinetics and thermodynamics of CO adsorption on a bulk iron catalyst applied in Fischer-Tropsch synthesis: a quantitative adsorption calorimetry, temperature-programmed desorption, and surface hydrogenation study.

    PubMed

    Graf, Barbara; Muhler, Martin

    2011-03-07

    The adsorption of carbon monoxide on an either unpromoted or potassium-promoted bulk iron catalyst was investigated at 303 K and 613 K by means of pulse chemisorption, adsorption calorimetry, temperature-programmed desorption and temperature-programmed surface reaction in hydrogen. CO was found to adsorb mainly molecularly in the absence of H(2) at 303 K, whereas the presence of H(2) induced CO dissociation at higher temperatures leading to the formation of CH(4) and H(2)O. The hydrogenation of atomic oxygen chemisorbed on metallic iron was found to occur faster than the hydrogenation of atomically adsorbed carbon. At 613 K CO adsorption occurred only dissociatively followed by recombinative CO(2) formation according to C(ads) + 2O(ads)→ CO(2(g)). The presence of the potassium promoter on the catalyst surface led to an increasing strength of the Fe-C bond both at 303 K and 613 K: the initial differential heat of molecular CO adsorption on the pure iron catalyst at 303 K amounted to 102 kJ mol(-1), whereas it increased to 110 kJ mol(-1) on the potassium-promoted sample, and the initial differential heat of dissociative CO adsorption on the unpromoted iron catalyst at 613 K amounted to 165 kJ mol(-1), which increased to 225 kJ mol(-1) in the presence of potassium. The calorimetric CO adsorption experiments also reveal a change of the energetic distribution of the CO adsorption sites present on the catalyst surface induced by the potassium promoter, which was found to block a fraction of the CO adsorption sites.

  12. US Army Qualification of Alternative Fuels Specified in MIL-DTL-83133H for Ground Systems Use. Final Qualification Report: JP-8 Containing Synthetic Paraffinic Kerosene Manufactured Via Fischer-Tropsch Synthesis or Hydroprocessed Esters and Fatty Acids

    DTIC Science & Technology

    2013-09-01

    Caterpillar C7 .....................................................................................................................32 DDC 8V92TA...the eight engines selected:  General Engine Products (GEP) 6.5L Turbo  Caterpillar (CAT) C7  Detroit Diesel Corporation (DDC)/MTU 8V92TA...V-8 engine and UNCLASSIFIED 20 UNCLASSIFIED the Caterpillar (CAT) C7 inline 6-cylinder engine. The GEP engine was selected because of its high

  13. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Technical progress report, January 1993--March 1993

    SciTech Connect

    Boakye, E.; Vittal, M.; Osseo-Asare, K.

    1993-04-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of manometer size is being carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis is on molybdenum- and iron-based catalysts, but the techniques being developed should also be generally applicable. The size of these very small and monodispersed particles will be accurately determined both separately and after in situ and ex situ coal impregnation. The as-prepared nanoparticles as well as the catalyst-impregnated coal or char matrix are characterized using a battery of techniques, including dynamic light scattering, x-ray diffraction and transmission electron microscopy. Catalytic activity tests are conducted under standardized coal liquefaction conditions. The effect of particle size of these unsupported catalysts on the product yield and distribution during conversion of a bituminous and a subbituminous coal are being determined. This quarter, the solubilization of ammonium tetrathiomolybdate and the synthesis of molybdenum sulfide in several microemulsion systems is discussed.

  14. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Technical progress report, October 1992--December 1992

    SciTech Connect

    Boakye, E.; Vittal, M.; Osseo-Asare, K.

    1993-02-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of manometer size is being carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis is on molybdenum- and iron-based catalysts, but the techniques being developed should also be generally applicable. The size of these very small and monodispersed particles will be accurately determined both separately and after in situ and ex situ coal impregnation. The as-prepared nanoparticles as well as the catalyst-impregnated coal or char matrix are characterized using a battery of techniques, including dynamic light scattering, x-ray diffraction and transmission electron microscopy. Catalytic activity tests are conducted under standardized coal liquefaction conditions. The effect of particle size of these unsupported catalysts on the product yield and distribution during conversion of a bituminous and a subbituminous coal are being determined.In this quarter, the synthesis of molybdenum sulfide in a microemulsion system with an alcohol-to-surfactant mass ratio of 3.5 is reported.

  15. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Technical progress report, April 1993--June 1993

    SciTech Connect

    Boakye, E.; Vittal, M.; Osseo-Asare, K.

    1993-07-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of manometer size is being carried out. It is based on the molecular design of inverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis is on molybdenum- and iron-based catalysts, but the techniques being developed should also be generally applicable. The size of these very small and monodispersed particles will be accurately determined both separately and after in situ and ex situ coal impregnation. The as-prepared nanoparticles as well as the catalyst-impregnated coal matrix are characterized using a battery of techniques, including g dynamic light scattering, x-ray diffraction and transmission electron microscopy. Catalytic activity tests are conducted under standardized coal liquefaction conditions. The effects of particle size of these unsupported catalysts on the product yield and distribution during conversion of a bituminous and a subbituminous coal are being determined. This report discusses molybdenum sulfide particle synthesis, characterization, and microemulsion characterization.

  16. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Technical progress report, April 1992--June 1992

    SciTech Connect

    Osseo-Asare, K.; Boakye, E.; Radovic, L.R.

    1992-07-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of manometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. The size of these very small and monodispersed particles will be accurately determined both separately and after in situ and ex situ coal impregnation. The as-prepared nanoparticles as well as the catalyst-impregnated coal or char matrix will be characterized using the following techniques: dynamic light scattering, x-ray diffraction, x-ray photoelectron spectroscopy, scanning and/or transmission electron microscopy, and selective chemisorption. Catalytic activity tests will be conducted under standardized conditions in both hydrogenation and hydrodesulfurization reactions. The effect of particle size of these unsupported catalysts on the product yield and distribution during liquefaction of a bituminous and a subbituminous coal will thus be quantitatively determined.This quarter, the effect of ammonium tetrathiomolybdate concentration on the synthesis of molybdenum sulfide in the 0.15 M NP-5/cyclohexane/water microemulsion system is discussed.

  17. New catalysts for coal liquefaction and new nanocrystalline catalysts synthesis methods

    SciTech Connect

    Linehan, J.C.; Matson, D.W.; Darab, J.G.

    1994-09-01

    The use of coal as a source of transportation fuel is currently economically unfavorable due to an abundant world petroleum supply and the relatively high cost of coal liquefaction. Consequently, a reduction in the cost of coal liquefaction, for example by using less and/or less costly catalysts or lower liquefaction temperatures, must be accomplished if coal is to play an significant role as a source of liquid feedstock for the petrochemical industry. The authors and others have investigated the applicability of using inexpensive iron-based catalysts in place of more costly and environmentally hazardous metal catalysts for direct coal liquefaction. Iron-based catalysts can be effective in liquefying coal and in promoting carbon-carbon bond cleavage in model compounds. The authors have been involved in an ongoing effort to develop and optimize iron-based powders for use in coal liquefaction and related petrochemical applications. Research efforts in this area have been directed at three general areas. The authors have explored ways to optimize the effectiveness of catalyst precursor species through use of nanocrystalline materials and/or finely divided powders. In this effort, the authors have developed two new nanophase material production techniques, Modified Reverse Micelle (MRM) and the Rapid Thermal Decomposition of precursors in Solution (RTDS). A second effort has been aimed at optimizing the effectiveness of catalysts by variations in other factors. To this, the authors have investigated the effect that the crystalline phase has on the capacity of iron-based oxide and oxyhydroxide powders to be effectively converted to an active catalyst phase under liquefaction conditions. And finally, the authors have developed methods to produce active catalyst precursor powders in quantities sufficient for pilot-scale testing. Major results in these three areas are summarized.

  18. Design, synthesis, and characterization of novel fine-particle, unsupported catalysts for coal liquefaction

    SciTech Connect

    Klein, M.T.

    1991-02-22

    The first task in our proposed study of catalysts for coal liquefaction was to prepare ultrafine dispersed metal sulfide particles by reactive precipitation from solutions of appropriate metal precursors. At this point, equipment to allow us to prepare these air-sensitive materials in an anaerobic environment has been acquired and assembled. Initial experiments aimed at synthesizing iron sulfide particles have been initiated. As part of the investigation of short contact time catalytic coal liquefaction, initial efforts focused on the noncatalytic pyrolysis reactions of coal and a model compound, Dibenzyl ether (DBE). Two different reactor configurations were examined; catalytic experiments are planned for the coming month.

  19. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Technical progress report, July 1992--September 1992

    SciTech Connect

    Boakye, E.; Vittal, M.; Osseo-Asare, K.

    1992-10-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of manometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle. nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. The size of these very small and monodispersed particles will be accurately determined both separately and after in situ and ex situ coal impregnation. The as-prepared nanoparticles as well as the catalyst-impregnated coal or char matrix will be characterized using the following techniques: dynamic light scattering, x-ray diffraction, x-ray photoelectron spectroscopy, scanning and/or transmission electron microscopy, and selective chemisorption. Catalytic activity tests will be conducted under standardized conditions in both hydrogenation and hydrodesulfurization reactions. The effect of particle size of these unsupported catalysts on the product yield and distribution during liquefaction of a bituminous and a subbituminous coal will thus be quantitatively determined.

  20. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Technical progress report, January 1992--March 1992

    SciTech Connect

    Osseo-Asare, K.; Boakye, E.; Radovic, L.R.

    1992-05-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of manometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. The size of these very small and monodispersed particles will be accurately determined both separately and after in situ and ex situ coal impregnation. The as-prepared nanoparticles as well as the catalyst-impregnated coal or char matrix will be characterized using the following techniques: dynamic light scattering, x-ray diffraction, x-ray photoelectron spectroscopy, scanning and/or transmission electron microscopy, and selective chemisorption. Catalytic activity tests will be conducted under standardized conditions in both hydrogenation and hydrodesulfurization reactions. The effect of particle size of these unsupported catalysts on the product yield and distribution during liquefaction of a bituminous and a subbituminous coal will thus be quantitatively determined.

  1. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Technical progress report, July--September 1993

    SciTech Connect

    Boakye, E.; Vittal, M.; Osseo-Asare, K.

    1993-10-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of manometer size is being carried out. It is based on the molecular design of inverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis is on molybdenum- and iron-based catalysts, but the techniques being developed should also be generally applicable. The size of these very small and monodispersed particles will be accurately determined both separately and after in situ and ex situ coal impregnation. The as-prepared nanoparticles as well as the catalyst-impregnated coal matrix are characterized using a battery of techniques, including dynamic light scattering, x-ray diffraction and transmission electron microscopy. Catalytic activity tests are conducted under standardized coal liquefaction conditions. The effects of particle size of these unsupported catalysts on the product yield and distribution during conversion of a bituminous and a subbituminous coal are being determined.

  2. Synthetic-fuel production using Texas lignite and a very-high-temperature gas-cooled reactor for process heat and electrical power generation

    SciTech Connect

    Ross, M.A.; Klein, D.E.

    1981-05-01

    This report presents two alternatives to increased reliance on foreign energy sources; each method utilizes the abundant domestic resources of coal, uranium, and thorium. Two approaches are studied in this report. First, the gasification and liquefaction of coal are accomplished with Lurgi gasifiers and Fischer-Tropsch synthesis. A 50,000 barrel per day facility, consuming 15 million tons of lignite coal per year, is used. Second, a nuclear-assisted coal conversion approach is studied using a very high temperature gas-cooled reactor with a modified Lurgi gasifier and Fischer-Tropsch synthesis. This is a preliminary report presenting background data and a means of comparison for the two approaches considered.

  3. Direct catalytic conversion of synthesis gas to lower olefins

    SciTech Connect

    Janardanarao, M. )

    1990-09-01

    Direct conversion of synthesis gas to lower olefins has been considered as a possible solution to meet the growing demand for chemical feedstocks such as ethylene, propylene, and butylenes. This review covers the various catalyst systems and operating conditions that have been used in meeting this objective. Though the product distribution in Fischer--Tropsch synthesis is governed by the existence of an Anderson--Schultz--Flory polymerization model, certain modifications in the catalyst formulations have produced a shift toward lower molecular weight olefins. At the present time, the yields and selectivities of lower olefins are far from optimal, but continued research efforts in this area may lead to the development of stable catalyst systems capable of producing highly desirable distributions of lower olefins.

  4. Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

    SciTech Connect

    Akio Ishikawa; Manuel Ojeda; Enrique Iglesia

    2005-09-30

    This project extends previously discovered Fe-based catalysts to hydrogen-poor synthesis gas streams derived from coal and biomass sources. These catalysts have shown unprecedented Fischer-Tropsch synthesis rate, selectivity for feedstocks consisting of synthesis gas derived from methane. During the first reporting period, we certified a microreactor, installed required analytical equipment, and reproduced synthetic protocols and catalytic results previously reported. During the second reporting period, we prepared several Fe-based compositions for Fischer-Tropsch synthesis and tested the effects of product recycle under both subcritical and supercritical conditions. During the third reporting period, we improved the catalysts preparation method, which led to Fe-based FT catalysts with the highest FTS reaction rates and selectivities so far reported, a finding that allowed their operation at lower temperatures and pressures with high selectivity to desired products (C{sub 5+}, olefins). During this fourth reporting period, we have determined the effects of different promoters on catalytic performance. More specifically, we have found that the sequence in which promoters are introduced has a marked positive impact on rates and selectivities. Cu or Ru chemical promoters should be impregnated before K to achieve higher Fischer-Tropsch synthesis rates. The catalyst prepared in this way was evaluated for 240 h, showing a high catalytic activity and stability after an initial period of time necessary for the formation of the active phases. Concurrently, we are studying optimal activation procedures, which involve the reduction and carburization of oxide precursors during the early stages of contact with synthesis gas. Activation at low temperatures (523 K), made possible by optimal introduction of Cu or Ru, leads to lower catalyst surface area than higher activation temperatures, but to higher reaction rates, because such low temperatures avoid concurrent deactivation

  5. Status and prospects in higher alcohols synthesis from syngas.

    PubMed

    Luk, Ho Ting; Mondelli, Cecilia; Ferré, Daniel Curulla; Stewart, Joseph A; Pérez-Ramírez, Javier

    2017-03-06

    Higher alcohols are important compounds with widespread applications in the chemical, pharmaceutical and energy sectors. Currently, they are mainly produced by sugar fermentation (ethanol and isobutanol) or hydration of petroleum-derived alkenes (heavier alcohols), but their direct synthesis from syngas (CO + H2) would comprise a more environmentally-friendly, versatile and economical alternative. Research efforts in this reaction, initiated in the 1930s, have fluctuated along with the oil price and have considerably increased in the last decade due to the interest to exploit shale gas and renewable resources to obtain the gaseous feedstock. Nevertheless, no catalytic system reported to date has performed sufficiently well to justify an industrial implementation. Since the design of an efficient catalyst would strongly benefit from the establishment of synthesis-structure-function relationships and a deeper understanding of the reaction mechanism, this review comprehensively overviews syngas-based higher alcohols synthesis in three main sections, highlighting the advances recently made and the challenges that remain open and stimulate upcoming research activities. The first part critically summarises the formulations and methods applied in the preparation of the four main classes of materials, i.e., Rh-based, Mo-based, modified Fischer-Tropsch and modified methanol synthesis catalysts. The second overviews the molecular-level insights derived from microkinetic and theoretical studies, drawing links to the mechanisms of Fischer-Tropsch and methanol syntheses. Finally, concepts proposed to improve the efficiency of reactors and separation units as well as to utilise CO2 and recycle side-products in the process are described in the third section.

  6. Synthesis of Organics in the Early Solar Nebula

    NASA Astrophysics Data System (ADS)

    Johnson, Natasha M.; Manning, S.; Nuth, J. A., III

    2007-10-01

    It is unknown what process or processes made the organics that are found or detected in extraterrestrial materials. One process that forms organics are Fischer-Tropsch type (FTT) reactions. Fischer-Tropsch type synthesis produces complex hydrocarbons by hydrogenating carbon monoxide via surface mediated reactions. The products of these reactions have been well-studied using `natural’ catalysts [1] and calculations of the efficiency of FTT synthesis in the Solar Nebula suggest that these types of reactions could make significant contributions to material near three AU [2]. We use FTT synthesis to coat Fe-silicate amorphous grains with organic material to simulate the chemistry in the early Solar Nebula. These coatings are composed of macromolecular organic phases [3]. Previous work also showed that as the grains became coated, Haber-Bosch type reactions took place resulting in nitrogen-bearing organics [4]. Our experiments consist of circulating CO, N2, and H2 gas through Fe- amorphous silicate grains that are maintained at a specific temperature in a closed system. The gases are passed through an FTIR spectrometer and are measured to monitor the reaction progress. Samples are analyzed using FTIR, and GCMS (including pyrolysis) and extraction techniques are used to analyze the organic coatings. These experiments show that these types of reactions are an effective means to produce complex hydrocarbons. We present the analysis of the produced organics (solid and gas phase) and the change in the production rate of several compounds as the grains become coated. Organics generated by this technique could represent the carbonaceous material incorporated in comets and meteorites. References: [1] Hayatsu and Anders 1981. Topics in Current Chemistry 99:1-37. [2] Kress and Tielens 2001. MAPS 36:75-91. [3] Johnson et al. 2004. #1876. 35th LPSC. [4] Hill and Nuth 2003. Astrobiology 3:291-304. This work was supported by a grant from NASA.

  7. Magnetocaloric Liquefaction

    SciTech Connect

    2016-10-05

    A new approach to magnetocaloric refrigeration is being developed by researchers at PNNL and their partners. The technology could replace the entire hydrogen liquefaction process and reduce the cost of liquefying hydrogen by 25 percent or more.

  8. Magnetocaloric Liquefaction

    ScienceCinema

    None

    2016-10-12

    A new approach to magnetocaloric refrigeration is being developed by researchers at PNNL and their partners. The technology could replace the entire hydrogen liquefaction process and reduce the cost of liquefying hydrogen by 25 percent or more.

  9. Attrition Resistant Fischer-Tropsch Catalysts Based on FCC Supports

    SciTech Connect

    Adeyiga, Adeyinka

    2010-02-05

    Commercial spent fluid catalytic cracking (FCC) catalysts provided by Engelhard and Albemarle were used as supports for Fe-based catalysts with the goal of improving the attrition resistance of typical F-T catalysts. Catalysts with the Ruhrchemie composition (100 Fe/5 Cu/4.2 K/25 spent FCC on mass basis) were prepared by wet impregnation. XRD and XANES analysis showed the presence of Fe{sub 2}O{sub 3} in calcined catalysts. FeC{sub x} and Fe{sub 3}O{sub 4} were present in the activated catalysts. The metal composition of the catalysts was analyzed by ICP-MS. F-T activity of the catalysts activated in situ in CO at the same conditions as used prior to the attrition tests was measured using a fixed bed reactor at T = 573 K, P = 1.38 MPa and H{sub 2}:CO ratio of 0.67. Cu and K promoted Fe supported over Engelhard provided spent FCC catalyst shows relatively good attrition resistance (8.2 wt% fines lost), high CO conversion (81%) and C{sub 5}+ hydrocarbons selectivity (18.3%).

  10. Development of improved iron Fischer-Tropsch catalysts

    SciTech Connect

    Bukur, D.B.

    1990-06-17

    The objective of proposed research is development of catalysts with enhanced slurry phase activity and better selectivity to fuel range products, through a more detailed understanding and systematic studies of the effects of pretreatment procedures and promoters/binders (silica) on catalyst performance.

  11. Development of improved iron Fischer-Tropsch catalysts

    SciTech Connect

    Bukur, D.B.; Patel, S.A.; Dalai, A.K.; Jayanthi, G.; Ledakowicz, S.

    1990-04-30

    The objective of proposed research is development of catalysts with enhanced slurry phase activity and better selectivity to fuel range products, through a more detailed understanding and systematic studies of the effects of pretreatment procedures and promoters/binders (silica) on catalyst performance.

  12. Fischer-Tropsch Synthetic Fuel Evaluations HMMWV Test Track Evaluation

    DTIC Science & Technology

    2009-09-01

    area code) Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std. Z39.18 v EXECUTIVE SUMMARY This test utilizes a HMMWV in comparing four...C-L053. The U.S. Army Tank- Automotive RD&E Center, Force Projection Technologies, Warren, Michigan administered the project. Mr. Luis Villahermosa...National Automotive Center served as project technical monitors. The authors would also like to recognize the contribution of Jeff Sellers for his

  13. Development of improved iron Fischer-Tropsch catalysts

    SciTech Connect

    Bukur, D.B.

    1992-01-10

    The objective of proposed research is development of catalysts with enhanced slurry phase activity and better selectivity to fuel range products, through a more detailed understanding and systematic studies of the effects of pretreatment procedures and promoters/binders (silica) on catalyst performance.

  14. Attrition resistant Fischer-Tropsch catalyst and support

    DOEpatents

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    2004-05-25

    A catalyst support having improved attrition resistance and a catalyst produced therefrom. The catalyst support is produced by a method comprising the step of treating calcined .gamma.-alumina having no catalytic material added thereto with an acidic aqueous solution having an acidity level effective for increasing the attrition resistance of the calcined .gamma.-alumina.

  15. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Technical progress report, January--March 1991

    SciTech Connect

    Osseo-Asare, K.; Radovic, L.R.

    1991-04-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. The size of these very small and monodispersed particles will be accurately determined both separately and after in situ and ex situ coal impregnation. The as-prepared nanoparticles as well as the catalyst-impregnated coal or char matrix will be characterized using the following techniques: dynamic light scattering, x-ray diffraction, x-ray photoelectron spectroscopy, scanning and/or transmission electron microscopy, and selective chemisorption.

  16. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Technical progress report, July--September 1991

    SciTech Connect

    Osseo-Asare, K.; Boakye, E.; Vaidyanathan, N.; Radovic, L.R.

    1991-10-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metalbearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. The size of these very small and monodispersed particles will be accurately determined both separately and after in situ and ex situ coal impregnation. The as-prepared nanoparticles as well as the catalyst-impregnated coal or char matrix will be characterized using the following techniques: dynamic light scattering, x-ray diffraction, x-ray photoelectron spectroscopy, scanning and/or transmission electron microscopy, and selective chemisorption.

  17. Liquefaction process

    DOEpatents

    Gorbaty, Martin L.; Stone, John B.; Poddar, Syamal K.

    1982-01-01

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by pretreatment with a combination of pretreating agents comprising SO.sub.2 and an oxidizing agent. The pretreatment is believed to convert at least a portion of the scale-forming components and particularly calcium, to the corresponding sulfate prior to liquefaction. The pretreatment may be accomplished with the combination of pretreating agents either simultaneously by using a mixture comprising SO.sub.2 and an oxidizing agent or sequentially by first treating with SO.sub.2 and then with an oxidizing agent.

  18. Liquefaction process

    DOEpatents

    Poddar, Syamal K.

    1981-01-01

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by pretreatment with a combination of pretreating agents comprising SO.sub.2 and an oxidizing agent. It is essential to effective operation that the moisture content of the solid carbonaceous material be within the range from about 10 to about 25 wt %, based on dry solid carbonaceous material, during the pretreatment. The pretreatment is believed to convert at least a portion of the scale-forming components and particularly calcium, to the corresponding sulfate prior to liquefaction. The pretreatment may be accomplished with the combination of pretreating agents either simultaneously by using a mixture comprising SO.sub.2 and a gaseous oxidizing agent or sequentially by first treating with SO.sub.2 and then with an oxidizing agent.

