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Sample records for naphtha fischer-tropsch c4-11-alkane

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

    2010-07-01

    ...-alkane, branched and linear. 721.10103 Section 721.10103 Protection of Environment ENVIRONMENTAL..., branched and linear. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS No...

  2. Research Opportunities for Fischer-Tropsch Technology

    Jackson, Nancy B.

    1999-01-01

    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

  3. Novel Fischer-Tropsch catalysts. [DOE patent

    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.

  4. Radiation effects on Fischer-Tropsch syntheses

    Hatada, M.; Matsuda, K.

    1977-01-01

    Radiation effects on Fischer-Tropsch synthesis has been examined using high dose rate electron beams and Fe-Cu-diatomaceous earth catalyst. Yields of saturated hydrocarbons were found to increase by irradiation, but the yields of these compounds were decreased by raising reaction temperature without irradiation, suggesting the presence of radiation chemical process in catalytic reactions. (author)

  5. Fischer-Tropsch. A futuristic view

    Vosloo, A.C. [Sasol Technology Research and Development, PO Box 1, 9570 Sasolburg (South Africa)

    2001-06-01

    Although the three processing steps that constitute the Fischer-Tropsch based Gas-to-Liquids (GTL) technology, namely syngas generation, syngas conversion and hydroprocessing, are all commercially proven and individually optimized, their combined use is not widely applied. In order to make the GTL technology more cost-effective, the focus must be on reducing both the capital and the operating costs of such a plant. Current developments in the area of syngas generation, namely oxygen transfer membranes and heat exchange reforming, have the potential to significantly reduce the capital cost and improve the thermal efficiency of a GTL plant. Further improvements in terms of the activity and selectivity of the Fischer-Tropsch catalyst can also make a significant reduction in the operating cost of such a plant.

  6. Fischer-Tropsch synthesis. Development and perspectives

    Schaub, G.; Rohde, M.; Mena Subiranas, A. [Karlsruhe Univ. (Germany). Engler-Bunte-Institut

    2006-07-01

    Production of synthetic hydrocarbons via Fischer-Tropsch (FT) synthesis has the potential to produce high-value automotive fuels and petrochemicals from fossil and renewable sources. The availability of cheap natural gas and solid raw materials like coal and biomass has given momentum to synthesis technologies first developed in the mid-twentieth century. The present paper summarizes the fundamentals and describes some general aspects regarding driving forces, catalyst and reaction, synthesis reactor, and overall process. In this way, it indicates the context of present and future developments. Worldwide plant capacities will increase significantly in the next future, with natural gas favored as feedstock. Substitution of petroleum as well as production of improved products (like automotive fuels) are the most significant incentives. Energy loss and additional fossil CO{sub 2} emissions caused by the conversion process will be a problem in extended applications with fossil feedstocks. The current R and D activities worldwide, in all areas related to Fischer-Tropsch synthesis, will contribute to further process improvements and extended applications. (orig.)

  7. Principles of selectivity in Fischer-Tropsch SYNTHESIS

    Schulz, H. [Karlsruhe Univ. (Germany). Engler-Bunte-Institut

    2006-07-01

    The detailed selectivity of Fischer-Tropsch synthesis with iron and cobalt as catalysts with high temporal resolution has been determined and used to derive the values of probability of chain growth, chain branching and olefin/paraffin molar ratio as a function of carbon number and time. Catalyst reassembling and self-organization of the Fischer-Tropsch regime are investigated. The basic principle of Fischer-Tropsch synthesis, suppression of desorption of growing chains is disclosed. This frustration governs FT-synthesis of the otherwise different systems with iron and cobalt. The advanced characterization of sites and elementary reactions (specifically with cobalt) is thought to be a more realistic basis for future theoretical calculations. (orig.)

  8. Alternative Fuel Research in Fischer-Tropsch Synthesis

    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.

  9. Liquefaction of syngas by fischer-tropsch process (abstract)

    Khalid, N.; Saeed, M.M.; Riaz, M.; Khan, A.S.A.

    2011-01-01

    The Fischer-Tropsch process is a set of chemical reactions that convert syngas into liquid hydrocarbons and is gaining attention under the background of the resource depletion leading to the price hike of the petroleum oil. The diesel fuel obtained from syngas by Fischer-Tropsch process seems to be of high quality and environmental friendly. The present study deals with the optimization of the experimental conditions for the production/synthesis of mineral diesel from syngas by Fischer-Tropsch process. The catalyst was prepared by coating cobalt nitrate on alumina followed by calcinations and characterization by analytical techniques such as BET, SEM/EDXA and X-Ray diffraction. For the conversion of syngas to liquid fuel, the fixed bed column technique was employed. Different operational parameters such as temperature of the column, flow rate and pressure of the syngas were studied. The product formed was verified by comparing the GC/FID spectrum of the synthesized mineral diesel with commercial sample by employing GC analysis. The qualitative results indicate the success of the Fischer-Tropsch process in the present study. (author)

  10. Niobia-supported Cobalt Catalysts for Fischer-Tropsch Synthesis

    den Otter, J.H.

    2016-01-01

    In this thesis niobia has been shown to be an attractive support for application in Fischer-Tropsch catalysis at industrially relevant conditions without apparent deactivation up to at least 200 hours of operation. This proves that the level of potentially poisoning contaminants is sufficiently low

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

    Choi, G.N.; Kramer, S.J.; Tam, S.S. [Bechtel Corp., San Francisco, CA (United States)

    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.

  12. Fischer-Tropsch Catalyst for Aviation Fuel Production

    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. Petroleum formation by Fischer-Tropsch synthesis in plate tectonics

    Szatmari, P. (Petrobras Research Center, Rio de Janeiro (Brazil))

    1989-08-01

    A somewhat speculative hypothesis of petroleum genesis in the upper lithosphere is proposed, based on Fischer-Tropsch synthesis. This hypothesis is distinct from both the organic (biogenic) model and the inorganic model of hydrocarbon degassing from the Earth's interior. The hypothesis presented in this paper proposes that petroleum liquids form by Fischer-Tropsch synthesis on magnetite and hematite catalysts when carbon dioxide (derived by massive metamorphic or igneous decarbonation of subducted sedimentary carbonates) reacts with hydrogen generated by the serpentinization (in the absence of air) of shallow-mantle lithosphere and ophiolite thrust sheets. Oblique plate movements may favor hydrocarbon formation by creating deep faults that aid fluid flow and serpentinization. The world's richest oil provinces, including those of the Middle East, may be tentatively interpreted to have formed by this mechanism. 8 figs., 1 tab.

  14. Moessbauer spectroscopic investigations of Fe/Mn-Fischer-Tropsch-catalysts

    Deppe, P.; Papp, H.; Rosenberg, M.

    1986-01-01

    The phase composition of Fe/Mn oxide catalysts of different compositions after 200 h of Fischer-Tropsch synthesis have been investigated by Moessbauer spectroscopy at room temperature, 77 K and 5 K. The final composition of the bulk catalysts depends strongly on the Mn content and the temperature of reduction before the synthesis. Catalytic activity and selectivity are partly correlated to this phase composition. (Auth.)

  15. 40 CFR 721.10178 - Distillates (Fischer-Tropsch), hydroisomerized middle, C10-13-branched alkane fraction.

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 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), hydroisomerized...

  16. The role of magnetite in Fischer-Tropsch synthesis

    Rao, K.R.P.M.; Huggins, F.E.; Mahajan, V.; Huffman, G.P.; Rao, V.U.S.

    1994-01-01

    Moessbauer spectroscopy studies of iron catalysts from a Fischer-Tropsch (FT) Pilot Plant run at different time-on-stream periods were carried out. Magnetite Fe 3 O 4 was found to be active for the water-gas-shift (WGS) reaction which accompanies the FT synthesis reaction over Fe-based catalysts. A correlation between the ratio of the occupancy of octahedral sites to the tetrahedral sites in magnetite to the WGS activity was found. Cation-deficient magnetite gave higher WGS activity as compared to the stoichiometric phase. (orig.)

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

    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.

  18. Important roles of Fischer-Tropsch synfuels in the global energy future

    Takeshita, Takayuki; Yamaji, Kenji

    2008-01-01

    This paper examines the potential roles of Fischer-Tropsch (FT) synfuels in the 21st century with a global energy model treating the entire fuel supply chain in detail. The major conclusions are the following. First, FT synfuels become a major alternative fuel regardless of CO 2 policy due to their low transportation costs and compatibility with existing petroleum infrastructure and vehicles. Secondly, the FT process brings stranded gas to world markets until around 2050. In a 550 ppm CO 2 stabilization case thereafter, producing FT synfuels from biomass, whose competitiveness is robust against its capital costs, and their interregional trade enable a worldwide diffusion of carbon-neutral fuels. This provides a significant source of income for developing regions, such as Latin America and Sub-Saharan Africa. Thirdly, FT synfuels play a crucial role in meeting the growing transportation energy demand and assuring diversified supplies of transportation fuels. Increasing portions of FT liquids are refined to FT-kerosene to be provided for the rapidly growing aviation sector in the second half of the century. Furthermore, upgrading FT-naphtha into FT-gasoline proves to be critically important. FT synfuels' participation could help the development in Africa through technological contributions of the South African leading companies in the world synfuel industry

  19. TECHNOLOGY DEVELOPMENT FOR IRON FISCHER-TROPSCH CATALYSTS

    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. Hydroprocessing of Fischer-Tropsch biowaxes to second-generation biofuels

    Schablitzky, Harald Walter; Hafner, C. [OMV Refining and Marketing, Centre of Excellence-Fuels, Innovation and Quality, Schwechat (Austria); Lichtscheidl, J.; Hutter, K. [OMV Refining and Marketing, New Technology, Schwechat (Austria); Rauch, R. [Bioenergy, Graz (Austria); Hofbauer, H. [Bioenergy, Graz (Austria); Vienna University of Technology, Institute of Chemical Engineering, Vienna (Austria)

    2011-03-15

    Upgrading of Fischer-Tropsch (FT) biowaxes to second-generation biofuels via hydroprocessing is the final step for increasing the fuel amount of the overall biomass conversion route: gasification of lignocellulosic biomass, FT synthesis, and hydroprocessing. The typical FT product portfolio consists of high molecular weight paraffinic waxes as the main product and FT fuels in the diesel and naphtha boiling range. OMV's objective and contribution to the project focus on achieving coprocessing of FT biowaxes with fossil feedstock using existing hydrotreating plants of crude oil refineries. Various test runs have been examined with a conventional refining catalyst under mild conditions (380-390 C, 5.8 MPa; WHSV, 0.7-1.3 h{sup -1}) in a pilot plant. Pure FT biowax is converted to gases, fuels, and an oil/waxy residue in a fixed-bed reactor with a porous catalyst layer technology. The presence of hydrogen in the reaction chamber reduces the fast deactivation of the catalyst caused by the formation of a coke layer around the catalyst particle surface and saturates cracked hydrocarbon fragments. Another approach is the creation of synthetic biodiesel components with excellent fuel properties for premium fuel application. Basically, premium diesel fuel differs from standard diesel quality by cetane number and cold flow properties. Hydroprocessed synthetic biodiesel (HPFT diesel) has compared to conventional diesel advantages in many aspects. Depending on the catalyst selected, premium diesel quality can be obtained by shifting cold flow operability properties of HPFT fuels to a range capable even under extreme cold conditions. In addition, a high-quality kerosene fraction is obtained to create bio jet fuels with an extremely deep freezing point, as low as -80 C. The isomerization degree, as well as the carbon number distribution of high paraffinic profile, and the branching degree have a major impact on the cold flow properties and cetane number. FT diesel has

  1. Controlled formation of iron carbides and their performance in Fischer-Tropsch synthesis

    Wezendonk, Tim A.; Sun, Xiaohui; Dugulan, A. Iulian; van Hoof, Arno J.F.; Hensen, Emiel J.M.; Kapteijn, Freek; Gascon, Jorge

    2018-01-01

    high-temperature Fischer-Tropsch (HTFT) resulted in the formation of χ-Fe5C2. Furthermore, the different activation methods did not alter other important catalyst properties, as pre- and post-reaction transmission electron microscopy (TEM

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

    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.

  3. Reduction and reoxidation of cobalt Fischer-Tropsch catalysts

    Hilmen, Anne-Mette

    1996-12-31

    The Fischer-Tropsch synthesis involves the hydrogenation of carbon monoxide to produce mainly hydrocarbons, water and carbon dioxide, but also alcohols, aldehydes and acids are formed. The distribution of these products is determined by the choice of catalyst and synthesis conditions. This thesis studies the reduction and reoxidation of 17%Co/Al{sub 2}O{sub 3} and 17%Co-1%Re/Al{sub 2}O{sub 3} by means of several characterization techniques. The effect of small amounts of Re on the reduction properties of Al{sub 2}O{sub 3}-supported Co catalysts has been studied by temperature-programmed reduction (TPR). An intimate mixture of CoAl{sub 2}O{sub 3} and Re/Al{sub 2}O{sub 3} catalysts showed a promoting effect of Re similar to that for co impregnated CoRe/Al{sub 2}O{sub 3}. A loose mixture of Co/Al{sub 2}O{sub 3} + Re/Al{sub 2}O{sub 3} did not show any effect of Re on the reduction of Co. But a promoting effect was observed if the mixture had been pre-treated with Ar saturated with water before the TPR. It is suggested that Re promotes the reduction of Co oxide by hydrogen spillover. It is shown that a high temperature TPK peak at 1200K assigned to Co aluminate is mainly caused by the diffusion of Co ions during the TPR and not during calcination. The Co particle size measured by x-ray diffraction on oxidized catalysts decreased compared to the particle size on the calcined catalysts, while the dispersion measured by volumetric chemisorption decreased somewhat after the oxidation-reduction treatment. The role of water in the deactivation of Co/Al{sub 2}O{sub 3} and CoRe/Al{sub 2}O{sub 3} Fischer-Tropsch catalysts has been extensively studied. There were significant differences in the reducibility of the phases formed for the two catalysts during exposure to H{sub 2}O/He. 113 refs., 76 figs., 18 tabs.

  4. KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYNTHESIS

    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.

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

    Burtron H. Davis

    1999-01-01

    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

  6. Gas to liquids. Fischer Tropsch: what does the future hold?

    Maisonnier, G.

    2005-01-01

    The process concerning the chemical transformation of natural gas into oil-based products (a so-called 'clean' diesel) known under the term GTL FT (Gas To Liquids - Fischer Tropsch) will turn a new page in its history with the start-up of a major unit in Qatar in 2006 Up until now only two GTL units were deployed, in the early 1990's (Moss as and Shell) without however resulting in the widespread expansion of this process. The technological breakthroughs achieved around the year 2000 combined with a favourable background context (concerning geopolitical tension, ears of oil production peaks, significant increases in the price of crude) now account for much of the interest shown in this solution. Consequently, outside Qatar, projects are also being looked at in various natural gas producing countries such as Nigeria or Algeria. It would be justified however to think that a new wave of natural gas recycling will gradually emerge as part of the global energy market. (author)

  7. KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYNTHESIS

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

    2003-01-01

    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 2 O, CO 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

  8. Overview of reactors for liquid phase Fischer-Tropsch synthesis

    Davis, Burtron H.

    2002-01-01

    The following overview is divided roughly into three sections. The first section covers the period from the late 1920s when the first liquid phase synthesis was first conducted until about 1960 when the interest in Fischer-Tropsch synthesis (FTS) declined because of the renewed view of an abundance of petroleum at a low price. The second period includes the activity that resulted from the oil shortage due to the Arab embargo in 1972 and covers from about 1960 to 1985 when the period of gloomy projections for rapidly increasing prices for crude had faded away. The third section covers the period from when the interest in FTS was no longer driven by the projected supply and/or price of petroleum but by the desire to monetize stranded natural gas and/or terminate flaring the gas associated with petroleum production and other environmental concerns (1985 to date). These sections are followed by a brief overview of the current status of the scientific and engineering understanding of slurry bubble column reactors

  9. Technology development for iron Fischer-Tropsch catalysts

    O`Brien, R.J.; Raje, A.; Keogh, R.A. [and others

    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.

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

    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.

  11. KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYNTHESIS

    Dragomir B. Bukur

    2004-01-01

    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 2 O, CO 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

  12. Comprehensive characterisation of products from cobalt catalysed Fischer-Tropsch reaction

    Marion, M.C.; Bertoncini, F.; Hugues, F.; Forestiere, A. [IFP, Vernaison (France)

    2006-07-01

    Fischer-Tropsch reaction synthesis has been studied in presence of supported cobalt catalysts. The experimental work has been performed by using a slurry pilot plant. All the gaseous and liquid products, including by-products recovered in the water phase produced, have been analysed in order to determine the whole products distribution and the catalyst selectivity. Apart from paraffin which are the main products obtained via cobalt-catalyzed Fischer-Tropsch synthesis, olefins and oxygenates by-products present also their own distribution. These detailed data are available thanks to new dedicated analytical methods developed in IFP laboratories. (orig.)

  13. KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYSTHESIS

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

    2005-01-01

    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 2 O, CO 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 (α) and olefin to paraffin ratio are independent of carbon number, whereas our experimental data show that they vary with the carbon number. Predicted molar flow

  14. Subtask 3.4 - Fischer - Tropsch Fuels Development

    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

  15. DEVELOPMENT OF PRECIPITATED IRON FISCHER-TROPSCH CATALYSTS

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

    1999-01-01

    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

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

    Kress, ME; Tielens, AGGM

    Fischer-Tropsch catalysis, the iron/nickel catalyzed conversion of CO and H(2) 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:

  17. Cobalt supported on carbon nanofibers as catalysts for the Fischer-Tropsch synthesis

    Bezemer, G.L.

    2006-01-01

    The Fischer-Tropsch (FT) process converts synthesis gas (H2/CO) over a heterogeneous catalyst into hydrocarbons. Generally, cobalt catalysts supported on oxidic carriers are used for the FT process, however it appears to be difficult to obtain and maintain fully reduced cobalt particles. To overcome

  18. Structure-performance relationships for supported cobalt Fischer-Tropsch catalysts

    Eschemann, T.O.|info:eu-repo/dai/nl/33082712X

    2015-01-01

    The Fischer-Tropsch synthesis (FTS) involves the heterogeneously catalyzed conversion of synthesis gas into water and hydrocarbons and offers a promising route for the synthesis of ultraclean fuels, chemicals and lubricants. The synthesis gas can be generated from different feedstocks, such as coal

  19. BASELINE DESIGN/ECONOMICS FOR ADVANCED FISCHER-TROPSCH TECHNOLOGY; FINAL

    None

    1998-01-01

    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)

  20. On the Deactivation of Cobalt-based Fischer-Tropsch Catalysts

    Cats, K.H.

    2016-01-01

    The Fischer-Tropsch Synthesis (FTS) process is an attractive way to obtain synthetic liquid fuel from alternative energy sources such as natural gas, coal or biomass. However, the deactivation of the catalyst, consisting of cobalt nanoparticles supported on TiO2, currently hampers the industrial

  1. Kinetics of Slurry Phase Fischer-Tropsch Synthesis

    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

  2. Kinetics of Slurry Phase Fischer-Tropsch Synthesis

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

    2006-01-01

    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

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

    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.

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

    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.

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

    Chun-Chan Kung; Hayatsu, R.; Studier, M.H.; Clayton, R.N.; Chicago Univ., IL; Chicago Univ., IL

    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 15 N/ 14 N ratios found in organic matter in carbonaceous chondrites. Polymeric material formed in the Fischer-Tropsch reaction was enriched in 15 N by only 3 promille relative to the starting material (NH 3 ). The 15 N enrichment in polymers from the Miller-Urey reaction was 10-12 promille. Both of these fractionations are small compared to the 80-90 promille 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. (orig.)

  6. Moessbauer investigations of the Fe-Cu-Mn catalysts for Fischer-Tropsch synthesis

    Spanu, V.; Filoti, G.; Ilie, I.; Zamfirescu, E.

    1990-01-01

    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 H 2 or in a H 2 +CO mixture. The influence of the reduction and reaction conditions on the catalyst structure was investigated. (orig.)

