Science.gov

Sample records for liquefaction fischer-tropsch synthesis

  1. Improved Fischer-Tropsch Synthesis catalysts for indirect coal liquefaction

    SciTech Connect

    Tong, G.T.; Wilson, R.B.; McCarty, J.G.

    1987-01-01

    The monoruthenium cluster catalyst with a molecular sieve support and the tetraruthenium cluster catalyst with a sodium-Y zeolite support have been examined for Fischer-Tropsch Synthesis (FTS) performance at high pressure (6.9 MPa) in a slurry reactor and compared with conventional ruthenium with an alumina support and clean fused iron catalysts. Of the four catalysts tested, only the conventional ruthenium catalyst exhibited a chain growth factor of 0.88 and a methane selectivity of 6.6%, which are typical of slurry reactor results reported for iron catalysts under similar conditions. The other three catalysts tested showed low chain growth factors (ranging from 0.44 to 0.57) and high methane selectivity (ranging from 20 to 32%). A cobalt catalyst with approximately 50% sulfur coverage was prepared and tested for FTS activity and selectivity at ambient pressure and compared with the FTS performance of the clean and fully sulfided cobalt catalysts. The introduction of sulfur caused a decrease in methane selectivity and an increase in olefin selectivity with only a moderate decline in activity. 1 ref., 2 tabs.

  2. Design of generic coal conversion facilities: Indirect coal liquefaction, Fischer-Tropsch synthesis

    SciTech Connect

    Not Available

    1991-10-01

    A comprehensive review of Fischer-Tropsch (F-T) technology, including fixed, fluidized, and bubble column reactors, was undertaken in order to develop an information base before initiating the design of the Fischer-Tropsch indirect liquefaction PDU as a part of the Generic Coal Conversion Facilities to be built at the Pittsburgh Energy Technology Center (PETC). The pilot plant will include a fixed bed and slurry bubble column reactor for the F-T mode of operation. The review encompasses current status of both these technologies, their key variables, catalyst development, future directions, and potential improvement areas. However, more emphasis has been placed on the slurry bubble column reactor since this route is likely to be the preferred technology for commercialization, offering process advantages and, therefore, better economics than fixed and fluidized bed approaches.

  3. Tailored fischer-tropsch synthesis product distribution

    DOEpatents

    Wang, Yong; Cao, Chunshe; Li, Xiaohong Shari; Elliott, Douglas C.

    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.

  4. 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.

  5. Slurry-phase Fischer-Tropsch synthesis

    SciTech Connect

    Zarochak, M.F.; McDonald, M.A.

    1986-01-01

    Fischer-Tropsch synthesis in the slurry phase has attracted attention in recent years due to its numerous advantages. Among these advantages are the ability of the liquid phase to handle the large heats of reaction and thereby control reaction temperature, the ability to handle low H/sub 2//CO ratio synthesis gas without needing a preliminary water-gas shift step, and the relatively low capital and operating costs for slurry systems. Slurry-phase work at PETC has focused on understanding effects of catalyst preparation and pretreatment, of reaction conditions (T, P, H/sub 2//CO), and of operating conditions (space velocity, methods of wax removal) on catalyst synthesis behavior (activity, selectivity, and maintenance of activity and selectivity). Better understanding of the effects of these factors on F-T synthesis leads to improvements in process technology. This work focuses on the effects of catalyst pretreatment on synthesis behavior. Developing an effective F-T catalyst pretreatment procedure is a problem limited almost exclusively to iron catalysts. This paper reports some recent results on the effects of pretreatment. Synthesis runs were made using one of two different pretreatments given a potassium-promoted precipitated iron catalyst. Besides these reaction experiments, catalyst samples were periodically withdrawn from the stirred autoclave for characterization by means of Moessbauer spectroscopy.

  6. Fischer-Tropsch synthesis in supercritical reaction media

    SciTech Connect

    Subramaniam, B.; Bochniak, D.; Snavely, K.

    1993-01-01

    Our goals for this quarter were to complete construction of the reactor and analytical units for carrying out Fischer-Tropsch (F-T) synthesis in liquid (n-hexadecane) and in supercritical n-hexane phases. Progress during this quarter was slower than expected.

  7. 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.

  8. Fischer-Tropsch synthesis of hydrocarbons

    SciTech Connect

    Lampert, A.; Erickson, J.; Smiley, B.; Vaughan, C.

    1983-09-01

    The performance of an iron-copper Fischer-Tropsch catalyst was studied in a slurry CSTR at 227/sup 0/C and 790 kPa (100 psig). Catalyst performance was similar to other iron-based catalysts studied previously with respect to conversion of CO, conversion of CO + H/sub 2/, and to the product distribution. CO conversion increased with decreasing space velocity, ranging from approximately 60% at 1570 h/sup -1/ to over 90% at 488 h/sup -1/. The H/sub 2/ to CO usage ratio was approximately 0.7, indicating that the catalyst is a good water-gas shift catalyst as well as a Fischer-Tropsch catalyst. Reaction products could be described by a Flory distribution with a chain growth probability (..cap alpha..) of 0.67, which is in the gasoline range. In some runs, methanol was added continuously to the reactor feed, but instead of being incorporated into the reaction, the methanol oxidized and deactivated the catalyst. 31 references, 12 figures, 10 tables.

  9. Fischer-Tropsch synthesis with coal derived syngas

    SciTech Connect

    Raje, A.; O`Brien, R.J.; Davis, B.H.

    1998-12-31

    The effect of potassium on catalyst activity, kinetic parameters and selectivity has been investigated for a precipitated iron catalyst with low H{sub 2}/CO ratio synthesis gas. A wide range of synthesis gas conversions have been obtained by varying space velocities over catalysts with various potassium loadings. Differing trends in catalyst activity with potassium loading were observed depending on the space velocity or synthesis gas conversion. As potassium loading increased, the catalyst activity either decreased (low conversions), passed through a maximum (intermediate conversions) or increased (high conversions). This is shown to be a result of the increasing dependency of the Fischer-Tropsch synthesis on the hydrogen formed by the water-gas shift reaction with increasing synthesis gas conversions. Both the rate constant and the adsorption parameter in a common two-parameter Fischer-Tropsch rate expression decreased with potassium loading; therefore, observed maxima in Fischer-Tropsch rate with potassium loading can be due to the opposing influences of these parameters.

  10. 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.

  11. 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.

  12. Synthesis of octane enhancers during slurry-phase Fischer Tropsch

    SciTech Connect

    Marcelin, G.

    1991-02-28

    The objective of this project is to investigate three possible routes to the formation of ethers, in particular methyl tert-butyl ether (MTBE), during slurry phase Fischer-Tropsch (FT) reaction. The three routes to be investigated are: addition of isobutylene during the formation of methanol and/or higher alcohols directly from CO and H{sub 2} during slurry-phase Fischer-Tropsch; addition of isobutylene to FT liquid products including alcohols in a slurry-phase reactor containing an MTBE or other acid catalyst; and addition of methanol to slurry phase FT synthesis making iso-olefins. Work conducted during the first quarter has concentrated in the design of a laboratory-scale bubble column slurry reactor (BCSR) capable of operating at suitable temperatures and pressures for each of the three routes defined above. For design purposes the reactor has been configured as a one-inch diameter bubble column reactor for conversion of synthesis gas and operating with a wax paraffin (C{sub 30}{sup +}) liquid medium. This design has been finalized, thereby reaching milestone M1. The paper discusses the important design parameters (hydrodynamics, mass transfer, kinetics, and heat transfer) as well as the relationship of lab scale to industrial scale BCSR, parameter estimations, and the design of the bench-scale BCSR. 23 refs., 3 figs., 3 tabs.

  13. Catalyst structure and method of Fischer-Tropsch synthesis

    DOEpatents

    Wang, Yong; Vanderwiel, David P.; Tonkovich, Anna Lee Y.; Gao, Yufei; Baker, Eddie G.

    2004-06-15

    The present invention includes Fischer-Tropsch catalysts, reactions using Fischer-Tropsch catalysts, methods of making Fischer-Tropsch catalysts, processes of hydrogenating carbon monoxide, and fuels made using these processes. The invention provides the ability to hydrogenate carbon monoxide with low contact times, good conversion rates and low methane selectivities. In a preferred method, the catalyst is made using a metal foam support.

  14. Catalyst structure and method of fischer-tropsch synthesis

    DOEpatents

    Wang, Yong [Richland, WA; Vanderwiel, David P [Richland, WA; Tonkovich, Anna Lee Y [Pasco, WA; Gao, Yufei [Kennewick, WA; Baker, Eddie G [Pasco, WA

    2002-12-10

    The present invention includes Fischer-Tropsch catalysts, reactions using Fischer-Tropsch catalysts, methods of making Fischer-Tropsch catalysts, processes of hydrogenating carbon monoxide, and fuels made using these processes. The invention provides the ability to hydrogenate carbon monoxide with low contact times, good conversion rates and low methane selectivities. In a preferred method, the catalyst is made using a metal foam support.

  15. Fischer-Tropsch synthesis for clean transportation fuels

    SciTech Connect

    Xu, L.; Bao, S.; O`Brien, R.J.; Raje, A.; Davis, B.H.

    1997-12-31

    The products from the Fischer-Tropsch synthesis and the rates of conversion of the reactants (H{sub 2} and CO) have been determined for a range of flow rates. Based upon conversion rates, an iron catalyst should be utilized at lower CO conversion levels. The fraction of CO converted to hydrocarbons decreases with increasing CO conversion. Thus, it is suggested that a F-T process employing recycle or multiple reactors is more appropriate for an iron catalyst than operating a single reactor at high (> 95%) CO conversion levels. The data indicate that an iron catalyst is preferred over a cobalt catalyst for some process conditions (e.g., high space velocity, high total pressure).

  16. 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.

  17. Process simulation model for indirect coal liquefaction using slurry reactor Fischer-Tropsch technology

    SciTech Connect

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

    1994-12-31

    A detailed baseline design for indirect coal liquefaction using advanced Fischer-Tropsch (F-T) technology has been developed for Illinois No. 6 coal. This design forms the basis for an ASPEN process flowsheet simulation (PFS) model which can simulate the entire liquefaction plant and predict the effects of key process variables on the overall plant performance. A linear programming (I-P) model based on a typical PADD II refinery was developed for product valuation and a discounted cash flow (DCF) spreadsheet model was developed for economic analysis. These closely coupled models constitute a research tool which the DOE can use to plan, guide and evaluate its ongoing and future research programs for the manufacture of synthetic liquid fuels by indirect coal liquefaction. This paper covers the use of the ASPEN process simulation model and DCF spreadsheet model to look at the sensitivity of the economics to certain global process variables such as coal feed rate, synthesis gas conversion per pass and wax yield, together with certain specific reactor operating variables such as temperature, superficial velocity, slurry concentration, catalyst activity and catalyst life. Results are reported in terms of investment cost, yields and operating costs, which are then combined to determine a crude oil equivalent (COE) price. The COE is a hypothetical breakeven crude oil price at which a typical PADD II refinery could buy either crude oil or the coal liquefaction products. It is a present day value and is defined assuming constant deltas between crude oil and its products (i.e. constant refinery processing costs and margins).

  18. 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.

  19. Fischer-Tropsch indirect coal liquefaction design/economics-mild hydrocracking vs. fluid catalytic cracking

    SciTech Connect

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

    1996-12-31

    In order to evaluate the economics of Fischer-Tropsch (F-T) indirect coal liquefaction, conceptual plant designs and detailed cost estimates were developed for plants producing environmentally acceptable, high-quality, liquid transportation fuels meeting the Clean Air Act requirements. The designs incorporate the latest developments in coal gasification technology and advanced (F-T) slurry reactor design. In addition, an ASPEN Plus process simulation model was developed to predict plant material and energy balances, utility requirements, operating and capital costs at varying design conditions. This paper compares mild hydrocracking and fluid catalytic cracking as alternative methods for upgrading the F-T wax.

  20. Synthesis gas solubility in Fischer-Tropsch slurry: Final report

    SciTech Connect

    Chao, K.C.; Lin, H.M.

    1988-01-01

    The objective is to investigate the phase equilibrium behavior of synthesis gases and products in a Fischer-Tropsch slurry reactor. A semi-flow apparatus has been designed and constructed for this purpose. Measurements have been made for hydrogen, cabon monoxide, methane, ethane, ethylene, and carbon dioxide in a heavy n-paraffin at temperatures from 100 to 300)degree)C and pressures 10 to 50 atm. Three n-paraffin waxes: n-eicosane (n-C/sub 20/), n-octacosane )n-C/sub 28/), and n-hexatriacontane (n-C/sub 36/), were studied to model the industrial wax. Solubility of synthesis gas mixtures of H/sub 2/ and CO in n-C/sub 28/ was also determined at two temperatures (200 and 300)degree)C) for each of three gas compositions (40.01, 50.01, and 66.64 mol%) of hydrogen). Measurements were extended to investigate the gas solubility in two industrial Fischer-Tropsch waxes: Mobilwax and SASOL wax. Observed solubility increases in the order: H/sub 2/, CO, CH/sub 4/, CO/sub 2/, C/sub 2/H/sub 4/, C/sub 2/H/sub 6/, at a given temperature pressure, and in the same solvent. Solubility increases with increasing pressure for all the gases. Lighter gases H/sub 2/ and CO show increased solubility with increasing temperature, while the heavier gases CO/sub 2/, ethane, and ethylene show decreased solubility with increasing temperature. The solubility of methane, the intermediate gas, changes little with temperature, and shows a shallow minimum at about 200)degrees)C or somewhat above. Henry's constant and partial molal volume of the gas solute at infinite dilution are determinedfrom the gas solubility data. A correlation is developed from the experimental data in the form on an equation of state. A computer program has been prepared to implement the correlation. 19 refs., 66 figs., 39 tabs.

  1. Process for upgrading wax from Fischer-Tropsch synthesis

    SciTech Connect

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

    1987-08-04

    A processor is described for converting synthesis gas to liquid hydrocarbons comprising the steps of: (a) charging the synthesis gas to a Fischer-Tropsch synthesis conversion zone containing a catalyst providing CO reducing characteristics to produce a waxy hydrocarbon liquid; (b) separating hydrocarbon wax from the waxy liquid; (c) catalytically cracking the wax in a fluidized bed of acid crystalline zeolite at cracking temperature under process conditions requiring a supply of heat to effect cracking, producing olefinic liquid hydrocarbon crackate in the gasoline and distillate boiling range along with olefinic light gas; (d) recovering distillate range hydrocarbons from the liquid crackate; (e) further converting the olefinic gasoline range hydrocarbon crackate and olefinic light gas under oligomerization conditions in contact with a shape selective medium pore acid oligomerization catalyst to upgrade at least a portion of the olefinic crackate and olefinic light gas to distillate range hydrocarbon product and producing by-product light fuel gas; (f) separating the light fuel gas from step (e) and passing the light fuel gas to cracking step (c) to supply heat.

  2. 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.

  3. 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.

  4. 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.

  5. Ultrafine particles of iron in Fischer-Tropsch synthesis

    SciTech Connect

    Mahajan, D.; Pandya, K.

    1994-12-31

    Though direct combustion of natural gas is the most efficient use of this abundant, inexpensive, and cleaner fossil fuel, its potential to replace existing less efficient feedstocks for downstream processes is enormous. Direct conversion of methane to useful products under mild conditions is an ongoing area of research, and a few reported successes include higher hydrocarbons (C{sub 2}-C{sub 6}) synthesis on Pt at 250{degrees}C, Hg-catalyzed synthesis of methanol at 180{degrees}C, and acetic acid synthesis catalyzed by aqueous RhCl{sub 3} at 100{degrees}C. Since these approaches are in early stages of development, improvements in other known routes are of interest. Fischer-Tropsch (F-T) synthesis is an indirect route to catalytic production of liquid fuels from synthesis gas derived from carbonaceous sources. The process is still uneconomical for widespread use due to low space-time-yield (STY), low product selectivity, and catalyst intolerance to sulfur. To address these aspects, a few reports describe the use of ultrafine particle (UFP) catalysts in slurry-phase F-T synthesis, We recently reported that a commercially available unsupported UFP FeZO{sub 3} material (NANOCAT{trademark}) (Mean particle diameter (MPD) = 3 nm; surface area (SA) - 255 m{sup 2}/g) slurried in a C{sub 30} hydrocarbon solvent, after reduction at 280{degrees}C under CO, catalyzed conversion of balanced synthesis gas (H{sub 2}/CO = 2/1) at {>=} 220{degrees}C and {<=} 3 MPa. Described below are additional runs carried out to further scrutinize the Fe UFP system.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Carbon Isotope Effects in the Fischer-Tropsch Synthesis

    NASA Astrophysics Data System (ADS)

    Taran, Y.; Kliger, G.; Sevastyanov, V.

    2006-05-01

    Carbon isotopic composition was measured in products of the Fischer-Tropsch synthesis in flow reactor on the modified by clays Fe-catalyst at 280-300C and 30 atm. The initial gas mixture (synthesis-gas, SG) consisted of 50 vol% of N2, 20% of CO and 30% of H2. Using the GS-MS technique we analyzed 13C/12C in CO, CO2, CH4, higher hydrocarbons until C4 and the oil fraction in the reaction products. Two catalysts with different modification were used: with high and low yield of olefins. Three of 70-hours runs for each catalyst were realized. Five gas samples were taken during each run: 10, 20, 30, 50 and 70 hours and one cumulative oil sample after each run. The 13C/12C distribution vs carbon number is time-dependent for the olefin-rich products. For the olefin-poor runs the stationary state is characterized by depletion in 13C of heavier than CH4 hydrocarbons, thus, showing the "synthetic" pattern, like in DesMarais et al. (1982) experiments or in Murchison meteorite. However, the olefin-rich runs demonstrate these patterns only in the non-stationary, initial (10 h, 20 h) time range. The steady-state (50-70h) distribution (high and stable conversion of CO) for olefin-rich runs shows almost no fractionation between CH4 and higher hydrocarbons. The concentration distribution of light hydrocarbons in our experiments was similar to that obtained by Hu et al. (1998), but with much higher conversion of CO (>95%).

  12. Effect of product upgrading on Fischer-Tropsch indirect coal liquefaction economics

    SciTech Connect

    Choi, G.N.; Kramer, S.J.; Tam, S.S.; Fox, J.M. III

    1995-12-31

    Conceptual plant designs with cost estimates for indirect coal liquefaction technology to produce environmentally acceptable transportation liquid fuels meeting the Clear Air Act requirements were developed for the US Department of Energy (DOE). The designs incorporate the latest development in coal gasification technology and advanced Fischer-Tropsch (F-T) slurry reactor design. ASPEN process simulation models were developed to provide detailed plant material and energy balances, utility requirements, operating and capital costs. A linear programming model based on a typical PADD II refinery was developed to assess the values of the produced F-T products. The results then were used in a discounted cash flow spreadsheet model to examine the effect of key process variables on the overall F-T economics. Different models were developed to investigate the various routes of upgrading the F-T products. The effects of incorporating a close-coupled ZSM-5 reactor to upgrade the vapor stream leaving the Fischer-Tropsch reactor have been reported previously. This paper compares two different schemes of F-T was upgrading, namely fluidized bed catalytic cracking verse mild hydrocracking.

  13. Process design and solvent recycle for the supercritical Fischer-Tropsch synthesis

    SciTech Connect

    Wensheng Linghu; Xiaohong Li; Kenji Asami; Kaoru Fujimoto

    2006-02-01

    A recycle reactor system for supercritical Fischer-Tropsch synthesis was successfully designed and tested. The new reactor system has these characteristics: (1) integration of supercritical Fischer-Tropsch reactions, natural separation of produced wax from liquid phase, and recycle of the solvent and (2) natural recycle of solvent driven by self-gravity. A 20% Co/SiO{sub 2} catalyst and n-hexane were used as a catalyst and supercritical fluid, respectively. The results show that the average CO conversion at the steady state was 45% with recycle and 58% without recycle. The lumped hydrocarbon products distribution did not have any obvious difference between with and without recycle operation; however, {alpha}-olefin content of products with recycle was lower than that without recycle. The XRD result indicates that most of the reduced cobalt remains in the metallic state during the Fischer-Tropsch reactions for both cases. 22 refs., 3 figs., 1 tab.

  14. Fischer-Tropsch Synthesis on ALD-synthesized Catalysts

    NASA Astrophysics Data System (ADS)

    Van Norman, Staci A.

    Cobalt catalysts were prepared on porous Al2O 3 and W/Al2O3 supports by atomic layer deposition (ALD) that used sequential reactions of cobaltocene (CoCp2) and H 2 at 483 to 523 K. This preparation method avoided formation of an intermediate oxide, so the catalysts could be activated at lower temperatures. Some of these catalysts had CO reaction rates per g of Co in Fischer-Tropsch synthesis (FTS) that were three times those reported for Co catalysts prepared by incipient wetness. The FTS reacts CO and H2 to form hydrocarbon liquids that can used as synthetic fuels. The rate of FTS depended on the number of ALD cycles, and catalysts prepared with one cycle had activities equivalent to incipient wetness Co catalysts; the highest reaction rate per g of catalyst was obtained for catalysts prepared using four ALD cycles. Two types of Co were observed on the alumina surface using TEM: Co particles with diameters between 0.6 and 1.8 nm (75% were smaller than 1 nm), and Co crystalline planes that were as large as 35 nm. Cobalt catalysts prepared by ALD retained adsorbed ligands that appeared to be stable for at least eight months at room temperature. Tungsten was deposited onto porous Al2O 3 by ALD to provide a catalyst support with higher thermal conductivity because the FTS reaction is highly exothermic. The W indeed increased thermal conductivity, and the resulting supports were used for Co ALD following deposition of an Al2O3 ALD layer. However, although Co deposits on ALD Al2O3, the Co had no activity for FTS, apparently because the ALD Al2O3 was amorphous. In contrast ALD Al 2O3 that was heat treated at high temperature was partially crystalline and served as a support for an active FTS catalyst.

  15. Synthesis of octane enhancer during slurry-phase Fischer-Tropsch

    SciTech Connect

    Marcelin, G.

    1991-12-15

    The objective of this project is to investigate three possible routes to the formation of ethers, in particular methyl tert-butyl ether (MTBE), during slurry phase Fischer-Tropsch reaction. The three reaction schemes to be investigated are: Addition of isobutylene during the formation of methanol and/or higher alcohols directly from CO and H{sub 2} during slurry-phase Fischer-Tropsch. Addition of isobutylene to FT liquid products including alcohols in a slurry-phase reactor containing an MTBE or other acid catalyst. Addition of methanol to slurry phase FT synthesis making iso-olefins.

  16. Synthesis of octane enhancers during slurry-phase Fischer-Tropsch

    SciTech Connect

    Marcelin, G.

    1992-06-10

    The objective of this project is to investigate three possible routes to the formation of ethers, in particular methyl tert-butyl ether (MTBE), during slurry phase Fischer-Tropsch reaction. The three reaction schemes to be investigated are: Addition of isobutylene during the formation of methanol and/or higher alcohols directly from CO and H{sub 2} during slurry-phase Fischer-Tropsch. Addition of isobutylene to FT liquid products including alcohols in a slurry-phase reactor containing an MTBE or other acid catalyst. Addition of methanol to slurry phase FT synthesis making iso-olefins.

  17. Synthesis of octane enhancers during slurry-phase Fischer-Tropsch

    SciTech Connect

    Marcelin, G.

    1991-10-15

    The objective of this project is to investigate three possible routes to the formation of ethers, in particular methyl tert-butytl ether (MTBE), during slurry phase Fischer-Tropsch reaction. The three reaction schemes to be investigated are: (1) Addition of isobutylene during the formation of methanol and/or higher alcohols directly from CO and H{sub 2} during slurry-phase Fischer-Tropsch; (2) addition of isobutylene to FT liquid products including alcohols in a slurry-phase reactor containing an MTBE or other acid catalyst; and, (3) addition of methanol to slurry phase FT synthesis making iso-olefins.

  18. Catalysts for Fischer-Tropsch

    SciTech Connect

    Srivastava, R.D. ); Rao, V.U.S.; Cinquegrane, G.; Stiegel, G.J. )

    1990-02-01

    The slurry-phase Fischer-Tropsch (F-T) process has attracted considerable attention recently. The process can make liquid fuels by reacting hydrogen-lean synthesis gas produced from modern energy-efficient gasifiers. continuing assessment of Fischer-Tropsch Synthesis (FTS) has a high priority within an indirect liquefaction program, a part of the liquid fuels program sponsored by the U.S. Department of Energy (DOE) and executed by the Pittsburgh Energy Technology Center (PETC). Funding for the indirect liquefaction program in 1990:0090 is anticipated to be about $8.5 million compared to $6.6 million in 1989 and a like amount in the year before. The studies within the program are conducted by industry, universities, national laboratories and in-house PETC research and development. This article reviews preparation and properties of iron-based catalysts, including recent patent activities and in-depth process analysis of slurry-phase FTS. The review provides an analysis of Fischer-Tropsch catalyst research and development trends and describes options to increase selectivity for iron-based catalysts in a slurry phase.

  19. Effect of potassium promotion on iron-based catalysts for Fischer-Tropsch synthesis

    SciTech Connect

    Raje, A.P.; O`Brien, R.J.; Davis, B.H.

    1998-11-15

    The effect of potassium on Fischer-Tropsch catalyst activity, kinetic parameters, and selectivity has been investigated for a precipitated iron catalyst that was employed with low H{sub 2}/CO ratio synthesis gas. A wide range of synthesis gas conversions have been obtained by varying space velocities over catalysts with various potassium loadings. Differing trends in catalyst activity with potassium loading were observed depending on the space velocity of synthesis gas conversion. As potassium loading increased, the catalyst activity either decreased (low conversion), passed through a maximum (intermediate conversion), or increased (high conversion). This is shown to be a result of the increasing dependency of the Fischer-Tropsch synthesis on the hydrogen formed by the water-gas shift reaction with increasing synthesis gas conversions. Both the rate constant and the adsorption parameter in a common two-parameter Fischer-Tropsch rate expression decreased with potassium loading; therefore, observed maxima in Fischer-Tropsch rate with potassium loading can be due to the opposing influences of these parameters. The effect of potassium on alkene selectivity was dependent on the number of carbon atoms of the hydrocarbons as well as the carbon monoxide conversion level. The extent of isomerization of 1-alkene product decreased with potassium loading, while the selectivity to methane decreased only slightly with increasing potassium content at CO conversions about 50% and higher.

  20. Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, January 1, 1995--March 31, 1995

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1996-05-01

    Our objectives for this quarter were: (1) to install and test the temperature probe and the flammable gas detector: (2) to conduct Fischer-Tropsch synthesis experiments at baseline conditions and at a high pressure in order to test the newly constructed fixed bed reactor assembly.

  1. The facile fabrication of magnetite nanoparticles and their enhanced catalytic performance in Fischer-Tropsch synthesis.

    PubMed

    Zheng, Shenke; Sun, Jiaqiang; Song, Dechen; Chen, Zheng; Chen, Jiangang

    2015-07-14

    Uniform and crystalline magnetite nanoparticles are facilely fabricated and utilized as an efficient catalyst in Fischer-Tropsch synthesis (FTS). The catalyst exhibits a high and stable activity with low methane selectivity, attributed to its remarkable structural and chemical stability at the realistic conditions of FTS. PMID:26074335

  2. Fischer-Tropsch synthesis in supercritical reaction media. Progress report, October 1, 1992--December 31, 1992

    SciTech Connect

    Subramaniam, B.; Bochniak, D.; Snavely, K.

    1993-01-01

    Our goals for this quarter were to complete construction of the reactor and analytical units for carrying out Fischer-Tropsch (F-T) synthesis in liquid (n-hexadecane) and in supercritical n-hexane phases. Progress during this quarter was slower than expected.

  3. 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

  4. 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.

  5. Amino acids in a Fischer Tropsch type synthesis

    NASA Technical Reports Server (NTRS)

    Brown, D. L.; Lawless, J. G.

    1974-01-01

    One postulation is described for the presence of organic compounds in meteorites which states that they were formed during the condensation of the solar nebula. A viable laboratory simulation of these conditions can be modeled after the industrial Fischer Tropsch reaction, which is known to produce organic compounds called hydrocarbons. In this simulation, a mixture of carbon monoxide, hydrogen and ammonia is heated in the presence of iron meteorite. The reaction products for amino acids, a class of organic compounds important to life, were examined. A large number of these compounds is found in meteorites and other chemical evolution experiments, but only small quantities of a few amino acids were found in the present simulation work. These results are at odds with the existing literature in which many amino acids were reported.

  6. 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).

  7. 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.

  8. 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.

  9. 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.

  10. New ultrasonically prepared Co-based catalysts for Fischer-Tropsch synthesis.

    PubMed

    Bianchi, C L; Martini, F; Ragaini, V

    2001-04-01

    An extensive study of different preparation methods for Co/SiO2 catalysts is reported in this paper. In addition to the conventional impregnation, other more innovative methods are used including ultrasound. The prepared samples are fully characterized and tested in the CO hydrogenation (Fischer-Tropsch synthesis). The best catalytic performance, both as CO conversion and hydrocarbons selectivity, is shown by one of the sample prepared using ultrasound. PMID:11326608

  11. 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.

  12. 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

  13. Fischer-Tropsch slurry catalysts for selective transportation fuel production

    SciTech Connect

    Carroll, W.E.; Cilen, N.; Withers, H.P. Jr.

    1986-01-01

    The future use of coal as a source of conventional transportation fuel will depend on the development of an economical and energy efficient liquefaction process. Technologies that have been commercially proven or that are close to commercialization include the fixed- and fluidized-bed Fischer-Tropsch (FT) synthesis, methanol synthesis (fixed-bed and slurry-phase) and the Mobil methanol-to-gasoline process. Of these technologies, the Fischer-Tropsch hydrocarbon synthesis produces the widest slate of products and has been in operation for the longest period.

  14. [Determination of low-carbon alcohols, aldehydes and ketones in aqueous products of Fischer-Tropsch synthesis by gas chromatography].

    PubMed

    Gai, Qingqing; Wu, Peng; Shi, Yulin; Bai, Yu; Long, Yinhua

    2015-01-01

    A method for the determination of low-carbon (C1-C8) alcohols, aldehydes and ketones in aqueous products of Fischer-Tropsch synthesis was developed by gas chromatography. It included the optimization of separation conditions, the precision and accuracy of determination, and the use of correction factors of the analytes to ethanol for quantification. The aqueous products showed that the correlation coefficients for ethanol in different content ranges were above 0.99, which means it had good linear correlations. The spiked recoveries in the aqueous samples of Fischer-Tropsch synthesis were from 93.4% to 109.6%. The accuracy of the method can satisfy the requirement for the analysis of the aqueous samples of Fischer-Tropsch synthesis. The results showed that the total mass fractions of the major low-carbon alcohols, aldehydes, ketones in aqueous products of Fischer-Tropsch synthesis were about 3%-12%, and the contents of ethanol were the highest (about 1.7%-7.3%). The largest share of the total proportion was n-alcohols, followed by isomeric alcohols, aldehydes and ketones were the lowest. This method is simple, fast, and has great significance for the analysis of important components in aqueous products of Fischer-Tropsch synthesis. PMID:25958675

  15. 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.

  16. Synthesis and catalytic properties of eggshell cobalt catalysts for the Fischer-Tropsch synthesis

    SciTech Connect

    Iglesia, E.; Soled, S.L.; Baumgartner, J.E.

    1995-04-15

    CO diffusional restrictions decrease the rate and C{sup +}{sub 5} selectivity in large (1-3 mm) catalyst pellets required for Fischer-Tropsch synthesis in packed bed reactors. Eggshell catalysts, in which the active Co component is preferentially located near the outer pellet surface, decrease these transport restrictions and increase Fischer-Tropsch synthesis rates and C{sup +}{sub 5} selectivity. Maximum C{sup +}{sub 5} selectivities occur on catalysts with intermediate shell thickness, because these catalysts avoid intrapellet CO concentration gradients but still restrict the diffusive removal of reactive olefin products, which can readsorb and continue to grow to higher molecular weight hydrocarbons. Eggshell catalysts were prepared by a novel impregnation technique using molten cobalt nitrate. The eggshell thickness is controlled by the melt viscosity and by the contact time between the melt and the support pellet. These impregnation procedures and the slow reduction of the impregnated nitrate salts lead to relatively high cobalt dispersions (0.05-0.07) even at the high Co concentrations (40-50 wt%) present within the shell region. 51 refs., 8 figs., 4 tabs.

  17. Performance testing with a gas-liquid-solid system in a mechanically-stirred reactor: The Fischer-Tropsch synthesis

    SciTech Connect

    Donnelly, T.J.; Satterfield, C.N.

    1987-01-01

    Careful attention to reactor operating procedures and methods of product trapping and analysis is required to obtain accurate and reliable data on selectivity and kinetics when a wide variety of products are formed. Useful methods are discussed in detail. The focus of attention is on use of iron-based Fischer-Tropsch catalysts studied in a well-mixed slurry reactor, but many of the findings apply to other catalysts and reactor systems used for Fischer-Tropsch synthesis or to other reactions in which a complex mixture of products is formed. Some apparent discrepancies in the literature regarding catalyst activity and selectivity in Fischer-Tropsch synthesis are explained by analysis of the pertinent experimental systems. 50 refs., 4 figs., 2 tabs.

  18. Fischer-Tropsch synthesis over MOF-supported cobalt catalysts (Co@MIL-53(Al)).

    PubMed

    Isaeva, V I; Eliseev, O L; Kazantsev, R V; Chernyshev, V V; Davydov, P E; Saifutdinov, B R; Lapidus, A L; Kustov, L M

    2016-07-26

    Novel nanohybrid materials were prepared by immobilizing Co nanoparticles on a microporous framework MIL-53(Al) as a porous host matrix. The synthesized cobalt-containing materials were characterized by XRD, STEM, and oxygen titration. The catalytic performance of Co@MIL-53(Al) nanohybrids was examined in Fischer-Tropsch synthesis (FTS) for the first time. A higher selectivity to C5+ hydrocarbons and lower selectivity to methane for Co@MIL-53(Al) as compared to conventional Co/Al2O3 were observed. PMID:27389315

  19. Reaction engineering of slurry phase Fischer-Tropsch synthesis with porous cobalt catalysts

    SciTech Connect

    Han, Y.H.; Li, F.; Fujimoto, Kaoru

    1997-12-31

    Fischer-Tropsch synthesis was conducted in the slurry phase using a stirred reactor and supported cobalt catalysts. Under well stirred conditions, neither the mass transfer between the gas-solid interface nor the liquid-solid interface was found to be the rate limiting step in the reaction sequence. The catalytic activity and product selectivity were markedly affected by the particle size for small pore (20 angstroms) catalyst while those of a large pore catalyst were not affected by the particle where the partial diameter is larger than 0.1 mm. The phenomena were well simulated by theoretical calculations.

  20. 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).

  1. Iron Aerogel and Xerogel Catalysts for Fischer-Tropsch Synthesis of Diesel Fuel

    SciTech Connect

    Bali, S.; Huggins, F; Huffman, G; Ernst, R; Pugmire, R; Eyring, E

    2009-01-01

    Iron aerogels, potassium-doped iron aerogels, and potassium-doped iron xerogels have been synthesized and characterized and their catalytic activity in the Fischer-Tropsch (F-T) reaction has been studied. Iron aerogels and xerogels were synthesized by polycondensation of an ethanolic solution of iron(III) chloride hexahydrate with propylene oxide which acts as a proton scavenger for the initiation of hydrolysis and polycondensation. Potassium was incorporated in the iron aerogel and iron xerogel by adding aqueous K{sub 2}CO{sub 3} to the ethanolic solutions of the Fe(III) precursor prior to addition of propylene oxide. Fischer-Tropsch activities of the catalysts were tested in a fixed bed reactor at a pressure of 100 psi with a H{sub 2}:CO ratio of 2:1. Iron aerogels were found to be active for F-T synthesis, and their F-T activities increased on addition of a K containing promoter. Moessbauer spectroscopic data are consistent with an open, nonrigid iron(III) aerogel structure progressing to an iron carbide/metallic iron catalyst via agglomeration as the F-T synthesis proceeds in the course of a 35 h fixed bed reaction test.

  2. Synthesis of octane enhancers during slurry-phase Fischer-Tropsch

    SciTech Connect

    Marcelin, G.

    1992-09-24

    The objective of this project is to investigate three possible routes to the formation of ethers, in particular methyl tert-butyl (MTBE), during slurry phase Fischer-Tropsch reaction. The three reaction schemes to be investigated are: addition of i-butylene during the formation of methanol and/or higher alcohols directly from CO and H[sub 2] during slurry-phase Fischer-Tropsch; addition of i-butylene to FT liquid products including alcohols in a slurry-phase reactor containing an MTBE or other acid catalyst; and addition of methanol to slurry phase FT synthesis making iso-olefins. During the seventh quarter we continued the shake down experiments for the SBCR and conducted an initial aborted run. We have also re-started experiments on Scheme 1, i.e., the addition of iso-butylene during CO hydrogenation. Using a dual bed arrangement, we have demonstrated the synthesis of MTBE from syngas and iso-butylene.

  3. State-of-the-art processes for manufacturing synthetic liquid fuels via the Fischer-Tropsch synthesis

    SciTech Connect

    A.Y. Krylova; E.A. Kozyukov

    2007-12-15

    Processes for manufacturing synthetic liquid fuels on the basis of the Fischer-Tropsch synthesis from alternative feedstock (natural gas, coal, biomass of various origins, etc.) are surveyed. State-of-the-art technology, companies that offer such processes, and the quality of products in comparison with their oil analogs, as well as economic features of the processes, are considered.

  4. 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

    2015-01-01

    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. PMID:25740709

  5. 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.

  6. 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.

  7. Fischer-Tropsch synthesis on hierarchically structured cobalt nanoparticle/carbon nanofiber/carbon felt composites.

    PubMed

    Zarubova, Sarka; Rane, Shreyas; Yang, Jia; Yu, Yingda; Zhu, Ye; Chen, De; Holmen, Anders

    2011-07-18

    The hierarchically structured carbon nanofibers (CNFs)/carbon felt composites, in which CNFs were directly grown on the surface of microfibers in carbon felt, forming a CNF layer on a micrometer range that completely covers the microfiber surfaces, were tested as a novel support material for cobalt nanoparticles in the highly exothermic Fischer-Tropsch (F-T) synthesis. A compact, fixed-bed reactor, made of disks of such composite materials, offered the advantages of improved heat and mass transfer, relatively low pressure drop, and safe handling of immobilized CNFs. An efficient 3-D thermal conductive network in the composite provided a relatively uniform temperature profile, whereas the open structure of the CNF layer afforded an almost 100 % effectiveness of Co nanoparticles in the F-T synthesis in the fixed bed. The greatly improved mass and heat transport makes the compact reactor attractive for applications in the conversion of biomass, coal, and natural gas to liquids. PMID:21563315

  8. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Chanenchuk, C.A.; Yates, I.C.; Satterfield, C.N.

    1990-01-01

    Experiments to study the cobalt-catalyzed and iron-catalyzed reactions of light 1-alkenes added to synthesis gas have been performed and analyzed. On cobalt, data have been obtained at 220{degrees}C, 0.45 to 1.48 MPA and a synthesis gas flow rate between 0.015 and 0.030 Nl/gcat/min with H{sub 2}/CO feeds of 1.45 to 2.25. On fused iron, data were collected at 248{degrees}C, 0.79 to 1.48 MPa and a synthesis gas flow rate between 0.005 and 0.030 Nl/gcat/min of H{sub 2}/CO feeds of 0.5 to 1.5 C{sub 2}H{sub 4}, C{sub 3}H{sub 6}, and 1-C{sub 4}H{sub 8} were added to the synthesis gas feed in concentrations ranging from 0.5 to 1.2 mol. % of total feed. 1-Alkenes incorporate into growing chains on the catalyst surface of both catalysts, probably by initiating and/or terminating the chain growth process. Only ethene is believed to propagate chain growth significantly. The propensity of the 1-alkenes to incorporate decreases with increasing carbon number of the 1-alkene. The double-{alpha} behavior which is exhibited by most Fischer-Tropsch catalysts can be explained as the sum of two growth processes, one stepwise single-carbon growth and the other 1-alkene incorporation. Both alkene addition study data and the effects of process variables on the selectivity of Fischer-Tropsch catalysts can be explained within the framework of this theory. 19 refs., 12 figs., 2 tabs.

  9. 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.

  10. 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.

  11. Titania-supported bimetallic catalysts combined with HZSM-5 for Fischer-Tropsch synthesis

    SciTech Connect

    Jothimurugesan, K.; Gangwal, S.K.

    1998-04-01

    The Fischer-Tropsch synthesis (FTS) can convert coal or natural gas derived synthesis gas (CO + H{sub 2}) to liquid fuels and high-value chemicals. Fischer-Tropsch synthesis was studied in a fixed-bed reactor over single-metal and bimetallic alloy catalysts, selected from Co, Ni, and Fe, supported on TiO{sub 2} at a total metal loading of 10 wt%. The catalysts, prepared by incipient wetness impregnation using nitrate precursors, were tested as is and in combination with a HZSM-5 zeolite. The test conditions were 1 MPa, 250 C, H{sub 2}/CO = 1, and weight hourly space velocity (WHSV) = 0.77 h{sup {minus}1}. Alloying of metals resulted in a significant enhancement in CO conversion without an increase in methane selectivity. A 50:50 weight ratio Co-Ni catalyst physically mixed with HZSM-5 (5% Co-5% Ni/TiO{sub 2} + HZSM-5) gave the highest CO conversion (45.2%) at the conditions tested. This compares to conversion of 8.9% and 10.5% with Co-only and Ni-only catalysts, respectively. Mixing the Co-Ni catalyst with HZSM-5 resulted in a significant reduction in methane selectivity and a significant increase in C{sub 4}{sup +} selectivity. The aromatic fraction increased from 1.5 to 8.1 wt%, the C{sub 2}{sup +} olefins were nearly eliminated, and i-C{sub 4}H{sub 10} increased from 2.3 to 58.5 wt % in the C{sub 4} fraction.

  12. 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. PMID:25727762

  13. 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

    2014-01-01

    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. PMID:25503569

  14. Kinetic model of product distribution over Fe catalyst for Fischer-Tropsch synthesis

    SciTech Connect

    Rongle Zhang; Jie Chang; Yuanyuan Xu; Liren Cao; Yongwang Li; Jinglai Zhou

    2009-09-15

    A new kinetic model of the Fischer-Tropsch synthesis (FTS) is proposed to describe the non-Anderson-Schulz-Flory (ASF) product distribution. The model is based on the double-polymerization monomers hypothesis, in which the surface C{sub 2}{asterisk} species acts as a chain-growth monomer in the light-product range, while C{sub 1}{asterisk} species acts as a chain-growth monomer in the heavy-product range. The detailed kinetic model in the Langmuir-Hinshelwood-Hougen-Watson type based on the elementary reactions is derived for FTS and the water-gas-shift reaction. Kinetic model candidates are evaluated by minimization of multiresponse objective functions with a genetic algorithm approach. The model of hydrocarbon product distribution is consistent with experimental data (

  15. ɛ-Iron carbide as a low-temperature Fischer-Tropsch synthesis catalyst

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    ɛ-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 ɛ-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 ɛ-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.