  19. Alkali promoted molybdenum (IV) sulfide based catalysts, development and characterization for alcohol synthesis from carbon monoxide and hydrogen

    NASA Astrophysics Data System (ADS)

    Molina, Belinda Delilah

    For more than a century transition metal sulfides (TMS) have been the anchor of hydro-processing fuels and upgrading bitumen and coal in refineries worldwide. As oil supplies dwindle and environmental laws become more stringent, there is a greater need for cleaner alternative fuels and/or synthetic fuels. The depletion of oil reserves and a rapidly increasing energy demand worldwide, together with the interest to reduce dependence on foreign oil makes alcohol production for fuels and chemicals via the Fischer Tropsch synthesis (FTS) very attractive. The original Fischer-Tropsch (FT) reaction is the heart of all gas-to-liquid technologies; it creates higher alcohols and hydrocarbons from CO/H2 using a metal catalyst. This research focuses on the development of alkali promoted MoS2-based catalysts to investigate an optimal synthesis for their assistance in the production of long chain alcohols (via FTS) for their use as synthetic transportation liquid fuels. Properties of catalytic material are strongly affected by every step of the preparation together with the quality of the raw materials. The choice of a laboratory method for preparing a given catalyst depends on the physical and chemical characteristics desired in the final composition. Characterization methods of K0.3/Cs0.3-MoS2 and K0.3 /Cs0.3-Co0.5MoS2 catalysts have been carried out through Scanning Electron Microscopy (SEM), BET porosity and surface analysis, Transmission Electron Microscopy (TEM) and X-Ray Diffraction (XRD). Various characterization methods have been deployed to correlate FTS products versus crystal and morphological properties of these heterogeneous catalysts. A lab scale gas to liquid system has been developed to evaluate its efficiency in testing FT catalysts for their production of alcohols.

  20. Active phase distribution changes within a catalyst particle during Fischer–Tropsch synthesis as revealed by multi-scale microscopy

    SciTech Connect

    Cats, K. H.; Andrews, J. C.; Stephan, O.; March, K.; Karunakaran, C.; Meirer, F.; de Groot, F. M. F.; Weckhuysen, B. M.

    2016-02-16

    In this study, the Fischer-Tropsch synthesis (FTS) reaction is one of the most promising processes to convert alternative energy sources, such as natural gas, coal or biomass, into liquid fuels and other high-value products. Despite its commercial implementation, we still lack fundamental insights into the various deactivation processes taking place during FTS. In this work, a combination of three methods for studying single catalyst particles at different length scales has been developed and applied to study the deactivation of Co/TiO2 Fischer-Tropsch synthesis (FTS) catalysts. By combining transmission X-ray microscopy (TXM), scanning transmission X-ray microscopy (STXM) and scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) we visualized changes in the structure, aggregate size and distribution of supported Co nanoparticles that occur during FTS. At the microscale, Co nanoparticle aggregates are transported over several μm leading to a more homogeneous Co distribution, while at the nanoscale Co forms a thin layer of ~1-2 nm around the TiO2 support. The formation of the Co layer is the opposite case to the “classical” strong metal-support interaction (SMSI) in which TiO2 surrounds the Co, and is possibly related to the surface oxidation of Co metal nanoparticles in combination with coke formation. In other words, the observed migration and formation of a thin CoOx layer are similar to a previously discussed reaction-induced spreading of metal oxides across a TiO2 surface.

  1. Active phase distribution changes within a catalyst particle during Fischer–Tropsch synthesis as revealed by multi-scale microscopy

    DOE PAGES

    Cats, K. H.; Andrews, J. C.; Stephan, O.; ...

    2016-02-16

    In this study, the Fischer-Tropsch synthesis (FTS) reaction is one of the most promising processes to convert alternative energy sources, such as natural gas, coal or biomass, into liquid fuels and other high-value products. Despite its commercial implementation, we still lack fundamental insights into the various deactivation processes taking place during FTS. In this work, a combination of three methods for studying single catalyst particles at different length scales has been developed and applied to study the deactivation of Co/TiO2 Fischer-Tropsch synthesis (FTS) catalysts. By combining transmission X-ray microscopy (TXM), scanning transmission X-ray microscopy (STXM) and scanning transmission electron microscopy-electronmore » energy loss spectroscopy (STEM-EELS) we visualized changes in the structure, aggregate size and distribution of supported Co nanoparticles that occur during FTS. At the microscale, Co nanoparticle aggregates are transported over several μm leading to a more homogeneous Co distribution, while at the nanoscale Co forms a thin layer of ~1-2 nm around the TiO2 support. The formation of the Co layer is the opposite case to the “classical” strong metal-support interaction (SMSI) in which TiO2 surrounds the Co, and is possibly related to the surface oxidation of Co metal nanoparticles in combination with coke formation. In other words, the observed migration and formation of a thin CoOx layer are similar to a previously discussed reaction-induced spreading of metal oxides across a TiO2 surface.« less

  2. Slurry Phase Iron Catalysts for Indirect Coal LIquefaction.

    SciTech Connect

    Datye, A.K.

    1997-08-08

    This report covers the fourth six month period of this three year grant under the University Coal Research program. During this period, we have begun the synthesis of precipitated catalysts using a bench-top spray dryer. The influence of binders on particle strength was also studied using the ultrasonic fragmentation approach to derive particle breaking stress. A similar approach was used to derive particle strength of catalysts obtained from Mr. Robert Gormley at FETC. Over the next six month period, this work will be continued while the catalysts prepared here will be examined by TPR to determine reducibility and the extent of adverse iron-silica interactions. A fundamental study of Fe/silica interactions has been performed using temperature programmed reaction and TEM to provide understanding of how the silica binders influence the activity of Fe catalysts. To understand differences in the reducibility of the iron phase caused by silica, we have set up a temperature programmed reduction facility. TPR in H, as well as in CO was performed of Fe/ SiO, catalysts prepared by impregnation as well as by precipitation. What is unique about these studies is that high resolution TEM was performed on samples removed from the reactor at various stages of reduction. This helps provide direct evidence for the phase changes that are detected by TPR. We have continued the analysis of catalysts received from slurry reactor runs at Texas A&M university (TAMU) and the University of Kentucky Center for Applied Energy Research (CAER) by x-ray diffraction. The purpose of the XRD analysis was to determine the phase composition of catalysts derived from a slurry reaction run using Fe Fischer-Tropsch catalysts. We had previously described how catalyst removed in the hot wax may oxidize to magnetite if the wax is air-exposed. We have now received catalysts from CAER that were removed under a protective inert blanket, and we are in the process of analyzing them, but preliminary work

  3. Bioechnology of indirect liquefaction

    SciTech Connect

    Datta, R.; Jain, M.K.; Worden, R.M.; Grethlein, A.J.; Soni, B.; Zeikus, J.G.; Grethlein, H.

    1990-05-07

    The project on biotechnology of indirect liquefaction was focused on conversion of coal derived synthesis gas to liquid fuels using a two-stage, acidogenic and solventogenic, anaerobic bioconversion process. The acidogenic fermentation used a novel and versatile organism, Butyribacterium methylotrophicum, which was fully capable of using CO as the sole carbon and energy source for organic acid production. In extended batch CO fermentations the organism was induced to produce butyrate at the expense of acetate at low pH values. Long-term, steady-state operation was achieved during continuous CO fermentations with this organism, and at low pH values (a pH of 6.0 or less) minor amounts of butanol and ethanol were produced. During continuous, steady-state fermentations of CO with cell recycle, concentrations of mixed acids and alcohols were achieved (approximately 12 g/l and 2 g/l, respectively) which are high enough for efficient conversion in stage two of the indirect liquefaction process. The metabolic pathway to produce 4-carbon alcohols from CO was a novel discovery and is believed to be unique to our CO strain of B. methylotrophicum. In the solventogenic phase, the parent strain ATCC 4259 of Clostridium acetobutylicum was mutagenized using nitrosoguanidine and ethyl methane sulfonate. The E-604 mutant strain of Clostridium acetobutylicum showed improved characteristics as compared to parent strain ATCC 4259 in batch fermentation of carbohydrates.

  4. Production of High Molecular Weight Organic Compounds on the Surfaces of Amorphous Iron Silicate Catalysts: Implications for Organic Synthesis in the Solar Nebula

    NASA Technical Reports Server (NTRS)

    Gilmour, I.; Hill, H. G. M.; Pearson, V. K.; Sephton, M. A.; Nuth, J. A., III

    2002-01-01

    The high molecular weight organic products of Fischer-Tropsch/Haber-Bosch syntheses on the surfaces of Fe-silicate catalysts have been studied by GCMS. Additional information is contained in the original extended abstract.

  5. Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

    SciTech Connect

    Enrique Iglesia; Akio Ishikawa; Manual Ojeda; Nan Yao

    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 close 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

  6. Fischer–Tropsch Synthesis: Characterization Rb Promoted Iron Catalyst

    SciTech Connect

    Sarkar,A.; Jacobs, G.; Ji, Y.; Hamdeh, H.; Davis, B.

    2008-01-01

    Rubidium promoted iron Fischer-Tropsch synthesis (FTS) catalysts were prepared with two Rb/Fe atomic ratios (1.44/100 and 5/100) using rubidium nitrate and rubidium carbonate as rubidium precursors. Results of catalytic activity and deactivation studies in a CSTR revealed that rubidium promoted catalysts result in a steady conversion with a lower deactivation rate than that of the corresponding unpromoted catalyst although the initial activity of the promoted catalyst was almost half that of the unpromoted catalyst. Rubidium promotion results in lower methane production, and higher CO2, alkene and 1-alkene fraction in FTS products. M{umlt o}ssbauer spectroscopic measurements of CO activated and working catalyst samples indicated that the composition of the iron carbide phase formed after carbidization was -Fe5 C2 for both promoted and unpromoted catalysts. However, in the case of the rubidium promoted catalyst, '-Fe2.2C became the predominant carbidic phase as FTS continued and the overall catalyst composition remained carbidic in nature. In contrast, the carbide content of the unpromoted catalyst was found to decline very quickly as a function of synthesis time. Results of XANES and EXAFS measurements suggested that rubidium was present in the oxidized state and that the compound most prevalent in the active catalyst samples closely resembled that of rubidium carbonate.

  7. Isotopic characterisation of prebiotic synthesis of organic material

    NASA Technical Reports Server (NTRS)

    Kerridge, J. F.; Chang, S.

    1986-01-01

    Many primitive meteorites contain an insoluble organic material, much like terrestrial kerogen, whose mode of origin is currently unknown. When sujbected to stepwise decomposition, this material, unlike its terrestrial counterpart, reveals characteristic release patterns for the stable isotopes of carbon, hydrogen and nitrogen as a function of fractional release of each element. The purpose of this study is to try to match those release patterns using organic matter synthesised in the laboratory under controlled conditions. If successful, such a study would shed light on the origin of kerogen-like organic matter in the early solar system and, by extension, on prebiotic organic synthesis in general. The range of possible syntheses, starting materials and reaction conditions to be investigated is considerable. Samples analysed to date include: a heavy oil produced by Fischer-Tropsch-type catalysis of CO + H2; a solid residue generated by a plasma discharge in CO + H2 + N2; a solid deposited on the electrodes of a Miller-Urey synthesis operating on CH4 + H2O + N2; and a solid residue formed by polymerization of light hydrocarbons procured by a Miller-Urey discharge acting on CH4. Significant structure is observed in the release patterns for the carbon and hydrogen isotopes from the synthetic samples, though there is little evidence for isotopic fractionation during the analysis itself.

  8. Stoichiometry of wood liquefaction

    SciTech Connect

    Davis, H.G.

    1980-10-01

    The overall chemistry of Douglas Fir liquefaction as evidenced by Rust Engineering Company's Test Run 8 at Albany, Oregon has been examined. It is concluded that the true total yield of non-gaseous product (oil + water solubles + char) is higher than was measured - probably as high as 52 to 55% of dry wood feed. Wood decomposes to give water and carbon dioxide, and carbon monoxide in the gas feed reacts with water to give carbon dioxide and hydrogen. However, there is a substantial net reaction of synthesis gas (CO + H/sub 2/) during the process. This indicates that the reaction CO + (wood product) = CO/sub 2/ + (reduced wood product) is important in formation of low oxygen product oil. Overall stoichiometry (approximate) is: 100 lbs wood + 0.5 Mol CO ..-->.. 1.1 Mol CO/sub 2/ + 0.5 Mol H/sub 2/O + 55 lbs non-vapor product. Consumption of synthesis gas in the process is (very approximately) 1300 SCF/bbl product. The product oil has a hydrogen/carbon atom ratio of 1.2 and is highly aromatic. This analysis of the reaction applies specifically to the particular mode of operation used at Albany; i.e., to the so-called PERC process with a very high recycle of product oil. However, it is shown that the total yield of non-gaseous products is quite insensitive to the average analysis of the product. Thus we would expect total yields in the 50s with alternate processes - such as the LBL water slurry process. What will be different and must be determined is the distribution among water insoluble oil, water solubles and char and the degree of reduction of oxygen content by reaction with carbon monoxide.

  9. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Technical progress report, October--December 1993

    SciTech Connect

    Boakye, E.; Radovic, L.R.; Osseo-Asare, K.

    1994-09-01

    Three different synthesis protocols were used to synthesize nanosize molybdenum sulfide particles in the microemulsion system polyoxyethylene(5)nonylphenyl ether (NP-5)/cyclohexane/water: (a) acid-solubilized microemulsion plus tetrathiomolybdate (ASMPT), (b) tetrathiomolybdate-solubilized microemulsion plus acid (TSMPA) and (c) microemulsion plus microemulsion (MPM), i.e., acid-solubilized microemulsion plus tetrathiomolybdate-solubilized microemulsion. The particle size was found to depend on the synthesis method, especially at water-to-surfactant molar ratios (R) greater than 2.5. At R=3.5-4.5, the average particle size increased according to the synthesis method in the order: ASMPT < MPM < TSMPA. Furthermore, for each synthesis protocol, the average particle diameter increased with the water-to-surfactant molar ratio (R). These trends are rationalized by considering: (a) the increase in the rate of exchange of materials between the inverse micelles as R is increased, and (b) the different effects of the electrolytes (i.e., sulfuric acid and ammonium tetrathiomolybdate plus sodium hydroxide) on microemulsion stability.

  10. Coal liquefaction quenching process

    DOEpatents

    Thorogood, Robert M.; Yeh, Chung-Liang; Donath, Ernest E.

    1983-01-01

    There is described an improved coal liquefaction quenching process which prevents the formation of coke with a minimum reduction of thermal efficiency of the coal liquefaction process. In the process, the rapid cooling of the liquid/solid products of the coal liquefaction reaction is performed without the cooling of the associated vapor stream to thereby prevent formation of coke and the occurrence of retrograde reactions. The rapid cooling is achieved by recycling a subcooled portion of the liquid/solid mixture to the lower section of a phase separator that separates the vapor from the liquid/solid products leaving the coal reactor.

  11. Synthesis and characterization of catalysts for the selective transformation of biomass-derived materials

    NASA Astrophysics Data System (ADS)

    Ghampson, Isaac Tyrone

    The experimental work in this thesis focuses on generating catalysts for two intermediate processes related to the thermal conversion of lignocellulosic biomass: the synthesis and characterization of mesoporous silica supported cobalt catalysts for the Fischer-Tropsch reaction, and an exploration of the reactivity of bulk and supported molybdenum-based nitride catalysts for the hydrodeoxygenation (HDO) of guaiacol, a lignin model compound. The first section of the work details the synthesis of a series of silica-supported cobalt Fischer-Tropsch catalysts with pore diameters ranging from 2-23 nm. Detailed X-ray diffraction measurements were used to determine the composition and particle diameters of the metal fraction, analyzed as a three-phase system containing Cofcc, Cohcp and CoO particles. Catalyst properties were determined at three stages in catalyst history: (1) after the initial calcination step to thermally decompose the catalyst precursor into Co3O4, (2) after the hydrogen reduction step to activate the catalyst to Co and (3) after the FT reaction. From the study, it was observed that larger pore diameters supported higher turnover frequency; smaller pore diameters yielded larger mole fraction of CoO; XRD on post-reduction and post-FTS catalyst samples indicated significant changes in dispersivity after reduction. In the next section, the catalytic behaviors of unsupported, activated carbon-, alumina-, and SBA-15 mesoporous silica-supported molybdenum nitride catalysts were evaluated for the hydrodeoxygenation of guaiacol (2-methoxy phenol) at 300°C and 5 MPa. The nitride catalysts were prepared by thermal decomposition of bulk and supported ammonium heptamolybdate to form MoO 3 followed by nitridation in either flowing ammonia or a nitrogen/hydrogen mixture. The catalytic properties were strongly affected by the nitriding and purging treatment as well as the physical and chemical properties of support. The overall reaction was influenced by the

  12. Cooperative research program in coal liquefaction

    SciTech Connect

    Huffman, G.P.

    1991-01-01

    This Quarterly Report on coal liquefaction research includes discussion in the areas of (1) Iron Based Catalysts for Coal Liquefaction; (2) Exploratory Research on Coal Conversion; (3) Novel Coal Liquefaction Concepts; (4) Novel Catalysts for Coal Liquefaction. (VC)

  13. Cooperative research program in coal liquefaction

    SciTech Connect

    Huffman, G.P.

    1992-01-01

    Research continues on coal liquefaction in the following areas: (1) Iron Based Catalysts for Coal Liquefaction; (2) Exploratory Research on Coal Conversion; (3) Novel Coal Liquefaction Concepts; (4) Novel Catalysts for Coal Liquefaction. (VC)

  14. Coal Liquefaction Processes.

    ERIC Educational Resources Information Center

    Yen, T. F.

    1979-01-01

    Described is a graduate level engineering course offered at the University of Southern California on coal liquefaction processes. Lecture topics and course requirements are discussed. A 64-item bibliography of papers used in place of a textbook is included. (BT)

  15. Coal liquefaction and hydrogenation

    DOEpatents

    Schindler, Harvey D.; Chen, James M.

    1985-01-01

    Disclosed is a coal liquefaction process using two stages. The first stage liquefies the coal and maximizes the product while the second stage hydrocracks the remainder of the coal liquid to produce solvent.

  16. Advanced Hydrogen Liquefaction Process

    SciTech Connect

    Schwartz, Joseph; Kromer, Brian; Neu, Ben; Jankowiak, Jerome; Barrett, Philip; Drnevich, Raymond

    2011-09-28

    The project identified and quantified ways to reduce the cost of hydrogen liquefaction, and reduce the cost of hydrogen distribution. The goal was to reduce the power consumption by 20% and then to reduce the capital cost. Optimizing the process, improving process equipment, and improving ortho-para conversion significantly reduced the power consumption of liquefaction, but by less than 20%. Because the efficiency improvement was less than the target, the program was stopped before the capital cost was addressed. These efficiency improvements could provide a benefit to the public to improve the design of future hydrogen liquefiers. The project increased the understanding of hydrogen liquefaction by modeling different processes and thoroughly examining ortho-para separation and conversion. The process modeling provided a benefit to the public because the project incorporated para hydrogen into the process modeling software, so liquefaction processes can be modeled more accurately than using only normal hydrogen. Adding catalyst to the first heat exchanger, a simple method to reduce liquefaction power, was identified, analyzed, and quantified. The demonstrated performance of ortho-para separation is sufficient for at least one identified process concept to show reduced power cost when compared to hydrogen liquefaction processes using conventional ortho-para conversion. The impact of improved ortho-para conversion can be significant because ortho para conversion uses about 20-25% of the total liquefaction power, but performance improvement is necessary to realize a substantial benefit. Most of the energy used in liquefaction is for gas compression. Improvements in hydrogen compression will have a significant impact on overall liquefier efficiency. Improvements to turbines, heat exchangers, and other process equipment will have less impact.

  17. Coal liquefaction and hydrogenation

    DOEpatents

    Schindler, Harvey D.

    1985-01-01

    The coal liquefaction process disclosed uses three stages. The first stage is a liquefaction. The second and third stages are hydrogenation stages at different temperatures and in parallel or in series. One stage is within 650.degree.-795.degree. F. and optimizes solvent production. The other stage is within 800.degree.-840.degree. F. and optimizes the C.sub.5 -850.degree. F. product.

  18. Design, synthesis, and characterization of novel fine-particle, unsupported catalysts for coal liquefaction. Technical progress report, October 26, 1990--January 26, 1991: Draft

    SciTech Connect

    Klein, M.T.

    1991-02-22

    The first task in our proposed study of catalysts for coal liquefaction was to prepare ultrafine dispersed metal sulfide particles by reactive precipitation from solutions of appropriate metal precursors. At this point, equipment to allow us to prepare these air-sensitive materials in an anaerobic environment has been acquired and assembled. Initial experiments aimed at synthesizing iron sulfide particles have been initiated. As part of the investigation of short contact time catalytic coal liquefaction, initial efforts focused on the noncatalytic pyrolysis reactions of coal and a model compound, Dibenzyl ether (DBE). Two different reactor configurations were examined; catalytic experiments are planned for the coming month.

  19. Liquefaction of cornstalk in hot-compressed phenol-water medium to phenolic feedstock for the synthesis of phenol-formaldehyde resin.

    PubMed

    Wang, Mingcun; Xu, Chunbao Charles; Leitch, Mathew

    2009-04-01

    Cornstalk powders were effectively liquefied in a hot-compressed phenol-water medium (1:4 wt/wt). The optimum liquefaction temperature was around 350 degrees C, where the liquid yield attained a maximum at about 70 wt%. The addition of sodium carbonate showed negligible effect over the Liquefaction product yields. When liquefied in phenol-water medium, essentially no phenol was combined with the liquid products, and the cornstalk-derived bio-oils were partially degraded monomeric and oligomeric products with a broad molecular distribution. Resol type bio-based phenol formaldehyde resins were readily synthesized from the cornstalk-derived bio-oils catalyzed by sodium hydroxide.

  20. Synthetic fuel production using Texas lignite and a very high temperature reactor for process heat

    SciTech Connect

    Ross, M.A.; Klein, D.E.

    1982-03-01

    Two approaches for synthetic fuel production from coal are studied using Texas lignite as the feedstock. First, the gasification and liquefaction of coal are accomplished using Lurgi gasifiers and Fischer-Tropsch synthesis. A 50 000 barrel/day facility, consuming 13.7 million tonne/yr (15.1 million ton/yr) of lignite, is considered. Second, a nuclear-assisted coal conversion approach is studied using a very high temperature gas-cooled reactor with a modified Lurgi gasifier and Fischer-Tropsch synthesis. The nuclear-assisted approach resulted in a 35% reduction in coal consumption. In addition, process steam consumption was reduced by one-half and the oxygen plants were eliminated in the nuclear assisted process. Both approaches resulted in a synthetic oil price higher than the March 1980 imported price of $29.65 per barrel: $36.15 for the lignite-only process and $35.16 for the nuclear-assisted process. No tax advantage was assumed for either process and the utility financing method was used for both economic calculations.

  1. Alkanes in Natural and Synthetic Petroleums: Comparison of Calculated and Actual Compositions.

    PubMed

    Friedel, R A; Sharkey, A G

    1963-03-22

    A similarity exists between the low molecular weight alkane isomers in crude oil and Fischer-Tropsch catalytic synthesis products. The composition of the C(4) through C(7) alkane isomers in a crude oil was calculated quantitatively with the equations previously used to calculate the alkane isomers in Fischer-Tropsch products. These results may have significance in ascertaining the origin of the volatile hydrocarbons in crude oils.

  2. Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

    Observation of methane in the Martian atmosphere has been reported by different detection techniques. Reduction of CO2 and/or CO during serpentization by mineral surface catalyzed Fischer-Tropsch Type (FTT) synthesis may be one possible process responsible for methane generation on Mars. With the evidence a recent study has discovered for serpentinization in deeply buried carbon rich sediments, and more showing extensive water-rock interaction in Martian history, it seems likely that abiotic methane generation via serpentinization reactions may have been common on Mars. Experiments involving mineral-catalyzed hydrothermal organic synthesis processes were conducted at 750 C and 5.5 Kbars. Alkanes, alcohols and carboxylic acids were identified as organic compounds. No "isotopic reversal" of delta C-13 values was observed for alkanes or carboxylic acids, suggesting a different reaction pathway than polymerization. Alcohols were proposed as intermediaries formed on mineral surfaces at experimental conditions. Carbon isotope data were used in this study to unravel the reaction pathways of abiotic formation of organic compounds in hydrothermal systems at high temperatures and pressures. They are instrumental in constraining the origin and evolution history of organic compounds on Mars and other planets.