  7. Influence of Reduction Promoters on Stability of Cobalt/g-Alumina Fischer-Tropsch Synthesis Catalysts

    Gary Jacobs; Wenping Ma; Burtron H. Davis

    2014-01-01

    This focused review article underscores how metal reduction promoters can impact deactivation phenomena associated with cobalt Fischer-Tropsch synthesis catalysts. Promoters can exacerbate sintering if the additional cobalt metal clusters, formed as a result of the promoting effect, are in close proximity at the nanoscale to other cobalt particles on the surface. Recent efforts have shown that when promoters are used to facilitate the reduction of small crystallites with the aim of increasing...

  8. Particle Size and Crystal Phase Effects in Fischer-Tropsch Catalysts

    Jin-Xun Liu; Peng Wang; Wayne Xu; Emiel J.M. Hensen

    2017-01-01

    Fischer-Tropsch synthesis (FTS) is an increasingly important approach for producing liquid fuels and chemicals via syngas—that is, synthesis gas, a mixture of carbon monoxide and hydrogen—generated from coal, natural gas, or biomass. In FTS, dispersed transition metal nanoparticles are used to catalyze the reactions underlying the formation of carbon-carbon bonds. Catalytic activity and selectivity are strongly correlated with the electronic and geometric structure of the nanoparticles, which...

  9. Fischer-Tropsch Synthesis on Multicomponent Catalysts: What Can We Learn from Computer Simulations?

    Fajin, Jose L. C.; Cordeiro, M. Natalia D. S.; Gomes, Jose R. B.

    2015-01-01

    In this concise review paper, we will address recent studies based on the generalized-gradient approximation (GGA) of the density functional theory (DFT) and on the periodic slab approach devoted to the understanding of the Fischer-Tropsch synthesis process on transition metal catalysts. As it will be seen, this computational combination arises as a very adequate strategy for the study of the reaction mechanisms on transition metal surfaces under well-controlled conditions and allows separati...

  10. Deactivation and Regeneration of Commercial Type Fischer-Tropsch Co-Catalysts—A Mini-Review

    Erling Rytter; Anders Holmen

    2015-01-01

    Deactivation of commercially relevant cobalt catalysts for Low Temperature Fischer-Tropsch (LTFT) synthesis is discussed with a focus on the two main long-term deactivation mechanisms proposed: Carbon deposits covering the catalytic surface and re-oxidation of the cobalt metal. There is a great variety in commercial, demonstration or pilot LTFT operations in terms of reactor systems employed, catalyst formulations and process conditions. Lack of sufficient data makes it difficult to correlat...

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

    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.

  12. Coupling of glycerol processing with Fischer-Tropsch synthesis for production of liquid fuels

    Simonetti, D.A.; Rass-Hansen, Jeppe; Kunkes, E.L.

    2007-01-01

    Liquid alkanes can be produced directly from glycerol by an integrated process involving catalytic conversion to H-2/CO gas mixtures (synthesis gas) combined with Fischer-Tropsch synthesis. Synthesis gas can be produced at high rates and selectivities suitable for Fischer-Tropsch synthesis (H-2/CO...... between 1.0 and 1.6) from concentrated glycerol feed solutions at low temperatures (548 K) and high pressures (1-17 bar) over a 10 wt% Pt-Re/C catalyst with an atomic Pt : Re ratio of 1 : 1. The primary oxygenated hydrocarbon intermediates formed during conversion of glycerol to synthesis gas are ethanol...... in the liquid organic effluent stream and increasing the selectivity to C5+ alkanes by a factor of 2 ( from 0.30 to 0.60). Catalytic conversion of glycerol and Fischer-Tropsch synthesis were coupled in a two-bed reactor system consisting of a Pt-Re/C catalyst bed followed by a Ru/TiO2 catalyst bed...

  13. The Application of Moessbauer Emission Spectroscopy to Industrial Cobalt Based Fischer-Tropsch Catalysts

    Loosdrecht, J. van de; Berge, P. J. van; Craje, M. W. J.; Kraan, A. M. van der

    2002-01-01

    The application of Moessbauer emission spectroscopy to study cobalt based Fischer-Tropsch catalysts for the gas-to-liquids process was investigated. It was shown that Moessbauer emission spectroscopy could be used to study the oxidation of cobalt as a deactivation mechanism of high loading cobalt based Fischer-Tropsch catalysts. Oxidation was observed under conditions that are in contradiction with the bulk cobalt phase thermodynamics. This can be explained by oxidation of small cobalt crystallites or by surface oxidation. The formation of re-reducible Co 3+ species was observed as well as the formation of irreducible Co 3+ and Co 2+ species that interact strongly with the alumina support. The formation of the different cobalt species depends on the oxidation conditions. Iron was used as a probe nuclide to investigate the cobalt catalyst preparation procedure. A high-pressure Moessbauer emission spectroscopy cell was designed and constructed, which creates the opportunity to study cobalt based Fischer-Tropsch catalysts under realistic synthesis conditions.

  14. Controlled formation of iron carbides and their performance in Fischer-Tropsch synthesis

    Wezendonk, Tim A.

    2018-04-19

    Iron carbides are unmistakably associated with the active phase for Fischer-Tropsch synthesis (FTS). The formation of these carbides is highly dependent on the catalyst formulation, the activation method and the operational conditions. Because of this highly dynamic behavior, studies on active phase performance often lack the direct correlation between catalyst performance and iron carbide phase. For the above reasons, an extensive in situ Mössbauer spectroscopy study on highly dispersed Fe on carbon catalysts (Fe@C) produced through pyrolysis of a Metal Organic Framework was coupled to their FTS performance testing. The preparation of Fe@C catalysts via this MOF mediated synthesis allows control over the active phase formation and therefore provides an ideal model system to study the performance of different iron carbides. Reduction of fresh Fe@C followed by low-temperature Fischer-Tropsch (LTFT) conditions resulted in the formation of the ε′-Fe2.2C, whereas carburization of the fresh catalysts under high-temperature Fischer-Tropsch (HTFT) resulted in the formation of χ-Fe5C2. Furthermore, the different activation methods did not alter other important catalyst properties, as pre- and post-reaction transmission electron microscopy (TEM) characterization confirmed that the iron nanoparticle dispersion was preserved. The weight normalized activities (FTY) of χ-Fe5C2 and ε′-Fe2.2C are virtually identical, whilst it is found that ε′-Fe2.2C is a better hydrogenation catalyst than χ-Fe5C2. The absence of differences under subsequent HTFT experiments, where χ-Fe5C2 is the dominating phase, is a strong indication that the iron carbide phase is responsible for the differences in selectivity.

  15. Synthetic production of fuels by the Fischer Tropsch reaction using iron catalysts

    Rodriguez Cepeda, Rodrigo; Pacheco Ochoa, Luis

    2004-01-01

    A series of iron catalysts were prepared on three different types of supports: alumina and two activated carbons from eucalyptus woods and tagua seeds. Potassium was used as promoter and palladium was deposited by the excess wetness impregnation method. The catalysts were characterized by N 2 adsorption at 77 K, XRD and TPR analysis and evaluated as Fischer-Tropsch catalysts. The carbon supported catalysts favour the production of liquid hydrocarbons and decrease the aqueous phase. Those supported with alumina form gases and aqueous phase as the main products. The α p parameters of the Schulz-Flory distribution show hydrocarbons between gasoline and diesel

  16. Effect of pre-heat treatment on a Fischer-Tropsch iron catalyst

    Rao, K.R.P.M.; Huggins, F.E.; Ganguly, B.; Mahajan, V.; Huffman, G.P.; Davis, B.; O'Brien, R.J.; Xu Liguang; Rao, V.U.S.

    1994-01-01

    Moessbauer spectroscopy was used to investigate the effect of heating the Fischer-Tropsch catalyst 100 Fe/5 Cu/4.2 K/24 SiO 2 in two different atmospheres while ramping the temperature of the catalyst from room temperature to 280 C in 5.5 h prior to pretreatment of the catalyst. Preheating in H 2 /CO = 0.7 gave rise to an iron (Fe 2+ ) silicate, while preheating in helium resulted in the formation of ε'-carbide Fe 2.2 C. Iron oxides and χ-carbide Fe 5 C 2 were also formed in both preheat treatments. (orig.)

  17. Activity and selectivity control through periodic composition forcing over Fischer-Tropsch catalysts

    Silveston, P L; Hudgins, R R; Adesina, A A; Ross, G S; Feimer, J L

    1986-01-01

    Data collected under steady-state and periodic composition forcing of the Fischer-Tropsch synthesis over three commonly used catalysts demonstrate that both activity and selectivity can be changed by the latter operating mode. Synthesis of hydrocarbons up to C/sub 7/are favored at the expense of the higher carbon numbers for the Co catalyst, while for the Ru catalyst, only the C/sub 3/ and lower species are favored. Only methane production is stimulated with the Fe catalyst. Fe and Ru catalysts shift production from alkenes to alkanes. Transient data is interpreted in the paper.

  18. Emissions from Diesel and Gasoline Vehicles Fuelled by Fischer-Tropsch Fuels and Similar Fuels

    Larsen, Ulrik; Lundorff, Peter; Ivarsson, Anders

    2007-01-01

    and an alkylate fuel (Aspen), which was taken to be the ultimate formula of FT gasoline. FT based diesel generally showed good emission performance, whereas the FT based gasoline not necessary lead to lower emissions. On the other hand, the Aspen fuel did show many advantages for the emissions from the gasoline...... vehicles fuelled by Fischer Tropsch (FT) based diesel and gasoline fuel, compared to the emissions from ordinary diesel and gasoline. The comparison for diesel fuels was based on a literature review, whereas the gasoline comparison had to be based on our own experiments, since almost no references were...

  19. Co-Zn-Al based hydrotalcites as catalysts for Fischer-Tropsch process

    Bianchi, C.L.; Pirola, C.; Boffito, D.C.; Di Fronzo, A. [Univ. degli Studi di Milano (Italy). Dipt. di Chimica Fisica ed Elettrochimica; Di Michele, A. [Univ. degli Studi di Perugia (Italy). Dipt. di Fisica; Vivani, R.; Nocchetti, M.; Bastianini, M.; Gatto, S. [Univ. degli Studi di Perugia (Italy). Dipt. di Chimica

    2011-07-01

    Co-Zn-Al based hydrotalcites have been investigated as catalysts for the well-known Fischer- Tropsch synthesis. A series of ternary hydrotalcites in nitrate form was prepared with the urea method in order to obtain active catalysts for the above mentioned process. The thermal activation at 350 C gives raise to finely dispersed metallic Co on the mixed oxides, so resulting in retaining the metal distribution of the parent compounds. An optimization study concerning the amount of cobalt of the prepared catalysts (range 15-70% mol, metal based) and the reaction temperature (220-260 C) is reported. All the samples have been fully characterized (BET, ICP-OES, XRPD, TG-DTA, FT-IR, SEM and TEM) and tested in a laboratory pilot plant. Tests to evaluate the stability of these materials were carried out in stressed conditions concerning both the activation and the operating temperatures and pressures (up to 350 C and 2.0 MPa). The obtained results suggest the possibility of using synthetic hydrotalcites as suitable Co-based catalysts for the Fischer-Tropsch synthesis. (orig.)

  20. Fischer-Tropsch synthesis in slurry-phase reactors using Co/SBA-15 catalysts

    Rodrigues, J.J.; Lima, L.A.; Lima, W.S.; Rodrigues, M.G.F. [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academica de Engenharia Quimica], e-mail: meiry@deq.ufcg.edu.br; Fernandes, F.A.N. [Universidade Federal do Ceara (UFCE), CE (Brazil). Dept. de Engenharia Quimica

    2011-07-15

    The objective of this work is to describe the production of bifunctional catalysts using the incipient humidity method, producing catalysts with 15 wt.% cobalt supported in SBA-15 molecular sieve, to be applied in the Fischer-Tropsch (FT) reaction. The originality of this work is its focus on the use of a 15 wt.% Co/SBA-15 catalyst in FT synthesis in slurry reactors. The deposition of cobalt over SBA-15 support was accomplished by impregnation with a 0.1-M aqueous solution of cobalt nitrate. The Fischer-Tropsch synthesis was carried out with the catalyst at 240 deg C and 20 atm, under a COH{sub 2} atmosphere (molar ratio= 1), in a slurry reactor for 8 hours. X-ray diffraction measurements showed that the calcined cobalt catalyst did not modify the structure of SBA-15, proving that Co was present under the form of Co{sub 3}O{sub 4} in the catalyst. The addition of cobalt in the SBA-15 decreased the specific superficial area of the molecular sieve. The 15 wt.% Co/SBA-15 catalyst had a 40% CO conversion rate and a high selectivity towards the production of C{sub 5}{sup +} (53.9% after 8 hours). (author)

  1. Cerium Modified Pillared Montmorillonite Supported Cobalt Catalysts for Fischer Tropsch Synthesis

    Ahmad, N.; Ali, Z.; Abbas, S. M.; Hussain, F.

    2015-01-01

    Fischer-Tropsch (FT) synthesis was accomplished over Al-pillared Montmorillonite supported 20 wt% Co modified with different weight% of cerium catalysts. These catalysts were prepared by impregnation method while structural characterizations of the prepared samples were performed by XRD, TPR, NH/sub 3/TPD, TGA, BET, XRF and SEM techniques. The Fischer Tropsch reaction was studied in fixed bed micro catalytic reactor at temperature range of 220, 260 and 275 degree C and at different pressure (1, 5 and 10 bars). From the activity results, it was found that by pillaring NaMMT with Al higher catalytic activity and lower methane selectivity of NaMMT was achieved. Furthermore, the results of FT synthesis reaction revealed that cerium incorporation increased the dispersion of Co/sub 3/O/sub 4/ on the surface and consequently resulted in enhanced catalytic activity. Additionally, the C/sub 5/-C/sub 12/ hydrocarbons and methane selectivity increased while C/sub 22+/ hydrocarbons selectivity was decreased over cerium modified catalysts. Higher reaction temperature (>220 degree C) resulted in significant enhancement in CO conversion and methane selectivity. Though, increase in pressure from 1 to 10 bars eventually resulted in increase in C/sub 5+/ hydrocarbons and decrease in methane and C/sub 2/-C/sub 5/ hydrocarbons selectivity. (author)

  2. Fischer-Tropsch Synthesis on Multicomponent Catalysts: What Can We Learn from Computer Simulations?

    José L. C. Fajín

    2015-01-01

    Full Text Available In this concise review paper, we will address recent studies based on the generalized-gradient approximation (GGA of the density functional theory (DFT and on the periodic slab approach devoted to the understanding of the Fischer-Tropsch synthesis process on transition metal catalysts. As it will be seen, this computational combination arises as a very adequate strategy for the study of the reaction mechanisms on transition metal surfaces under well-controlled conditions and allows separating the influence of different parameters, e.g., catalyst surface morphology and coverage, influence of co-adsorbates, among others, in the global catalytic processes. In fact, the computational studies can now compete with research employing modern experimental techniques since very efficient parallel computer codes and powerful computers enable the investigation of more realistic molecular systems in terms of size and composition and to explore the complexity of the potential energy surfaces connecting reactants, to intermediates, to products of reaction. In the case of the Fischer-Tropsch process, the calculations were used to complement experimental work and to clarify the reaction mechanisms on different catalyst models, as well as the influence of additional components and co-adsorbate species in catalyst activity and selectivity.

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

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

    2016-01-01

    The Fischer-Tropsch Synthesis converts synthesis gas from alternative carbon resources, including natural gas, coal, and biomass, to hydrocarbons used as fuels or chemicals. In particular, iron-based catalysts at elevated temperatures favor the selective production of C2-C4 olefins, which are

  4. The formation and influence of carbon on cobalt-based Fischer-Tropsch synthesis catalysts : an integrated review

    Moodley, D.J.; Loosdrecht, van de J.; Saib, A.M.; Niemantsverdriet, J.W.; Davis, B.H.; Occelli, M.L.; Speight, J.G.

    2010-01-01

    Cobalt-based Fischer-Tropsch synthesis (FTS) catalysts are the systems of choice for use in gas-to-liquid (GTL) processes. As with most catalysts, cobalt systems gradually lose their activity with increasing time on stream. There are various mechanisms that have been proposed for the deactivation of

  5. Large-scale production of Fischer-Tropsch diesel from biomass. Optimal gasification and gas cleaning systems

    Boerrigter, H.; Van der Drift, A.

    2004-12-01

    The paper is presented in the form of copies of overhead sheets. The contents concern definitions, an overview of Integrated biomass gasification and Fischer Tropsch (FT) systems (state-of-the-art, gas cleaning and biosyngas production, experimental demonstration and conclusions), some aspects of large-scale systems (motivation, biomass import) and an outlook

  6. Effects of manganese oxide and sulphate on the olefin selectivity of iron catalysts in the Fischer Tropsch reaction

    Dijk, van W.L.; Niemantsverdriet, J.W.; Kraan, van der A.M.; van der Baan, Hessel

    1982-01-01

    Although it has been claimed by various authors that the addition of manganese oxide, MnO, to an iron catalyst gives a marked increase in the olefin selectivity of iron catalysts, we have been unable to confirm these claims in Fischer Tropsch experiments at 513 K for an iron manganese oxide catalyst

  7. The role of zeolites in the deactivation of multifunctional fischer-tropsch synthesis catalysts: the interaction between HZSM-5 and Fe-based Ft-catalysts

    P. C. Zonetti

    2013-12-01

    Full Text Available In order to produce gasoline directly from syngas, HZSM-5 can be added to the Fischer-Tropsch catalyst. However, this catalytic system shows an important deactivation rate. Aiming at describing this phenomenon, Fe-based catalysts and physical mixtures containing these catalysts and HZSM-5 were employed in this reaction. All these systems were characterized using the following techniques: XRD, XPS, TPR and TPD of CO. This work shows that HZSM-5 interacts with the Fe-based Fischer-Tropsch catalyst during the reduction step, decreasing the Fe concentration on the catalytic surface and thus lowering the activity of the catalytic system in the Fischer-Tropsch Synthesis.

  8. The role of zeolites in the deactivation of multifunctional Fischer-Tropsch Synthesis catalysts: the interaction between HZSM-5 and Fe-based FT-catalysts

    Zonetti, P.C.; Gaspar, A.B.; Mendes, F.M.T.; Appel, L.G.; Avillez, R. R. de; Sousa-Aguiar, E.F.

    2013-01-01

    In order to produce gasoline directly from syngas, HZSM-5 can be added to the Fischer-Tropsch catalyst. However, this catalytic system shows an important deactivation rate. Aiming at describing this phenomenon, Fe-based catalysts and physical mixtures containing these catalysts and HZSM-5 were employed in this reaction. All these systems were characterized using the following techniques: XRD, XPS, TPR and TPD of CO. This work shows that HZSM-5 interacts with the Fe-based Fischer-Tropsch catalyst during the reduction step, decreasing the Fe concentration on the catalytic surface and thus lowering the activity of the catalytic system in the Fischer-Tropsch Synthesis. (author)

  9. The role of zeolites in the deactivation of multifunctional Fischer-Tropsch Synthesis catalysts: the interaction between HZSM-5 and Fe-based FT-catalysts

    Zonetti, P.C.; Gaspar, A.B.; Mendes, F.M.T.; Appel, L.G., E-mail: lucia.appel@int.gov.br [Instituto Nacional de Tecnologia (INT/MCT), Rio de Janeiro, RJ (Brazil); Avillez, R. R. de [Pontificia Universidade Catolica do Rio de Janeiro (PUC-Rio), RJ (Brazil); Sousa-Aguiar, E.F. [Centro de Pesquisa Leopoldo Americo Miguez de Mello (CENPES/PETROBRAS), Rio de Janeiro, RJ (Brazil)

    2013-10-15

    In order to produce gasoline directly from syngas, HZSM-5 can be added to the Fischer-Tropsch catalyst. However, this catalytic system shows an important deactivation rate. Aiming at describing this phenomenon, Fe-based catalysts and physical mixtures containing these catalysts and HZSM-5 were employed in this reaction. All these systems were characterized using the following techniques: XRD, XPS, TPR and TPD of CO. This work shows that HZSM-5 interacts with the Fe-based Fischer-Tropsch catalyst during the reduction step, decreasing the Fe concentration on the catalytic surface and thus lowering the activity of the catalytic system in the Fischer-Tropsch Synthesis. (author)

  10. Fe/MCM-41 sylilated catalyst: structural changes determination during the Fischer-Tropsch reaction

    Bengoa, J. F.; Fellenz, N. A.; Cagnoli, M. V.; Cano, L. A.; Gallegos, N. G.; Alvarez, A. M.; Marchetti, S. G.