  16. Fischer-Tropsch Synthesis: Characterization and Reaction Testing of Cobalt Carbide

    SciTech Connect

    Khalid S.; Mohandas J.C.; Gnanamani M.K.; Jacobs G.; Ma W.; Ji Y.; Davis B.H.

    2011-08-15

    Hydrogenation of carbon monoxide was investigated for cobalt carbide synthesized from Co{sub 3}O{sub 4} by CO carburization in a fixed-bed reactor. The cobalt carbide synthesized was characterized by BET surface area, X-ray diffraction, scanning electron microscopy, X-ray absorption near edge spectroscopy, and extended X-ray absorption fine structure spectroscopy. The catalysts were tested in the slurry phase using a continuously stirred tank reactor at P = 2.0 MPa, H{sub 2}/CO = 2:1 in the temperature range of 493-523 K, and with space velocities varying from 1 to 3 Nl h{sup -1} g{sub cat}{sup -1}. The results strongly suggest that a fraction of cobalt converts to a form with greater metallic character under the conditions employed. This was more pronounced on a Fischer-Tropsch synthesis run conducted at a higher temperature (523 versus 493 K).

  17. Nitrided iron catalysts for the Fischer-Tropsch synthesis in the eighties

    SciTech Connect

    Anderson, R.B.

    1980-01-01

    A survey covers the preparation and structure of nitrided iron catalysts and their activity, selectivity, and stability for the reaction of synthesis gas in comparison with iron catalysts pretreated by various other methods, as measured in laboratory reactors; a comparison of product distributions obtained in fluidized-bed, slurry, and oil-circulation fixed bed pilot plants with nitrided catalysts and by the Kellogg entrained catalyst process SASOL, which uses a reduced iron catalyst; and possible methods for refining the Fischer-Tropsch products from nitrided iron catalysts for producing gasoline, including bauxite treatment, the Mobil process for converting oxygenates to high-octane gasoline and C/sub 3/-C/sub 4/ olefins, and an alkylation-polymerization process for converting the C/sub 3/-C/sub 4/ fraction to high-octane blending stocks.

  18. Chain growth in the Fischer-Tropsch synthesis

    SciTech Connect

    Stockwell, D.M.

    1987-01-01

    Methanation and hydrocarbon synthesis from CO and H/sub 2/ was studied using 10 wt% Ni/Al/sub 2/O/sub 3/ and 10 wt% Fe/Al/sub 2/O/sub 3/ catalysts at 1 atm. Transient responses to the switches between various feed mixtures, especially isotopically labeled feeds, to a gradientless microreactor were used to obtain information on the amounts and reactivities of intermediates on and in the catalysts. On Ni/Al/sub 2/O/sub 3/, about 0.5 monolayer of adsorbed CO and smaller amounts of C are present during reaction. Infrared and CO/D/sub 2/ suggest that significant amounts of CH/sub x/ (x = 1-3) are not present. Chain growth experiments with /sup 13/CO/H/sub 2/ indicate that the hydrocarbons are formed primarily from C, but the results also indicate that the process is not fully understood. All steps in methanation and chain growth appear to be fast, except for the limiting steps CO ..-->.. C and C ..-->.. CH. On Fe/Al/sub 2/O/sub 3/, methanation and chain growth occur via CH, with all steps except the initial conversion of CH apparently being fast. Bulk iron carbides and an inactive form of carbon, different from C on Ni/Al/sub 2/O/sub 3/, do not participate significantly. The CH deactivates slowly with time on stream; only a small portion produces most of the products after 2 h on stream. Other work concerned H/sub 2/ chemisorption on various supported metal catalysts. Using TPD, an unusual spike was found after low temperature adsorption on Ru/SiO/sub 2/. The activated adsorption of H/sub 2/ on Fe/SiO/sub 2/, Fe/Al/sub 2/O/sub 3/, Ni/AlO/sub 3/, and Rh/TiO/sub 2/ was compared. It was suggested that, by analogy to titania-supported metals, the origin of the activation barrier may lie in a decoration phenomenon. It was proposed that SiO/sub x/ and AlO/sub x/ species may have been derived from small amounts of support which dissolved in the impregnating solution.

  19. 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.

  20. Aspen Process Flowsheet Simulation Model of a Battelle Biomass-Based Gasification, Fischer-Tropsch Liquefaction and Combined-Cycle Power Plant

    SciTech Connect

    1998-10-30

    This study was done to support the research and development program of the National Renewable Energy Laboratory (NREL) in the thermochemical conversion of biomass to liquid transportation fuels using current state-of-the-art technology. The Mitretek study investigated the use of two biomass gasifiers; the RENUGAS gasifier being developed by the Institute of Gas Technology, and the indirectly heated gasifier being developed by Battelle Columbus. The Battelle Memorial Institute of Columbus, Ohio indirectly heated biomass gasifier was selected for this model development because the syngas produced by it is better suited for Fischer-Tropsch synthesis with an iron-based catalyst for which a large amount of experimental data are available. Bechtel with Amoco as a subcontractor developed a conceptual baseline design and several alternative designs for indirect coal liquefaction facilities. In addition, ASPEN Plus process flowsheet simulation models were developed for each of designs. These models were used to perform several parametric studies to investigate various alternatives for improving the economics of indirect coal liquefaction.

  1. Elementary steps in Fischer-Tropsch synthesis: CO bond scission, CO oxidation and surface carbiding on Co(0001)

    NASA Astrophysics Data System (ADS)

    Weststrate, C. J.; van Helden, P.; van de Loosdrecht, J.; Niemantsverdriet, J. W.

    2016-06-01

    Dissociation of CO on a Co(0001) surface is explored in the context of Fischer-Tropsch synthesis on cobalt catalysts. Experiments show that CO dissociation can occur on defect sites around 330 K, with an estimated barrier between 90 and 104 kJ mol- 1. Despite the ease of CO dissociation on defect sites, extensive carbon deposition onto the cobalt surface up to 0.33 ML requires a combination of high surface temperature and a relatively high CO pressure. Experimental data on the CO oxidation reaction indicate a high reaction barrier for the CO + O reaction, and it is argued that, due to the rather strong Co-O bond, (i) oxygen removal is the rate-limiting step during surface carbidization and (ii) in the context of Fischer-Tropsch synthesis, removal of surface oxygen rather than CO bond scission might be limiting the overall reaction rate.

  2. Preparation of a novel structured catalyst based on aligned carbon nanotube arrays for a microchannel Fischer-Tropsch synthesis reactor

    SciTech Connect

    Chin, Ya-Huei; Hu, Jianli; Cao, Chunshe; Gao, Yufei; Wang, Yong

    2005-12-15

    A novel catalyst microstructure based on aligned multiwall carbon nanotube arrays was synthesized. Its advanced heat and mass transport characteristics coupled with high surface area led to superior performances for Fischer-Tropsch synthesis in a microchannel chemical reactor. The fabrication of such a novel catalyst structure first involved metalorganic chemical vapor deposition (MOCVD) growth of a dense Al2O3 thin film over FeCrAlY foam substrate to enhance adhesion between catalyst layer and metal substrate. Aligned arrays of multiwall carbon nanotubes were grown over the substrate by catalytic decomposition of ethylene. These nanotube bundles were directly attached to the FeCrAlY substrate through a thin layer of oxide thin film. When the outer surfaces of nanobundles were coated with a catalyst layer, a unique hierarchical catalyst structure with nanoporous interstitials between the bundles was created. Thus, engineered catalysts based on such a novel hierarchical structure minimizes mass transfer encountered in the gas-liquid-solid three phase reactions. In addition, high thermal conductivity of carbon nanotube and the direct attachment of these nanobundles to the metal foam allow efficient heat removal from catalytic sites. The advanced heat and mass transfer on this novel structured catalyst was demonstrated in Fischer-Tropsch synthesis in a microchannel fixed bed reactor. The presence of carbon nanotube arrays improved dispersion of active metals and reduced mass transfer limitation, leading to a factor of four enhancement of Fischer-Tropsch synthesis activity. The improved temperature control with the carbon nanotube arrays also allows the Fischer-Tropsch synthesis being operated at temperatures as high as 265 C without reaction runaway favoring methane formation.

  3. 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*. PMID:24123803

  4. 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

    2015-01-01

    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. PMID:25387082

  5. Fischer-Tropsch synthesis in slurry-reactor systems. Quarterly report, August 1, 1981-October 31, 1981

    SciTech Connect

    Satterfield, C.N.; Bartos, T.; Huff, G.A. Jr.; Stenger, H.

    1981-01-01

    A large quantity of data were obtained with the fused iron catalyst under intrinsic kinetic conditions, covering for the first time 50 and 200 psi. These data are being analyzed for information about overall rates and product selectivity. Preliminary conclusions about a rate model are presented. Study of the effects of suspended solids on gas-liquid mass transfer was started. Most previous information is on aqueous systems, which is not readily translatable into predicted effects in organic liquids such as Fischer-Tropsch liquids. The most promising and useful method at present appears to be a chemical method based on absorption of CO/sub 2/ into an organic solution of an amine. A paper on a stirred-autoclave apparatus for studying the Fischer-Tropsch synthesis in a slurry bed in included.

  6. Gasoline range ether synthesis from light naphtha products of fluid catalytic cracking of Fischer-Tropsch wax

    SciTech Connect

    Reagan, W.J.

    1994-12-31

    The Fluid Catalytic Cracking of Fischer-Tropsch wax (C{sub 20}{sup +} paraffins) produces two to four time the concentration of reactive iso-olefins (isobutylene, isoamylenes, isohexenes) than observed from conventional gas oil feedstocks. Methanol reacts with these olefins to form the corresponding tertiary alkyl ethyl ethers: MTBE, TAME and MTHE`s. These etherification reactions are mildly exothermic and equilibrium limited. The reaction temperature and the olefin molecular structure are important variables for maximum ether yields. The base naphtha research octane number increases by 2-4 numbers after the etherification reaction. The presence of hydrogen has a detrimental affect on ether yields because of hydrogenation of reactive olefins to paraffins. The catalytic cracking of Fischer-Tropsch wax provides a non-conventional source of olefins for ether synthesis that can supplement existing and dwindling petroleum supplies.

  7. 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.

  8. 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.

  9. Researching Fe catalyst suitable for CO{sub 2}-containing syngas for Fischer-Tropsch synthesis

    SciTech Connect

    Wensheng Ning; Naoto Koizumi; Muneyoshi Yamada

    2009-09-15

    Fischer-Tropsch (FT) synthesis is a technology to produce liquid fuels from coal, natural gas, and biomass as an alternate to crude oil. However, the quantity of emitted CO{sub 2} from the FT process consisting of syngas preparation, FT synthesis, and product workup is one of the serious disadvantages of FT process. The conversion of CO{sub 2} into hydrocarbons is one of the promising methods to decrease CO{sub 2} emissions. Effects of promoter addition on the activity of precipitated Fe catalysts for the conversion of CO{sub 2} were studied using pure CO{sub 2} and CO{sub 2}-containing syngas feeds. The results suggested that CO{sub 2} can be activated by suitable promoter(s) for hydrocarbon synthesis at low temperature. Low K content is suitable for increasing hydrocarbon yield. The Fe catalysts promoted by equal Zn and Cu have higher CO and CO{sub 2} conversion and decreased CH{sub 4} selectivity. 36 refs., 7 figs., 3 tabs.

  10. 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.

  11. 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.

  12. Research Opportunities for Fischer-Tropsch Technology

    SciTech Connect

    Jackson, Nancy B.

    1999-06-30

    Fischer-Tropsch synthesis was discovered in Germany in the 1920's and has been studied by every generation since that time. As technology and chemistry, in general, improved through the decades, new insights, catalysts, and technologies were added to the Fischer-Tropsch process, improving it and making it more economical with each advancement. Opportunities for improving the Fischer-Tropsch process and making it more economical still exist. This paper gives an overview of the present Fischer-Tropsch processes and offers suggestions for areas where a research investment could improve those processes. Gas-to-liquid technology, which utilizes the Fischer Tropsch process, consists of three principal steps: Production of synthesis gas (hydrogen and carbon monoxide) from natural gas, the production of liquid fuels from syngas using a Fischer-Tropsch process, and upgrading of Fischer-Tropsch fuels. Each step will be studied for opportunities for improvement and areas that are not likely to reap significant benefits without significant investment.

  13. 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

  14. 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. PMID:23428163

  15. Manganese-oxide-supported iron Fischer-Tropsch synthesis catalysts: physical and catalytic characterization

    SciTech Connect

    Kreitman, K.M.; Baerns, M.; Butt, J.B.

    1987-06-01

    It has been claimed that catalysts containing iron and manganese are especially selective for production of low molecular weight olefins in the Fischer-Tropsch (FT) synthesis. In this study a new system, manganese-oxide-supported iron, Fe/MnO, was prepared, subjected to various calcination and reduction treatments, and then employed as a FT catalyst. Reaction studies were run with approximately 1/1: CO/H/sub 2/ feed at 515 and 540 K and 7.8 and 14.8 bar pressure. Although low conversions were employed, the synthesis rate decreased strongly with increasing conversion. Compared to conventional Fe catalysts, the Fe/MnO was more active for water-gas shift and less selective for methane and alcohols, especially at higher conversions, lower temperature, and higher pressure. Olefin selectivity was high, hydrogen chemisorption was depressed, and secondary hydrogenation was not apparent. In general it is concluded that the manganese-supported iron does promote FT selectivity for low molecular weight olefins, but at the expense of high CO/sub 2/ formation.

  16. Nanocrystalline Ferrihydrite-Based Catalysts for Fischer-Tropsch Synthesis: Part I. Reduction and Carburization Behavior.

    PubMed

    Chun, Dong Hyun; Park, Ji Chan; Rhim, Geun Bae; Lee, Ho-Tae; Yang, Jung-Il; Jung, Heon

    2016-02-01

    Temperature-programmed reduction using H2 (H2-TPR) and CO (CO-TPR) was carried out to investigate the reduction and carburization behavior of nanocrystalline ferrihydrite-based Fe/Cu/K/SiO2 catalysts for use in Fischer-Tropsch synthesis (FTS). Unlike pure ferrihydrite, the ferrihydrite-based catalysts did not pass through the intermediate decomposition step of ferrihydrite (Fe9O2(OH)23) into hematite (a-Fe2O3) as they were reduced into magnetite (Fe3O4). This is attributed to the enhanced thermal stability induced by SiO2. For the ferrihydrite-based catalysts, the reduction of ferrihydrite into magnetite occurred in two stages because the reduction promoter, Cu, is not homogeneously distributed on the catalyst surfaces. The Cu-rich sites are likely to be reduced in the first stage, and the Cu-lean sites may be reduced in the second stage. After the ferrihydrite is reduced to magnetite, the reduction process of magnetite was similar to that for conventional hematite-based FTS catalysts: 'magnetite --> metallic iron' and 'magnetite --> wüstite (FeO) or fayalite (Fe2SiO4) --> metallic iron' in the H2 atmosphere; 'magnetite --> iron carbides' in the CO atmosphere. PMID:27433641

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

    SciTech Connect

    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.

  18. Insight into CH(4) formation in iron-catalyzed Fischer-Tropsch synthesis.

    PubMed

    Huo, Chun-Fang; Li, Yong-Wang; Wang, Jianguo; Jiao, Haijun

    2009-10-21

    Spin-polarized density functional theory calculations have been performed to investigate the carbon pathways and hydrogenation mechanism for CH(4) formation on Fe(2)C(011), Fe(5)C(2)(010), Fe(3)C(001), and Fe(4)C(100). We find that the surface C atom occupied sites are more active toward CH(4) formation. In Fischer-Tropsch synthesis (FTS), CO direct dissociation is very difficult on perfect Fe(x)C(y) surfaces, while surface C atom hydrogenation could occur easily. With the formation of vacancy sites by C atoms escaping from the Fe(x)C(y) surface, the CO dissociation barrier decreases largely. As a consequence, the active carburized surface is maintained. Based on the calculated reaction energies and effective barriers, CH(4) formation is more favorable on Fe(5)C(2)(010) and Fe(2)C(011), while Fe(4)C(100) and Fe(3)C(001) are inactive toward CH(4) formation. More importantly, it is revealed that the reaction energy and effective barrier of CH(4) formation have a linear relationship with the charge of the surface C atom and the d-band center of the surface, respectively. On the basis of these correlations, one can predict the reactivity of all active surfaces by analyzing their surface properties and further give guides for catalyst design in FTS. PMID:19780531

  19. Potential for Coal-to-Liquids Conversion in the United States-Fischer-Tropsch Synthesis

    SciTech Connect

    Patzek, Tad W. Croft, Gregory D.

    2009-09-15

    The United States has the world's largest coal reserves and Montana the highest potential for mega-mine development. Consequently, a large-scale effort to convert coal to liquids (CTL) has been proposed to create a major source of domestic transportation fuels from coal, and some prominent Montanans want to be at the center of that effort. We calculate that the energy efficiency of the best existing Fischer-Tropsch (FT) process applied to average coal in Montana is less than 1/2 of the corresponding efficiency of an average crude oil refining process. The resulting CO{sub 2} emissions are 20 times (2000%) higher for CTL than for conventional petroleum products. One barrel of the FT fuel requires roughly 800 kg of coal and 800 kg of water. The minimum energy cost of subsurface CO{sub 2} sequestration would be at least 40% of the FT fuel energy, essentially halving energy efficiency of the process. We argue therefore that CTL conversion is not the most valuable use for the coal, nor will it ever be, as long as it is economical to use natural gas for electric power generation. This finding results from the low efficiency inherent in FT synthesis, and is independent of the monumental FT plant construction costs, mine construction costs, acute lack of water, and the associated environmental impacts for Montana.

  20. 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

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

    SciTech Connect

    Bochniak, D.J.; Subramaniam, B.

    1998-08-01

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

  2. In situ reduction study of cobalt model Fischer-Tropsch synthesis catalysts.

    PubMed

    du Plessis, Hester Esna; Forbes, Roy Peter; Barnard, Werner; Erasmus, Willem Johannes; Steuwer, Axel

    2013-07-28

    Fischer-Tropsch (FT) synthesis is an important process to manufacture hydrocarbons and oxygenated hydrocarbons from mixtures of carbon monoxide and hydrogen (syngas). The catalysis process occurs on, for example, cobalt metal surfaces at elevated temperatures and pressures. A fundamental understanding of the reduction pathway of supported cobalt oxides, and the intermediate species present during the activation, can assist in developing improved industrial supported cobalt catalysts. Hard synchrotron X-rays have the unique ability to probe atomic processes both in terms of phases present as well as the crystallographic and local structure (using the pair distribution function approach) under realistic conditions. In this manuscript we present results from measurements during in situ hydrogen activation of a model Co/alumina catalyst using in situ synchrotron X-ray powder diffraction and pair-distribution function (PDF) analysis on beam line ID31 at the ESRF in Grenoble, France. The PDF analysis showed a substantially improved understanding of the reduction of cobalt oxides, as for the first time all cobalt could be accounted for by using total scattering analysis. PMID:23752408

  3. Utilization of cobalt catalyst for high temperature Fischer-Tropsch synthesis in a fluidized bed reactor

    NASA Astrophysics Data System (ADS)

    Mabry, James C.

    The research determined that the improved heat transfer characteristics of a fluidized bed reactor (FBR) will allow the use of cobalt catalyst for high temperature Fischer-Tropsch synthesis (HTFT). Cobalt was loaded onto a gamma alumina support, the catalyst was characterized using TPR, BET/BJH, XRD, and PSA to track changes in the catalyst morphology. The reactor was characterized to determine the minimum fluidization velocity and the maximum velocity prior to entering lean phase fluidization with pneumatic transport of the catalyst. The highest minimum fluidization velocity was found to be about 2800 sccm, there was no maximum velocity found for the reactor setup. Once characterized, the reactor was operated at pressures of 145, 217.6, and 290.1 psig, a syngas flow rate of 4000 sccm, and at temperatures of 330 and 350 °C. The optimal conditions found in this study were 330 °C and 217 psig. At these conditions CO conversion was 83.53 % for a single pass. Methane, CO2, and light gases (C2 -- C4) selectivities were at low rates of 31.43, 5.80, and 3.48 % respectively. Alcohol selectivity at these conditions was non-existent. The olefin and wax selectivities were the lowest of the data set at 7.05 and 3.18 % respectively. Liquid transportation fuels selectivity was the highest at 56.11 %.

  4. 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. PMID:27433720

  5. The renaissance of iron-based Fischer-Tropsch synthesis: on the multifaceted catalyst deactivation behaviour.

    PubMed

    de Smit, Emiel; Weckhuysen, Bert M

    2008-12-01

    Iron-based Fischer-Tropsch catalysts, which are applied in the conversion of CO and H2 into longer hydrocarbon chains, are historically amongst the most intensively studied systems in heterogeneous catalysis. Despite this, fundamental understanding of the complex and dynamic chemistry of the iron-carbon-oxygen system and its implications for the rapid deactivation of the iron-based catalysts is still a developing field. Fischer-Tropsch catalysis is characterized by its multidisciplinary nature and therefore deals with a wide variety of fundamental chemical and physical problems. This critical review will summarize the current state of knowledge of the underlying mechanisms for the activation and eventual deactivation of iron-based Fischer-Tropsch catalysts and suggest systematic approaches for relating chemical identity to performance in next generation iron-based catalyst systems (210 references). PMID:19020686

  6. Low nitrogen iron-containing Fischer-Tropsch catalyst and conversion of synthesis gas therewith

    SciTech Connect

    Bell, W.K.; Haag, W.O.; Kirker, G.W.; Klocke, D.J.

    1987-08-11

    This patent describes a process for converting syngas to hydrocarbons comprising: (a) contacting an iron-containing Fischer-Tropsch catalyst with a syngas stream under conditions effective to achieve high conversion of the syngas to substantial amounts of C/sub 3//sup +/ carbon compounds; (b) contacting the effluent stream from (a) with a shape selective crystalline zeolite having a Constraint Index of about 1 to 12; and (c) recovering from the effluent stream of (b) gasoline and distillate materials; the improvement which comprises preparing the iron-containing Fischer-Tropsch catalyst by a process which continuously precipitates an aqueous solution containing iron nitrate with aqueous ammonia at a pH of about 6.5 to 6.9 and a temperature ranging from about 70/sup 0/ to 100/sup 0/C and thereafter washing the resulting precipitate with an aqueous wash solution to produce a Fischer-Tropsch catalyst containing less than about 500 ppm nitrogen.

  7. Studying the fischer tropsch synthesis on alumina support cobalt base catalyst in fixed bed reactor

    NASA Astrophysics Data System (ADS)

    Oues, Adnan Khalil

    A Fischer-Tropsch catalyst composed of cobalt supported on alumina was prepared. This catalyst was cobalt/alumina (Co/AL2O3). The physical characterization of the catalyst was conducted using surface area analysis through the BET method, and particle size analysis. Fischer-Tropsch experiments were conducted in a fixed bed reactor. A flow rate of 100sml/min was selected based experimentally. Two temperatures were 330, and 350°C, and three different pressures as follows 145, 217.6, and 290 psig. The results were evaluated and studied based on conversion of hydrogen and carbon monoxide, in addition to selectivity of products.

  8. Role of CO{sub 2} in the initiation of chain growth during the Fischer-Tropsch synthesis

    SciTech Connect

    Davis, B.H.; Xu, L.; Bao, S.; Tau, L.M.; Chawla, B.; Dabbagh, H.

    1994-12-31

    Data are presented to show that alcohols produce hydrocarbons during the Fischer-Tropsch Synthesis (FTS) that are not consistent with a simple initiation mechanism. The data is believed to be consistent with accumulation of hydrocarbon products in the reactor during the synthesis CO{sub 2} is produced directly from the alcohol, and not by the reverse carbonylation reaction. CO{sub 2} also initiates chain growth in the FTS, and the initiation intermediate is presumed to be the same intermediate as in the water-gas-shift reaction.

  9. Ordered mesoporous carbon nanochannel reactors for high-performance Fischer-Tropsch synthesis.

    PubMed

    Ha, Kyoung-Su; Kwak, Geunjae; Jun, Ki-Won; Hwang, Jongkook; Lee, Jinwoo

    2013-06-01

    A hexagonally ordered mesoporous carbon, CMK-3, was utilized as a support for a Fischer-Tropsch catalyst. Each array of elongated pore structures with Co nanoparticles can be regarded as a nanochannel reactor. Due to the pore confinement and the hydrophobic nature of the support, this catalyst demonstrated excellent catalytic performance. PMID:23482917

  10. Activation studies with a precipitated iron catalyst for Fischer-Tropsch synthesis. II. Reaction studies

    SciTech Connect

    Bukur, D.B.; Nowicki, L.; Manne, R.K.; Lang, Xiaosu

    1995-09-01

    Effects of pretreatment conditions on catalyst performance (activity, selectivity, and stability with time) during Fischer-Tropsch (FT) synthesis were studied in a fixed-bed reactor using a commercial precipitated iron catalyst (100 Fe/5 Cu/4.2K/25 SiO{sub 2} on a mass basis). The catalyst activity increased slightly with time-on-stream after hydrogen reductions, which was accompanied with conversion of metallic iron and part of iron oxides to {epsilon}{prime}-carbide ({epsilon}{prime}-Fe{sub 22}C). Initial activity of the H{sub 2}-reduced catalyst at 280{degrees}C for 8 or 24 h was markedly lower than that obtained in other tests. This is attributed to slow carburization of large oxide particles and partial poisoning of catalyst sites by migration of sulfur from the bulk to the surface of the catalyst during the reduction. Pretreatments with carbon monoxide and syngas resulted in partial conversion of Fe{sub 2}O{sub 3} to {chi}-carbide ({chi}-Fe{sub 5}C{sub 2}). During FT synthesis the CO- and the syngas-pretreated catalyst deactivated slowly with time-on-stream, due to partial conversion of {chi}-carbide to less active iron oxide phases and buildup of carbonaceous deposits which block the active sites. The hydrogen-reduced catalyst at 280{degrees}C, for 1-24h, produced more methane and gaseous hydrocarbons than the CO- or the syngas-pretreated catalyst and favored secondary reactions (1-olefin hydrogenation, isomerization, and readsorption). 41 refs., 5 figs., 2 tabs.

  11. 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. PMID:22083868

  12. 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.

  13. [Analysis of oxygenates from fischer-Tropsch synthesis oil using column liquid chromatography and gas chromatography-mass spectrography].

    PubMed

    Fan, Gaixian; Xu, Yuanyuan; Li, Ying; Li, Ying; Xiang, Hongwei; Li, Yongwang

    2007-11-01

    A liquid chromatographic column filled with silica gel of 100 - 200 mesh was used to separate cold trap oil from Fischer-Tropsch synthesis with dimethylsulfoxide (DMSO) as eluent. With this pretreatment method, the cold trap oil was separated into two major classes, namely, hydrocarbons and oxygenates. Minor components were also enriched and determined, and small peaks adjacent to big peaks and tailings were also well solved. The oxygenates were then analyzed with gas chromatography-mass spectrometry (GC-MS), and 139 components were identified. PMID:18257312

  14. Wrong-way behavior of fixed-bed reactor in a Fischer-Tropsch synthesis

    SciTech Connect

    Liu Quansheng; Zhang Zhixin; Zhou Jinglai

    1997-12-31

    Fischer-Tropsch Synthesis is one important way to produce liquid fuel from coal-based or natural gas-based syngas. This reaction system is a highly exothermic reaction system, so usually it is finished in a multitubular catalytic fixed-bed reactor of the heat-exchanger type. The control of the reactor maximal temperature and the temperature profile is the key to this type reactor. Generally one can use a steady state model to analyze the temperature profile of a fixed-bed reactor. In the view of dynamics, one should use a dynamic model to analyze the dynamic features of the reactors. The wrong-way behavior is one of these features and is caused by the difference in the speeds of propagation of the concentration and temperature disturbances in the bed. The wrong-way behavior refers to a transient temperature rise in the bed induced by a sudden reduction in the feed temperature. The cold feed cools the upstream section of the bed, and decreases the reaction rate and the conversion in this region, the cold fluid with higher than usual concentration of unconverted reactant eventually contacts hot catalyst particles in downstream section of the bed. This leads to very rapid reaction and a vigorous rate of heat release, which causes a transient temperature rise. The wrong-way behavior may damage the catalyst and initiate undesired side reactions and may lead to unexpected pitfalls in the operation and control and even to a runaway. The goal of this work is to assess the wrong-way behavior of the F-T reactor and the impact of the water-gas shift side-reaction on the wrong-way behavior.

  15. Manganese oxide-supported iron Fischer-Tropsch synthesis catalysts: physical and catalytic characterization

    SciTech Connect

    Kreitman, K.M.

    1986-01-01

    In this study, manganese oxide-supported iron (Fe/MnO) was prepared by impregnation of powdered manganese (II) oxide with aqueous iron(III) nitrate and subjected to various calcination and reduction treatments. It was then employed as a catalyst for Fischer-Tropsch Synthesis (FTS) and its steady-state activity and selectivity behavior was observed. The FTS reaction studies were run with nearly equimolal carbon monoxide/hydrogen feed at 515 and 540 K, 7.9 and 14.8 bar pressure. Feed conversion level was kept low in order to avoid transport limitations, and was varied by adjusting space velocity. The FTS reaction rate decreased strongly with increasing conversion. Compared to unpromoted iron catalysts, the Fe/MnO catalysts were more active for the water-gas shift reaction and less selective for methane and alcohols, especially at higher conversion, lower temperature and higher pressure. The olefin selectivity was high and secondary hydrogenation was not apparent. Catalysts calcined at higher temperature exhibited stronger effects of promotion, and yielded unusually high selectivity for C/sub 2/ to C/sub 4/ hydrocarbons at low temperature and high pressure. The general conclusion is that manganese promotion or iron can promote FTS selectivity towards low molecular weight olefins, but at the expense of high carbon dioxide formation. The Fe/MnO was also physically examined using Moessbauer spectroscopy and X-ray diffraction. Iron and manganese were found to interact strongly in the calcined catalyst, though extensive phase separation occurred during reduction. The promoting effects are apparently due to partial surface coverage of iron with MnO, the extent of which is enhanced by wetter reducing conditions.

  16. Fischer-Tropsch synthesis in slurry reactor systems. Quarterly report, November 1, 1983-January 31, 1984

    SciTech Connect

    Satterfield, C.N.; Bartos, T.; Hanlon, R.; Matsumoto, D.; Stenger, H.

    1984-01-01

    We have now completed and partially analyzed a series of studies on the effects of the nature of the liquid present on activity and seletivity of the Fischer-Tropsch synthesis, and the effects of partial poisoning of the catalyst by H/sub 2/S or dibenzothiophene (DBT). We discovered that the presence of a small amount of DBT (97.8 mg S per g of Fe in the catalyst) cut methane formation nearly in half under a set of reaction conditions of commercial importance (263/sup 0/C, 1.48 MPa, H/sub 2//CO feed ratio = 0.69). The selectivity remained constant for at least 200 hours. This is a very important finding since reduction of methane formation is highly desirable. The catalyst activity simultaneously dropped ten-fold but it should be possible to compensate for this in other ways at least in part such as by operation at higher pressure and/or temperature. Alternately, it may develop that lesser levels of catalyst poisoning may be nearly as effective with less loss of activity. These effects are not observed with H/sub 2/S. As far as we know the effects caused by DBT are brand new and have not been observed before. We plan to exploit this lead in several ways, including optimization of DBT level and reaction conditions; study of other heterocyclic sulfur compounds, effects of activation procedures and correlation of methane selectivity with catalyst carbiding as determined by Mossbauer spectroscopy. Also of some importance was the observation that operation in the presence of an aromatic liquid (phenanthrene) increased the rate of reaction by a factor of 1.5 to 1.8, everything else being held constant.

  17. An innovative catalyst system for slurry-phase Fischer-Tropsch synthesis: Cobalt plus a water-gas-shift catalyst

    SciTech Connect

    Satterfield, C.N.; Yates, I.C.; Chanenchuk, C.

    1991-07-01

    The feasibility of using a mechanical mixture of a Co/MgO/SiO{sub 2} Fischer-Tropsch catalyst and a Cu-ZnO/Al{sub 2}O{sub 3} water-gas-shift (WGS) catalyst for hydrocarbon synthesis in a slurry reactor has been established. Such a mixture can combine the superior product distribution from cobalt with the high activity for the WGS reaction characteristic of iron. Weight ratios of Co/MgO/SiO{sub 2} to Cu-ZnO/Al{sub 2}O{sub 3} of 0.27 and 0.51 for the two catalysts were studied at 240{degrees}C, 0.79 MPa, and in situ H{sub 2}/CO ratios between 0.8 and 3.0. Each catalyst mixture showed stable Fischer-Tropsch activity for about 400 hours-on-stream at a level comparable to the cobalt catalyst operating alone. The Cu-ZnO/Al{sub 2}O{sub 3} catalyst exhibited a very slow loss of activity under these conditions, but when operated alone it was stable in a slurry reactor at 200--220{degrees}C, 0.79--1.48 MPa, and H{sub 2}/CO in situ ratios between 1.0 and 2.0. The presence of the water-gas-shift catalyst did not affect the long-term stability of the primary Fischer-Tropsch selectivity, but did increase the extent of secondary reactions, such as l-alkene hydrogenation and isomerization.

  18. 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.

  19. Synthesis of octane enhancer during slurry-phase Fischer-Tropsch. Quarterly technical progress report No. 4, July 1, 1991--September 30, 1991

    SciTech Connect

    Marcelin, G.

    1991-12-15

    The objective of this project is to investigate three possible routes to the formation of ethers, in particular methyl tert-butyl ether (MTBE), during slurry phase Fischer-Tropsch reaction. The three reaction schemes to be investigated are: Addition of isobutylene during the formation of methanol and/or higher alcohols directly from CO and H{sub 2} during slurry-phase Fischer-Tropsch. Addition of isobutylene to FT liquid products including alcohols in a slurry-phase reactor containing an MTBE or other acid catalyst. Addition of methanol to slurry phase FT synthesis making iso-olefins.

  20. Synthesis of octane enhancers during slurry-phase Fischer-Tropsch. Quarterly technical progress report No. 3, April 1, 1991--June 30, 1991

    SciTech Connect

    Marcelin, G.

    1991-10-15

    The objective of this project is to investigate three possible routes to the formation of ethers, in particular methyl tert-butytl ether (MTBE), during slurry phase Fischer-Tropsch reaction. The three reaction schemes to be investigated are: (1) Addition of isobutylene during the formation of methanol and/or higher alcohols directly from CO and H{sub 2} during slurry-phase Fischer-Tropsch; (2) addition of isobutylene to FT liquid products including alcohols in a slurry-phase reactor containing an MTBE or other acid catalyst; and, (3) addition of methanol to slurry phase FT synthesis making iso-olefins.

  1. Synthesis of octane enhancers during slurry-phase Fischer-Tropsch. Quarterly technical progress report No. 5, October 1, 1991--December 31, 1991

    SciTech Connect

    Marcelin, G.

    1992-06-10

    The objective of this project is to investigate three possible routes to the formation of ethers, in particular methyl tert-butyl ether (MTBE), during slurry phase Fischer-Tropsch reaction. The three reaction schemes to be investigated are: Addition of isobutylene during the formation of methanol and/or higher alcohols directly from CO and H{sub 2} during slurry-phase Fischer-Tropsch. Addition of isobutylene to FT liquid products including alcohols in a slurry-phase reactor containing an MTBE or other acid catalyst. Addition of methanol to slurry phase FT synthesis making iso-olefins.

  2. Effect of 1-olefin addition on supercritical phase Fischer-Tropsch synthesis over Co/SiO{sub 2} catalyst

    SciTech Connect

    Yan, S.R.; Zhang, Z.X.; Zhou, J.L.; Fan, L.; Fujimoto, Kaoru

    1997-12-31

    Hydrocarbon wax produced by Fischer-Tropsch Synthesis (FTS) has been used in many fields for its high quality, such as high melting point, high hardness value, low viscosity, being nitrogen sulfur and aromatics-free. Selective synthesis of FT wax has generated great interest, especially in the case of lower oil-prices. As a polymerization process, however, in conventional gas phase FTS, selectivity of wax is constrained by the Anderson-Schultz-Flory (ASF) kinetics. Supercritical phase Fischer-Tropsch synthesis co-fed with 1-tetradecene over Co/SiO{sub 2} catalysts has been carried out. It was found that added 1-tetradecene could reach the surface of the catalyst by the aid of a supercritical fluid, and participate in the chain growth process there, which was indistinguishable from the original chain propagation. Consequently, the yield of hydrocarbons larger than C{sub 14} increased significantly, while the selectivity of C{sub 1}-C{sub 13} decreased correspondingly, which made the carbon number distribution deviate from ASF kinetics drastically. In addition, the analytical results of wax showed that average molecular weight and degree of saturation of the wax increased, while the content of oxygenates in the wax decreased due to the addition of 1-tetradecene.

  3. 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.

  4. 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.

  5. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1988-01-01

    This report details experiments performed on three different copper-based catalysts: Cu/Cr[sub 2]O[sub 3], Cu/MnO/Cr[sub 2]O[sub 3] and Cu/ZnO/Al[sub 2]O[sub 3]. Of these three catalysts, the Cu/ZnO/Al[sub 2]O[sub 3] exhibits the greatest stability when slurried in octacosane. More than 1000 hours-on-stream indicate that the catalyst activity is not detrimentally affected by high pressure, high H[sub 2]/CO ratio, or the presence of alkenes. All of these are necessary stability characteristics for the water-gas shift catalyst, if it is to be used in combination with a cobalt Fischer-Tropsch catalyst. A review of documented reduction procedures for cobalt-based Fischer-Tropsch catalysts is presented.

  6. 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

  7. Mössbauer investigations of the Fe-Cu-Mn catalysts for Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Spânu, Viorica; Filoti, G.; Ilie, Ioana; Zamfirescu, Elena

    1990-07-01

    In the selective process of the syngas conversion to synthetic gasoline a bifunctional catalytic system has to be used. It was obtained by combination a Fischer-Tropsch catalyst with the HZSM-5 zeolite. The phase compositions of the precursor and the fresh catalyst were established as well as the optimum thermal treatment. The catalyst was reduced in pure H2 or in a H2+CO mixture. The influence of the reduction and reaction conditions on the catalyst structure was investigated.

  8. Ordered mesoporous CoMOx (M = Al or Zr) mixed oxides for Fischer-Tropsch synthesis.

    PubMed

    Ahn, Chang-Il; Lee, Yun Jo; Um, Soong Ho; Bae, Jong Wook

    2016-04-01

    A superior structural stability of the ordered mesoporous CoMOx synthesized by using the KIT-6 template was observed under Fischer-Tropsch reaction conditions. The enhanced stability was attributed to a strong interaction of the irreducible metal oxides with the mesoporous Co3O4 by forming Co3O4-ZrO2 (or Co3O4-Al2O3), which resulted in showing a stable activity. PMID:26963504

  9. Parametric study of Fischer-Tropsch synthesis in supercritical phase carbon dioxide

    NASA Astrophysics Data System (ADS)

    Gautam, Jitendra

    The results from studies on Fischer Tropsch synthesis wherein syngas was dissolved in CO2 are presented. The syngas generally used was typical of that obtained from coal gasification, i.e. CO:H2 of one. Under these conditions Co-based catalysts without any water gas shift catalyst does not perform well while Fe -- based catalysts have been found to be useful. However, the Fe based catalysts have a propensity towards CO2 selectivity via the primary FT reaction, Boudouard reaction and the water gas shift reaction. The use of CO2 as a solvent was found to suppress the CO2 and CH4 selectivity while enhancing the hydrocarbon selectivity and CO conversion when FT synthesis was conducted using coal derived syngas on Fe-Zn-K catalysts. The effects were found to be significantly pronounced at pressures higher than or equal to 1200 psig. It should be noted that CO2 is supercritical at pressures higher than 1070 psig and 31.4 °C. The effect of CO2 partial pressure, reactor pressure, reaction temperature, catalyst loading and H 2:CO ratio in syngas on the liquid product distribution was evaluated. Some of the notable findings include product tenability by varying temperature and pressure as well as varying the CO2 partial pressure and the syngas composition. Increasing the reactor pressure was found to favor longer chain growth. In addition, it was noted that the ratio between CO2:syngas in the reaction mixture is an important factor in the liquid product distribution. A higher value of the ratio is seen to favor hydrocarbon synthesis, while a lower value of the ratio favors oxygenate production particularly pentanols and butanols. In addition, the data on the once through fractionation of the products utilizing the solubilities in supercritical CO2 and pressure tuning were encouraging. It was found that the products can be easily fractionated into narrow carbon chain length distributions downstream of the reactor by simply reducing the pressures in each collection vessel. It

  10. Carbon isotope effects in the open-system Fischer Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Taran, Yuri A.; Kliger, George A.; Sevastianov, Vyacheslav S.

    2007-09-01

    Carbon isotopic composition was measured for products of the Fischer-Tropsch synthesis: catalytic reaction between CO and H 2 to produce CO, CO 2, light hydrocarbons C1-C4 and "oil" fraction. Hydrogen isotopes were also measured in the oil fraction and the produced water. Experimental runs were conducted in the flow-through reactor at 260-310 °C and 30 bar using the synthesis gas composed of 5N 2 + 3H 2 + 2CO, on Fe-catalyst mixed with ZSM-5 synthetic zeolite. In the two of seven runs a Fe + Co-catalyst was used that gives a lower yield of unsaturated hydrocarbons in reaction products. The isotopic effects depended on the conversion of the carbon monoxide. Under steady-state conditions (CO conversion more than 90%) a strong kinetic fractionation was observed between CO and CO 2 (˜-10‰) and CO and hydrocarbons (˜+38‰). At low conversion a clear "inverse" isotopic trend of the depletion in 13C of longer hydrocarbon chains was observed. On average, Δ 12 = δ 13C(CH 4) - δ 13C(C 2H 6) correlates well with the CO conversion: the C 2H 6 is ˜6‰ isotopically lighter than CH 4 at low conversion and ˜2‰ heavier at steady-state regime. Under steady-state conditions there almost no difference was observed in the isotopic composition of methane and ethane and higher hydrocarbons. The chemical composition of light hydrocarbons in the products of flow-through, dynamic FTS is different from that found in the static FTS-type experiments with Fe-catalyst, but isotopic effects are similar. Our results suggest that the isotopic distribution of carbon found in so-called "abiogenic" hydrocarbons from some natural gases (δ 13C1 > δ 13C2 > δ 13C3 >⋯) is somewhat similar to that at low conversion of CO, but do not resemble the distribution characteristic for the high conversion products, at least, on Fe-catalyst. Other processes (a simple mixing of two or more endmembers) or other P-T conditions of the carbon reduction could be responsible for the "inverse" isotopic

  11. Synthesis of octane enhancers during slurry-phase Fischer-Tropsch. [801Methyl tert-butyl ether

    SciTech Connect

    Marcelin, G.