  3. Meteorites and the RNA World: A Thermodynamic Model of Nucleobase Synthesis within Planetesimals

    NASA Astrophysics Data System (ADS)

    Pearce, Ben K. D.; Pudritz, Ralph E.

    2016-11-01

    The possible meteorite parent body origin of Earth's pregenetic nucleobases is substantiated by the guanine (G), adenine (A), and uracil (U) measured in various meteorites. Cytosine (C) and thymine (T), however, are absent in meteorites, making the emergence of an RNA and later RNA/DNA/protein world problematic. We investigated the meteorite parent body (planetesimal) origin of all nucleobases by computationally modeling 18 reactions that potentially contribute to nucleobase formation in such environments. Out of this list, we identified the two most important reactions for each nucleobase and found that these involve small molecules such as HCN, CO, NH3, and water that ultimately arise from the protoplanetary disks in which planetesimals are built. The primary result of this study is that cytosine is unlikely to persist within meteorite parent bodies due to aqueous deamination. Thymine has a thermodynamically favorable reaction pathway from uracil, formaldehyde, and formic acid but likely did not persist within planetesimals containing H2O2 due to an oxidation reaction with this molecule. Finally, while Fischer-Tropsch (FT) synthesis is found to be the dominant source of nucleobases within our model planetesimal, non-catalytic (NC) synthesis may still be significant under certain chemical conditions (e.g., within CR2 parent bodies). We discuss several major consequences of our results for the origin of the RNA world.

  4. Iron particle size effects for direct production of lower olefins from synthesis gas.

    PubMed

    Torres Galvis, Hirsa M; Bitter, Johannes H; Davidian, Thomas; Ruitenbeek, Matthijs; Dugulan, A Iulian; de Jong, Krijn P

    2012-10-03

    The Fischer-Tropsch synthesis of lower olefins (FTO) is an alternative process for the production of key chemical building blocks from non-petroleum-based sources such as natural gas, coal, or biomass. The influence of the iron carbide particle size of promoted and unpromoted carbon nanofiber supported catalysts on the conversion of synthesis gas has been investigated at 340-350 °C, H(2)/CO = 1, and pressures of 1 and 20 bar. The surface-specific activity (apparent TOF) based on the initial activity of unpromoted catalysts at 1 bar increased 6-8-fold when the average iron carbide size decreased from 7 to 2 nm, while methane and lower olefins selectivity were not affected. The same decrease in particle size for catalysts promoted by Na plus S resulted at 20 bar in a 2-fold increase of the apparent TOF based on initial activity which was mainly caused by a higher yield of methane for the smallest particles. Presumably, methane formation takes place at highly active low coordination sites residing at corners and edges, which are more abundant on small iron carbide particles. Lower olefins are produced at promoted (stepped) terrace sites that are available and active, quite independent of size. These results demonstrate that the iron carbide particle size plays a crucial role in the design of active and selective FTO catalysts.

  5. Liquefaction for cataract extraction

    PubMed Central

    Labiris, Georgios; Toli, Aspasia; Polychroni, Damaskini; Gkika, Maria; Angelonias, Dimitrios; Kozobolis, Vassilios P.

    2016-01-01

    A systematic review of the recent literature regarding the implementation of the liquefaction in cataract surgery and its short-term and long-term outcomes in various parameters that affect the quality of patients' life, including visual rehabilitation and possible complications was performed based on the PubMed, Medline, Nature and the American Academy of Ophthalmology databases in November 2013 and data from 14 comparative studies were included in this narrative review. Liquefaction is an innovative technology for cataract extraction that uses micropulses of balanced salt solution to liquefy the lens nucleus. Most studies reported that liquefaction is a reliable technology for mild to moderate cataracts, while fragmentation difficulties may be encountered with harder nuclei. PMID:26949656

  6. Liquefaction for cataract extraction.

    PubMed

    Labiris, Georgios; Toli, Aspasia; Polychroni, Damaskini; Gkika, Maria; Angelonias, Dimitrios; Kozobolis, Vassilios P

    2016-01-01

    A systematic review of the recent literature regarding the implementation of the liquefaction in cataract surgery and its short-term and long-term outcomes in various parameters that affect the quality of patients' life, including visual rehabilitation and possible complications was performed based on the PubMed, Medline, Nature and the American Academy of Ophthalmology databases in November 2013 and data from 14 comparative studies were included in this narrative review. Liquefaction is an innovative technology for cataract extraction that uses micropulses of balanced salt solution to liquefy the lens nucleus. Most studies reported that liquefaction is a reliable technology for mild to moderate cataracts, while fragmentation difficulties may be encountered with harder nuclei.

  7. Liquefaction with microencapsulated catalysts

    DOEpatents

    Weller, Sol W.

    1985-01-01

    A method of dispersing a liquefaction catalyst within coal or other carbonaceous solids involves providing a suspension in oil of microcapsules containing the catalyst. An aqueous solution of a catalytic metal salt is emulsified in the water-immiscible oil and the resulting minute droplets microencapsulated in polymeric shells by interfacial polycondensation. The catalyst is subsequently blended and dispersed throughout the powdered carbonaceous material to be liquefied. At liquefaction temperatures the polymeric microcapsules are destroyed and the catalyst converted to minute crystallites in intimate contact with the carbonaceous material.

  8. Synthesis of single phase. alpha. -Fe, Fe sub 3 C and Fe sub 7 C sub 3 nano-particles by CO sub 2 laser pyrolysis technique

    SciTech Connect

    Eklund, P.C.; Bi, X.X.

    1992-01-01

    Iron-containing catalysts have been known to be useful in assisting the Fischer-Tropsch (FT) reaction for synthesizing hydrocarbons. However, it has been well recognized that iron catalyst are not stable during the reaction but converted into iron carbides. It is thus important to understand the role of the iron carbides in the catalytic reaction of the FT-synthesis. It has been found difficult to produce iron carbide nano-particles as a single phase, because iron carbide phases are only metastable under 1 atm pressure. Iron carbide bulk particles prepared so far are often contaminated with metallic iron, iron oxides and free carbon. In this study, we investigate the synthesis of iron carbide nano-particles using CO{sub 2} laser pyrolysis technique. We show that this technique is successful in synthesizing {alpha}-Fe, Fe{sub 3}C and Fe{sub 7}C{sub 3} nano-particles in their single phase with sizes in the range of 5--20nm. In particular, we have produced for the first time the Fe{sub 7}C{sub 3} which has been known to exist but unable to be produced as a single phase. Furthermore, it is interesting that Fe{sub 5}C{sub 2} which has carbon and iron ratio between Fe{sub 3}C and Fe{sub 7}C{sub 3}, is not seen in any run of our synthesis.

  9. Design and modification of zeolite capsule catalyst, a confined reaction field, and its application in one-step isoparaffin synthesis from syngas

    SciTech Connect

    Guohui Yang; Jingjiang He; Yi Zhang; Yoshiharu Yoneyama; Yisheng Tan; Yizhuo Han; Tharapong Vitidsant; Noritatsu Tsubaki

    2008-05-15

    Four kinds of zeolite capsule catalyst with different crystallization conditions were prepared and utilized for the middle isoparaffin direct synthesis via Fischer-Tropsch synthesis (FTS) reaction. Characterization results exhibited that these capsule catalysts had a compact, integral H-ZSM-5 shell. In FTS reactions on these zeolite capsule catalysts, hydrocarbons of C11+ were totally suppressed, accompanied by a sharp anti-Anderson-Schultz-Flory (ASF) law product distribution. The selectivity of light isoparaffin was improved obviously, but with the increase of the olefin's selectivity. Two-stage isoparaffin synthesis reaction, using the combination of zeolite capsule catalyst with hydrogenation catalyst of Pd/SiO{sub 2} in a single reactor as dual-bed catalyst, was also conducted for converting the residual olefins produced by the single zeolite capsule catalyst. Dependent on the palladium role of hydrogenation and hydrogen spillover, almost all the olefins effused from the first stage of zeolite capsule catalyst were hydrogenated, mostly converted to isoparaffin. The selectivity of isoparaffin in the final products was increased markedly as expected. 10 refs., 7 figs., 2 tabs.

  10. Applied reaction dynamics: Efficient synthesis gas production via single collision partial oxidation of methane to CO on Rh(111)

    NASA Astrophysics Data System (ADS)

    Gibson, K. D.; Viste, M.; Sibener, S. J.

    2006-10-01

    Supersonic molecular beams have been used to determine the yield of CO from the partial oxidation of CH4 on a Rh(111) catalytic substrate, CH4+(1/2)O2→CO +2H2, as a function of beam kinetic energy. These experiments were done under ultrahigh vacuum conditions with concurrent molecular beams of O2 and CH4, ensuring that there was only a single collision for the CH4 to react with the surface. The fraction of CH4 converted is strongly dependent on the normal component of the incident beam's translational energy, and approaches unity for energies greater than ˜1.3eV. Comparison with a simplified model of the methane-Rh(111) reactive potential gives insight into the barrier for methane dissociation. These results demonstrate the efficient conversion of methane to synthesis gas, CO +2H2, are of interest in hydrogen generation, and have the optimal stoichiometry for subsequent utilization in synthetic fuel production (Fischer-Tropsch or methanol synthesis). Moreover, under the reaction conditions explored, no CO2 was detected, i.e., the reaction proceeded with the production of very little, if any, unwanted greenhouse gas by-products. These findings demonstrate the efficacy of overcoming the limitations of purely thermal reaction mechanisms by coupling nonthermal mechanistic steps, leading to efficient C-H bond activation with subsequent thermal heterogeneous reactions.

  11. Method for coal liquefaction

    DOEpatents

    Wiser, Wendell H.; Oblad, Alex G.; Shabtai, Joseph S.

    1994-01-01

    A process is disclosed for coal liquefaction in which minute particles of coal in intimate contact with a hydrogenation catalyst and hydrogen arc reacted for a very short time at a temperature in excess of 400.degree. C. at a pressure of at least 1500 psi to yield over 50% liquids with a liquid to gaseous hydrocarbon ratio in excess of 8:1.

  12. Zinc sulfide liquefaction catalyst

    DOEpatents

    Garg, Diwakar

    1984-01-01

    A process for the liquefaction of carbonaceous material, such as coal, is set forth wherein coal is liquefied in a catalytic solvent refining reaction wherein an activated zinc sulfide catalyst is utilized which is activated by hydrogenation in a coal derived process solvent in the absence of coal.

  13. Coal liquefaction process

    DOEpatents

    Carr, Norman L.; Moon, William G.; Prudich, Michael E.

    1983-01-01

    A C.sub.5 -900.degree. F. (C.sub.5 -482.degree. C.) liquid yield greater than 50 weight percent MAF feed coal is obtained in a coal liquefaction process wherein a selected combination of higher hydrogen partial pressure, longer slurry residence time and increased recycle ash content of the feed slurry are controlled within defined ranges.

  14. Alternative fuel and chemicals from synthesis gas

    SciTech Connect

    1996-05-01

    Development of a reliable and cost-effective method of wax/catalyst separation is a key step toward a commercially viable slurry reactor process with iron oxide-based catalyst for Fischer-Tropsch (F-T) synthesis of hydrocarbon transportation fuels. Although a variety of suitable catalysts (including, for example, cobalt-based catalysts) are available, iron oxide-based catalysts are preferred for coal-derived, CO-rich syngas because, in addition to catalyzing the F-T reaction, they simultaneously catalyze the reaction stifling CO to H{sub 2}, obviating a separate shift process block and associated costs. Because of the importance of development of this wax/catalyst separation, a study was initiated in February 1991. P. Z. Zhou of Burns and Roe reviewed the status of F-T wax/catalyst separation techniques. This led to the selection of a filtration system for the separation. Pilot tests were conducted by Mott Porous Metal Products in 1992 to develop this system. Initial results were good, but problems were encountered in follow-up testing. As a result of the testing, a filter was selected for use on the pilot plant. In LaPorte, Texas, APCI has been operating a pilot plant for the development of various synthesis gas technologies with DOE and industry support. The APCI F-T program builds on the DOE-sponsored laboratory-scale work by Mobil, reported in the mid-1980s, which used an iron oxide catalyst to produce high-quality F-T liquids in relatively compact reactors. Separation of the catalyst solids from the wax still represents a challenge. In the summer of 1992, testing of the selected filter was begun as part of the pilot plant testing. The filter performed poorly. Separation of the catalyst was primarily by sedimentation. It was recommended that the wax/catalyst separation be developed further.

  15. Liquefaction potential index: Field assessment

    USGS Publications Warehouse

    Toprak, S.; Holzer, T.L.

    2003-01-01

    Cone penetration test (CPT) soundings at historic liquefaction sites in California were used to evaluate the predictive capability of the liquefaction potential index (LPI), which was defined by Iwasaki et al. in 1978. LPI combines depth, thickness, and factor of safety of liquefiable material inferred from a CPT sounding into a single parameter. LPI data from the Monterey Bay region indicate that the probability of surface manifestations of liquefaction is 58 and 93%, respectively, when LPI equals or exceeds 5 and 15. LPI values also generally correlate with surface effects of liquefaction: Decreasing from a median of 12 for soundings in lateral spreads to 0 for soundings where no surface effects were reported. The index is particularly promising for probabilistic liquefaction hazard mapping where it may be a useful parameter for characterizing the liquefaction potential of geologic units.

  16. Synthesis of single phase {alpha}-Fe, Fe{sub 3}C and Fe{sub 7}C{sub 3} nano-particles by CO{sub 2} laser pyrolysis technique. Quarterly progress report, January--March, 1992

    SciTech Connect

    Eklund, P.C.; Bi, X.X.

    1992-07-01

    Iron-containing catalysts have been known to be useful in assisting the Fischer-Tropsch (FT) reaction for synthesizing hydrocarbons. However, it has been well recognized that iron catalyst are not stable during the reaction but converted into iron carbides. It is thus important to understand the role of the iron carbides in the catalytic reaction of the FT-synthesis. It has been found difficult to produce iron carbide nano-particles as a single phase, because iron carbide phases are only metastable under 1 atm pressure. Iron carbide bulk particles prepared so far are often contaminated with metallic iron, iron oxides and free carbon. In this study, we investigate the synthesis of iron carbide nano-particles using CO{sub 2} laser pyrolysis technique. We show that this technique is successful in synthesizing {alpha}-Fe, Fe{sub 3}C and Fe{sub 7}C{sub 3} nano-particles in their single phase with sizes in the range of 5--20nm. In particular, we have produced for the first time the Fe{sub 7}C{sub 3} which has been known to exist but unable to be produced as a single phase. Furthermore, it is interesting that Fe{sub 5}C{sub 2} which has carbon and iron ratio between Fe{sub 3}C and Fe{sub 7}C{sub 3}, is not seen in any run of our synthesis.

  17. Cooperative research program in coal liquefaction

    SciTech Connect

    Huffman, G.P.; Sendlein, L.V.A.

    1991-01-01

    This report is a coordinated effort of the Consortium for Fossil Fuel Liquefaction Science. The topics concerning coal liquefaction discussed are: sulfate promoted metal oxides as direct coal liquefaction catalysts; low temperature depolymerization and liquefaction of premium R.S. coal samples; construction of continuous flow-through gas reactor for liquefaction investigations; generic structural characterization and liquefaction research; macerals, model compounds and iron catalyst dispersion; coal structure/liquefaction yield correlation by means of advanced NMR techniques; GC/MS of model compound mixtures; catalytic cracking, hydrogenation and liquefaction of coals under milder conditions; ENDOR investigations of coal liquefaction under mild conditions; catalytic dehydrogenation of model compounds in relation to direct coal liquefaction; surface characterization of catalyst added coal samples; computational chemistry of model compounds and molecular fragments of relevance to coal liquefaction; chemical characterization and hydrogenation reactions of single coal particles; thermolytic cleavage of selected coal-related linkages at mild temperatures; solvent sorption and FTIR studies on the effect of catalytic depolymerization reactions in coal; bioprocessing of coal; chemical routes to breaking bonds; novel liquefaction concepts cyclic olefins: novel new donors for coal liquefaction; better hydrogen transfer in coal liquefaction; catalytic hydropyrolysis and energized extraction of coals; gallium catalyst in mild coal liquefaction; potential of temperature microscope in coal liquefaction; evaluation of nitride catalysts for hydrotreatment and coal liquefaction; coprocessing and coal liquefaction with novel catalysts.

  18. Probabilistic analysis of deposit liquefaction

    SciTech Connect

    Loh, C.H.; Cheng, C.R.; Wen, Y.K.

    1995-12-31

    This paper presents a procedure to perform the risk analysis for ground failure by liquefaction. The liquefaction is defined as the result of cumulative damage caused by seismic loading. The fatigue life of soil can be determined on the basis of the N-S relationship and Miner`s cumulative damage law. The rain-flow method is used to count the number of cycles of stress response of the soil deposit. Finally, the probability of liquefaction is obtained by integrating over all the possible ground motion and the fragility curves of liquefaction potential.

  19. Ace in the Hole: Fischer-Tropsch Fuels and National Security

    DTIC Science & Technology

    2010-05-24

    hydrogen. Coal, pet coke and biomass also require large capital expenditure for processing equipment (e.g. coal gasification equipment) and removal of...not require the complex gasification equipment 18 as do coal and biomass . GTL has little waste, and it yields by-products that are all...any hydrocarbon source (coal or natural gas), or carbohydrate source ( biomass ), and breaks it down to the simple components of carbon monoxide (CO

  20. Synthetic Fischer-Tropsch (FT) JP-5/JP-8 Aviation Turbine Fuel Elastomer Compatibility

    DTIC Science & Technology

    2005-02-01

    of nitrile coupons and O-rings with selected petroleum-derived fuels, Fisher-Tropsch (FT) synthetic JP-5/JP-8 fuel, and blends of FT JP-5/JP-8 with...SUPPLEMENTARY NOTES The original document contains color images. 14. ABSTRACT When some elastomer ( rubber ) compounds, and specifically those used for...various amounts of aromatic blend stock. This study provided a baseline for predicting the effects of static elastomer swell to the potential degree of

  1. Separation of Fischer-Tropsch Wax Products from Ultrafine Iron Catalyst Particles

    SciTech Connect

    James K. Neathery; Gary Jacobs; Amitava Sarkar; Burtron H. Davis

    2006-03-31

    The morphological and chemical nature of ultrafine iron catalyst particles (3-5 nm diameters) during activation/FTS was studied by HRTEM, EELS, and Moessbauer spectroscopy. With the progress of FTS, the carbide re-oxidized to magnetite and catalyst activity gradually decreased. The growth of oxide phase continued and average particle size also increased simultaneously. The phase transformation occurred in a ''growing oxide core'' manner with different nano-zones. The nano-range carbide particles did not show fragmentation or attrition as generally observed in micrometer range particles. Nevertheless, when the dimension of particles reached the micrometer range, the crystalline carbide phase appeared to be sprouted on the surface of magnetite single crystal. In the previous reporting period, a design and operating philosophy was developed for an integrated wax filtration system for a 4 liter slurry bubble column reactor to be used in Phase II of this research program. During the current reporting period, we have started construction of the new filtration system and began modifications to the 4 liter slurry bubble column reactor (SBCR) reactor. The system will utilize a primary wax separation device followed by a Pall Accusep or Membralox ceramic cross-flow membrane. As of this writing, the unit is nearly complete except for the modification of a moyno-type pump; the pump was shipped to the manufacturer to install a special leak-free, high pressure seal.

  2. Particle size effect for cobalt Fischer-Tropsch catalysts based on in situ CO chemisorption

    NASA Astrophysics Data System (ADS)

    Yang, Jia; Frøseth, Vidar; Chen, De; Holmen, Anders

    2016-06-01

    The cobalt particle size effect on activity and selectivity for CO hydrogenation was revisited on cobalt catalysts supported on a large variety of supports at 483 K, 1.85 bar, and H2/CO/Ar = 15/1.5/33.5 Nml/min. The size dependence of the activity and selectivity was analyzed in terms of site coverage and rate constants based on SSITKA experimental results. It was found that the Co particle size index estimated by the conventional method, namely, ex situ hydrogen chemisorption, could not correlate well the activity and selectivity as a function of the particle size index. The same holds for the site coverage of CO and intermediates leading to methane formation. However, the cobalt particle size index based on in situ CO chemisorption measured at 373 K provides a good correlation for turnover frequencies (TOFs) at reaction conditions. It was observed that TOF for CO conversion (TOFCO) increased with increasing particle size index of cobalt and SSITKA experiments showed that this was possibly due to increased site coverage of CO. The TOF for methane formation (TOFCH4) increased with particle size and remained constant at higher particle sizes possibly due to combined effect from the site coverage of intermediates leading to methane (θCHx) and the pseudo-first-order rate constant (kt). The results suggest that the support can play an important role for the size dependence of the activity and selectivity of CO hydrogenation on Co catalysts.

  3. ULTRA-CLEAN FISCHER-TROPSCH FUELS PRODUCTION AND DEMONSTRATION PROJECT

    SciTech Connect

    Steve Bergin

    2004-10-18

    The Report Abstract provides summaries of the past year's activities relating to each of the main project objectives. Some of the objectives will be expanded on in greater detail further down in the report. The following objectives have their own addition sections in the report: SFP Construction and Fuel Production, Impact of SFP Fuel on Engine Performance, Fleet Testing at WMATA and Denali National Park, Demonstration of Clean Diesel Fuels in Diesel Electric Generators in Alaska, and Economic Analysis. ICRC provided overall project organization and budget management for the project. ICRC held meetings with various project participants. ICRC presented at the Department of Energy's annual project review meeting. The plant began producing fuel in October 2004. The first delivery of finished fuel was made in March of 2004 after the initial start-up period.

  4. Properties of Fischer-Tropsch (FT) Blends for Use in Military Equipment

    DTIC Science & Technology

    2006-04-01

    of advanced rockets , scramjets and combined cycle propulsion systems. The near-term use of FT fuels in existing military fleets is not without...production of FT fuels . Fortunately, the capture of CO2 can be accommodated by today’s coal gasification processes. Furthermore, CO2 storage has been...Corporation Leo L. Stavinoha Stavinoha Enterprises ABSTRACT Clean, very low sulfur fuels produced from domestic resources are of interest to the U.S

  5. Separation of Fischer-Tropsch Wax Products from Ultrafine Iron Catalyst Particles

    SciTech Connect

    James K. Neathery; Gary Jacobs; Amitava Sarkar; Adam Crawford; Burtron H. Davis

    2006-09-30

    In the previous reporting period, modifications were completed for integrating a continuous wax filtration system for a 4 liter slurry bubble column reactor. During the current reporting period, a shakedown of the system was completed. Several problems were encountered with the progressive cavity pump used to circulate the wax/catalyst slurry though the cross-flow filter element and reactor. During the activation of the catalyst with elevated temperature (> 270 C) the elastomer pump stator released sulfur thereby totally deactivating the iron-based catalyst. Difficulties in maintaining an acceptable leak rate from the pump seal and stator housing were also encountered. Consequently, the system leak rate exceeded the expected production rate of wax; therefore, no online filtration could be accomplished. Work continued regarding the characterization of ultra-fine catalyst structures. The effect of carbidation on the morphology of iron hydroxide oxide particles was the focus of the study during this reporting period. Oxidation of Fe (II) sulfate results in predominantly {gamma}-FeOOH particles which have a rod-shaped (nano-needles) crystalline structure. Carbidation of the prepared {gamma}-FeOOH with CO at atmospheric pressure produced iron carbides with spherical layered structure. HRTEM and EDS analysis revealed that carbidation of {gamma}-FeOOH particles changes the initial nano-needles morphology and generates ultrafine carbide particles with irregular spherical shape.

  6. Ultra-Clean Fischer-Tropsch Fuels Production and Demonstration Project

    SciTech Connect

    Steve Bergin

    2005-10-14

    The Report Abstract provides summaries of the past year's activities relating to each of the main project objectives. Some of the objectives will be expanded on in greater detail further down in the report. The following objectives have their own addition sections in the report: Dynamometer Durability Testing, the Denali Bus Fleet Demonstration, Bus Fleet Demonstrations Emissions Analysis, Impact of SFP Fuel on Engine Performance, Emissions Analysis, Feasibility Study of SFPs for Rural Alaska, and Cold Weather Testing of Ultra Clean Fuel.