    2010-01-01

    Two Fe/MCM-41 systems, one of them sylilated, were obtained to be used as catalysts in Fischer-Tropsch reaction. They have more than 90% of the iron species located inside the support channels, leading to a narrow crystal size distribution accessible to reactive gases. The samples were characterized by X-ray diffraction, atomic absorption spectroscopy, N 2 adsorption, Moessbauer spectroscopy and Fourier transformer infrared spectroscopy. Moessbauer spectroscopy allowed us to demonstrate that the catalytic active species were the same in both catalysts. The only difference between them was the surface hydrophobicity, which decreases the 'water gas shift reaction' in the sylilated catalyst. Besides, this solid is more active for hydrocarbon production, with a lower methane yield.

  11. Moessbauer study of CO-precipitated Fischer-Tropsch iron catalysts

    Rao, K.R.P.M.; Huggins, F.E.; Mahajan, V.; Huffman, G.P.; Bukur, D.B.; Rao, V.U.S.

    1994-01-01

    Moessbauer spectroscopy studies of precipitated Fischer-Tropsch (FT) iron catalysts, viz. 100 Fe/5 Cu/4.2 K/x SiO 2 , 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 Fe 5 C 2 whose amount decreases with an increase of SiO 2 content. The χ-carbide is converted into magnetite Fe 3 O 4 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. (orig.)

  12. Transient Effects in Fischer-Tropsch Reactor with a Fixed Bed of Catalyst Particles

    I. V. Derevich

    2015-01-01

    Full Text Available Based on analysis of small temperature disturbances in the Fischer-Tropsch reactor with a fixed bed of catalyst particles various scenarios of thermal instability were investigated. There are two possible scenarios of thermal instability of the reactor. First, thermal explosion may occur due to growth of temperature disturbances inside a catalytic granule. Second scenario connected with loss of thermal stability as a result of an initial increase in temperature in the reactor volume. The boundaries of thermal stability of the reactor were estimated by solving the eigenvalue problems for spherical catalyst particles and cylindrical reactor. Processes of diffusional resistance inside the catalytic granule and heat transfer from wall of the reactor tube are taken into account. Estimation of thermal stability area is compared with the results of numerical simulation of behavior of temperature and concentration of synthesis gas.

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

    Jackson, N.B.; Kohler, S.; Harrington, M. [Sandia National Lab., Albuquerque, NM (United States)] [and others

    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.

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

    Howard, B.H.; Boff, J.J.; Zarochak, M.F. [Pittsburgh Energy Technology Center, PA (United States)] [and others

    1995-12-31

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

  15. Alkali promotion effect in Fischer-Tropsch cobalt-alumina catalyst

    Eliseev, O.L.; Tsapkina, M.V.; Davydov, P.E.; Kazantsev, R.V. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry; Belousova, O.S.; Lapidus, A.L. [Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation)

    2011-07-01

    Promoting Co-alumina Fischer-Tropsch synthesis catalysts with alkali and alkaline-earth metals was studied. XRD, oxygen titration and CO chemisorption were used for the characterization of the catalysts. The best results in terms of catalyst selectivity and long-chain alkanes content in synthesized products were obtained with K-promoted catalyst. Catalytic performance strongly depends on K:Co atomic ratio as well as preparation procedure. Effect of K loading on selectivities is non-linear with extreme point at K:Co=0.01. Significant increase in C{sub 5+} selectivity of K-promoted catalyst may be explained as a result of strong CO adsorption on the catalyst surface, as was confirmed in CO chemisorption experiments. (orig.)

  16. Immobilised carbon nanotubes as carrier for Co-Fischer-Tropsch synthesis catalysts

    Thiessen, J.; Rose, A.; Kiendl, I.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering; Curulla-Ferre, D. [Total S.A., Gas and Power, Paris La Defense (France)

    2011-07-01

    A possibility to immobilise carbon nanotubes (CNT) to make them applicable in a technical scale fixed bed reactor is studied. The approach to fabricate millimetre scale composites containing CNT presented in this work is to confine the nano-carbon in macro porous ceramic particles. Thus CNT were grown on the inner surface of silica and alumina pellets and spheres, respectively. Cobalt nano particles were successfully deposited on the carbon surface inside the two types of ceramic carriers and the systems were tested in Fischer - Tropsch synthesis (FTS). The cobalt mass related activity of these novel catalysts is similar to a conventional system. The selectivities of the Co/CNT/ceramic composites were compared with non supported CNT and carbon nanofibres (CNF). (orig.)

  17. Morphology Changes of Co Catalyst Nanoparticles at the Onset of Fischer-Tropsch Synthesis

    Høydalsvik, Kristin; Fløystad, Jostein B.; Voronov, Alexey

    2014-01-01

    Cobalt nanoparticles play an important role as catalysts for the Fischer-Tropsch synthesis, which is an attractive route for production of synthetic fuels. It is of particular interest to understand the varying conversion rate during the first hours after introducing synthesis gas (H-2 and CO......) to the system. To this end, several in situ characterization studies have previously been done on both idealized model systems and commercially relevant catalyst nanoparticles, using bulk techniques, such as X-ray powder diffraction and X-ray absorption spectroscopy. Since catalysis takes place at the surface...... of the cobalt particles, it is important to develop methods to gain surface-specific structural information under realistic processing conditions. We addressed this challenge using small-angle X-ray scattering (SAXS), a technique exploiting the penetrating nature of X-rays to provide information about particle...

  18. Emissions from Diesel and Gasoline Vehicles Fuelled by Fischer-Tropsch Fuels and Similar Fuels

    Larsen, Ulrik; Lundorff, Peter; Ivarsson, Anders

    2007-01-01

    The described investigation was carried out under the umbrella of IEA Advanced Motor Fuels Agreement. The purpose was to evaluate the emissions of carbon monoxide (CO), unburned hydrocarbons (HC), nitrogen oxides (NOx), particulate matter (PM) and polycyclic aromatic hydrocarbons (PAH) from...... vehicles fuelled by Fischer Tropsch (FT) based diesel and gasoline fuel, compared to the emissions from ordinary diesel and gasoline. The comparison for diesel fuels was based on a literature review, whereas the gasoline comparison had to be based on our own experiments, since almost no references were...... found in this field. In this context measurement according to the Federal Test Procedure (FTP) and the New European Driving Cycle (NEDC) were carried out on a chassis dynamometer with a directly injected gasoline vehicle. Experiments were carried out with a reference fuel, a fuel based 70% on FT...

  19. Particle Size and Crystal Phase Effects in Fischer-Tropsch Catalysts

    Jin-Xun Liu

    2017-08-01

    Full Text Available Fischer-Tropsch synthesis (FTS is an increasingly important approach for producing liquid fuels and chemicals via syngas—that is, synthesis gas, a mixture of carbon monoxide and hydrogen—generated from coal, natural gas, or biomass. In FTS, dispersed transition metal nanoparticles are used to catalyze the reactions underlying the formation of carbon-carbon bonds. Catalytic activity and selectivity are strongly correlated with the electronic and geometric structure of the nanoparticles, which depend on the particle size, morphology, and crystallographic phase of the nanoparticles. In this article, we review recent works dealing with the aspects of bulk and surface sensitivity of the FTS reaction. Understanding the different catalytic behavior in more detail as a function of these parameters may guide the design of more active, selective, and stable FTS catalysts.

  20. Computational Fluid Dynamics Study of Channel Geometric Effect for Fischer-Tropsch Microchannel Reactor

    Na, Jonggeol; Jung, Ikhwan; Kshetrimayum, Krishnadash S.; Park, Seongho; Park, Chansaem; Han, Chonghun

    2014-01-01

    Driven by both environmental and economic reasons, the development of small to medium scale GTL(gas-to-liquid) process for offshore applications and for utilizing other stranded or associated gas has recently been studied increasingly. Microchannel GTL reactors have been preferred over the conventional GTL reactors for such applications, due to its compactness, and additional advantages of small heat and mass transfer distance desired for high heat transfer performance and reactor conversion. In this work, multi-microchannel reactor was simulated by using commercial CFD code, ANSYS FLUENT, to study the geometric effect of the microchannels on the heat transfer phenomena. A heat generation curve was first calculated by modeling a Fischer-Tropsch reaction in a single-microchannel reactor model using Matlab-ASPEN integration platform. The calculated heat generation curve was implemented to the CFD model. Four design variables based on the microchannel geometry namely coolant channel width, coolant channel height, coolant channel to process channel distance, and coolant channel to coolant channel distance, were selected for calculating three dependent variables namely, heat flux, maximum temperature of coolant channel, and maximum temperature of process channel. The simulation results were visualized to understand the effects of the design variables on the dependent variables. Heat flux and maximum temperature of cooling channel and process channel were found to be increasing when coolant channel width and height were decreased. Coolant channel to process channel distance was found to have no effect on the heat transfer phenomena. Finally, total heat flux was found to be increasing and maximum coolant channel temperature to be decreasing when coolant channel to coolant channel distance was decreased. Using the qualitative trend revealed from the present study, an appropriate process channel and coolant channel geometry along with the distance between the adjacent

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

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

    2016-01-01

    Metal-carbon nanosystems consisting of nanodimensional bimetallic particles of Fe- Co dispersed in a carbon matrix for the Fischer-Tropsch synthesis were studied. Prepared metal-carbon nanopowders samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). It was shown formation of FeCo nanoparticles with body-centered cubic structures started at 400 °C. FeCo nanoparticles have spherical form, the mean size is 7 - 12 nm and uniform distribution in a carbon matrix. The metal-carbon nanosystem demonstrates a catalytic activity in the Fischer- Tropsch synthesis. The maximum yield of liquid hydrocabons C 5+ was 92 g/m 3 while the selectivity for the target product - 35%. (paper)

  2. Development of Hydrotalcite Based Cobalt Catalyst by Hydrothermal and Co-precipitation Method for Fischer-Tropsch Synthesis

    Muhammad Faizan Shareef

    2017-10-01

    Full Text Available This paper presents the effect of a synthesis method for cobalt catalyst supported on hydrotalcite material for Fischer-Tropsch synthesis. The hydrotalcite supported cobalt (HT-Co catalysts were synthesized by co-precipitation and hydrothermal method. The prepared catalysts were characterized by using various techniques like BET (Brunauer–Emmett–Teller, SEM (Scanning Electron Microscopy, TGA (Thermal Gravimetric Analysis, XRD (X-ray diffraction spectroscopy, and FTIR (Fourier Transform Infrared Spectroscopy. Fixed bed micro reactor was used to test the catalytic activity of prepared catalysts. The catalytic testing results demonstrated the performance of hydrotalcite based cobalt catalyst in Fischer-Tropsch synthesis with high selectivity for liquid products. The effect of synthesis method on the activity and selectivity of catalyst was also discussed. Copyright © 2017 BCREC Group. All rights reserved Received: 3rd November 2016; Revised: 26th February 2017; Accepted: 9th March 2017; Available online: 27th October 2017; Published regularly: December 2017 How to Cite: Sharif, M.S., Arslan, M., Iqbal, N., Ahmad, N., Noor, T. (2017. Development of Hydrotalcite Based Cobalt Catalyst by Hydrothermal and Co-precipitation Method for Fischer-Tropsch Synthesis. Bulletin of Chemical Reaction Engineering & Catalysis, 12(3: 357-363 (doi:10.9767/bcrec.12.3.762.357-363

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

    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

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

    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.

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

    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.

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

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

    2011-01-01

    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 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 3 ) 3 species even after calcinations and H 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 3 ) 3 for the re-adsorption of α-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

  7. Cobalt Fischer-Tropsch catalysts: influence of cobalt dispersion and titanium oxides promotion

    Azib, H

    1996-04-10

    The aim of this work is to study the effect of Sol-Gel preparation parameters which occur in silica supported cobalt catalysts synthesis. These catalysts are particularly used for the waxes production in natural gas processing. The solids have been characterized by several techniques: transmission electron microscopy (TEM), X-ray absorption near edge spectroscopy (XANES), programmed temperature reduction (TPR), infrared spectroscopy (IR), ultraviolet spectroscopy (UV), Magnetism, thermodesorption of H{sub 2} (TPD). The results indicate that the control of the cobalt dispersion and oxide phases nature is possible by modifying Sol-Gel parameters. The catalytic tests in Fischer-Tropsch synthesis were conducted on a pilot unit under pressure (20 atm) and suggested that turnover rates were independent of Co crystallite size, Co phases in the solids (Co deg., cobalt silicate) and titanium oxide promotion. On the other methane, the C{sub 3}{sup +} hydrocarbon selectivity is increased with increasing crystallite size. Inversely, the methane production is favoured by very small crystallites, cobalt silicate increase and titanium addition. However, the latter, used as a cobalt promoter, has a benefic effect on the active phase stability during the synthesis. (author). 149 refs., 102 figs., 71 tabs.

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

    Gangwal, Santosh K. [Southern Research Institute, Durham, NC (United States); McCabe, Kevin [Southern Research Institute, Durham, NC (United States)

    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.

  9. Greenhouse impact assessment of peat-based Fischer-Tropsch diesel life-cycle

    Kirkinen, Johanna; Soimakallio, Sampo; Maekinen, Tuula; Savolainen, Ilkka

    2010-01-01

    New raw materials for transportation fuels need to be introduced, in order to fight against climate change and also to cope with increasing risks of availability and price of oil. Peat has been recognised suitable raw material option for diesel produced by gasification and Fischer-Tropsch (FT) synthesis. The energy content of Finnish peat reserves is remarkable. In this study, the greenhouse impact of peat-based FT diesel production and utilisation in Finland was assessed from the life-cycle point of view. In 100 year's time horizon the greenhouse impact of peat-based FT diesel is likely larger than the impact of fossil diesel. The impact can somewhat be lowered by producing peat from the agricultural peatland (strong greenhouse gas emissions from the decaying peatlayer are avoided) with new peat production technique, and utilising the produced biomass from the after-treatment area for diesel also. If diesel production is integrated with pulp and paper mill to achieve energy efficiency benefits and if the electricity demand can be covered by zero emission electricity, the greenhouse impact of peat-based FT diesel reduces to the level of fossil diesel when agricultural peatland is used, and is somewhat higher when forestry-drained peatland is used as raw material source.

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

    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.

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

    1992-09-01

    The objectives of the study are to: Develop a baseline design for indirect liquefaction using advanced Fischer-Tropsch (F-T) technology. Prepare the capital and operating costs for the baseline design. Develop a process flow sheet simulation (PFS) model. This report summarizes the activities completed during the period December 23, 1992 through March 15, 1992. In Task 1, Baseline Design and Alternates, the following activities related to the tradeoff studies were completed: approach and basis; oxygen purity; F-T reactor pressure; wax yield; autothermal reformer; hydrocarbons (C{sub 3}/C{sub 4}s) recovery; and hydrogenrecovery. In Task 3, Engineering Design Criteria, activities were initiated to support the process tradeoff studies in Task I and to develop the environmental strategy for the Illinois site. The work completed to date consists of the development of the F-T reactor yield correlation from the Mobil dam and a brief review of the environmental strategy prepared for the same site in the direct liquefaction baseline study.Some work has also been done in establishing site-related criteria, in establishing the maximum vessel diameter for train sizing and in coping with the low H{sub 2}/CO ratio from the Shell gasifier. In Task 7, Project Management and Administration, the following activities were completed: the subcontract agreement between Amoco and Bechtel was negotiated; a first technical progress meeting was held at the Bechtel office in February; and the final Project Management Plan was approved by PETC and issued in March 1992.

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

    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.

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

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

    1999-03-01

    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.

  14. Development of the Fischer-Tropsch Process: From the Reaction Concept to the Process Book

    Boyer C.

    2016-05-01

    Full Text Available The process development by IFP Energies nouvelles (IFPEN/ENI/Axens of a Fischer-Tropsch process is described. This development is based on upstream process studies to choose the process scheme, reactor technology and operating conditions, and downstream to summarize all development work in a process guide. A large amount of work was devoted to the catalyst performances on one hand and the scale-up of the slurry bubble reactor with dedicated complementary tools on the other hand. Finally, an original approach was implemented to validate both the process and catalyst on an industrial scale by combining a 20 bpd unit in ENI’s Sannazzaro refinery, with cold mock-ups equivalent to 20 and 1 000 bpd at IFPEN and a special “Large Validation Tool” (LVT which reproduces the combined effect of chemical reaction condition stress and mechanical stress equivalent to a 15 000 bpd industrial unit. Dedicated analytical techniques and a dedicated model were developed to simulate the whole process (reactor and separation train, integrating a high level of complexity and phenomena coupling to scale-up the process in a robust reliable base on an industrial scale.

  15. The effect of zirconium on cobalt catalyst in fischer-tropsch synthesis

    Moradi, GH.R.; Mahbob Basir, M.; Taeb, A.

    2003-01-01

    A series of 10 wt % Co/SiO 2 catalysts with different loading ratios of zirconia (0, 5, 10, 15, 20) has been prepared through an original pseudo sol-gel method. All catalysts were characterized by BET, XRD, SEM, and TPR experiments. The catalytic performance of the catalysts for the so-called fischer- tropsch synthesis was examined under H 2 /CO=2 at 230 d ig C and 8 bar in a fixed bed microreactor. By increasing zirconia, the Co-SiO 2 interaction decreases and is replaced by Co-Zr interaction which favours reduction of the catalyst at lower temperatures. While it leads to a higher degree of reduction and as increase in the metallic cobalt atoms on the surface. The activity of the promoted catalysts increases with the addition of zirconia (max. by a factor 2.5). The C 1 0 + selectivity increased with the addition of zirconia (from 42.3% in unpromoted catalyst to 68.8 % in the 20 % ZrO 2 promoted. This can be attributed to the higher amount of the surface Cobalt metal present and to the larger Cobalt particle size

  16. Effect of Drying Temperature on Iron Fischer-Tropsch Catalysts Prepared by Solvent Deficient Precipitation

    Michael K. Albretsen

    2017-01-01

    Full Text Available A novel solvent deficient precipitation (SDP method to produce nanoparticles was studied for its potential in Fischer-Tropsch synthesis (FTS catalysis. Using Fe(NO33·9H2O as the iron-containing precursor, this method produces ferrihydrite particles which are then dried, calcined, reduced, and carbidized to form the active catalytic phase for FTS. Six different drying profiles, including final drying temperatures ranging between 80 and 150°C, were used to investigate the effect of ammonium nitrate (AN, a major by-product of reaction between Fe(NO33·9H2O and NH4HCO3 in the SDP method. Since AN has two phase-transitions within this range of drying temperatures, three different AN phases can exist during the drying of the catalyst precursors. These AN phases, along with physical changes occurring during the phase transitions, may affect the pore structure and the agglomeration of ferrihydrite crystallites, suggesting possible reasons for the observed differences in catalytic performance. Catalysts dried at 130°C showed the highest FTS rate and the lowest methane selectivity. In general, better catalytic performance is related to the AN phase present during drying as follows: phase III > phase II > phase I. However, within each AN phase, lower drying temperatures led to better catalytic properties.

  17. Influence of Reduction Promoters on Stability of Cobalt/g-Alumina Fischer-Tropsch Synthesis Catalysts

    Gary Jacobs

    2014-03-01

    Full Text Available This focused review article underscores how metal reduction promoters can impact deactivation phenomena associated with cobalt Fischer-Tropsch synthesis catalysts. Promoters can exacerbate sintering if the additional cobalt metal clusters, formed as a result of the promoting effect, are in close proximity at the nanoscale to other cobalt particles on the surface. Recent efforts have shown that when promoters are used to facilitate the reduction of small crystallites with the aim of increasing surface Co0 site densities (e.g., in research catalysts, ultra-small crystallites (e.g., <2–4.4 nm formed are more susceptible to oxidation at high conversion relative to larger ones. The choice of promoter is important, as certain metals (e.g., Au that promote cobalt oxide reduction can separate from cobalt during oxidation-reduction (regeneration cycles. Finally, some elements have been identified to promote reduction but either poison the surface of Co0 (e.g., Cu, or produce excessive light gas selectivity (e.g., Cu and Pd, or Au at high loading. Computational studies indicate that certain promoters may inhibit polymeric C formation by hindering C-C coupling.