    1992-06-24

    The objective of this project is to investigate three possible routes to the formation of ethers, in particular methyl tert-butyl ether (MTBE), during slurry phase Fischer-Tropsch reaction. The three reaction schemes to be investigated are: (1) Addition of isobutylene during the formation of methanol and/or higher alcohols directly from CO and H{sub 2} during slurry-phase Fischer-Tropsch. (2) Addition of isobutylene to FT liquid products including alcohols in a slurry-phase reactor containing an MTBE or other acid catalyst. (3) Addition of methanol to slurry phase FT synthesis making iso-olefins. During the sixth quarter we completed the construction of the slurry bubble column reactor (SBCR), conducted initial shake-down experiments in a cold-flow mode, and finalized the selection process of the acid catalysts for conversion of syngas-produced alcohols and isobutylene to MTBE (scheme 2). Tasks 3, 4, and 5 are awaiting complete implementation of the SBCR system.

  12. 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

  13. 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.

  14. Role of CO{sub 2} in the initiation of chain growth during the Fischer-Tropsch Synthesis

    SciTech Connect

    Raje, A.P.; Davis, B.H.

    1996-10-01

    Data is presented to show that alcohols produce hydrocarbons during the Fischer-Tropsch Synthesis (FTS) that are not consistent with a simple initiation mechanism. The data is believed to be consistent with accumulation of hydrocarbon products in the reactor during the synthesis. CO{sub 2} is produced directly from the alcohol, and not by the reverse carbonylation reaction. CO{sub 2} also initiates chain growth in the FTS, and the initiation intermediate is presumed to be the same intermediate as in the water-gas-shift reaction. The data from the conversion with added {sup 14}CO{sub 2} are therefore inconsistent with the widely accepted carbide intermediate for FTS with an iron catalyst. The analysis of the heavier hydrocarbons indicate that it is likely that the chain growth involves two independent chains.

  15. Role of CO{sub 2} in the initiation of chain growth during the Fischer-Tropsch synthesis

    SciTech Connect

    DAvis, B.H.; Xu, L.; Bao, S.

    1995-12-01

    Data is presented to show that alcohols produce hydrocarbons during the Fischer-Tropsch Synthesis (FTS) that are not consistent with a simple initiation mechanism. The data is believed to be consistent with accumulation of hydrocarbon products in the reactor during the synthesis. CO{sub 2} is produced directly from the alcohol, and not by the reverse carbonylation reaction. CO{sub 2} also initiates chain growth in the FTS, and the initiation intermediate is presumed to be the same intermediate as in the water-gas-shift reaction. The data from the conversion with added {sup 14}CO{sub 2} are therefore inconsistent with the widely accepted carbide intermediate for FTS with an iron catalyst.

  16. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Chanenchuk, C.A.; Yates, I.C.; Satterfield, C.N.

    1990-01-01

    A Co/MgO/SiO[sub 2] Fischer-Tropsch catalyst was operated simultaneously with a Cu/ZnO/Al[sub 2]O[sub 3] water-gas-shift catalyst in a slurry reactor for over 400 hours. The process conditions were held constant at a temperature of 240[degrees]C, a pressure of 0.79 MPa, and a 1.1 H[sub 2]/CO feed of 0.065 Nl/min-g.cat. The Fischer-Tropsch activity remained constant at the level predicted by the operation of the Co/MgO/SiO[sub 2] catalyst alone. The water-gas-shift reaction was near equilibrium. The hydrocarbon product distribution of the combined catalyst system was stable and matched that of the CO/MgO/SiO[sub 2] operating alone under similar conditions. The combined catalyst system exhibited a high selectivity to n-alkanes. Neither catalysts's operation appeared to have a detrimental effect on that of the other, showing promise for future option.

  17. Studies on the Role of Nitrogen in the Feed for Fischer-Tropsch Synthesis Under Fixed-Bed Reactor System.

    PubMed

    Hong, Gi Hoon; Jung, Jae-Sun; Kim, Na-Young; Lee, Sang Yong; Moon, Dong Ju

    2016-02-01

    In this study, Co/Al203 catalyst for Fischer-Tropsch synthesis was prepared via slurry impregnation method and the catalyst was characterized by various techniques such as TPR, XRD, TGA and N2 physisorption. To dissolve the wax, after-reaction catalyst was dewaxed using n-Hexane at 60 *C. The experiments were performed in a bench-scale fixed-bed reactor, under the reaction condition of 230 degrees C, 20 bar and feed volume ratio of H2:CO:N2 = 2:1:0.5-1.5. The methane selectivity and the ratio of olefin to paraffin among C2-C4 hydrocarbons were increased with higher contents of nitrogen in feed gas which result in higher partial pressure ratio of H2 to CO, and also affect methane selectivity which has a significant role in increased CO conversion. PMID:27433695

  18. Thermodynamic analysis of nanoparticle size effect on kinetics in Fischer-Tropsch synthesis by lanthanum promoted iron catalyst

    NASA Astrophysics Data System (ADS)

    Nakhaei Pour, Ali; Housaindokht, Mohammad Reza; Behroozsarand, Alireza; Khodagholi, Mohammad Ali

    2014-08-01

    The kinetic parameters of the Fischer-Tropsch synthesis (FTS) on iron catalyst are analyzed by size-dependent thermodynamic method. A Langmuir-Hinshelwood kinetic equation is considered for evaluation of catalytic activity of lanthanum promoted iron catalyst. A series of unsupported iron catalysts with different particle sizes were prepared via microemulsion method. The experimental results showed that catalyst activity pass from a maximum value by increasing the iron particle size. Also, data presented that iron particle size has considerable effects on adsorption parameters and FTS rates. The ratio of surface tension ( σ) to nanoparticle radius ( r) is important in FTS reaction on iron catalyst. Finally, the results showed that by increasing of iron particle size from 18 to 45 nm the activation energies of catalysts and heats of adsorption of catalysts as two main parameters of FTS reaction increased from 89 to 114 kJ/mol and from 51 to 71 kJ/mol, respectively.

  19. Enhanced Fischer-Tropsch synthesis performance of iron-based catalysts supported on nitric acid treated N-doped CNTs

    NASA Astrophysics Data System (ADS)

    Li, Zhenhua; Liu, Renjie; Xu, Yan; Ma, Xinbin

    2015-08-01

    Iron-based catalysts supported on N-doped CNTs (NCNTs) treated by various concentrations of nitric acid for Fischer-Tropsch synthesis (FTS) were investigated. An improved catalytic performance for the iron catalyst supported on acid treated NCNTs was obtained and the suitable nitric acid concentration was 10 M. The physiochemical properties of the NCNTs and the corresponding catalysts were characterized by BET, TEM, XRD, XPS, TGA and H2-TPR. The acid treatment removed the impurity and amorphous carbon, damaged the bamboo-like structure and increased the number of oxygen-containing functional groups and graphitization degree on the NCNTs. The more iron particles located inside the channels of NCNTs, the better catalytic FTS performance due to high dispersion and reducibility.

  20. 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).

  1. 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.

  2. Reoxidation and deactivation of supported cobalt Fischer-Tropsch catalysts

    SciTech Connect

    Schanke, D.; Hilmen, A.M.; Bergene, E.

    1995-12-01

    The Fischer-Tropsch synthesis is an attractive possibility for conversion of natural gas into high quality liquid fuels. Due to its low water-gas shift activity, good activity/selectivity properties and relatively low price, cobalt is the choice of catalytic metal for natural gas conversion via Fischer-Tropsch synthesis. In the cobalt-catalyzed Fischer-Tropsch reaction, oxygen is mainly rejected as water. In this paper we describe the influence of water on supported cobalt catalysts. The deactivation of supported Co catalysts was studied in a fixed-bed reactor using synthesis gas feeds containing varying concentrations of water vapour.

  3. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, October 1, 1989--December 31, 1989

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1989-12-31

    The rate of synthesis gas consumption over a cobalt FischerTropsch catalyst was measured in a well-mixed, continuous-flow, slurry reactor at 220 to 240{degrees}C, 0.5 to 1.5 MPa, H{sub 2}/CO feed ratios of 1.5 to 3.5 and conversions of 7 to 68% of hydrogen and 11 to 73% of carbon monoxide. The inhibiting effect of carbon monoxide was determined quantitatively and a Langmuir-Hinshelwood-type equation of the following form was found to best represent the results: -R{sub H{sub 2+Co}} = (a P{sub CO}P{sub H{sub 2}})/(1 + b P{sub CO}){sup 2}. The apparent activation energy was 93 to 95 kJ/mol. Data from previous studies on cobalt-based Fischer-Tropsch catalysts are also well correlated with this rate expression.

  4. Upgrading oxygenated Fischer-Tropsch derivatives and one-step direct synthesis of ethyl acetate from ethanol - examples of the desirability of research on simple chemical compounds transformations.

    PubMed

    Klimkiewicz, Roman

    2014-01-01

    Oxygenates formed as by-products of Fischer-Tropsch syntheses can be transformed into other Fischer-Tropsch derived oxygenates instead of treating them as unwanted chemicals. One-step direct synthesis of ethyl acetate from ethanol is feasible with the use of some heterogeneous catalysts. Despite their apparent simplicity, both transformations are discussed as targeted fields of research. Furthermore, the two concepts are justified due to the environmental protection. Arguments regarding the Fischer-Tropsch process are focused on the opportunities of the utilization of undesirable by-products. The effective striving for their utilization can make the oxygenates the targeted products of this process. Arguments regarding the one-step direct synthesis of ethyl acetate underline the environmental protection and sustainability as a less waste-generating method but, above all, highlight the possibility of reducing the glycerol overproduction problem. The production of ethyl acetate from bioethanol and then transesterification of fats and oils with the use of ethyl acetate allows managing all the renewable raw materials. Thus, the process enables the biosynthesis of biodiesel without glycerine by-product and potentially would result in the increase in the demand for ethyl acetate. Graphical Abstract. PMID:25648719

  5. Slurry-phase Fischer-Tropsch synthesis and kinetic studies over supported cobalt carbonyl derived catalysts

    SciTech Connect

    Withers, H.P. Jr.; Eliezer, K.F.; Mitchell, J.W. )

    1990-09-01

    This paper reports the preparation characterization, and performance of cobalt carbonyl cluster based catalysts for use in slurry-phase Fischer--Tropsch (FT) technology investigated. Using metal carbonyls as active metal precursors allows for the control of metal particle size on the support surface, thus offering the potential for better control of activity and selectivity of the FT reaction. Silica as the support provided the highest catalyst activities. A Co{sub 2}(CO){sub 8}/Zr(OPr){sub 4}/SiO{sub 2} catalyst (3.5% cobalt, 6.6% zirconium) was developed as the most active system in the FT slurry reactor and also gave the best liquid fuel selectivity. Selectivity patterns correlated to the Schulz--Flory prediction. These catalysts exhibited low water/gas shift activity. Diesel fuel product produced by this catalyst was high quality. A kinetic expression that took water inhibition into account was verified, yielding an activation energy of 97 kJ/mol for syngas conversion ranging from 34% to 71% at 240--280{degrees} C.

  6. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1988-01-01

    A cobalt Fischer-Tropsch catalyst (CO/MgO/silica) was reduced and slurried in combination with reduced Cu/ZnO/Al[sub 2]0[sub 3] water-gas-shift catalyst. Combined catalyst system was run at fixed process conditions for more than 400 hours. The system showed stable selectivity. The Cu/ZnO/Al[sub 2]0[sub 3] water-gas-shift catalyst remained reasonably active in the presence of the cobalt catalyst. Hydrocarbon selectivity of the cobalt and Cu/ZnO/Al[sub 2]0[sub 3] catalyst system compared favorably to selectivity of iron-based catalysts. Methane selectivity was slightly higher for the cobalt-based system, but C[sub 5][sup +] selectivity was essentially the same. The hydrocarbon product distribution appeared to exhibit a double-a behavior. a[sub 1] was near 0.80 which is higher than that of iron catalysts, while a[sub 2] was calculated to be 0.86 which is somewhat lower than would be typical for an iron-based catalyst.

  7. 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.

  8. Shape and Size of Cobalt Nanoislands Formed Spontaneously on Cobalt Terraces during Fischer-Tropsch Synthesis.

    PubMed

    Banerjee, Arghya; Navarro, Violeta; Frenken, Joost W M; van Bavel, Alexander P; Kuipers, Herman P C E; Saeys, Mark

    2016-06-01

    Cobalt-based catalysts undergo a massive and spontaneous reconstruction to form uniform triangular nanoislands under Fischer-Tropsch (FT) conditions. This reconstruction is driven by the unusual and synergistic adsorption of square-planar carbon and CO at the 4-fold edge sites of the nanoislands, driving the formation of triangular islands. The size of the nanoislands is determined by the balance between energy gain from creating C/CO-covered edges and energy penalty to create C/CO-covered corners. For carbon chemical potentials corresponding to FT conditions, triangular Co islands with 45 Co atoms (about 2 nm) are the most stable surface structure. Decreasing the carbon chemical potential and hence the stability of square-planar carbon favors the formation of larger islands, until reconstruction becomes unfavorable and CO-covered terraces are thermodynamically the most stable. The predicted structure of the islands is consistent with in situ scanning tunneling microscopy images obtained for the first time under realistic FT reaction conditions on a Co(0001) surface. PMID:27176712

  9. Proposal of a new product characterization model for the iron-based low-temperature Fischer-Tropsch synthesis

    SciTech Connect

    F. Gideon Botes

    2007-06-15

    A new product characterization model has been proposed for the iron-based low-temperature Fischer-Tropsch (Fe-LTFT) synthesis. The chain-length-dependent desorption model is based on the premise that the increase in chain-growth probability and decrease in the olefin/paraffin ratio with the carbon number in the Fe-LTFT synthesis is essentially a characteristic of the primary product spectrum. The model could successfully describe the olefin and paraffin distributions in the C{sub 3+} range. The ethylene/ethane ratio is overestimated by the model because of the high reactivity of ethylene for secondary hydrogenation. However, the total C{sub 2} formation rate was predicted almost perfectly, while the methane formation rate was described adequately, using parameter values that were obtained from the C{sub 3}-C{sub 10} product fraction. This is a true extrapolation, because the C{sub 1} and C{sub 2} data were not used at all for the estimation of the parameter values. This may be the first product characterization model that can successfully be extrapolated to the C{sub 1} and C{sub 2} components without introducing additional (unique) parameter values for these products. 26 refs., 6 figs., 1 tab.

  10. Study of the carburization of an iron catalyst during the Fischer-Tropsch synthesis: influence on its catalytic activity

    SciTech Connect

    Pijolat, M.; Perrichon, V.; Bussiere, P.

    1987-09-01

    The fast transformation of an ironalumina catalyst into Fe/sub 2+x/C during the H/sub 2/ + CO reaction was followed by in situ Moessbauer spectroscopy at 523 K and the behavior was compared with changes in catalytic activity for Fischer-Tropsch synthesis. After a few hours of synthesis, no metallic iron could be detected by either Moessbauer or IR spectroscopy, whereas the CO conversion was still half of that observed initially. The nature of the sites responsible for the remaining activity is discussed. The interpretation of the Moessbauer spectra has permitted the determination of the stoichiometry of the Fe/sub 2+x/C carbide (0 less than or equal to x less than or equal to 0.4), and hence the following of the change of x during the reaction. Thus, the activity in CO hydrogenation could be related to the number of carbon vacancies in the iron carbide, i.e., to the extent of the metallic character of this carbide. This concept of the variation of hydrogenating properties of the carbide with the carbon content has been supported by similar catalytic results obtained in the room temperature hydrogenation of ethylene performed on carbides of different stoichiometry

  11. 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.

  12. 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

  13. 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.

  14. 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. PMID:27433672

  15. Mathematical modeling of Fischer-Tropsch synthesis in an industrial slurry bubble column - article no. A 23

    SciTech Connect

    Nasim Hooshyar; Shohreh Fatemi; Mohammad Rahmani

    2009-07-01

    The increase in society's need for fuels and decrease in crude oil resources are important reasons to make more interest for both academic and industry in converting gas to liquids. Fischer-Tropsch synthesis is one of the most attractive methods of Gas-to-Liquids (GTL) processes and the reactor in which, this reaction occurs, is the heart of this process. This work deals with modeling of a commercial size slurry bubble column reactor by two different models, i.e. single bubble class model (SBCM) and double bubble class model (DBCM). The reactor is assumed to work in a churn-turbulent flow regime and the reaction kinetic is a Langmuir-Hinshelwood type. Cobalt-based catalyst is used for this study as it plays an important role in preparing heavy cuts and the higher yield of the liquid products. Parameter sensitivity analysis was carried out for different conditions such as catalyst concentration, superficial gas velocity, H{sub 2} over CO ratio, and column diameter. The results of the SBCM and DBCM revealed that there is no significant difference between single and double bubble class models in terms of temperature, concentration and conversion profiles in the reactor, so the simpler SBCM with less number of model parameters can be a good and reliable model of choice for analyzing the slurry bubble column reactors.

  16. The influence of particle size and structure on the Mossbauer spectra of iron carbides formed during Fischer-Tropsch synthesis

    SciTech Connect

    Gatte, R.R.; Phillips, J.

    1986-01-01

    Characterization of the active and stable phase of iron-based Fischer-Tropsch catalysts has been a topic of investigation for several years. Yet, a great deal of controversy still surrounds the identity of the phase(s) present during synthesis. This stems from the fact that neither X-ray nor Mossbauer studies have proven capable of unambiguously characterizing the metastable carbides formed. Investigations of the metastable, octahedral carbides (as they have been termed) have been going on for many years, dating back to at least 1949. The iron structure has been assigned as HCP (or 'nearly' HCP) with the carbon atoms occupying the octahedral holes. The most notable of these are the epsilon and epsilon' carbides. X-ray results have, however, been rather unsatisfactory for many reasons. For instance, the commercial catalysts studied contained many metallic additives and in most cases the small crystallite sizes gave rise to broad, poorly resolved lines. In recent years, emphasis has shifted toward the use of Mossbauer spectroscopy for in-situ studies of the carburization behavior. It is shown that if spectra are collected for a single sample over a range of temperatures, and if relaxation effects are properly accounted for, the Mossbauer results can give not only accurate identification of the phase(s) present but also quantitative particle size information and qualitative information regarding particle structure and the nature of particle/support interaction.

  17. 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.

  18. 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.

  19. Reoxidation and deactivation of supported cobalt Fischer-Tropsch catalysts

    SciTech Connect

    Schanke, D.; Bergene, E.; Adnanes, E.

    1995-12-31

    As a result of the highly exothermic nature of the Fischer-Tropsch reaction, heat transfer considerations limit the maximum conversion per pass in fixed-bed processes, whereas slurry reactors can operate at higher conversions. During Fischer-Tropsch synthesis on cobalt catalysts, high conversions will generate high partial pressures of water at the reactor exit, due to the low water gas shift activity of cobalt. In addition, the extensive back-mixing in slurry reactors will give a relatively uniform concentration profile in the reactor, characterized by a high concentration of water and low reactant concentrations. From the commercial iron-catalyzed Fischer-Tropsch synthesis in fixed-bed (Arge) reactors it is known that the catalyst deactivates by oxidation of iron by CO{sub 2} and H{sub 2}O near the exit of the reactor. Although bulk oxidation of cobalt during Fischer-Tropsch synthesis is not thermodynamically favored, it was early speculated that surface oxidation of cobalt could occur during Fischer-Tropsch synthesis. The purpose of the present work is to describe the influence of water on the deactivation behavior of Al{sub 2}O{sub 3} supported cobalt catalysts. The possibility of cobalt oxidation during Fischer-Tropsch synthesis was investigated by model studies.

  20. A new synthesis of carbon encapsulated Fe5C2 nanoparticles for high-temperature Fischer-Tropsch synthesis.

    PubMed

    Hong, Seok Yong; Chun, Dong Hyun; Yang, Jung-Il; Jung, Heon; Lee, Ho-Tae; Hong, Sungjun; Jang, Sanha; Lim, Jung Tae; Kim, Chul Sung; Park, Ji Chan

    2015-10-28

    Using a simple thermal treatment under a CO flow, uniform micrometer-sized iron oxalate dihydrate cubes prepared by hydrothermal reaction were transformed into Fe5C2@C nanoparticles to form a mesoporous framework; the final structure was successfully applied to the high-temperature Fischer-Tropsch reaction and it showed high activity (CO conversion = 96%, FTY = 1.5 × 10(-4) molCO gFe(-1) s(-1)) and stability. PMID:26416550

  1. Study of Fischer-Tropsch synthesis over iron-based catalysts using a well-stirred slurry reactor

    SciTech Connect

    Dictor, R.A.

    1984-01-01

    Fischer-Tropsch synthesis over iron catalysts has been researched for well over 60 years, yet relatively few detailed investigations of the kinetics and selectivity of hydrocarbon synthesis have been done using unpromoted bulk iron-based catalysts. In this investigation, Fe/sub 2/O/sub 3/, potassium-promoted Fe/sub 2/O/sub 3/, fused iron, Fe/sub 3/C, and Fe were tested for their activity and selectivity for hydrocarbon synthesis, and comparisons were made between the catalysts. Experiments were done using a well-stirred slurry reaction which was free of temperature and concentration gradients. The effluent from the reactor was analyzed on line using a dual-column gas chromatograph. The compositions of fresh and used catalyst samples were determined using X-ray diffraction. The activity of fused iron catalyst increases with extent of reduction in H/sub 2/ - attributed to increases in surface area. Principal products are normal 1-olefins and paraffins, CO/sub 2/, H/sub 2/O; branched olefins, aldehydes and alcohols are also formed. The catalyst has very little hydrogenation or isomerization activity due to potassium promotion. Aldehydes reduce to alcohols; the water-gas-shift reaction occurs. The kinetics and selectivity observed using potassium-promoted Fe/sub 2/O/sub 3/ were nearly identical to those of fused iron. In the absence of promoter, the products are almost exclusively n-olefins, n-paraffins, CH/sub 3/OH, H/sub 2/O, CO/sub 2/. Fe/sub 2/O/sub 3/ is active for hydrogenation and isomerization.

  2. Fischer-Tropsch synthesis: kinetics and effect of water for a Co/SiO{sub 2} catalyst

    SciTech Connect

    Tapan K. Das; Whitney A. Conner; Jinlin Li; Gary Jacobs; Mark E. Dry; Burtron H. Davis

    2005-08-01

    The addition of water during Fischer-Tropsch synthesis over a 12.4 wt% Co/SiO{sub 2} catalyst led to a significant increase in CO conversion. A positive reversible impact of water on catalyst activity was observed at partial pressures of water of {lt}25 vol% added H{sub 2}O. The CO conversion recovered to the reference activity after the termination of water addition. Therefore, this enhanced reversible activity for Co/SiO{sub 2} catalysts seems to be due to a kinetic effect of water. The catalyst was characterized using different techniques, including temperature-programmed reduction (TPR), Brunauer-Emmett-Teller (BET) surface area analysis, and H{sub 2} chemisorption. The rate expression has been obtained over the catalyst, using a 1-L continuously stirred tank reactor (CSTR) that was operated at a temperature of 483 K, a pressure of 2.21 MPa (21.42 atm), H{sub 2}/CO feed ratios of 1.0-2.4, and 10%-70% CO conversion over a range of reactant partial pressures. The data of this study are fitted by a power-law expression of the form r{sub CO} = kP{sub CO}{sup -0.25}P{sub H{sub 2}}{sup -.5}/(1 + mP{sub H{sub 2}O}/P{sub H{sub 2}), where k = 0.89 mol h{sup -1} g{sub cat}{sup -1} and m = -0.155. 41 refs., 13 figs., 8 tabs.

  3. Evidence of highly active cobalt oxide catalyst for the Fischer-Tropsch synthesis and CO2 hydrogenation.

    PubMed

    Melaet, Gérôme; Ralston, Walter T; Li, Cheng-Shiuan; Alayoglu, Selim; An, Kwangjin; Musselwhite, Nathan; Kalkan, Bora; Somorjai, Gabor A

    2014-02-12

    Hydrogenations of CO or CO2 are important catalytic reactions as they are interesting alternatives to produce fine chemical feedstock hence avoiding the use of fossil sources. Using monodisperse nanoparticle (NP) catalysts, we have studied the CO/H2 (i.e., Fischer-Tropsch synthesis) and CO2/H2 reactions. Exploiting synchrotron based in situ characterization techniques such as XANES and XPS, we were able to demonstrate that 10 nm Co NPs cannot be reduced at 250 °C while supported on TiO2 or SiO2 and that the complete reduction of cobalt can only be achieved at 450 °C. Interestingly, cobalt oxide performs better than fully reduced cobalt when supported on TiO2. In fact, the catalytic results indicate an enhancement of 10-fold for the CO2/H2 reaction rate and 2-fold for the CO/H2 reaction rate for the Co/TiO2 treated at 250 °C in H2 versus Co/TiO2 treated at 450 °C. Inversely, the activity of cobalt supported on SiO2 has a higher turnover frequency when cobalt is metallic. The product distributions could be tuned depending on the support and the oxidation state of cobalt. For oxidized cobalt on TiO2, we observed an increase of methane production for the CO2/H2 reaction whereas it is more selective to unsaturated products for the CO/H2 reaction. In situ investigation of the catalysts indicated wetting of the TiO2 support by CoO(x) and partial encapsulation of metallic Co by TiO(2-x). PMID:24460136

  4. Iron oxide pillared clay with large gallery height: Synthesis and properties as a Fischer-Tropsch catalyst

    SciTech Connect

    Rightor, E.G.; Tsou, Mingshin; Pinnavaia, T.J. )

    1991-07-01

    New iron oxide pillared montmorillonites have been prepared by the reaction of Na{sup +} montmorillonite with base-hydrolyzed solutions of Fe{sup 3+} salts and subsequent thermal conversion of the intercalated polycations. Depending on the hydrolysis conditions used to generate the pillaring solutions, pillared products with basal spacings in the range 18 to 25 {angstrom} were obtained. Under optimum hydrolysis conditions (base/metal = 2.0 meq/mol, aging time = 23-147 hr) the pillared products contained 6.8-9.8 Fe{sup 3+} ions per O{sub 20}(OH){sub 4} unit cell and exhibited basal spacings of 25-29 {angstrom}. These latter spacings corresponded to exceptionally large gallery heights of 15-19 {angstrom}. Upon calcination at 300C, the spacings decreased to 23-27 {angstrom}. N{sub 2} BET surface areas after outgassing at 350C were in the range 270 to 350 m{sup 2}/g. The pillared products are active catalysts that have undergone Fischer-Tropsch synthesis of hydrocarbons at 275 C and 120 {minus}psi (CO:H{sub 2}=1:2). The hydrocarbon distribution in the C{sub 1}-C{sub 6} range (1.3% conversion) followed Anderson-Schulz-Flory statistics with a chain propagation probability of {alpha} = 0.49. X-ray energy dispersive analysis indicated that substantial amounts of the intercalated iron migrated to the edge sites of the clay particles under reaction conditions. The redistribution of iron resulted in a distribution of gallery heights sufficiently heterogeneous to preclude Bragg X-ray scattering along the 001 direction. Iron migration also occurred upon exposure of the pillared products to the ambient atmosphere for prolonged periods ({ge}3 months).

  5. Kinetically Relevant Steps and H2/D2 Isotope Effects in Fischer-Tropsch Synthesis on Fe and Co Catalysts

    SciTech Connect

    Ojeda, Manuel; Li, Anwu; Nabar, Rahul P.; Nilekar, Anand U.; Mavrikakis, Manos; Iglesia, Enrique

    2010-11-25

    H2/D2 isotope effects on Fischer-Tropsch synthesis (FTS) rate and selectivity are examined here by combining measured values on Fe and Co at conditions leading to high C5+ yields with theoretical estimates on model Fe(110) and Co(0001) surfaces with high coverages of chemisorbed CO (CO*). Inverse isotope effects (rH/rD < 1) are observed on Co and Fe catalysts as a result of compensating thermodynamic (H2 dissociation to H*; H* addition to CO* species to form HCO*) and kinetic (H* reaction with HCO*) isotope effects. These isotopic effects and their rigorous mechanistic interpretation confirm the prevalence of H-assisted CO dissociation routes on both Fe and Co catalysts, instead of unassisted pathways that would lead to similar rates with H2 and D2 reactants. The small contributions from unassisted pathways to CO conversion rates on Fe are indeed independent of the dihydrogen isotope, as is also the case for the rates of primary reactions that form CO2 as the sole oxygen rejection route in unassisted CO dissociation paths. Isotopic effects on the selectivity to C5+ and CH4 products are small, and D2 leads to a more paraffinic product than does H2, apparently because it leads to preference for chain termination via hydrogen addition over abstraction. These results are consistent with FTS pathways limited by H-assisted CO dissociation on both Fe and Co and illustrate the importance of thermodynamic contributions to inverse isotope effects for reactions involving quasi-equilibrated H2 dissociation and the subsequent addition of H* in hydrogenation catalysis, as illustrated here by theory and experiment for the specific case of CO hydrogenation.

  6. Diffusion limitations in Fischer-Tropsch catalysts

    SciTech Connect

    Post, M.F.M.; Van'tHoog, A.C.; Minderhoud, J.K.; Sie, S.T. . Lab.)

    1989-07-01

    The extent of diffusion limitations in the catalytic conversion of synthesis gas to hydrocarbons by the Fischer-Tropsch reaction has been established for a number of iron- and cobalt-based catalysts. The studies were performed in a fixed-bed microreactor system at temperatures in the range 473-523 {Kappa}. Variation of catalyst particle size in the range 0.2.-2.6 mm shows that the conversion of synthesis gas decreases considerably when the average particle size is increased. The effects of variation of particle size and pore diameter have been quantified with the Thiele model for diffusion limitations. Evidence has accumulated that the limited mobility of reactant molecules in the liquid-filled pores of Fischer-Tropsch catalysts is the main cause of retardation of the reaction rates. The experimentally determined reaction rates with various catalysts operated under different conditions show an excellent fit with the theoretical model.

  7. An innovative catalyst system for slurry-phase Fischer-Tropsch synthesis: Cobalt plus a water-gas-shift catalyst. Final technical report

    SciTech Connect

    Satterfield, C.N.; Yates, I.C.; Chanenchuk, C.

    1991-07-01

    The feasibility of using a mechanical mixture of a Co/MgO/SiO{sub 2} Fischer-Tropsch catalyst and a Cu-ZnO/Al{sub 2}O{sub 3} water-gas-shift (WGS) catalyst for hydrocarbon synthesis in a slurry reactor has been established. Such a mixture can combine the superior product distribution from cobalt with the high activity for the WGS reaction characteristic of iron. Weight ratios of Co/MgO/SiO{sub 2} to Cu-ZnO/Al{sub 2}O{sub 3} of 0.27 and 0.51 for the two catalysts were studied at 240{degrees}C, 0.79 MPa, and in situ H{sub 2}/CO ratios between 0.8 and 3.0. Each catalyst mixture showed stable Fischer-Tropsch activity for about 400 hours-on-stream at a level comparable to the cobalt catalyst operating alone. The Cu-ZnO/Al{sub 2}O{sub 3} catalyst exhibited a very slow loss of activity under these conditions, but when operated alone it was stable in a slurry reactor at 200--220{degrees}C, 0.79--1.48 MPa, and H{sub 2}/CO in situ ratios between 1.0 and 2.0. The presence of the water-gas-shift catalyst did not affect the long-term stability of the primary Fischer-Tropsch selectivity, but did increase the extent of secondary reactions, such as l-alkene hydrogenation and isomerization.

  8. Bulk and surface structure of a Ni Fe/Al2O3 catalyst for Fischer-Tropsch synthesis studied by Mössbauer, infrared spectroscopy and magnetic methods

    NASA Astrophysics Data System (ADS)

    Boellaard, E.; van der Kraan, A. M.; Geus, J. W.

    1992-04-01

    Deposition precipitation of a stoichiometric nickel-ironcyanide complex onto an alumina support and subsequent calcination and reduction has resulted in the formation of a homogeneous metallic alloy which exhibits activity for Fischer-Tropsch synthesis. During hydrocarbon synthesis conditions only a fraction of the metallic phase is converted in a phase which is most likely a thermally unstable (nickel-)iron carbide.

  9. Application of a novel TPR EXAFS/XANES method using a multi-sample holder to characterize promoted iron and cobalt fFischer-Tropsch synthesis catalysts.

    SciTech Connect

    Jacobs, G.; Sarkar, A.; Ji, Y.; Davis, B. H.; Cronauer, D.; Kropf, A. J.; Marshall, C. L.; Chemical Sciences and Engineering Division; Univ. of Kentucky

    2008-01-01

    Coal-to-liquids. Iron-based Fischer-Tropsch synthesis catalysts are not only used commercially for high temperature Fischer-Tropsch synthesis, but are increasingly becoming the focus for converting low H{sub 2}/CO ratio synthesis gas at lower temperature. Such low temperature processing yields hydrocarbon distributions with higher {alpha} values, and as a consequence, much less light hydrocarbon gas production (and especially, less methane). Another benefit to the use of iron-based catalysts is that the product slate is richer in {alpha}-olefinic products, which are more valuable than the paraffinic products produced using cobalt-based catalysts. Iron-based catalysts are often used to convert low H{sub 2}/CO ratio syngas, because the catalysts can intrinsically adjust the syngas ratio upward by converting a fraction of CO by reaction with H{sub 2}O to produce H{sub 2} and CO{sub 2} via the water-gas shift reaction.

  10. Low nitrogen iron-containing Fischer-Tropsch catalyst for conversion of synthesis gas and process for preparing the catalyst

    SciTech Connect

    Bell, W.K.; Haag, W.O.; Kirker, G.W.; Klocke, D.J.

    1986-10-14

    A process is described for preparing an iron-containing Fischer-Tropsch catalyst by continuously precipitating an aqueous solution containing iron nitrate with aqueous ammonia, to form a precipitate-containing product which is thereafter dried. In the improvement described here a catalyst containing less than 500 ppm nitrogen is produced which comprises maintaining a pH of about 6.5 to 6.9 and a temperature of about 70/sup 0/ to 100/sup 0/ C. during precipitation.

  11. Fischer-tropsch synthesis in supercritical fluids. Quarterly technical progress report, October 1, 1994--December 21, 1994

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1995-01-31

    Progress reports are presented for the following two tasks: (1) diffusion coefficients of F-T products in supercritical fluids; and (2) Fischer-Tropsch reaction related studies. The objectives for this quarter for task 1 were to measure molecular diffusion coefficients and effective diffusivities at the same conditions. The objectives for task 2 were to conduct two additional tests with the Ruhrchemie catalyst and a catalyst synthesized in our laboratory under supercritical conditions.

  12. Synthesis of octane enhancers during slurry-phase Fischer-Tropsch. Quarterly technical progress report No. 7, April 1, 1992--June 30, 1992

    SciTech Connect

    Marcelin, G.

    1992-09-24

    The objective of this project is to investigate three possible routes to the formation of ethers, in particular methyl tert-butyl (MTBE), during slurry phase Fischer-Tropsch reaction. The three reaction schemes to be investigated are: addition of i-butylene during the formation of methanol and/or higher alcohols directly from CO and H{sub 2} during slurry-phase Fischer-Tropsch; addition of i-butylene to FT liquid products including alcohols in a slurry-phase reactor containing an MTBE or other acid catalyst; and addition of methanol to slurry phase FT synthesis making iso-olefins. During the seventh quarter we continued the shake down experiments for the SBCR and conducted an initial aborted run. We have also re-started experiments on Scheme 1, i.e., the addition of iso-butylene during CO hydrogenation. Using a dual bed arrangement, we have demonstrated the synthesis of MTBE from syngas and iso-butylene.

  13. Fe5C2 nanoparticles: a facile bromide-induced synthesis and as an active phase for Fischer-Tropsch synthesis.

    PubMed

    Yang, Ce; Zhao, Huabo; Hou, Yanglong; Ma, Ding

    2012-09-26

    Iron carbide nanoparticles have long been considered to have great potential in new energy conversion, nanomagnets, and nanomedicines. However, the conventional relatively harsh synthetic conditions of iron carbide hindered its wide applications. In this article, we present a facile wet-chemical route for the synthesis of Hägg iron carbide (Fe(5)C(2)) nanoparticles, in which bromide was found to be the key inducing agent for the conversion of Fe(CO)(5) to Fe(5)C(2) in the synthetic process. Furthermore, the as-synthesized Fe(5)C(2) nanoparticles were applied in the Fischer-Tropsch synthesis (FTS) and exhibited intrinsic catalytic activity in FTS, demonstrating that Fe(5)C(2) is an active phase for FTS. Compared with a conventional reduced-hematite catalyst, the Fe(5)C(2) nanoparticles showed enhanced catalytic performance in terms of CO conversion and product selectivity. PMID:22938192

  14. Recent developments in the application of nanomaterials to understanding molecular level processes in cobalt catalysed Fischer-Tropsch synthesis.

    PubMed

    Beaumont, S K

    2014-03-21

    This perspective offers an overview of using nanomaterials for understanding cobalt catalysed Fischer-Tropsch chemistry. Nanomaterials now afford unprecedented control of size, shape and structure at the nanometre scale. This makes them invaluable tools for studying heterogeneous catalysis. The Fischer-Tropsch reaction, especially using cobalt based catalysts, is a linchpin in many processes for utilising other feedstocks (via gasification) that have been envisaged as short/medium term replacements for crude oil. The underlying chemistry has therefore garnered considerable renewed interest. The current state of the art in mechanistic understanding is summarised and the application of nanomaterials to developing this further is explored. Several specific questions, to which nanomaterials have already contributed answers, are addressed: how do nanomaterials contribute to our understanding of cobalt particle size effects, reducibility, and the effect of support porosity and how do precious metal promoters operate in cobalt catalysed Fischer-Tropsch chemistry? Future possible uses for nanomaterials in studying this field are also identified. PMID:24487570

  15. BASELINE DESIGN/ECONOMICS FOR ADVANCED FISCHER-TROPSCH TECHNOLOGY

    SciTech Connect

    1998-04-01

    Bechtel, along with Amoco as the main subcontractor, developed a Baseline design, two alternative designs, and computer process simulation models for indirect coal liquefaction based on advanced Fischer-Tropsch (F-T) technology for the U. S. Department of Energy's (DOE's) Federal Energy Technology Center (FETC).

  16. A new synthesis of carbon encapsulated Fe5C2 nanoparticles for high-temperature Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Hong, Seok Yong; Chun, Dong Hyun; Yang, Jung-Il; Jung, Heon; Lee, Ho-Tae; Hong, Sungjun; Jang, Sanha; Lim, Jung Tae; Kim, Chul Sung; Park, Ji Chan

    2015-10-01

    Using a simple thermal treatment under a CO flow, uniform micrometer-sized iron oxalate dihydrate cubes prepared by hydrothermal reaction were transformed into Fe5C2@C nanoparticles to form a mesoporous framework; the final structure was successfully applied to the high-temperature Fischer-Tropsch reaction and it showed high activity (CO conversion = 96%, FTY = 1.5 × 10-4 molCO gFe-1 s-1) and stability.Using a simple thermal treatment under a CO flow, uniform micrometer-sized iron oxalate dihydrate cubes prepared by hydrothermal reaction were transformed into Fe5C2@C nanoparticles to form a mesoporous framework; the final structure was successfully applied to the high-temperature Fischer-Tropsch reaction and it showed high activity (CO conversion = 96%, FTY = 1.5 × 10-4 molCO gFe-1 s-1) and stability. Electronic supplementary information (ESI) available: Details of experimental procedures, SEM images of FeNi and FeCo oxalate hydrate particles, particle size and pore size distributions, FT activity and selectivity, hydrocarbon product distribution, ASF plot, and Mössbauer parameters of the Fe5C2@C catalyst. See DOI: 10.1039/c5nr05787f

  17. Synthesis of octane enhancers during slurry-phase Fischer-Tropsch. Quarterly technical progress report No. 6, January 1, 1992--March 31, 1992

    SciTech Connect

    Marcelin, G.

    1992-06-24

    The objective of this project is to investigate three possible routes to the formation of ethers, in particular methyl tert-butyl ether (MTBE), during slurry phase Fischer-Tropsch reaction. The three reaction schemes to be investigated are: (1) Addition of isobutylene during the formation of methanol and/or higher alcohols directly from CO and H{sub 2} during slurry-phase Fischer-Tropsch. (2) Addition of isobutylene to FT liquid products including alcohols in a slurry-phase reactor containing an MTBE or other acid catalyst. (3) Addition of methanol to slurry phase FT synthesis making iso-olefins. During the sixth quarter we completed the construction of the slurry bubble column reactor (SBCR), conducted initial shake-down experiments in a cold-flow mode, and finalized the selection process of the acid catalysts for conversion of syngas-produced alcohols and isobutylene to MTBE (scheme 2). Tasks 3, 4, and 5 are awaiting complete implementation of the SBCR system.

  18. 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

  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. Microkinetic modelling of the formation of C 1 and C 2 products in the Fischer-Tropsch synthesis over cobalt catalysts

    NASA Astrophysics Data System (ADS)

    Storsæter, Sølvi; Chen, De; Holmen, Anders

    2006-05-01

    The heats of adsorption of different C 1 and C 2 molecules assumed to be present during the initial steps of the Fischer-Tropsch synthesis and activation energies for elementary steps envisioned to occur in the synthesis are calculated for Co by using the unity bond index-quadratic exponential potential (UBI-QEP) method. The preexponential factors for the elementary steps are calculated from transition-state theory, and the rate constants are calculated according to the Arrhenius equation. The activation barrier for hydrogenation of CO is found to be lower compared to hydrogen assisted dissociation of CO, which has a smaller activation barrier than direct dissociation of CO. The reaction steps with high activation barriers are eliminated. Based on this elimination two sets of elementary steps for formation of C 1 and C 2 alkenes and alkanes in the Fischer-Tropsch synthesis are established: one based on hydrogen assisted CO dissociation (carbide mechanism) and one based on CO hydrogenation (CO insertion mechanism). In addition, one mechanism of producing CO 2 from the water-gas shift reaction is proposed. The resulting mechanisms are combined and used in the microkinetic model, which are fitted to experimental results at methanation conditions ( T = 483 K or 493 K, p = 1.85 bar and H 2/CO = 10) over a Co/Al 2O 3 Fischer-Tropsch catalyst. A good tuning is obtained by adjusting the C-Co and H-Co binding strengths. The microkinetic modelling based on these assumptions indicates that CO is mainly converted through hydrogenation of CO and that C 2 compounds are mainly produced by insertion of CO into a metal-methyl bond. Thus, from the surface coverages and reaction rates predicted by the microkinetic modelling the mechanism can be further reduced to only include the CO insertion mechanism. Hydrogenation of CHO to CH 2O is found to be the rate determining initiation step, and insertion of CO into a metal-methyl bond is found to be the rate determining step for chain

  1. Cobalt catalysts for the conversion of methanol to hydrocarbons and for Fischer-Tropsch Synthesis

    SciTech Connect

    Mauldin, C.H.