  7. Fischer-Tropsch diesel emulsions stabilised by microfibrillated cellulose and nonionic surfactants.

    PubMed

    Lif, Anna; Stenstad, Per; Syverud, Kristin; Nydén, Magnus; Holmberg, Krister

    2010-12-15

    Water-in-diesel emulsion fuels have been prepared with a combination of sorbitan monolaurate and glycerol monooleate as emulsifier and with microfibrillated cellulose (MFC) of different hydrophilic/hydrophobic character as stabilizer. The MFC was treated with either octadecylamine or poly(styrene-co-maleic anhydride), resulting in very hydrophobic fibrils. The most stable emulsion was achieved with a combination of hydrophilic (untreated) and hydrophobic MFC and only minute amounts of the stabilizer gave a pronounced effect. Even with the optimized formulation the lifetime of the emulsion was shorter than previously reported when a conventional polymeric stabilizer was used, however. The water drop sizes in the emulsions were determined by three methods: optical images, light scattering, and NMR diffusometry. All three methods gave water drops sizes of ca 2 μm. The NMR diffusometry indicated that besides the micrometer-sized emulsion drops a significant fraction of the water is present in small droplets of micelle size. The chemical exchange of water between these two populations of pools is believed to be the reason for the relatively low stability of the system.

  8. Mössbauer studies of ferrihydrite for Fischer-Tropsch catalysts

    NASA Astrophysics Data System (ADS)

    Lim, Jung Tae; Kim, Chul Sung; Chun, Dong Hyun; Park, Ji Chan

    2016-01-01

    The 6-line ferrihydrite sample for Ficher-Tropsch catalysts was prepared by using a combination of a co-precipitation technique and a spraydrying method. The crystallographic and magnetic properties of 6-line ferrihydrite sample were investigated by using x-ray diffractometer (XRD), vibrating sample magnetometer (VSM), and Mössbauer spectrometer. The XRD patterns of the ferrihydrite sample, measured at 295 K, showed 6-lines peak and its structure was found to be a single-phased hexagonal with space group of P3m1 according to JCPDS card. The temperaturedependent magnetization curves were measured under 1000 Oe between 4.2 and 300 K, and showed blocking temperature ( T B ) around 110 K. Also, Mössbauer spectra of the 6-line ferrihydrite sample were taken at various temperatures ranging from 4.2 to 295 K. At temperature below T B , the obtained spectra were analyzed as two-sextets for Fe sites, while At temperature above T B , the obtained spectra showed a doublet due to relaxation, resulting from the spin dynamic effect.

  9. Method for coal liquefaction

    DOEpatents

    Wiser, W.H.; Oblad, A.G.; Shabtai, J.S.

    1994-05-03

    A process is disclosed for coal liquefaction in which minute particles of coal in intimate contact with a hydrogenation catalyst and hydrogen arc reacted for a very short time at a temperature in excess of 400 C at a pressure of at least 1500 psi to yield over 50% liquids with a liquid to gaseous hydrocarbon ratio in excess of 8:1. 1 figures.

  10. Coal liquefaction process

    DOEpatents

    Karr, Jr., Clarence

    1977-04-19

    An improved coal liquefaction process is provided which enables conversion of a coal-oil slurry to a synthetic crude refinable to produce larger yields of gasoline and diesel oil. The process is characterized by a two-step operation applied to the slurry prior to catalytic desulfurization and hydrogenation in which the slurry undergoes partial hydrogenation to crack and hydrogenate asphaltenes and the partially hydrogenated slurry is filtered to remove minerals prior to subsequent catalytic hydrogenation.

  11. Coal Liquefaction desulfurization process

    DOEpatents

    Givens, Edwin N.

    1983-01-01

    In a solvent refined coal liquefaction process, more effective desulfurization of the high boiling point components is effected by first stripping the solvent-coal reacted slurry of lower boiling point components, particularly including hydrogen sulfide and low molecular weight sulfur compounds, and then reacting the slurry with a solid sulfur getter material, such as iron. The sulfur getter compound, with reacted sulfur included, is then removed with other solids in the slurry.

  12. Is a renaissance of coal imminent?--challenges for catalysis.

    PubMed

    Traa, Yvonne

    2010-04-07

    In the introduction, the reserves and resources of coal and other fossil fuels are discussed, also with regard to the regional distribution and consumption. Then, coalification and the classification of coal are described. The main part of the article is devoted to the most important processes using coal where challenges for catalysis still exist, with a focus on recent literature. First, technologies based on the production of synthesis gas, i.e., Fischer-Tropsch synthesis as well as MTO/MTP (Methanol To Olefins/Methanol To Propylene), are discussed. Secondly, direct coal liquefaction is treated. The last part of the article is devoted to "clean" coal and gives an outlook on the future of coal.

  13. Coal liquefaction process

    DOEpatents

    Maa, Peter S.

    1978-01-01

    A process for liquefying a particulate coal feed to produce useful petroleum-like liquid products which comprises contacting; in a series of two or more coal liquefaction zones, or stages, graded with respect to temperature, an admixture of a polar compound; or compounds, a hydrogen donor solvent and particulate coal, the total effluent being passed in each instance from a low temperature zone, or stage to the next succeeding higher temperature zone, or stage, of the series. The temperature within the initial zone, or stage, of the series is maintained about 70.degree. F and 750.degree. F and the temperature within the final zone, or stage, is maintained between about 750.degree. F and 950.degree. F. The residence time within the first zone, or stage, ranges, generally, from about 20 to about 150 minutes and residence time within each of the remaining zones, or stages, of the series ranges, generally, from about 10 minutes to about 70 minutes. Further steps of the process include: separating the product from the liquefaction zone into fractions inclusive of a liquid solvent fraction; hydrotreating said liquid solvent fraction in a hydrogenation zone; and recycling the hydrogenated liquid solvent mixture to said coal liquefaction zones.

  14. DEVELOPMENT OF ALTERNATIVE FUELS AND CHEMICALS FROM SYNTHESIS GAS

    SciTech Connect

    Peter J. Tijrn

    2003-05-31

    This Final Report for Cooperative Agreement No. DE-FC22-95PC93052, the ''Development of Alternative Fuels and Chemicals from Synthesis Gas,'' was prepared by Air Products and Chemicals, Inc. (Air Products), and covers activities from 29 December 1994 through 31 July 2002. The overall objectives of this program were to investigate potential technologies for the conversion of synthesis gas (syngas), a mixture primarily of hydrogen (H{sub 2}) and carbon monoxide (CO), to oxygenated and hydrocarbon fuels and industrial chemicals, and to demonstrate the most promising technologies at the LaPorte, Texas Alternative Fuels Development Unit (AFDU). Laboratory work was performed by Air Products and a variety of subcontractors, and focused on the study of the kinetics of production of methanol and dimethyl ether (DME) from syngas, the production of DME using the Liquid Phase Dimethyl Ether (LPDME{trademark}) Process, the conversion of DME to fuels and chemicals, and the production of other higher value products from syngas. Four operating campaigns were performed at the AFDU during the performance period. Tests of the Liquid Phase Methanol (LPMEOH{trademark}) Process and the LPDME{trademark} Process were made to confirm results from the laboratory program and to allow for the study of the hydrodynamics of the slurry bubble column reactor (SBCR) at a significant engineering scale. Two campaigns demonstrated the conversion of syngas to hydrocarbon products via the slurry-phase Fischer-Tropsch (F-T) process. Other topics that were studied within this program include the economics of production of methyl tert-butyl ether (MTBE), the identification of trace components in coal-derived syngas and the means to economically remove these species, and the study of systems for separation of wax from catalyst in the F-T process. The work performed under this Cooperative Agreement has continued to promote the development of technologies that use clean syngas produced from any one of a

  15. Cooperative research in coal liquefaction

    SciTech Connect

    Huffman, G.P.; Sendlein, L.V.A.

    1991-05-28

    Significant progress was made in the May 1990--May 1991 contract period in three primary coal liquefaction research areas: catalysis, structure-reactivity studies, and novel liquefaction processes. A brief summary of the accomplishments in the past year in each of these areas is given.

  16. Magnetic refrigerator for hydrogen liquefaction

    NASA Astrophysics Data System (ADS)

    Numazawa, T.; Kamiya, K.; Utaki, T.; Matsumoto, K.

    2014-07-01

    This paper reviews the status of magnetic refrigeration system for hydrogen liquefaction. There is no doubt that hydrogen is one of most important energy sources in the near future. In particular, liquid hydrogen can be utilized for infrastructure construction consisting of storage and transportation. When we compare the consuming energy of hydrogen liquefaction with high pressurized hydrogen gas, FOM must be larger than 0.57 for hydrogen liquefaction. Thus, we need to develop a highly efficient liquefaction method. Magnetic refrigeration using the magneto-caloric effect has potential to realize not only the higher liquefaction efficiency >50%, but also to be environmentally friendly and cost effective. Our hydrogen magnetic refrigeration system consists of Carnot cycle for liquefaction stage and AMR (active magnetic regenerator) cycle for precooling stages. For the Carnot cycle, we develop the high efficient system with >80% liquefaction efficiency by using the heat pipe. For the AMR cycle, we studied two kinds of displacer systems, which transferred the working fluid. We confirmed the AMR effect with the cooling temperature span of 12 K for 1.8 T of the magnetic field and 6 s of the cycle. By using the simulation, we estimate the efficiency of the hydrogen liquefaction plant for 10 kg/day. A FOM of 0.47 is obtained for operation temperature between 20 K and 77 K including LN2 work input.

  17. Technical, Energetics, and Economic Comparison of NRL Oxidative Coal Liquefaction Process with some Developed Coal Liquefaction Processes.

    DTIC Science & Technology

    1980-03-05

    the synthesis step becomes two processes. synthesis CO + H2 catalyst ) methanol conversion methanol catalyst > gasoline + water Wiser states that...structure illustrates the main types of linkage between ring clusters and also some of the heteroatom forms that are found in coal. 20 APPENDIX II...used more widely as petroleum and natural gas resources are depleted and hydrogen for coal liquefaction processes will be produced predominantly from

  18. Coal liquefaction process

    DOEpatents

    Wright, Charles H.

    1986-01-01

    A process for the liquefaction of coal wherein raw feed coal is dissolved in recycle solvent with a slurry containing recycle coal minerals in the presence of added hydrogen at elevated temperature and pressure. The highest boiling distillable dissolved liquid fraction is obtained from a vacuum distillation zone and is entirely recycled to extinction. Lower boiling distillable dissolved liquid is removed in vapor phase from the dissolver zone and passed without purification and essentially without reduction in pressure to a catalytic hydrogenation zone where it is converted to an essentially colorless liquid product boiling in the transportation fuel range.

  19. Coal liquefaction process

    DOEpatents

    Wright, C.H.

    1986-02-11

    A process is described for the liquefaction of coal wherein raw feed coal is dissolved in recycle solvent with a slurry containing recycle coal minerals in the presence of added hydrogen at elevated temperature and pressure. The highest boiling distillable dissolved liquid fraction is obtained from a vacuum distillation zone and is entirely recycled to extinction. Lower boiling distillable dissolved liquid is removed in vapor phase from the dissolver zone and passed without purification and essentially without reduction in pressure to a catalytic hydrogenation zone where it is converted to an essentially colorless liquid product boiling in the transportation fuel range. 1 fig.

  20. Hydrothermal Liquefaction of Biomass

    SciTech Connect

    Elliott, Douglas C.

    2010-12-10

    Hydrothermal liquefaction technology is describes in its relationship to fast pyrolysis of biomass. The scope of work at PNNL is discussed and some intial results are presented. HydroThermal Liquefaction (HTL), called high-pressure liquefaction in earlier years, is an alternative process for conversion of biomass into liquid products. Some experts consider it to be pyrolysis in solvent phase. It is typically performed at about 350 C and 200 atm pressure such that the water carrier for biomass slurry is maintained in a liquid phase, i.e. below super-critical conditions. In some applications catalysts and/or reducing gases have been added to the system with the expectation of producing higher yields of higher quality products. Slurry agents ('carriers') evaluated have included water, various hydrocarbon oils and recycled bio-oil. High-pressure pumping of biomass slurry has been a major limitation in the process development. Process research in this field faded away in the 1990s except for the HydroThermal Upgrading (HTU) effort in the Netherlands, but has new resurgence with other renewable fuels in light of the increased oil prices and climate change concerns. Research restarted at Pacific Northwest National Laboratory (PNNL) in 2007 with a project, 'HydroThermal Liquefaction of Agricultural and Biorefinery Residues' with partners Archer-Daniels-Midland Company and ConocoPhillips. Through bench-scale experimentation in a continuous-flow system this project investigated the bio-oil yield and quality that could be achieved from a range of biomass feedstocks and derivatives. The project was completed earlier this year with the issuance of the final report. HydroThermal Liquefaction research continues within the National Advanced Biofuels Consortium with the effort focused at PNNL. The bench-scale reactor is being used for conversion of lignocellulosic biomass including pine forest residue and corn stover. A complementary project is an international collaboration with

  1. Catalytic liquefaction of biomass

    SciTech Connect

    Davis, H.; Figueroa, C.; Karatas, C.; Kloden, D.; Schaleger, L.; Yaghoubzadeh, N.

    1981-10-01

    The bench-scale continuous liquefaction unit or CLU is in operation as a back-mixed reactor. Its capabilities include temperatures up to 370/sup 0/C, reaction times of about 10 to 30 minutes and pressures up to 4000 PSIG. It is in use exploring a factorial experiment in temperature, time, slurry pH, gas to slurry feed ratio and other variables. From early runs at times of about 20 minutes, temperatures of 350/sup 0/C or higher and slurry pH's above 8 are desirable. The reactor has been used only on Douglas fir wood slurries. However, it is available for a wide range of biomass or even fossil feedstocks. New methods of characterizing oil and water-soluble products have been developed and applied to CLU products. Conditions under which formate ion, probable intermediate in both water gas shift reaction and reduction of biomass oxygen by CO, is formed in large quantities have been found. Raw wood chips have been shown to undergo solvolysis - total dissolution - when mixed with wood liquefaction oil and heated under certain conditions. This phenomenon must occur to some degree in the initial stages of the PERC process. Solvolysis is suggested as a possible way to get the benefits of oil recycle without the uneconomicaly high recycle ratios of the PERC process.

  2. Sorbents for High Temperature Removal of Arsenic from Coal-Derived Synthesis Gas

    SciTech Connect

    Alptekin, G.O.; Copeland, R.; Dubovik, M.; Gershanovich, Y.

    2002-09-20

    Gasification technologies convert coal and other heavy feedstocks into synthesis gas feed streams that can be used in the production of a wide variety of chemicals, ranging from hydrogen through methanol, ammonia, acetic anhydride, dimethyl ether (DME), methyl tertiary butyl ether (MTBE), high molecular weight liquid hydrocarbons and waxes. Syngas can also be burned directly as a fuel in advanced power cycles to generate electricity with very high efficiency. However, the coal-derived synthesis gas contains a myriad of trace contaminants that may poison the catalysts that are used in the downstream manufacturing processes and may also be regulated in power plant emissions. Particularly, the catalysts used in the conversion of synthesis gas to methanol and other liquid fuels (Fischer-Tropsch liquids) have been found to be very sensitive to the low levels of poisons, especially arsenic, that are present in the synthesis gas from coal. TDA Research, Inc. (TDA) is developing an expendable high capacity, low-cost chemical absorbent to remove arsenic from coal-derived syngas. Unlike most of the commercially available sorbents that physically adsorb arsenic, TDA's sorbent operates at elevated temperatures and removes the arsenic through chemical reaction. The arsenic content in the coal gas stream is reduced to ppb levels with the sorbent by capturing and stabilizing the arsenic gas (As4) and arsenic hydrides (referred to as arsine, AsH3) in the solid state. To demonstrate the concept of high temperature arsenic removal from coal-derived syngas, we carried out bench-scale experiments to test the absorption capacity of a variety of sorbent formulations under representative conditions. Using on-line analysis techniques, we monitored the pre- and post-breakthrough arsine concentrations over different sorbent samples. Some of these samples exhibited pre-breakthrough arsine absorption capacity over 40% wt. (capacity is defined as lb of arsenic absorbed/lb of sorbent), while

  3. Integrated coal cleaning, liquefaction, and gasification process

    DOEpatents

    Chervenak, Michael C.

    1980-01-01

    Coal is finely ground and cleaned so as to preferentially remove denser ash-containing particles along with some coal. The resulting cleaned coal portion having reduced ash content is then fed to a coal hydrogenation system for the production of desirable hydrocarbon gases and liquid products. The remaining ash-enriched coal portion is gasified to produce a synthesis gas, the ash is removed from the gasifier usually as slag, and the synthesis gas is shift converted with steam and purified to produce the high purity hydrogen needed in the coal hydrogenation system. This overall process increases the utilization of as-mined coal, reduces the problems associated with ash in the liquefaction-hydrogenation system, and permits a desirable simplification of a liquids-solids separation step otherwise required in the coal hydrogenation system.

  4. Some thoughts on the strategy of direct coal liquefaction -- Partial liquefaction and utilization of heavy liquefaction products

    SciTech Connect

    Liu, Z.; Yang, J.

    1998-12-31

    Hydrogenation has long been the only goal of coal liquefaction. However, analysis show that partial hydrogenation along with carbon rejection may be a better strategy for coal liquefaction, which reduces hydrogen consumption and reaction severity, eliminates the necessity for expensive catalyst, and may results in better economy for overall liquefaction. The hydrogenation and carbon rejection approach can be called partial liquefaction of coal. This paper presents analysis supporting the strategy of partial coal liquefaction based on the point of view of mass and energy balance, chemical reaction kinetics, reactivity of coal constituents and possible use of the heavy liquefaction products.

  5. A thermodynamic assessment of the potential synthesis of condensed hydrocarbons during cooling and dilution of volcanic gases.

    PubMed

    Zolotov, M Y; Shock, E L

    2000-01-10

    The possibility for abiotic synthesis of condensed hydrocarbons in cooling/diluting terrestrial volcanic gases has been evaluated on the basis of the consideration of metastable chemical equilibria involving gaseous CO, CO2, H2 and H2O. The stabilities of n-alkanes and polycyclic aromatic hydrocarbons (PAHS) have been evaluated for several typical volcanic gas compositions under various conditions for cooling/diluting of quenched volcanic gas. The modeling shows that n-alkanes and PAHs have a thermodynamic potential to form metastably from H2 and CO below approximately 250 degrees C within the stability field of graphite. Despite the predominance of CO2 in volcanic gases, synthesis of hydrocarbons from CO2 and H2 is less favored energetically than from CO and H2. Both low temperature and a high H/C atomic ratio in volcanic gas generally favor stability of hydrocarbons with higher H/C ratios. PAHs are thermodynamically stable at temperatures approximately 10 degrees -50 degrees C higher than large n-alkanes; however, at lower temperatures, PAHs and n-alkanes have similar stabilities and are likely to form metastable mixtures. Both the energetic drive to form hydrocarbons and possible temperatures of formation increase as the oxidation state (fO2) of the volcanic gases decreases and as the cooling/dilution ratios of volcanic gases increase. Synthesis of hydrocarbons is energetically more likely in cooling trapped gases than in ashcloud eruptive columns. Mechanisms for hydrocarbon formation may include Fischer-Tropsch-type synthesis catalyzed by magnetite from solid volcanic products. On the early Earth, Mars, and Jupiter's satellite Europa, several factors would have provided more favorable conditions for hydrocarbon synthesis in volcanic gases than under current terrestrial conditions and might have contributed to the production of organic compounds required for the emergence of life.

  6. Two stage liquefaction of coal

    DOEpatents

    Neuworth, Martin B.

    1981-01-01

    A two stage coal liquefaction process and apparatus comprising hydrogen donor solvent extracting, solvent deashing, and catalytic hydrocracking. Preferrably, the catalytic hydrocracking is performed in an ebullating bed hydrocracker.

  7. Viscosity Depressants for Coal Liquefaction

    NASA Technical Reports Server (NTRS)

    Kalfayan, S. H.

    1983-01-01

    Proposed process modification incorporates viscosity depressants to prevent coal from solidifying during liquefaction. Depressants reduce amount of heat needed to liquefy coal. Possible depressants are metallic soaps, such as stearate, and amides, such as stearamide and dimer acid amides.

  8. Free report from Liquefaction Workshop

    NASA Astrophysics Data System (ADS)

    The technical report Proceedings From the 2nd U.S.-Japan Workshop on Liquefaction, Large Ground Deformation and Their Effects on Lifelines is available free of charge from the National Center for Earthquake Engineering Research, headquartered at the State University of New York at Buffalo. The 499-page proceedings contain more than 30 reports on case studies of liquefaction and earthquake-induced ground deformation from previous earthquakes in the U.S. and Japan.

  9. Direct coal liquefaction process

    DOEpatents

    Rindt, J.R.; Hetland, M.D.

    1993-10-26

    An improved multistep liquefaction process for organic carbonaceous mater which produces a virtually completely solvent-soluble carbonaceous liquid product. The solubilized product may be more amenable to further processing than liquid products produced by current methods. In the initial processing step, the finely divided organic carbonaceous material is treated with a hydrocarbonaceous pasting solvent containing from 10% and 100% by weight process-derived phenolic species at a temperature within the range of 300 C to 400 C for typically from 2 minutes to 120 minutes in the presence of a carbon monoxide reductant and an optional hydrogen sulfide reaction promoter in an amount ranging from 0 to 10% by weight of the moisture- and ash-free organic carbonaceous material fed to the system. As a result, hydrogen is generated via the water/gas shift reaction at a rate necessary to prevent condensation reactions. In a second step, the reaction product of the first step is hydrogenated.

  10. Innovative gas liquefaction TLP

    SciTech Connect

    Not Available

    1983-04-01

    A number of companies have been involved in the development of offshore plants and have furnished an entire series of self-contained units for offshore uses ranging from the production of methanol, LPG, ammonia or urea from natural gas or associated gas, to complete seawater desalination plants mounted on barges. One of the latest design concepts for an offshore plant is the Salzgitter Group's innovative gas liquefaction plant on a tension leg platform (TLP). An outstanding feature of the design is that it is actually a TLP and jack-up platform combined. The proposed plant is suited for use in water depths of 250 to 350 m but can also be designed for water depths of 1,000 m.

  11. Direct coal liquefaction process

    DOEpatents

    Rindt, John R.; Hetland, Melanie D.

    1993-01-01

    An improved multistep liquefaction process for organic carbonaceous mater which produces a virtually completely solvent-soluble carbonaceous liquid product. The solubilized product may be more amenable to further processing than liquid products produced by current methods. In the initial processing step, the finely divided organic carbonaceous material is treated with a hydrocarbonaceous pasting solvent containing from 10% and 100% by weight process-derived phenolic species at a temperature within the range of 300.degree. C. to 400.degree. C. for typically from 2 minutes to 120 minutes in the presence of a carbon monoxide reductant and an optional hydrogen sulfide reaction promoter in an amount ranging from 0 to 10% by weight of the moisture- and ash-free organic carbonaceous material fed to the system. As a result, hydrogen is generated via the water/gas shift reaction at a rate necessary to prevent condensation reactions. In a second step, the reaction product of the first step is hydrogenated.

  12. Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic

  13. Fundamental studies of coal liquefaction

    SciTech Connect

    Not Available

    1995-01-01

    The authors have examined the pyrolysis of Argonne samples of Wyodak and Illinois No. 6 coal in argon, undecane, Tetralin, and water. The effects of the pyrolysis on individual particles of coal were monitored visually in a cell with diamond windows capable of operation to temperature and pressures in excess of 500{degrees}C and 3000 psi. The changes in the particles from ambient to 460{degrees}C were recorded in real time on video tape, and images were then taken from the tape record and analyzed. The study showed that in argon both coals developed tars at 350{degrees}-370{degrees}C. The tars then quickly evaporated, leaving core particles remarkably similar in size and shape to the initial particles. These observations suggest that coal does not melt nor become fully liquid when heated. Nor does the softened coal undergo crosslinking to generate coke. Rather the simple loss of volatiles leaves behind the core residue as coke. Contrary to the common view, there appears to be no link between the bond-breaking processes yielding tar and the interaction of the coal with H-donors leading to liquefaction. Water as a medium was surprising in its effect. Both coals began to shrink at 300{degrees}-350{degrees}C, with the effect appearing to be more of an erosion rather than a uniform loss of substance as seen in Tetralin. The Wyodak continued to shrink to 460{degrees}C to about half its initial size. With the Illinois No. 6 coal, however, the process reversed at around 420{degrees}C, and the particles appeared to grow with the evolution of a tar, continuing to 460{degrees}C. The authors submit that this final observation is evidence for hydrothermal synthesis of hydrocarbons at these conditions.