  18. Deactivation and Regeneration of Commercial Type Fischer-Tropsch Co-Catalysts—A Mini-Review

    Erling Rytter

    2015-03-01

    Full Text Available Deactivation of commercially relevant cobalt catalysts for Low Temperature Fischer-Tropsch (LTFT synthesis is discussed with a focus on the two main long-term deactivation mechanisms proposed: Carbon deposits covering the catalytic surface and re-oxidation of the cobalt metal. There is a great variety in commercial, demonstration or pilot LTFT operations in terms of reactor systems employed, catalyst formulations and process conditions. Lack of sufficient data makes it difficult to correlate the deactivation mechanism with the actual process and catalyst design. It is well known that long term catalyst deactivation is sensitive to the conditions the actual catalyst experiences in the reactor. Therefore, great care should be taken during start-up, shutdown and upsets to monitor and control process variables such as reactant concentrations, pressure and temperature which greatly affect deactivation mechanism and rate. Nevertheless, evidence so far shows that carbon deposition is the main long-term deactivation mechanism for most LTFT operations. It is intriguing that some reports indicate a low deactivation rate for multi-channel micro-reactors. In situ rejuvenation and regeneration of Co catalysts are economically necessary for extending their life to several years. The review covers information from open sources, but with a particular focus on patent literature.

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

    Patzek, Tad W.; Croft, Gregory D.

    2009-01-01

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

    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.

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

    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.

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

    Bukur, D.B.; Ledakowicz, S.; Koranne, M. [Texas A and M Univ., College Station, TX (United States). Dept. of Chemical Engineering] [and others

    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.

  3. Biosyngas Fischer. Tropsch conversion by high Fe loaded supported catalysts prepared with ultrasound and microwave

    Pirola, C.; Di Fronzo, A.; Boffito, D.C.; Bianchi, C. [Milano Univ. (Italy). Dipt. di Chimica; Di Michele, A. [Perugia Univ. (Italy). Dipt. di Fisica

    2012-07-01

    Catalysts with iron high loading of 30 wt%, promoted with K (2.0 wt%) and Cu (3.75 wt%), have been synthesized according to three different methods: (1) the traditional impregnation method (TR); (2) Ultrasound (US) assisted TR method; (3) Microwave (MW) assisted TR method. All the samples have been fully characterized by BET, ICP/OES, XRPD, TG-DTA, FT-IR, TPR, SEM and TEM and tested in a laboratory pilot plant for Fischer-Tropsch synthesis working at 220 C and 20 bar. The results of the catalysts characterization indicated that the morphology of the samples strongly depends on the method of preparation. The best FTS results in term of C{sub 2+} yield (41%) has been obtained using MW with a good value of the selectivity towards heavy hydrocarbons, while in term of CO conversion (58%), using US. The samples prepared with non-traditional methods show FTS better results, probably due to a more wide and uniform distribution of Fe in the medium during the synthesis phase. (orig.)

  4. The role of palladium in iron based Fischer-Tropsch catalysts prepared by flame spray pyrolysis

    Minnermann, M.; Zielasek, V.; Baeumer, M. [Bremen Univ. (DE). Inst. of Applied and Physical Chemistry (IAPC); Pokhrei, S.; Maedler, L. [Bremen Univ. (DE). Foundation Inst. of Materials Science (IWT); Thiel, K. [Fraunhofer Institute for Manufactoring Technology and Applied Materials Research, Bremen (Germany)

    2011-07-01

    Flame spray pyrolysis (FSP) is a novel technique for the fabrication of nanostructured catalysts with far-reaching options to control structure and composition even in cases where complex composites need to be prepared. In this study, we took advantage of this technique to synthesize highly dispersed pure and Pd-doped iron oxide nanoparticles and investigated them as Fischer-Tropsch (FT) catalysts. By systematically varying the Pd content over a large range from 0.1 wt % to 10 wt %, we were able to directly analyze the influence of the Pd content on activity and selectivity. In addition to catalytic measurements, the structure and composition of the particles were characterized before and after these measurements, using transmission electron microscopy, adsorption measurements, X-ray diffraction and EXAFS. The comparison revealed, on the one hand, that small Pd clusters (diameter: 1-2 nm) evolve from initially homogeneously distributed Pd and, on the other hand, that the iron oxide transforms into iron carbides depending on the Pd content. The presence of Pd influences the particle size in the pristine samples (8 - 11 nm), resulting in specific surface areas that increase as the Pd content increases. However, after activation and reaction the specific surface areas become similar due to partial agglomeration and sintering. In a fixed bed FT reaction test, enhanced FT activity was observed with increasing Pd content while the selectivity shifts to longer chain hydrocarbons, mainly paraffins. (orig.)

  5. Emissions from Road Vehicles Fuelled by Fischer Tropsch Based Diesel and Gasoline

    Larsen, U; Lundorf, P; Ivarsson, A; Schramm, J [Technical University of Denmark (Denmark); Rehnlund, B [Atrax Energi AB (Sweden); Blinge, M [The Swedish Transport Institute (Sweden)

    2006-11-15

    The described results were carried out under the umbrella of IEA Advanced Motor Fuels Agreement. The purpose was to evaluate the emissions of carbon monoxide (CO), unburned hydrocarbons (HC), nitrogen oxides (NOx), particulate matter (PM) and polycyclic aromatic hydrocarbons (PAH) from vehicles fuelled by Fischer Tropsch (FT) based diesel and gasoline fuel, compared to the emissions from ordinary diesel and gasoline. The comparison for diesel fuels was based on a literature review, whereas the gasoline comparison had to be based on our own experiments, since almost no references were found in this field. In this context measurement according to the Federal Test Procedure (FTP) and the New European Driving Cycle (NEDC) were carried out on a chassis dynamometer with a directly injected gasoline vehicle. Experiments were carried out with a reference fuel, a fuel based 70% on FT and an alkylate fuel (Aspen), which was supposed to be very similar, in many ways, to FT fuel. FT based diesel generally showed good emission performance, whereas the FT based gasoline not necessary lead to lower emissions. On the other hand, the Aspen fuel did show many advantages for the emissions from the gasoline vehicle.

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

    Oguejiofor, G.C. [Nnamdi Azikiwe University, Awka (Nigeria). Dept. of Chemical Engineering

    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.

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

    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.

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

    Adeyinka A. Adeyiga

    2001-01-01

    The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H 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 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 2 /CO=0.67 and 2.0 NL/g-cat/h with C 5 + 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 alpha iron

  9. Life cycle assessment of climate impact of Fischer-Tropsch diesel based on peat and biomass

    Holmgren, Kristina; Hagberg, Linus

    2009-02-15

    By combining biomass gasification and Fischer-Tropsch synthesis it is possible to produce biodiesel. Vapo is investigating the possibilities for a plant where a mixture of different biomass fractions and peat would be used as raw material. In this study the climate impact of such synthetic diesel is calculated in terms of radiative forcing. The calculations show that the following parameters have large impact on the results: the emission factors associated with external power demand (purchased electricity) the use of carbon capture and storage the time perspective used in the analysis the raw material mix (amount of peat vs. amount of forest residues) the reference scenario for the peat production (type of peatland) All the FT-diesel scenarios with a peat input of 90% will have higher climate impact than fossil diesel after 100 years, except when CCS is applied and Swedish electricity mix is assumed for the external power demand. In order to have lower climate impact than conventional diesel after 100 years, the peat input must be significantly lower than the biomass input. Substantial reductions of the climate impact can be achieved by applying CCS. With CCS, all peat based FT-diesel scenarios (except the ones based on 90% peat) result in lower climate impact than fossil diesel after both 100 and 300 years. For scenarios with marginal electricity, the reductions are 50-84% after 100 years compared to conventional diesel. For scenarios with Swedish electricity mix the reductions are 100-135% (i.e. zero or negative radiative forcing). The scenarios in this study are based on the assumption that the biodiesel refinery is located close to a harbour so that transportation of captured CO{sub 2} to a storage site can be made by ship. An inland location would require truck transport or pipelines and the cost, infrastructure and logistics for this might not be feasible

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

    Subbarao Duvvuri

    2011-11-01

    Full Text Available Abstract 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%.

  11. Fischer-Tropsch synthesis in a two-phase reactor with presaturation

    Wache, W. [Bayernoil Raffineriegesellschaft mbH, Ingolstadt (Germany); Datsevich, L.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering

    2006-07-01

    In industry, the Fischer-Tropsch (FTS) synthesis is mostly carried out in multiphase slurry or multitubular reactors (MTR), where gaseous reactants and liquid products (hydrocarbons up to waxes) are contacted in the presence of a solid catalyst. Such reactors are characterized by a complex temperature control, necessity of gas recycling, complicated design and problematic scale-up. A new alternative to conventional FTS-processes is the presaturated-one-liquid-phase (POLF) technology. The basic principle of this concept is a recirculation of the liquid phase, in which a gaseous reactant(s) is (are) solved before entering the fixed-bed reactor. In a simple column reactor, this technology ensures the effective heat removal and intensive fluid-solid mass transfer. In comparison to conventional reactors, the plant design is very simple, the temperature control is uncomplicated and there is no danger of any runaways. That results in lower investment and operation costs as well as in higher reliability. The experiments show that the conversion of CO and the product distribution of hydrocarbons are practically independent on the mode of operation (two- or three-phase system). However, in the lab-scale apparatus, water is accumulated in the loop, which leads to a loss of the catalyst activity (due to Fe-carbonate). In a technical process, the water accumulation in a loop can be eluded by taking an oil free of water from the oil work-up unit. Our experiments with the removal of water from the stream by a zeolite demonstrate a much promising applicability of the POLF process to the industrial FTS. (orig.)

  12. Thermodynamic optimization of biomass gasification for decentralized power generation and Fischer-Tropsch synthesis

    Buragohain, Buljit; Mahanta, Pinakeswar; Moholkar, Vijayanand S.

    2010-01-01

    In recent years, biomass gasification has emerged as a viable option for decentralized power generation, especially in developing countries. Another potential use of producer gas from biomass gasification is in terms of feedstock for Fischer-Tropsch (FT) synthesis - a process for manufacture of synthetic gasoline and diesel. This paper reports optimization of biomass gasification process for these two applications. Using the non-stoichometric equilibrium model (SOLGASMIX), we have assessed the outcome of gasification process for different combinations of operating conditions. Four key parameters have been used for optimization, viz. biomass type (saw dust, rice husk, bamboo dust), air or equivalence ratio (AR = 0, 0.2, 0.4, 0.6, 0.8 and 1), temperature of gasification (T = 400, 500, 600, 700, 800, 900 and 1000 o C), and gasification medium (air, air-steam 10% mole/mole mixture, air-steam 30%mole/mole mixture). Performance of the gasification process has been assessed with four measures, viz. molar content of H 2 and CO in the producer gas, H 2 /CO molar ratio, LHV of producer gas and overall efficiency of gasifier. The optimum sets of operating conditions for gasifier for FT synthesis are: AR = 0.2-0.4, Temp = 800-1000 o C, and gasification medium as air. The optimum sets of operating conditions for decentralized power generation are: AR = 0.3-0.4, Temp = 700-800 o C with gasification medium being air. The thermodynamic model and methodology presented in this work also presents a general framework, which could be extended for optimization of biomass gasification for any other application.

  13. How to make Fischer-Tropsch catalyst scale-up fully reliable?

    Fischer, L.; Heraud, J.P.; Forret, A.; Gazarian, J. [IFP Energies nouvelles, Solaize (France); Cornaro, U. [Eni S.p.A., San Donato Milanese (Italy). R and M Div.; Carugati, A. [Eni S.p.A., San Donato Milanese (Italy). E and P Div.

    2011-07-01

    Several players use Fischer-Tropsch catalysts and technologies industrially [1,2] or declare to be ready for industrial application [e.g. 3]. Present R and D aims to further increase capacities per train [4] or improve catalyst selectivity towards middle distillates [5]. For transforming promising laboratory results into industrial reality, representative catalyst testing is of particular importance for slurry bubble column FT. In the Italian eni's refinery of Sannazzaro, a 20 BPD slurry bubble column pilot plant has cumulated more than 20,000 hours time on stream in different campaigns. Non reactive slurry bubble columns corresponding to reactor capacities between 20 BPD and 1000 BPD permitted to determine the profiles for gas hold up and liquid velocities as a function of gas flow, catalyst loading, reactor diameter and internals. A hydrodynamic model based on those data led to design a Large Validation Tool, which can reproduce under reaction conditions a high mechanical stress on the catalyst equivalent to the one experienced in an industrial 15000 BPD reactor. While those tools have proven to be efficient for developing an industrial scale FT catalyst [3], they predict today in a representative manner fines formation, activity and selectivity of improved catalysts and / or for optimization of operation conditions to increase the capacity per train. We compare the here presented approach to others. We have found that it is mandatory to combine chemical stress from the reaction products with mechanical stress as experienced in an industrial slurry bubble column, in order to evaluate in a reliable way catalyst performance stability and fines formation. The potential of improvements are discussed. (orig.)

  14. Effect of Lanthanum as a Promoter on Fe-Co/SiO2 Catalyst for Fischer-Tropsch Synthesis

    Ali Abbasi

    2014-03-01

    Full Text Available Iron-Cobalt catalyst is well known from both operational and economical aspects for Fischer-Tropsch synthesis. Effort to increase the efficiency of this kind of catalyst is an important research topic. In this work, the effect of lanthanum on characteristic behavior, conversion and selectivity of a Fe-Co/SiO2 Fischer-Tropsch catalyst was studied. The Fe-Co-La/SiO2 Catalysts were prepared using an incipient wetness impregnation method. These catalysts were then characterized by XRF-EDAX, BET and TPR techniques, and their performance were evaluated in a lab-scale reactor at 250ºC, H2/CO = 1.8 of molar ratio, 16 barg pressure and GHSV=600 h-1. TPR analysis showed that the addition of La lowered the reduction temperature of Fe-Co catalyst, and due to a lower temperature, the sintering of the catalyst can be mitigated. Furthermore, from the micro reactor tests (about 4 days, it was found that lanthanum promoted catalyst had higher selectivity toward hydrocarbons, and lower selectivity toward CO2.Received: 8th July 2013; Revised: 18th November 2013; Accepted: 1st December 2013[How to Cite: Abbasi, A., Ghasemi, M., Sadighi, S. (2014. Effect of Lanthanum as a Promoter on Fe-Co/SiO2 Catalyst for Fischer-Tropsch Synthesis. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (1: 23-27. (doi:10.9767/bcrec.9.1.5142.23-27][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.1.5142.23-27

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

    Jorge A. Delgado

    2017-03-01

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

  16. Rate and selectivity modification in Fischer-Tropsch synthesis over charcoal supported molybdenum by forced concentration cycling

    Dun, J.W.; Gulari, E.

    1985-01-01

    Forced concentration cycling of the feed between pure CO and pure H/sub 2/ was used to successfully change both the selectivities and reactivities of promoted and unpromoted charcoal supported molybdenum catalysts in Fischer-Tropsch synthesis. It was found that with the unpromoted catalyst the rate enhancement increases with temperature and selectivity shifts towards methane. At the lower temperatures concentration cycling increases selectivity to ethane and higher hydrocarbons to levels only achievable with promised catalysts. Periodic operation with the potassium promoted catalyst results in small rate enhancements but the olefin to paraffin ratio is dramatically changed without changing the carbon number distribution

  17. Techno-economic performance analysis of bio-oil based Fischer-Tropsch and CHP synthesis platform

    Ng, Kok Siew; Sadhukhan, Jhuma

    2011-01-01

    The techno-economic potential of the UK poplar wood and imported oil palm empty fruit bunch derived bio-oil integrated gasification and Fischer-Tropsch (BOIG-FT) systems for the generation of transportation fuels and combined heat and power (CHP) was investigated. The bio-oil was represented in terms of main chemical constituents, i.e. acetic acid, acetol and guaiacol. The compositional model of bio-oil was validated based on its performance through a gasification process. Given the availability of large scale gasification and FT technologies and logistic constraints in transporting biomass in large quantities, distributed bio-oil generations using biomass pyrolysis and centralised bio-oil processing in BOIG-FT system are technically more feasible. Heat integration heuristics and composite curve analysis were employed for once-through and full conversion configurations, and for a range of economies of scale, 1 MW, 675 MW and 1350 MW LHV of bio-oil. The economic competitiveness increases with increasing scale. A cost of production of FT liquids of 78.7 Euro/MWh was obtained based on 80.12 Euro/MWh of electricity, 75 Euro/t of bio-oil and 116.3 million Euro/y of annualised capital cost. -- Highlights: → Biomass to liquid process and gas to liquid process synthesis. → Biorefinery economic analysis. → Pyrolysis oil to biofuel. → Gasification and Fischer-Tropsch. → Process integration, pinch analysis and energy efficiency.

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

    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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Optimization of hydrogen production via coupling of the Fischer-Tropsch synthesis reaction and dehydrogenation of cyclohexane in GTL technology

    Rahimpour, M.R.; Bahmanpour, A.M.

    2011-01-01

    In this study, a thermally-coupled reactor containing the Fischer-Tropsch synthesis reaction in the exothermic side and dehydrogenation of cyclohexane in the endothermic side has been modified using a hydrogen perm-selective membrane as the shell of the reactor to separate the produced hydrogen from the dehydrogenation process. Permeated hydrogen enters another section called permeation side to be collected by Argon, known as the sweep gas. This three-sided reactor has been optimized using differential evolution (DE) method to predict the conditions at which the reactants' conversion and also the hydrogen recovery yield would be maximized. Minimizing the CO 2 and CH 4 yield in the reactor's outlet as undesired products is also considered in the optimization process. To reach this goal, optimal initial molar flow rate and inlet temperature of three sides as well as pressure of the exothermic side have been calculated. The obtained results have been compared with the conventional reactor data of the Research Institute of Petroleum Industry (RIPI), the membrane dual - type reactor suggested for Fischer-Tropsch synthesis, and the membrane coupled reactor presented for methanol synthesis. The comparison shows acceptable enhancement in the reactor's performance and that the production of hydrogen as a valuable byproduct should also be considered.

  20. An investigation of the physical and chemical changes occuring in a Fischer-Tropsch fixed bed catalyst during hydrocarbon synthesis

    Duvenhage, D.J.

    1990-01-01

    Deactivation studies: making use of fixed bed reactors, wet chemical analysis, surface area, pore volume determinations and X-ray diffraction spectrometry, scanning electron microscope spectrometry and secondary ion mass spectrometry techniques; were performed on a low temperature iron Fischer-Tropsch catalyst. It was revealed that this catalyst is mainly deactivated by sulphur poisoning, oxidation of the catalytic reactive phases, sintering of the iron crystallites and to a lesser extent deactivation through fouling of the catalytic surface by carbonaceous deposits. It was found that the top entry section of the catalyst bed deactivated relatively fast, the bottom exit section also deactivated, but not as fast as the top section. The central portion of the catalyst bed was least affected. Sulphur contaminants in the feed gas, even though present in only minute quantities, results in a loss of catalyst performance of the top section of the catalyst bed, while water, produced as a product from the Fischer-Tropsch reaction, oxidized and sintered the catalyst over the bottom section of the catalyst bed. 88 figs., 7 tabs., 224 refs

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

    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

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

    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 65 wt%, regardless of pretreatment gas and pressure, with

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

    Rao, K.R.P.M.; Huggins, F.E.; Huffman, G.P. [Univ. of Kentucky, Lexington, (United States)] [and others

    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.

  4. KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYNTHESIS. FOURTH ANNUAL TECHNICAL PROGRESS REPORT

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

    2006-01-01

    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

  5. Bulk and surface structure of a NixFe/Al2O3 catalyst for Fischer-Tropsch synthesis studied by Moessbauer, infrared spectroscopy and magnetic methods

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

    1992-01-01

    Deposition precipitation of a stoichiometric nickel-ironcyanide complex onto a 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. (orig.)