    1986-02-04

    This patent describes a catalyst useful for the conversion at reaction conditions of methanol or synthesis gas to hydrocarbons by contact with a catalyst. The catalyst cobalt and thorium in catalytically active amounts, and rhenium, composited with an inorganic oxide support in weight ratio of rhenium:cobalt ranging from about 0.025:1 to about 0.10:1.

  2. Moessbauer spectroscopy study of iron-based catalysts used in Fischer-Tropsch synthesis

    SciTech Connect

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

    1995-12-01

    Mossbauer investigations of iron-based catalysts containing the promoters K, and Cu, and binders consisting of oxides of Al, Si and Zr were carried out. Catalysts subjected to pretreatment in gas atmospheres containing mixtures of CO, H{sub 2}, and He have been studied. It is shown that the nature of binders, promoters and pretreatment of a catalyst influence the iron-phases formed during pretreatment and FT synthesis. Activation of the catalysts in CO leads to rapid and almost complete formation of {chi}-Fe{sub 5}C{sub 2} during activation and gives rise to high (H{sub 2}+CO) conversion. On the other hand, activation of the catalysts in synthesis gas leads to slow and incomplete formation of carbides and low (H{sub 2}+CO) conversion.

  3. 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.

  4. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1990-01-01

    Experiments on cobalt-catalyzed reactions of light 1-alkenes added to synthesis gas were performed. Data have been collected at 220C, 0.45 to 1.48 MPa and a synthesis gas flow rate between 0.015 and 0.030 Nl/(gcat[center dot]min) with H[sub 2]/CO of 1.45 to 2.25. Ethylene, propene, and butene were added to synthesis gas feed from 0.5 to 1.2 mole% of total feed. For each material balance in which 1-alkenes were added, a material balance was performed at similar process conditions without 1-alkenes added, as base case''. Material balances without added 1-alkenes were also repeated to verify of catalyst selectivity stability. 49 material balances were performed during a single run lasting over 2,500 hours-on-stream. The hydrocarbon data have been completely analyzed; data correlations are still being made. Since C[sub 3]/C[sub 1] ratios by ethene addition, C[sub 4]/C[sub 1] ratios by propene addition, and C[sub 5]/C[sub 1] ratios by 1-butene addition, it appears that 1-alkenes may incorporate into growing chains on the surface of the catalyst. Further evidence for incorporation can be seen by comparing selectivity to n-alcohol one carbon number higher than added 1-alkene. Yield of this n-alcohol increases when alkenes are present. Sensitivity of hydrocarbon distribution to process variables seems to be greater on Co than on Fe catalysts.

  5. Cobalt catalysts for the conversion of methanol and for Fischer-tropsch synthesis to produce hydrocarbons

    SciTech Connect

    Mauldin, C.H.; Davis, S.M.; Arcuri, K.B.

    1987-05-05

    A regeneration stable catalyst is described for the conversion at reaction conditions of methanol or synthesis gas to liquid hydrocarbons which consists essentially of from about 2 percent to about 25 percent cobalt, based on the weight of the catalyst composition, composited with titania, or a titania-containing support, to which is added sufficient of a zirconium, hafnium, cerium, or uranium promoter to provide a weight ratio of the zirconium, hafnium, cerium, or uranium metal:cobalt greater than about 0.101:1.

  6. Titania-supported catalysts and their preparation for use in Fischer-Tropsch synthesis

    SciTech Connect

    Mauldin, C.H.; Riley, K.L.

    1991-02-12

    This patent describes a support composition for forming a catalyst useful for the conversion of synthesis gas to hydrocarbons. It comprises: titania in which there is incorporated from 0.1 to about 20 wt% of an inorganic oxide binder selected from the group consisting of alumina and zirconia based on the weight of the titania-binder support, to provide a titania-binder support having a pore volume ranging from about 0.2 cc/g to about 0.5 cc/g, and surface area ranging from about 8 m{sup 2}/g to about 70 m{sup 2}/g.

  7. Improved cobalt catalysts, and use thereof for Fischer-Tropsch synthesis

    SciTech Connect

    Mauldin, C.H.

    1987-06-02

    This patent describes a process useful for the conversion of synthesis gas feed comprised of hydrogen and carbon monoxide to hydrocarbons. The process comprises contacting the feed at reaction conditions with a catalyst which comprises cobalt, or cobalt and thoria in catalytically active amount composited with tatania or titania-containing support, to which is added sufficient rhenium to obtain, with a similar feed at corresponding process conditions, improved activity, as contrasted with a catalyst composition otherwise similar except that it does not contain rhenium.

  8. Reactions of selected 1-olefins and ethanol added during the Fischer-Tropsch synthesis: Topical report

    SciTech Connect

    Hanlon, R.T.; Satterfield, C.N.

    1987-10-30

    The effects of addition during synthesis of C/sub 2/, C/sub 4/, C/sub 6/, C/sub 10/ or C/sub 20/, normal 1-olefins, was studied in a continuous well-stirred liquid phase reactor. Studies were at 248/sup 0/C and 0.78 to 1.48 MPa, using a reduced fused magnetite catalyst containing potassium. Incorporation of these olefins into growing chains could be detected, but was relatively minor. Instead the olefin was hydrogenated to the corresponding paraffin or isomerized to the 2-olefin. Excluding ethylene, which is unusually reactive, the reactivity of the olefins increased with molecular weight. Disappearance of all added species was much less at low synthesis conversions than at high, attributed to competitive adsorption with CO. The reactions of added ethanol were also studied. Ethanol or ethylene decreased the hydrogenation capabilities of the catalyst as reflected in decreased formation of CH/sub 4/ and increased olefin/paraffin ratio of the products. Neither addition affected the chain growth probability, ..cap alpha... 21 refs., 11 figs., 5 tabs.

  9. Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, April 1, 1995--June 30, 1995

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1996-05-01

    Our objective for this quarter was to study the effect of co-feeding a 1-olefin on the Ruhrchemie catalyst activity and selectivity, during-both conventional Fisher-Tropsch synthesis (FTS) and FTS under supercritical conditions. We used propane as the supercritical fluid and 1-dodecene (1-C{sub 12}H{sub 24}) in this test. Motivation for this study was the work of Fujimoto and co-workers who reported that suppression of methane and enhancement of high molecular weight hydrocarbons selectivities occurs with co-feeding of 1-olefins (1-heptene, 1-tetradecene, or 1-hexadecene) during FTS under supercritical conditions, but not during the conventional FTS (Co-La catalyst supported on silica in supercritical n-pentane).The diffusion coefficients of products in supercritical fluids is discussed.

  10. Diffusivities of synthesis gas and Fischer-Tropsch products in slurry media. Quarterly report, September-December 1984

    SciTech Connect

    Akgerman, A.

    1985-01-01

    The goal of this research is to develop a fast and accurate method for measuring liquid diffusion coefficients for the Fischer-Tropsch system at temperatures from ambient to 573 K and pressures from ambient to 7 MPa. The Taylor dispersion technique will be utilized for measuring the diffusivities of carbon monoxide, hydrogen, heptane, octane, nonane, decane, and decanol in molten Fischer-Tropsch wax. The theoretical criteria for measuring diffusivities by the Taylor dispersion method have been given. In addition, the practical departures from an ideal experiment have been discussed; correction for the non-ideal conditions are found in Appendix B (Alizadeh et al., 1980). The effect of varying viscosity on secondary flow effects has been pointed out; it appears that under typical laboratory space limitations, using commercially available tubing, and with diffusivities on the order of 10/sup -9/ m/sup 2//s, it will not be possible to completely eliminate these effects. An apparatus for measuring diffusivity at high temperatures and pressures, where data has heretofore been scarce, is presented. With this apparatus rapid measurements may be made, and with the aid of computer control the measurements may be repeated and large volumes of data generated with minimum requirements of the operator. We anticipate our accuracy being between 0.5 and 4%. 20 references, 4 figures.

  11. Fischer-Tropsch Synthesis. Reduction Behavior and Catalytic Activity of Fe-Ce Systems

    SciTech Connect

    Perez-Alonso, F.J.; Ojeda, M.; Herranz, T.; Fierro, J.L.G.

    2005-04-26

    Several Fe-Ce catalysts for FT synthesis were prepared following two different methods: coprecipitation from Fe and Ce nitrate solutions and a physical mixture of pure Fe and Ce precursors. The iron phases present in the activated catalysts were identified by XRD and Moessbauer spectroscopy. A good correlation between both techniques was found. The results revealed that the cerium oxide in the samples prepared by coprecipitation produces two effects: (i), stabilization of metastable species (Fe1-xO), and (ii), a decrease in the crystallite size of the iron species upon increasing Ce-contents, as inferred from an increase in superparamagnetic species. The catalysts were tested in CO hydrogenation in a flow reactor. It was found that selectivity towards light olefins increases for the coprecipitated Ce-containing catalysts, whereas CO conversion followed the opposite trend. Since the Fe1-xO phase was detected in these catalysts, it is suggested that the formation of the Fe1-xO phase would be responsible for the drop in catalytic activity.

  12. Fischer-Tropsch Synthesis. Reduction Behavior and Catalytic Activity of Fe-Ce Systems

    NASA Astrophysics Data System (ADS)

    Pérez-Alonso, F. J.; Ojeda, M.; Herranz, T.; Fierro, J. L. G.; Bengoa, J. F.; Marchetti, S. G.

    2005-04-01

    Several Fe-Ce catalysts for FT synthesis were prepared following two different methods: coprecipitation from Fe and Ce nitrate solutions and a physical mixture of pure Fe and Ce precursors. The iron phases present in the activated catalysts were identified by XRD and Mössbauer spectroscopy. A good correlation between both techniques was found. The results revealed that the cerium oxide in the samples prepared by coprecipitation produces two effects: (i), stabilization of metastable species (Fe1-xO), and (ii), a decrease in the crystallite size of the iron species upon increasing Ce-contents, as inferred from an increase in superparamagnetic species. The catalysts were tested in CO hydrogenation in a flow reactor. It was found that selectivity towards light olefins increases for the coprecipitated Ce-containing catalysts, whereas CO conversion followed the opposite trend. Since the Fe1-xO phase was detected in these catalysts, it is suggested that the formation of the Fe1-xO phase would be responsible for the drop in catalytic activity.

  13. Fischer-Tropsch synthesis in slurry reactor systems. Quarterly report, May 1, 1984-July 31, 1984

    SciTech Connect

    Satterfield, C.N.; Bartos, T.; Hanlon, R.; Huff, G.A. Jr.; Matsumoto, D.

    1984-01-01

    We suspect that a number of reports in the published literature of catalyst preparations that supposedly minimize wax formation are erroneous in that wax may actually have accumulated in catalyst pores and that insufficient time may have been allowed for the effluent to represent true intrinsic kinetics. Mathematical simulations show the effect of pressure, temperature, rate constant, feed composition, space velocity and Flory parameter ..cap alpha.., on time required for pores to fill, upon liquid product distribution and vapor composition leaving the reactor. The pore filling rate and condensed product composition vary with position through the reactor but not with time. The maximum filling rate does not occur at the same position in the bed as the maximum synthesis rate. For reaction conditions of industrial interest, the greatest effect is caused by the assumed carbon number distribution of the products. A rigorous parameter to generalize the results is not immediately evident. We reported studies of the effect of the nature of the liquid on the activity and selectivity of a reduced fused magnetite catalyst. For interpretation of such studies it is necessary to have data on solubilities of hydrogen and carbon monoxide in the liquids of interest. New data at elevated temperatures and pressure are reported for octacosane, phenanthreene and Fomblin, a perfluorinated polyether, and compared to previous literature on a variety of liquids. When hydrogen solubilities are reported on a volumetric basis, substances of a similar chemical nature have very similar solubilities.

  14. Fischer-Tropsch synthesis over iron-based catalysts in slurry reactors. Reaction rates, kinetics and implications for improving hydrocarbon productivity

    SciTech Connect

    Raje, A.P.; Davis, B.H.

    1996-10-01

    The Fischer-Tropsch (FT) synthesis is carried out over a high activity precipitated iron catalyst promoted with silica and potassium in a slurry reactor. Reaction rates (FTS and water gas shift) and partial pressures are evaluated over a wide range of CO conversions (10 to 90%) and space velocities at 270{degrees}C, 175 psig and a H{sub 2}/CO ratio of 0.67. The partial pressure of water exhibits a maximum at intermediate CO conversion. Both the fraction of CO converted to hydrocarbons and the hydrocarbon space time yield decrease with increasing CO conversion. This implies that it would be beneficial to have lower conversion per pass in the reactor with recycle to achieve a high overall conversion. The data as well as experiments with water and CO{sub 2} addition enable us to determine a kinetic expression for the catalyst which shows negligible inhibition of the reaction rate by water or CO{sub 2}.

  15. Promotional effects of Al{sub 2}O{sub 3} addition to Co/SiO{sub 2} catalysts for Fischer-Tropsch synthesis

    SciTech Connect

    Yi Zhang; Satoshi Nagamori; Sukamon Hinchiranan; Tharapong Vitidsant; Noritatsu Tsubaki

    2006-03-15

    The addition of a small amount of Al{sub 2}O{sub 3} to silica-supported cobalt catalysts significantly increased the dispersion of cobalt and Co-metallic surface area, resulting in the remarkable enhancement of the Fischer-Tropsch synthesis (FTS) activity in the slurry-phase reaction. The addition of Al{sub 2}O{sub 3} adjusted the interaction between cobalt and the silica support quite well, realizing the favored dispersion and reduction degree of supported cobalt and leading to high catalytic activity in FTS. The properties of various catalysts were characterized by in situ DRIFT, XRD, TPR, N{sub 2} physisorption, and H{sub 2} chemisorption. 16 refs., 3 figs., 2 tabs.

  16. Straightforward synthesis of bimetallic Co/Pt nanoparticles in ionic liquid: atomic rearrangement driven by reduction-sulfidation processes and Fischer-Tropsch catalysis

    NASA Astrophysics Data System (ADS)

    Silva, Dagoberto O.; Luza, Leandro; Gual, Aitor; Baptista, Daniel L.; Bernardi, Fabiano; Zapata, Maximiliano J. M.; Morais, Jonder; Dupont, Jairton

    2014-07-01

    Unsupported bimetallic Co/Pt nanoparticles (NPs) of 4.4 +/- 1.9 nm can be easily obtained by a simple reaction of [bis(cylopentadienyl)cobalt(ii)] and [tris(dibenzylideneacetone) bisplatinum(0)] complexes in 1-n-butyl-3-methylimidazolium hexafluorophosphate IL at 150 °C under hydrogen (10 bar) for 24 h. These bimetallic NPs display core-shell like structures in which mainly Pt composes the external shell and its concentration decreases in the inner-shells (CoPt3@Pt-like structure). XPS and EXAFS analyses show the restructuration of the metal composition at the NP surface when they are subjected to hydrogen and posterior H2S sulfidation, thus inducing the migration of Co atoms to the external shells of the bimetallic NPs. Furthermore, the isolated bimetallic NPs are active catalysts for the Fischer-Tropsch synthesis, with selectivity for naphtha products.

  17. Effect of H{sub 2}/CO ratio on Fischer-Tropsch synthesis in a slurry reactor with cobalt-based catalyst

    SciTech Connect

    Inga, J.R.; Morsi, B.I.

    1995-12-31

    The effect of syngas having different H{sub 2}/CO ratios on Fischer-Tropsch synthesis in a slurry bubble column reactor with a Cobalt-based catalyst was assessed using a simple reactor model. The data and catalyst used in this model were from Bechtel studies (1990). It was found that hydrogen is likely to become the rate limiting reactant, even at relatively low catalyst activities, not because of gas-liquid mass transfer, but due to the depletion of hydrogen in the gas phase. This will reduce the H{sub 2}/CO ratio in the liquid phase which will consequently decrease the reaction rate and affect the product selectivity. The increase of catalyst concentration appeared not to affect the reactor performance, when using a syngas with low H{sub 2}/CO ratios.

  18. Straightforward synthesis of bimetallic Co/Pt nanoparticles in ionic liquid: atomic rearrangement driven by reduction-sulfidation processes and Fischer-Tropsch catalysis.

    PubMed

    Silva, Dagoberto O; Luza, Leandro; Gual, Aitor; Baptista, Daniel L; Bernardi, Fabiano; Zapata, Maximiliano J M; Morais, Jonder; Dupont, Jairton

    2014-08-01

    Unsupported bimetallic Co/Pt nanoparticles (NPs) of 4.4 ± 1.9 nm can be easily obtained by a simple reaction of [bis(cylopentadienyl)cobalt(ii)] and [tris(dibenzylideneacetone) bisplatinum(0)] complexes in 1-n-butyl-3-methylimidazolium hexafluorophosphate IL at 150 °C under hydrogen (10 bar) for 24 h. These bimetallic NPs display core-shell like structures in which mainly Pt composes the external shell and its concentration decreases in the inner-shells (CoPt3@Pt-like structure). XPS and EXAFS analyses show the restructuration of the metal composition at the NP surface when they are subjected to hydrogen and posterior H2S sulfidation, thus inducing the migration of Co atoms to the external shells of the bimetallic NPs. Furthermore, the isolated bimetallic NPs are active catalysts for the Fischer-Tropsch synthesis, with selectivity for naphtha products. PMID:24975109

  19. Stability and reactivity of ϵ-χ-θ iron carbide catalyst phases in Fischer-Tropsch synthesis: controlling μ(C).

    PubMed

    de Smit, Emiel; Cinquini, Fabrizio; Beale, Andrew M; Safonova, Olga V; van Beek, Wouter; Sautet, Philippe; Weckhuysen, Bert M

    2010-10-27

    The stability and reactivity of ϵ, χ, and θ iron carbide phases in Fischer-Tropsch synthesis (FTS) catalysts as a function of relevant reaction conditions was investigated by a synergistic combination of experimental and theoretical methods. Combined in situ X-ray Absorption Fine Structure Spectroscopy/X-ray Diffraction/Raman Spectroscopy was applied to study Fe-based catalysts during pretreatment and, for the first time, at relevant high pressure Fischer-Tropsch synthesis conditions, while Density Functional Theory calculations formed a fundamental basis for understanding the influence of pretreatment and FTS conditions on the formation of bulk iron carbide phases. By combining theory and experiment, it was found that the formation of θ-Fe(3)C, χ-Fe(5)C(2), and ϵ-carbides can be explained by their relative thermodynamic stability as imposed by gas phase composition and temperature. Furthermore, it was shown that a significant part of the Fe phases was present as amorphous carbide phases during high pressure FTS, sometimes in an equivalent amount to the crystalline iron carbide fraction. A catalyst containing mainly crystalline χ-Fe(5)C(2) was highly susceptible to oxidation during FTS conditions, while a catalyst containing θ-Fe(3)C and amorphous carbide phases showed a lower activity and selectivity, mainly due to the buildup of carbonaceous deposits on the catalyst surface, suggesting that amorphous phases and the resulting textural properties play an important role in determining final catalyst performance. The findings further uncovered the thermodynamic and kinetic factors inducing the ϵ-χ-θ carbide transformation as a function of the carbon chemical potential μ(C). PMID:20925335

  20. Selective Fischer-Tropsch synthesis on metal powder catalysts prepared by the potassium reduction of halides in THF

    SciTech Connect

    Miyake, M.; Takebe, K.; Nomura, M.

    1987-06-01

    Metal powders such as Fe, Co, Ni, Fe-Co, and Fe-Ni prepared by reducing metal iodides or bromides with potassium metal in refluxing THF were used as catalysts for Fischer-Tropsch syntheses. These metal powders contained very small particles and have BET surface areas (28-36 m/sup 2//g). The metal powder catalysts, such as Fe and Fe-Co (80:20), gave 1-butene with more than 35 wt% selectivity at a rather high CO conversion of over 10 wt% at 533-553 K, while products on the Co catalyst obeyed conventional Schulz-Flory type distribution. The Ni catalyst showed little activity. Effects of reaction variables (temperature, H/sub 2//CO feed gas ratio, and composition of Fe-Co) were investigated.

  1. Fischer-Tropsch synthesis in slurry-reactor systems. Quarterly report, November 1, 1981 to January 31, 1982

    SciTech Connect

    Satterfield, C.N.; Bartos, T.; Huff, G.A. Jr.; Stenger, H.

    1982-01-01

    A detailed study of mass transfer effects with a reduced fused magnetite catalyst has now been completed and is summarized in an appended paper, Mass Transfer and Product Selectivity in a Mechanically-Stirred Fischer-Tropsch Slurry Reactor, by Charles N. Satterfield and George A. Huff, Jr. Analysis of our heavier hydrocarbon products indicates that they yield a value of ..cap alpha.. = 0.93 on a Flory plot, considerably higher than the values of ..cap alpha.. of about 0.7 found with lighter products. Iron catalysts may exhibit two kinds of sites with considerably different kinetic behavior. At the request of Drs. Sapienza and Sleigeir of the Brookhaven National Laboratory, we ran a sample of their SOSS catalyst in our reactor facility at 100 psig. Activity was low, but this may have been because this particular catalyst is possibly better suited for higher pressures.

  2. Comparative study of oil-slurry process to fixed-bed process in the Fischer-Tropsch synthesis

    SciTech Connect

    Sakai, T.; Kunugi, T.

    1982-01-01

    Differences between the oil-slurry process and the fixed-bed process on catalyst activity and C/sub 1/-C/sub 4/ product selectivity in the Fischer-Tropsch systhesis are described for a precipitated iron catalyst at reaction temperatures of 200 to 250/sup 0/C. Other reaction conditions used were those usually used for the two processes but were not the same for both processes. The data indicated that the catalyst activity is due to the presence of metallic iron suppresses the formation of CH/sub 4/ and favors the C/sub 3/ and C/sub 4/ hydrocarbon formation, and the experimental data preclude the formation of iron carbide for the oil-slurry process. An activation energy of 79.1kJ/mole was obtained at temperatures of 230 to 242/sup 0/C. (BLM)

  3. Investigation on the Fischer-Tropsch synthesis with nitrogen-containing syngas over CoPtZrO{sub 2}/Al{sub 2}O{sub 3} catalyst

    SciTech Connect

    Dongyan Xu; Hongmin Duan; Wenzhao Li; Hengyong Xu

    2006-05-15

    The Fischer-Tropsch synthesis with nitrogen-containing syngas derived from combined air partial oxidation and CO{sub 2} reforming of methane has been performed in a fixed-bed reactor. The effects of key factors including reaction temperature, pressure, and nitrogen content of the syngas on the performance of CoPtZrO{sub 2}/Al{sub 2}O{sub 3} catalyst were mainly investigated. The results indicate that the syngas containing a high content of nitrogen is suitable for Fischer-Tropsch synthesis and that a high initial catalytic activity can be achieved under typical operating conditions. The decreasing of catalytic activity with time on stream before reaching steady state was observed, which is mainly due to the blockage of catalyst pores by heavy hydrocarbons. 22 refs., 7 figs.

  4. 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.

  5. 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.

  6. 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. PMID:24825772

  7. Separation of catalyst from Fischer-Tropsch slurry

    SciTech Connect

    White, C.M.; Quiring, M.S.; Jensen, K.L.; Hickey, R.F.; Gillham, L.D.

    1998-04-01

    This paper describes a process for the separation of catalysts used in Fischer-Tropsch synthesis. The separation is accomplished by extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic. The purified catalyst can be upgraded by various methods.

  8. Conversion of cellulosic wastes to liquid hydrocarbon fuels: Vol. 2, A kinetic study of the modified Fischer-Tropsch synthesis over an alumina-supported cobalt oxide catalyst: Final report

    SciTech Connect

    Kuester, J.L.

    1986-11-01

    A modified Fischer-Tropsch reaction with the incorporation of ethylene in the synthesis gas has been studied kinetically. The feed mixture was also comprised of methane and carbon dioxide in a proportion similar to a real pyrolysis gas composition. The feed gas was provided by a manifold of compressed gas cylinders. An alumina-supported cobalt oxide catalyst was prepared by an impregnation method and used in the experimentation.

  9. 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

    2015-04-01

    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. PMID:25683326

  10. 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.

  11. 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. PMID:24933030

  12. 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.

  13. 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.

  14. Abiogenic Fischer-Tropsch synthesis of methane at the Baogutu reduced porphyry copper deposit, western Junggar, NW-China

    NASA Astrophysics Data System (ADS)

    Cao, MingJian; Qin, KeZhang; Li, GuangMing; Evans, Noreen J.; Jin, LuYing

    2014-09-01

    Methane is widely developed in hydrothermal fluids from reduced porphyry copper deposits, but its origin remains enigmatic. The occurrence of methane in fluid inclusions at the Late Carboniferous Baogutu reduced porphyry copper deposit in western Junggar, Xinjiang, NW-China, presents an excellent opportunity to address this problem. A systematic study including fluid inclusion Laser-Raman and CO2-CH4 carbon isotope analyses, igneous and hydrothermal mineral H-O isotope analyses, and in situ major, trace element and Sr isotopic analyses of hydrothermal epidote was conducted to constrain the origin of CH4 and CH4-rich fluids. The δ2H and δ18O of water in equilibrium with igneous biotite ranges from -65.0‰ to -66.0‰ and +7.2‰ to +7.4‰, respectively, indicating notable degassing of probably supercritical fluids in the magma chamber. The wide range of δ2H (-58.0‰ to -107.0‰, n = 23) for water within quartz suggests the existence of significant hydrothermal fluid boiling. Water-rock interaction is the most likely mechanism leading to the wide range of δ18O values for water in vein quartz with water/rock ratios (wt.% in O) of 0.15 to 0.75 and 0.13 to 0.46 for a closed and open system, respectively. Detailed Laser-Raman analyses indicate CO2 in apatite included in granodiorite porphyry phenocrystic biotite that records the carbon species of the early stage magmatic stage, whereas later hydrothermal fluids containing CH4 with trace or without CO2 are found in inclusions of vein quartz. We propose that CH4 is probably transformed from CO2 by Fischer-Tropsch type reactions at 500 °C, assumed from CO2-CH4 C isotope equilibrium. The (87Sr/86Sr)i of hydrothermal epidote yields values of 0.70369-0.70404, consistent with that reported for the whole rocks. The δ13CCH4 (-28.6‰ to -22.6‰) and δ2HCH4 (-108.0‰ to -59.5‰) are characteristic of abiogenic methane. The measured δ13CCO2 shows a slightly depleted 13C (-13.5‰ to -7.2‰) relative to upper mantle

  15. 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

    2011-12-01

    The Hybrid Energy Systems Testing (HYTEST) Laboratory at the Idaho National Laboratory was established to develop and test hybrid energy systems with the principal objective of reducing dependence on imported fossil fuels. A central component of the HYTEST is the slurry bubble column reactor (SBCR) in which the gas-to-liquid reactions are performed to synthesize transportation fuels using the Fischer Tropsch (FT) process. These SBCRs operate in the churn-turbulent flow regime, which is characterized by complex hydrodynamics, coupled with reacting flow chemistry and heat transfer. Our team is developing a research tool to aid in understanding the physicochemical processes occurring in the SBCR. 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) consisting of thirteen species, which are CO reactant, H2 reactant, hydrocarbon product, and H2O product in small bubbles, large bubbles, and the bulk fluid plus catalyst is outlined. Mechanistic submodels for interfacial momentum transfer in the churn-turbulent flow regime are incorporated, along with bubble breakup/coalescence and two-phase turbulence submodels. The absorption and kinetic models, specifically changes in species concentrations, have been incorporated into the mass continuity equation. The reaction rate is based on the macrokinetic model for a cobalt catalyst developed by Yates and Satterfield. The model includes heat generation produced by the exothermic chemical reaction, as well as heat removal from a constant temperature heat exchanger. A property method approach is employed to incorporate vapor-liquid equilibrium (VLE) in a robust manner. Physical and thermodynamic properties as functions of changes in both pressure and temperature are obtained from VLE calculations performed external to the CMFD solver. The novelty of this approach is in its simplicity, as well as its

  16. Diesel production from Fischer-Tropsch: the past, the present, and new concepts

    SciTech Connect

    Dieter Leckel

    2009-05-15

    Fischer-Tropsch synthesis is technically classified into two categories, the high-temperature Fischer-Tropsch (HTFT) and the low-temperature Fischer-Tropsch (LTFT) processes. The criterion for this classification is the operating temperature of the synthesis, which ranges between 310-340{sup o}C for the HTFT process and 210-260{sup o}C for the LTFT process. A Fischer-Tropsch facility can be divided into roughly three sections, synthesis gas (syngas) generation, FT synthesis, and refining of the synthetic crude (syncrude). Fischer-Tropsch refineries differ regarding the product upgrading, and both transportation fuels and chemicals can be produced. Regarding the FT refinery history, the configuration of each refinery also reflects the requirements of the fuel specification at that time. This paper gives a condensed overview of how Fischer-Tropsch facilities changed during the last 70 years and focuses in particular on the diesel fuel produced. Some conceptual flow schemes are additionally presented with emphasis on the combined upgrading of the high boiling part of the FT product spectrum with liquids derived from coal pyrolysis. 52 refs., 14 figs., 12 tabs.

  17. Six-flow operations for catalyst development in Fischer-Tropsch synthesis: Bridging the gap between high-throughput experimentation and extensive product evaluation

    SciTech Connect

    Sartipi, Sina E-mail: J.Gascon@tudelft.nl; Jansma, Harrie; Bosma, Duco; Boshuizen, Bart; Makkee, Michiel; Gascon, Jorge E-mail: J.Gascon@tudelft.nl; Kapteijn, Freek

    2013-12-15

    Design and operation of a “six-flow fixed-bed microreactor” setup for Fischer-Tropsch synthesis (FTS) is described. The unit consists of feed and mixing, flow division, reaction, separation, and analysis sections. The reactor system is made of five heating blocks with individual temperature controllers, assuring an identical isothermal zone of at least 10 cm along six fixed-bed microreactor inserts (4 mm inner diameter). Such a lab-scale setup allows running six experiments in parallel, under equal feed composition, reaction temperature, and conditions of separation and analysis equipment. It permits separate collection of wax and liquid samples (from each flow line), allowing operation with high productivities of C5+ hydrocarbons. The latter is crucial for a complete understanding of FTS product compositions and will represent an advantage over high-throughput setups with more than ten flows where such instrumental considerations lead to elevated equipment volume, cost, and operation complexity. The identical performance (of the six flows) under similar reaction conditions was assured by testing a same catalyst batch, loaded in all microreactors.

  18. Six-flow operations for catalyst development in Fischer-Tropsch synthesis: Bridging the gap between high-throughput experimentation and extensive product evaluation

    NASA Astrophysics Data System (ADS)

    Sartipi, Sina; Jansma, Harrie; Bosma, Duco; Boshuizen, Bart; Makkee, Michiel; Gascon, Jorge; Kapteijn, Freek

    2013-12-01

    Design and operation of a "six-flow fixed-bed microreactor" setup for Fischer-Tropsch synthesis (FTS) is described. The unit consists of feed and mixing, flow division, reaction, separation, and analysis sections. The reactor system is made of five heating blocks with individual temperature controllers, assuring an identical isothermal zone of at least 10 cm along six fixed-bed microreactor inserts (4 mm inner diameter). Such a lab-scale setup allows running six experiments in parallel, under equal feed composition, reaction temperature, and conditions of separation and analysis equipment. It permits separate collection of wax and liquid samples (from each flow line), allowing operation with high productivities of C5+ hydrocarbons. The latter is crucial for a complete understanding of FTS product compositions and will represent an advantage over high-throughput setups with more than ten flows where such instrumental considerations lead to elevated equipment volume, cost, and operation complexity. The identical performance (of the six flows) under similar reaction conditions was assured by testing a same catalyst batch, loaded in all microreactors.

  19. 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.

  20. A Facile Synthesis of SiO2@Co/mSiO2 Egg-Shell Nanoreactors for Fischer-Tropsch Reaction.

    PubMed

    Kwon, Jae In; Kim, Tae Wan; Park, Ji Chan; Yang, Jung-Il; Lee, Kwan Young

    2016-02-01

    Recently, a convenient melt-infiltration method, using a hydrated metal salt with porous support, was developed to prepare various metal/metal-oxide nanocatalysts. Until now, millimeter-scale, bead-shaped, cobalt egg-shell catalysts have been used to enhance the rate of reactant diffusion and catalyst performance. In the present work, new SiO2@Co/mSiO2 egg-shell nanoreactors (~300 nm) were synthesized with controlled Co content of 10 and 20 wt%. This was accomplished using a selective melt-infiltration process with porous silica shells around solid-silica cores. The SiO2@Co(10 wt%)/mSiO2 egg-shell catalyst that bears small cobalt nanoparticles of -2 nm was successfully employed for the industrially valuable Fischer-Tropsch synthesis reaction, showing the high activity of -8.0 x 10(-5) mol(CO) x gCo(-1) x S(-1). PMID:27433671

  1. Six-flow operations for catalyst development in Fischer-Tropsch synthesis: bridging the gap between high-throughput experimentation and extensive product evaluation.

    PubMed

    Sartipi, Sina; Jansma, Harrie; Bosma, Duco; Boshuizen, Bart; Makkee, Michiel; Gascon, Jorge; Kapteijn, Freek

    2013-12-01

    Design and operation of a "six-flow fixed-bed microreactor" setup for Fischer-Tropsch synthesis (FTS) is described. The unit consists of feed and mixing, flow division, reaction, separation, and analysis sections. The reactor system is made of five heating blocks with individual temperature controllers, assuring an identical isothermal zone of at least 10 cm along six fixed-bed microreactor inserts (4 mm inner diameter). Such a lab-scale setup allows running six experiments in parallel, under equal feed composition, reaction temperature, and conditions of separation and analysis equipment. It permits separate collection of wax and liquid samples (from each flow line), allowing operation with high productivities of C5+ hydrocarbons. The latter is crucial for a complete understanding of FTS product compositions and will represent an advantage over high-throughput setups with more than ten flows where such instrumental considerations lead to elevated equipment volume, cost, and operation complexity. The identical performance (of the six flows) under similar reaction conditions was assured by testing a same catalyst batch, loaded in all microreactors. PMID:24387446

  2. Diffusion limitations in Fischer-Tropsch catalysts

    SciTech Connect

    Post, M.F.M.; Sie, S.T. Badhuisweg 3, 1031 CM Amsterdam )

    1988-01-01

    Indirect conversion of natural hydrocarbon resources such as natural gas into transportation fuels or chemicals usually involves the conversion to carbon monoxide and hydrogen (synthesis gas), followed by a catalytic conversion to the desired products via e.g. the Fischer-Tropsch (FT) reaction. In a fixed-bed mode of operation, the FT catalyst generally consists of particles of a few mm in size, for pressure-drop and heat-transfer considerations. To investigate whether diffusion limitations inside larger catalyst particles play a role during the synthesis reaction, the authors have made an extensive study using a number of iron- and cobalt-based catalysts, in which they have evaluated and quantified the effects of catalyst particle size and pore diameter on reaction rates. The effects due to variation of particle size and pore diameter have been quantified with the Thiele model for diffusion limitations.

  3. Technology development for iron Fischer-Tropsch catalysts. Quarterly report, April--June 1993

    SciTech Connect

    Davis, B.H.

    1993-11-01

    The Fischer-Tropsch process has attracted a great deal of attention in terms of catalytic activity and selectivity to produce higher number hydrocarbons by reacting carbon monoxide and hydrogen at high pressures in the presence of catalysts. Shortly after the initial discovery, Fischer and Tropsch developed more active catalysts for indirect liquefaction. The product distribution resulting from the Fischer-Tropsch synthesis (FTS) varies widely depending upon the catalysts, the temperature and pressure of reactions, pretreatment conditions, etc. It is desirable to improve the selectivity while maintaining the activity intact. One approach to achieve this task is the addition of promoters such as oxides of K, Mn, Ti, Mo, Ni, and Co, etc. It was observed that most of these promoted catalysts exhibit an increase in selectivity to higher hydrocarbons. For example, the addition of thoria as a promoter to cobalt-kieselguhr catalysts resulted in an enhanced yield of C{sub 5}{sup +} hydrocarbons. Even a small amount of thoria promoter ({approximately}0.4 wt %) addition to Co/ZSM-5 causes a remarkable increase in the conversion, shift activity, and C{sub 5}{sup +} selectivity. Thoria added as a promoter to a precipitated iron oxide catalyst appears to decrease wax selectivity. It is generally believed that the factors such as dispersion effects of rare earth oxides and thoria, the redox properties, and the basic properties of rare earth oxides and thorium oxides, greatly influence the activity and selectivity.

  4. 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.

  5. Surface characterization of iron Fischer-Tropsch catalysts

    SciTech Connect

    Kuivila, C.S.; Butt, J.B.; Stair, P.C.

    1986-01-01

    In this paper the authors address XPS characterization of the iron phases associated with Fischer-Tropsch catalysts. Results obtained for single-phase metal, oxide, and carbide samples are presented. Methods for estimating the extent of carbide formation during low conversion synthesis, and the extent of catalyst oxidation at high conversions are illustrated. This approach is used to monitor the evolution of an initially reduced, unsupported iron catalyst during synthesis at low conversion levels.

  6. 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.

  7. 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.

  8. Application of equilibrium analysis to a Fischer-Tropsch product

    SciTech Connect

    Norval, G.W. ); Phillips, M.J. )

    1990-11-01

    In the Fischer-Tropsch (FT) process, synthesis gas is converted, inter alia, to aliphatic hydrocarbons, consisting predominantly of n-alkanes and n-alkenes, over iron- or cobalt-based catalysts. The product composition follows an Anderson-Schults-Flory (ASF) distribution. In this paper, the authors demonstrate that the ASF distribution (Eq. (1)) can be derived from an equilibrium basis, and the consequences arising therefrom are discussed.

  9. 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

  10. Technology development for iron and cobalt Fischer-Tropsch catalysts

    SciTech Connect

    Davis, B.H.

    1999-11-01

    The impact of deuterium on the Fischer-Tropsch (FT) synthesis was studied with a precipitated iron catalyst in the slurry phase. Deuterium has been used by several research groups to better understand the mechanism of CO hydrogenation. Inverse (k{sub H}/k{sub D} < 1), normal (k{sub H}/k{sub D} > 1) and no isotope effect (k{sub H}/k{sub D} = 1) have been reported. The conflicting results are thought to arise because rate of reaction is a combination of kinetic and equilibrium factors. In summary, the presence of boron produced only minor changes on the properties of the cobalt catalyst. In earlier studies, it was shown that the presence of boron made the catalyst less susceptible to poisoning by sulfur. Steady-state supercritical Fischer-Tropsch synthesis was studied in the work using a fixed-bed reactor and an unpromoted Co/SiO{sub 2} catalyst. This serves as the baseline for promoted catalyst studies. A pentane-hexane mixture was used as the supercritical solvent. Overall reactor pressure, syngas partial pressure and contact time were kept constant to obtain a valid comparison of the impact of solvent density in the catalytic activity and selectivity. Three different partial pressures of the mixture were chosen based on the density-pressure curve in order to investigate the pressure tuning effect to Fischer-Tropsch synthesis near critical region.

  11. Influence of pH of the impregnation solution on the catalytic properties of Co/{gamma}-alumina for Fischer-Tropsch synthesis

    SciTech Connect

    Jong Wook Bae; Yun-Jo Lee; Jo-Yong Park; Ki-Won Jun

    2008-09-15

    The Co/{gamma}-Al{sub 2}O{sub 3} catalysts were prepared by the slurry impregnation of an aqueous solution of cobalt(II) nitrate precursor. Nitric acid or ammonium hydroxide was added to the cobalt nitrate solution, during impregnation, to give an acidic or basic environment. The changes in the particle size of cobalt species were estimated by X-ray diffraction (XRD) and hydrogen chemisorption. The reduction degree of cobalt oxides was measured by temperature-programmed reduction (TPR). The catalysts prepared under acidic conditions showed a higher reduction degree compared to those prepared at higher pH because of the reduced salt-support interaction. During the Fischer-Tropsch synthesis at 220{sup o}C, employing the catalysts prepared at a different pH (0.80, 4.94, 9.96, and 11.12), a considerable difference in the initial activity was observed, depending upon the cobalt metal surface area. However, after stabilization, all of the catalysts attained a similar level of conversion, possibly because of the active-site rearrangement, deactivation, and wax formation on the catalyst surface. At a higher reaction temperature of 240{sup o}C, the catalysts prepared at lower solution pH exhibited higher conversion than those prepared at higher solution pH. The cobalt species on the catalysts prepared under acidic conditions had a heterogeneous particle size distribution, showing higher steady-state activity, because of the reduced interaction with the support. The product distribution revealed a higher selectivity to C{sub 1} and C{sub 8+} on the catalyst prepared with a higher solution pH. 44 refs., 6 figs., 3 tabs.

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

    PubMed

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

    2016-07-21

    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. PMID:27353432

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

    NASA Astrophysics Data System (ADS)

    Salvi, Stefano; Williams-Jones, Anthony 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® Q capillary column. The measured gas species are, in order of abundance, CH 4, H 2, C 2H 6, CO 2, N 2, CA, n-C 4H 10, n-C 5H 12, C 2H 2, i-C 4H 10 and C 2H 4 Minor amounts of i-C 5H 12, n-C 6H 14, i-C 6H 14, and neo-C 6H 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 C0 2. The carbonic fluid coexisted immiscibly with a brine ( Salvi and Williams-Jones, 1992), 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 2 during the alteration of arfvedsonite to aegirine, and the subsequent reaction of this H 2 with orthomagmatic C0 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 C0 2.

  14. Compression-ignition fuel properties of Fischer-Tropsch syncrude

    SciTech Connect

    Suppes, G.J.; Terry, J.G.; Burkhart, M.L.; Cupps, M.P.

    1998-05-01

    Fischer-Tropsch conversion of natural gas to liquid hydrocarbon fuel typically includes Fischer-Tropsch synthesis followed by refining (hydrocracking and distillation) of the syncrude into mostly diesel or kerosene with some naphtha (a feedstock for gasoline production). Refining is assumed necessary, possibly overlooking the exception fuel qualities of syncrude for more direct utilization as a compression-ignition (CI) fuel. This paper evaluates cetane number, viscosity, cloud-point, and pour-point properties of syncrude and blends of syncrude with blend stocks such as ethanol and diethyl ether. The results show that blends comprised primarily of syncrude are potentially good CI fuels, with pour-point temperature depression being the largest development obstacle. The resulting blends may provide a much-needed and affordable alternative CI fuel. Particularly good market opportunities exist with Environmental Policy Act (EPACT) applications.

  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. 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.

  17. 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.

  18. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, June 30, 1988--September 30, 1988

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1988-12-31

    This report details experiments performed on three different copper-based catalysts: Cu/Cr{sub 2}O{sub 3}, Cu/MnO/Cr{sub 2}O{sub 3} and Cu/ZnO/Al{sub 2}O{sub 3}. Of these three catalysts, the Cu/ZnO/Al{sub 2}O{sub 3} exhibits the greatest stability when slurried in octacosane. More than 1000 hours-on-stream indicate that the catalyst activity is not detrimentally affected by high pressure, high H{sub 2}/CO ratio, or the presence of alkenes. All of these are necessary stability characteristics for the water-gas shift catalyst, if it is to be used in combination with a cobalt Fischer-Tropsch catalyst. A review of documented reduction procedures for cobalt-based Fischer-Tropsch catalysts is presented.