  14. Carbon Isotopes of Alkanes in Hydrothermal Abiotic Organic Synthesis Processes at High Temperatures and Pressures: An Experimental Study

    NASA Technical Reports Server (NTRS)

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

    2010-01-01

    Observation of methane in the Martian atmosphere has been reported by different detection techniques [1-4]. With more evidence showing extensive water-rock interaction in Martian history [5-7], abiotic formation by Fischer-Tropsch Type (FTT) synthesis during serpentization reactions may be one possible process responsible for methane generation on Mars [8, 9]. While the experimental studies performed to date leave little doubt that chemical reactions exist for the abiotic synthesis of organic compounds by mineral surface-catalyzed reactions [10-12], little is known about the reaction pathways by which CO2 and/or CO are reduced under hydrothermal conditions. Carbon and hydrogen isotope measurements of alkanes have been used as an effective tool to constrain the origin and reaction pathways of hydrocarbon formation. Alkanes generated by thermal breakdown of high molecular weight organic compounds have carbon and hydrogen isotopic signatures completely distinct from those formed abiotically [13-15]. Recent experimental studies, however, showed that different abiogenic hydrocarbon formation processes (e.g., polymerization vs. depolymerization) may have different carbon and hydrogen isotopic patterns [16]. Results from previous experiments studying decomposition of higher molecular weight organic compounds (lignite) also suggested that pressure could be a crucial factor affecting fractionation of carbon isotopes [17]. Under high pressure conditions, no experimental data are available describing fractionation of carbon isotope during mineral catalyzed FTT synthesis. Thus, hydrothermal experiments present an excellent opportunity to provide the requisite carbon isotope data. Such data can also be used to identify reaction pathways of abiotic organic synthesis under experimental conditions.

  15. Bioechnology of indirect liquefaction. Final report

    SciTech Connect

    Datta, R.; Jain, M.K.; Worden, R.M.; Grethlein, A.J.; Soni, B.; Zeikus, J.G.; Grethlein, H.

    1990-05-07

    The project on biotechnology of indirect liquefaction was focused on conversion of coal derived synthesis gas to liquid fuels using a two-stage, acidogenic and solventogenic, anaerobic bioconversion process. The acidogenic fermentation used a novel and versatile organism, Butyribacterium methylotrophicum, which was fully capable of using CO as the sole carbon and energy source for organic acid production. In extended batch CO fermentations the organism was induced to produce butyrate at the expense of acetate at low pH values. Long-term, steady-state operation was achieved during continuous CO fermentations with this organism, and at low pH values (a pH of 6.0 or less) minor amounts of butanol and ethanol were produced. During continuous, steady-state fermentations of CO with cell recycle, concentrations of mixed acids and alcohols were achieved (approximately 12 g/l and 2 g/l, respectively) which are high enough for efficient conversion in stage two of the indirect liquefaction process. The metabolic pathway to produce 4-carbon alcohols from CO was a novel discovery and is believed to be unique to our CO strain of B. methylotrophicum. In the solventogenic phase, the parent strain ATCC 4259 of Clostridium acetobutylicum was mutagenized using nitrosoguanidine and ethyl methane sulfonate. The E-604 mutant strain of Clostridium acetobutylicum showed improved characteristics as compared to parent strain ATCC 4259 in batch fermentation of carbohydrates.

  16. Liquefaction processes and systems and liquefaction process intermediate compositions

    DOEpatents

    Schmidt, Andrew J.; Hart, Todd R.; Billing, Justin M.; Maupin, Gary D.; Hallen, Richard T.; Anderson, Daniel B.

    2014-07-12

    Liquefaction processes are provided that can include: providing a biomass slurry solution having a temperature of at least 300.degree. C. at a pressure of at least 2000 psig; cooling the solution to a temperature of less than 150.degree. C.; and depressurizing the solution to release carbon dioxide from the solution and form at least part of a bio-oil foam. Liquefaction processes are also provided that can include: filtering the biomass slurry to remove particulates; and cooling and depressurizing the filtered solution to form the bio-oil foam. Liquefaction systems are provided that can include: a heated biomass slurry reaction zone maintained above 300.degree. C. and at least 2000 psig and in continuous fluid communication with a flash cooling/depressurization zone maintained below 150.degree. C. and between about 125 psig and about atmospheric pressure. Liquefaction systems are also provided that can include a foam/liquid separation system. Liquefaction process intermediate compositions are provided that can include a bio-oil foam phase separated from an aqueous biomass solids solution.

  17. Fischer–Tropsch synthesis: Effect of ammonia on supported cobalt catalysts

    DOE PAGES

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Bertaux, Clement; ...

    2016-02-22

    The effect of ammonia in syngas on the performance of various supported cobalt catalysts (i.e., Al2O3, TiO2 and SiO2) was investigated during Fischer-Tropsch synthesis (FTS) using a continuously stirred tank reactor (CSTR). The addition of ammonia (10 ppmv NH3) caused a significant deactivation for all supported cobalt catalysts, but the rate of deactivation was higher for the silica-supported catalysts relative to the alumina and titania-supported catalysts used in this work. Ammonia addition had a positive effect on product selectivity (i.e., lower light gas products and higher C5+) for alumina and titania-supported catalysts compared to ammonia free conditions, whereas, the additionmore » of ammonia increased lighter hydrocarbon (C1-C4) products and decreased higher hydrocarbon (C5+) selectivity compared to ammonia-free synthesis conditions for the silica-supported catalyst. For alumina and titania-supported catalysts, the activity almost recovered with mild in-situ hydrogen treatment of the ammonia exposed catalysts. For the silica-supported catalyst, the loss of activity is somewhat irreversible (i.e., cannot be regained after the mild hydrogen treatment). Addition of ammonia led to a significant loss in BET surface area and changes in pore diameter (consistent with pore collapse of a fraction of pores into the microporous range as described in the literature), as well as formation of catalytically inactive cobalt support compounds for the silica-supported catalyst. On the other hand, the pore characteristics of alumina and titania-supported catalysts were not significantly changed. In conclusion, XANES results of the ammonia exposed silica-supported catalysts further confirm the formation of cobalt-support compounds (cobalt silicates).« less

  18. Fischer–Tropsch synthesis: Effect of ammonia on supported cobalt catalysts

    SciTech Connect

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Bertaux, Clement; Khalid, Syed; Davis, Burtron H.

    2016-02-22

    The effect of ammonia in syngas on the performance of various supported cobalt catalysts (i.e., Al2O3, TiO2 and SiO2) was investigated during Fischer-Tropsch synthesis (FTS) using a continuously stirred tank reactor (CSTR). The addition of ammonia (10 ppmv NH3) caused a significant deactivation for all supported cobalt catalysts, but the rate of deactivation was higher for the silica-supported catalysts relative to the alumina and titania-supported catalysts used in this work. Ammonia addition had a positive effect on product selectivity (i.e., lower light gas products and higher C5+) for alumina and titania-supported catalysts compared to ammonia free conditions, whereas, the addition of ammonia increased lighter hydrocarbon (C1-C4) products and decreased higher hydrocarbon (C5+) selectivity compared to ammonia-free synthesis conditions for the silica-supported catalyst. For alumina and titania-supported catalysts, the activity almost recovered with mild in-situ hydrogen treatment of the ammonia exposed catalysts. For the silica-supported catalyst, the loss of activity is somewhat irreversible (i.e., cannot be regained after the mild hydrogen treatment). Addition of ammonia led to a significant loss in BET surface area and changes in pore diameter (consistent with pore collapse of a fraction of pores into the microporous range as described in the literature), as well as formation of catalytically inactive cobalt support compounds for the silica-supported catalyst. On the other hand, the pore characteristics of alumina and titania-supported catalysts were not significantly changed. In conclusion, XANES results of the ammonia exposed silica-supported catalysts further confirm the formation of cobalt-support compounds (cobalt silicates).

  19. Liquefaction Potential of Adiyaman Peat

    NASA Astrophysics Data System (ADS)

    Karaca, Huseyin; Depci, Tolga; Karta, Mesut; Coskun, M. Ali

    2016-10-01

    In the present study, liquefaction potential of Adiyaman peat was studied by direct liquefaction technique to obtain oil as a fuel purposes due to its high carbon and hydrogen content and low sulphur ratio. The peat and liquefaction products, named char, asphaltene, preasphaltene and oil, were characterized by XRD, FTIR, SEM, DTA/TG and elemental analysis. The compositions of the obtained oil were also identified by GC/MS. The results indicated that the obtained oil was paraffinic-low waxy oil with 21.73 MJ/kg of calorific value and 0.93 g/cm3 density and it was composed of naphthalene and phenolic groups. The oil conversion ratio was found to be 29 %.

  20. Liquefaction sites, Imperial Valley, California.

    USGS Publications Warehouse

    Youd, T.L.; Bennett, M.J.

    1983-01-01

    Sands that did and did not liquefy at two sites during the 1979 Imperial Valley, Calif., earthquake (ML = 6.6) are identified and their properties evaluated. SPT tests were used to evaluate liquefaction susceptibility. Loose fine sands in an abandoned channel liquefied and produced sand boils, ground fissures, and a lateral spread at the Heber Road sites. Evidence of liquefaction was not observed over moderately dense over-bank sand east of the channel nor over dense point-bar sand to the west. -from ASCE Publications Information

  1. Surfactant-assisted coal liquefaction

    NASA Technical Reports Server (NTRS)

    Hsu, G. C.

    1977-01-01

    Improved process of coal liquefaction utilizing nonaqueous surfactant has increased oil yield from 50 to about 80%. Asphaltene molecule formation of colloid particles is prevented by surfactant. Separated molecules present more surface area for hydrogenation reaction. Lower requirements for temperature, pressure, and hydrogen lead to reduction in capital and operation costs.

  2. Liquefaction, flow, and associated ground failure

    USGS Publications Warehouse

    Youd, T. Leslie

    1973-01-01

    Ambiguities in the use of the term liquefaction and in defining the relation between liquefaction and ground failure have led to encumbered communication between workers in various fields and between specialists in the same field, and the possibility that evaluations of liquefaction potential could be misinterpreted or misapplied. Explicit definitions of liquefaction and related concepts are proposed herein. These definitions, based on observed laboratory behavior, are then used to clarify the relation between liquefaction and ground failure. Soil liquefaction is defined as the transformation of a granular material from a solid into a liquefied state as a consequence of increased pore-water pressures. This definition avoids confusion between liquefaction and possible flow-failure conditions after liquefaction. Flow-failure conditions are divided into two types: (1) unlimited flow if pore-pressure reductions caused by dilatancy during flow deformation are not sufficient to solidify the material and thus arrest flow, and (2) limited flow if they are sufficient to solidify the material after a finite deformation. After liquefaction in the field, unlimited flow commonly leads to flow landslides, whereas limited flow leads at most to lateral-spreading landslides. Quick-condition failures such as loss of bearing capacity form a third type of ground failure associated with liquefaction.

  3. Evaluations in support of regulatory and research decisions by the U. S. Environmental Protection Agency for the control of toxic hazards from hazardous wastes, glyphosate, dalapon, and synthetic fuels

    SciTech Connect

    Scofield, R.

    1984-01-01

    This report includes toxicological and regulatory evaluations performed in support of U.S. EPA regulation of toxic materials and hazardous wastes. The first section of the report describes evaluations which support: (a) the regulation of small-volume generators of hazardous wastes, (b) the regulation of hazardous wastes from pesticide manufacturing, and (c) the disposal of the herbicide, silvex. The second section describes the environmental fate, transport, and effect of glyphosate and dalapon. The third section deals with synthetic fuels, including evaluations of synfuel-product toxicity, uncontrolled air emissions, and particular focus on the toxicity of products from several indirect coal liquefaction processes including methanol synthesis, Fischer-Tropsch, Mobil M-Gasoline, and Lurgi gasification technologies. Three direct coal liquefaction processes were examined for product toxicity and air emissions: Solvent Refined Coal (I and II) and the Exxon Donor Solvent Process. Also described in the third section is an evaluation of environmental and health hazards associated with the use of synthetic fuels from indirect coal liquefaction, direct coal liquefaction, and shale oil. Finally, the fourth section discusses some problems associated with performing, on a contractual basis, scientific and technical evaluations in support of U.S. EPA regulatory and research decisions.

  4. Quantification of seismic liquefaction risk

    SciTech Connect

    Arango, I.; Ostadan, F.; Lewis, M.R.; Gutierrez, B.J.

    1996-02-29

    Explicit goals of acceptable risk for natural phenomena hazards (earthquake, extreme wind, and flood) have been established by the Department of Energy (DOE) 1994. Closely associated to the earthquake risk is the issue of seismically-induced liquefaction. Because deterministic methods currently available to answer the question to whether a site is liquefiable or not are incapable of providing a clue as to the likelihood or risk of liquefaction, the application of the criteria to a given facility requires that alternative evaluation techniques be formulated. This paper describes the application to a nuclear facility of a newly developed probabilistic methodology which rigorously accounts for geotechnical and seismologic uncertainties. The results of the analyses are compared with the acceptable levels of risk presented by DOE. This comparison is used to emphasize the power of the methodology as a tool in the decision-making processes.

  5. Steam pretreatment for coal liquefaction

    SciTech Connect

    Graff, R.A.; Balogh-Nair, V.

    1991-01-01

    Steam pretreatment is the reaction of coal with steam at temperatures well below those usually used for solubilization. The objective of the proposed work is to test the application of steam pretreatment to coal liquefaction. This quarter, a 300 ml stirred autoclave for liquefaction tests was received and installation initiated. Four coal samples were obtained from the Penn State Sample Bank. Continuous flow pretreatment procedures were reestablished. Extraction yields after pretreatment of the new sample of Illinois No. 6 coal are in agreement with previous results even though the particle size is considerably larger. Purification of the model compound {beta}-naphthylmethyl phenyl ether has been completed. However, {alpha}-naphthylmethyl phenyl ether has been found to undergo acid catalyzed rearrangement during purification on silica. An alternative method for purification is being examined. 4 refs., 3 figs., 1 tab.

  6. Surfactant-Assisted Coal Liquefaction

    NASA Technical Reports Server (NTRS)

    Hickey, Gregory S.; Sharma, Pramod K.

    1993-01-01

    Obtaining liquid fuels from coal which are economically competitive with those obtained from petroleum based sources is a significant challenge for the researcher as well as the chemical industry. Presently, the economics of coal liquefaction are not favorable because of relatively intense processing conditions (temperatures of 430 degrees C and pressures of 2200 psig), use of a costly catalyst, and a low quality product slate of relatively high boiling fractions. The economics could be made more favorable by achieving adequate coal conversions at less intense processing conditions and improving the product slate. A study has been carried out to examine the effect of a surfactant in reducing particle agglomeration and improving hydrodynamics in the coal liquefaction reactor to increase coal conversions...

  7. Complete liquefaction methods and apparatus

    SciTech Connect

    Turner, Terry D.; Wilding, Bruce M.

    2013-10-15

    A method and apparatus are described to provide complete gas utilization in the liquefaction operation from a source of gas without return of natural gas to the source thereof from the process and apparatus. The mass flow rate of gas input into the system and apparatus may be substantially equal to the mass flow rate of liquefied product output from the system, such as for storage or use.

  8. Proceedings, twenty-fourth annual international Pittsburgh coal conference

    SciTech Connect

    2007-07-01

    Topics covered include: gasification technologies; coal production and preparation; combustion technologies; environmental control technologies; synthesis of liquid fuels, chemicals, materials and other non-fuel uses of coal; hydrogen from coal; advanced synthesis gas cleanup; coal chemistry, geosciences and resources; Fischer-Tropsch technology; coal and sustainability; global climate change; gasification (including underground gasification); materials, instrumentation and controls; and coal utilisation byproducts.

  9. Evaluation of wastewater treatment requirements for thermochemical biomass liquefaction

    SciTech Connect

    Elliott, D.C. )

    1992-04-01

    Biomass can provide a substantial energy source. Liquids are preferred for use as transportation fuels because of their high energy density and handling ease and safety. Liquid fuel production from biomass can be accomplished by any of several different processes including hydrolysis and fermentation of the carbohydrates to alcohol fuels, thermal gasification and synthesis of alcohol or hydrocarbon fuels, direct extraction of biologically produced hydrocarbons such as seed oils or algae lipids, or direct thermochemical conversion of the biomass to liquids and catalytic upgrading to hydrocarbon fuels. This report discusses direct thermochemical conversion to achieve biomass liquefaction and the requirements for wastewater treatment inherent in such processing. 21 refs.

  10. Recording-based identification of site liquefaction

    NASA Astrophysics Data System (ADS)

    Hu, Yuxian; Zhang, Yushan; Liang, Jianwen; Zhang, Ray Ruichong

    2005-12-01

    Reconnaissance reports and pertinent research on seismic hazards show that liquefaction is one of the key sources of damage to geotechnical and structural engineering systems. Therefore, identifying site liquefaction conditions plays an important role in seismic hazard mitigation. One of the widely used approaches for detecting liquefaction is based on the time-frequency analysis of ground motion recordings, in which short-time Fourier transform is typically used. It is known that recordings at a site with liquefaction are the result of nonlinear responses of seismic waves propagating in the liquefied layers underneath the site. Moreover, Fourier transform is not effective in characterizing such dynamic features as time-dependent frequency of the recordings rooted in nonlinear responses. Therefore, the aforementioned approach may not be intrinsically effective in detecting liquefaction. An alternative to the Fourier-based approach is presented in this study, which proposes time-frequency analysis of earthquake ground motion recordings with the aid of the Hilbert-Huang transform (HHT), and offers justification for the HHT in addressing the liquefaction features shown in the recordings. The paper then defines the predominant instantaneous frequency (PIF) and introduces the PIF-related motion features to identify liquefaction conditions at a given site. Analysis of 29 recorded data sets at different site conditions shows that the proposed approach is effective in detecting site liquefaction in comparison with other methods.

  11. Solvent treatment of coal for improved liquefaction

    DOEpatents

    Appell, Herbert R.; Narain, Nand K.; Utz, Bruce R.

    1986-05-06

    Increased liquefaction yield is obtained by pretreating a slurry of solid carbonaceous material and a liquid hydrocarbonaceous solvent at a temperature above 200.degree. C. but below 350.degree. C. for a period of 10 minutes to four hours prior to exposure to liquefaction temperatures.

  12. Whole Algae Hydrothermal Liquefaction Technology Pathway

    SciTech Connect

    Biddy, M.; Davis, R.; Jones, S.

    2013-03-01

    This technology pathway case investigates the feasibility of using whole wet microalgae as a feedstock for conversion via hydrothermal liquefaction. Technical barriers and key research needs have been assessed in order for the hydrothermal liquefaction of microalgae to be competitive with petroleum-derived gasoline-, diesel-, and jet-range hydrocarbon blendstocks.

  13. Novel supports for coal liquefaction catalysts

    SciTech Connect

    Haynes, H.W. Jr.

    1992-01-01

    This research is divided into three parts: (1) Evaluation of Alkaline-Earth-Promoted CoMo/Alumina Catalysts in a Bench Scale Hydrotreater, (2) Development of a Novel Catalytic Coal Liquefaction Microreactor (CCLM) Unit, and (3) Evaluation of Novel Catalyst Preparations for Direct Coal Liquefaction. (VC)

  14. Hydrogen-donor coal liquefaction process

    DOEpatents

    Wilson, Jr., Edward L.; Mitchell, Willard N.

    1980-01-01

    Improved liquid yields are obtained during the hydrogen-donor solvent liquefaction of coal and similar carbonaceous solids by maintaining a higher concentration of material having hydrogenation catalytic activity in the downstream section of the liquefaction reactor system than in the upstream section of the system.

  15. Development of improved iron Fischer-Tropsch catalysts. Quarterly technical progress report, 1 April 1990--30 June 1990

    SciTech Connect

    Bukur, D.B.

    1990-06-17

    The objective of proposed research is development of catalysts with enhanced slurry phase activity and better selectivity to fuel range products, through a more detailed understanding and systematic studies of the effects of pretreatment procedures and promoters/binders (silica) on catalyst performance.

  16. Development of improved iron Fischer-Tropsch catalysts. Quarterly technical progress report, 1 January 1990--31 March 1990

    SciTech Connect

    Bukur, D.B.; Patel, S.A.; Dalai, A.K.; Jayanthi, G.; Ledakowicz, S.

    1990-04-30

    The objective of proposed research is development of catalysts with enhanced slurry phase activity and better selectivity to fuel range products, through a more detailed understanding and systematic studies of the effects of pretreatment procedures and promoters/binders (silica) on catalyst performance.

  17. 40 CFR 721.10178 - Distillates (Fischer-Tropsch), hydroisomerized middle, C10-13-branched alkane fraction.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...), hydroisomerized middle, C10-13-branched alkane fraction. 721.10178 Section 721.10178 Protection of Environment...), hydroisomerized middle, C10-13-branched alkane fraction. (a) Chemical substance and significant new uses subject... middle, C10-13-branched alkane fraction (PMN P-04-319; CAS No. 642928-30-1) is subject to reporting...

  18. Development of improved iron Fischer-Tropsch catalysts. Quarterly technical progress report, 1 October 1991--31 December 1991

    SciTech Connect

    Bukur, D.B.

    1992-01-10

    The objective of proposed research is development of catalysts with enhanced slurry phase activity and better selectivity to fuel range products, through a more detailed understanding and systematic studies of the effects of pretreatment procedures and promoters/binders (silica) on catalyst performance.

  19. Development of precipitated iron Fischer-Tropsch catalysts. Quarterly technical progress report, 1 October 1995--31 December 1995

    SciTech Connect

    Bukur, D.B.

    1996-02-14

    Two stirred tank slurry reactor tests of catalysts with nominal compositions 100 Fe/3Cu/4 K/2 Ca/16 SiO{sub 2} (run SB-3115) and 100 Fe/5 Cu/6 K/24 SiO{sub 2} (run SA-3155) were completed under task 5, The Effect of Source of Potassium and Basic Oxide Promoter, during the reporting period. Our assessment of the effects of addition of CaO promoter to our baseline catalysts B and C and the use of potassium silicate as the source of potassium promoter is as follows: in general, the addition of CaO promoter did not result in improved performance of the baseline catalysts; the use of CaO promoter may be best suited for operation at higher reaction pressures; the baseline procedure utilizing impregnation of Fe-Cu-SiO{sub 2} precursor with aqueous solution of KHCO{sub 3} as the source of potassium promoter is the preferred method of preparation; and the procedure which utilizes aqueous K{sub 2}SiO{sub 3} solution as the source of potassium also provides satisfactory results, and may be used as an alternative. A slurry reactor test (run SB-3425) was completed during the reporting period, following the catalyst pretreatment with H{sub 2} at 250{degrees}C for 4 h (Task 6. Pretreatment Effect Research). This pretreatment resulted in higher catalyst activity than our baseline procedure (H{sub 2} at 240{degrees}C for 2 h) but also higher methane and gaseous hydrocarbon selectivities (about 10-20% higher).

  20. Development of precipitated iron Fischer-Tropsch catalysts. Quarterly technical progress report, 1 July 1995--30 September 1995

    SciTech Connect

    Bukur, D.B.