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

    Sartipi, S.; Jansma, H.; Bosma, D.; Boshuizen, B.; Makkee, M.; Gascon, J.; Kapteijn, F.

    2013-01-01

    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

  7. Insight on Biomass Supply and Feedstock Definition for Fischer-Tropsch Based BTL Processes

    Coignac, Julien

    2013-01-01

    Process chains of thermo chemical conversion of lignocellulosic biomass through gasification and Fischer-Tropsch synthesis (known as BTL) represent promising alternatives for biofuels production. Since biomass is heterogeneous and not homogeneously spread over territories, one of the major technological stakes of the project is to develop a flexible industrial chain capable of co-treating the widest possible range of biomass and fossil fuel feedstock. The present study aims at characterizing biomass diversity (availability and potentials by area, cost and mineral composition) by carrying out a state of the art, as a preliminary step in order to define a series of biomass to be tested in the demonstration plant and therefore define specifications for the process. Fifty different biomass were considered for their bio-energy application potential and were finally classified into four categories: agricultural by-products, dedicated energy crops, (Very) Short Rotation Coppice ((V)SRC) and forestry biomass. Biomass availability and potentials were investigated by the mean of a literature review of past and current projects (e.g. RENEW project, Biomass Energy Europe Project, etc.) and scientific articles. Most collected data are technical potentials, meaning that they take into account biophysical limits of crops and forests, technological possibilities, competition with other land uses and ecological constraints (e.g. natural reserves). Results show various emerging markets: North and South America have considerable amounts of agricultural by-products, forest residues, and large land areas which could be dedicated to energy crops; Africa shows relevant possibilities to grow Short Rotation Forestry (SRF) and energy crops; Russia has large available quantities of agricultural by-products and forest residues, as well as little valuable land where energy crops and SRC could be grown, and Asia shows relevant amounts of forest residues and possibilities of growing SRC, as well

  8. New perspectives in the Fischer-Tropsch synthesis using cobalt supported on mesoporous molecular sieves; Novas perspectivas na sintese de Fischer-Tropsch usando cobalto suportado em peneiras moleculares mesoporosas

    Souza, M.J.B.; Silva, A.O.S. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil). Dept. de Engenharia Quimica; Fernandes Junior, V.J.; Araujo, A.S. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil). Dept. de Quimica

    2004-07-01

    The conversion of synthesis gas to liquid products via Fischer-Tropsch synthesis (FTS) is an important process in the generation of clean fuels of sulfur and nitrogen compounds. Catalysts based on iron are very used in the conventional process due its cheap manufacture price. Recently the use of cobalt as promoter gave good results. MCM-41 mesoporous materials were discovered by Mobil scientists in the nineties and ever since they have great successes as support and catalyst in several processes of the oil industry as catalytic cracking, reformer and hydrotreating. In this work are presented new alternatives for FTS with the use of cobalt supported on molecular sieves of the type MCM-41. A comparative study with the usual catalysts based on silica was accomplished with different levels of cobalt. (author)

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

    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

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

    Shah, Jayesh [Lummus Technology Inc., Bloomfield, NJ (United States); Hess, Fernando [Lummus Technology Inc., Bloomfield, NJ (United States); Horzen, Wessel van [Lummus Technology Inc., Bloomfield, NJ (United States); Williams, Daniel [Lummus Technology Inc., Bloomfield, NJ (United States); Peevor, Andy [JM Davy, London (United Kingdom); Dyer, Andy [JM Davy, London (United Kingdom); Frankel, Louis [Canonsburgh, PA (United States)

    2016-06-01

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

  11. A combined in situ XAS-XRPD-Raman study of Fischer-Tropsch synthesis over a carbon supported Co catalyst

    Tsakoumis, Nikolaos E.; Dehghan, Roya; Johnsen, Rune

    2013-01-01

    A cobalt based Fischer-Tropsch synthesis (FTS) catalyst, supported on a carbon nanofibers/carbon felt composite (Co/CNF/CF) was studied in situ at realistic conditions. The catalyst was monitored by Xray absorption spectroscopy (XAS), high-resolution X-ray powder diffraction (HR-XRPD) and Raman...... spectroscopy, while changes in the gas phase were observed by mass spectrometry (MS). Transmission electron microscopy (TEM) was also applied to characterise the catalyst. The catalyst has a bimodal particle size distribution and exhibits a high deactivation rate. During the in situ study the catalyst appears...... to reduce further at the induction period of FTS, while crystallite growth is been detected in the same period. At steady state FTS the amount of metallic Co is constant. A change in the volumetric flow towards higher conversions did not affect the degree of reduction or the crystallite size of the catalyst...

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

    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.

  13. Preparation, characterization and testing of SiC-based catalytic sponges as structured catalysts for Fischer-Tropsch synthesis

    Baudry, A.; Schaub, G. [Karlsruhe Institute of Technology (KIT), Karlsruhe (Germany). Engler-Bunte-Inst.

    2011-07-01

    Solid sponges (open-cell foams) may be used as catalyst support, due to favorable thermal properties and low pressure drop. As an example, they may lead to improved temperature control in Fischer-Tropsch applications, if compared to fixed beds of catalyst particles. The aim of this study was to develop and test a wet method for impregnating ceramic foam materials with a CoRe/{gamma}-Al{sub 2}O{sub 3} catalyst. Defined catalyst layers were generated on 20 ppi SiC-sponges. Resulting catalytic activities are nearly identical to those of the corresponding powder catalyst material. The difference observed can be explained by either mass transfer limitation or backmixing in the fixed bed configuration used. (orig.)

  14. Evidence for H2/D2 isotope effects on Fischer-Tropsch synthesis over supported ruthenium catalysts

    Kellner, C.S.; Bell, A.T.

    1981-01-01

    The effects of using D 2 rather than H 2 during Fischer-Tropsch synthesis were investigated using alumina- and silica-supported Ru catalysts. For the alumina-supported catalysts, the rate of CD 4 formation was 1.4 to 1.6 times faster than the formation of CH 4 . A noticeable isotope effect was also observed for higher molecular weight products. The magnitude of the isotope effects observed using the silica-supported catalyst was much smaller than that found using the alumina-supported catalysts. The formation of olefins relative to paraffins was found to be higher when H 2 rather than D 2 was used, independent of the catalyst support. The observed isotope effects are explained in terms of a mechanism for CO hydrogenation and are shown to arise from a complex combination of the kinetic and equilibrium isotope effects associated with elementary processes occurring on the catalyst surface

  15. Studies of carbon deposition and consumption on Ru/TiO2 during Fischer-Tropsch synthesis

    Yokomizo, G.; Bell, A.T.; Duncan, T.M.

    1986-01-01

    Isotropic tracer techniques have been used to characterize the dynamics of carbon deposition on the surface of a Ru/TiO 2 catalyst during Fischer-Tropsch synthesis and 13 C-NMR spectroscopy has been used to characterize the structure of the deposited carbon. Elemental carbon, designated C/sub α/ is formed very rapidly, whereas alkyl carbon, designated C/sub β/ accumulates much more slowly. The influence of catalyst reduction on temperature, reaction conditions, and time under reaction conditions on the surface concentrations and reactivity of C/sub α/ and C/sub β/ will be discussed. It will be shown that C/sub β/ progressively becomes less reactive and may be the precursor to the formation of graphitic carbon

  16. A preliminary plant design study for the production of diesel from coal via fischer-tropsch synthesis

    Kamil, M.; Saleem, M.

    2010-01-01

    Pakistan's reliance on conventional means of producing energy has proven to be an inadequate strategy for overcoming it. The situation direly demands diversification of our energy resources not only to overcome current fiasco but also in planning for future. Among the other alternative sources, coal is the main source for producing cheaper electricity being available as huge reserves. This paper presents the preliminary plant design and cost estimation for the production of diesel from coal via coal gasification and fischer-Tropschs synthesis. Prelimnary design calculations and cost estimation are presented along with underlying assumptions. The results reveal that the diesel produced from this process might be cheaper than the crude oil based diesel. (author)

  17. Characterization of catalysts by Moessbauer spectroscopy: An application to the study of Fischer-Tropsch, hydrotreating and super Claus catalysts

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

    1993-01-01

    Moessbauer spectroscopy is an excellent in-situ technique for the identification of phases present in catalysts. Applied to metallic iron catalysts used in the Fischer-Tropsch reaction it reveals a detailed picture of the carburization process and provides insight into the relation between the properties of the catalytic material and its activity. The influence of a support and the effect of alloying iron with an (in)active metal on the catalytic performance is discussed for Fe, Cu-Fe and Ni-Fe systems. In addition, Moessbauer spectroscopy is used for the identification of 'Co-sulfide' species present in sulfided Co and CoMo catalysts applied in one of the largest chemical processes in the world, the hydrotreatment of crude oil. A structural model is proposed. Finally, the contribution of Moessbauer spectroscopic studies to the development of a new catalyst for cleaning of Claus tail gas via selective oxidation of hydrogen sulfide to elemental sulfur is discussed. (orig.)

  18. Effect of pretreatment temperature on catalytic performance of the catalysts derived from cobalt carbonyl cluster in Fischer-Tropsch Synthesis

    Byambasuren O

    2017-02-01

    Full Text Available The monometallic cobalt-based catalysts were prepared by pretreating the catalysts derived from carbonyl cluster precursor (CO6Co2CC(COOH2 supported on γ-Al2O3 with hydrogen at 180, 220, and 260°C respectively. The temperature effect of the pretreatments on the structure evolution of cluster precursors and the catalytic performance of the Fischer-Tropsch (F-T synthesis was investigated. The pretreated catalyst at 220°C with unique phase structure exhibited best catalytic activity and selectivity among three pretreated catalysts. Moreover, the catalysts exhibited high dispersion due to the formation of hydrogen bonds between the cluster precursor and γ-Al2O3 support.

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

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

    2015-01-01

    Graphical abstract: - Highlights: • Determined that the reduction of Co nanoparticles on silica nanosprings 200 °C higher than the reduction temperature of Co in a solgel support. • The high reduction temperature of Co supported on silica nanosprings is attributed to the heat transfer properties of the nanosprings due to their high surface area. Co-silica nanospring Fischer-Tropsch catalyst can be used to produce drop in fuels such as JP-4. - Abstract: 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 Co 3 O 4 spinel phase. A two-step reduction of Co 3 O 4 to CoO and then to Co 0 is observed, which is consistent with the results of H 2 -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 H 2 revealed signatures of Co 0 , CoO, and Co 3 O 4 . The reduction saturates at a Co o 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 H 2 , 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 C 6 -C 17 hydrocarbons than the catalyst reduced at 409 °C and is consistent with the XPS analysis.

  20. Model studies of secondary hydrogenation in Fischer-Tropsch synthesis studied by cobalt catalysts

    Aaserud, Christian

    2003-07-01

    Mass transfer effects are very important in Fischer-Tropsch (FT) synthesis. In order to study the FT synthesis without the influence of any transport limitations, cobalt foils have been used as model catalysts. The effect of pretreatment (number of calcinations and different reduction times) for cobalt foil catalysts at 220 {sup o}C, 1 bar and H{sub 2}/CO = 3 has been studied in a microreactor. The foils were examined by Scanning electron microscopy (SEM). It was found that the catalytic activity of the cobalt foil increases with the number of pretreatments possibly due to an increase in the surface area of the cobalt foil. The SEM results support the assumption that the surface area of the cobalt foil increases with the number of pretreatments. The reduction time was also found to influence the catalytic activity of the cobalt foil. Highest activity was obtained using a reduction time of only five min (compared to one and thirty min). The decrease in activity after reduction for thirty min compared to five min was suggested to be due to restructuring of the surface of the cobalt foil and a reduction time of only 1 min was not enough to reduce the cobalt foil sufficiently. Time of reduction did also influence the product distribution. Increased reduction time resulted in a lower selectivity to light products and increased selectivity to heavier components. The paraffin/olefin ratio increased with increasing CO-conversion also for cobalt foils. The paraffin/olefin ratio also increased when the reduction period of the cobalt foil was increased at a given CO-conversion. Hydrogenation of propene to propane has been studied as a model reaction for secondary hydrogenation of olefins in the FT synthesis. The study has involved promoted and unpromoted cobalt FT catalysts supported on different types of supports and also unsupported cobalt. Hydrogenation of propene was carried out at 120 {sup o}C, 1.8 bar and H{sub 2}/C{sub 3}H{sub 6} 6 in a fixed bed microreactor. The rate

  1. Ruthenium Modification on Mn and Zr-Modified Co/SiO2 Catalysts for Slurry-Phase Fischer-Tropsch Synthesis

    Tomohisa Miyazawa

    2015-01-01

    Full Text Available The addition of Ru to Mn and Zr-modified Co/SiO2 catalysts, while applying different preparation orders and loading amounts, was investigated as a means of enhancing the Fischer-Tropsch synthesis reaction. The coimpregnation of Zr/SiO2 with Co, Mn and Ru gave the most attractive catalytic properties. This can be attributed to the higher dispersion of Co metal resulting from the coimpregnation of Co and Mn as well as enhanced reducibility due to the presence of Ru. The addition of a moderate amount of Ru together with the appropriate order of addition affected both the Co reducibility and the catalytic activity, primarily because of increased reducibility. The addition of even 0.1 wt.% Ru resulted in an obvious enhancement of Fischer-Tropsch synthesis activity.

  2. FeRu/TiO2 and Fe/TiO2 catalysts after reduction and Fischer-Tropsch synthesis studied by Moessbauer spectroscopy

    Kraan, A.M. van der; Nonnekens, R.C.H.; Niemantsverdriet, J.W.

    1986-01-01

    A series of TiO 2 -supported bimetallic FeRu catalysts with different Fe:Ru ratios (infinity; 10:1; 3:1; 1:1; 1:3) has been studied by means of in situ Moessbauer spectroscopy. The influence of reduction and Fischer-Tropsch synthesis on the state of iron in the FeRu/TiO 2 catalysts is derived. (Auth.)

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

    Sartipi, S.; Jansma, H.; Bosma, D.; Boshuizen, B.; Makkee, M.; Gascon, J.; Kapteijn, F.

    2013-01-01

    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...

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

    Kengne, Blaise-Alexis Fouetio [Department of Physics, University of Idaho, Moscow, ID 83844-0903 (United States); Alayat, Abdulbaset M. [Environmental Science Program, University of Idaho, Moscow, ID 83844-3006 (United States); Luo, Guanqun [Department of Forest, Rangeland & Fire Sciences, University of Idaho, Moscow, ID 83844-1132 (United States); McDonald, Armando G. [Environmental Science Program, University of Idaho, Moscow, ID 83844-3006 (United States); Department of Forest, Rangeland & Fire Sciences, University of Idaho, Moscow, ID 83844-1132 (United States); Brown, Justin; Smotherman, Hayden [Department of Physics, University of Idaho, Moscow, ID 83844-0903 (United States); McIlroy, David N., E-mail: dmcilroy@uidaho.edu [Department of Physics, University of Idaho, Moscow, ID 83844-0903 (United States)

    2015-12-30

    Graphical abstract: - Highlights: • Determined that the reduction of Co nanoparticles on silica nanosprings 200 °C higher than the reduction temperature of Co in a solgel support. • The high reduction temperature of Co supported on silica nanosprings is attributed to the heat transfer properties of the nanosprings due to their high surface area. Co-silica nanospring Fischer-Tropsch catalyst can be used to produce drop in fuels such as JP-4. - Abstract: 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 Co{sub 3}O{sub 4} spinel phase. A two-step reduction of Co{sub 3}O{sub 4} to CoO and then to Co{sup 0} is observed, which is consistent with the results of H{sub 2}-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{sup −6} Torr of H{sub 2} revealed signatures of Co{sup 0}, CoO, and Co{sub 3}O{sub 4}. The reduction saturates at a Co{sup o} 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 H{sub 2}, 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 C{sub 6}-C{sub 17} hydrocarbons than the catalyst reduced at 409 °C and is consistent with the XPS analysis.

  5. Black Liquor Gasification with Motor Fuel Production - BLGMF II - A techno-economic feasibility study on catalytic Fischer-Tropsch synthesis for synthetic diesel production in comparison with methanol and DME as transport fuels

    Ekbom, Tomas; Berglin, Niklas; Loegdberg, Sara [Nykomb Synergetics AB, Stockholm (Sweden)

    2005-06-15

    The present project presents additional results to the former BLGMF project, which investigate Black Liquor Gasification with Motor Fuels (BLGMF) production. The objectives were to investigate, based on the KAM 2 program Ecocyclic Pulp Mill (2,000 ADt/day of pulp) the feasibility of synthetic fuels production. Specifically the route to Fischer-Tropsch diesel fuels is investigated as comparison to earlier work on methanol/DME. As modern kraft pulp mills have a surplus of energy, they could become key suppliers of renewable fuels. It is thus of great interest to convert the spent cooking product 'black liquor' to an energy carrier of high value. The resulting biomass-to-fuel energy efficiency when only biomass is used as an external energy source was 43% for FTD or 65% for FT products compared with 66% for methanol and 67% for DME. The FTD calculation is considerably more complicated and based on assumptions, therefore the uncertainty is higher. Would the diesel be taken out with a T95% of 320 deg C the FTD efficiency would be 45%. FT synthesis also opens up a possibility to produce e.g. lube oils from waxes produced. The total net FT-products output equals 4115 barrels/day. The FTD production cost is calculated as the energy share of the total production cost and assumes an offset of naphtha covering its own costs, where it is essential that it finds a market. Assuming same petrol (methanol) and diesel (DME, FTD) costs for the consumer the payback time were 2.6, 2.9 and 3.4 years with an IRR of 40%, 45% and 30%, respectively. In conclusion, there are necessary resources and potential for large-scale methanol (or DME, FTD) production and substantial economic incentive for making plant investments and achieving competitive product revenues.

  6. Study of (Fe/HZM-5) catalyst be used in the Fischer-Tropsch synthesis: preparation and characterization; Estudo do catalisador (Fe/HZSM-5) a ser utilizado na sintese de Fischer-Tropsch: preparacao e caracterizacao

    Gonzaga, Arthur C. [Universidade Estadual do Maranhao (UEMA0), MA (Brazil); Sousa, Bianca V. de; Lima, Wellington S.; Rodrigues, Meiry G.F. [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academica de Engenharia Quimica

    2008-07-01

    In this work it was developed an iron catalyst supported on the ZSM-5 zeolite to be used in the Fischer-Tropsch Synthesis (FTS). The NH{sub 4}{sup +}ZSM-5 zeolitic support was submitted to the wet impregnation, using the 0.1 M of the Fe(NO{sub 3}){sub 3}.9H{sub 2}O solution to obtain the Fe/NH{sub 4}{sup +}ZSM-5 sample in the content of iron 5% wt. After, the material was submitted for the drying process and in the following, for the calcination one, obtaining the Fe/HZSM-5 form. The EDS characterization analyses showed that in the Fe/HZSM-5 sample the iron is in the Fe{sub 2}O{sub 3} form and that the impregnation and calcination processes did not cause significant exchanges in the zeolitic support framework. The results of the N{sub 2} physical adsorption of the 5% Fe/HZSM-5 showed the presence of the micropores and mesopores. From these results, the obtained material (5% Fe/HZSM-5) presents a great potential to be used like a catalyst in the FTS. (author)

  7. X-ray physico-chemical imaging during activation of cobalt-based Fischer-Tropsch synthesis catalysts

    Beale, Andrew M.; Jacques, Simon D. M.; Di Michiel, Marco; Mosselmans, J. Frederick W.; Price, Stephen W. T.; Senecal, Pierre; Vamvakeros, Antonios; Paterson, James

    2017-11-01

    The imaging of catalysts and other functional materials under reaction conditions has advanced significantly in recent years. The combination of the computed tomography (CT) approach with methods such as X-ray diffraction (XRD), X-ray fluorescence (XRF) and X-ray absorption near-edge spectroscopy (XANES) now enables local chemical and physical state information to be extracted from within the interiors of intact materials which are, by accident or design, inhomogeneous. In this work, we follow the phase evolution during the initial reduction step(s) to form Co metal, for Co-containing particles employed as Fischer-Tropsch synthesis (FTS) catalysts; firstly, working at small length scales (approx. micrometre spatial resolution), a combination of sample size and density allows for transmission of comparatively low energy signals enabling the recording of `multimodal' tomography, i.e. simultaneous XRF-CT, XANES-CT and XRD-CT. Subsequently, we show high-energy XRD-CT can be employed to reveal extent of reduction and uniformity of crystallite size on millimetre-sized TiO2 trilobes. In both studies, the CoO phase is seen to persist or else evolve under particular operating conditions and we speculate as to why this is observed. This article is part of a discussion meeting issue 'Providing sustainable catalytic solutions for a rapidly changing world'.