  19. 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.

  20. 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

  1. Technology development for iron Fischer-Tropsch catalysis. Quarterly technical progress report, October--December, 1994

    SciTech Connect

    1994-12-31

    Fischer-Tropsch catalysts must undergo a pretreatment in order to be active. As part of the authors comprehensive study to maximize the activity of iron based precipitated Fischer-Tropsch catalysts, they are currently attempting to optimize the activation procedure. Although they are able to achieve high activity using CO pretreatment, the catalysts tend to deactivate suddenly and rapidly after 500 hr of synthesis. Kolbel reports high CO conversion comparable to these results at a lower gas flow (2.4 vs. 3.4 nL/hr-g(Fe)); however, he achieved greater stability with conversions reported to be 90% after 1,400 hrs. One possibility for Kolbel`s higher stability could be due to the activation procedure. Herein are reported the initial results of a study to optimize the catalyst composition and the operating conditions for the iron based slurry phase Fischer-Tropsch synthesis when synthesis gas activation is utilized.

  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. 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

  4. 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

  5. Fischer-Tropsch synthesis in slurry reactor systems. Technical progress report for period ending July 31, 1981

    SciTech Connect

    Satterfield, C.N.; Huff, G.A. Jr.

    1981-01-01

    This is the first technical progress report on this grant, which had an effective date of initiation of March 9, 1981. During this period preliminary experimental results were obtained on the effects of reactant transport across the gas-liquid interface on synthesis gas conversion and product selectivity, utilizing an iron catalyst in a laboratory-scale, well-mixed slurry reactor.

  6. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst, January 1, 1990--March 30, 1990

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1990-01-01

    Experiments to study cobalt-catalyzed reactions of light 1-alkenes added to synthesis gas feed have been performed. Data have been collected at 220{degrees}C, 0.45 to 1.48 MPa and a synthesis gas flow rate between 0.015 and 0.030 Nl/(gcatmin) with H{sub 2}/CO of 1.45 to 2.25. C{sub 2}H{sub 4}, C{sub 3}H{sub 6}, and C{sub 4}H{sub 8} were added to the synthesis gas feed in concentrations ranging from 0.5 to 1.2 mole% of total feed. For each material balance in which 1-alkenes were added, a material balance was performed at similar process conditions without 1-alkenes added. This use of base case'' process conditions should make data analysis and interpretation easier. Material balances without 1-alkenes were also repeated to allow verification of catalyst selectivity stability. A total of 49 balances were performed during a single run which lasted over 2500 hours-on-stream. The hydrocarbon data have not yet been completed analyzed.

  7. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst, January 1, 1990--March 30, 1990

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1990-12-31

    Experiments to study cobalt-catalyzed reactions of light 1-alkenes added to synthesis gas feed have been performed. Data have been collected at 220{degrees}C, 0.45 to 1.48 MPa and a synthesis gas flow rate between 0.015 and 0.030 Nl/(gcatmin) with H{sub 2}/CO of 1.45 to 2.25. C{sub 2}H{sub 4}, C{sub 3}H{sub 6}, and C{sub 4}H{sub 8} were added to the synthesis gas feed in concentrations ranging from 0.5 to 1.2 mole% of total feed. For each material balance in which 1-alkenes were added, a material balance was performed at similar process conditions without 1-alkenes added. This use of ``base case`` process conditions should make data analysis and interpretation easier. Material balances without 1-alkenes were also repeated to allow verification of catalyst selectivity stability. A total of 49 balances were performed during a single run which lasted over 2500 hours-on-stream. The hydrocarbon data have not yet been completed analyzed.

  8. 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.

  9. 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.

  10. 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.

  11. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, July 1, 1990--September 30, 1990

    SciTech Connect

    Chanenchuk, C.A.; Yates, I.C.; Satterfield, C.N.

    1990-12-31

    A Co/MgO/SiO{sub 2} Fischer-Tropsch catalyst was operated simultaneously with a Cu/ZnO/Al{sub 2}O{sub 3} water-gas-shift catalyst in a slurry reactor for over 400 hours. The process conditions were held constant at a temperature of 240{degrees}C, a pressure of 0.79 MPa, and a 1.1 H{sub 2}/CO feed of 0.065 Nl/min-g.cat. The Fischer-Tropsch activity remained constant at the level predicted by the operation of the Co/MgO/SiO{sub 2} catalyst alone. The water-gas-shift reaction was near equilibrium. The hydrocarbon product distribution of the combined catalyst system was stable and matched that of the CO/MgO/SiO{sub 2} operating alone under similar conditions. The combined catalyst system exhibited a high selectivity to n-alkanes. Neither catalysts`s operation appeared to have a detrimental effect on that of the other, showing promise for future option.

  12. Multicomponent modelling of Fischer-Tropsch slurry reactors

    SciTech Connect

    Van Vuuren, D.S.; Heydenrych, M.D.

    1985-08-01

    In the multicomponent model developed for a Fischer-Tropsch slurry reactor, the water-gas shift reaction is assumed to be in equilibrium. This is supported by literature data on iron-based catalysts above 523 K and synthesis gas conversion above about 50%. A Schulz-Flory product distribution is used. Investigation of the effects of back-mixing and interphase mass transfer using the model shows that, although the mass transfer rates in full-scale reactors are fast compared with reaction rates, the ratio of the mass transfer rates of reactants and products is important in determining gas velocity and gas hold-up and hence reactor performance.

  13. 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.

  14. Mechanism and microkinetics of the Fischer-Tropsch reaction.

    PubMed

    van Santen, R A; Markvoort, A J; Filot, I A W; Ghouri, M M; Hensen, E J M

    2013-10-28

    The increasing availability of quantum-chemical data on surface reaction intermediates invites one to revisit unresolved mechanistic issues in heterogeneous catalysis. One such issue of particular current interest is the molecular basis of the Fischer-Tropsch reaction. Here we review current molecular understanding of this reaction that converts synthesis gas into longer hydrocarbons where we especially elucidate recent progress due to the contributions of computational catalysis. This perspective highlights the theoretical approach to heterogeneous catalysis that aims for kinetic prediction from quantum-chemical first principle data. Discussion of the Fischer-Tropsch reaction from this point of view is interesting because of the several mechanistic options available for this reaction. There are many proposals on the nature of the monomeric single C atom containing intermediate that is inserted into the growing hydrocarbon chain as well as on the nature of the growing hydrocarbon chain itself. Two dominant conflicting mechanistic proposals of the Fischer-Tropsch reaction that will be especially compared are the carbide mechanism and the CO insertion mechanism, which involve cleavage of the C-O bond of CO before incorporation of a CHx species into the growing hydrocarbon chain (the carbide mechanism) or after incorporation into the growing hydrocarbon chain (the CO insertion mechanism). The choice of a particular mechanism has important kinetic consequences. Since it is based on molecular information it also affects the structure sensitivity of this particular reaction and hence influences the choice of catalyst composition. We will show how quantum-chemical information on the relative stability of relevant reaction intermediates and estimates of the rate constants of corresponding elementary surface reactions provides a firm foundation to the kinetic analysis of such reactions and allows one to discriminate between the different mechanistic options. The paper will

  15. Product evaluation of Fischer-Tropsch derived fuels

    SciTech Connect

    Marano, J.J.; Rogers, S.; Choi, G.N.; Kramer, S.J.

    1994-12-31

    The Clean Air Act Amendments (CAAA) of 1990 have placed stringent requirements on the quality of transportation fuels. Most petroleum refiners are scrambling to meet provisions of the Amendments to be implemented between 1995 and 2000. These requirements will also have significant implications for the production of alternative fuels. These have been examined for Fischer-Tropsch (F-T) derived fuels. This analysis was conducted in conjunction with the U.S. Department of Energy (DOE) sponsored project, Baseline Design/Economics for Advanced Fischer-Tropsch Technology, conducted by Bechtel and Amoco. The goal of this study was to develop a baseline design for indirect liquefaction of Illinois No. 6 coal using gasification, syngas conversion in slurry reactors with iron catalysts, and conventional refinery upgrading of the F-T derived hydrocarbon liquids. One alternative case using ZSM-5 upgrading technology was also considered. This study included complete capital and operating cost estimates for the processes. To perform economic analyses for the different design cases, the products from the liquefaction plant had to be valued relative to conventional transportation fuels. This task was accomplished by developing a Linear Programming (LP) model for a typical midwest refinery, and then feeding the F-T liquids to the refinery. In this way, the breakeven value determined for these materials is indicative of the price they could command if available in the marketplace. Inputs to the LP model include: refinery size, configuration, feedstocks, products, specifications, prices, and operating and capital recovery costs. The model was set up to be representative of conditions anticipated for the turn of the century. This required inclusion of fuel specifications from the CAAA of 1990 which have or will come into force by the year 2000.

  16. DEVELOPMENT OF PRECIPITATED IRON FISCHER-TROPSCH CATALYSTS

    SciTech Connect

    Dr. Dragomir B. Bukur; Dr. X. Lang; Dr. S. Chokkaram; Dr. L. Nowicki; G. Wei; Dr. Y. Ding; Dr. B. Reddy; Dr. S. Xiao

    1999-07-22

    Despite the current worldwide oil glut, the US will ultimately require large-scale production of liquid (transportation) fuels from coal. Slurry phase Fischer-Tropsch (F-T) technology, with its versatile product slate, may be expected to play a major role in production of transportation fuels via indirect coal liquefaction. Some of the F-T catalysts synthesized and tested at Texas A and M University under DOE Contract No. DE-AC22-89PC89868 were more active than any other known catalysts developed for maximizing production of high molecular weight hydrocarbons (waxes). The objectives of the present contract were to demonstrate repeatability of catalyst performance and reproducibility of preparation procedures of two of these catalysts on a laboratory scale. Improvements in the catalyst performance were attempted through the use of: (a) higher reaction pressure and gas space velocity to maximize the reactor productivity; (b) modifications in catalyst preparation steps; and (c) different pretreatment procedures. Repeatability of catalyst performance and reproducibility of catalyst synthesis procedure have been successfully demonstrated in stirred tank slurry reactor tests. Reactor space-time-yield was increased up to 48% by increasing reaction pressure from 1.48 MPa to 2.17 MPa, while maintaining the gas contact time and synthesis gas conversion at a constant value. Use of calcination temperatures above 300 C, additional CaO promoter, and/or potassium silicate as the source of potassium promoter, instead of potassium bicarbonate, did not result in improved catalyst performance. By using different catalyst activation procedures they were able to increase substantially the catalyst activity, while maintaining low methane and gaseous hydrocarbon selectivities. Catalyst productivity in runs SA-0946 and SA-2186 was 0.71 and 0.86 gHC/g-Fe/h, respectively, and this represents 45-75% improvement in productivity relative to that achieved in Rheinpreussen's demonstration plant

  17. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, October 1, 1988--December 31, 1988

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1988-12-31

    A cobalt Fischer-Tropsch catalyst (CO/MgO/silica) was reduced and slurried in combination with reduced Cu/ZnO/Al{sub 2}0{sub 3} water-gas-shift catalyst. Combined catalyst system was run at fixed process conditions for more than 400 hours. The system showed stable selectivity. The Cu/ZnO/Al{sub 2}0{sub 3} water-gas-shift catalyst remained reasonably active in the presence of the cobalt catalyst. Hydrocarbon selectivity of the cobalt and Cu/ZnO/Al{sub 2}0{sub 3} catalyst system compared favorably to selectivity of iron-based catalysts. Methane selectivity was slightly higher for the cobalt-based system, but C{sub 5}{sup +} selectivity was essentially the same. The hydrocarbon product distribution appeared to exhibit a double-a behavior. a{sub 1} was near 0.80 which is higher than that of iron catalysts, while a{sub 2} was calculated to be 0.86 which is somewhat lower than would be typical for an iron-based catalyst.

  18. 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.

  19. 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.

  20. The surface chemistry of iron Fischer-Tropsch catalysts

    SciTech Connect

    Dwyer, D.J.; Hardenburgh, J.H.

    1986-04-01

    The indirect conversion of coal to liquid hydrocarbons via steam gasification followed by synthesis gas (CO/H/sub 2/) chemistry has been the subject of intensive study for a number of decades. A key technological challenge facing researchers in this area is control over the product distribution during the hydrocarbon synthesis step. In the case of iron Fischer-Tropsch catalysts, it has been known that the addition of alkali to the metal catalyst has a significant impact on the product distribution. Iron catalysts treated with alkali produce less methane more alkenes and higher molecular weight products. In spite of numerous investigations, the details of this promotional effect are not understood on a molecular level. To explore the role of alkali in the surface chemistry of iron catalysts, the authors have carried out a combined surface science and catalytic kinetic study of a model iron catalyst with and without surface alkali.

  1. Technology development for iron Fischer-Tropsch catalysts

    SciTech Connect

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

    1991-01-01

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

  2. Technology development for iron Fischer-Tropsch catalysts

    SciTech Connect

    Not Available

    1991-01-01

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

  3. Technology development for iron Fischer-Tropsch catalysts

    SciTech Connect

    Not Available

    1990-01-01

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

  4. New developments in cobalt-based Fischer-Tropsch catalysis and processes

    SciTech Connect

    Singleton, A.H.; Davis, B.E.; Oukaci, R.

    1997-12-31

    The Williams Companies, Inc. of Tulsa, Oklahoma, has announced a breakthrough in gas-to-liquids (GTL) technology that revolutionizes the production of transportation fuels from natural gas. Building on its twenty years of research in Fischer-Tropsch (F-T) conversion technology, Williams has developed a new process that significantly outperforms existing GTL technologies for large-scale (ca. 50,000 BPSD) applications and advances the state-of the-art of converting natural gas into high quality liquid transportation fuels. By employing a new generation of cobalt-based catalysts, Williams` GasCat{sup SM} F-T process achieves high productivity, resulting in superior catalytic reactor performance compared to existing F-T techniques. The GasCat process also reduces capital requirements and operating costs by employing advanced slurry bubble column reactor (SBCR) technology. Although the process is applicable to coal derived synthesis gas, GasCat has enormous implications for large remote gas reserves worldwide, due to the limited options previously available for exploiting the potential of such reservoirs. While the paper presents the details and significance of this new development as it relates to natural gas, it obviously has similar significance to the indirect liquefaction of coal.

  5. 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. PMID:24339240

  6. 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.

  7. 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 comparisons. Particular attention will be devoted to generating reproducible kinetic and selectivity data and to developing reproducible improved catalyst compositions.

  8. 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.

  9. Development of 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.

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

    SciTech Connect

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

    1987-01-01

    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.

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

    SciTech Connect

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

    1989-01-01

    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.

  12. 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.

  13. Blends of Fischer-Tropsch crude: A lower cost route to diesel fuel

    SciTech Connect

    Suppes, G.J.; Terry, J.; Burkhart, M.; Cupps, M.P.

    1998-12-31

    Fischer-Tropsch conversion of gasification products to liquid hydrocarbon fuel typically includes Fischer-Tropsch synthesis followed by refining (hydrocracking and distillation) of the syncrude into mostly diesel or kerosene with some naphtha (a feedstock for gasoline production). Refining is assumed necessary, possibly overlooking the exceptional fuel qualities of syncrude for more direct utilization as a compression-ignition (CI) fuel. This paper evaluates cetane number, viscosity, cloud point, and pour point properties of syncrude and blends of syncrude with blend stocks such as ethanol and diethyl ether. The results show that blends comprised primarily of syncrude are potentially good CI fuels with pour-point temperature depression being the largest development obstacle. The resulting blends may provide an alternative CI fuel which costs less than petroleum based diesel, depending on the feedstock and feedstock preparation costs. Particularly good market opportunities exist with Energy Policy Act (EPACT) applications.

  14. Effect of potassium promoter on cobalt nano-catalysts for fischer-tropsch reaction

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

    In the present work effect of potassium on cobalt nano-catalysts for Fischer-Tropsch reaction has been presented. The catalysts were prepared using a wet impregnation method and promoted with potassium. Samples were characterized by nitrogen adsorption, H2-TPR, and TEM. The Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor 220 δC, 1 atm, H2/CO = 2 and a velocity (SV) =12 L/g.h. for 5 h. Addition of potassium into Co/CNTs decreased the average size of cobalt nanoparticles and the catalyst reducibility. Potassium-promoted Co catalyst resulted in appreciable increase in the selectivity of C5+ hydrocarbons and suppressed methane formation. The 0.06%KCo/CNTs catalyst enhanced the C5+ hydrocarbons selectivity by a factor of 23.5% and reduced the methane selectivity by a factor of 39.6%

  15. The optimally performing Fischer-Tropsch catalyst.

    PubMed

    Filot, Ivo A W; van Santen, Rutger A; Hensen, Emiel J M

    2014-11-17

    Microkinetics simulations are presented based on DFT-determined elementary reaction steps of the Fischer-Tropsch (FT) reaction. The formation of long-chain hydrocarbons occurs on stepped Ru surfaces with CH as the inserting monomer, whereas planar Ru only produces methane because of slow CO activation. By varying the metal-carbon and metal-oxygen interaction energy, three reactivity regimes are identified with rates being controlled by CO dissociation, chain-growth termination, or water removal. Predicted surface coverages are dominated by CO, C, or O, respectively. Optimum FT performance occurs at the interphase of the regimes of limited CO dissociation and chain-growth termination. Current FT catalysts are suboptimal, as they are limited by CO activation and/or O removal. PMID:25168456

  16. Upgrading of light Fischer-Tropsch products

    SciTech Connect

    Shah, P.P.

    1990-11-30

    The upgrading of Fischer-Tropsch (F-T) light ends was studied at UOP in a program sponsored by the Pittsburgh Energy Technology Center of the US Department of Energy. The goal of the program was to increase the overall yield of marketable transportation fuels from the F-T upgrading complex by focusing on liquefied petroleum gas (LPG) and naphtha. An overview of the entire light-ends program is presented in this paper. Although this contract is specifically concerned with light products (C{sub 3}-C{sub 11}), a separate DOE-sponsored program at UOP investigated the characterization and upgrading of the heavy end of the F-T product spectrum: F-T wax. An economic analysis of the light and heavy ends upgrading was performed to evaluate the conversion of F-T products to marketable transportation fuels. 9 refs., 7 figs., 9 tabs.

  17. 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. PMID:15310958

  18. 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.

  19. 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.

  20. 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.

  1. An exploratory program for using hydrous metal oxide ion exchangers as Fischer-Tropsch catalysts

    SciTech Connect

    Lynch, A.W.; Dosch, R.G.; Sault, A.G.

    1990-01-01

    The purpose of this program is to investigate the potential of hydrous metal oxide (HMO) ion exchangers, invented at Sandia National Laboratories, as Fischer-Tropsch (F-T) catalysts. Metals known to be active in F-T synthesis (e.g. Fe, Co) were ion exchanged on hydrous metal oxide supports. Although HMO catalysts based on Zr, Nb, and Ta have been investigated in direct coal liquefaction studies, this effect focused on formulations based on the hydrous titanium oxide (HTO) system. The program has the goals of developing a catalyst with (1) high activity, (2) selectively to fuel range or other useful products, and (3) better properties for use in slurry reactors. The program has three main tasks: (1) catalyst synthesis, to develop methods for preparing catalysts having desirable F-T properties, (2) characterization, to investigate catalysts proving to have desirable properties by a variety of analytical techniques to determine correlations between activity and material properties and (3) testing to determine activity and selectivity of catalysts. This paper discussed results of activity testing of Ruhrchemie catalyst and some catalyst formulations prepared using ion exchange on hydrous titanium oxide and precipitation. For example, at 250{degree}C the Ruhrchemie catalyst converts {approximately}50% of the syngas feed to reaction products. In comparison, iron catalysts prepared by ion exchange and precipitation had conversions ranging from 20 to 50% over a temperature range of 250 to 275{degree}C of the syngas feed. In addition, results are Auger surface analysis of Ruhrchemie catalyst are presented. 6 refs., 2 figs., 2 tabs.

  2. 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.

  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.

    1997-05-14

    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 5 catalysts synthesized in this program for activity, selectivity and aging characteristics.

  5. Technology development for iron Fischer-Tropsch catalysts

    SciTech Connect

    Frame, R.R.

    1991-01-01

    Objectives are to develop active, stable iron 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. For a H[sub 2]-CO in molar ratio of 0.5 to 1.0, catalyst performance target is 88% CO+H[sub 2] conversion at a minimum space velocity of 2.4 NL/hr/gFe, with no more than 4% methane/ethane selectivity and 1% conversion loss per week. During this period, it was found that the performance of the slurry-phase iron and copper oxide-based catalyst depends on the amount of K. Five catalysts with differing K contents were studied. The catalysts with the lowest K were more active than the ones with higher K levels. The one with the middle K level was judged best.

  6. XPS characterization of iron Fischer-Tropsch catalysts

    SciTech Connect

    Kuivila, C.S.; Stair, P.C.; Butt, J.B.

    1986-04-01

    Analysis of Fe(2p) XPS and iron Auger spectra, combined with C(1s) XPS measurements, provides a valuable technique for studying the compositional behavior of Fischer-Tropsch catalysts. The extent of catalyst oxidation during synthesis at high conversions may be estimated in terms of the area contribution of oxide phases to the Fe(2p) spectrum. Similarities between the metal and carbide core level spectra are likely to complicate the determination of these phases when oxides are present. Analysis of the metal and carbide contributions to the iron Auger spectrum provides an alternate method for monitoring surface carbide formation during low conversion synthesis. The ''surface compositions'' obtained in this manner are at best semi-quantitative, since the contribution of a particular phase to the XPS or Auger spectrum will depend on both the amount and distribution of that phase within the detected volume. In spite of this, the spectrum fitting technique should prove to be useful in characterizing the time and conversion dependent nature of the active catalyst surface.

  7. INTEGRATED FISCHER TROPSCH MODULAR PROCESS MODEL

    SciTech Connect

    Donna Post Guillen; Richard Boardman; Anastasia M. Gribik; Rick A. Wood; Robert A. Carrington

    2007-12-01

    With declining petroleum reserves, increased world demand, and unstable politics in some of the world’s richest oil producing regions, the capability for the U.S. to produce synthetic liquid fuels from domestic resources is critical to national security and economic stability. Coal, biomass and other carbonaceous materials can be converted to liquid fuels using several conversion processes. The leading candidate for large-scale conversion of coal to liquid fuels is the Fischer Tropsch (FT) process. Process configuration, component selection, and performance are interrelated and dependent on feed characteristics. This paper outlines a flexible modular approach to model an integrated FT process that utilizes a library of key component models, supporting kinetic data and materials and transport properties allowing rapid development of custom integrated plant models. The modular construction will permit rapid assessment of alternative designs and feed stocks. The modeling approach consists of three thrust areas, or “strands” – model/module development, integration of the model elements into an end to end integrated system model, and utilization of the model for plant design. Strand 1, model/module development, entails identifying, developing, and assembling a library of codes, user blocks, and data for FT process unit operations for a custom feedstock and plant description. Strand 2, integration development, provides the framework for linking these component and subsystem models to form an integrated FT plant simulation. Strand 3, plant design, includes testing and validation of the comprehensive model and performing design evaluation analyses.

  8. The hydrocarbon selectivity of cobalt Fischer-Tropsch catalysts

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1991-07-01

    A cobalt Fischer-Tropsch catalyst was studied in a continuous-flow, well-stirred slurry reactor at 220 to 240{degrees}C, 0.5 to 1.5 MPa, H{sub 2}/CO feed ratios between 1.5 and 3.5, H{sub 2} conversions between 6 and 68%, and CO conversions between 11 and 73%. Increasing space velocity (decreasing conversion) or decreasing reactor H{sub 2}/CO ratio decreased the yield of (undesired) C{sub 1} products and increased the yield of (desired) C{sub 10}+ products. Reactor temperature and pressure had little effect on the carbon number distribution. These findings are interpreted in terms of the extent of the readsorption of 1-alkenes into growing chains on the catalyst surface. The relative selectivity to 1-alkenes by the primary synthesis and secondary reaction of l-alkenes to n-alkanes and 2-alkenes depends on reactor H{sub 2}/CO ratio and CO concentration. 25 refs., 15 figs.

  9. Romania program targets methanol and Fischer-Tropsch research

    SciTech Connect

    Not Available

    1987-03-01

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

  10. 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.

  11. TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

    SciTech Connect

    Burtron H. Davis

    1999-04-30

    The impact of activation procedure on the phase composition of precipitated iron Fischer-Tropsch (FT) catalysts has been studied. Catalyst samples taken during activation and FT synthesis have been characterized by Moessbauer spectroscopy. Formation of iron carbide is necessary for high FT activity. Hydrogen activation of precipitated iron catalysts results in reduction to predominantly metallic iron and Fe{sub 3}O{sub 4}. Metallic iron is not stable under FT 3 4 conditions and is rapidly converted to {epsilon}{prime}-Fe{sub 2.2}C. Activation with carbon monoxide or syngas 2.2 with low hydrogen partial pressure reduces catalysts to {chi}-Fe{sub 5}C{sub 2} and a small amount of 5 2 superparamagnetic carbide. Exposure to FT conditions partially oxidizes iron carbide to Fe{sub 3}O{sub 4}; however, catalysts promoted with potassium or potassium and copper maintain a constant carbide content and activity after the initial oxidation. An unpromoted iron catalyst which was activated with carbon monoxide to produce 94% {chi}-Fe{sub 5}C{sub 2}, deactivated rapidly as the carbide was oxidized to Fe{sub 3}O{sub 4}. No difference in activity, stability or deactivation rate was found for {chi}-Fe{sub 5}C{sub 2} and {epsilon}{prime}-Fe{sub 2.2}C.

  12. 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.

  13. 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

  14. Activation and promotion studies in a mixed slurry reactor with an iron-manganese Fischer-Tropsch catalyst

    SciTech Connect

    Pennline, H.W.; Zarochak, M.F.; Stencel, J.M.; Diehl, J.R.

    1987-03-01

    Synthesis gas was reacted over a coprecipitated iron-manganese Fischer-Tropsch catalyst in a slurry reactor. The effect of various activation parameters - temperature, pressure, and gas composition - on subsequent catalyst activity and product selectivity was investigated. The gas composition had the most dramatic effect on the catalyst activation and the ensuing synthesis gas conversion. The effect of potassium promotion on catalyst activity and product selectivity was also studied in slurry reactor tests.

  15. TECHNOLOGY DEVELOPMENT FOR IRON AND CONBALT FISCHER-TROPSCH CATALYSTS

    SciTech Connect

    Burtron H. Davis

    2000-10-01

    The use of alkali promoters has been widely practiced. However, data to compare various promoters is limited for the iron-based catalysts and much of the available data were obtained at low pressure or under a variety of reaction conditions. The importance of the alkali promoter in determining catalytic activity, stability and selectivity merits a comparison of the promoters under suitable reaction conditions. The present study utilizes medium pressure synthesis conditions to compare the alkali promoters under the same reaction conditions and over a wide range of conversion levels. Iron-based Fischer-Tropsch (FT) catalysts undergo a series of phase transformations during activation and use. Activation with carbon monoxide or syngas typically results in the conversion of Fe{sub 2}O{sub 3} to Fe{sub 3}O{sub 4} and ultimately to one or more carbides. During FT synthesis, iron carbides can be oxidized to Fe{sub 3}O{sub 4} if the H{sub 2}O/H{sub 2} or CO{sub 2}/CO ratios are high enough. There has been considerable debate about the active phase of the FT synthesis. Some studies have indicated an active oxide species while most have supported a carbide species. Moessbauer spectroscopy has proven to be an effective technique for the analysis of iron-based FT catalysts. In situ Moessbauer studies have been reported; however, these studies have been performed at low pressure and low conversions. Studies performed at industrially relevant conditions have generally involved removing the catalyst from the reactor followed by passivation which, if not performed properly, will oxidize the catalyst. Herein are reported the Moessbauer results obtained on an unpromoted precipitated iron catalyst that was activated and reacted in a slurry phase, continuous stirred tank reactor at high conversion and under industrially relevant conditions.

  16. Attrition Resistant Iron-Based Fischer-Tropsch Catalysts

    SciTech Connect

    Jothimurugesan, K.; Goodwin, J.G.; Spivey, J.J.; Gangwal, S.K.

    1997-03-26

    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 when using low CO/H{sub 2} ratio synthesis gases derived from modem coal gasifiers. This is because in addition to reasonable F-T activity, the FT catalysts also possess high water gas shift (WGS) activity. 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, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance 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. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity.

  17. Attrition Resistant Iron-Based Fischer-Tropsch Catalysts.

    SciTech Connect

    Jothimurugesan, K.; Goodwin, J.S.; Spivey, J.J.; Gangwal, S.K.

    1997-09-22

    The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO and 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 when using low CO/H{sub 2} ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. 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, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance 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. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity.

  18. 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.

  19. Fischer-Tropsch wax characterization and upgrading: Final report

    SciTech Connect

    Shah, P.P.; Sturtevant, G.C.; Gregor, J.H.; Humbach, M.J.; Padrta, F.G.; Steigleder, K.Z.

    1988-06-06

    The characterization and upgrading of Fischer-Tropsch wax was studied. The focus of the program was to maximize the yield of marketable transportation fuels from the Fischer-Tropsch process. The wax was characterized using gel permeation chromatography (GPC), high resolution mass spectrometry (HRMS), infrared spectroscopy (IR), gas chromatography (GC), nuclear magnetic resonance (NMR) and various other physical analyses. Hydrocracking studies conducted in a pilot plant indicate that Fischer-Tropsch wax is an excellent feedstock. A high yield of excellent quality diesel fuel was produced with satisfactory catalyst performance at relatively mild operating conditions. Correlations for predicting key diesel fuel properties were developed and checked against actual laboratory blend data. The blending study was incorporated into an economic evaluation. Finally, it is possible to take advantage of the high quality of the Fischer-Tropsch derived distillate by blending a lower value light cycle oil (produced from a refinery FCC unit) representing a high aromatic and low cetane number. The blended stream meets diesel pool specifications (up to 60 wt % LCO addition). The value added to this blending stream further enhances the upgrading complex return. 22 refs., 39 figs., 48 tabs.

  20. ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

    SciTech Connect

    JAMES G. GOODWIN, JR.; JAMES J. SPIVEY; K. JOTHIMURUGESAN; SANTOSH K. GANGWAL

    1998-09-17

    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 when using low CO/H{sub 2} ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. 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, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance 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. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity. The effect of silica addition via coprecipitation and as a binder to a doubly promoted Fischer-Tropsch synthesis iron catalyst (100 Fe/5 Cu/4.2 K) was studied. The catalysts were prepared by coprecipitation, followed by binder addition and drying in a 1

  1. ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

    SciTech Connect

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

    1999-03-29

    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 when using low CO/H2 ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. 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, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance 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. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity. The effect of silica addition via coprecipitation and as a binder to a doubly promoted Fischer-Tropsch synthesis iron catalyst (100 Fe/5 Cu/4.2 K) was studied. The catalysts were prepared by coprecipitation, followed by binder addition and drying in a 1 m

  2. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, April 1, 1990--June 30, 1990

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1990-12-31

    Experiments on cobalt-catalyzed reactions of light 1-alkenes added to synthesis gas were performed. Data have been collected at 220C, 0.45 to 1.48 MPa and a synthesis gas flow rate between 0.015 and 0.030 Nl/(gcat{center_dot}min) with H{sub 2}/CO of 1.45 to 2.25. Ethylene, propene, and butene were added to synthesis gas feed from 0.5 to 1.2 mole% of total feed. For each material balance in which 1-alkenes were added, a material balance was performed at similar process conditions without 1-alkenes added, as ``base case``. Material balances without added 1-alkenes were also repeated to verify of catalyst selectivity stability. 49 material balances were performed during a single run lasting over 2,500 hours-on-stream. The hydrocarbon data have been completely analyzed; data correlations are still being made. Since C{sub 3}/C{sub 1} ratios by ethene addition, C{sub 4}/C{sub 1} ratios by propene addition, and C{sub 5}/C{sub 1} ratios by 1-butene addition, it appears that 1-alkenes may incorporate into growing chains on the surface of the catalyst. Further evidence for incorporation can be seen by comparing selectivity to n-alcohol one carbon number higher than added 1-alkene. Yield of this n-alcohol increases when alkenes are present. Sensitivity of hydrocarbon distribution to process variables seems to be greater on Co than on Fe catalysts.

  3. 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.

  4. 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.

  5. Development of process evaluation of improved Fischer-Tropsch slurry catalysts. Quarterly technical progress report, 1 April--30 June 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.

  6. Development and process evaluation of improved Fischer-Tropsch slurry catalysts. Quarterly technical progress report, 1 October-31 December 1987

    SciTech Connect

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

    1987-12-31

    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.

  7. Fine details on the selectivity and kinetics of the Fischer-Tropsch synthesis over precipitated cobalt catalysts by combination of quantitative gas chromatography and modelling

    SciTech Connect

    Hurlbut, R.S.; Puskas, I,; Schumacher, D.J.

    1995-12-31

    This report summarizes a part of our work carried out on the conversion of natural gas-derived synthesis gas to liquid fuels. Particularly, we were interested to find a catalyst which can convert dilute synthesis gas - such as obtainable from natural gas by partial oxidation with air - to predominantly liquid products at low pressures. For this purpose we needed to generate fundamental kinetic information on the controllability of the molecular weight distribution, which is defined by the chain growth probability of the reaction, because relatively little information is available on the subject. A wealth of information suggests, that with some exceptions in the low molecular weight regimes, the product distributions can be described by Anderson-Schulz-Flory (ASF) kinetics, using either a single chain growth probability, or separate chain growth probabilities for the light and heavy products. The causes of the {open_quotes}dual{close_quotes} chain growth probabilities still have not been defined. Three causes have been suggested which could account for the dual chain growth probabilities: (1) Differences in the catalytic sites; (2) transport-enhanced 1-olefin readsorption and incorporation into the heavy product fractions; and (3) operating characteristics of the reactor.

  8. Synthesis of octane enhancers during slurry-phase Fischer-Tropsch. Quarterly technical progress report No. 8, July 1, 1992--September 30, 1992

    SciTech Connect

    Marcelin, G.

    1993-07-07

    The initial work on the synthesis of MTBE during CO hydrogenation shows that MTBE cannot be formed directly on metal sites and likely requires the presence of an acid site. However, MTBE can be made successfully when an acid site, provided by the zeolites, is present in the vicinity of the methanol-synthesis metal sites. When i-butylene was added during CO hydrogenation over a composite catalyst consisting of Li-Pd/SiO{sub 2} and a hydrogen-zeolite, MTBE was formed in measurable amounts. The major by-product of this reaction scheme was isobutane and the dimer of i-butylene. In general, ZSM-5 was found to be superior to LZ210-12 HY zeolite. CO hydrogenation over a bifunctional PdNaY catalyst shows that branched hydrocarbons as well as MEOH can be made successfully at the same time. Addition of i-butylene over this catalyst only (i.e. without other zeolite) results in the formation of trace amounts of MTBE.

  9. Recent developments in Sasol Fischer-Tropsch technology

    SciTech Connect

    Dry, M.E.

    1986-04-01

    When considering improvements in the Fischer-Tropsch (FT) route for producing liquid fuels from coal, it is important to bear in mind the relative costs of the various process steps. The advantage of a big improvement in the selectivity of the FT synthesis (an ideal case would be one which produces only gasoline and diesel fuel) is that this would lower the costs of both the product separation and the refinery sections, which, together account for 22% of the total, Obvious provisos, however, are that the cost of the catalyst should not be markedly increased and that its conversion activity should remain high; otherwise the gains in say the refinery would be negated by increased FT synthesis costs. Elimination of certain products do not necessarily improve the economics. If the FT process made no ethylene, the expensive cryogenic separation unit could be replaced by a cheaper process but this would not be a real gain as the market value of ethylene relative to that of liquid fuels justifies its recovery. A similar situation holds for the alcohols and ketones produced in the FT process. If these products were absent then the expensive process of first recovering them from the FT water and then refining them would significantly lower the overall costs. (Note that these products would have to be completely absent and not just lowered as the latter would have little impact on the economics of recovery as the volume of water to be processed would remain unchanged.) These low molecular mass alcohols and ketones, however, sell at high prices; and furthermore, the alcohols are valuable as gasoline octane boosters. Thus the production and recovery of these components are justified.

  10. 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.

  11. Mechanism of promotion of iron Fischer-Tropsch catalysts: Final report

    SciTech Connect

    Tau, L.M.; Dabbagh, H.; Chawla, B.; Davis, B.H.

    1987-12-31

    The kinetic isotope method (KIM) has been utilized in a study designed to determine the way in which promoters for iron catalysts impact the variety of primary and secondary reactions in the Fischer-Tropsch synthesis (FTS). The KIM involves the addition of known or suspected intermediates to the synthesis gas feed. In order to follow the conversion of the added compound, and the products formed as a result of the addition, the added compound is labeled with a radioactive isotope of carbon. An analysis of the Fischer-Tropsch synthesis products readily permits one to identify those compounds that are derived from the added compound. Using this technique, results were obtained with unpromoted iron, iron promoted by Al/sub 2/O/sub 3/, ThO/sub 2/, ZrO/sub 2/, and SiO/sub 2/, and alkali promoted iron catalysts. A combination of gas chromatographic, dry column chromatographic and liquid chromatographic techniques allowed us to determine the /sup 14/C present in compounds over the C/sub 1/--C/sub 22/ range in the alkane and alkene fractions. A continuous stirred tank reactor (CSTR) was used for most of the experimental studies. 108 refs., 100 figs., 6 tabs.

  12. 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.

  13. Nano-sized cobalt based Fischer-Tropsch catalysts for gas-to-liquid process applications.

    PubMed

    Kang, Jung Shik; Awate, S V; Lee, Yun Ju; Kim, So Jung; Park, Moon Ju; Lee, Sang Deuk; Hong, Suk-In; Moon, Dong Ju

    2010-05-01

    Nano-sized cobalt supported catalysts were prepared for Fischer-Tropsch synthesis in gas-to-liquid (GTL) process. The dependence of crystallite size and reducibility of Co3O4 on the supports were investigated with FTS activity. XRD peaks revealed nano crystallites (< 5.47 nm) of Co3O4 crystallites. TEM showed round shaped particles with size less than 5 nm. Support with higher acidity decreased crystallite size of Co3O4. XRD data of used catalysts showed Co3O4 crystallites smaller than 3.5 nm which do not reduce easily to Co(0) state. The crystallite size of Co3O4 plays a role in its reduction to Co(0). TPR results showed that the reduction temperature shifts to higher temperature due to metal-support interaction. The variation in the activity of the catalysts depends on the support which in turn affects the crystallite size, dispersion, reducibility and activity of Co species in Fischer-Tropsch Synthesis (FTS). In this study, Co/Al2O3 showed higher CO conversion than the other catalysts. However, the C5+ production was in order Co/SiO2 (78.1%) > Co/Al2O3 (70.0%) > Co/R_TiO2 (61%) > Co/A_TiO2 (57.5%). PMID:20359031

  14. Fischer-Tropsch slurry phase process variations. Quarterly report, April 1-June 30, 1986

    SciTech Connect

    Satterfield, C.N.; Hanlon, R.; Matsumoto, D.K.

    1986-01-01

    In studies at 232/sup 0/C and 248/sup 0/C and 0.92 MPa, during the first 20 hours on stream, both Fischer-Tropsch synthesis activity and CO consumption increased to quasi-steady-state values. The bulk catalyst, initially ..cap alpha..-Fe, was converted to a mixture of ..cap alpha..-Fe and iron carbides, as determined by Moessbauer spectroscopy. During the first few hours, methane selectivity decreased markedly while the olefin/paraffin ratio increased. No change was observed in the C/sub 2/-C/sub 8/ product distribution with time on stream. When an industrial iron-based Fischer-Tropsch catalyst is first put on stream some 20 to 40 hours may elapse before its activity and selectivity approach steady-state conditions and during this time the phases present in the catalyst usually change markedly. The present study used a fused triply-promoted magnetite catalyst, sold for use in ammonia synthesis, which is very similar to one of the kinds of iron catalyst used industrially at SASOL in South Africa. It was completely reduced initially. Reaction was carried out in semi-continuous fashion in a well-stirred 1-litter autoclave. We were particularly concerned with studying the activity and selectivity of this catalyst as it approached steady-state behavior and determining if this correlated with the phases present in the catalyst as determined by Moessbauer spectroscopy. 20 refs., 9 figs., 1 tab.

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

    SciTech Connect

    Matthew Neurock

    2002-09-11

    As the US seeks to develop an energy strategy that reduces the reliance on foreign oil, there is a renewed interest in research and development of the Fischer Tropsch synthesis of converting syngas into long chain hydrocarbon products. This report investigates some of the basic elementary steps for Fischer-Tropsch synthesis over ideal Co and Ru metal surfaces by using ab initio density functional theoretical calculations. This includes activation of CO of CO, the hydrogenation of CH{sub x} intermediates, and the adsorption and dissociation of water. The activation of CO is studied in detail showing a strong dependence on the surface coverage, defect sites and Co-Ru alloy formation. The barriers for CO activation over the ideal (0001) surfaces are quite high making CO activation at the terrace sites unlikely under operating conditions. The calculations for the overall reaction energies at the step edges indicate that these sites are much more reactive. The hydrogenation of the CHx intermediates occurs in a sequential fashion. CH1 was found to be the most stable intermediate over various surfaces. The barriers to form both CH* as well as CH{sub 4} are both found to be highly activated and potentially difficult steps. Water which is a reaction product was found to be weakly adsorbed on Co. Analysis of the microscopic reverse reaction of water activation indicates that this process has a very low activation barrier. Consequently, any water which forms desorbs or is activated to form surface hydroxyl intermediates.

  16. Bridging the pressure and material gap in heterogeneous catalysis: cobalt Fischer-Tropsch catalysts from surface science to industrial application.

    PubMed

    Oosterbeek, Heiko

    2007-07-21

    The Fischer-Tropsch (FT) process is the heart of many natural gas conversion processes as it enables the conversion of a mixture of CO and H(2) into valuable long-chain hydrocarbons. Here we report on the use of state-of-the-art surface science techniques to obtain information on the relationship between the surface atomic structure of model catalysts and their performance in the Fischer-Tropsch reaction. Cobalt single crystals and polycrystals were modified with non-reducible oxides as to resemble industrial catalysts. Reflection absorption infrared spectroscopy was used for examining the CO adsorption behaviour at room temperature as well as at 493 K at CO pressures spanning 10(-7) to 300 mbar on both (modified) Co single/polycrystals and an industrial catalyst. Polarization modulation was applied to cancel the CO gas phase absorption. Subsequently, they were subjected to reaction tests in the same apparatus at 1 bar and 493 K. This allowed us to close the material, pressure and instrument gap in the field of Fischer-Tropsch synthesis on cobalt-based catalysts. PMID:17612722

  17. Cobalt cluster effects in zirconium promoted Co/SiO{sub 2} Fischer-Tropsch catalysts

    SciTech Connect

    Feller, A.; Claeys, M.; Steen, E. van

    1999-07-01

    The effect of zirconium addition to the catalyst formulation of Co/SiO{sub 2} Fischer-Tropsch catalysts was investigated. With increasing zirconium content the strong interaction between silica and cobalt is reduced and a somewhat weaker cobalt-zirconium interaction is observed. Therefore the degree of reduction of catalysts, which were reduced at 400 C for 16 h, increases strongly. The cobalt crystallite size increases with increasing zirconium content, leading to smaller cobalt metal surface areas for the freshly reduced catalyst. Cobalt particles can be found in clusters on the silica support. The size of cobalt clusters decreases and thus the number of cobalt particles within a cluster decreases with increasing zirconium content. At steady-state conditions the CO-conversion of the promoted catalyst in the Fischer-Tropsch synthesis increases with increasing zirconium content. The C{sub 5+}-selectivity and the secondary hydrogenation activity pass a maximum with increasing zirconium content. The observed changes in activity and selectivity are explained in terms of an increase in the amount of metallic cobalt available under reaction conditions, leading to an increased activity, and a decrease in the cobalt cluster size, which diminishes the probability for secondary reactions. Furthermore, it was concluded that secondary double bond isomerization can be catalyzed to some extent by zirconia.