    1995-12-20

    The following accomplishments were made on task 4. Reproducibility of Catalyst Preparation: (1) Five slurry reactor tests were completed. Three tests were conducted using catalyst C (100 Fe/3 Cu/4 K/16 SiO{sub 2}) from three different batches (runs SB-2695, SB-2145 and SA-2715), and two tests were conducted with catalyst B (100 Fe/5 Cu/6 K/24 SiO{sub 2}) from two different preparation batches (runs SA-2615 and SB-2585). Performance of catalysts from different batches (activity, selectivity and deactivation rates) was similar to that of catalysts from the original batch (synthesized during DOE Contract DE- AC22-89PC89868). Thus, another major objective of the present contract, demonstration of reproducibility of catalyst preparation procedure and performance, has been accomplished. With these tests the work on Task 4 has been successfully completed. Two fixed bed reactor tests of catalysts B and C synthesized using potassium silicate solution as the source of potassium promoter were completed during this period (Task 5. The Effect of Source of Potassium and Basic Oxide Promoter). Activity of catalysts prepared using potassium silicate as the source of potassium promotion was somewhat higher, and their methane selectivities were higher than those of the corresponding catalysts prepared by incipient wetness impregnation using KHCO{sub 3} as the source of potassium promoter. However, these differences were not large, and may have been caused by experimental artifacts (e.g. existence of local hot spots in a reactor). A slurry reactor test (SA-2405) of catalyst with nominal composition 100 Fe/5 Cu/2 Ca/24 SiO{sub 2} was completed (Task 5). In general, the catalyst activity, space-time-yield, and hydrocarbon selectivities in this run during testing at:260{degrees}C, 2.17 MPa (300 psig), 2-2.6 Nl/g-cat/h and H{sub 2}CO=0.67 were quite good, and comparable to the best results obtained in our Laboratory.

  1. Effects of Weak Surface Modification on Co/SiO2 Catalyst for Fischer-Tropsch Reaction

    PubMed Central

    Ning, Wensheng; Shen, Hehong; Jin, Yangfu; Yang, Xiazhen

    2015-01-01

    A weak surface modification is applied to Co/SiO2 catalyst by hydrothermal treatment at 180°C for 5 h. Aluminum is introduced to Co/SiO2 catalysts during the surface modification. The effects of surface modification on Co/SiO2 catalyst are studied by changing the operating sequences of surface modification and cobalt impregnation in the catalyst preparation. Surface modification before cobalt impregnation makes Co3O4 particle small and dispersed into the deep part of enlarged pore in SiO2, while surface modification after cobalt impregnation does not obviously change the particle size of Co3O4. The improved amplitude of catalytic activity is similar for the two kinds of catalysts, but they are benefited from different factors. The content of iso-hydrocarbons in the products is increased by the surface modifications. PMID:25938725

  2. Conversion of cellulosic wastes to liquid fuels

    SciTech Connect

    Kuester, J.L.

    1980-09-01

    The current status and future plans for a project to convert waste cellulosic (biomass) materials to quality liquid hydrocarbon fuels is described. 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 process is capable of accepting a wide variety of feedstocks. Potential products include medium quality gas, normal propanol, diesel fuel and/or high octane gasoline. A fluidized bed pyrolysis system is used for gasification. The pyrolyzer can be fluidized 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. The following tasks were specified in the statement of work for the contract period: (1) feedstock studies; (2) gasification system optimization; (3) waste stream characterization; and (4) liquid fuels synthesis. In addition, several equipment improvements were implemented.

  3. 77 FR 58118 - Freeport LNG Development, L.P., FLNG Liquefaction, LLC, FLNG Liquefaction 2, LLC, FLNG...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-09-19

    ... Energy Regulatory Commission Freeport LNG Development, L.P., FLNG Liquefaction, LLC, FLNG Liquefaction 2, LLC, FLNG Liquefaction 3, LLC; Notice of Application Take notice that on August 31, 2012, Freeport LNG... natural gas liquefaction and export facilities will be constructed adjacent to the existing Freeport...

  4. Slurry phase iron catalysts for indirect coal liquefaction. Second semi-annual progress report, January 5, 1996--July 4, 1996

    SciTech Connect

    Datye, A.K.

    1996-08-02

    During this period, work was continued on understanding the attrition of precipitated iron catalysts and work initiated on synthesizing catalysts containing silica binders. Use of a sedigraph particle size analyzer with an ultrasonic probe provides a simple method to test the strength of catalyst agglomerates, allowing the strength comparison of silica and hematite catalysts (the former is considerably stronger). Study of Fe/silica interactions was continued. Addition of a colloidal silica precursor to calcined Fe{sub 2}O{sub 3} catalyst had no detrimental effect on reducibility of the hematite to {alpha}-Fe. XRD and electron microscopy will be used to analyze the crystal structure and types of C present in samples from long Fischer-Tropsch runs.

  5. Coal liquefaction with preasphaltene recycle

    DOEpatents

    Weimer, Robert F.; Miller, Robert N.

    1986-01-01

    A coal liquefaction system is disclosed with a novel preasphaltene recycle from a supercritical extraction unit to the slurry mix tank wherein the recycle stream contains at least 90% preasphaltenes (benzene insoluble, pyridine soluble organics) with other residual materials such as unconverted coal and ash. This subject process results in the production of asphaltene materials which can be subjected to hydrotreating to acquire a substitute for No. 6 fuel oil. The preasphaltene-predominant recycle reduces the hydrogen consumption for a process where asphaltene material is being sought.

  6. Gasification of coal liquefaction residues

    SciTech Connect

    Lancet, M. S.

    1981-02-03

    A method is described for gasifying the bottoms fraction from a coal liquefaction process. The bottoms fraction are mixed with at least one finely-divided calcium compound selected from the group consisting of calcium oxide, calcium carbonate and calcium hydroxide with the calcium compound being of a size no larger than about -200 tyler mesh and present in an amount sufficient to produce agglomerate particles upon mixing with the bottoms fraction and thereafter the resulting agglomerate particles are gasified by reacting the agglomerate particles with steam in a fluidized bed.

  7. Synthesis and stabilization of supported metal catalysts by atomic layer deposition.

    PubMed

    Lu, Junling; Elam, Jeffrey W; Stair, Peter C

    2013-08-20

    Supported metal nanoparticles are among the most important catalysts for many practical reactions, including petroleum refining, automobile exhaust treatment, and Fischer-Tropsch synthesis. The catalytic performance strongly depends on the size, composition, and structure of the metal nanoparticles, as well as the underlying support. Scientists have used conventional synthesis methods including impregnation, ion exchange, and deposition-precipitation to control and tune these factors, to establish structure-performance relationships, and to develop better catalysts. Meanwhile, chemists have improved the stability of metal nanoparticles against sintering by the application of protective layers, such as polymers and oxides that encapsulate the metal particle. This often leads to decreased catalytic activity due to a lack of precise control over the thickness of the protective layer. A promising method of catalyst synthesis is atomic layer deposition (ALD). ALD is a variation on chemical vapor deposition in which metals, oxides, and other materials are deposited on surfaces by a sequence of self-limiting reactions. The self-limiting character of these reactions makes it possible to achieve uniform deposits on high-surface-area porous solids. Therefore, design and synthesis of advanced catalysts on the nanoscale becomes possible through precise control over the structure and composition of the underlying support, the catalytic active sites, and the protective layer. In this Account, we describe our advances in the synthesis and stabilization of supported metal catalysts by ALD. After a short introduction to the technique of ALD, we show several strategies for metal catalyst synthesis by ALD that take advantage of its self-limiting feature. Monometallic and bimetallic catalysts with precise control over the metal particle size, composition, and structure were achieved by combining ALD sequences, surface treatments, and deposition temperature control. Next, we describe

  8. Highly Dispersed Pseudo-Homogeneous and Heterogeneous Catalysts Synthesized via Inverse Micelle Solutions for the Liquefaction of Coal

    SciTech Connect

    Hampden-Smith, M.; Kawola, J.S.; Martino, A.; Sault, A.G.; Yamanaka, S.A.

    1999-01-05

    The mission of this project was to use inverse micelle solutions to synthesize nanometer sized metal particles and test the particles as catalysts in the liquefaction of coal and other related reactions. The initial focus of the project was the synthesis of iron based materials in pseudo-homogeneous form. The frost three chapters discuss the synthesis, characterization, and catalyst testing in coal liquefaction and model coal liquefaction reactions of iron based pseudo-homogeneous materials. Later, we became interested in highly dispersed catalysts for coprocessing of coal and plastic waste. Bifunctional catalysts . to hydrogenate the coal and depolymerize the plastic waste are ideal. We began studying, based on our previously devised synthesis strategies, the synthesis of heterogeneous catalysts with a bifunctional nature. In chapter 4, we discuss the fundamental principles in heterogeneous catalysis synthesis with inverse micelle solutions. In chapter 5, we extend the synthesis of chapter 4 to practical systems and use the materials in catalyst testing. Finally in chapter 6, we return to iron and coal liquefaction now studied with the heterogeneous catalysts.

  9. Hierarchical structured α-Al2O3 supported S-promoted Fe catalysts for direct conversion of syngas to lower olefins.

    PubMed

    Zhou, Xiangping; Ji, Jian; Wang, Di; Duan, Xuezhi; Qian, Gang; Chen, De; Zhou, Xinggui

    2015-05-25

    Hierarchical structured α-Al2O3 is shown to be able to effectively disperse and immobilize iron species, in comparison with commercial α-Al2O3. After promotion using an appropriate amount of sulfur, iron catalysts exhibit not only enhanced Fischer-Tropsch synthesis activity and selectivity toward lower olefins, but also increased resistance against carbon deposits.

  10. Attrition resistant bulk iron catalysts and processes for preparing and using same

    DOEpatents

    Jothimurugesan, Kandaswamy; Goodwin, Jr., James G.; Gangwal, Santosh K.

    2007-08-21

    An attrition resistant precipitated bulk iron catalyst is prepared from iron oxide precursor and a binder by spray drying. The catalysts are preferably used in carbon monoxide hydrogenation processes such as Fischer-Tropsch synthesis. These catalysts are suitable for use in fluidized-bed reactors, transport reactors and, especially, slurry bubble column reactors.

  11. Study of the Feasibility of a Coal-to-Liquids Plant in Interior Alaska

    DTIC Science & Technology

    2011-05-12

    Syngas Treatment – Fischer-Tropsch (F-T) Synthesis & Upgrading ...Separation Unit Coal Preparation Gasifier Syngas Treatment F-T and Upgrading Power Generation oxygen dried coal or slurried coal raw syngas syngas air...Water Balance Example clean syngas from Gas Purification 261 psi steam to Power Generation prelleated BFW blowdO\\’ffl to Water

  12. Continuous enzymatic liquefaction of starch for saccharification.

    PubMed

    Carr, M E; Black, L T; Bagby, M O

    1982-11-01

    A process was explored for continuous enzymatic liquefaction of corn starch at high concentration and subsequently saccharification to glucose. The process appears to be quite efficient for conversion of starch to glucose and enzymatic liquefaction and should be readily adaptable to industrial fermentation processes. Preliminary work indicated that milled corn or other cereal grains also can be suitably converted by such a process. Essentially, the process involved incorporation of a thermostable, bacterial alpha-amylase for liquefaction and, subsequently, of a glucoamylase into the continuous mixer under conditions conductive to rapid enzymatic hydrolyses. Also studied was the effect on substrate liquefaction of variable such as starch concentration (40-70 degrees ), level of alpha-amylase (0.14-0.4%, dry starch basis), temperature (70-100 degrees C), pH (5.8-7.1), and residence time (6 and 12 min). The degree of liquefaction was assessed by determining (1) the Brookfield viscosity, (2) the amount of reducing groups, and (3) the rate and extent of glucose formed after glucoamylase treatment. Best liquefaction process conditions were achieved by using 50-60% starch concentration, at 95 degrees C, with 0.4% alpha-amylase, and a 6-min residence period in the mixture. Under these conditions, rate and extents of glucose obtained after glucoamylase treatment approached those obtained in longer laboratory batch liquefactions. The amount of glucose formed in 24h with the use of 0.4% glucoamylase was 86% of theory after a 6-min continuous liquefaction, compared to 90% for a 30-min laboratory batch liquefaction (95 degrees C, 0.4% alpha-amylase).

  13. Continuous enzymatic liquefaction of starch for saccharification

    SciTech Connect

    Carr, M.E.; Black, L.T.; Bagby, M.O.

    1982-01-01

    A process was explored for continuous enzymatic liquefaction of corn starch at high concentration and subsequent saccharification to glucose. The process appears to be quite efficient for conversion of starch to glucose and enzymatic liquefaction and should be readily adaptable to industrial fermentation processes. Preliminary work indicated that milled corn or other cereal grains also can be suitably converted by such a process. Essentially, the process involved incorporation of a thermostable, bacterial alpha-amylase for liquefaction and, subsequently, of a glucoamylase into the continuous mixer under conditions conductive to rapid enzymatic hydrolyses. Also studied was the effect on substrate liquefaction of variables such as starch concentration (40-70%), level of alpha-amylase (0.14-0.4%, dry starch basis), temperature (70-100 degrees C), pH (5.8-7.1), and residence time (6 and 12 minutes). The degree of liquefaction was assessed by determining 1) the Brookfield viscosity, 2) the amount of reducing groups, and 3) the rate and extent of glucose formed after glucoamylase treatment. Best liquefaction processing conditions were achieved by using 50-60% starch concentration, at 95 degrees C, with 0.4% alpha-amylase, and a 6 minute residence period in the mixer. Under these conditions, rates and extents of glucose obtained after glucoamylase treatment approached those obtained in longer laboratory batch liquefactions. The amount of glucose formed in 24 hours with the use of 0.4% glucoamylase was 86% of theory after a 6-min continuous liquefaction, compared to 90% for a 30-min laboratory batch liquefaction (95 degrees C, 0.4% alpha-amylase). (Refs. 15).

  14. Coal liquefaction with subsequent bottoms pyrolysis

    DOEpatents

    Walchuk, George P.

    1978-01-01

    In a coal liquefaction process wherein heavy bottoms produced in a liquefaction zone are upgraded by coking or a similar pyrolysis step, pyrolysis liquids boiling in excess of about 1000.degree. F. are further reacted with molecular hydrogen in a reaction zone external of the liquefaction zone, the resulting effluent is fractionated to produce one or more distillate fractions and a bottoms fraction, a portion of this bottoms fraction is recycled to the reaction zone, and the remaining portion of the bottoms fraction is recycled to the pyrolysis step.

  15. Cooperative Research Program in coal liquefaction. Technical report, May 1, 1994--October 31, 1994

    SciTech Connect

    1994-12-31

    Progress reports are presented for the following tasks: coliquefaction of coal with waste materials; catalysts for coal liquefaction to clean transportation fuels; fundamental research in coal liquefaction; and in situ analytical techniques for coal liquefaction and coal liquefaction catalysts.

  16. Cooperative research program in coal liquefaction. Quarterly report, August 1, 1991--October 31, 1991

    SciTech Connect

    Huffman, G.P.

    1991-12-31

    This Quarterly Report on coal liquefaction research includes discussion in the areas of (1) Iron Based Catalysts for Coal Liquefaction; (2) Exploratory Research on Coal Conversion; (3) Novel Coal Liquefaction Concepts; (4) Novel Catalysts for Coal Liquefaction. (VC)

  17. Cooperative research program in coal liquefaction. Quarterly report, November 1, 1991--January 31, 1992

    SciTech Connect

    Huffman, G.P.

    1992-06-01

    Research continues on coal liquefaction in the following areas: (1) Iron Based Catalysts for Coal Liquefaction; (2) Exploratory Research on Coal Conversion; (3) Novel Coal Liquefaction Concepts; (4) Novel Catalysts for Coal Liquefaction. (VC)

  18. Advancement of liquefaction assessment in Chinese building codes

    NASA Astrophysics Data System (ADS)

    Sun, H.; Liu, F.; Jiang, M.

    2015-09-01

    China has suffered extensive liquefaction hazards in destructive earthquakes. The post-earthquake reconnaissance effort in the country largely advances the methodology of liquefaction assessment distinct from other countries. This paper reviews the evolution of the specifications regarding liquefaction assessment in the seismic design building code of mainland China, which first appeared in 1974, came into shape in 1989, and received major amendments in 2001 and 2010 as a result of accumulated knowledge on liquefaction phenomenon. The current version of the code requires a detailed assessment of liquefaction based on in situ test results if liquefaction concern cannot be eliminated by a preliminary assessment based on descriptive information with respect to site characterization. In addition, a liquefaction index is evaluated to recognize liquefaction severity, and to choose the most appropriate engineering measures for liquefaction mitigation at a site being considered.

  19. Histotripsy Liquefaction of Large Hematomas.

    PubMed

    Khokhlova, Tatiana D; Monsky, Wayne L; Haider, Yasser A; Maxwell, Adam D; Wang, Yak-Nam; Matula, Thomas J

    2016-07-01

    Intra- and extra-muscular hematomas result from repetitive injury as well as sharp and blunt limb trauma. The clinical consequences can be serious, including debilitating pain and functional deficit. There are currently no short-term treatment options for large hematomas, only lengthy conservative treatment. The goal of this work was to evaluate the feasibility of a high intensity focused ultrasound (HIFU)-based technique, termed histotripsy, for rapid (within a clinically relevant timeframe of 15-20 min) liquefaction of large volume (up to 20 mL) extra-vascular hematomas for subsequent fine-needle aspiration. Experiments were performed using in vitro extravascular hematoma phantoms-fresh bovine blood poured into 50 mL molds and allowed to clot. The resulting phantoms were treated by boiling histotripsy (BH), cavitation histotripsy (CH) or a combination in a degassed water tank under ultrasound guidance. Two different transducers operating at 1 MHz and 1.5 MHz with f-number = 1 were used. The liquefied lysate was aspirated and analyzed by histology and sized in a Coulter Counter. The peak instantaneous power to achieve BH was lower than (at 1.5 MHz) or equal to (at 1 MHz) that which was required to initiate CH. Under the same exposure duration, BH-induced cavities were one and a half to two times larger than the CH-induced cavities, but the CH-induced cavities were more regularly shaped, facilitating easier aspiration. The lysates contained a small amount of debris larger than 70 μm, and 99% of particulates were smaller than 10 μm. A combination treatment of BH (for initial debulking) and CH (for liquefaction of small residual fragments) yielded 20 mL of lysate within 17.5 minutes of treatment and was found to be most optimal for liquefaction of large extravascular hematomas.

  20. Liquefaction of lignin by polyethyleneglycol and glycerol.

    PubMed

    Jin, Yanqiao; Ruan, Xuemin; Cheng, Xiansu; Lü, Qiufeng

    2011-02-01

    Enzymatic hydrolysis lignin (EHL), isolated from the enzymatic hydrolysis residues of the biomass, was liquefied using the mixed solvents of polyethyleneglycol (PEG) and glycerol at the temperature of 130-170°C with sulfuric acid as a catalyst. The influences of liquefaction parameters, such as the molecular weight of PEG, mass ratio of sulfuric acid to EHL, liquefaction temperature and time, and mass ratio of liquid (liquefying cosolvent) to solid (EHL) on the residue content and hydroxyl number were discussed. The FT-IR spectrum result showed that the liquefaction product of EHL was polyether polyol. The hydroxyl number of the liquefaction product was 80-120 mgKOH/g higher than that of PEG.

  1. Evaluation of liquefaction potential for building code

    SciTech Connect

    Nunziata, C.; De Nisco, G.; Panza, G. F.

    2008-07-08

    The standard approach for the evaluation of the liquefaction susceptibility is based on the estimation of a safety factor between the cyclic shear resistance to liquefaction and the earthquake induced shear stress. Recently, an updated procedure based on shear-wave velocities (V{sub s}) has been proposed which could be more easily applied.These methods have been applied at La Plaja beach of Catania, that experienced liquefaction because of the 1693 earthquake. The detailed geotechnical and V{sub s} information and the realistic ground motion computed for the 1693 event let us compare the two approaches. The successful application of the V{sub s} procedure, slightly modified to fit historical and safety factor information, even if additional field performances are needed, encourages the development of a guide for liquefaction potential analysis, based on well defined V{sub s} profiles to be included in the italian seismic code.

  2. Products of direct liquefaction of biomass

    SciTech Connect

    Davis, H.G.; Eames, M.A.; Figueroa, C.; Gansley, R.R.; Schaleger, L.L.; Watt, D.W.

    1982-10-01

    Several methods of characterizing products of biomass liquefaction including GC-MS, wet analysis, infrared and various forms of liquid chromatography have been tried. Of these the SESC sequential elution technique has been particularly helpful in separating whole product oils into chemically distinguishable fractions. Variations in the distribution of SESC fractions have been used to show effects of changing conditions and changing feedstocks in biomass liquefaction. They have also been used to follow the effects of catalytic hydrogenation. Liquefaction of aspen results in higher yields than liquefaction of Douglas fir. The aspen oil product is richer in SESC fractions 1-4, is more fluid and has lower oxygen content. Catalytic hydrogenation is effective in increasing the percentage of oil in the more volatile SESC fractions 1-4.

  3. Coal liquefaction process streams characterization and evaluation

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1992-03-01

    CONSOL R D is conducting a three-year program to characterize process and product streams from direct coal liquefaction process development projects. The program objectives are two-fold: (1) to obtain and provide appropriate samples of coal liquids for the evaluation of analytical methodology, and (2) to support ongoing DOE-sponsored coal liquefaction process development efforts. The two broad objectives have considerable overlap and together serve to provide a bridge between process development and analytical chemistry.

  4. Liquefaction mechanism for layered soils

    SciTech Connect

    Fiegel, G.L.; Kutter, B.L. . Dept. of Civil and Environmental Engineering)

    1994-04-01

    Results from four centrifuge model tests are presented. Three of the model tests involve layered soil deposits subject to base shaking; one model test involves a uniform soil deposit of sand subject to base shaking. The layered soil models consisted of fine sand overlain by a layer of relatively impermeable silica flour (silt). Pore-water pressures, accelerations, and settlements were measured during all four tests. Results from the model tests involving layered soils suggest that during liquefaction a water interlayer or very loose zone of soil may develop at the sand-silt interface due to the difference in permeabilities. In each layered model test, boils were observed on the surface of the silt layer. These boils were concentrated in the thinnest zones of the overlying silt layer and provided a vent for the excess pore-water pressure generated in the fine sand.

  5. Iron catalyzed coal liquefaction process

    DOEpatents

    Garg, Diwakar; Givens, Edwin N.

    1983-01-01

    A process is described for the solvent refining of coal into a gas product, a liquid product and a normally solid dissolved product. Particulate coal and a unique co-catalyst system are suspended in a coal solvent and processed in a coal liquefaction reactor, preferably an ebullated bed reactor. The co-catalyst system comprises a combination of a stoichiometric excess of iron oxide and pyrite which reduce predominantly to active iron sulfide catalysts in the reaction zone. This catalyst system results in increased catalytic activity with attendant improved coal conversion and enhanced oil product distribution as well as reduced sulfide effluent. Iron oxide is used in a stoichiometric excess of that required to react with sulfur indigenous to the feed coal and that produced during reduction of the pyrite catalyst to iron sulfide.

  6. The liquefaction method for assessing paleoseismicity

    SciTech Connect

    Tuttle, M.P.

    1994-12-01

    Paleoseismicity studies expand our knowledge of seismic activity into the prehistoric period and thereby can improve our understanding of the earthquake potential of various regions. Paleoseismology is proving especially useful in eastern North America, where the recurrence interval of large earthquakes is longer than the historic record of earthquakes. Because surface traces of seismogenic faults have been difficult to identify in eastern North America, most paleoseismicity studies have employed features resulting from liquefaction. The goals of paleoliquefaction studies are to determine the recurrence intervals, magnitudes, and source areas of prehistoric earthquakes. To accomplish these goals, one must be able to identify earthquake-induced liquefaction features, determine their ages, and map their distribution. This report reviews (1) characteristics of earthquake-induced liquefaction features as well as other soft-sediment deformation structures, (2) methods for dating liquefaction features, and (3) relationships between liquefaction and the magnitude and distance of causative earthquakes. Recent studies by the author in Quebec Province, Canada and in the New Madrid seismic zone of the central United States provide the basis for this report. For additional information on the use of liquefaction features in paleoseismology see Amick et al. (1990) and Obermeier et al. (1990 and 1992).

  7. Further studies on developing technology for indirect liquefaction

    SciTech Connect

    Gray, D.; Neuworth, M.B.; Tomlinson, G.