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

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

    2014-01-01

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

  9. Raising distillate selectivity and catalyst life time in Fischer-Tropsch synthesis by using a novel dual-bed reactor

    Tavasoli, A.; Sadaghiani, K.; Khodadadi, A. A.; Mortazavi, Y.

    2007-01-01

    In a novel dual bed reactor Fischer-Tropsch synthesis was studied by using two diff rent cobalt catalysts. An alkali-promoted cobalt catalyst was used in the first bed of a fixed-bed reactor followed by a Raiment promoted cobalt catalyst in the second bed. The activity, product selectivity and accelerated deactivation of the system were assessed and compared with a conventional single bed reactor system. The methane selectivity in the dual-bed reactor was about 18.9% less compared to that of the single-bed reactor. The C 5+ selectivity for the dual-bed reactor was 10.9% higher than that of the single-bed reactor. Accelerated deactivation of the catalysts in the dual-bed reactor was 42% lower than that of the single-bed reactor. It was revealed that the amount of catalysts activity recovery after regeneration at 400 d eg C in the dual-bed system is higher than that of the single-bed system

  10. Effect of Manganese Promotion on Al-Pillared Montmorillonite Supported Cobalt Nanoparticles for Fischer-Tropsch Synthesis

    Ahmad, N.; Hussain, S. T.; Abbas, S. M.; Khan, Y.; Muhammad, B.; Ali, N.

    2013-01-01

    The effect of Mn-promotion on high surface area Al-pillared montmorillonite (AlMMT) supported Co nanoparticles prepared by hydrothermal method have been investigated. A series of different weight% Mn-promoted Co nanoparticles were prepared and characterized by XRD, TPR, TGA, BET and SEM techniques. An increase in the surface area of MMT is observed with Al-pillaring. Fischer-Tropsch catalytic activity of the as prepared catalysts was studied in a fixed bed micro reactor at 225 .deg. C, H 2 /CO = 2 and at 1 atm pressure. The data showed that by the addition of Mn the selectivity of C 1 dropped drastically while that of C 2 -C 12 hydrocarbons increased significantly over all the Mn-promoted Co/AlMMT catalysts. The C 13 -C 20 hydrocarbons remained almost same for all the catalysts while the selectivity of C 21+ long chain hydrocarbons decreased considerably with the addition of Mn. The catalyst with 3.5%Mn showed lowest C 21+ and highest C 2 -C 12 hydrocarbons selectivity due to cracking of long chain hydrocarbons over acidic sites of MMT

  11. From Nanoparticles to Process An Aberration Corrected TEM Study of Fischer Tropsch Catalysts at Various Steps of the Process

    Braidy, N.; Blanchard, J.; Abatzoglou, N.; Andrei, C.

    2011-01-01

    χThe nanostructure of Fischer-Tropsch (FT) Fe carbides are investigated using aberration-corrected high-resolution transmission electron microscopy (TEM). The plasma-generated Fe carbides are analyzed just after synthesis, following reduction via a H2 treatment step and once used as FT catalyst and deactivated. The as-produced nanoparticles (NPs) are seen to be abundantly covered with graphitic and amorphous carbon. Using the extended information limit from the spherical aberration-corrected TEM, the NPs could be indexed as a mixture of NPs in the θ-Fe 3 C and χ-Fe 5 C 2 phases. The reduction treatment exposed the NPs by removing most of the carbonaceous speSubscript textcies while retaining the χ-Fe 5 C 2 . Fe-carbides NPs submitted to conditions typical to FT synthesis develop a Fe3O4 shell which eventually consumes the NPs up to a point where 3-4 nm residual carbide is left at the center of the particle. Subscript textVarious mechanisms explaining the formation of such a microstructure are discussed. (author)

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

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

    2011-12-15

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

  13. Fischer-Tropsch diesel production in a well-to-wheel perspective: A carbon, energy flow and cost analysis

    van Vliet, Oscar P.R.; Faaij, Andre P.C.; Turkenburg, Wim C.

    2009-01-01

    We calculated carbon and energy balances and costs of 14 different Fischer-Tropsch (FT) fuel production plants in 17 complete well-to-wheel (WTW) chains. The FT plants can use natural gas, coal, biomass or mixtures as feedstock. Technical data, and technological and economic assumptions for developments for 2020 were derived from the literature, recalculating to 2005 euros for (capital) costs. Our best-guess WTW estimates indicate BTL production costs break even when oil prices rise above $75/bbl, CTL above $60/bbl and GTL at $36/bbl. CTL, and GTL without carbon capture and storage (CCS), will emit more CO 2 than diesel from conventional oil. Driving on fuel from GTL with CCS may reduce GHG emissions to around 123 g CO 2 /km. Driving on BTL may cause emissions of 32-63 g CO 2 /km and these can be made negative by application of CCS. It is possible to have net climate neutral driving by combining fuels produced from fossil resources with around 50% BTL with CCS, if biomass gasification and CCS can be made to work on an industrial scale and the feedstock is obtained in a climate-neutral manner. However, the uncertainties in these numbers are in the order of tens of percents, due to uncertainty in the data for component costs, variability in prices of feedstocks and by-products, and the GHG impact of producing biomass. (author)

  14. Fischer-Tropsch diesel production over calcium-promoted Co/alumina catalyst: Effect of reaction conditions

    A.R. de la Osa; A. De Lucas; A. Romero; J.L. Valverde; P. Sanchez [University of Castilla-La Mancha, Ciudad Real (Spain). Chemical Engineering Department

    2011-05-15

    The effects of reaction conditions on the Fischer-Tropsch activity and product distribution of an alkali-earth metal promoted cobalt based catalyst were studied. The influence of the promoter on the reducibility and cobalt particle size was studied by different techniques, including N{sub 2} adsorption, X-ray diffraction, temperature-programmed reduction, temperature-programmed desorption and acid-base titrations. Experiments were carried out on a bench-scale fixed bed reactor and catalysts were prepared by incipient wetness impregnation. It was observed that addition of a small amount of calcium oxide as a promoter (0.6 wt.%) improved the cobalt oxide reducibility and reduced the formation of cobalt-aluminate species. A positive correlation between basicity and particle size was observed. In terms of FTS results, CO conversion and C{sub 5}{sup +} selectivity were found to be enhanced by the addition of this promoter. It was important to note that the addition of calcium shifted the distribution to mainly C{sub 16}-C{sub 18} hydrocarbons fraction, which could be greatly considered for a diesel formulation. Furthermore, the variation of the reaction conditions seemed to influence product distribution in a lesser extent than unpromoted catalyst. Also, a displacement of hydrocarbon distribution to higher molecular weight with decreasing space velocity and temperature was observed. Moreover, the addition of calcium to the cobalt based catalyst was found to greatly maintain selectivity to C{sub 5}{sup +} for a wide range of H{sub 2}/CO molar ratios. 60 refs., 10 figs., 5 tabs.

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

    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. Incentivizing wood-based Fischer-Tropsch diesel through financial policy instruments: An economic assessment for Norway

    Bright, Ryan M.; Stromman, Anders H.

    2010-01-01

    The objective of this study is to evaluate a select set of financial incentive instruments that can be employed by the Norwegian government for encouraging early investment and production experience in wood-based Fischer-Tropsch diesel (FTD) technologies as a means to accelerate reductions in greenhouse gas emissions (GHG) stemming from road-based transport. We start by performing an economic analysis of FTD produced from Norwegian forest biomass at a pioneer commercial plant in Norway, followed with a cost growth analysis to estimate production costs after uncertainty in early plant performance and capital cost estimates are considered. Results after the cost growth analysis imply that the initial production cost estimates for a pioneer producer may be underestimated by up to 30%. Using the revised estimate we then assess, through scenarios, how various financial support mechanisms designed to encourage near-term investment would affect production costs over a range of uncertain future oil prices. For all policy scenarios considered, we evaluate trade-offs between the levels of public expenditure, or subsidy, and private investor profitability. When considering the net present value of the subsidy required to incentivize commercial investment during a future of low oil prices, we find that GHG mitigation via wood-FTD is likely to be considered cost-ineffective. However, should the government expect that mean oil prices in the coming two decades will hover between $97 and 127/bbl, all the incentive policies considered would likely spur investment at net present values ≤$-100/tonne-fossil-CO 2 -equivalent avoided.

  17. Ototoxic potential of JP-8 and a Fischer-Tropsch synthetic jet fuel following subacute inhalation exposure in rats.

    Fechter, Laurence D; Gearhart, Caroline A; Fulton, Sherry

    2010-07-01

    This study was undertaken to identify the ototoxic potential of two jet fuels presented alone and in combination with noise. Rats were exposed via a subacute inhalation paradigm to JP-8 jet fuel, a kerosene-based fuel refined from petroleum, and a synthetic fuel produced by the Fischer-Tropsch (FT) process. Although JP-8 contains small ( approximately 5%) concentrations of aromatic hydrocarbons some of which known to be ototoxic, the synthetic fuel does not. The objectives of this study were to identify a lowest observed adverse effect level and a no observed adverse effect level for each jet fuel and to provide some preliminary, but admittedly, indirect evidence concerning the possible role of the aromatic hydrocarbon component of petroleum-based jet fuel on hearing. Rats (n = 5-19) received inhalation exposure to JP-8 or to FT fuel for 4 h/day on five consecutive days at doses of 500, 1000, and 2000 mg/m(3). Additional groups were exposed to various fuel concentrations followed by 1 h of an octave band of noise, noise alone, or no exposure to fuel or noise. Significant dose-related impairment in the distortion product otoacoustic emissions (DPOAE) was seen in subjects exposed to combined JP-8 plus noise exposure when JP-8 levels of at least 1000 mg/m(3) were presented. No noticeable impairment was observed at JP-8 levels of 500 mg/m(3) + noise. In contrast to the effects of JP-8 on noise-induced hearing loss, FT exposure had no effect by itself or in combination with noise exposure even at the highest exposure level tested. Despite an observed loss in DPOAE amplitude seen only when JP-8 and noise were combined, there was no loss in auditory threshold or increase in hair cell loss in any exposure group.

  18. Lump Kinetic Analysis of Syngas Composition Effect on Fischer-Tropsch Synthesis over Cobalt and Cobalt-Rhenium Alumina Supported Catalyst

    Dewi Tristantini

    2016-03-01

    Received: 10th November 2015; Revised: 10th February 2016; Accepted: 16th February 2016 How to Cite: Tristantini, D., Suwignjo, R.K. (2016. Lump Kinetic Analysis of Syngas Composition Effect on Fischer-Tropsch Synthesis over Cobalt and Cobalt-Rhenium Alumina Supported Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 84-92. (doi:10.9767/bcrec.11.1.424.84-92 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.424.84-92

  19. Effect of K promoter on the structure and catalytic behavior of supported iron-based catalysts in fischer-tropsch synthesis

    F. E. M Farias

    2011-09-01

    Full Text Available Effects of K addition on the performance of supported Fe catalysts for Fischer - Tropsch synthesis (FTS were studied in a slurry reactor at 240 to 270ºC, 2.0 to 4.0 MPa and syngas H2/CO = 1.0. The catalysts were characterized by N2 adsorption, H2 temperature programmed reduction, X - ray diffraction, X - ray fluorescence, thermogravimetric analysis, scanning electron microscopy and dispersive X - ray spectroscopy. A strong interaction was observed between Fe and K, which inhibited the reduction of Fe catalyst. Addition of potassium increased the production of heavy hydrocarbons (C20+.

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

    Fu Tingjun; Huang Chengdu; Lv Jing; Li Zhenhua

    2014-01-01

    A silica-supported cobalt catalyst was prepared by hydrogen dielectric-barrier discharge (H 2 -DBD) plasma. Compared to thermal hydrogen reduction, H 2 -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 H 2 -DBD plasma treatment is a promising alternative for preparing Co/SiO 2 catalysts from the viewpoint of energy savings and efficiency

  1. Comparative study of regulated and unregulated gaseous emissions during NEDC in a light-duty diesel engine fuelled with Fischer Tropsch and biodiesel fuels

    Bermudez, Vicente; Lujan, Jose M.; Pla, Benjamin; Linares, Waldemar G. [CMT-Motores Termicos, Universidad Politecnica de Valencia, Camino de Vera s/n, 46022 Valencia (Spain)

    2011-02-15

    In this study, regulated and unregulated gaseous emissions and fuel consumption with five different fuels were tested in a 4-cylinder, light-duty diesel EURO IV typically used for the automotive vehicles in Europe. Three different biodiesel fuels obtained from soybean oil, rapeseed oil and palm oil, a Fischer Tropsch fuel and an ultra low sulphur diesel were studied. The test used was the New European Driving Cycle (NEDC), this allowed tests to be carried out on an engine warmed up beforehand to avoid the effect of cold starts and several tests a day. Regulated emissions of NO{sub X}, CO, HC and CO{sub 2} were measured for each fuel. Unburned Hydrocarbon Speciation and formaldehyde were also measured in order to determine the maximum incremental reactivity (MIR) of the gaseous emissions. Pollutants were measured without the diesel oxidation catalyst (DOC) to gather data about raw emissions. When biodiesel was used, increases in regulated and unregulated emissions were observed and also significant increases in engine fuel consumption. The use of Fischer Tropsch fuel, however, caused lower regulated and unregulated emissions and fuel consumption than diesel. (author)

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

    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

  3. Enhanced anaerobic degradation of Fischer-Tropsch wastewater by integrated UASB system with Fe-C micro-electrolysis assisted.

    Wang, Dexin; Ma, Wencheng; Han, Hongjun; Li, Kun; Xu, Hao; Fang, Fang; Hou, Baolin; Jia, Shengyong

    2016-12-01

    Coupling of the Fe-C micro-electrolysis (IC-ME) into the up-flow anaerobic sludge blanket (UASB) was developed for enhanced Fischer-Tropsch wastewater treatment. The COD removal efficiency and methane production in R 3 with IC-ME assisted both reached up to 80.6 ± 1.7% and 1.38 ± 0.11 L/L·d that higher than those values in R 1 with GAC addition (63.0 ± 3.4% and 0.95 ± 0.09 L/L·d) and R 2 with ZVI addition (74.5 ± 2.8% and 1.21 ± 0.09 L/L·d) under the optimum HRT (5 d). The Fe corrosion as electron donor reduced the ORP values and stimulated the activities of hydrogenotrophic methanogens to lower H 2 partial pressure in R 2 and R 3 . Additionally, Fe 2+ as by-product of iron corrosion, its presence could effectively increase the percentage of protein content in tightly bound extracellular polymeric substances (TB-EPS) to promote better bioflocculation, increasing to 90.5 mg protein/g·VSS (R 2 ) and 106.3 mg protein/g·VSS (R 3 ) while this value in R1 was simply 56.6 mg protein/g·VSS. More importantly, compared with R 1 , the excess accumulation of propionic acid and butyric acid in system was avoided. The macroscopic galvanic cells around Fe-C micro-electrolysis carriers in R 3 , that larger than microscopic galvanic cells in R 2 , further accelerate to transfer the electrons from anodic Fe to cathodic carbon that enhance interspecies hydrogen transfer, making the decomposition of propionic acid and butyric acid more thermodynamically feasible, finally facilitate more methane production. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Membrane Bioreactor (MBR) as Alternative to a Conventional Activated Sludge System Followed by Ultrafiltration (CAS-UF) for the Treatment of Fischer-Tropsch Reaction Water from Gas-to-Liquids Industries

    Laurinonyte, Judita; Meulepas, Roel J.W.; Brink, van den Paula; Temmink, Hardy

    2017-01-01

    The potential of a membrane bioreactor (MBR) system to treat Fischer-Tropsch (FT) reaction water from gas-to-liquids (GTL) industries was investigated and compared with the current treatment system: a conventional activated sludge system followed by an ultrafiltration (CAS-UF) unit. The MBR and

  5. Short-term global warming mitigation costs of fischer-tropsch diesel production and policy scenarios in Norway

    Bright, Ryan M.; Stroemman, Anders Hammer

    2010-07-01

    Full text: Increasing the supply of advanced biofuels like synthetic diesel produced from woody biomass require attractive investment environments so that novel technologies are deployed and technological learning can lead to reduced production costs and accelerated market diffusion. Technology-specific biofuel policy designed to minimize perceived risk may encourage shortterm investment into those biofuels offering superior environmental benefits - particularly climate mitigation benefits - thereby leading to steeper learning curves and deeper greenhouse gas (GHG) emission cuts over the medium- and long-term horizon. We perform both a Life Cycle Assessment (LCA) and an economic analysis of Fischer-Tropsch diesel (FTD) produced from Norwegian forest biomass at an 'nth' commercial plant (a plant with the same technologies that have been employed in previous commercial plants). This is followed with a cost growth analysis in order to derive production costs likely to be borne by pioneer commercial plants in Norway in the short-term (2016). LCA results are used to calculate shortterm GHG mitigation costs. We then assess, through scenarios, how various policy measures and financial support mechanisms would reduce production costs for incentivizing short-term investment and expediting commercial deployment in Norway. Because 'top-down' or 'market pull' biofuel support policy like excise tax exemptions or carbon taxes do not directly encourage investment into specific biofuel technologies like wood-FTD in the short term, we choose to analyze three 'bottom-up' or 'market push' policy scenarios to assess their effects on reducing levelized unit production costs. These include a Capital Grant, a low-interest Loan Guarantee, a Corporate Tax Credit, and a Feedstock Credit scenario. Under the Capital Grant scenario, we assess the change in levelized production and thus GHG abatement costs when a 50% capital grant (TCI) is

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

    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

  7. Performance of Cobalt-Based Fischer-Tropsch Synthesis Catalysts Using Dielectric-Barrier Discharge Plasma as an Alternative to Thermal Calcination

    Bai Suli; Huang Chengdu; Lv Jing; Li Zhenhua

    2012-01-01

    Co-based catalysts were prepared by using dielectric-barrier discharge (DBD) plasma as an alternative method to conventional thermal calcination. The characterization results of N 2 -physisorption, temperature programmed reduction (TPR), transmission electron microscope (TEM), and X-ray diffraction (XRD) indicated that the catalysts prepared by DBD plasma had a higher specific surface area, lower reduction temperature, smaller particle size and higher cobalt dispersion as compared to calcined catalysts. The DBD plasma method can prevent the sintering and aggregation of active particles on the support due to the decreased treatment time (0.5 h) at lower temperature compared to the longer thermal calcination at higher temperature (at 500° C for 5 h). As a result, the catalytic performance of the Fischer-Tropsch synthesis on DBD plasma treated Co/SiO 2 catalyst showed an enhanced activity, C 5+ selectivity and catalytic stability as compared to the conventional thermal calcined Co/SiO 2 catalyst.

  8. Development of an Innovative XRD-DRIFTS Prototype Allowing Operando Characterizations during Fischer-Tropsch Synthesis over Cobalt-Based Catalysts under Representative Conditions

    Scalbert Julien

    2015-03-01

    Full Text Available An original system combining both X-Ray Diffraction and diffuse reflectance infrared Fourier transform spectroscopy was developed with the aim to characterize Fischer-Tropsch catalysts in relevant reaction conditions. The catalytic properties of a model PtCo/silica catalyst tested with this prototype have shown to be in the same range of those obtained in similar conditions with classical fixed-bed reactors. No bulk cobalt oxidation nor sintering were observed on operando XRD patterns. The formation of linear carbonyls and adsorbed hydrocarbons species at the surface of the catalyst was observed on operando DRIFT spectra. The surface of the catalyst was also suspected to be covered with carbon species inducing unfavorable changes in selectivity.