  18. CHAIN-LIMITING OPERATION OF FISCHER-TROPSCH REACTOR

    SciTech Connect

    Apostolos A. Nikolopoulos; Santosh K. Gangwal

    2000-11-01

    The use of pulsing to limit the chain growth of the hydrocarbon products of the Fischer-Tropsch (FT) synthesis in order to maximize the yield of diesel-range (C{sub 10}-C{sub 20}) products was examined on three high-chain-growth-probability ({alpha} {ge} 0.9) FT catalysts. On a Co-ZrO{sub 2}/SiO{sub 2} FT synthesis catalyst the 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 the instantaneous selectivity to CH{sub 4}. An optimum set of H{sub 2} pulse parameters (pulse frequency and duration) is required for maximizing the yield of desirable diesel-range C{sub 10}-C{sub 20} products. On a high-{alpha} Fe/K/Cu/SiO{sub 2} FT synthesis catalyst H{sub 2} pulsing enhances the yield of C{sub 10}-C{sub 20} but at the same time decreases the catalyst activity (CO conversion) and increases the selectivity to CH{sub 4}. On the other hand, pulsing with CO also increases the yield of C{sub 10}-C{sub 20} but has no impact on the selectivity to CH{sub 4} or CO{sub 2} and decreases catalytic activity only moderately. In contrast to these catalysts, H{sub 2} pulsing on a high-{alpha} Ru/alumina FT synthesis catalyst has only minimal effect on activity and product distribution, showing enhanced activity towards methanation and water-gas-shift at the expense of FT synthesis. However, these observations are based on experiments performed at a significantly lower reaction pressure (ca. 26 atm) and higher reaction temperature (210-250 C) than those commonly used for supported-Ru FT catalysts (typically 100-1000 atm, 160-170 C).

  19. 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

  20. Emissions from Trucks using Fischer-Tropsch Diesel Fuel

    SciTech Connect

    Paul Norton; Keith Vertin; Brent Bailey; Nigel N. Clark; Donald W. Lyons; Stephen Goguen; James Eberhardt

    1998-10-19

    The Fischer-Tropsch (F-T) catalytic conversion process can be used to synthesize diesel fuels from a variety of feedstocks, including coal, natural gas and biomass. Synthetic diesel fuels can have very low sulfur and aromatic content, and excellent autoignition characteristics. Moreover, Fischer-Tropsch diesel fuels may also be economically competitive with California B- diesel fuel if produced in large volumes. overview of Fischer-Tropsch diesel fuel production and engine emissions testing is presented. Previous engine laboratory tests indicate that F-T diesel is a promising alternative fuel because it can be used in unmodified diesel engines, and substantial exhaust emissions reductions can be realized. The authors have performed preliminary tests to assess the real-world performance of F-T diesel fuels in heavy-duty trucks. Seven White-GMC Class 8 trucks equipped with Caterpillar 10.3 liter engines were tested using F-T diesel fuel. Vehicle emissions tests were performed using West Virginia University's unique transportable chassis dynamometer. The trucks were found to perform adequately on neat F-T diesel fuel. Compared to a California diesel fuel baseline, neat F-T diesel fuel emitted about 12% lower oxides of nitrogen (NOx) and 24% lower particulate matter over a five-mile driving cycle.

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

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 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, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 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 721.10103 - 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...

  4. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 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...

  5. 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...

  6. 40 CFR 721.10178 - Distillates (Fischer-Tropsch), hydroisomerized middle, C10-13-branched alkane fraction.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 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),...

  7. 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

  8. Mössbauer study of CO-precipitated Fischer-Tropsch iron catalysts

    NASA Astrophysics Data System (ADS)

    Rao, K. R. P. M.; Huggins, Frank E.; Mahajan, Vikram; Huffman, Gerald P.; Bukur, D. B.; Rao, V. U. S.

    1994-12-01

    Mössbauer spectroscopy studies of precipitated Fischer-Tropsch (FT) iron catalysts, viz. 100 Fe/5 Cu/4.2 K/ x SiO2, where x=0,8, 16, 24, 25, 40, or 100, have shown that reduction of the oxide precursor in CO gives rise to χ-carbide Fe5C2 whose amount decreases with an increase of SiO2 content. The χ-carbide is converted into magnetite Fe3O4 while catalyzing the FT synthesis reaction. A correlation between FT activity and the content of χ-carbide in the catalysts was found, which indicated that χ-carbide is active for FT synthesis reaction.

  9. Catalyst and reactor development for a liquid phase Fischer-Tropsch process

    SciTech Connect

    Not Available

    1989-01-01

    The preparation, characterization, and performance of a range of metal catalysts for use in slurry phase Fischer-Tropsch technology was investigated with the objective of developing new compositions with improved selectivity for gasoline and diesel fuel range hydrocarbons. A series of conventional catalysts was identified for testing for both gas and slurry phases. A gas phase screening protocol was set up to allow reasonably rapid determination of each catalyst's synthesis gas conversion characteristic over a range of operating conditions. The catalysts selected represented a range of catalytic metals known to promote conversion of synthesis gas to hydrocarbon liquids. Both precipitates and supported variations of these metals were studied. Catalysts studied include: ruthenium-based catalysts with osmium, and cobalt carbonyl supported on zirconia promoted. 23 refs., 2 figs., 10 tabs.

  10. Technology development for iron Fischer-Tropsch catalysis. Quarterly technical progress report No. 2, January 1, 1995--March 31, 1995

    SciTech Connect

    Davis, B.H.

    1995-05-02

    The Fischer-Tropsch synthesis has been studied over the best low-alpha catalyst developed at the CAER. A wide range of synthesis gas conversions were obtained by varying the space velocity. The experimental results show that: (1) the rate of the water gas shift reaction is lower than the rate of the Fischer-Tropsch reaction at low conversions (< 60%) whereas it closely approaches the rate of the Fischer-Tropsch synthesis at high conversions, (2) the fraction of CO converted to hydrocarbons is higher at low and intermediate conversions whereas it is smaller at high conversions, (3) the H{sub 2}/CO ratio of the product gas is equal to the H{sub 2}/CO ratio of the inlet synthesis gas at an intermediate conversion level of 67%. These findings suggest that it would be beneficial to carry out the reaction at intermediate conversions. This would result in an optimum use of CO to produce hydrocarbons rather than CO{sub 2}. High overall conversions can be obtained by either using a second reactor or recycling the product gas using a single reactor. If the intermediate conversion in a single pass is maintained at 67% there would be no need to adjust the H{sub 2}/CO ratio of the recycle stream or the feed to the second reactor as the product gas from a single pass would have the same H{sub 2}/CO ratio as the feed synthesis gas. The optimum reaction rate expression for synthesis gas conversion which has been developed for this catalyst shows that CO is strongly adsorbed on the catalyst and that the reaction products such as water and CO{sub 2} do not inhibit the reaction rate.

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

    PubMed

    Maitlis, Peter M; Zanotti, Valerio

    2009-04-01

    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

  12. A study on Raney iron catalyst for Fischer-Tropsch process in a slurry-phase reactor

    SciTech Connect

    Lu, Y.; Zhang, Z.; Zhou, J.

    1997-12-31

    Raney Fe, prepared by extracting Al from Fe-Al alloy, exhibits a better activity during slurry phase FT synthesis and shows distinct selectivity in low weight hydrocarbon (alkanes). Its properties, a BET surface area of at least 22m{sup 2}/g, an average pore diameter of 30nm, and similar attrition resistance as fused iron, significantly contribute to the catalyst performance such as activity, product selectivity and free separation from the waxes. This paper describes catalyst preparation and performance tests in a slurry Fischer-Tropsch synthesis. Three catalysts were compared: fused iron, precipitated iron, and Raney iron.

  13. Microkinetics of oxygenate formation in the Fischer-Tropsch reaction.

    PubMed

    van Santen, Rutger A; Ghouri, Minhaj; Hensen, Emiel M J

    2014-06-01

    Microkinetics simulations are presented on the intrinsic activity and selectivity of the Fischer-Tropsch reaction with respect to the formation of long chain oxygenated hydrocarbons. Two different chain growth mechanisms are compared: the carbide chain growth mechanism and the CO insertion chain growth mechanism. The microkinetics simulations are based on quantum-chemical data on reaction rate parameters of the elementary reaction steps of the Fischer-Tropsch reaction available in the literature. Because the overall rate constant of chain growth remains too low the CO insertion chain growth mechanism is not found to produce higher hydrocarbons, except for ethylene and acetaldehyde or the corresponding hydrogenated products. According to the carbide mechanism available quantum-chemical data are consistent with high selectivity to long chain oxygenated hydrocarbon production at low temperature. The anomalous initial increase with temperature of the chain growth parameter observed under such conditions is reproduced. It arises from the competition between the apparent rate of C-O bond activation to produce "CHx" monomers to be inserted into the growing hydrocarbon chain and the rate of chain growth termination. The microkinetics simulations data enable analysis of selectivity changes as a function of critical elementary reaction rates such as the rate of activation of the C-O bond of CO, the insertion rate of CO into the growing hydrocarbon chain or the rate constant of methane formation. Simulations show that changes in catalyst site reactivity affect elementary reaction steps differently. This has opposing consequences for oxygenate production selectivity, so an optimizing compromise has to be found. The simulation results are found to be consistent with most experimental data available today. It is concluded that Fischer-Tropsch type catalysis has limited scope to produce long chain oxygenates with high yield, but there is an opportunity to improve the yield of C2

  14. Deactivation of slurry phase Fischer-Tropsch catalysts

    SciTech Connect

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

    1996-12-31

    The influence of the liquid medium on Fischer-Tropsch (F-T) chemistry has received only minimal attention in the literature. The focus of this investigation was to determine the impact of the liquid starting medium on syngas (H{sub 2}+CO) conversion in a 1-liter CSTR. The results of the work indicate a greater deactivation rate for the F-T reaction in heavier starting media, average carbon number {ge}48, versus a medium with an average carbon number of 28.

  15. Separation of Fischer-Tropsch from Catalyst by Supercritical Extraction.

    SciTech Connect

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

    1997-10-31

    The objective of this research project is to evaluate the potential of supercritical fluid (SCF) extraction for the recovery and fractionation of the wax product from the slurry bubble column (SBC) reactor of the Fischer-Tropsch (F-T) process. The wax, comprised mostly of branched and linear alkanes with a broad molecular weight distribution up to C{sub 100}, will be extracted with a hydrocarbon solvent that has a critical temperature near the operating temperature of the SBC reactor, i.e., 200-300{degrees}C. Initial work is being performed using n-hexane as the solvent.

  16. TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

    SciTech Connect

    Burtron H. Davis

    1999-01-30

    The effects of copper on Fischer-Tropsch activity, selectivity and water-gas shift activity were studied over a wide range of syngas conversion. Three catalyst compositions were prepared for this study: (a) 100Fe/4.6Si/1.4K, (b) 100Fe/4.6Si/0.10Cu/1.4K and (c) 100Fe/4.6Si/2.0Cu/1.4K. The results are reported in Task 2. The literature review for cobalt catalysts is approximately 90% complete. Due to the size of the document, it has been submitted as a separate report labeled Task 6.

  17. 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.

  18. Iron and cobalt Fischer-Tropsch catalysts prepared by the solvated metal-atom technique

    SciTech Connect

    Meier, P.F.; Pennella, F.; Klabunde, K.J.; Imizu, Y.

    1986-10-01

    It is reasonable that at low metal loadings a more active catalyst would result from deposition on a support of a metal in the reduced, metallic state. Deposition of less than 5 wt% cobalt on alumina in the form of cobalt carbonyl produced catalysts of good activity. The Solvated Metal Atom Deposition Technique (SMAD) provides a method of catalyst preparation for which the deposition of metallic catalysts on a support has been demonstrated. This note reports a comparative study of the Fischer-Tropsch synthesis activity of iron and cobalt catalysts prepared by this technique and supported on silica with less than 5 wt% of the metal, and of analogous catalysts prepared by conventional impregnation techniques. 16 references.

  19. Catalytic conversion of olefinic fischer tropsch light oil to heavier hydrocarbons

    SciTech Connect

    Owen, H.; Tabak, S. A.; Wright, B. S.

    1985-05-28

    A process for converting synthol light oil product of Fischer-Tropsch synthesis to heavy distillate comprising the steps of contacting the light oil at elevated temperature and pressure with acid zeolite conversion catalyst to oligomerize olefins and convert oxygenated hydrocarbons contained in the light oil thereby providing an effluent containing light heavy distillate range hydrocarbon, hydrocarbon vapor and byproduct water; flashing and separating the effluent to recover a heavy distillate-rich liquid phase and a light hydrocarbon-rich vapor phase containing byproduct water; condensing the vapor phase to provide a liquid hydrocarbon recycle stream; removing byproduct water from the recycle stream; combining the light oil with the pressurized recycle stream as heat sink to prevent excessive reaction temperature during catalytic conversion.

  20. Design and performance of a high-pressure Fischer-Tropsch fluidized bed reactor

    SciTech Connect

    Weimer, A.W.; Quarderer, G.J.; Cochran, G.A.; Conway, M.M. )

    1988-01-01

    A 900 kg/day, CO/H/sub 2/, high-pressure, fluidized bed, pilot reactor was designed from first principles to achieve high reactant conversions and heat removal rates for the Fischer-Tropsch (F-T) synthesis of liquefied petroleum gases (LPG's). Suppressed bubble growth at high pressure allowed high reactant conversions which nearly matched those obtained at identical conditions in a lab scale fixed bed reactor. For GHSV approximately 1400 hr/sup -1/ and T = 658 {Kappa} at P approximately 7000 {kappa}Pa, reactant conversion exceeded 75%. The reactor heat removal capability exceeded twice design performance with the fluidized bed easily operating under thermally stable conditions. The fluidized catalyst was a potassium promoted, molybdenum on carbon (Mo/{Kappa}/C) catalyst which did not produce any detrimental waxy products. Long catalyst lifetimes of 1000 hrs on steam between regenerations allowed the fluidized bed to be operated in a batch mode.

  1. Fischer-Tropsch slurry phase process variations to understand wax formation

    SciTech Connect

    Satterfield, C.N.; Hanlon, R.T.; Matsumoto, D.K.; Donnelly, T.J.; Yates, I.C.

    1989-10-01

    Use of a slurry-type reactor with an iron catalyst for Fischer- Tropsch synthesis from low H{sub 2}/CO syngas offers the potential advantages of excellent temperature control, flexibility in catalyst addition and removal and internal water gas shift. The most important likely process variations were studied to determine how they affect product selectivity. A C-73 reduced fused magnetite was used as a base-line catalyst since it is mechanically rugged and resistant to process upsets, but several precipitated iron catalysts were also studied and the performances of the various catalysts are compared. We have also developed an improved method of analyzing product distribution data. Information is provided on changes in product distribution during start-up, effect of water content, and correlations of these with composition of the iron catalyst as determined by Mossbauer spectroscopy. Methods of reliable performance testing in a slurry reactor are discussed. 26 refs., 27 figs.

  2. Role of copper promotion in precipitated iron Fischer-Tropsch catalysts

    SciTech Connect

    O`Brien, R.J.; Xu, L.; Davis, B.H.

    1996-10-01

    Slurry phase Fischer-Tropsch synthesis was conducted on precipitated iron-silicon catalysts. The affect of copper promotion on the activity and selectivity of carbon monoxide, hydrogen and syngas activated catalysts is presented. High activity and stability have been obtained for potassium promoted catalysts when operating at 270{degrees}C; however, it has been found that promotion with potassium and copper is essential to obtaining good activity in a wax producing mode at 230{degrees}C. Promotion with copper is critical to achieving good activity when pretreating catalysts with hydrogen or with syngas at high pressure. XRD and Mossbauer data indicate that copper facilitates the reduction of iron oxide to metallic iron and iron carbides during hydrogen and syngas pretreatments.

  3. Monetization of Nigeria coal by conversion to hydrocarbon fuels through Fischer-Tropsch process

    SciTech Connect

    Oguejiofor, G.C.

    2008-07-01

    Given the instability of crude oil prices and the disruptions in crude oil supply chains, this article offers a complementing investment proposal through diversification of Nigeria's energy source and dependence. Therefore, the following issues were examined and reported: A comparative survey of coal and hydrocarbon reserve bases in Nigeria was undertaken and presented. An excursion into the economic, environmental, and technological justifications for the proposed diversification and roll-back to coal-based resource was also undertaken and presented. The technology available for coal beneficiation for environmental pollution control was reviewed and reported. The Fischer-Tropsch synthesis and its advances into Sasol's slurry phase distillate process were reviewed. Specifically, the adoption of Sasol's advanced synthol process and the slurry phase distillate process were recommended as ways of processing the products of coal gasification. The article concludes by discussing all the above-mentioned issues with regard to value addition as a means of wealth creation and investment.

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

    SciTech Connect

    Matthew Neurock; Siddharth Chopra

    2003-09-11

    As the US seeks to develop an energy strategy that reduces the reliance on foreign oil, there is a renewed interest in the research and development of the Fischer Tropsch synthesis for converting syngas into long chain hydrocarbon products. This report investigates some of the basic elementary steps for Fischer-Tropsch synthesis over ideal Pt, Ru and carbon-covered Pt and Ru metal surfaces by using ab initio density functional theoretical calculations. We examine in detail the adsorption sites as well as the binding energies for C, CH, CH{sub 2}, CH3 and CH4 on Pt(111), Ru(0001), 2x2-C-Pt(111) and 2x2-C-Ru(0001). The results indicate that the binding energies increase with decreasing the hydrogen in the fragment molecule, i.e. CH{sub 4} < CH{sub 3} < CH{sub 2} < CH < C. More specifically the work analyzes the elementary steps involved in the activation of methane. This is simply the reverse set of steps necessary for the hydrogenation of C to CH{sub 4}. The results indicate that these hydrocarbon intermediates bind more strongly to Ru than Pt. The introduction of co-adsorbed carbon atoms onto both Ru(0001) as well as Pt(111) significantly increased the overall energies as well as the activation barriers for C-H bond activation. The results suggest that Ru may be so active that it initially can initially activate CH4 into CH or C but ultimately it dies because the CH and C intermediates poison the surface and thus kill its activity. Methane can dissociate on Pt but subsequent hydrocarbon coupling reactions act to remove the surface carbon.

  5. Development of attrition resistant iron-based Fischer-Tropsch catalysts

    SciTech Connect

    2000-09-20

    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. The use of iron-based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem with use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, makes the separation of catalyst from the oil/wax product very difficult if not impossible, and results a steady loss of catalyst from the reactor. The objective of this research is to develop robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry bubble column reactor. Specifically we aim to develop to: (1) improve the performance and preparation procedure of the high activity, high attrition resistant, high alpha iron-based catalysts synthesized at Hampton University (2) seek improvements in the catalyst performance through variations in process conditions, pretreatment procedures and/or modifications in catalyst preparation steps and (3) investigate the performance in a slurry reactor. The effort during the reporting period has been devoted to effects of pretreating procedures, using H{sub 2}, CO and syngas (H{sub 2}/CO = 0.67) as reductants, on the performance (activity, selectivity and stability with time) of a precipitated iron catalyst (100Fe/5Cu/4.2K/10SiO{sub 2} on a mass basis ) during F-T synthesis were studied in a fixed-bed reactor.

  6. Polymer bound Fischer-Tropsch catalysts

    SciTech Connect

    Hsu, W.-L.; Kurr, R.J.; Maly, N.A.; Parker, D.K.; Stozier, R.W.

    1986-06-24

    A process is described for the conversion of synthesis gas to hydrocarbons which comprises contacting the synthesis gas with a catalyst in the vapor phase at a temperature from 175/sup 0/C to 300/sup 0/C and a pressure of at least 1000 kPa. The improvement described here comprising using as the catalyst a catalyst.

  7. Studying Fischer-Tropsch catalysts using transmission electron microscopy and model systems of nanoparticles on planar supports.

    SciTech Connect

    Thune, P. C.; Weststrate, C. J.; Moodley, P.; Saib, A. M.; van de Loosdrecht, J.; Miller, J. T.; Niemantsverdriet, J. W.

    2011-01-01

    Nanoparticle model systems on planar supports form a versatile platform for studying morphological and compositional changes of catalysts due to exposure to realistic reaction conditions. We review examples from our work on iron and cobalt catalysts, which can undergo significant rearrangement in the reactive environment of the Fischer-Tropsch synthesis. The use of specially designed, silicon based supports with thin film SiO{sub 2} enables the application of transmission electron microscopy, which has furnished important insight into e.g. the mechanisms of catalyst regeneration.

  8. Lower molecular weight hydrocarbon formation in an open flow system by Fischer Tropsch reaction. [in primitive solar system

    NASA Technical Reports Server (NTRS)

    Hobo, T.; Ponnamperuma, C.; Hook, A. G.; Donn, B.

    1978-01-01

    A Fischer Tropsch type mechanism has been proposed for the synthesis of organic compounds in the primitive solar system. The evidence for hydrocarbon formation, especially those of higher molecular weight, under simulated conditions of the early solar nebula has been presented (Studier et al., 1968, 1972; Gelpi et al., 1970). In this paper, we report studies on the formation of specifically the lower molecular weight hydrocarbons. By using an open flow reaction system and two closed systems, several factors which may affect the production of these compounds have been examined.

  9. Fischer-Tropsch slurry phase process variations to understand wax formations: Quarterly report, January 1, 1988-March 31, 1988

    SciTech Connect

    Satterfield, C.N.

    1988-01-01

    A method has been developed for caluclating the three parameters needed to characterize the carbon number distribution of products of the Fischer-Tropsch synthesis. using non-linear regression, experiemental data are fit by a modified Schulz-Flory model which has two chain growth probabilities. Excellent fit is shown for data from precipitated and fused iron catalysts. The model is used to calculate selectivity information of interest in catalyst comparison and reactor design. Advantages of this model over asymptotic regression methods are discussed in detail. 26 refs., 6 figs.

  10. Baseline design/economics for advanced Fischer-Tropsch technology. Quarterly report, April--June 1992

    SciTech Connect

    Not Available

    1992-10-01

    Effective September 26, 1991, Bechtel, with Amoco as the main subcontractor, initiated a study to develop a computer model and baseline design for advanced Fischer-Tropsch (F-T) technology for the US Department of Energy`s Pittsburgh Energy Technology Center (PETC). The objectives of the study are to: Develop a baseline design for indirect liquefaction using advanced F-T technology; prepare the capital and operating costs for the baseline design; and develop a process flow sheet simulation (PI-S) model. The baseline design, the economic analysis, and the computer model win be the major research planning tools that PETC will use to plan, guide, and evaluate its ongoing and future research and commercialization programs relating to indirect coal liquefaction. for the manufacture of synthetic liquid fuels from coal. This report is Bechtel`s third quarterly technical progress report covering the period from March 16, 1992 through June 21, 1992. This report consists of seven sections: Section 1 - introduction; Section 2 - summary; Section 3 - carbon dioxide removal tradeoff study; Section 4 - preliminary plant designs for coal preparation; Section 5 - preliminary design for syngas production; Section 6 - Task 3 - engineering design criteria; and Section 7 - project management.

  11. Baseline design/economics for advanced Fischer-Tropsch technology. Quarterly report, October--December 1992

    SciTech Connect

    Not Available

    1992-12-31

    Bechtel, with Amoco as the main subcontractor, initiated a study on September 26, 1991, for the US Department of Energy`s (DOE`s) Pittsburgh Energy Technology Center (PETC) to develop a computer model and baseline design for advanced Fischer-Tropsch (F-T) technology. This 24-month study, with an approved budget of $2.3 million, is being performed under DOE Contract Number AC22-91PC90027. (1) Develop a baseline design and two alternative designs for indirect liquefaction using advanced F-T technology. The baseline design uses Illinois No. 6 Eastern Coal and conventional refining. There is an alternative refining case using ZSM-5 treatment of the vapor stream from the slurry F-T reactor and an alternative coal case using Western coal from the Powder River Basin. (2) Prepare the capital and operating costs for the baseline design and the alternatives. Individual plant costs for the alternative cases will be prorated on capacity, wherever possible, from the baseline case. (3) Develop a process flowsheet simulation (PFS) model. The baseline design, the economic analysis and computer model will be major research planning tools that PETC will use to plan, guide and evaluate its ongoing and future research and commercialization programs relating to indirect coal liquefaction for the manufacture of synthetic liquid fuels from coal.

  12. Development and process evaluation of improved Fischer-Tropsch slurry catalysts. Sixth quarterly technical progress report, 1 January--31 March 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 comparisons. Particular attention will be devoted to generating reproducible kinetic and selectivity data and to developing reproducible improved catalyst compositions.

  13. Development and process evaluation of improved Fischer-Tropsch slurry catalysts. [Tenth] quarterly technical progress report, 1 January--31 March 1989

    SciTech Connect

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

    1989-12-31

    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.

  14. 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

  15. 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.

  16. Studies of the Fischer-Tropsch reaction on Co(0001)

    NASA Astrophysics Data System (ADS)

    Geerlings, J. J. C.; Zonnevylle, M. C.; de Groot, C. P. M.

    1991-01-01

    The Fischer-Tropsch reaction has been studied over Co(0001) in the temperature range between 220 and 300 °C at 1 bar total pressure and an H 2 : CO ratio of 2 : 1. It was found that the activation energies for methane, ethane and propane formation are equ which suggests similar rate determining steps. We propose that α-hydrogenation of a C nH 2 n+1 surface species is rate limiting. Olefins are formed via β-dehydrogenation of the same species. The olefins take part in a consecutive reaction and are finally converted to paraffins. The product distribution was found to follow Schulz-Flory kinetics with a chain growth probability of 0.2 at 250 °C. Post-reaction spectroscopy with EELS and Auger indicated the presence of CO and CH x ( x = 1, 2, 3) fragments on the surface.

  17. 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

  18. Development of improved iron Fischer-Tropsch catalysts. Final technical report: Project 6464

    SciTech Connect

    Bukur, D.B.; Ledakowicz, S.; Koranne, M.

    1994-02-28

    Despite the current worldwide oil glut, the United States will ultimately require large-scale production of liquid (transportation) fuels from coal. Slurry phase Fischer Tropsch (FT) technology, with its versatile product slate, may be expected to play a major role in production of transportation fuels via indirect coal liquefaction. Texas A&M University (TAMU) with sponsorship from the US Department of Energy, Center for Energy and Mineral Resources at TAMU, Texas Higher Education Coordinating Board, and Air Products and Chemicals, Inc., has been working on development of improved iron FT catalysts and characterization of hydrodynamic parameters in two- and three-phase bubble columns with FT derived waxes. Our previous studies have provided an improved understanding of the role of promoters (Cu and K), binders (silica) and pretreatment procedures on catalyst activity, selectivity and longevity (deactivation). The objective of the present contract was to develop improved catalysts with enhanced slurry phase activity and higher selectivity to liquid fuels and wax. This was accomplished through systematic studies of the effects of pretreatment procedures and variations in catalyst composition (promoters and binders). The major accomplishments and results in each of these two main areas of research are summarized here.

  19. Effect of the porous structure of the support on hydrocarbon distribution in the Fischer-Tropsch reaction

    NASA Astrophysics Data System (ADS)

    Bartolini, Monica; Molina, Jhoanna; Alvarez, Juan; Goldwasser, Mireya; Pereira Almao, Pedro; Zurita, M. Josefina Pérez

    2015-07-01

    Emissions standards are increasingly stringent due mainly to its impact on the environment. Although the diesel engine is an attractive solution for carbon dioxide reduction, a challenge remains to simultaneously control nitrogen oxides and matter particulate emissions to accepted levels. On engine tests, it has been observed that Fischer-Tropsch diesel significantly reduces CO, HC, PAHs and particulate emissions compared to oil derived diesel. However, selectivity control in Fischer Tropsch Synthesis is still a key challenge due the Anderson-Schultz-Flory polymerization mechanism followed by hydrocarbon distribution. In this work we are presenting the first steps towards a new strategy that can tune, in one step, the selectivity to desired products by taking advantage of the shape selectivity properties of SBA-15 mesoporous silica used as support. Co-SBA-15 (30%wt) catalysts with different pore size were prepared by excess solution impregnation. Our results show that pore diameter not only affects the size and reducibility of Co particles but it also significantly influence the liquid products distribution, with the high molecular weight hydrocarbon fraction increasing on large pores, attributed to the existence of a shape selectivity effect induced by the textural properties of the catalyst namely its pore size and pore volume.

  20. Compositional aspect of iron Fischer-Tropsch catalyst: An XPS/reaction study

    SciTech Connect

    Kuivila, C.S.; Stair, P.C.; Butt, J.B. )

    1989-08-01

    The catalytic and compositional behaviors of prereduced and unreduced iron catalysts for Fischer-Tropsch synthesis were investigated. Catalytic behavior was evaluated by measuring rates of hydrocarbon formation 3:1 H{sub 2}:CO mixture at 1 atm and 250C. Iron phases which evolved near the catalyst surfaces were characterized by X-ray photoelectron spectroscopy, and bulk phases present following reaction were determined by Moessbauer spectroscopy. At low conversion levels the prereduced catalyst was gradually converted to iron carbide with no significant oxide phase formed. Synthesis activities increased initially with the formation of active surface carbon, but eventually lost some activity due to graphitic carbon formation. At higher conversions, the prereduced catalyst showed some formation of surface oxide phases and an inhibition of the synthesis rate due to water adsorption. Surface carbon accumulation was also suppressed under these conditions. Unreduced Fe{sub 2}O{sub 3} showed no initial synthesis activity, but underwent a gradual activation to become even more active than the prereduced catalyst. The oxide catalyst was eventually completely reduced to Fe{sub 3}O{sub 4}, and any metallic phase formed was rapidly converted to iron carbide. Compared to reduced materials, the oxide catalyst accumulated considerably less surface carbon and showed no loss of activity for reaction times up to 48 h. XPS analysis suggests that Fe{sub 3}O{sub 4} is active for synthesis.

  1. 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

  2. Technology development for iron Fischer-Tropsch catalysis. Quarterly technical progress report, 1996

    SciTech Connect

    Davis, B.H.

    1996-11-01

    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 ``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 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, select and aging characteristics. The research is divided into four major topical areas: (a) catalyst preparation and characterization, (b) product characterization, (c) reactor operations, and (d) data assessment. Accomplishments for this period are described.

  3. Nanoscale attrition during activation of precipitated iron Fischer-Tropsch catalysts: Implications for catalyst design

    SciTech Connect

    Datye, A.K.; Shroff, M.D.; Jin, Y.; Brooks, R.P.; Wilder, J.A.

    1996-12-31

    The Fischer-Tropsch Synthesis (FTS) for the production of liquid hydrocarbons from coal-based synthesis gas has been the subject of renewed interest for conversion of coal to liquid fuels. The use of synthesis gas from modem energy-efficient gasifiers requires catalysts that can operate under low H{sub 2}/CO ratios, typically 0.7-0.9. Since the FTS stoichiometry requires a H{sub 2}/CO ratio of 2.0, catalysts that operate at lower ratios must catalyze the water gas shift reaction to make up the deficit in H{sub 2}. The use of iron-based catalysts for the process is attractive in view of their low cost, ready availability and high water-gas shift reactivity. Furthermore, iron catalysts at elevated pressures (10-15 atmospheres) produce the desired range of liquid hydrocarbons. AU these features make the use of Fe as an F-T catalyst extremely desirable. Since the reaction is highly exothermic, the preferred reactor type for industrial operation is the slurry bubble column reactor. The catalyst for this reactor is precipitated iron oxide which is spray dried to yield particles with diameter of 30-70 {mu}m. One major limitation of these catalysts is that they tend to undergo attrition during use, leading to problems in catalyst separation and recovery of liquid products from the reactor.

  4. Compositional aspects of iron Fischer-Tropsch catalysts: an x-ray photoelectron

    SciTech Connect

    Kuivila, C.S.

    1987-01-01

    Iron catalysts employed in the Fischer-Tropsch synthesis consist of metallic, carbide, and oxide phases. The catalytic and compositional behavior of prereduced and unreduced iron catalysts were investigated in this study. Catalytic behavior was evaluated by measuring the rates of hydrocarbon formation in a 3:1 H/sub 2//CO mixture at one atmosphere and 250/sup 0/C. Iron phases which evolved near the catalyst surfaces were characterized by x-ray photoelectron spectroscopy, and bulk phases present following the synthesis reactions were determined by Mossbauer spectroscopy. At low conversion levels, prereduced iron catalysts were gradually converted to iron carbide. At total CO conversion levels in the range of 30 to 40%, prereduced catalysts were converted primarily to iron carbide, although some surface oxide phases also formed. Unreduced Fe/sub 2/O/sub 3/ exhibited no initial synthesis activity, but underwent gradual activation and eventually became more active than the prereduced catalysts. The various phases of the iron catalysts were related to varying olefin production rates.

  5. 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.

  6. The development of a selective ruthenium Fischer-Tropsch catalyst

    SciTech Connect

    Abrevaya, H.

    1989-01-01

    A new stable Fischer-Tropsch catalyst with very high selectivity to distillate fuels and with low light ends production was developed. This catalyst, which was made by a reverse micelle technique, contains 2.8% (by weight) ruthenium in the form of 4--6 nm particles on alumina and a proprietary modifier. The new modified ruthenium catalyst did not noticeably deactivate during 814 hours at about 80% CO conversion, 2H{sub 2}:1 CO feed ratio, 208{degree}C at inlet, 62 atm and 150 gas hourly space velocity. In order to determine the catalyst's tolerance, the operational severity was increased between 814 hours and 1700 hours by increasing the temperature and space velocity to 225{degree}C at inlet and to 205 hr{sup {minus}1}, respectively. A deactivation rate of about 0.016%/hour was measured under these more severe conditions at about 70% conversion level. These results with the new modified ruthenium catalyst compare favorably with those reported for the two commercial Sasol processes. The Arge process makes approximately 38% distillate fuel with 14--18% light ends, while the Synthol process makes about 48% distillate with 38% light ends. 82 refs., 360 figs., 66 tabs.

  7. Thermodynamic models to predict gas-liquid solubilities in the methanol synthesis, the methanol-higher alcohol synthesis, and the Fischer-Tropsch synthesis via gas-slurry processes

    SciTech Connect

    Breman, B.B.; Beenackers, A.A.

    1996-10-01

    Various thermodynamic models were tested concerning their applicability to predict gas-liquid solubilities, relevant for synthesis gas conversion to methanol, higher alcohols, and hydrocarbons via gas-slurry processes. Without any parameter optimization the group contribution equation of state (GCEOS) turns out to be the best model with an average, relative deviation of 19.0%. If a single binary interaction parameter is optimized for each binary system, the Peng-Robinson equation of state, the regular solutions theory, and the Flory-Staverman model all give good predictions with average, relative deviations 4.0, 10.4, and 10.0%, respectively. As expected, the predictions from these models improve further and agree excellently with the experimental values by optimizing two binary interaction parameters for each binary system (average relative deviations <2% for all models). The gas-liquid solubilities could also be correlated accurately to the temperature (average relative deviation = 2.1%) by assuming a constant enthalpy of solution (CEOS) models. For particular binary systems the Flory-Staverman model and the CEOS model give also reasonably accurate predictions of the gas-liquid solubilities by calculating the binary interaction parameters from pure component properties. Such an approach is promising for predicting as yet unknown gas-liquid solubilities without the need for experimental data.

  8. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 12, June 26, 1993--September 26, 1993

    SciTech Connect

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

    1994-07-01

    The objectives of this contract are to develop a technology for the production of active and stable iron Fischer-Tropsch catalysts for use in slurry-phase synthesis reactors and to develop a scale-up 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%.

  9. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 2, December 26, 1990--March 26, 1991

    SciTech Connect

    Not Available

    1991-12-31

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

  10. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 3, March 27, 1991--June 30, 1991

    SciTech Connect

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

    1991-12-31

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

  11. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 1, September 26, 1990--December 26, 1990

    SciTech Connect

    Not Available

    1990-12-31

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

  12. 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%.

  13. Technology development for iron Fischer-Tropsch catalysts. Technical progress report number 13, 26 September 1993--26 December 1993

    SciTech Connect

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

    1994-08-01

    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 scale up 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%. Results are presented from experimental work performed during this report period.

  14. 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.

  15. Separation of Fischer-Tropsch catalyst/wax mixtures using dense gas extraction

    SciTech Connect

    Eyring, M.W.; Rohar, P.C.; Hickey, R.F.; White, C.M.; Quiring, M.S.

    1995-12-31

    The separation of a Fischer-Tropsch catalyst from wax products is an important issue when the synthesis is conducted in a slurry bubble column reactor. This paper describes a new technique based on dense gas extraction of the soluble hydrocarbon components from the insoluble catalyst particles using light hydrocarbons as propane, butane, and pentane an the solvent. The extractions were conducted in a continuous unit operated near the critical point of the extraction gas on a catalyst/wax mixture containing about 4.91 wt% catalyst. The catalyst-free wax was collected in the second stage collector while the catalyst and some insoluble wax components were collected in the first stage collector. The yield of catalyst-free wax was about 60 wt% of the food mixture. The catalyst content of the catalyst/wax mixture in the first stage was about 14.8 wt%. The catalyst content in the second stage collector was less than 1 part in 100,000.

  16. Separation of Fischer-Tropsch catalyst/wax mixtures using dense gas extraction

    SciTech Connect

    Eyring, M.W.; Rohar, P.C.; Hickey, R.F.

    1995-12-01

    The separation of a Fischer-Tropsch catalyst from wax products is an important issue when the synthesis is conducted in a slurry bubble column reactor. This paper describes a new technique based on dense gas extraction of the soluble hydrocarbon components from the insoluble catalyst particles using light hydrocarbons as propane, butane, and pentane as the solvent. The extractions were conducted in a continuous unit operated near the critical point of the extraction gas on a catalyst/wax mixture containing about 4.91 wt% catalyst. The catalyst-free wax was collected in the second stage collector while the catalyst and some insoluble wax components were collected in the first stage collector. The yield of catalyst-free wax was about 60 wt% of the feed mixture. The catalyst content of the catalyst/wax mixture in the first stage was about 14.8 wt%. The catalyst content in the second stage collector was less than 1 part in 100,000.

  17. 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.

  18. First-principles calculations of Fischer-Tropsch processes catalyzed by nitrogenase enzymes

    NASA Astrophysics Data System (ADS)

    Varley, Joel; Grabow, Lars; Nørskov, Jens

    2012-02-01

    The nitrogenase enzyme system of the bacteria Azotobacter vinelandii, which is used in nature to catalyze ammonia synthesis, has been found recently to catalyze the efficient conversion of carbon monoxide (CO) into hydrocarbons under ambient temperature and pressure [1]. These findings indicate that nitrogenase enzymes could inspire more efficient catalysts for electrochemical CO and CO2 reduction to liquid fuels. The nitrogenase variants, in which vanadium substitutes the molybdenum in the active site of the enzyme, show distinct features in their reaction pathways to hydrocarbon production. To compare and contrast the catalytic properties of these nitrogenase enzymes, we perform first-principles calculations to map out the reaction pathways for both nitrogen fixation and for the reduction of CO to higher-order hydrocarbons. We discuss the trends and differences between the two enzymes and detail the relevant chemical species and rate-limiting steps involved in the reactions. By utilizing this information, we predict the electrochemical conditions necessary for the catalytic reduction of CO into fuels by the nitrogenase active sites, analogous to a Fischer-Tropsch process requiring less extreme conditions. [4pt] [1] Y. Hu, C.C. Lee, M.W. Ribbe, Science 333, 753 (2011)

  19. 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. PMID:24616239

  20. Technology developments to enable the commercial viability of the Fischer-Tropsch process

    SciTech Connect

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

    1996-12-31

    The well established Fischer-Tropsch (F-T) technologies for catalytic conversion of coal-based synthesis gas to hydrocarbon liquid and wax products have been practiced for many years in locations (such as South Africa) where political reasons have forced the production operations even though unusual commercial competitive economics would not be sufficiently attractive to justify the process. This has generated a substantive technical experience with F-T technologies and products that is currently being adapted to use with syngas produced from coal, natural gas, and other sources of hydrocarbon gas in many niche markets over the world. Energy International, one of the Williams Companies, is currently developing this process for use in near-term commercial applications based on improvements in catalyst and process design that can substantially reduce the economic cost of producing hydrocarbon fuels, chemicals, and waxes. This improved economic basis for use of F-T technology derives from on-going efforts supported by the Department of Energy`s Pittsburgh Energy Technology Center and Energy International. In important laboratory developments and evaluations, the use of cobalt catalysts has been shown to have the potential for greater products yields and better controls on the reactor operating conditions so as to produce the more desirable and economically effective sets of quality products. This presentation will review the technical improvements achieved with the new catalysts and the impact on the economic viability of the F-T process.

  1. Hydrodynamics of the three-phase slurry Fischer-Tropsch bubble column reactors

    SciTech Connect

    Bukur, D.B.; Daly, J.G.; Patel, S.A.

    1990-09-01

    This report describes results of a study on hydrodynamics of three-phase bubble columns for Fischer-Tropsch synthesis. Experiments were conducted in two stainless bubble columns of 0.05 m and 0.21 m in diameter and 3 m tall, at 265{degrees}C and atmospheric pressure using nitrogen gas and two types of liquid medium (hydrotreated reactor wax designated FT-300, and raw reactor wax from fixed bed rectors at SASOL). The effects of solids types (iron oxide and silica), concentration (0--30 wt %), size (0--5 {mu}m and 20--44 {mu}m), slurry (liquid) velocity (up to 0.02 m/s) on the gas holdup and axial solids concentration profiles, were investigated. Phase volume fractions were determined using conventional (differential pressure measurements together with determination of slurry concentration along the column) and novel (dual energy nuclear density gauge) experimental techniques. Bubble size distribution and the Sauter mean bubble diameter were obtained using the dynamic gas disengagement (DGD) method. Flow regime transitions in both columns were determined using statistical analysis of both pressure and density fluctuations. Correlations for prediction of gas holdups and axial solids dispersion coefficient have been developed from experimental data obtained in this study. Data needed for calculation of the gas-liquid interfacial area (average gas holdup and Sauter mean bubble diameter) have been presented and can be used to estimate the mass transfer rate in slurry bubble column reactors. 105 refs., 19 figs., 38 tabs.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. A comparison of the activity, selectivity and kinetics of several iron-based Fischer-Tropsch catalysts

    SciTech Connect

    Dictor, R.A.; Bell, A.T.