    1982-03-01

    Our investigations have resulted in the conclusion that fluid-bed gasifiers, such as Westinghouse or entrained-flow gasifiers such as Texaco and Shell-Koppers, offer significant advantages over the BGC Lurgi gasifier when Illinois No. 6 coal is employed as the feedstock. Dry-ash Lurgi gasification has additional disadvantages which appear to make it unsuitable for applications with mildly caking coal such as Illinois No. 6. The results of our analyses of Illinois No. 6 coal do not alter our prior conclusions regarding the use of advanced gasification systems for indirect liquefaction. BGC/Lurgi, Westinghouse, Texaco and Shell-Koppers gasifiers offer significant advantages over dry-ash Lurgi and should be given detailed consideration for a US liquefaction facility. The final decision will probably be driven by the relative state of development at the time a decision is required, process license and guarantees which could be negotiated, the market value of an SNG co-product, and the specific characteristics of the coal feedstock to be used. Again, it should be stressed that all these potential improvements are contingent upon performance levels being achieved for both Kolbel synthesis and advanced gasifiers that are equal to those reported in the literature sources used in this study.

  8. Experience in feeding coal into a liquefaction process development unit

    NASA Technical Reports Server (NTRS)

    Akhtar, S.; Friedman, S.; Mazzocco, N. J.; Yavorsky, P. M.

    1977-01-01

    A system for preparing coal slurry and feeding it into a high pressure liquefaction plant is described. The system was developed to provide supporting research and development for the Bureau of Mines coal liquefaction pilot plant. Operating experiences are included.

  9. Coal liquefaction and gas conversion: Proceedings. Volume 1

    SciTech Connect

    Not Available

    1993-12-31

    Volume I contains papers presented at the following sessions: AR-Coal Liquefaction; Gas to Liquids; and Direct Liquefaction. Selected papers have been processed separately for inclusion in the Energy Science and Technology Database.

  10. Investigations into coal coprocessing and coal liquefaction

    SciTech Connect

    Guffey, F.D.; Netzel, D.A.; Miknis, F.P.; Thomas, K.P.; Zhang, Tiejun; Haynes, H.W. Jr.

    1994-06-01

    The conversion of coal to liquid suitable as feedstock to a petroleum refinery is dependent upon several process variables. These variables include temperature, pressure, coal rank, catalyst type, nature of the feed to the reactor, type of process, etc. Western Research Institute (WRI) has initiated a research program in the area of coal liquefaction to address the impact of some of these variables upon the yield and quality of the coal-derived liquid. The principal goal of this research is to improve the efficiency of the coal liquefaction process. Two different approaches are currently being investigated. These include the coprocessing of a heavy liquid, such as crude oil, and coal using a dispersed catalyst and the direct liquefaction of coal using a supported catalyst. Another important consideration in coal liquefaction is the utilization of hydrogen, including both externally- and internally-supplied hydrogen. Because the incorporation of externally-supplied hydrogen during conversion of this very aromatic fossil fuel to, for example, transportation fuels is very expensive, improved utilization of internally-supplied hydrogen can lead to reducing processing costs. The objectives of this investigation, which is Task 3.3.4, Coal Coprocessing, of the 1991--1992 Annual Research Plan, are: (1) to evaluate coal/oil pretreatment conditions that are expected to improve the liquid yield through more efficient dispersion of an oil-soluble, iron-based catalyst, (2) to characterize the coke deposits on novel, supported catalysts after coal liquefaction experiments and to correlate the carbon skeletal structure parameters of the coke deposit with catalyst performance as measured by coal liquefaction product yield, and (3) to determine the modes of hydrogen utilization during coal liquefaction and coprocessing. Experimental results are discussed in this report.

  11. Coal liquefaction process research quarterly report, October-December 1979

    SciTech Connect

    Bickel, T.C.; Curlee, R.M.; Granoff, B.; Stohl, F.V.; Thomas, M.G.

    1980-03-01

    This quarterly report summarizes the activities of Sandia's continuing program in coal liquefaction process research. The overall objectives are to: (1) provide a fundamental understanding of the chemistry of coal liquefaction; (2) determine the role of catalysts in coal liquefaction; and (3) determine the mechanism(s) of catalyst deactivation. The program is composed of three major projects: short-contact-time coal liquefaction, mineral effects, and catalyst studies. These projects are interdependent and overlap significantly.

  12. Liquefaction Of Coal With Surfactant And Disposable Catalyst

    NASA Technical Reports Server (NTRS)

    Hickey, Gregory S.; Sharma, Pramod K.

    1996-01-01

    Fuels derived from coal more competitive with petroleum products. Improved coal-liquefaction process exploits synergistic effects of disposable iron oxide catalyst and cheap anionic surfactant. Efficiency of conversion achieved in significantly higher than efficiencies obtained with addition of either surfactant or catalyst alone. No costly pretreatment necessary, and increase in conversion achieved under processing conditions milder than those used heretofore in liquefaction of coal. Quality of distillates obtained after liquefaction in process expected superior to distillates obtained after liquefaction by older techniques.

  13. Evaluation of two conceptual wastewater treatment schemes for a Lurgi-based indirect coal liquefaction plant

    SciTech Connect

    Villiers-Fisher, J.F.; Singh, S.P.N.

    1984-09-01

    The objective of this study was to evaluate two conceptual treatment schemes for decontaminating the wastewaters likely to be generated in a conceptual dry-ash Lurgi-based indirect coal liquefaction plant. The conceptual indirect coal liquefaction plant is an integrated (i.e., all utilities generated onsite) facility designed to convert 15,000 tons of moisture- and ash-free coal per stream day to motor gasoline using dry-ash Lurgi coal gasification, Imperial Chemical Industries' methanol synthesis, and Mobil's methanol-to-gasoline processes. The conceptual plant is premised to be located at a generic site in the eastern United States and processes a generic Interior Basin high-sulfur bituminous coal. The following conclusions can be drawn from this assessment: (1) On paper, wastewater treatment facilities can be designed that are projected to treat the indirect coal liquefaction plant wastewaters to a level where the effluent will likely meet the current regulations for aqueous effluents for allied industries such as coke ovens and petroleum refineries. (2) The estimated capital investments, in 1983 US dollars, for the Case I (surface-discharge) and Case II (zero-aqueous-discharge) schemes are approximately $440 million and $550 million, respectively. These costs represent about 15 and 20% of the estimated capital investment for the integrated indirect coal liquefaction plant. (3) Case II (zero-aqueous-discharge) wastewater treatment is likely to result in the accumulation of approximately 1 million tons of toxic solid wastes during the 30 years of plant operation.

  14. A Potential Cost Effective Liquefaction Mitigation Countermeasure: Induced Partial Saturation

    SciTech Connect

    Bian Hanbing; Jia Yun; Shahrour, Isam

    2008-07-08

    This work is devoted to illustrate the potential liquefaction mitigation countermeasure: Induced Partial Saturation. Firstly the potential liquefaction mitigation method is briefly introduced. Then the numerical model for partially saturated sandy soil is presented. At last the dynamic responses of liquefiable free filed with different water saturation is given. It shows that the induced partial saturation is efficiency for preventing the liquefaction.

  15. Coal liquefaction and gas conversion contractors review conference: Proceedings

    SciTech Connect

    1995-11-01

    This volume contains 55 papers presented at the conference. They are divided into the following topical sections: Direct liquefaction; Indirect liquefaction; Gas conversion (methane conversion); and Advanced research liquefaction. Papers in this last section deal mostly with coprocessing of coal with petroleum, plastics, and waste tires, and catalyst studies. Selected papers are indexed separately for inclusion in the Energy Science and Technology Database.

  16. Liquefaction probability curves for surficial geologic deposits

    USGS Publications Warehouse

    Holzer, Thomas L.; Noce, Thomas E.; Bennett, Michael J.

    2011-01-01

    Liquefaction probability curves that predict the probability of surface manifestations of earthquake-induced liquefaction are developed for 14 different types of surficial geologic units. The units consist of alluvial fan, beach ridge, river delta topset and foreset beds, eolian dune, point bar, flood basin, natural river and alluvial fan levees, abandoned river channel, deep-water lake, lagoonal, sandy artificial fill, and valley train deposits. Probability is conditioned on earthquake magnitude and peak ground acceleration. Curves are developed for water table depths of 1.5 and 5.0 m. Probabilities are derived from complementary cumulative frequency distributions of the liquefaction potential index (LPI) that were computed from 927 cone penetration tests. For natural deposits with a water table at 1.5 m and subjected to a M7.5 earthquake with peak ground acceleration (PGA)  =  0.25g, probabilities range from 0.5 for beach ridge, point bar, and deltaic deposits. The curves also were used to assign ranges of liquefaction probabilities to the susceptibility categories proposed previously for different geologic deposits. For the earthquake described here, probabilities for susceptibility categories have ranges of 0–0.08 for low, 0.09–0.30 for moderate, 0.31–0.62 for high, and 0.63–1.00 for very high. Retrospective predictions of liquefaction during historical earthquakes based on the curves compare favorably to observations.

  17. BIOMASS TO BIO-OIL BY LIQUEFACTION

    SciTech Connect

    Wang, Huamin; Wang, Yong

    2013-01-10

    Significant efforts have been devoted to develop processes for the conversion of biomass, an abundant and sustainable source of energy, to liquid fuels and chemicals, in order to replace diminishing fossil fuels and mitigate global warming. Thermochemical and biochemical methods have attracted the most attention. Among the thermochemical processes, pyrolysis and liquefaction are the two major technologies for the direct conversion of biomass to produce a liquid product, often called bio-oil. This chapter focuses on the liquefaction, a medium-temperature and high-pressure thermochemical process for the conversion of biomass to bio-oil. Water has been most commonly used as a solvent and the process is known as hydrothermal liquefaction (HTL). Fundamentals of HTL process, key factors determining HTL behavior, role of catalyst in HTL, properties of produced bio-oil, and the current status of the technology are summarized. The liquefaction of biomass by using organic solvents, a process called solvolysis, is also discussed. A wide range of biomass feedstocks have been tested for liquefaction including wood, crop residues, algae, food processing waste, and animal manure.

  18. DIRECT LIQUEFACTION PROOF-OF-CONCEPT PROGRAM

    SciTech Connect

    A.G. Comolli; T.L.K. Lee; J. Hu; G. Popper; M.D. Elwell; J. Miller; D. Parfitt; P. Zhou

    1999-12-30

    This report presents the results of the bench-scale work, Bench Run PB-09, HTI Run Number 227-106, conducted under the DOE Proof-of-Concept Option Program indirect coal liquefaction at Hydrocarbon Technologies Inc. in Lawrenceville, New Jersey. Bench Run PB-09 was conducted using two types of Chinese coal, Shenhua No.2 and Shenhua No.3, and had several goals. One goal was to study the liquefaction performance of Shenhua No.2 and Shenhua No.3 with respect to coal conversion and distillate production. Another goal of Bench Run PB-09 was to study the effect of different GelCatw formulations and loadings. At the same time, the space velocity and the temperature of the fmt reactor, K-1, were varied to optimize the liquefaction of the two Chinese coals. The promoter-modified HTI GelCat{trademark} catalyst was very effective in the direct liquefaction of coal with nearly 92% maf coal conversion with Shenhua No.3 and 93% maf coal conversion with 9 Shenhua No.2. Distillate yields (CQ-524 C)varied from 52-68% maf for Shenhua No.3 coal to 54-63% maf for Shenhua No.2 coal. The primary conclusion from Bench Run PB-09 is that Shenhua No.3 coal is superior to Shenhua No.2 coal in direct liquefaction due to its greater distillate production, although coal conversion is slightly lower and C{sub 1}-C{sub 3} light gas production is higher for Shenhua No.3. The new promoter modified GelCat{trademark} proved successful in converting the two 9 Chinese coals and, under some conditions, producing good distillate yields for a coal-only bench run. Run PB-09 demonstrated significantly better performance of China Shenhua coal using HTI's coal direct liquefaction technology and GelCat{trademark} catalyst than that obtained at China Coal Research Institute (CCRI, coal conversion 88% and distillate yield 61%).

  19. Synergic effect of methanol and water on pine liquefaction.

    PubMed

    Zhao, Yun-Peng; Zhu, Wei-Wei; Wei, Xian-Yong; Fan, Xing; Cao, Jing-Pei; Dou, You-Quan; Zong, Zhi-Min; Zhao, Wei

    2013-08-01

    Pine liquefaction (PL) and re-liquefaction of its liquefaction residues in sub- and supercritical methanol, water or methanol/water mixed solvents (MWMSs) was investigated. The results show that isometric MWMS has the highest synergic effect on PL. Moreover, the total yield of bio-oil (BO) and conversion from pine and its residue both liquefied in the MWMS were obvious higher than those from PL in methanol (water) and re-liquefaction of its residue in water (methanol), suggesting that the interaction between the two solvents is responsible for synergic effect. This approach facilitates understanding the mechanism for biomass liquefaction in mixed solvents and developing efficient utilization process of biomass.

  20. Decision Tree Approach for Soil Liquefaction Assessment

    PubMed Central

    Gandomi, Amir H.; Fridline, Mark M.; Roke, David A.

    2013-01-01

    In the current study, the performances of some decision tree (DT) techniques are evaluated for postearthquake soil liquefaction assessment. A database containing 620 records of seismic parameters and soil properties is used in this study. Three decision tree techniques are used here in two different ways, considering statistical and engineering points of view, to develop decision rules. The DT results are compared to the logistic regression (LR) model. The results of this study indicate that the DTs not only successfully predict liquefaction but they can also outperform the LR model. The best DT models are interpreted and evaluated based on an engineering point of view. PMID:24489498

  1. Biomass Indirect Liquefaction Strategy Workshop Summary Report

    SciTech Connect

    none,

    2014-07-01

    This report is based on the proceedings of the U.S. Department of Energy Bioenergy Technologies Office Biomass Indirect Liquefaction Strategy Workshop. The workshop, held March 20–21, 2014, in Golden, Colorado, discussed and detailed the research and development needs for biomass indirect liquefaction. Discussions focused on pathways that convert biomass-based syngas (or any carbon monoxide, hydrogen gaseous stream) to liquid intermediates (alcohols or acids) and further synthesize those intermediates to liquid hydrocarbons that are compatible as either a refinery feed or neat fuel.

  2. Liquefaction chemistry and kinetics: Hydrogen utilization studies

    SciTech Connect

    Rothenberger, K.S.; Warzinski, R.P.; Cugini, A.V.

    1995-12-31

    The objectives of this project are to investigate the chemistry and kinetics that occur in the initial stages of coal liquefaction and to determine the effects of hydrogen pressure, catalyst activity, and solvent type on the quantity and quality of the products produced. The project comprises three tasks: (1) preconversion chemistry and kinetics, (2) hydrogen utilization studies, and (3) assessment of kinetic models for liquefaction. The hydrogen utilization studies work will be the main topic of this report. However, the other tasks are briefly described.

  3. Two-stage coal liquefaction process

    DOEpatents

    Skinner, Ronald W.; Tao, John C.; Znaimer, Samuel

    1985-01-01

    An improved SRC-I two-stage coal liquefaction process which improves the product slate is provided. Substantially all of the net yield of 650.degree.-850.degree. F. heavy distillate from the LC-Finer is combined with the SRC process solvent, substantially all of the net 400.degree.-650.degree. F. middle distillate from the SRC section is combined with the hydrocracker solvent in the LC-Finer, and the initial boiling point of the SRC process solvent is increased sufficiently high to produce a net yield of 650.degree.-850.degree. F. heavy distillate of zero for the two-stage liquefaction process.

  4. Decision tree approach for soil liquefaction assessment.

    PubMed

    Gandomi, Amir H; Fridline, Mark M; Roke, David A

    2013-01-01

    In the current study, the performances of some decision tree (DT) techniques are evaluated for postearthquake soil liquefaction assessment. A database containing 620 records of seismic parameters and soil properties is used in this study. Three decision tree techniques are used here in two different ways, considering statistical and engineering points of view, to develop decision rules. The DT results are compared to the logistic regression (LR) model. The results of this study indicate that the DTs not only successfully predict liquefaction but they can also outperform the LR model. The best DT models are interpreted and evaluated based on an engineering point of view.

  5. Low severity coal liquefaction promoted by cyclic olefins

    SciTech Connect

    Curtis, C.W.

    1991-01-01

    The objective of this project is to evaluate the efficacy of low severity coal liquefaction in the presence of highly reactive hydrogen donors, cyclic olefins. The work that was performed this quarter involved performing a literature search in which different aspects of low severity coal liquefaction were examined. In addition, two new mater's graduate students learned the fundamental differences between high severity coal liquefaction and low severity coal liquefaction by examining the literature and reading texts on coal liquefaction. The literature review presented for the first quarter's work is a compilation of the material which we have found to data involving low severity coal liquefaction. Additional review of low severity liquefaction literature is being conducted this quarter and will be reported in the next quarterly report. In addition, a summary of the work involving the reactivity of cyclic olefins in the absence and presence of coal will be presented next quarter.

  6. Low severity coal liquefaction promoted by cyclic olefins

    SciTech Connect

    Curtis, C.W.

    1991-01-01

    The objective of this project is to evaluate the efficacy of low severity coal liquefaction in the presence of highly reactive hydrogen donors, cyclic olefins. The work that was performed this quarter involved performing a literature search in which different aspects of low severity coal liquefaction were examined. In addition, two new master's graduate students learned the fundamental differences between high severity coal liquefaction and low severity coal liquefaction by examining the literature and reading texts on coal liquefaction. The literature review presented for the first quarter's work is a compilation of the material which we have found to date involving low severity coal liquefaction. Additional review of low severity liquefaction literature is being conducted this quarter and will be reported in the next quarterly report. In addition, a summary of the work involving the reactivity of cyclic olefins in the absence and presence of coal will be presented next quarter.

  7. Catalyst for coal liquefaction process

    DOEpatents

    Huibers, Derk T. A.; Kang, Chia-Chen C.

    1984-01-01

    An improved catalyst for a coal liquefaction process; e.g., the H-Coal Process, for converting coal into liquid fuels, and where the conversion is carried out in an ebullated-catalyst-bed reactor wherein the coal contacts catalyst particles and is converted, in addition to liquid fuels, to gas and residual oil which includes preasphaltenes and asphaltenes. The improvement comprises a catalyst selected from the group consisting of the oxides of nickel molybdenum, cobalt molybdenum, cobalt tungsten, and nickel tungsten on a carrier of alumina, silica, or a combination of alumina and silica. The catalyst has a total pore volume of about 0.500 to about 0.900 cc/g and the pore volume comprises micropores, intermediate pores and macropores, the surface of the intermediate pores being sufficiently large to convert the preasphaltenes to asphaltenes and lighter molecules. The conversion of the asphaltenes takes place on the surface of micropores. The macropores are for metal deposition and to prevent catalyst agglomeration. The micropores have diameters between about 50 and about 200 angstroms (.ANG.) and comprise from about 50 to about 80% of the pore volume, whereas the intermediate pores have diameters between about 200 and 2000 angstroms (.ANG.) and comprise from about 10 to about 25% of the pore volume, and the macropores have diameters between about 2000 and about 10,000 angstroms (.ANG.) and comprise from about 10 to about 25% of the pore volume. The catalysts are further improved where they contain promoters. Such promoters include the oxides of vanadium, tungsten, copper, iron and barium, tin chloride, tin fluoride and rare earth metals.

  8. Methods of natural gas liquefaction and natural gas liquefaction plants utilizing multiple and varying gas streams

    SciTech Connect

    Wilding, Bruce M; Turner, Terry D

    2014-12-02

    A method of natural gas liquefaction may include cooling a gaseous NG process stream to form a liquid NG process stream. The method may further include directing the first tail gas stream out of a plant at a first pressure and directing a second tail gas stream out of the plant at a second pressure. An additional method of natural gas liquefaction may include separating CO.sub.2 from a liquid NG process stream and processing the CO.sub.2 to provide a CO.sub.2 product stream. Another method of natural gas liquefaction may include combining a marginal gaseous NG process stream with a secondary substantially pure NG stream to provide an improved gaseous NG process stream. Additionally, a NG liquefaction plant may include a first tail gas outlet, and at least a second tail gas outlet, the at least a second tail gas outlet separate from the first tail gas outlet.

  9. ASPEN modeling of the Tri-State indirect liquefaction process

    SciTech Connect

    Begovich, J.M.; Clinton, J.H.; Johnson, P.J.; Barker, R.E.

    1983-01-01

    The ASPEN process simulator has been used to model an indirect liquefaction flowsheet patterned after that of the Tri-State project. This flowsheet uses Lurgi moving-bed gasification with synthesis gas conversion to methanol followed by further processing to gasoline using the Mobil MTG process. Models developed in this study include the following: Lurgi gasifier, Texaco gasifier, synthesis gas cooling, Rectisol, methanol synthesis, methanol-to-gasoline, CO-shift, methanation, and naphtha hydrotreating. These models have been successfully developed in modular form so that they can be used to simulate a number of different flowsheets or process alternatives. Simulations of the Tri-State flowsheet have been made using two different coal feed rates and two types of feed coal. The overall simulation model was adjusted to match the Tri-State flowsheet values for methanol, LPG, isobutane, and gasoline. As a result of this adjustment, the MTG reactor yield structure necessary to match the flowsheet product rates was determined. The models were exercised at different flow rates and were unaffected by such changes, demonstrating their range of operability. The use of Illinois No. 6 coal, with its lower ash content, resulted in slightly higher production rates for each of the products as compared to use of the Kentucky coal.

  10. Fine particle clay catalysts for coal liquefaction

    SciTech Connect

    Olson, E.S.

    1991-01-01

    The efficient production of environmentally acceptable distillate fuels requires catalysts for hydrogenation and cleavage of the coal macromolecules and removal of oxygen, nitrogen, and sulfur heteroatoms. The goal of the proposed research is to develop new catalysts for the direct liquefaction of coal. This type of catalyst consists of fine clay particles that have been treated with reagents which form pillaring structures between the aluminosilicate layers of the clay. The pillars not only hold the layers apart but also constitute the active catalytic sites for hydrogenation of the coal and the solvent used in the liquefaction. The pillaring catalytic sites are composed of pyrrhotite, which has been previously demonstrated to be active for coal liquefaction. The pyrrhotite sites are generated in situ by sulfiding the corresponding oxyiron species. The size of the catalyst will be less than 40 nm in order to promote intimate contact with the coal material. Since the clays and reagents for pillaring and activating the clays are inexpensive, the catalysts can be discarded after use, rather than regenerated by a costly process. The proposed work will evaluate methods for preparing the fine particle iron-pillared clay dispersions and for activating the particles to generate the catalysts. Characterization studies of the pillared clays and activated catalysts will be performed. The effectiveness of the pillared clay dispersion for hydrogenation and coal liquefaction will be determined in several types of testing.

  11. Fired heater for coal liquefaction process

    DOEpatents

    Ying, David H. S.

    1984-01-01

    A fired heater for a coal liquefaction process is constructed with a heat transfer tube having U-bends at regular intervals along the length thereof to increase the slug frequency of the multi-phase mixture flowing therethrough to thereby improve the heat transfer efficiency.

  12. Coal liquefaction process with enhanced process solvent

    DOEpatents

    Givens, Edwin N.; Kang, Dohee

    1984-01-01

    In an improved coal liquefaction process, including a critical solvent deashing stage, high value product recovery is improved and enhanced process-derived solvent is provided by recycling second separator underflow in the critical solvent deashing stage to the coal slurry mix, for inclusion in the process solvent pool.

  13. Fine particle clay catalysts for coal liquefaction

    SciTech Connect

    Olson, E.S.