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

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

    2016-09-01

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

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

    Cronauer, D.C.

    2011-01-01

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

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

    Cronauer, D. C. (Chemical Sciences and Engineering Division)

    2011-04-11

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

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

    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

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

    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) produces FT products that include lesser amounts of n-alkanes and greater alkene, alcohol, and polycyclic aromatic hydrocarbon (PAH) compounds. We have begun to experimentally investigate FT synthesis in the context of abiotic generation of organic compounds in the early solar nebula. It is generally thought that the early solar nebula included abundant hydrogen and carbon monoxide gases and nano-particulate matter such as iron and metal silicates that could have catalyzed the FT reaction. The effect of FT reaction temperature, catalyst type, and experiment duration on the resulting products is being investigated. These solid organic products are analyzed by thermal-stepwise pyrolysis-GCMS and yield the types and distribution of hydrocarbon compounds released as a function of temperature. We show how the FT products vary by reaction temperature, catalyst type, and experimental duration and compare these products to organic compounds found to be indigenous to ordinary chondrite meteorites. We hypothesize that the origin of organics in some chondritic meteorites, that represent an aggregation of materials from the early solar system, may at least in part be from FT synthesis that occurred in the early solar nebula.

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

    Ali, Sardar, E-mail: alikhan-635@yahoo.com [Centralized Analytical Laboratory, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Zabidi, Noor Asmawati Mohd, E-mail: noorasmawati-mzabidi@petronas.com.my [Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Subbarao, Duvvuri, E-mail: duvvuri-subbarao@petronas.com.my [Department of Chemical Engineering, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia)

    2014-10-24

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

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

    Hicks, Yolanda R.; Tacina, M.

    2013-01-01

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

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

    Sartipi, Sina, E-mail: S.Sartipi@tudelft.nl, E-mail: J.Gascon@tudelft.nl; Jansma, Harrie; Bosma, Duco; Boshuizen, Bart; Makkee, Michiel; Gascon, Jorge, E-mail: S.Sartipi@tudelft.nl, E-mail: J.Gascon@tudelft.nl; Kapteijn, Freek [Department of Chemical Engineering, Catalysis Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft (Netherlands)

    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.

  17. Anion-modified zirconia. Effect of metal promotion and hydrogen reduction on hydroisomerization of n-hexadecane and Fischer-Tropsch waxes

    Zhang, S.; Zhang, Y.; Tierney, J.W.; Wender, I. [Department of Chemical and Petroleum Engineering, 1249 Benedum Hall, University of Pittsburgh, 15261 Pittsburgh, PA (United States)

    2001-01-01

    The effect of metal promoters on the activity and selectivity of tungstated zirconia (8 wt.% W) for n-hexadecane isomerization in a trickle bed continuous reactor is studied by using different metals (Pt, Ni, and Pd) and, in one case, by varying metal loading. Platinum is found to be the best promoter. The effect of hydrogen reduction is investigated using platinum-promoted tungstated zirconia catalysts (Pt/WO{sub 3}/ZrO{sub 2}, 0.5 wt.% Pt and 6.5 wt.% W). Pretreatment at temperatures between 300 and 400C for 3 h in hydrogen is found to be slightly beneficial for achieving high yields of isohexadecane. A platinum promoted sulfated zirconia (Pt/SO{sub 4}/ZrO{sub 2}) is compared with a Pt/WO{sub 3}/ZrO{sub 2} catalyst for the hydroisomerization of n-hexadecane in the same reactor at the same n-hexadecane conversion. The former is a good cracking catalyst and the latter is suitable for use as a hydroisomerization catalyst. In a 27-ml microautoclave reactor, studies of the hydroisomerization and hydrocracking of two Fischer-Tropsch (F-T) wax samples are carried out. Severe cracking can be effectively suppressed using a Pt/WO{sub 3}/ZrO{sub 2} catalyst so as to obtain branched isomers in the diesel fuel or lube-base oil range.

  18. Enhanced treatment of Fischer-Tropsch wastewater using up-flow anaerobic sludge blanket system coupled with micro-electrolysis cell: A pilot scale study.

    Wang, Dexin; Han, Yuxing; Han, Hongjun; Li, Kun; Xu, Chunyan

    2017-08-01

    The coupling of micro-electrolysis cell (MEC) with an up-flow anaerobic sludge blanket (UASB) system in pilot scale was established for enhanced treatment of Fischer-Tropsch (F-T) wastewater. The lowest influent pH (4.99±0.10) and reduced alkali addition were accomplished under the assistance of anaerobic effluent recycling of 200% (stage 5). Simultaneously, the optimum COD removal efficiency (93.5±1.6%) and methane production (2.01±0.13m 3 /m 3 ·d) at the lower hydraulic retention time (HRT) were achieved in this stage. In addition, the dissolved iron from MEC could significantly increase the protein content of tightly bound extracellular polymeric substances (TB-EPS), which was beneficial to formation of stable granules. Furthermore, the high-throughput 16S rRNA gene pyrosequencing in this study further confirmed that Geobacter species could utilize iron oxides particles as electron conduit to perform the direct interspecies electron transfer (DIET) with Methanothrix, finally facilitating the syntrophic degradation of propionic acid and butyric acid and contributing completely methane production. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

    Alptekin, Gokhan [TDA Research, Inc., Wheat Ridge, CO (United States)

    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.

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

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

    2011-01-01

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

  1. Preparation for Pt-Loaded Zeolite Catalysts Using w/o Microemulsion and Their Hydrocracking Behaviors on Fischer-Tropsch Product

    Toshiaki Hanaoka

    2015-02-01

    Full Text Available Pt-loaded β-type zeolite catalysts with constant Pt content (0.11 wt.% and similar pore structure were prepared using a water-in-oil (w/o microemulsion. The effect of Pt particle synthesis conditions using microemulsion (a type of Pt complex-forming agents and the molar ratio of complex-forming agent to Pt4+ on loaded Pt particle size was investigated. The Pt particle size of the Pt catalyst using tetraethylammonium chloride (TEAC as a complex-forming agent with the molar TEAC/Pt ratio 10 was the minimum value (3.8 nm, and was much smaller than that (6.7 nm prepared by the impregnation method. The utilization of the complex-forming agent of which hydrophobic groups occupied a small volume and the appropriate complex-forming agent/Pt ratio were favorable for synthesis of small Pt particles. The effect of loaded Pt particle size on the hydrocracking of the Fischer-Tropsch (FT product was investigated using the Pt-loaded zeolite catalysts at 250 °C with an initial H2 pressure of 0.5 MPa, and reaction time of 1 h. The Pt catalyst with a Pt particle size of 4.2 nm prepared using the microemulsion exhibited the maximum corresponding jet fuel yield (30.0%, which was higher than that of the impregnated catalyst.

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

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

    2013-01-01

    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

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

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

    2015-01-01

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

  4. A general chelate-assisted co-assembly to metallic nanoparticles-incorporated ordered mesoporous carbon catalysts for Fischer-Tropsch synthesis.

    Sun, Zhenkun; Sun, Bo; Qiao, Minghua; Wei, Jing; Yue, Qin; Wang, Chun; Deng, Yonghui; Kaliaguine, Serge; Zhao, Dongyuan

    2012-10-24

    The organization of different nano objects with tunable sizes, morphologies, and functions into integrated nanostructures is critical to the development of novel nanosystems that display high performances in sensing, catalysis, and so on. Herein, using acetylacetone as a chelating agent, phenolic resol as a carbon source, metal nitrates as metal sources, and amphiphilic copolymers as a template, we demonstrate a chelate-assisted multicomponent coassembly method to synthesize ordered mesoporous carbon with uniform metal-containing nanoparticles. The obtained nanocomposites have a 2-D hexagonally arranged pore structure, uniform pore size (~4.0 nm), high surface area (~500 m(2)/g), moderate pore volume (~0.30 cm(3)/g), uniform and highly dispersed Fe(2)O(3) nanoparticles, and constant Fe(2)O(3) contents around 10 wt %. By adjusting acetylacetone amount, the size of Fe(2)O(3) nanoparticles is readily tunable from 8.3 to 22.1 nm. More importantly, it is found that the metal-containing nanoparticles are partially embedded in the carbon framework with the remaining part exposed in the mesopore channels. This unique semiexposure structure not only provides an excellent confinement effect and exposed surface for catalysis but also helps to tightly trap the nanoparticles and prevent aggregating during catalysis. Fischer-Tropsch synthesis results show that as the size of iron nanoparticles decreases, the mesoporous Fe-carbon nanocomposites exhibit significantly improved catalytic performances with C(5+) selectivity up to 68%, much better than any reported promoter-free Fe-based catalysts due to the unique semiexposure morphology of metal-containing nanoparticles confined in the mesoporous carbon matrix.

  5. A novel water perm-selective membrane dual-type reactor concept for Fischer-Tropsch synthesis of GTL (gas to liquid) technology

    Rahimpour, M.R.; Mirvakili, A.; Paymooni, K.

    2011-01-01

    The present study proposes a novel configuration of Fischer-Tropsch synthesis (FTS) reactors in which a fixed-bed water perm-selective membrane reactor is followed by a fluidized-bed hydrogen perm-selective membrane reactor. This novel concept which has been named fixed-bed membrane reactor followed by fluidized-bed membrane reactor (FMFMDR) produces gasoline from synthesis gas. The walls of the tubes of a fixed-bed reactor (water-cooled reactor) of FMFMDR configuration are coated by a high water perm-selective membrane layer. In this new configuration, two membrane reactors instead of one membrane reactor are developed for FTS reactions. In other words, two different membrane layers are used. In order to investigate the performance of FMFMDR, a one-dimensional heterogeneous model is taken into consideration. The simulation results of three schemes named fluidized-bed membrane dual-type reactor (FMDR), FMFMDR and conventional fixed-bed reactor (CR) are presented. They have been compared in terms of temperature, gasoline and CO 2 yields, H 2 and CO conversions and the water permeation rate through the membrane layer. Results show that the gasoline yield in FMFMDR is higher than the one in FMDR. The FMFMDR configuration not only decreases the undesired product such as CO 2 but also produces more gasoline. -- Research highlights: → The application of H-SOD membrane layer in FTS reactors. → Approximate 7.5% and 37% increase in the gasoline yield in terms of [g/g feed x 100] in comparison with FMDR and CR, respectively. → A remarkable decrease in CO 2 emission to the environment. → A good configuration mainly due to reduction in catalysts sintering as a result of in situ water removal.

  6. Reductions in greenhouse gas emissions and oil use by DME (di-methyl ether) and FT (Fischer-Tropsch) diesel production in chemical pulp mills

    Joelsson, Jonas M.; Gustavsson, Leif

    2012-01-01

    Using energy systems analysis, we examine the potential to reduce CO 2 emissions and oil use by integrating motor biofuel production with pulp mills. BLG-DME (black liquor gasification with di-methyl ether production) is compared with solid biomass gasification with BIG-FT (solid biomass gasification with Fischer-Tropsch fuel production). The studied systems are expanded with stand-alone production of biomass-based electricity and motor fuel so that they yield the same functional unit in terms of motor fuel and electricity as well as pulp or paper product, in order to facilitate comparison. More motor biofuel can be produced in integration with the studied mills with BLG-DME than with BIG-FT because the black liquor flow is large compared with other fuel streams in the mill and the integration potential for BIG-FT is limited by the mill’s heat demand. When both systems are required to produce the same functional unit, the BLG-DME system achieves higher system efficiency and larger reductions in CO 2 emissions and oil use per unit of biomass consumed. In general, integration of motor biofuel production with a pulp mill is more efficient than stand-alone motor biofuel production. Larger reductions in CO 2 emissions or oil use can, however, be achieved if biomass replaces coal or oil in stationary applications. -- Highlights: ► CO 2 emission and oil use reductions quantified for pulp mill-based biorefineries. ► Black liquor gasification gives larger reductions than solid biomass gasification. ► Lower mill steam demand increases the black liquor gasification advantage. ► Biomass directly replacing coal or oil in stationary plants gives larger reductions.

  7. Reductions in greenhouse gas emissions and oil use by DME (di-methyl ether) and FT (Fischer-Tropsch) diesel production in chemical pulp mills

    Joelsson, Jonas M., E-mail: joelsson.jonas@hotmail.com [Ecotechnology and Environmental Science, Mid Sweden University, SE-831 25 Oestersund (Sweden); Gustavsson, Leif [Linnaeus University, SE- 351 95 Vaexjoe (Sweden)

    2012-03-15

    Using energy systems analysis, we examine the potential to reduce CO{sub 2} emissions and oil use by integrating motor biofuel production with pulp mills. BLG-DME (black liquor gasification with di-methyl ether production) is compared with solid biomass gasification with BIG-FT (solid biomass gasification with Fischer-Tropsch fuel production). The studied systems are expanded with stand-alone production of biomass-based electricity and motor fuel so that they yield the same functional unit in terms of motor fuel and electricity as well as pulp or paper product, in order to facilitate comparison. More motor biofuel can be produced in integration with the studied mills with BLG-DME than with BIG-FT because the black liquor flow is large compared with other fuel streams in the mill and the integration potential for BIG-FT is limited by the mill's heat demand. When both systems are required to produce the same functional unit, the BLG-DME system achieves higher system efficiency and larger reductions in CO{sub 2} emissions and oil use per unit of biomass consumed. In general, integration of motor biofuel production with a pulp mill is more efficient than stand-alone motor biofuel production. Larger reductions in CO{sub 2} emissions or oil use can, however, be achieved if biomass replaces coal or oil in stationary applications. -- Highlights: Black-Right-Pointing-Pointer CO{sub 2} emission and oil use reductions quantified for pulp mill-based biorefineries. Black-Right-Pointing-Pointer Black liquor gasification gives larger reductions than solid biomass gasification. Black-Right-Pointing-Pointer Lower mill steam demand increases the black liquor gasification advantage. Black-Right-Pointing-Pointer Biomass directly replacing coal or oil in stationary plants gives larger reductions.

  8. Effect of CO{sub 2} and H{sub 2}O content in syngas on activity and selectivity of a cobalt based Fischer-Tropsch synthesis catalyst

    Poehlmann, F.; Kaiser, P.; Kern, C.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering

    2013-11-01

    When liquid hydrocarbons are to be used as CO{sub 2} neutral storage media for electrical energy, it is necessary to convert CO{sub 2} from e.g. flue gas and hydrogen from water electrolysis to synthesis gas (CO/H{sub 2}). This can be achieved by a high temperature reverse water gas shift (RWGS) reaction. Due to thermodynamic limitations, the product gas of RWGS reactors operated at technically feasible temperatures of around 900 C will always contain significant amounts of water and carbon dioxide, which can influence the activity of Fischer-Tropsch synthesis (FTS) catalysts for the actual hydrocarbon production. In this study, a commercial cobalt catalyst was investigated under low temperature FTS conditions (2.5 MPa, 215 C) regard to activity and selectivity in the presence of H{sub 2}O and CO{sub 2}. A continuous flow apparatus including a fixed-bed reactor for the synthesis step was used to conduct all experiments. The experimental data reveals that the CO/CO{sub 2}-ratio does not affect the activity and product selectivity until the CO{sub 2}-concentration reaches 75 vol.-% (CO{sub 2}/(CO+CO{sub 2})). On increasing the carbon dioxide concentration to 100 vol.-% (H{sub 2}/CO{sub 2} = 2), the methane selectivity rose up to 70 % and even above. Addition of water caused an initial loss of activity. After the initial loss of activity the FT catalyst activity was found to remain constant, irrespectively of if the water was removed from the feed or not. Thus, the deactivation was permanent. (orig.)

  9. Influence of oxalate ligand functionalization on Co/ZSM-5 activity in Fischer Tropsch synthesis and hydrodeoxygenation of oleic acid into hydrocarbon fuels.

    Ayodele, Olumide Bolarinwa

    2017-08-30

    Achieving high degree of active metal dispersions at the highest possible metal loading and high reducibility of the metal remains a challenge in Fischer Tropsch synthesis (FTS) as well as in hydrogeoxygenation (HDO).This study therefore reports the influence of oxalic acid (OxA) functionalization on the metal dispersion, reducibility and activity of Co supported ZSM-5 catalyst in FTS and HDO of oleic acid into paraffin biofuel. The Brunauer-Emmett-Teller (BET) results showed that cobalt oxalate supported ZSM-5 catalyst (CoOx/ZSM-5) synthesized from the incorporation of freshly prepared cobalt oxalate complex into ZSM-5 displayed increase in surface area, pore volume and average pore size while the nonfunctionalized cobalt supported on ZSM-5 (Co/ZSM-5) catalyst showed reduction in those properties. Furthermore, both XRD and XPS confirmed the presence of Co° formed from the decomposition of CoOx during calcination of CoOx/ZSM-5 under inert atmosphere. The HRTEM showed that Co species average particle sizes were smaller in CoOx/ZSM-5 than in Co/ZSM-5, and in addition, CoOx/ZSM-5 shows a clear higher degree of active metal dispersion. The FTS result showed that at CO conversion over Co/ZSM-5 and CoOx/ZSM-5 catalysts were 74.28% and 94.23% and their selectivity to C 5+ HC production were 63.15% and 75.4%, respectively at 4 h TOS. The HDO result also showed that the CoOx/ZSM-5 has higher OA conversion of 92% compared to 59% over Co/ZSM-5. In addition CoOx/ZSM-5 showed higher HDO and isomerization activities compared to Co/ZSM-5.

  10. Comparative electrophysiological evaluation of hippocampal function following repeated inhalation exposures to JP-8, Jet A, JP-5, and the synthetic Fischer Tropsch fuel.

    Rohan, Joyce G; McInturf, Shawn M; Miklasevich, Molly K; Gut, Chester P; Grimm, Michael D; Reboulet, James E; Howard, William R; Mumy, Karen L

    2018-01-01

    Exposure to fuels continues to be a concern in both military and general populations. The aim of this study was to examine effects of in vivo rat repeated exposures to different types of jet fuel utilizing microelectrode arrays for comparative electrophysiological (EP) measurements in hippocampal slices. Animals were exposed to increasing concentrations of four jet fuels, Jet Propellant (JP)-8, Jet A, JP-5, or synthetic Fischer Tropsch (FT) fuel via whole-body inhalation for 20 d (6 hr/d, 5 d/week for 28 d) and synaptic transmission as well as behavioral performance were assessed. Our behavioral studies indicated no significant changes in behavioral performance in animals exposed to JP-8, Jet A, or JP-5. A significant deviation in learning pattern during the Morris water maze task was observed in rats exposed to the highest concentration of FT (2000 mg/m 3 ). There were also significant differences in the EP profile of hippocampal neurons from animals exposed to JP-8, Jet A, JP-5, or FT compared to control air. However, these differences were not consistent across fuels or dose dependent. As expected, patterns of EP alterations in brain slices from JP-8 and Jet A exposures were more similar compared to those from JP-5 and FT. Further longitudinal investigations are needed to determine if these EP effects are transient or persistent. Such studies may dictate if and how one may use EP measurements to indicate potential susceptibility to neurological impairments, particularly those that result from inhalation exposure to chemicals or mixtures.

  11. Carbon-14 studies on the role of oxygen-containing compounds in the reaction mechanism of the Fischer-Tropsch synthesis

    Aksoy, H.A.