    1986-03-01

    Much attention in the area of Fischer-Tropsch chemistry has been directed at slurry-phase reactor systems because of facilitated temperature control and the ability to operate continuously using hydrogen-lean feeds. The ability to predict and control the behavior of bubble column Ft reactors requires a detailed understanding of the reaction kinetics and mass transfer limitations. The authors examined the effects of temperature, reactant partial pressures, gas velocity and feed ratio on catalyst activity and selectivity for a number of catalysts: Fe/sub 2/O/sub 3/, potassium-promoted Fe/sub 2/O/sub 3/, Fe, Fe/sub 3/C, and a fused iron ammonia synthesis catalyst. The goal of this communication is to determine the effects of structural features (e.g., surface area, promoters, etc.) on the activities and selectivities of these catalysts.

  7. Development of Detailed Kinetic Models for Fischer-Tropsch Fuels

    SciTech Connect

    Westbrook, C K; Pitz, W J; Carstensen, H; Dean, A M

    2008-10-28

    Fischer-Tropsch (FT) fuels can be synthesized from a syngas stream generated by the gasification of biomass. As such they have the potential to be a renewable hydrocarbon fuel with many desirable properties. However, both the chemical and physical properties are somewhat different from the petroleum-based hydrocarbons that they might replace, and it is important to account for such differences when considering using them as replacements for conventional fuels in devices such as diesel engines and gas turbines. FT fuels generally contain iso-alkanes with one or two substituted methyl groups to meet the pour-point specifications. Although models have been developed for smaller branched alkanes such as isooctane, additional efforts are required to properly capture the kinetics of the larger branched alkanes. Recently, Westbrook et al. developed a chemical kinetic model that can be used to represent the entire series of n-alkanes from C{sub 1} to C{sub 16} (Figure 1). In the current work, the model is extended to treat 2,2,4,4,6,8,8-heptamethylnonane (HMN), a large iso-alkane. The same reaction rate rules used in the iso-octane mechanism were incorporated in the HMN mechanism. Both high and low temperature chemistry was included so that the chemical kinetic model would be applicable to advanced internal combustion engines using low temperature combustion strategies. The chemical kinetic model consists of 1114 species and 4468 reactions. Concurrently with this effort, work is underway to improve the details of specific reaction classes in the mechanism, guided by high-level electronic structure calculations. Attention is focused upon development of accurate rate rules for abstraction of the tertiary hydrogens present in branched alkanes and properly accounting for the pressure dependence of the ?-scission, isomerization, and R + O{sub 2} reactions.

  8. Predicting the performance of system for the co-production of Fischer-Tropsch synthetic liquid and power from coal

    SciTech Connect

    Wang, X.; Xiao, Y.; Xu, S.; Guo, Z.

    2008-01-15

    A co-production system based on Fischer-Tropsch (FT) synthesis reactor and gas turbine was simulated and analyzed. Syngas from entrained bed coal gasification was used as feedstock of the low-temperature slurry phase Fischer-Tropsch reactor. Raw synthetic liquid produced was fractioned and upgraded to diesel, gasoline, and liquid petrol gas (LPG). Tail gas composed of unconverted syngas and FT light components was fed to the gas turbine. Supplemental fuel (NG, or refinery mine gas) might be necessary, which was dependent on gas turbine capacity expander through flow capacity, etc. FT yield information was important to the simulation of this co-production system. A correlation model based on Mobil's two step pilot plant was applied. User models that can predict product yields and cooperate with other units were embedded into Aspen plus simulation. Performance prediction of syngas fired gas turbine was the other key of this system. The increase in mass flow through the turbine affects the match between compressor and turbine operating conditions. The calculation was carried out by GS software developed by Politecnico Di Milano and Princeton University. Various cases were investigated to match the FT synthesis island, power island, and gasification island in co-production systems. Effects of CO{sub 2} removal/LPG recovery, co-firing, and CH{sub 4} content variation were studied. Simulation results indicated that more than 50% of input energy was converted to electricity and FT products. Total yield of gasoline, diesel, and LPG was 136-155 g/N m{sup 3} (CO+H{sub 2}). At coal feed of 21.9 kg/s, net electricity exported to the grid was higher than 100 MW. Total production of diesel and gasoline (and LPG) was 118,000 t (134,000 t)/year. Under the economic analysis conditions assumed in this paper the co-production system was economically feasible.

  9. Fischer-Tropsch Performance of an SiO2-Supported Co-Based Catalyst Prepared by Hydrogen Dielectric-Barrier Discharge Plasma

    NASA Astrophysics Data System (ADS)

    Fu, Tingjun; Huang, Chengdu; Lv, Jing; Li, Zhenhua

    2014-03-01

    A silica-supported cobalt catalyst was prepared by hydrogen dielectric-barrier discharge (H2-DBD) plasma. Compared to thermal hydrogen reduction, H2-DBD plasma treatment can not only fully decompose the cobalt precursor but also partially reduce the cobalt oxides at lower temperature and with less time. The effect of the discharge atmosphere on the property of the plasma-prepared catalyst and the Fischer-Tropsch synthesis activity was studied. The results indicate that H2-DBD plasma treatment is a promising alternative for preparing Co/SiO2 catalysts from the viewpoint of energy savings and efficiency.

  10. Fischer-Tropsch kinetic studies with cobalt-manganese oxide catalysts

    SciTech Connect

    Keyser, M.J.; Everson, R.C.; Espinoza, R.L.

    2000-01-01

    An investigation was undertaken to establish the reaction mechanism for the Fischer-Tropsch reaction, in the presence of the water-gas shift reaction, over a cobalt-manganese oxide catalyst under conditions favoring the formation of gaseous, liquid, and solid (waxes) hydrocarbons (210--250 C and 6--26 bar). A micro-fixed-bed reactor was used with a cobalt-manganese oxide catalyst prepared by a coprecipitation method. An integral reactor model involving both Fischer-Tropsch and water-gas shift reaction kinetics was used to describe the overall performance. Reaction rate equations based on Langmuir-Hinshelwood-Hougen-Watson models for the Fischer-Tropsch reaction (hydrocarbon forming) and empirical reaction rate equations for the water-gas shift reaction from the literature were tested. Different combinations of the reaction rate equation were evaluated with the aid of a nonlinear regression procedure. It was found that a reaction rate equation for the Fischer-Tropsch reaction based on the enolic theory performed slightly better than a reaction rate equation based on the carbide theory. Reaction rate constants for the cobalt-manganese oxide catalyst are reported, and it is concluded that this catalyst also behaves very much like iron-based catalysts.

  11. 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

  12. 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.

  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. 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.

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

    PubMed

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

    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

  16. 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

  17. SBA-15-Supported Iron Catalysts for Fischer-Tropsch Production of Diesel Fuel

    SciTech Connect

    Kim,D.; Dunn, B.; Huggins, F.; Huffman, G.; Kang, M.; Yie, J.; Eyring, E.

    2006-01-01

    Iron supported on SBA-15, a mesoporous structured silica, has been developed as a catalyst for the Fischer-Tropsch synthesis of hydrocarbons. The catalysts retain the high surface area of the support, {approx}500 m{sup 2}/g, average pore size, and pore volume. Inclusion of aluminum into the SBA-15 did not significantly alter these parameters. XRD, XAFS, and Moessbauer spectroscopies were used to characterize the catalyst before and after being subjected to the reaction conditions. Prior to reaction, the iron was distributed among {alpha}-Fe{sub 2}O{sub 3}3, ferrihydrite, and minor {gamma}-Fe{sub 2}O{sub 3}. After reaction, the iron phases detected were nonmagnetic iron oxides, iron carbide, and metallic iron. The length of the induction period typically seen with iron-based F-T catalysts was strongly dependent on the amount of aluminum present in the catalyst. With no aluminum, the induction period lasted about 25 h, whereas the induction period decreased to less than 5 h with an Al:Si mass ratio of 0.010. A further increase in aluminum content lengthened the induction period, but always remained less than that without aluminum. Catalyst activity and product selectivity were also strongly dependent on aluminum content with the maximum diesel fuel fraction, C{sub 11+}, occurring with the Al:Si ratio of 0.010 and a CO conversion of 37%. The small concentration of aluminum may serve to increase the rate of iron carbide formation, whereas higher concentrations may begin to inhibit the rate.

  18. SBA-15-supported iron catalysts for Fischer-Tropsch production of diesel fuel

    SciTech Connect

    Dae Jung Kim; Brian C. Dunn; Frank Huggins; Gerald P. Huffman; Min Kang; Jae Eui Yie; Edward M. Eyring

    2006-12-15

    Iron supported on SBA-15, a mesoporous structured silica, has been developed as a catalyst for the Fischer-Tropsch synthesis of hydrocarbons. The catalysts retain the high surface area of the support, {approximately}500 m{sup 2}/g, average pore size, and pore volume. Inclusion of aluminum into the SBA-15 did not significantly alter these parameters. XRD, XAFS, and Moessbauer spectroscopies were used to characterize the catalyst before and after being subjected to the reaction conditions. Prior to reaction, the iron was distributed among {alpha}-Fe{sub 2}O{sub 3}, ferrihydrite, and minor {gamma}Fe{sub 2}O{sub 3}. After reaction, the iron phases detected were nonmagnetic iron oxides, iron carbide, and metallic iron. The length of the induction period typically seen with iron-based F-T catalysts was strongly dependent on the amount of aluminum present in the catalyst. With no aluminum, the induction period lasted about 25 h, whereas the induction period decreased to less than 5 h with an Al:Si mass ratio of 0.010. A further increase in aluminum content lengthened the induction period, but always remained less than that without aluminum. Catalyst activity and product selectivity were also strongly dependent on aluminum content with the maximum diesel fuel fraction, C{sub 11+}, occurring with the Al:Si ratio of 0.010 and a CO conversion of 37%. The small concentration of aluminum may serve to increase the rate of iron carbide formation, whereas higher concentrations may begin to inhibit the rate. 23 refs., 6 figs., 2 tabs.

  19. Nanoscale attrition during activation of precipitated iron Fischer- Tropsch catalysts: Implications for catalyst design

    SciTech Connect

    Datye, A.K.; Shroff, M.D.; Jin, Y.; Brooks, R.P.; Wilder, J.A.; Harrington, M.S.; Sault, A.G.; Jackson, N.B.

    1996-06-01

    This work has shown that the kaolin binder that has been used in commercial Fischer-Tropsch Synthesis catalysts doe not offer any significant attrition resistance. This is due in part to its morphology (plate-like) and to its particle size being much greater than the primary crystallite size of the iron oxide catalyst. From a microscopic examination of these catalysts, it appears that if the nanoscale attrition of the iron catalyst is to be avoided, the iron must be well dispersed on the binder, and the binder must provide an interlocking microstructure that provides strength and stability to the 30-70 {mu}m agglomerates. The study of Fe/SiO{sub 2} catalysts has shown that co-precipitation of the iron and silica leads to formation of an amorphous glassy phase which is difficult to reduce even at 723K. On the other hand, when the iron was precipitated on a preformed silica, 25-40% of the iron could be reduced and carbided. The supported iron catalyst, after reduction, formed 15-20 nm iron carbide particles that look very similar to those on the unsupported catalyst. The major difference is these nanometer sized particles are anchored on a support and therefore would not be expected to breakup further and contribute to the fines generated as catalyst attrition proceeds. However, since only a fraction of the silica-supported iron can be reduced to the active carbide phase, our present efforts are devoted to moderating the Fe/SiO{sub 2} interaction by introducing an interfacial oxide phase. We are also studying the role of added Cu on the ease of reducibility of Fe/SiO{sub 2}. The implication of this work is that other binder materials should be explored that have a morphology that can strengthen the agglomerates and minimize the Fe-SiO{sub 2} interfacial reactions. This work is presently underway in our laboratory.

  20. DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

    SciTech Connect

    Adeyinka A. Adeyiga

    2001-09-01

    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. The use of iron-based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem with use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, makes the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. Recently, fundamental understanding of physical attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried Fe-based catalyst having aps of 70 mm with high attrition resistance. This Fe-based attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H{sub 2}/CO=0.67 and 2.0 NL/g-cat/h with C{sub 5}{sup +} selectivity of >78% and methane selectivity of <5%. However, further development of the catalyst is needed to address the chemical attrition due to phase changes that any Fe-catalyst goes through potentially causing internal stresses within the particle and resulting in weakening, spalling or cracking. The objective of this research is to develop robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry bubble column reactor. Specifically we aim to develop to: (i) improve the performance and preparation procedure of the high activity, high attrition resistant, high

  1. Moessbauer spectroscopy studies of iron-catalysts used in Fischer-Tropsch (FT) processes. Quarterly technical progress report, October 1, 1996--December 31, 1996

    SciTech Connect

    Huffman, G.P.; Rao, K.R.P.M.

    1996-12-31

    The U.S. Department of Energy has currently a program to develop Fischer-Tropsch catalysts which are active at low H{sub 2}/Co ratio of 0.67. The Center for Applied Energy Research, University of Kentucky and Texas A&M University have been developing Fischer- Tropsch catalysts which are active at a low H{sub 2}/Co ratio of 0.67. It is of interest to find out any relationships that may exist between the iron phases that are produced during activation and FT synthesis and the activity of the catalysts. Moessbauer spectroscopy investigations were carried out on 32 iron-base catalysts during the period under review. Eleven catalysts withdrawn from slurry type of reactors during and at the end of FT synthesis were received from the University of Kentucky. Twenty one catalysts withdrawn at the end of the run from both the slurry and fixed-bed reactors were received from Texas A&M University.

  2. Fischer-Tropsch slurry phase process variations to understand wax formations: Quarterly report for period October 1, 1987 to December 31, 1987

    SciTech Connect

    Satterfield, C.N.

    1987-01-01

    Effects of high syngas conversion on the secondary reactions of olefins formed by Fischer-Tropsch synthesis on a reduced fused magnetite catalyst were simulated by studies of olefins in the presence of hydrogen and low concentrations of CO, or none at all. kinetic models were developed for the effect of CO partial pressure on hydrogenation rates at 232)degree)C and 0.30 to 0.79 MPa. In the absence of carbon monoxide, olefin hydrogenation was more rapid than in its presence. A model indicated that a hydrogenated carbon monoxide species on the catalyst may be responsible for the inhibition of olefin hydrogenation, and that olefin adsorption is rate-limiting. The formation of secondary olefins appeared to follow similar trends with carbon monoxide partial pressure. Olefin incorporation was not observed in the small amount of Fischer-Tropsch products obtained in these experiments. The chain growth probability, alpha, appeared to correlate with the H/sub 2/CO feed ratio. 14 refs., 13 figs., 1 tab.

  3. 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.

  4. 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.

  5. The role of Fischer-Tropsch catalysis in solar nebula chemistry

    NASA Astrophysics Data System (ADS)

    Kress, Monika E.; Tielens, Alexander G. G. M.

    2001-01-01

    Fischer-Tropsch catalysis, the iron/nickel catalyzed conversion of CO and H2 to hydrocarbons, would have been the only thermally-driven pathway available in the solar nebula to convert CO into other forms of carbon. A major issue in meteoritics is to determine the origin of meteoritic organics: are they mainly formed from CO in the solar nebula via a process such as Fischer-Tropsch, or are they derived from interstellar organics? In order to determine the role that Fischer-Tropsch catalysis may have played in the organic chemical evolution of the solar nebula, we have developed a kinetic model for this process. Our model results agree well with experimental data from several existing laboratory studies. In contrast, empirical rate equations, which have been derived from experimental rate data for a limited temperature (T) and pressure (P) range, are inconsistent with experimental rate data for higher T and lower P. We have applied our model to pressure and temperature profiles for the solar nebula, during the epoch in which meteorite parent bodies condensed and agglomerated. We find that, under nebular conditions, the conversion rate of CO to CH4 does not simply increase with temperature as the empirically-derived equations suggest. Instead, our model results show that this process would have been most efficient in a fairly narrow region that coincides with the present position of the asteroid belt. Our results support the hypothesis that Fischer-Tropsch catalysis may have played a role in solar nebula chemistry by converting CO into less volatile materials that can be much more readily processed in the nebula and in parent bodies.

  6. The role of Fischer-Tropsch catalysis in Jovian subnebular chemistry

    NASA Astrophysics Data System (ADS)

    Mousis, O.; Alibert, Y.; Sekine, Y.; Sugita, S.; Matsui, T.

    2006-12-01

    We examine the production of methane via Fischer-Tropsch catalysis in an evolving turbulent model of the Jovian subnebula and its implications for the composition of satellitesimals produced in situ. We show that there is a catalytically-active region in the Jovian subnebula from 65 Jupiter radii that moves inwards with time. The pressure range in this region is about 10-4 to 10-3 bar and implies that, if transport processes and the cooling of the subnebula are not considered, CO and CO2 are entirely converted into CH4 via Fischer-Tropsch catalysis in about 10^1-102 and 10^3-104 years, respectively. On the other hand, the comparison of the chemical conversion times with the viscous timescale of the subdisk in the catalytically-active region implies that only CO can be fully converted into CH4, the conversion of CO2 thus being restricted to a limited production of CH4. Moreover, the time required by the Jovian subnebula to cool down from the optimal temperature for Fischer-Tropsch catalysis to the condensation temperature of ices is at least two orders of magnitude higher than the viscous timescale. This implies that any CH4 produced in the catalytically-active zone will be accreted onto Jupiter long before being incorporated into the forming ices. We then conclude that in an evolving turbulent subnebula, even if Fischer-Tropsch catalysis is active, it has no influence on the composition of the forming satellitesimals that will ultimately take part in the formation of regular icy satellites, in opposition to what has been expected from stationary models.

  7. The role of Fischer Tropsch catalysis in the origin of methane-rich Titan

    NASA Astrophysics Data System (ADS)

    Sekine, Yasuhito; Sugita, Seiji; Shido, Takafumi; Yamamoto, Takashi; Iwasawa, Yasuhiro; Kadono, Toshihiko; Matsui, Takafumi

    2005-11-01

    Fischer-Tropsch catalysis, which converts CO and H 2 into CH 4 on the surface of iron catalyst, has been proposed to produce the CH 4 on Titan during its formation process in a circum-planetary subnebula. However, Fischer-Tropsch reaction rate under the conditions of subnebula have not been measured quantitatively yet. In this study, we conduct laboratory experiments to determine CH 4 formation rate and also conduct theoretical calculation of clathrate formation to clarify the significance of Fischer-Tropsch catalysis in a subnebula. Our experimental result indicates that the range of conditions where Fischer-Tropsch catalysis proceeds efficiently is narrow ( T˜500-600 K) in a subnebula because the catalysts are poisoned at temperatures above 600 K under the condition of subnebula (i.e., H 2/CO = 1000). This suggests that an entire subnebula may not become rich in CH 4 but rather that only limited region of a subnebula may enriched in CH 4 (i.e., CH 4-rich band formation). Our experimental result also suggests that both CO and CO 2 are converted into CH 4 within time significantly shorter than the lifetime of the solar nebula at the optimal temperatures around 550 K. The calculation result of clathration shows that CO 2-rich satellitesimals are formed in the catalytically inactive outer region of subnebula. In the catalytically active inner region, CH 4-rich satellitesimals are formed. The resulting CH 4-rich satellitesimals formed in this region play an important role in the origin of CH 4 on Titan. When our experimental data are applied to a high-pressure model for subnebula evolution, it would predict that there should be CO 2 underneath the Iapetus subsurface and no thick CO 2 ice layer on Titan's icy crust. Such surface and subsurface composition, which may be observed by Cassini-Huygens mission, would provide crucial information on the origin of icy satellites.

  8. X-ray nanoscopy of cobalt Fischer-Tropsch catalysts at work.

    PubMed

    Cats, Korneel H; Gonzalez-Jimenez, Ines D; Liu, Yijin; Nelson, Johanna; van Campen, Douglas; Meirer, Florian; van der Eerden, Ad M J; de Groot, Frank M F; Andrews, Joy C; Weckhuysen, Bert M

    2013-05-21

    Transmission X-ray microscopy has been used to investigate individual Co/TiO2 Fischer-Tropsch (FT) catalyst particles in 2-D and 3-D with 30 nm spatial resolution. Tomographic elemental mapping showed that Co is heterogeneously concentrated in the centre of the catalyst particles. In addition, it was found that Co is mostly metallic during FT at 250 °C and 10 bar. No evidence for Co oxidation was found. PMID:23586073

  9. 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.

  10. Fischer-Tropsch synthesis on functionalized carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Pokhrel, Sewa

    The aim of this research was to investigate the role of chemical functionalization on carbon nanotubes surfaces and its effect on FT catalysis. Multi walled carbon nanotubes (MWNT) were first treated with acid (HCl) to remove the residual metal particles and were then functionalized using H2O2 and HNO3 to introduce oxygen-containing groups to the MWNT surface. These treatments also add defects on MWNT surface. Morphological analyses were performed on the MWNT samples with TEM and it was found that the peroxide and acid treated MWNTs showed an increase oxygen functional groups and created additional surface defects on the MWNTs. Results of FT experiments showed enhanced CO conversion, FT activity and product selectivity towards liquid hydrocarbons due to functionalization. The liquid selectivity was found to be significantly high for H2O 2 treated catalyst. HNO3 treated catalyst had highest activity although selectivity to methane and CO2 was found higher than the H2O2 treated catalyst. It was observed that the chemical treatments increase the carbon chain length of the produced hydrocarbons. While comparing hydrocarbon distribution of as-produced and H2O2 treated MWNT, it was found that carbon-chain length increases for peroxide treated catalyst. Along with as-produced and functionalized nanotube, FT experiments were also conducted using B-doped sponge, un-doped sponge and N-doped CNT catalyst. B-doped sponge showed enhanced CO conversion and FT activity as compared to un-doped sponge. Conversion and product selectivity were found to be affected by temperature when test was conducted with N-CNT. Operating conditions like temperature, syngas feed flow rate and syngas ratio were also to impact the FT performance.

  11. 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.

  12. Emissions characteristics of Military Helicopter Engines Fueled with JP-8 and a Fischer-Tropsch Fuel

    SciTech Connect

    Corporan, E.; DeWitt, M.; Klingshirn, Christopher D; Striebich, Richard; Cheng, Mengdawn

    2010-01-01

    The rapid growth in aviation activities and more stringent U.S. Environmental Protection Agency regulations have increased concerns regarding aircraft emissions, due to their harmful health and environmental impacts, especially in the vicinity of airports and military bases. In this study, the gaseous and particulate-matter emissions of two General Electric T701C engines and one T700 engine were evaluated. The T700 series engines power the U.S. Army's Black Hawk and Apache helicopters. The engines were fueled with standard military JP-8 fuel and were tested at three power settings. In addition, one of the T701C engines was operated on a natural-gas-derived Fischer-Tropsch synthetic paraffinic kerosene jet fuel. Test results show that the T701C engine emits significantly lower particulate-matter emissions than the T700 for all conditions tested. Particulate-matter mass emission indices ranged from 0.2-1.4 g/kg fuel for the T700 and 0.2-0.6 g/kg fuel for the T701C. Slightly higher NOx and lower CO emissions were observed for the T701C compared with the T700. Operation of the T701C with the Fischer-Tropsch fuel rendered dramatic reductions in soot emissions relative to operation on JP-8, due primarily to the lack of aromatic compounds in the alternative fuel. The Fischer-Tropsch fuel also produced smaller particles and slight reductions in CO emissions.

  13. The role of Fischer-Tropsch catalysis in Jovian subnebular chemistry

    NASA Astrophysics Data System (ADS)

    Mousis, O.; Alibert, Y.; Sekine, Y.; Sugita, S.; Matsui, T.

    2006-06-01

    We examine the production of methane via Fischer-Tropsch catalysis in an evolving turbulent model of the Jovian subnebula and its implications for the composition of satellitesimals produced in situ. We show that there is a catalytically-active region in the Jovian subnebula from 65 Jupiter radii that moves inwards with time. The pressure range in this region is about 10-4 to 10-3 bar and implies that, if transport processes and the cooling of the subnebula are not considered, CO and CO_2 are entirely converted into CH_4 via Fischer-Tropsch catalysis in about 10^1-10^2 and 10^3-10^4 years, respectively. On the other hand, the comparison of the chemical conversion times with the viscous timescale of the subdisk in the catalytically-active region implies that only CO can be fully converted into CH_4, the conversion of CO_2 thus being restricted to a limited production of CH_4. Moreover, the time required by the Jovian subnebula to cool down from the optimal temperature for Fischer-Tropsch catalysis to the condensation temperature of ices is at least two orders of magnitude higher than the viscous timescale. This implies that any CH_4 produced in the catalytically-active zone will be accreted onto Jupiter long before being incorporated into the forming ices.

  14. Technology development for iron Fischer-Tropsch catalysis. Quarterly technical progress report No. 5, October 1, 1995--December 31, 1995

    SciTech Connect

    Davis, B.H.

    1996-01-19

    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 ``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 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. The research is divided into four major topical areas: (a) catalyst preparation and characterization, (b) product characterization, (c) reactor operations, and (d) data assessment. Accomplishments to date are described.

  15. Technology development for iron Fischer-Tropsch catalysis. Quarterly technical progress report No. 6, January 1, 1996--March 31, 1996

    SciTech Connect

    Davis, B.H.

    1996-05-01

    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 ``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. The research is divided into four major topical areas: (a) catalyst preparation and characterization, (b) product characterization, (c) reactor operations, and (d) data assessment. Accomplishments for this period are discussed.

  16. Technology development for iron Fischer-Tropsch catalysis. Quarterly technical progress report No. 7, April 1, 1996--June 30, 1996

    SciTech Connect

    Davis, B.H.

    1996-08-07

    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 ``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 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. The research is divided into four major topical areas: (a) catalyst preparation and characterization, (b) product characterization, (c) reactor operations, and (d) data assessment.

  17. Technology development for iron Fischer-Tropsch catalysis. Quarterly technical progress report No. 3, April 1, 1995--June 30, 1995

    SciTech Connect

    1995-08-18

    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. 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 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. The research is divided into four major topical areas: (a) catalyst preparation and characterization, (b) product characterization, (c) reactor operations, and (d) data assessment.

  18. Technology development for iron Fischer-Tropsch catalysis. Quarterly technical progress report No. 4, July 1, 1995--September 30, 1995

    SciTech Connect

    Davis, B.H.

    1996-01-09

    The affect of copper promotion on the activity and selectivity of hydrogen pretreated, precipitated iron Fischer-Tropsch catalysts was studied. Fischer-Tropsch synthesis was carried out in the slurry phase in one in one liter continuous stirred tank reactors at a space velocity of 3.lNL h{sup {minus}1} g{sup {minus}1}(Fe), H{sub 2}:CO = 0.7 at either 270{degree}C or 230{degree}C. Catalysts with atomic compositions relative to iron of 10OFe/4.4Si/l.OK and 10OFe/4.4Si/2.6Cu/l.OK were used at 270{degree}C and catalysts with the compositions of 100Fe/4.4Si/4.2K and 10OFe/4.4Si/2.6Cu/4.2K were used at 230{degree}C. XRD and Moessbauer spectroscopy both show that the 10OFe/4.4Si/2.6Cu/l.OK catalyst contained approximately 24% {alpha}-Fe with the remainder Fe{sub 3}O{sub 4} after a 24 h pretreatment with hydrogen at 220{degree}C. Copper promotion was found to substantially increase the activity and productivity of the catalysts. Catalysts promoted with copper reached maximum activity within 100 h of synthesis while catalysts with no copper went through an induction period. The activity of the hydrogen pretreated 10OFe/4.4Si/2.6Cu/1.0K catalyst operated at 270{degree}C was comparable to the activity of the the 100Fe/4.4Si/l.OK catalyst after pretreatment with carbon monoxide or syngas at one atmosphere pressure. However, the activity of the hydrogen pretreated 1O0Fe/4.4Si/2.6Cu/4.2K catalyst at 230{degree}C was found to be substantially lower than the same catalyst pretreated with carbon monoxide or syngas at one atmosphere pressure.

  19. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 7, April 1, 1992--June 30, 1992

    SciTech Connect

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

    1992-12-31

    The objective of this contract are to develop a technology for the production of active and stable iron 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 H{sub 2} and 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/gFe. The desired sum of methane and ethane selectivities is no more than 4%, and the conversion loss per week is not to exceed 1%. Contract Tasks are as follows: 1.0--Catalyst development, 1.1--Technology assessment, 1.2--Precipitated catalyst preparation method development, 1.3--Novel catalyst preparation methods investigation, 1.4--Catalyst pretreatment, 1.5--Catalyst characterization, 2.0--Catalyst testing, 3.0--Catalyst aging studies, and 4.0--Preliminary design and cost estimate of a catalyst synthesis facility. This paper reports progress made on catalyst development.

  20. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 9, September 26, 1992--December 26, 1992

    SciTech Connect

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

    1992-12-31

    The objectives of this contract are to develop a technology for the production of active and stable iron 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 and carbon monoxide 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/gFe. The desired sum of methane and ethane selectivities is no more than 4%, and the conversion loss per week is not to exceed 1%. Contract Tasks are as follows: 1.0--Catalyst development, 1.1--Technology assessment, 1.2--Precipitated catalyst preparation method development, 1.3--Novel catalyst preparation methods investigation, 1.4--Catalyst pretreatment, 1.5--Catalyst characterization, 2.0--Catalyst testing, 3.0--Catalyst aging studies, and 4.0--Preliminary design and cost estimate of a catalyst synthesis facility. This paper reports progress on Task 1.3.

  1. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 6, December 26, 1991--March 31, 1992

    SciTech Connect

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

    1992-12-31

    The objective of this contract are to develop a technology for the production of active and stable iron 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 H{sub 2} and 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/gFe. The desired sum of methane and ethane selectivities is no more than 4%, and the conversion loss per week is not to exceed 1%. Contract Tasks are as follows: 1.0--Catalyst development, 1.1--Technology assessment, 1.2--Precipitated catalyst preparation method development, 1.3--Novel catalyst preparation methods investigation, 1.4--Catalyst pretreatment, 1.5--Catalyst characterization, 2.0--Catalyst testing, 3.0--Catalyst aging studies, and 4.0--Preliminary design and cost estimate of a catalyst synthesis facility. This paper reports progress made on catalyst development.

  2. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 10, December 26, 1992--March 26, 1993

    SciTech Connect

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

    1993-12-31

    The objectives of this contract are to develop a technology for the production of active and stable iron 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 and carbon monoxide 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/gFe. The desired sum of methane and ethane selectivities is no more than 4%, and the conversion loss per week is not to exceed 1%. Contract tasks are as follows: 1.0: Catalyst development; 1.1--Technology assessment; 1.2--Precipitated catalyst preparation method development; 1.3--Novel catalyst preparation methods investigation; 1.4--Catalyst pretreatment; 1.5--Catalyst characterization; 2.0--Catalyst testing; 3.0--Catalyst aging studies, and 4.0--Preliminary design and cost estimate of a catalyst synthesis facility. This paper reports progress made on Task 1.2 and 2.0.

  3. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 8, July 1, 1992--September 30, 1992

    SciTech Connect

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

    1992-12-31

    The objectives of this contract are to develop a technology for the production of active and stable iron 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 and carbon monoxide 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/gFe. The desired sum of methane and ethane selectivities is no more than 4%, and the conversion loss per week is not to exceed 1%. Contract Tasks are as follows: 1.0--Catalyst development, 1.1--Technology assessment, 1.2--Precipitated catalyst preparation method development, 1.3--Novel catalyst preparation methods investigation, 1.4--Catalyst pretreatment, 1.5--Catalyst characterization, 2.0--Catalyst testing, 3.0--Catalyst aging studies, and 4.0--Preliminary design and cost estimate of a catalyst synthesis facility. This paper reports progress made on Task 1.

  4. 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

  5. Assessing the economic impact of indirect liquefaction process improvements: Volume 1, Development of the integrated indirect liquefaction model and baseline case

    SciTech Connect

    Gray, D.; Tomlinson, G.C. . Civil Systems Div.)

    1990-10-01

    This report documents the development of an integrated indirect liquefaction system model, which processes input coal to refined liquid products, and the model's application in the analysis of a baseline case. The baseline case uses Shell gasification of coal followed by gas cleaning to produce a clean synthesis gas for slurry-phase Fischer-Tropsch synthesis. The raw liquid products are refined to produce gasoline and diesel. Costs of liquid products have been estimated for the baseline plant. The model also alloys many sensitivity studies to be performed so that the economic impacts of research and development advances can be quantified. When used in this manner, the model can provide research guidance for future indirect liquefaction studies. 18 refs., 12 figs., 12 tabs.

  6. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 4, June 26, 1991--September 26, 1991

    SciTech Connect

    Frame, R.R.

    1991-12-31

    Objectives are to develop active, stable iron 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. For a H{sub 2}-CO in molar ratio of 0.5 to 1.0, catalyst performance target is 88% CO+H{sub 2} conversion at a minimum space velocity of 2.4 NL/hr/gFe, with no more than 4% methane/ethane selectivity and 1% conversion loss per week. During this period, it was found that the performance of the slurry-phase iron and copper oxide-based catalyst depends on the amount of K. Five catalysts with differing K contents were studied. The catalysts with the lowest K were more active than the ones with higher K levels. The one with the middle K level was judged best.

  7. Characterization of working iron Fischer-Tropsch catalysts using quantitative diffraction methods

    NASA Astrophysics Data System (ADS)

    Mansker, Linda Denise

    This study presents the results of the ex-situ characterization of working iron Fischer-Tropsch synthesis (F-TS) catalysts, reacted hundreds of hours at elevated pressures, using a new quantitative x-ray diffraction analytical methodology. Compositions, iron phase structures, and phase particle morphologies were determined and correlated with the observed reaction kinetics. Conclusions were drawn about the character of each catalyst in its most and least active state. The identity of the active phase(s) in the Fe F-TS catalyst has been vigorously debated for more than 45 years. The highly-reduced catalyst, used to convert coal-derived syngas to hydrocarbon products, is thought to form a mixture of oxides, metal, and carbides upon pretreatment and reaction. Commonly, Soxhlet extraction is used to effect catalyst-product slurry separation; however, the extraction process could be producing irreversible changes in the catalyst, contributing to the conflicting results in the literature. X-ray diffraction doesn't require analyte-matrix separation before analysis, and can detect trace phases down to 300 ppm/2 nm; thus, working catalyst slurries could be characterized as-sampled. Data were quantitatively interpreted employing first principles methods, including the Rietveld polycrystalline structure method. Pretreated catalysts and pure phases were examined experimentally and modeled to explore specific behavior under x-rays. Then, the working catalyst slurries were quantitatively characterized. Empirical quantitation factors were calculated from experimental data or single crystal parameters, then validated using the Rietveld method results. In the most active form, after pretreatment in H 2 or in CO at Pambient, well-preserved working catalysts contained significant amounts of Fe7C3 with trace alpha-Fe, once reaction had commenced at elevated pressure. Amounts of Fe3O 4 were constant and small, with carbide dpavg < 15 nm. Small amounts of Fe7C3 were found in unreacted

  8. 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.

  9. Preparation, surface characterization and performance of a Fischer-Tropsch catalyst of cobalt supported on silica nanosprings

    NASA Astrophysics Data System (ADS)

    Kengne, Blaise-Alexis Fouetio; Alayat, Abdulbaset M.; Luo, Guanqun; McDonald, Armando G.; Brown, Justin; Smotherman, Hayden; McIlroy, David N.

    2015-12-01

    The reduction of cobalt (Co) catalyst supported on silica nanosprings for Fischer-Tropsch synthesis (FTS) has been monitored by X-ray photoelectron spectroscopy (XPS) and compared to FT catalytic activity. The cobalt is present in the starting catalyst as a Co3O4 spinel phase. A two-step reduction of Co3O4 to CoO and then to Co0 is observed, which is consistent with the results of H2-temperature programmed reduction. During the reduction the two steps occur concurrently. The deconvolution of the Co 2p core level state for the catalyst reduced at 385 °C and 1.0 × 10-6 Torr of H2 revealed signatures of Co0, CoO, and Co3O4. The reduction saturates at a Coo concentration of approximately 41% after 20 h, which correlates with the activity and lifetime of the catalyst during FTS testing. Conversely, at 680 °C and 10 Torr of H2, the catalyst is completely reduced after 10 h. The evolution of the Co d-band at the Fermi level in the valence band XPS spectrum definitively verifies the metallic phase of Co. FTS evaluation of the Co/NS catalyst reduced at 609 °C showed higher production rate (3-fold) of C6-C17 hydrocarbons than the catalyst reduced at 409 °C and is consistent with the XPS analysis.

  10. 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.

  11. 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.

  12. 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.

  13. The chemical oxidation and refinement of raw Fischer-Tropsch wax

    SciTech Connect

    Zhu Jisheng; Chen Languang; Sun Shuhe; Cheng Shaoxin

    1995-12-31

    Raw Fischer-Tropsch wax (FT wax) produced from the pilot plant (100t/a, Daixian, Shanxi Province) and the demonstration plant (2,000t/a, Jincheng, Shanxi Province) of coal-based synthetic gasoline process was refined by chemical oxidation. The properties of refined FT wax were greatly improved. The results show that the refined wax with very high melting point (108 C) and satisfactory hardness (penetration about 5, 25 C 100g/5s) consists of a large amount of paraffins, but a minute amount of acids, alcohols and other organic compounds.

  14. Structural framework of a medium Fischer-Tropsch wax fraction determined by electron crystallography

    NASA Astrophysics Data System (ADS)

    Dorset, Douglas L.; Basson, Ilsa

    2000-10-01

    The structural framework of a medium hardness Fischer-Tropsch wax distillate is established quantitatively by electron crystallography and compared to model paraffin assemblies with a similar Gaussian distribution of chain lengths. The lamellar packing closely resembles the crystal structure of refined petroleum waxes with a similar distribution of defects near the lamellar interface. Nevertheless, clear differences associated with the absorption of smaller chains within the lamellar interface, detected by NMR, are not resolved by these diffraction measurements, perhaps due to artefacts induced by the high vacuum of the experiment and/or specimen preparation.

  15. Fischer-Tropsch reaction studies with supported ruthenium catalysts

    SciTech Connect

    Everson, R.C.; Mulder, H. )

    1993-09-01

    An investigation was undertaken to examine the production of low molecular weight alkenes (C[sub 2][sup =] to C[sup =][sub 4]) and high molecular weight hydrocarbons (C[sub 5]+) from synthesis gas in a fixed bed reactor with supported ruthenium catalyst. The catalyst used consisted of 0.5% ruthenium on gamma-alumina with a 43% metal dispersion. An experimental reactor consisting of a single 12.5-mm-diameter stainless-steel tube with catalyst packings up to 1 m long, surrounded by an aluminium block with heating elements and an outer insulating ceramic block was used. The effect of temperature, synthesis gas composition (CO/H[sub 2]), weight hourly space velocity (WHSV), and bed length on carbon monoxide conversion and selectivity was examined and results are reported. The presence of secondary reactions consisting of hydrogenation and chain growth involving alkenes along the reactor bed was observed. These reactions favour the formation of alkanes and high molecular weight hydrocarbons. The alkene to alkane ratio in the product can be increased by restricting the hydrogenation reaction with the use of a synthesis gas mixture with a high carbon monoxide to hydrogen ratio.

  16. ENVIRONMENTAL AND ECONOMIC ASPECTS OF INDIRECT COAL LIQUEFACTION PROCESSES: A REPORT EMPHASIZING THE RELATIONSHIP BETWEEN PRODUCT MIX AND EFFICIENCY

    EPA Science Inventory

    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 envi...

  17. DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

    SciTech Connect

    Adeyinka A. Adeyiga

    2003-12-01

    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 Fe FT 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. 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. The catalysts were prepared by co-precipitation, followed by binder addition and spray drying at 250 C in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. The results show that use of small amounts of precipitated SiO{sub 2} alone in spray-dried Fe catalysts can result in good attrition resistance. All catalysts investigated with SiO{sub 2} wt% {le} 12 produced fines less than 10 wt% during the jet cup attrition test, making them suitable for long-term use in a slurry bubble column reactor. Thus, concentration rather than type of SiO{sub 2

  18. An Auger electron spectroscopy study of the activation of iron Fischer-Tropsch catalysts. I. Hydrogen activation

    SciTech Connect

    Sault, A.G. )

    1993-03-01

    Activation procedures can have a dramatic effect on the activity of iron-based catalysts for Fischer-Tropsch (F-T) synthesis. CO conversion over a 100 Fe/3 Cu/0.2 K catalyst (parts by weight) can vary by nearly a factor of 3, depending on activation. In contrast, a 100 Fe/5 Cu/4.2 K/25 SiO[sub 2] catalyst displays only minor variations in activity with activation conditions. An ultra-high vacuum surface analysis chamber coupled to an atmospheric pressure reactor has been used to measure the surface compositions of these catalysts following various hydrogen activation procedures. Activation of the 100 Fe/3 Cu/0.2 K catalyst in H[sub 2] results in rapid reduction of iron to the metallic state, and segregation of sulfur to the catalyst surface. The sulfur arises from bulk sulfate impurities present in the metal nitrates used to prepare the catalyst. Sulfur coverage increases with both activation time and temperature, due to an increase in the rate of sulfur diffusion with temperature. F-T activity of this catalyst varies inversely with sulfur coverage, consistent with the well-known poisoning effect of sulfur on F-T synthesis. For the 100 Fe/5 Cu/4.2 K/25 SiO[sub 2] catalyst no significant variations in surface composition are observed as a function of hydrogen activation temperature, consistent with the absence of any variations in catalyst activity. Only partial reduction of iron to a mixture of Fe[sub x]O and Fe[sub 3]O[sub 4] is observed for this catalyst for all activation conditions investigated. Using electron beam effects to remove potassium and silica shows that one or both of these components inhibits reduction of iron to the metallic state in the 100 Fe/5 Cu/4.2 K/25 SiO[sub 2] catalyst. 48 refs., 3 tabs.