    1991-01-01

    The efficient production of environmentally acceptable distillate fuels requires catalysts for hydrogenation and cleavage of the coal macromolecules and removal of oxygen, nitrogen, and sulfur heteroatoms. The goal of the proposed research is to develop new catalysts for the direct liquefaction of coal. This type of catalyst consists of fine clay particles that have been treated with reagents which form pillaring structures between the aluminosilicate layers of the clay. The pillars not only hold the layers apart but also constitute the active catalytic sites for hydrogenation of the coal and solvent used in the liquefaction. The pillaring catalytic sites are composed of pyrrhotite, which has been previously demonstrated to be active for coal liquefaction. The pyrrhotite sites are generated in situ by sulfiding the corresponding oxyiron species. The size of the catalyst will be less than 40 nm in order to promote intimate contact with the coal material. Since the clays and reagents for pillaring and activating the clays are inexpensive, the catalysts can be discarded after use, rather than regenerated by a costly process. The proposed work will evaluate methods for preparing the fine particle iron-pillared clay dispersions and for activating the particles to generate the catalysts. Characterization studies of the pillared clays and activated catalysts will performed. The effectiveness of the pillared clay dispersion for hydrogenation and coal liquefaction will be determined in several types of testing. 5 refs., 1 tab.

  14. Liquefaction of sub-bituminous coal

    DOEpatents

    Schindler, Harvey D.; Chen, James M.

    1986-01-01

    Sub-bituminous coal is directly liquefied in two stages by use of a liquefaction solvent containing insoluble material as well as 850.degree. F.+ material and 850.degree. F.- material derived from the second stage, and controlled temperature and conversion in the second stage. The process is in hydrogen balance.

  15. EXXON donor solvent coal liquefaction process

    NASA Technical Reports Server (NTRS)

    Epperly, W. R.; Swabb, L. E., Jr.; Tauton, J. W.

    1978-01-01

    A solvent coal liquefaction process to produce low-sulfur liquid products from a wide range of coals is described. An integrated program of laboratory and engineering research and development in conjunction with operation of a 250 T/D pilot plant is discussed.

  16. Liquefaction hazard for the region of Evansville, Indiana

    USGS Publications Warehouse

    Haase, Jennifer S.; Choi, Yoon S.; Nowack, Robert L.; Cramer, Chris H.; Boyd, Oliver S.; Bauer, Robert A.

    2011-01-01

    Maps of liquefaction hazard for each scenario earthquake present (1) Mean liquefaction potential index at each site, and (2) Probabilities that liquefaction potential index values exceed 5 (threshold for expression of surface liquefaction) and 12 (threshold for lateral spreading). Values for the liquefaction potential index are high in the River alluvium group, where the soil profiles are predominantly sand, while values in the Lacustrine terrace group are lower, owing to the predominance of clay. Liquefaction potential index values in the Outwash terrace group are less consistent because the soil profiles contain highly variable sequences of silty sand, clayey sand, and sandy clay, justifying the use of the Monte Carlo procedure to capture the consequences of this complexity.

  17. Two-stage coal liquefaction without gas-phase hydrogen

    DOEpatents

    Stephens, H.P.

    1986-06-05

    A process is provided for the production of a hydrogen-donor solvent useful in the liquefaction of coal, wherein the water-gas shift reaction is used to produce hydrogen while simultaneously hydrogenating a donor solvent. A process for the liquefaction of coal using said solvent is also provided. The process enables avoiding the use of a separate water-gas shift reactor as well as high pressure equipment for liquefaction. 3 tabs.

  18. Advanced liquefaction using coal swelling and catalyst dispersion techniques

    SciTech Connect

    Curtis, C.W. ); Gutterman, C. ); Chander, S. )

    1991-01-01

    Research in this project centers upon developing a new approach to the direct liquefaction of coal to produce an all-distillate product slate at a sizable cost reduction over current technology. The approach integrates all aspects of the coal liquefaction process including coal selection, pretreatment, coal swelling with catalyst impregnation, coal liquefaction experimentation, product recovery with characterization, alternate bottoms processing, and a technical assessment including an economic evaluation. Work has centered upon obtaining bulk samples of feedstocks for the project, up-dating the background literature, and preparing and testing a computer program to perform material balance calculations for the continuous flow liquefaction unit.

  19. Whole Algae Hydrothermal Liquefaction Technology Pathway

    SciTech Connect

    Biddy, Mary J.; Davis, Ryan; Jones, Susanne B.; Zhu, Yunhua

    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 hydrocarbon fuels 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 pathway case investigates the feasibility of using whole wet microalgae as a feedstock for conversion via hydrothermal liquefaction. Technical barriers and key research needs have been assessed in order for the hydrothermal liquefaction of microalgae to be competitive with petroleum-derived gasoline, diesel and jet range blendstocks.

  20. Cryogenic hydrogen-induced air liquefaction technologies

    NASA Technical Reports Server (NTRS)

    Escher, William J. D.

    1990-01-01

    Extensively utilizing a special advanced airbreathing propulsion archives database, as well as direct contacts with individuals who were active in the field in previous years, a technical assessment of cryogenic hydrogen-induced air liquefaction, as a prospective onboard aerospace vehicle process, was performed and documented. The resulting assessment report is summarized. Technical findings are presented relating the status of air liquefaction technology, both as a singular technical area, and also that of a cluster of collateral technical areas including: compact lightweight cryogenic heat exchangers; heat exchanger atmospheric constituents fouling alleviation; para/ortho hydrogen shift conversion catalysts; hydrogen turbine expanders, cryogenic air compressors and liquid air pumps; hydrogen recycling using slush hydrogen as heat sink; liquid hydrogen/liquid air rocket-type combustion devices; air collection and enrichment systems (ACES); and technically related engine concepts.

  1. Coal liquefaction process streams characterization and evaluation

    SciTech Connect

    Mitchell, G.; Davis, A. . Energy and Fuels Research Center); Burke, F.P.; Winschel, R.A.; Brandes, S.D. . Energy and Fuels Research Center)

    1991-12-01

    This study demonstrated the use of the gold tube carbonization technique and reflectance microscopy analysis for the examination of process-derived materials from direct coal liquefaction. The carbonization technique, which was applied to coal liquefaction distillation resids, yields information on the amounts of gas plus distillate, pyridine-soluble resid, and pyridine-insoluble material formed when a coal liquid sample is heated to 450{degree}C for one hour at 5000 psi in an inert atmosphere. The pyridine-insolubles then are examined by reflectance microscopy to determine the type, amount, and optical texture of isotropic and anisotropic carbon formed upon carbonization. Further development of these analytical methods as process development tools may be justified on the basis of these results.

  2. Pillared montmorillonite catalysts for coal liquefaction

    SciTech Connect

    Sharma, R.K.; Olson, E.S.

    1994-12-31

    Pillared clays contain large micropores and have considerable potential for catalytic hydrogenation and cleavage of coal macromolecules. Pillared montmorillonite-supported catalysts were prepared by the intercalation of polynuclear hydroxychromium cations and subsequent impregnation of nickel and molybdenum. Infrared and thermogravimetric studies of pyridine-adsorbed catalysts indicated the presence of both Lewis and Bronsted acid sites. Thus, the catalysts have both acidic properties that can aid in hydrocracking and cleavage of carbon-heteroatom bonds as well as hydrogen-activating bimetallic sites. These catalysts were applied to the hydrodesulfurization and liquefaction of coal-derived intermediates. The reactions of model organosulfur compounds and coal liquids were carried out at 300{degrees}-400{degrees}C for 3 hours in the presence of 1000 psi of molecular hydrogen. Reaction products were analyzed by GC/FT-IR/MS/AED. The catalysts have been found to be very effective in removing sulfur from model compounds as well as liquefaction products.

  3. Mild coal pretreatment to improve liquefaction reactivity

    SciTech Connect

    Miller, R.L.

    1991-01-01

    This report describes work completed during the fourth quarter of a three year project to study the effects of mild chemical pretreatment on coal dissolution reactivity during low severity liquefaction or coal/oil coprocessing. The overall objective of this research is to elucidate changes in the chemical and physical structure of coal by pretreating with methanol or other simple organic solvent and a trace amount of hydrochloric acid and measure the influence of these changes on coal dissolution reactivity. This work is part of a larger effort to develop a new coal liquefaction or coal/oil coprocessing scheme consisting of three main process steps: (1) mile pretreatment of the feed coal to enhance dissolution reactivity and dry the coal, (2) low severity thermal dissolution of the pretreated coal to obtain a very reactive coal-derived residual material amenable to upgrading, and (3) catalytic upgrading of the residual products to distillate liquids.

  4. Direct liquefaction of low-rank coals

    SciTech Connect

    Rindt, J.R.; Hetland, M.D.; Knudson, C.L.; Willson, W.G.

    1988-04-01

    Co-processing of low-rank coals (LRCs) with petroleum resids under mild conditions may produce a product that extends petroleum refinery feeds with a partially coal-derived material. These co-processing products may also provide a lower-cost way to introduce coal-derived materials into the commercial market. In this staged process, the petroleum resid acts as a solvent, aiding in the solubilization of the coal during the first stage, and both the dissolved coal and the resid are upgraded during a second-stage catalytic hydrogenation. Another method of upgrading coal in a liquefaction process is the ChemCoal Process. The process uses chemical methods to transform coal into clean solid and liquid products. It features low-severity conversion of coal in a phenolic solvent, using an alkali promotor and carbon monoxide as the reductant. Oil agglomeration has been used to reduce the ash and mineral matter in bituminous coals to obtain a product with increased heating value, reduced moisture, and lower sulfur content. This method can be used to produce a clean coal feedstock for liquefaction. During agglomeration, an oil is used to preferentially wet the organic phases of the coal, and water is used to wet the minerals, resulting in a separation of ash and water from the coal. The primary objective of this project is to expand the scientific and engineering data base of LRC liquefaction by investigating direct liquefaction processes that will produce the most competitive feedstocks or liquid fuels. The work effort which was proposed for the second year of this cooperative agreement dealt primarily with co-processing and the ChemCoal Process.

  5. Fired heater for coal liquefaction process

    DOEpatents

    Ying, David H. S.; McDermott, Wayne T.; Givens, Edwin N.

    1985-01-01

    A fired heater for a coal liquefaction process is operated under conditions to maximize the slurry slug frequency and thereby improve the heat transfer efficiency. The operating conditions controlled are (1) the pipe diameter and pipe arrangement, (2) the minimum coal/solvent slurry velocity, (3) the maximum gas superficial velocity, and (4) the range of the volumetric flow velocity ratio of gas to coal/solvent slurry.

  6. EXPLORATORY RESEARCH ON NOVEL COAL LIQUEFACTION CONCEPT

    SciTech Connect

    Brandes, S.D.; Winschel, R.A.

    1998-11-30

    The report presents a summary the work performed under DOE Contract No. DE-AC22-95PC95050. Investigations performed under Task 4--Integrated Flow Sheet Testing are detailed. In this program, a novel direct coal liquefaction technology was investigated by CONSOL Inc. with the University of Kentucky Center for Applied Energy Research and LDP Associates. The process concept explored consists of a first-stage coal dissolution step in which the coal is solubilized by hydride ion donation. In the second stage, the products are catalytically upgraded to refinery feedstocks. Integrated first-stage and solids-separation steps were used to prepare feedstocks for second-stage catalytic upgrading. An engineering and economic evaluation was conducted concurrently with experimental work throughout the program. Approaches to reduce costs for a conceptual commercial plant were recommended at the conclusion of Task 3. These approaches were investigated in Task 4. The economic analysis of the process as it was defined at the conclusion of Task 4, indicates that the production of refined product (gasoline) via this novel direct liquefaction technology is higher than the cost associated with conventional two-stage liquefaction technologies.

  7. Hydrogen donor solvent coal liquefaction process

    DOEpatents

    Plumlee, Karl W.

    1978-01-01

    An indigenous hydrocarbon product stream boiling within a range of from about C.sub.1 -700.degree. F., preferably C.sub.1 -400.degree. F., is treated to produce an upgraded hydrocarbon fuel component and a component which can be recycled, with a suitable donor solvent, to a coal liquefaction zone to catalyze the reaction. In accordance therewith, a liquid hydrocarbon fraction with a high end boiling point range up to about 700.degree. F., preferably up to about 400.degree. F., is separated from a coal liquefaction zone effluent, the separated fraction is contacted with an alkaline medium to provide a hydrocarbon phase and an aqueous extract phase, the aqueous phase is neutralized, and contacted with a peroxygen compound to convert indigenous components of the aqueous phase of said hydrocarbon fraction into catalytic components, such that the aqueous stream is suitable for recycle to the coal liquefaction zone. Naturally occurring phenols and alkyl substituted phenols, found in the aqueous phase, are converted, by the addition of hydroxyl constituents to phenols, to dihydroxy benzenes which, as disclosed in copending Application Ser. Nos. 686,813 now U.S. Pat. No. 4,049,536; 686,814 now U.S. Pat. No. 4,049,537; 686,827 now U.S. Pat. No. 4,051,012 and 686,828, K. W. Plumlee et al, filed May 17, 1976, are suitable hydrogen transfer catalysts.

  8. Coal liquefaction process with increased naphtha yields

    DOEpatents

    Ryan, Daniel F.

    1986-01-01

    An improved process for liquefying solid carbonaceous materials wherein the solid carbonaceous material is slurried with a suitable solvent and then subjected to liquefaction at elevated temperature and pressure to produce a normally gaseous product, a normally liquid product and a normally solid product. The normally liquid product is further separated into a naphtha boiling range product, a solvent boiling range product and a vacuum gas-oil boiling range product. At least a portion of the solvent boiling-range product and the vacuum gas-oil boiling range product are then combined and passed to a hydrotreater where the mixture is hydrotreated at relatively severe hydrotreating conditions and the liquid product from the hydrotreater then passed to a catalytic cracker. In the catalytic cracker, the hydrotreater effluent is converted partially to a naphtha boiling range product and to a solvent boiling range product. The naphtha boiling range product is added to the naphtha boiling range product from coal liquefaction to thereby significantly increase the production of naphtha boiling range materials. At least a portion of the solvent boiling range product, on the other hand, is separately hydrogenated and used as solvent for the liquefaction. Use of this material as at least a portion of the solvent significantly reduces the amount of saturated materials in said solvent.

  9. Coal liquefaction process streams characterization and evaluation

    SciTech Connect

    Campbell, J.A.; Linehan, J.C.; Robins, W.H. )

    1992-07-01

    Under contract from the DOE , and in association with CONSOL Inc., Battelle, Pacific Northwest Laboratory (PNL) evaluated four principal and several complementary techniques for the analysis of non-distillable direct coal liquefaction materials in support of process development. Field desorption mass spectrometry (FDMS) and nuclear magnetic resonance (NMR) spectroscopic methods were examined for potential usefulness as techniques to elucidate the chemical structure of residual (nondistillable) direct coal liquefaction derived materials. Supercritical fluid extraction (SFE) and supercritical fluid chromatography/mass spectrometry (SFC/MS) were evaluated for effectiveness in compound-class separation and identification of residual materials. Liquid chromatography (including microcolumn) separation techniques, gas chromatography/mass spectrometry (GC/MS), mass spectrometry/mass spectrometry (MS/MS), and GC/Fourier transform infrared (FTIR) spectroscopy methods were applied to supercritical fluid extracts. The full report authored by the PNL researchers is presented here. The following assessment briefly highlights the major findings of the project, and evaluates the potential of the methods for application to coal liquefaction materials. These results will be incorporated by CONSOL into a general overview of the application of novel analytical techniques to coal-derived materials at the conclusion of CONSOL's contract.

  10. Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

    NASA Technical Reports Server (NTRS)

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

    2010-01-01

    We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V

  11. A Characterization and Evaluation of Coal Liquefaction Process Streams

    SciTech Connect

    G. A. Robbins; R. A. Winschel; S. D. Brandes

    1998-06-09

    CONSOL characterized 38 process strea m samples from HTI Run PB- 04, in which Black Thunder Mine Coal, Hondo vacuum resid, autom obile shredder residue (ASR), and virgin plastics were used as liquefaction feedstocks with dispersed catalyst. A paper on kinetic modeling of resid reactivity was presented at the DOE Coal Lique -faction and Solid Fuels Contractors Review Conference, September 3- 4, 1997, i n Pittsburgh, PA. The paper, "The Reactivity of Direct Coal Liquefaction Resids", i s appended (Appendix 1). Three papers on characterization of samples from coal/ resid/ waste p lastics co- liquefaction were presented or submitted for presen tation at conferences. Because of their similarity, only one of the papers is appended to this report. The paper, "Characterization o f Process Samples From Co- Liquefaction of Coal and Waste Polymers", (Appendix 2) was presented at the DOE Coal Liquefaction and Solid Fuels C ontractors Review Conference, September 3- 4, 1997, in Pittsburgh, PA. The paper, "Characterization of Process Stream Samples From Bench- Scale Co -Liquefaction Runs That Utilized Waste Polymers as Feedstocks" was presented at the 214th National Meeting of the Ameri can Chemical Society, September 7- 11, 1997, in Las Vegas, NV. The paper, "Characterization of Process Oils from Coal/ Waste Co- Liquefaction" wa s submitted for presentation at the 14th Japan/ U. S. Joint Technical Meeting on Coa l Liquefaction and Materials for Coal Liquefaction on October 28, 1997, in Tokyo, Japan. A joint Burns and Roe Services Corp. and CONSOL pap er on crude oil assays of product oils from HTI Run PB- 03 was presented at the DOE Coal Liquefaction and Solid Fuel s Contractors Review Conference, September 3- 4, 1997, in Pittsburgh, PA. The paper , "Characterization of Liquid Products from All- Slurry Mode Liquefaction", is appende d (Appendix 3).

  12. Survey study of the efficiency and economics of hydrogen liquefaction

    NASA Technical Reports Server (NTRS)

    1975-01-01

    The production of liquid hydrogen, with coal as the starting material, is reported. The minimum practicable energy and cost for liquefaction of gaseous hydrogen in the 1985-2000 time period is presented to investigate the possible benefits of the integration of coal gasification processes with the liquefaction process.

  13. Co-liquefaction of micro- and macroalgae in subcritical water.

    PubMed

    Jin, Binbin; Duan, Peigao; Xu, Yuping; Wang, Feng; Fan, Yunchang

    2013-12-01

    Co-liquefaction of microalgae (Spirulina platensis, SP) and macroalgae (Entermorpha prolifera, EP) was studied in subcritical water by using a stainless-steel batch reactor at different temperature (250 to 370°C), time (5 to 120 min), SP/EP mass ratio (0 to 100%), and water/algae mass ratio (1:1 to 6:1). The results suggested that a positive synergetic effect existed during the co-liquefaction of SP and EP, and this synergetic effect was dependent on reaction conditions. Co-liquefaction alleviated the severe reaction conditions compared to the separate liquefaction of SP and EP and also promoted the in situ deoxygenation of the bio-oil. The higher-heating-value of bio-oil produced from the co-liquefaction of SP and EP (wSP:wEP=1) is 35.3 MJ/kg. The energy recovery from the co-liquefaction is larger than the average value from the separate liquefaction of SP and EP. Co-liquefaction did not affect the molecular composition but affect the relative amount of each component in the bio-oil.

  14. Liquefaction hazard analysis for infrastructure development in gulf of Jakarta

    NASA Astrophysics Data System (ADS)

    Dinata, Indra A.; Darlan, Yudi; Sadisun, Imam A.; Pindratno, Haris; Saryanto, Agus

    2016-05-01

    Gulf of Jakarta is an area of active sedimentation. There exist a wide sediment deposition area on the north coast of Jakarta. Generally, these sediments have not been consolidated, so that the conditions in these area is an important factor to determining liquefaction in these area. Liquefaction may occur because of earthquake that cause loss of strength and stiffness in soils. Analysis of liquefaction potential based from SPT data taken at gulf of Jakarta, include susceptibility rate and the factors that triggering. Liquefaction analysis methods compared with each other to get the factor of safety against liquefaction according to the characteristics of the soil. Liquefaction analysis at surface using susceptibility rating factor (SRF). SRF method controled by factors: history, geology, composition, and groundwater. Each factors have parameters that determine the value of SRF.From the analysis, Gulf of Jakarta has susceptibility rating from liquefaction with SRF value 12 - 35. The value shows that Gulf of Jakarta dominated by area that have susceptibility rating from medium to high. High susceptibility rating from liquefaction concentrated at coast area.

  15. Prevention of deleterious deposits in a coal liquefaction system

    DOEpatents

    Carr, Norman L.; Prudich, Michael E.; King, Jr., William E.; Moon, William G.

    1984-07-03

    A process for preventing the formation of deleterious coke deposits on the walls of coal liquefaction reactor vessels involves passing hydrogen and a feed slurry comprising feed coal and recycle liquid solvent to a coal liquefaction reaction zone while imparting a critical mixing energy of at least 3500 ergs per cubic centimeter of reaction zone volume per second to the reacting slurry.

  16. Liquefaction at Oceano, California, during the 2003 San Simeon earthquake

    USGS Publications Warehouse

    Holzer, T.L.; Noce, T.E.; Bennett, M.J.; Tinsley, J. C.; Rosenberg, L.I.

    2005-01-01

    The 2003 M 6.5 San Simeon, California, earthquake caused liquefaction-induced lateral spreading at Oceano at an unexpectedly large distance from the seismogenic rupture. We conclude that the liquefaction was caused by ground motion that was enhanced by both rupture directivity in the mainshock and local site amplification by unconsolidated fine-grained deposits. Liquefaction occurred in sandy artificial fill and undisturbed eolian sand and fluvial deposits. The largest and most damaging lateral spread was caused by liquefaction of artificial fill; the head of this lateral spread coincided with the boundary between the artificial fill and undisturbed eolian sand deposits. Values of the liquefaction potential index, in general, were greater than 5 at liquefaction sites, the threshold value that has been proposed for liquefaction hazard mapping. Although the mainshock ground motion at Oceano was not recorded, peak ground acceleration was estimated to range from 0.25 and 0.28g on the basis of the liquefaction potential index and aftershock recordings. The estimates fall within the range of peak ground acceleration values associated with the modified Mercalli intensity = VII reported at the U.S. Geological Survey (USGS) "Did You Feel It?" web site.

  17. Evaluation of mycobacterial virulence using rabbit skin liquefaction model.

    PubMed

    Zhang, Guoping; Zhu, Bingdong; Shi, Wanliang; Wang, Mingzhu; Da, Zejiao; Zhang, Ying

    2010-01-01

    Liquefaction is an important pathological process that can subsequently lead to cavitation where large numbers of bacilli can be coughed up which in turn causes spread of tuberculosis in humans. Current animal models to study the liquefaction process and to evaluate virulence of mycobacteria are tedious. In this study, we evaluated a rabbit skin model as a rapid model for liquefaction and virulence assessment using M. bovis BCG, M. tuberculosis avirulent strain H37Ra, M. smegmatis, and the H37Ra strains complemented with selected genes from virulent M. tuberculosis strain H37Rv. We found that with prime and/or boosting immunization, all of these live bacteria at enough high number could induce liquefaction, and the boosting induced stronger liquefaction and more severe lesions in shorter time compared with the prime injection. The skin lesions caused by high dose live BCG (5×10 (6) ) were the most severe followed by live M. tuberculosis H37Ra with M. smegmatis being the least pathogenic. It is of interest to note that none of the above heat-killed mycobacteria induced liquefaction. When H37Ra was complemented with certain wild type genes of H37Rv, some of the complemented H37Ra strains produced more severe skin lesions than H37Ra. These results suggest that the rabbit skin liquefaction model can be a more visual, convenient, rapid and useful model to evaluate virulence of different mycobacteria and to study the mechanisms of liquefaction.

  18. 46 CFR 148.450 - Cargoes subject to liquefaction.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... in this section— (1) Cargo subject to liquefaction means a material that is subject to moisture migration and subsequent liquefaction if shipped with moisture content in excess of the transportable moisture limit. (2) Moisture migration is the movement of moisture by settling and consolidation of...

  19. 46 CFR 148.450 - Cargoes subject to liquefaction.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... in this section— (1) Cargo subject to liquefaction means a material that is subject to moisture migration and subsequent liquefaction if shipped with moisture content in excess of the transportable moisture limit. (2) Moisture migration is the movement of moisture by settling and consolidation of...

  20. 46 CFR 148.450 - Cargoes subject to liquefaction.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... in this section— (1) Cargo subject to liquefaction means a material that is subject to moisture migration and subsequent liquefaction if shipped with moisture content in excess of the transportable moisture limit. (2) Moisture migration is the movement of moisture by settling and consolidation of...