  19. 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

    2006-03-03

    Efforts during this second year focused on four areas: (1) continued searching and summarizing of published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) investigation of CO adsorption/desorption and temperature programmed hydrogenation (TPH) of carbonaceous species after FTS on unsupported iron and alumina-supported iron catalysts; (3) activity tests of alumina-supported iron catalysts in a fixed bed reactor; (4) sequential design of experiments, for the collection of rate data in a Berty CSTR reactor, and nonlinear-regression analysis to obtain kinetic parameters. Literature sources describing mechanistic and kinetic studies of Fischer-Tropsch synthesis on iron catalysts were compiled in a review. Temperature-programmed desorption/reaction methods (the latter using mass-spectrometry detection and also thermogravimetric analyzer (TGA)) were utilized to study CO adsorption/-desorption on supported and unsupported iron catalysts. Molecular and dissociative adsorptions of CO occur on iron catalysts at 25-150 C. The amounts adsorbed and bond strengths of adsorption are influenced by supports and promoters. That CO adsorbs dissociatively on polycrystalline Fe at temperatures well below those of FT reaction indicates that CO dissociation is facile and unlikely to be the rate-limiting step during FTS. Carbonaceous species formed after FT reaction for only 5 minutes at 200 C were initially hydrogenated under mild, isothermal condition (200 C and 1 atm), followed by TPH to 800 C. During the mild, isothermal hydrogenation, only about 0.1-0.2 mL of atomic carbon is apparently removed, while during TPH to 800 C multilayer equivalents of atomic, polymeric, carbidic, and graphitic carbons are removed. Rates of CO conversion on alumina-supported iron catalysts at 220-260 C and 20 atm are correlated well by a Langmuir-Hinshelwood expression, derived assuming carbon hydrogenation to CH and OH recombination to water to be

  20. Control and impact of the nanoscale distribution of supported cobalt particles used in Fischer-Tropsch catalysis.

    PubMed

    Munnik, Peter; de Jongh, Petra E; de Jong, Krijn P

    2014-05-21

    The proximity of nanoparticles may affect the performance, in particular the stability, of supported metal catalysts. Short interparticle distances often arise during catalyst preparation by formation of aggregates. The cause of aggregation of cobalt nanoparticles during the synthesis of highly loaded silica-supported catalysts was found to originate from the drying process after impregnation of the silica grains with an aqueous cobalt nitrate precursor. Maximal spacing of the Co3O4 nanoparticles was obtained by fluid-bed drying at 100 °C in a N2 flow. Below this temperature, redistribution of liquid occurred before and during precipitation of a solid phase, leading to aggregation of the cobalt particles. At higher temperatures, nucleation and growth of Co3O4 occurred during the drying process also giving rise to aggregation. Fischer-Tropsch catalysis performed under industrially relevant conditions for unpromoted and Pt-promoted cobalt catalysts revealed that the size of aggregates (13-80 nm) of Co particles (size ~9 nm) had little effect on activity. Large aggregates exhibited higher selectivities to long chain alkanes, possibly related to higher olefin formation with subsequent readsorption and secondary chain growth. Most importantly, larger aggregates of Co particles gave rise to extensive migration of cobalt (up to 75%) to the external surface of the macroscopic catalyst grains (38-75 μm). Although particle size did not increase inside the silica support grains, migration of cobalt to the external surface partly led to particle growth, thus causing a loss of activity. This cobalt migration over macroscopic length scales was suppressed by maximizing the distance between nanoparticles over the support. Clearly, the nanoscale distribution of particles is an important design parameter of supported catalysts in particular and functional nanomaterials in general. PMID:24801898

  1. An Auger electron spectroscopy study of the activation of iron Fischer-Tropsch catalysts. II. Carbon monoxide activation

    SciTech Connect

    Sault, A.G. ); Datye, A.K. )

    1993-03-01

    Activation procedures can have a dramatic effect on the activity of iron-based catalysts for Fischer-Tropsch (F-T) synthesis. CO conversion over a 100 Fe/3 Cu/0.2 K catalyst (parts by weight) can vary by nearly a factor of 3, depending on activation treatment. In contrast, a 100 Fe/5 Cu/4.2 K/25 SiO[sub 2] catalyst displays little dependence of F-T activity on activation treatment. An ultra-high vacuum surface analysis chamber coupled to an atmospheric reactor has been used to measure the surface composition of these catalysts following activation in carbon monoxide at 280[degrees]C, while transmission electron microscopy (TEM) and BET surface area measurements have been used to investigate catalyst morphology. CO activation of the 100 Fe/5 Cu/4.2 K/25 SiO[sub 2] catalyst at 280[degrees]C results in partial reduction of iron to a mixture of Fe[sub x]O and Fe[sub 3]O[sub 4], and an overall surface composition very similar to that obtained following hydrogen activation at 220 or 280[degrees]C, consistent with the invariance of F-T activity with activation treatment for this catalyst. Activation of the 100 Fe/3 Cu/0.2 K catalyst in CO at 280[degrees]C results in the formation of iron carbide particles, growth of graphitic carbon (C[sub g]) filaments, and formation of a thick, porous, C[sub g] layer covering the carbide particles. Differences in F-T activity between the hydrogen- and CO-activated 100 Fe/3 Cu/0.2 K catalyst are discussed in terms of surface composition and catalyst morphology. The difference in sensitivity of the two catalysts to activation conditions is related to differences in the extent of reduction of the catalysts. 45 refs., 4 figs., 1 tab.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Upgrading Fischer-Tropsch LPG (liquefied petroleum gas) with the Cyclar process

    SciTech Connect

    Gregor, J.H.; Gosling, C.D.; Fullerton, H.E.

    1989-04-28

    The use of the UOP/BP Cyclar{reg sign} process for upgrading Fischer-Tropsch (F-T) liquefied petroleum gas (LPG) was studied at UOP{reg sign}. The Cyclar process converts LPG into aromatics. The LPG derived from F-T is highly olefinic. Two routes for upgrading F-T LPG were investigated. In one route, olefinic LPG was fed directly to a Cyclar unit (Direct Cyclar). The alternative flow scheme used the Huels CSP process to saturate LPG olefins upstream of the Cyclar unit (Indirect Cyclar). An 18-run pilot plant study verified that each route is technically feasible. An economic evaluation procedure was designed to choose between the Direct and Indirect Cyclar options for upgrading LPG. Four situations involving three different F-T reactor technologies were defined. The main distinction between the cases was the degree of olefinicity, which ranged between 32 and 84 wt % of the fresh feed. 8 refs., 80 figs., 44 tabs.

  8. 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. PMID:24522290

  9. An experimental study on Fischer-Tropsch catalysis: Implications for impact phenomena and nebular chemistry

    NASA Astrophysics Data System (ADS)

    Sekine, Yasuhito; Sugita, Seiji; Shido, Takafumi; Yamamoto, Takashi; Iwasawa, Yasuhiro; Kadono, Toshihiko; Matsui, Takafumi

    2006-05-01

    Fischer-Tropsch catalysis, by which CO and H2 are converted to CH4 on the surface of transition metals, has been considered to be one of the most important chemical reactions in many planetary processes, such as the formation of the solar and circumplanetary nebulae, the expansion of vapor clouds induced by cometary impacts, and the atmospheric re-entry of vapor condensate due to asteroidal impacts. However, few quantitative experimental studies have been conducted for the catalytic reaction under conditions relevant to these planetary processes. In this study, we conduct Fischer-Tropsch catalytic experiments at low pressures (1.3 × 10-4 bar ≤ P ≤ 5.3 × 10 -1 bar) over a wide range of H2/CO ratios (0.25-1000) using pure iron, pure nickel, and iron-nickel alloys. We analyze what gas species are produced and measure the CH4 formation rate. Our results indicate that the CH4 formation rate for iron catalysts strongly depends on both pressure and the H2/CO ratio, and that nickel is a more efficient catalyst at lower pressures and lower H2/CO ratios. This difference in catalytic properties between iron and nickel may come from the reaction steps concerning disproportionation of CO, hydrogenation of surface carbon, and the poisoning of the catalyst. These results suggest that nickel is important in the atmospheric re-entry of impact condensate, while iron is efficient in circumplanetary subnebulae. Our results also indicate that previous numerical models of iron catalysis based on experimental data at 1 bar considerably overestimate CH4 formation efficiency at lower pressures, such as the solar nebula and the atmospheric re-entry of impact condensate.

  10. Correlating Fischer-Tropsch activity to Ru nanoparticle surface structure as probed by high-energy X-ray diffraction.

    PubMed

    Quek, Xian-Yang; Filot, Ivo A W; Pestman, Robert; van Santen, Rutger A; Petkov, Valeri; Hensen, Emiel J M

    2014-06-01

    Synchrotron X-ray diffraction coupled to atomic pair distribution function analysis and Reverse Monte Carlo simulations is used to determine the atomic-scale structure of Ru nanoparticle catalysts for the Fischer-Tropsch reaction. The rate of CO hydrogenation strongly correlates with the abundance of surface atoms with coordination numbers of 10 and 11. DFT calculations confirm that CO dissociation proceeds with a low barrier on these Ru surface atom ensembles. PMID:24763733

  11. 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

  12. 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

  13. Toward an understanding of methane selectivity in the Fischer-Tropsch process

    NASA Astrophysics Data System (ADS)

    Psarras, Peter C.

    The purpose of this research is to elucidate a better understanding of the conditions relevant to methane selectivity in the Fischer-Tropsch (FT) process. The development of more efficient FT catalysts can result in great commercial profit. The industrially relevant FT process has long been hampered by the production of methane. Nearly 60 percent of FT capital is devoted to the removal of methane and purification of feed-stock gases through steam-reforming. Naturally, a more efficient FT catalyst would need to have a reasonable balance between catalytic activity and suppression of methane formation (low methane selectivity). Though a significant amount of work has been devoted to understanding the mechanisms involved in methane selectivity, the exact mechanism is still not well understood. Density functional theory (DFT) methods provide an opportunity to explore the FT catalytic process at the molecular level. This work represents a combination of various DFT approaches in an attempt to gather new insight on the conditions relevant to methane selectivity. A thorough understanding of the electronic environment involved in the surface-adsorbate interaction is necessary to the advancement of more efficient Fischer-Tropsch catalysts. This study investigates the promotive effect of four late transition metals (Cu, Ag, Au and Pd) on three FT catalytic surfaces (Fe, Co and Ni). The purpose of this research is to examine the surface-adsorbate interaction from two perspectives: 1) interactions occurring between FT precursors and small, bimetallic surface analogs (clusters), and 2) plane-wave calculations of the interactions between FT precursors and simulated bulk surfaces. Our results suggest that promising candidates for the reduction of FT methane selectivity include Au and Pd on Ni, Au and Ag on Co, and Cu, Ag, and Pd on Fe. Additionally, cluster models were susceptible to effects not encountered in the plane-wave approach. Thermodynamic trends can be made more

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    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, H2-TPR, and H2 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 H2/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.

  16. Moessbauer spectroscopy studies of iron-catalysts used in Fischer-Tropsch (FT) processes. Quarterly technical progress report, January--March, 1995

    SciTech Connect

    Huffman, G.P.; Rao, K.R.P.M.

    1995-10-01

    Moessbauer spectroscopy investigations were carried out on 14 iron-based catalysts during the period under review. The catalyst 100Fe/4.4Si/0.71K (all atomic ratios) was subjected to activation first in syngas and subsequently in CO gas atmosphere. Fischer-Tropsch (FT) synthesis was carried out on the above catalyst. Another catalyst 100Fe/4.4Si/2.6Cu/0.71K (all atomic ratios) activated in syngas and subjected to FT synthesis was also studied to understand the effect of added Cu on the phase distribution and its effect on the FT activity. The following trends were observed: (1) activation of the catalyst in syngas, H{sub 2}/CO, lead to the formation of Fe{sub 3}O{sub 4} and no carbides were formed, the FT activity was found to be low at 9--12% (H{sub 2}+CO) conversion; (2) activation of the catalyst in CO for 22hrs lead to the formation of 33% of {chi}-carbide and the FT activity was found to be high at 88% maximum; (3) addition of copper to the catalyst has improved the FT activity for those catalysts pretreated in syngas at elevated pressures.

  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; 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

  18. Low-pressure hydrocracking of coal-derived Fischer-Tropsch waxes to diesel

    SciTech Connect

    Dieter Leckel

    2007-06-15

    Coal-derived low-temperature Fischer-Tropsch (LTFT) wax was hydrocracked at pressures of 3.5-7.0 MPa using silica-alumina-supported sulfided NiW/NiMo and an unsulfided noble metal catalyst, modified with MoO{sub 3}. A low-pressure operation at 3.5 MPa produced a highly isomerized diesel, having low cloud points (from -12 to -28{sup o}C) combined with high cetane numbers (69-73). These properties together with the extremely low sulfur ({lt}5 ppm) and aromatic ({lt}0.5%) contents place coal/liquid (CTL) derived distillates as highly valuable blending components to achieve Eurograde diesel specifications. The upgrading of coal-based LTFT waxes through hydrocracking to high-quality diesel fuel blend components in combination with commercial-feasible coal-integrated gasification combined cycle (coal-IGCC) CO{sub 2} capture and storage schemes should make CTL technology more attractive. 28 refs., 7 figs., 8 tabs.

  19. SEPARATION OF FISCHER-TROPSCH WAX FROM CATALYST BY SUPERCRITICAL EXTRACTION

    SciTech Connect

    MARK C. THIES; PATRICK C. JOYCE

    1998-07-31

    The objective of this research project is to evaluate the potential of supercritical fluid (SCF) extraction for the recovery and fractionation of the wax product from the slurry bubble column (SBC) reactor of the Fischer-Tropsch (F-T) process. The wax, comprised mostly of branched and linear alkanes with a broad molecular weight distribution up to C{sub 100}, will be extracted with a hydrocarbon solvent that has a critical temperature near the operating temperature of the SBC reactor, i.e., 200-300 C. Initial work is being performed using n-hexane as the solvent. The success of the project depends on two factors. First, the supercritical solvent must be able to dissolve the F-T wax; furthermore, this must be accomplished at conditions that do not entrain the solid catalyst. Second, the extraction must be controlled so as not to favor the removal of the low molecular weight wax compounds. That is, a constant carbon-number distribution in the wax slurry must be maintained at steady-state column operation. Three major tasks are being undertaken to evaluate our proposed SCF extraction process. Task 1: Equilibrium solubility measurements for model F-T wax components in supercritical fluids at conditions representative of those in a SBC reactor. Task 2: Thermodynamic modeling of the measured VLE data for extending our results to real wax systems. Task 3: Process design studies of our proposed process. Additional details of the task structure are given.

  20. SEPARATION OF FISCHER-TROPSCH WAX FROM CATALYST BY SUPERCRITICAL EXTRACTION

    SciTech Connect

    MARK C. THIES; PATRICK C. JOYCE

    1998-10-31

    The objective of this research project is to evaluate the potential of supercritical fluid (SCF) extraction for the recovery and fractionation of the wax product from the slurry bubble column (SBC) reactor of the Fischer-Tropsch (F-T) process. The wax, comprised mostly of branched and linear alkanes with a broad molecular weight distribution up to C{sub 100}, will be extracted with a hydrocarbon solvent that has a critical temperature near the operating temperature of the SBC reactor, i.e., 200-300 C. Initial work is being performed using n-hexane as the solvent. The success of the project depends on two factors. First, the supercritical solvent must be able to dissolve the F-T wax; furthermore, this must be accomplished at conditions that do not entrain the solid catalyst. Second, the extraction must be controlled so as not to favor the removal of the low molecular weight wax compounds. That is, a constant carbon-number distribution in the wax slurry must be maintained at steady-state column operation. Three major tasks are being undertaken to evaluate our proposed SCF extraction process. Task 1: Equilibrium solubility measurements for model F-T wax components in supercritical fluids at conditions representative of those in a SBC reactor. Task 2: Thermodynamic modeling of the measured VLE data for extending our results to real wax systems. Task 3: Process design studies of our proposed process. Additional details of the task structure are given.

  1. SEPARATION OF FISCHER-TROPSCH WAX FROM CATALYST BY SUPERCRITICAL EXTRACTION

    SciTech Connect

    Patrick C. Joyce; Mark C. Thies

    1999-03-31

    The objective of this research project was to evaluate the potential of supercritical fluid (SCF) extraction for the recovery and fractionation of the wax product from the slurry bubble column (SBC) reactor of the Fischer-Tropsch (F-T) process. The wax, comprised mostly of branched and linear alkanes with a broad molecular weight distribution up to C{sub 100}, is to be extracted with a hydrocarbon solvent that has a critical temperature near the operating temperature of the SBC reactor, i.e., 200-300 C. Aspen Plus{trademark} was used to perform process simulation studies on the proposed extraction process, with Redlich-Kwong-Soave (RKS) being used for the thermodynamic property model. In summary, we have made comprehensive VLE measurements for short alkane + long alkane systems over a wide range of pressures and temperatures, dramatically increasing the amount of high-quality data available for these simple, yet highly relevant systems. In addition, our work has demonstrated that, surprisingly, no current thermodynamic model can adequately predict VLE behavior for these systems. Thus, process simulations (such as those for our proposed SCF extraction process) that incorporate these systems can currently only give results that are qualitative at best. Although significant progress has been made in the past decade, more experimental and theoretical work remain to be done before the phase equilibria of asymmetric alkane mixtures can be predicted with confidence.

  2. 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.

  3. 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.

  4. Use of silicate crystallite mesoporous material as catalyst support for Fischer Tropsch reaction

    NASA Astrophysics Data System (ADS)

    Iwasaki, T.; Reinikainen, M.; Onodera, Y.; Hayashi, H.; Ebina, T.; Nagase, T.; Torii, K.; Kataja, K.; Chatterjee, A.

    1998-06-01

    Novel uniform mesoporous materials (silicate crystallite mesoporous material, SCMM) were synthesized by hydrothermal treatment of Si, Mg and/or Al containing hydroxide precipitates, along with quaternary ammonium salt, and were applied as catalyst support for Fischer-Tropsch reaction. SCMM is composed of aggregates of homogeneous layer silicate crystallites, as identified by X-ray diffraction (XRD) patterns and transmission electron microscopy (TEM) photographs which are structurally analogous to smectite clay. The mesopore of SCMM corresponds to interparticle space of disk-shaped crystallites (6-25 nm in diameter) aggregated by edge-to-face bonding. Two kinds of SCMM with variable negative charge locations were used as support materials of Co-catalysts for hydrogenation of CO. Conversion of CO was high on SCMM compared with that of silica gel. Furthermore, the main products obtained were hydrocarbons. In case of SCMM type with negative charge near the surface, olefins and branched hydrocarbons were efficiently produced in CO conversion reaction; where as another SCMM type having negative charge at the middle of crystallite platelets produced mainly normal hydrocarbons for the same reaction. This may be due to the role of the negative charge of SCMM which affects the chemical state of Co-catalyst supported on SCMM. The function of SCMM as compared to other mesoporous materials is better in terms of homogeneous and site-specific distribution of negative charge, which is further helpful in controlling the surface phenomenon as confirmed by the existence of linear CO species adsorbed on Co.

  5. Iron alloy Fischer-Tropsch catalysts. V. FeCo on Y zeolite

    SciTech Connect

    Lin, T.; Schwartz, L.H.; Butt, J.B.

    1986-01-01

    A series of Fe, Co, and FeCo catalysts on Y-zeolite support, prepared both by ion exchange and impregnation, has been investigated and compared with a previously reported series supported on wide-pore SiO/sub 2/. Characterization methods were X-ray diffraction, H/sub 2/ and CO chemisorption, Moessbauer spectroscopy, and atomic absorption. The oxidation, reduction, and carburization behavior of the iron-containing catalysts were observed by Moessbauer spectroscopy. The reversibility of FeY (ion exchanged) in oxidation-reduction cycles was confirmed. The ion-exchanged catalysts (FeY, FeCoY) do not show any iron metal, or alloy or carbide phase after reduction or attempted carburization. In contrast with prior results with silica-supported Fe and FeCo, where there appear to be significant differences, Fe/HY (impregnated) and FeCo/HY appear quite similar in characterization by Moessbauer spectroscopy and in reaction behavior. A 1/1:CO/H/sub 2/ feed was used to investigate the Fischer-Tropsch reaction at 1 atm and 523 K. Some additional runs were made at a total pressure of 13.6 atm. As in prior studies it was found that the CO turnover frequency in general decreases with increasing CO conversion. A higher selectivity for higher molecular weight products is found for HY-supported catalysts, and in all cases an approximate behavior in accord with the Schultz-Anderson distribution was observed. 23 references.

  6. Novel Fischer-Tropsch slurry catalysts and process concepts for selective transportation fuel production: Final report

    SciTech Connect

    Withers, H.P. Jr.; Eliezer, K.F.; Mitchell, J.W.

    1987-12-01

    The preparation, characterization and performance of cobalt and ruthenium carbonyl cluster-based catalysts for use in slurry-phase Fischer-Tropsch (FT) technology was investigated. The use of metal carbonyls as active metal precursor allows for the possible control of metal particle size on the support surface and thus offers the potential for better control of activity and selectivity of the FT reaction. Accomplishments included reproducible catalyst preparation, improvements in activity by use of a silica support, understanding diffeences between nitrate and carbonyl precursors, a nd good activity maintenance in the slurry reactor. A CO/sub 2/(CO)/sub 8/Zr(OPr)/sub 4/SiO/sub 2/ catalyst (3.5% CO, 6.6% Zr) was developed as the most active system in the slurry reactor and also gave the best liquid fuel selectivity. Silica support provided the highest catalyst activities. This catalyst was successfully tested in an extended slurry-phase run that achieved 6 months on stream with a 10% loss in activity. Ru catalysts showed the highest activity in the fixed-bed reactor but deactivated rapidly in the slurry reactor. In the analysis of the kinetic data, catalyst deactivation was assumed to proceed linearly between baseline experients at fixed temperture. Causes of the deactivation are not fully understood. 27 refs., 37 figs., 20 tabs.

  7. Development of a stable cobalt-ruthenium Fischer-Tropsch catalyst

    SciTech Connect

    Abrevaya, H.

    1991-01-01

    The objective of this contract is to examine the relationship between catalytic properties and the function of cobalt Fischer-Tropsch catalysts and to apply this fundamental knowledge to the development of a stable cobalt-based catalyst with a low methane-plus-ethane selectivity for use in slurry reactors. An experimental cobalt catalyst 585R2723 was tested three times in the fixed-bed reactor. The objective of the tests was to identify suitable testing conditions for screening catalyst. The {alpha}-alumina was determined to be a suitable diluent medium for controlling the catalyst bed temperature close to the inlet temperature. With 13 g of catalyst and 155 g of diluent, the catalyst maximum temperature were within 2{degree}C from the inlet temperatures. As a result of this work, 210{degree}C and 21 atm were shown to result in low methane selectivity and were used as initial conditions in the catalyst screening test. Ethane, which along with methane is undesirable, is typically produced with low selectivity and follows the same trend as methane. Other work reported here indicated that methane selectivity increases with increasing temperature but is not excessively high at 230{degree}C. Consequently, the catalyst screening test should include an evaluation of the catalyst performance at 230{degree}C. During Run 67, the increase in temperature from 210{degree}C to 230{degree}C was initiated at 30 hours on-stream.

  8. Separation of fischer-Tropsch Wax from Catalyst by Supercritical Extraction.

    SciTech Connect

    Joyce, P.C.; Thies, M.C.; Sherrard, D.; Biales, J.; Kilpatrick, P.; Roberts, G.

    1997-07-31

    Although alkanes are the major constituent of a Fischer-Tropsch wax, significant quantities (e.g., up to 30 wt %) of long-chain alcohol and alkene compounds can also be found in a F-T wax. With the lack of experimental data, the effect that the hydroxy and double-bond functional groups have on the phase behavior of systems containing long- chain hydrocarbons is unknown. Therefore, the phase behavior of the system n-hexane/1-hexadecanol was measured for comparison with the previously measured system n-hexane/hexadecane. Vapor and liquid equilibrium compositions and mixture critical points were measured at 198.9, 251.3, 299.2, and 349.9 {degrees}C at pressures ranging from 6.2 to 46.4 bar. Temperature and pressure measurements for all isotherms are believed to be accurate to better than plus or minus 3 and 4 percent, respectively. Results indicate that the addition of the alcohol group to a C 16 hydrocarbon chain significantly affects the phase behavior with hexane, with the two-phase region extending to significantly higher (i.e., up to about 10 bar higher) pressures. The presence of an alcohol group was also found to be an impediment to obtaining a good fit of the experimental data with the Peng-Robinson equation.

  9. 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.

  10. 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.

  11. 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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    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.

  12. 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.

  13. 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

    2015-11-01

    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. PMID:26547178

  14. Kinetics of the Fischer-Tropsch reaction on a precipitated promoted iron catalyst. 1. Experimental procedure and results

    SciTech Connect

    Lox, E.S.; Froment, G.F. )

    1993-01-01

    The Fischer-Tropsch reaction on a commercial promoted precipitated iron catalyst was studied in a tubular reactor under non-deactivating conditions of temperatures between 523 and 623 K, pressures between 0.6 and 2.1 MPa, hydrogen to carbon monoxide feed ratios between 3.0 and 6.0 mol/mol, and W/F[degree][sub CO] values between 9.2 and 63.0 kg[center dot]s/mol. The selectivity for carbon dioxide, methane, and hydrocarbons of different functionality with 2-15 carbon atoms in the molecule was obtained as a function of the carbon monoxide conversion, the reactor temperature, and the total pressure. The initial rate of formation of these products was measured as a function of the total pressure and the partial pressures of hydrogen and carbon monoxide at the reactor inlet. These experiments, combined with the information gained from the catalyst characterization, indicated that carbon dioxide is formed by the water gas shift reaction. Methane, n-paraffins, and 1-olefins with two and more carbon atoms in the molecule are all primary products of the Fischer-Tropsch reaction. The composition of the hydrocarbon product fraction, as a function of the number of carbon atoms in the hydrocarbon molecule, could be described by the Schulz-Flory distribution, although it is shown that the latter only approximately holds for the effluent of an integral reactor.

  15. Effects of H/sub 2/O and CO/sub 2/ on the activity and composition of iron Fischer-Tropsch catalysts

    SciTech Connect

    McDonald, M.A.

    1986-01-01

    The composition of an iron Fischer-Tropsch (F-T) catalyst is strongly affected by the % conversion of H/sub 2/-CO syngas. At low % conversion, the strongly reducing syngas mixture tends to covert metallic or oxidic iron species to a bulk iron carbide phase or phases. As % syngas conversion increases, H/sub 2/ and CO are converted to organic products, and to H/sub 2/O and CO/sub 2/. The gas mixture can therefore oxidize an iron catalyst. However, the catalyst's synthesis behavior (activity, selectivity, activity and selectivity maintenance) also depends strongly on % syngas conversion. Thus, an iron catalyst's composition and synthesis behavior are not easily correlated under typical F-T reaction conditions. This study was designed to determine how the build-up of H/sub 2/O and CO/sub 2/ during reaction affect F-T catalyst composition and synthesis behavior. Reaction rate measurements were conducted at differential % syngas conversion using catalyst wafers mounted in an in-situ cell. This cell allowed Mossbauer effect spectroscopy of the used catalyst for determination of the catalyst composition. Additional H/sub 2/O and CO/sub 2/ were added to syngas to determine the effects on catalyst composition, activity and selectivity. Furthermore, these experiments were carried out at pressures well above atmospheric, the pressure range required for good iron F-T catalyst behavior. Thus, results presented here are more closely related to the state of working F-T catalysts than are previous in-situ Mossbauer studies of iron catalysts, which were done almost exclusively at atmospheric pressure. This paper focuses on initial experiments involving the addition of only H/sub 2/O, not CO/sub 2/, to a syngas stream.

  16. Development of a stable cobalt-ruthenium Fischer-Tropsch catalyst. Technical progress report No. 14, January 1, 1993--March 31, 1993

    SciTech Connect

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

    1994-05-01

    The objective of this contract is to examine the relationship between catalytic properties and the function of cobalt Fischer-Tropsch catalysts and to apply this fundamental knowledge to the development of a stable cobalt-based catalyst with a low methane-plus-ethane selectivity for use in slurry reactors.

  17. Emissions of Volatile Particulate Components from Turboshaft Engines running JP-8 and Fischer-Tropsch Fuels

    SciTech Connect

    Cheng, Mengdawn; Corporan, E.; DeWitt, M.; Landgraf, Bradley J

    2009-01-01

    Rotating-wing aircraft or helicopters are heavily used by the US military and also a wide range of commercial applications around the world, but emissions data for this class of engines are limited. In this study, we focus on emissions from T700-GE-700 and T700-GE-701C engines; T700 engine was run with military JP-8 and T701C run with both JP-8 and Fischer-Tropsch (FT) fuels. Each engine was run at three engine power settings from the idle to maximum power in sequence. Exhaust particles measured at the engine exhaust plane (EEP) have a peak mobility diameter less than 50nm in all engine power settings. At a 4-m downstream location, sulfate/sulfur measurements indicate all particulate sulfur exists practically as sulfate, and the particulate sulfur and sulfate contents increased as the engine power increased. The conversion of sulfur to sulfate was found not to be dependent on engine power setting. Analysis also showed that conversion of sulfur to sulfate was not by the adsorption of sulfur dioxide gas on the soot particles and then subsequently oxidized to form sulfate, but by gas-phase conversion of SO2 via OH or O then subsequently forming H2SO4 and condensing on soot particles. Without the sulfur and aromatic components, use of the FT fuel led to significant reduction of soot emissions as compared to that of the JP-8 fuel producing less number of particles than that of the JP-8 fuel; however, the FT fuel produced much higher number concentrations of particles smaller than 7nm than that of JP-8 in all engine power settings. This indicates non-aromatics components in the FT fuel could have contributed to the enhancement of emissions of particles smaller than 7nm. These small particles are volatile, not observed at the EEP, and may be important in playing a role for the formation of secondary particles in the atmosphere or serving as a site for effective cloud nuclei condensation to occur.

  18. Specialty applications offer added options to transportation fuel outlets for Fischer-Tropsch conversion

    SciTech Connect

    Oukaci, R.; Singleton, A.H.

    1998-12-31

    In the past decade estimated global reserves of natural gas have increased by more than 30 percent to more than 5,300 trillion standard cubic feet (TCF). Of the current total, about 2,800 TCF are surplus to any current or anticipated demand. This ``overhand`` of natural gas availability has precipitated the development of various forms of the Fischer-Tropsch process for converting this resource to liquid hydrocarbons having premium value as transportation fuel feedstocks. The Williams Companies has been active in this field through the development of the GasCat process that focuses on supported cobalt catalysts and the slurry bubble column reactor applied to reserves capable of producing 500 million SCFD and higher quantities of natural gas, converting this into liquids production of 50,000 barrels/day and greater. In the course of the development of the GasCat process, an evaluation has been made of certain specialty applications of the hydrocarbons that can be produced. The high normal paraffin content (98%+), high purity (no S-, N-, O-compounds, aromatics, or metal inclusions) of the liquid products, as well as their low or no odor, generally difficult to achieve with petroleum products, make these F-T products exceptionally valuable solvents for a wide range of specialty applications. Similarly, the normal paraffinic nature and high purity of the F-T waxes provide the latter with outstanding properties that may result in a gradual displacement of petroleum waxes in many applications. An extensive evaluation of F-T products upgrading processes for redirection of F-T product slate to higher value specialty chemicals and waxes was carried out using F-T reactor effluents collected during some long catalyst performance runs. The specialty products were evaluated by GC, FTIR, NMR and a number of ASTM methods to determine their composition and physical properties. The results suggest that the smaller but higher value specialty applications may beneficially influence

  19. 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

  20. 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

  1. 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

  2. Study of the effects of potassium addition to supported iron catalysts in the Fischer-Tropsch reaction

    SciTech Connect

    Miller, D.G.; Moskovits, M.

    1988-10-20

    The Fischer-Tropsch activity of supported iron catalysts prepared via electrochemical techniques has been evaluated as a function of potassium addition. Catalyst pretreatment in 0.09, 0.18, and 0.27 M K/sub 2/CO/sub 3/ solutions generated potassium levels of 1.7, 2.8, and 3.9 wt %, respectively. Pretreatment in 0.18 M KOH provided a catalyst with 2.3 wt% potassium and facilitated comparison of the effects of the basicity of the pretreatment solution upon catalyst activity. A maximum in catalyst activity and CO conversion was noted upon increasing K content, followed by a sharp decline in activity at potassium levels in excess of the maximum. The hydrogenation ability of the catalyst decreased, and a shift to higher molecular weight products was observed, with increasing potassium content. The type of pretreatment solution had little effect on the catalyst activity or the product selectivity.

  3. Selectivity to olefins of Fe/SiO{sub 2}-MgO catalysts in the Fischer-Tropsch reaction

    SciTech Connect

    Gallegos, N.G.; Alvarez, A.M.; Cagnoli, M.V.; Bengoa, J.F.

    1996-06-01

    SiO{sub 2} covered with MgO has been used as support of iron catalysts in the Fischer-Tropsch reaction. Catalysts of 5% (w/w) iron concentration and 2, 4, and 8% (w/w) of MgO on SiO{sub 2} were prepared. Selective chemisorption of CO, volumetric oxidation, and Moessbauer spectroscopy were used to characterize the type of iron species and the metallic crystal sizes. MgO covers the SiO{sub 2} surface and modifies the metallic crystal size. The activity to total hydrocarbons increases with the amount of MgO added. An optimal concentration of about 4% (w/w) was found to have the highest selectivity to olefins. 45 refs., 13 figs., 3 tabs.

  4. Quantitative separation and evaluation of Fischer-Tropsch reaction products having low sup 14 C-isotopic activity

    SciTech Connect

    Dabbagh, H.A.; Chawla, B.; Halasz, J.; Davis, B.H. )

    1990-01-01

    A method has been developed to effect the separation of Fischer-Tropsch products, predominately hydrocarbons, into, first, alkane and alkene fractions, and, secondly, each of these fractions into their normal and branched components. Conditions for methods using a dry silica column for the first separation and molecular sieves for the second separation have identified that permit collection of sufficiently large samples for subsequent separations. The first separation has been effected so the normal to branched chain ratio has not been altered. Liquid chromatographic conditions have been found whereby the n-alkane fraction can then be separated to provide a pure sample of each alkane in the C{sub 8}--C{sub 24} carbon number range. The alkane fractions have been collected so that the {sup 14}C activity can be determined for each alkane.

  5. 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

  6. 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

  7. Catalyst and reactor development for a liquid-phase Fischer-Tropsch process. Quarterly technical progress report, 1 April 1981-30 June 1981

    SciTech Connect

    Brockington, J.W.; Dyer, P.N.; Pierantozzi, R.; Brain, B.W.; Bauer, J.V.

    1981-07-01

    In October 1980, Air Products and Chemicals, Inc. began a three year contract with the DOE: Catalyst and Reactor Development for a Liquid Phase Fischer-Tropsch Process. The program contains four major tasks: (1) Project Work Plan, (2) Slurry Catalyst Development, (3) Slurry Reactor Design Studies, and (4) Pilot Facility Design. This report describes work on Tasks 2 and 3 carried out in the third quarter of the contract. In Task 2, the computerized search of the Fischer-Tropsch literature was continued, and improvements were made in data processing programs. Shakedown tests were completed on the first 300 ml slurry reactor, and construction of the second and third reactors began. Five modified conventional slurry catalysts were prepared, and two batches were tested in the gas phase giving information on selectivity as a function of composition and activation. Four supported cluster catalyst were synthesized, and seven were tested in the gas phase.

  8. 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

  9. Synthesis and characterization of Fe colloid catalysts in inverse micelle solutions

    SciTech Connect

    Martino, A.; Stoker, M.; Hicks, M.

    1995-10-01

    We have studied the formation of Fe clusters in inverse micelles. We have characterized the clusters with respect to size with transmission electron microscopy (TEM) and with respect to chemical composition with Mossbauer spectroscopy, electron diffraction, and x-ray photoelectron spectroscopy (XPS). In addition, we have tested these iron based clusters for catalytic activity in a model hydrogenolysis reaction. The formation of ultra-small metal particles is of particular interest in the area of chemical catalysis. The clusters are high surface area, highly dispersed, unsupported materials. In addition, catalytic enhancement due to unique material properties (i.e. quantum size effects) is possible. Metal clusters prepared by a number of techniques have been studied as potential catalysts. Reactant adsorption and the reactivity in various processes depends strongly on particle size. We are studying iron clusters as potential catalysts in hydrogenation reactions, Fischer-Tropsch synthesis, and coal liquefaction.

  10. 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.

  11. 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

  12. Fischer-Tropsch synthesis with Fe/Cu/La/SiO2 nano-structured catalyst.

    PubMed

    Pour, Ali Nakhaei; Taghipoor, Sohrab; Shekarriz, Marzieh; Shahri, Seyed Mehdi Kamali; Zamani, Yahya

    2009-07-01

    Nano-structure Fe2O3, CuO and La2O3 components were prepared by micro-emulsion method and then Fe/Cu/La/SiO2 nano-structure catalyst was prepared by mixing and re-slurring the mixture by tetraethylorthosilicate (TEOS). The catalyst composition was designated in term of the atomic ration as: 100Fe/5.64Cu/0.1La/19Si. Structural characterization of nano-structured Fe2O3, CuO and La2O3 components was performed by Transmission Electron Microscopy (TEM), powder X-ray diffraction, Temperature Programmed Reduction (TPR) techniques. Particle size for obtained components was about 20, 21.6 and 12.6 nm for Fe2O3, CuO and La2O3 respectively determined by using XRD pattern (Scherrer equation) and TEM images. Catalytic activity and product selectivity were conducted in a fixed-bed stainless steel reactor and compared with conventional iron catalyst. The results reveal that reducing particle size of catalyst increased the catalyst performance. Also, olefin/paraffin ratios decreased in comparison with conventional catalyst. PMID:19916468

  13. 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.

  14. Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, October 1--December 31, 1995

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1996-06-01

    Objectives for this quarter were to attempt to develop a model to predict the molecular diffusion coefficients to a high degree of accuracy so the authors may be able to predict both the molecular diffusion coefficient and thus the effective diffusivity a priori. They are working on a semi-empirical equation based on the rough hard sphere theory to predict diffusion coefficients in supercritical fluids. In addition, they planned to take additional data in order to extend the database available for development of the predictive equation. The paper discusses accomplishments and problems related to the diffusion coefficients of F-T products in supercritical fluids. Data are presented on the diffusion coefficients of 1-octene in ethane, propane, and hexane.

  15. Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, July 1, 1993--September 30, 1993

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1993-12-31

    During this quarter we have tested and calibrated six thermocouples of the temperature probe assembly. We obtained additional information on potential supercritical fluids from several vendors. We found out that all three potential supercritical solvents (propane, butane, and hexane) have less than 1 ppM sulfur impurities, whereas the maximum amount of sulfur in the feed should be less than 0.05 ppM. This remains to be a potential problem, since high levels of sulfur in the feed will result in catalyst poisoning. However, this would be the case with all three potential solvents, and thus we have decided to use propane as the supercritical fluid in our reaction studies based on its cost and favorable supercritical properties. In our shake down tests we will not use a catalyst guard bed for sulfur removal. If we experience problems with catalyst deactivation due to sulfur in feed, the guard bed will be installed in the propane feed line. We have ordered 1-tetradecene and will begin measuring diffusion coefficients of this compound in subcritical propane.

  16. Studies on nanosized iron based modified catalyst for Fischer-Tropsch synthesis application.

    PubMed

    Park, MoonJu; Kang, Jung Shik; Na, Ki Poong; Lee, Sang Deuk; Awate, S V; Moon, Dong Ju

    2011-02-01

    To improve catalytic performance iron based catalyst, the effects of some metal promoters, especially potassium, copper and other transition metal oxides as well as different supports have been reported. A series of Fe/K/Cu catalysts promoted with magnesium and ceria by precipitation method, followed by impregnation method; keeping Cu and K content same. The catalysts were characterized by XRD, N2 physisorption, TPR and TEM techniques. From XRD, the presence of hematite (Fe2O3) phase was detected in all precipitated iron catalysts and CFe2.5 phase in all used catalysts. TPR results showed that addition of Mg facilitated the reduction of Fe2O3 and decrease in reduction temperature. The catalytic performance was investigated in a fixed-bed reactor at 250 degrees C, 2 MPa pressure and H2/CO molar ratio of 2. Concentration of Mg was found to affect the CO conversion and product distribution. It was found that precipitated iron catalyst Fe/Mg/Cu/K with Mg/Fe ratio of 0.1 showed highest conversion (60.6%) and C5(+) selectivity (92.4%) among all catalysts tested. PMID:21456209

  17. Self-healing catalysts: Co(3)O(4) nanorods for Fischer-Tropsch synthesis.

    PubMed

    Wen, Cun; Dunbar, Darrius; Zhang, Xin; Lauterbach, Jochen; Hattrick-Simpers, Jason

    2014-05-01

    We combine kinetic and spectroscopic data to demonstrate the concept of a self-healing catalyst, which effectively eliminates the need for catalyst regeneration. The observed self-healing is triggered by controlling the crystallographic orientation at the catalyst surface. PMID:24668124

  18. The Effect of Cobalt Loading on Fischer Tropsch Synthesis Over Silicon Carbide Supported Catalyst.

    PubMed

    Lee, Jae Suk; Jung, Jae Sun; Moon, Dong Ju

    2015-01-01

    A series of Co (5-30 wt%) based SiC supported catalysts were prepared by impregnation method and investigated for FTS reaction. The FTS reaction was carried out in a fixed bed reactor system with the H2/CO molar ratio of 2, reaction temperature of 230 degrees C and reaction pressure of 20 bar for 120 h. All catalysts were characterized by N2 physisorption, XRD, TPR, SEM and TEM techniques. It was found that 15 wt% Co/SiC catalyst showed better catalytic performance with high selectivity of C(5+) hydrocarbons than the other catalysts. The results, suggest that the catalytic performance of the catalysts depends on average pore size of support and surface density of cobalt, metal and support interactions. PMID:26328368

  19. Effect of Liquid Composition on the Slurry Fischer-Tropsch Synthesis. 2. Product Selectivity

    SciTech Connect

    Stenger, H.G.; Satterfield, C.N.

    1984-04-01

    With a reduced, fused magnetite catalyst, secondary reactions, consisting of olefin hydrogenation, olefin isomerization, and incorporation of ethylene and/or ethyl alcohol into product, were slightly greater in octacosane than in phenanthrene at 232/sup 0/C but essentially the same at 263/sup 0/C. This is attributed to competitiv adsorption effects with phenanthrene which adsorbs significantly onto the catalyst at 232/sup 0/C, but not at 263/sup 0/C. All secondary reactions are enhanced by conditions minimizing CO adsorption. Oxygenates were greatly diminished at high conversions. C/sub 2/ incorporation into product stops chain growth by a scavenging effect. In the presence of a perfluoropolyether (Fomblin), in which hydrocarbons are immiscible, catalyst is preferentially wetted by hydrocarbons and secondary reactions are greatly enhanced by mass transfer resistances.

  20. Secondary reactions of low-molecular weight olefins during Fischer-Tropsch synthesis

    SciTech Connect

    Jordan, D.S.; Bell, A.T.

    1986-01-01

    The objectives of this study were to investigate the influence of ethylene addition on the hydrogenation of CO over Ru/SiO/sub 2/ and to compare the product distribution obtained with those for CO hydrogenation in the absence of ethylene and ethylene homologation in the absence of CO. To enable identification of the source of carbon in the products, /sup 13/C-labeled CO and unlabeled C/sub 2/H/sub 4/ were used. Products were analyzed by isotope-ratio gas chromatography-mass spectrometry. Among the issues investigated were the influence of ethylene addition on the reactions of CO and the participation of ethylene in processes of hydrocarbon chain initiation and growth. The influence of ethylene addition on methane formation was also examined.