    1975-01-01

    In this work the behaviour of organic oxygen compounds has been studied in the reaction mechanism of Fischer-Tropsch synthesis using the tracer method. As an oxygen carrying tracer materials i-propanole (2- 14 C), acetone (2- 14 C) and ethanole (1- 14 C) have been added to the synthesis gas. The synthesis experiments are performed under standard conditions: The synthesis products are separated in suitable fractions and then studied by gas- and radio-gaschromatography. As a result the C-number distributions of the synthesis products are obtained as a function of concentration (weight %, mol %) and radioactivity (activity %). On this basis the relative molar activities have been calculated for certain compounds and fractions. Adding i-propanole- 14 C a great part of the tracer compound is transformed to acetone- 14 C, however adding acetone- 14 C to the synthesis gas a large amount of i-propanole- 14 C is produced. The main hydrocarbon reaction product from i-propanol and acetone is propane. Besides propane also propene is produced with equal molar radioactivity. This indicates that the formation of adsorbed oxygen compounds, as they may also be produced by chemisorption from alcohols or carbonyle compounds, is the first step in the formation of hydrocarbons by hydrogenolytic separation of oxygen. Comparing the results obtained with ethanole- 14 C and i-propanole- 14 C as a tacer material, for ethane an essentially lower molar activity is obtained when adding ethanole- 14 C compared with propane when adding i-propanole- 14 C. This corresponds with a particularly low desorption probability at the C 2 -hydrocarbon level. (orig./HK) [de

  12. Effect of CO Concentration on the α-Value of Plasma-Synthesized Co/C Catalyst in Fischer-Tropsch Synthesis

    James Aluha

    2017-02-01

    Full Text Available A plasma-synthesized cobalt catalyst supported on carbon (Co/C was tested for Fischer-Tropsch synthesis (FTS in a 3-phase continuously-stirred tank slurry reactor (3-φ-CSTSR operated isothermally at 220 °C (493 K, and 2 MPa pressure. Initial syngas feed stream of H2:CO ratio = 2 with molar composition of 0.6 L/L (60 vol % H2 and 0.3 L/L (30 vol % CO, balanced in 0.1 L/L (10 vol % Ar was used, flowing at hourly space velocity (GHSV of 3600 cm3·h−1·g−1 of catalyst. Similarly, other syngas feed compositions of H2:CO ratio = 1.5 and 1.0 were used. Results showed ~40% CO conversion with early catalyst selectivity inclined towards formation of gasoline (C4–C12 and diesel (C13–C20 fractions. With prolonged time-on-stream (TOS, catalyst selectivity escalated towards the heavier molecular-weight fractions such as waxes (C21+. The catalyst’s α-value, which signifies the probability of the hydrocarbon chain growth was empirically determined to be in the range of 0.85–0.87 (at H2:CO ratio = 2, demonstrating prevalence of the hydrocarbon-chain propagation, with particular predisposition for wax production. The inhibiting CO effect towards FTS was noted at molar H2:CO ratio of 1.0 and 1.5, giving only ~10% and ~20% CO conversion respectively, although with a high α-value of 0.93 in both cases, which showed predominant production of the heavier molecular weight fractions.

  13. Modeling and optimization of Fischer-Tropsch synthesis over Co-Mn-Ce/SiO_2 catalyst using hybrid RSM/LHHW approaches

    Zohdi-Fasaei, Hossein; Atashi, Hossein; Farshchi Tabrizi, Farshad; Mirzaei, Ali Akbar

    2017-01-01

    Operating conditions considerably affect the energy required for Fischer-Tropsch synthesis, depending on the catalyst composition and reactor type (catalyst system). This paper reports the use of cobalt-manganese-cerium supported on silica as a novel CO hydrogenation catalyst, to produce hydrocarbons in a fixed bed micro-reactor. Response surface methodology (RSM) was applied to study the effects of temperature, pressure, feed ratio and their interactions on CO consumption rate, and the selectivity of light olefins (light olefinity), methane and C_5_+ hydrocarbons. Quadratic mathematical models adequately described the responses in this catalyst system. According to Langmuir Hinshelwood Hougen Watson (LHHW) approach, kinetic mechanism of the reaction was found to be an associative adsorption of H_2 and CO. Statistical analysis demonstrated that pressure and feed ratio were the most important factors for the production of C_5_+ and light alkenes, respectively. Model graphs indicated that minimum methane selectivity was achieved at 523.15 k and 2 bar. The maximum amounts of light olefins and heavier hydrocarbons were obtained at H_2/CO = 1 and H_2/CO = 2, respectively. Characterization of precursor and calcined catalyst (before and after the reaction) was carried out using SEM and BET techniques. - Highlights: • The performance of a new catalytic system was studied using RSM as a research plan. • Interactions between significant factors were investigated using mathematical models. • Based on LHHW approach, kinetic mechanism was molecular adsorptions of H_2 and CO. • RSM rate expression was in consistent with the LHHW kinetic model. • Hybrid RSM/LHHW is promising for optimization, mechanism and selectivity studies.

  14. Method for customizing an organic Rankine cycle to a complex heat source for efficient energy conversion, demonstrated on a Fischer Tropsch plant

    DiGenova, Kevin J.; Botros, Barbara B.; Brisson, J.G.

    2013-01-01

    Highlights: ► Methods for customizing organic Rankine cycles are proposed. ► A set of cycle modifications help to target available heat sources. ► Heat sources with complex temperature–enthalpy profiles can be matched. ► Significant efficiency improvements can be achieved over basic ORC’s. -- Abstract: Organic Rankine cycles (ORCs) provide an alternative to traditional steam Rankine cycles for the conversion of low grade heat sources into power, where conventional steam power cycles are known to be inefficient. A large processing plant often has multiple low temperature waste heat streams available for conversion to electricity by a low temperature cycle, resulting in a composite heat source with a complex temperature–enthalpy profile. This work presents a set of ORC design concepts: reheat stages, multiple pressure levels, and balanced recuperators; and demonstrates the use of these design concepts as building blocks to create a customized cycle that matches an available heat source. Organic fluids are modeled using a pure substance database. The pinch analysis technique of forming composite curves is applied to analyze the effect of each building block on the temperature–enthalpy profile of the ORC heat requirement. The customized cycle is demonstrated on a heat source derived from a Fischer Tropsch reactor and its associated processes. Analysis shows a steam Rankine cycle can achieve a 20.6% conversion efficiency for this heat source, whereas a simple organic Rankine cycle using hexane as the working fluid can achieve a 20.9% conversion efficiency. If the ORC building blocks are combined into a cycle targeted to match the temperature–enthalpy profile of the heat source, this customized ORC can achieve 28.5% conversion efficiency.

  15. Synthetic gasoline and diesel oil produced by Fischer-Tropsch Technology. A possibility for the future? IEA/AMF annex XXXI

    Rehnlund, B., (Atrax Energy AB, Goeteborg (SE)); Blinge, M., (The Swedish Transport Research Institute, TFK (SE)); Schramm, J.; Larsen, Ulrik, (Technical Univ. of Denmark, DTU, Kgs. Lyngby (DK))

    2007-03-15

    This report is the result of an annex (annex XXXI, Fischer-Tropsch Fuels) initiated by the International Energy Agency's Implementing Agreement on Advanced Motor Fuels. The annex has been managed by Atrax Energi AB, Bjorn Rehnlund, acting as the operating agent of the annex. The work in the annex has been carried out in co-operation with the Swedish Transportation Research Institute - TFK, Magnus Blinge and the Technical University of Denmark - DTU, Jesper Schramm and Ulrik Larsen. In this report the possibilities to produce synthetic gasoline and synthetic diesel oil from biomass, and also from natural gas, by Fischer-Tropsch (FT) Technology are analysed and discussed. After an introduction of the technology as such, environmental aspects and the life cycle perspective of synthetic gasoline and diesel oil are discussed, and some possible national/regional scenarios are analysed and presented. Vehicle emission tests with synthetic gasoline carried out at DTU are described and discussed in this report as well. Based on the result of the analysis and the vehicle emission tests presented in the report, a first SWOT analysis of Fischer-Tropsch technology is then presented, and finally some main conclusions are drawn. During the execution of the annex Sasol in South Africa, Nykomb Synergetics in Sweden, Chemrec in Sweden, the Technical University of Denmark, VTT in Finland, the Varnamo gasification research project in Sweden, and the Black liquor gasification project in Pitea, Sweden have been visited. Some of the most important conclusions are that: 1) FT-Fuels such as FT-Diesel (FTD) and FT-Gasoline (FTG) produced through CoalTo-Liquid, (CTL), Gas-To-Liquid (GTL) and Biomass-To-Liquid (BTL) technologies can contribute to reducing the dependency on crude oil. 2) FTD and FTG are attractive for use in neat form and also as components in blends with low quality diesel and gasoline, to upgrade fuels to meet the ever more stringent regulations. 3) Production and use of

  16. Extension of the Single-Event Methodology to Metal Catalysis: Application to Fischer-Tropsch Synthesis Extension de la méthodologie des événements constitutifs à la catalyse métallique : Application à la synthèse Fischer-Tropsch

    Lozano-Blanco G.

    2010-10-01

    Full Text Available The single-event methodology has been extended to metal catalysis using Fischer-Tropsch synthesis on an iron-based catalyst as case study. The reaction mechanism has been assessed in terms of elementary steps that could be categorized in reaction families such as reductive elimination, β-hydride elimination and methylene insertion. A computer code has been developed for the generation of the reaction network containing these elementary steps. The representation of reacting and intermediate species explicitly takes into account metal-carbon bonds as well as the presence of oxygen. The model has been validated using iron-based catalytic data at 623 K, 0.6 to 2.1 MPa, inlet molar H2/CO ratio between 2 and 6. 14 parameters, among which 10 activation energies and 4 atomic chemisorption enthalpies have been adjusted to the experimental data. Experimentally observed trends in alkane and 1-alkene product yields with the carbon number were adequately reproduced as well as the individual molar yields of the non-hydrocarbon products. La méthodologie par événements constitutifs a été étendue à la catalyse métallique en utilisant la synthèse Fischer-Tropsch sur un catalyseur au fer comme cas d'étude. Le mécanisme réactionnel a été décomposé en étapes élémentaires qui peuvent être classées par type de réactions, telles que l'élimination réductrice, l'élimination d'hydrure en β, et l'insertion de groupe méthylène. Un code de calcul a été développé pour générer le réseau réactionnel impliquant ces étapes élémentaires. La représentation des réactifs et des espèces intermédiaires prend en compte explicitement les liaisons carbone-métal et inclut la présence d'atomes d'oxygène. Le modèle a été validé sur une base de données obtenues sur un catalyseur à base de fer à 623 K, sur une plage de 0,6 à 2,1 MPa, un ratio H2/CO en entrée variant de 2 à 6. Quatorze paramètres, dont 10 énergies d'activation et 4

  17. 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

    Warringham, Robbie; McFarlane, Andrew R.; Lennon, David, E-mail: David.Lennon@Glasgow.ac.uk [School of Chemistry, University of Glasgow, Joseph Black Building, Glasgow, Scotland G12 8QQ (United Kingdom); MacLaren, Donald A. [School of Physics and Astronomy, University of Glasgow, The Kelvin Building, Glasgow, Scotland G12 8QQ (United Kingdom); Webb, Paul B.; Tooze, Robert P. [Sasol Technology UK Ltd., Purdie Building, North Haugh, St Andrews, Fife KY16 9ST (United Kingdom); Taylor, Jon; Ewings, Russell A.; Parker, Stewart F. [ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX (United Kingdom)

    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.

  18. 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

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

    2015-01-01

    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-Fe 2 O 3 ) 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

  19. Synthesis of Hydrocarbons from H2-Deficient Syngas in Fischer-Tropsch Synthesis over Co-Based Catalyst Coupled with Fe-Based Catalyst as Water-Gas Shift Reaction

    Ting Ma

    2015-01-01

    Full Text Available The effects of metal species in an Fe-based catalyst on structural properties were investigated through the synthesis of Fe-based catalysts containing various metal species such, as Mn, Zr, and Ce. The addition of the metal species to the Fe-based catalyst resulted in high dispersions of the Fe species and high surface areas due to the formation of mesoporous voids about 2–4 nm surrounded by the catalyst particles. The metal-added Fe-based catalysts were employed together with Co-loaded beta zeolite for the synthesis of hydrocarbons from syngas with a lower H2/CO ratio of 1 than the stoichiometric H2/CO ratio of 2 for the Fischer-Tropsch synthesis (FTS. Among the catalysts, the Mn-added Fe-based catalyst exhibited a high activity for the water-gas shift (WGS reaction with a comparative durability, leading to the enhancement of the CO hydrogenation in the FTS in comparison with Co-loaded beta zeolite alone. Furthermore, the loading of Pd on the Mn-added Fe-based catalyst enhanced the catalytic durability due to the hydrogenation of carbonaceous species by the hydrogen activated over Pd.

  20. 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

    Jacobs, G.; Chaney, J.A.; Patterson, P.M.; Das, T.K.; Maillot, J.C.; Davis, B.H.

    2004-01-01

    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 Co 3 O 4 to CoO and CoO to Co 0 . 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 L III 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. (orig.)

  1. Upgrading of Visbreaker Naphtha

    Stratiev, D.; Argirov, G.; Tzingov, T. [Research and Development Dept., Lukoil Neftochim Bourgas, Bourgas (Bulgaria); Minkov, D. [Bourgas ' ' Assen Zlatarov' ' , Bourgas (Bulgaria)

    2006-10-15

    This work investigates the feasibility of hydrotreatment of mixtures of straight run naphtha (SRN), visbreaker naphtha (VBN) and naphtha from a middle distillate hydrotreating unit (MDHN). Hydrotreating experiments were carried out in a trickle bed pilot reactor charged with Albermarle KF 752-3Q Co-Mo catalyst under the following conditions: reactor inlet temperature (RIT) of 290 C; total reactor pressure of 3.5 MPa; liquid hourly space velocity (LHSV) in the range 1-2 hr{sup -1}; treating gas/oil ratio of 300 Nm{sup 3}/m{sup 3}. The treating gas purity was 99 mole.% hydrogen. It was found that under the conditions studied the degree of hydrogenation of feedstock olefins was about 98% and reactor {delta}T showed a linear relationship with the feedstock olefins content. It was estimated that the metallurgical material limitation of 420 C in a commercial hydrotreating reactor could be reached at 90% of VBN in the feedstock mixture and 290 C reactor inlet temperature. The hydrogenate obtained by hydrotreatment of light VBN (final boiling point of 122 C) is suitable as a feedstock for pyrolysis, since it has a low content of aromatics and naphthenes (the characteristic index of 2A + N amounts to 33.2). The hydrogenate obtained by hydrotreatment of full range VBN (final boiling point of 205 C) is suitable as a feedstock for reforming since its characteristic index of 2A + N of 57.6 is close to that of SRN (2A + N = 55.8), which is a typical reformer feedstock. The highest characteristic index of 2A + N = 74 was displayed by MDHN. (orig.)

  2. Fe3O4 nanocubes assembled on RGO nanosheets: Ultrasound induced in-situ and eco-friendly synthesis, characterization and their excellent catalytic performance for the production of liquid fuel in Fischer-tropsch synthesis.

    Abbas, Mohamed; Zhang, Juan; Lin, Ke; Chen, Jiangang

    2018-04-01

    In this study, Fe 3 O 4 nanocubes (NCs) decorated on RGO nanosheets (NSs) structures were successfully synthesized through an innovative and environmentally-friendly rapid sonochemical method. More importantly, iron(II) sulfate heptahydrate and GO were employed as precursors and water as reaction medium, meanwhile, NaOH within the generated free radicals from the high intensity ultrasound were sufficient as reducing and base agent in our clean synthesis. Moreover, the hydrothermal method as a conventional approach was employed to synthesize the same catalysts for the comparison with the ultrasonocation technique. The as-synthesized Fe 3 O 4 and RGO/Fe 3 O 4 NSs catalysts were exposed to industrially relevant Fischer-tropsch synthesis (FTS) conditions at various reaction temperatures (250-290 °C), and they subjected to fully characterization before and after FTS reaction using XRD, TEM, HRTEM, EDS mapping, XPS, FTIR, BET, H 2 -TPR, H 2 -TPD and CO-TPD to understand the structure-performance relationships. Notably, the catalysts produced using the sonochemical method had a better CO conversion rate [Fe 3 O 4 (80%), RGO/Fe 3 O 4 (82%)] than the hydrothermally synthesized catalysts. However, compared to the naked-Fe 3 O 4 catalysts, the sonochemically and hydrothermally synthesized RGO-supported Fe 3 O 4 catalysts had higher long chain hydrocarbon (C5+) selectivity values (72% and 67%) and C 2 -C 4 olefin/paraffin selectivity ratio (3.2 and 2) and low CH4 selectivity values (6% and 8.5%), respectively. This can be attributed to their high surface area, the degree of reducibility, and content of Hägg iron carbide (χ-Fe 5 C 2 ) as the most active phase of the FTS reaction. Proposed reaction mechanisms for the sonochemical and hydrothermal reaction synthesis of Fe 3 O 4 and RGO/Fe 3 O 4 nanoparticles are discussed. In conclusion, our developed surfactantless-sonochemical method holds promise for the eco-friendly synthesis of highly efficient catalysts materials for

  3. Fischer-Tropsch synthesis: Support and cobalt cluster size effects on kinetics over Co/Al{sub 2}O{sub 3} and Co/SiO{sub 2} catalysts

    Wenping Ma; Gary Jacobs; Dennis E. Sparks; Muthu K. Gnanamani; Venkat Ramana Rao Pendyala; Chia H. Yen; Jennifer L.S. Klettlinger; Thomas M. Tomsik; Burtron H. Davis [University of Kentucky, Lexington, KY (USA). Center for Applied Energy Research

    2011-02-15

    The influence of support type and cobalt cluster size (i.e., with average diameters falling within the range of 8-40 nm) on the kinetics of Fischer-Tropsch synthesis (FT) were investigated by kinetic tests employing a CSTR and two Co/{gamma}-Al{sub 2}O{sub 3} catalysts having different average pore sizes, and two Co/SiO{sub 2} catalysts prepared on the same support but having different loadings. A kinetic model -r{sub CO}=kP{sup a}{sub co}P{sup b}{sub H2}/(1 + mP{sub H2O}/P{sub H2}) that contains a water effect constant 'm' was used to fit the experimental data obtained with all four catalysts. Kinetic parameters suggest that both support type and average Co particle size impact FT behavior. Cobalt cluster size influenced kinetic parameters such as reaction order, rate constant, and the water effect parameter.Decreasing the average Co cluster diameter by about 30% led to an increase in the intrinsic reaction rate constant k, defined on a per g of catalyst basis, by 62-102% for the {gamma}-Al{sub 2}O{sub 3} and SiO{sub 2}-supported cobalt catalysts. Moreover, less inhibition by adsorbed CO and greater H{sub 2} dissociation on catalysts having smaller Co particles was suggested by the higher a and lower b values obtained for the measured reaction orders. Irrespective of support type, the catalysts having smaller average Co particles were more sensitive to water. Comparing the catalysts having strong interactions between cobalt and support (Co/Al{sub 2}O{sub 3}) to the ones with weak interactions (Co/SiO{sub 2}), the water effect parameters were found to be positive (indicating a negative influence on CO conversion) and negative (denoting a positive effect on CO conversion), respectively. Greater a and a/b values were observed for both Al{sub 2}O{sub 3}-supported Co catalysts, implying greater inhibition of the FT rate by strongly adsorbed CO on Co/Al{sub 2}O{sub 3} relative to Co/SiO{sub 2}. 78 refs., 4 figs., 3 tabs.

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

    Johnson, Gregory R.; Werner, Sebastian; Bell, Alexis T. (LBNL); (UCB)

    2016-03-04

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

  5. Improved Fischer-Tropsch Slurry Reactors

    Lucero, Andrew

    2009-01-01

    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. PowerEnerCat was unable to raise their cash contribution for the project, and the work was stopped. This report summarizes some of the progress of the project and the concepts that were intended for experimental tests.

  6. Fischer-Tropsch synthesis : catalysts and chemistry

    Loosdrecht, van de J.; Botes, F.G.; Ciobica, I.M.; Ferreira, A.C.; Gibson, P.; Moodley, D.J.; Saib, A.M.; Visagie, J.L.; Weststrate, C.J.; Niemantsverdriet, J.W.; Reedijk, J.; Poeppelmeier, K.

    2013-01-01

    The Fischer–Tropsch synthesis represents a time-tested and fully proven technology for the conversion of synthesis gas (CO + H2) into paraffins, olefins, and oxygenated hydrocarbons. Depending on the origin of the syngas, one speaks of gas-to-liquids, coal-to-liquids, biomass-to-liquids, or

  7. Cerium promoted Fischer-Tropsch catalysts

    Fiato, R.A.; Bar-Gadda, R.; Miseo, S.

    1987-01-01

    This patent describes a hydrocarbon synthesis catalyst composition comprising sintered combination metal oxides having the following components in the stated weight percentage of the catalyst composition: (a) about 5 to about 80 weight percent Fe oxide; (b) about 4 to about 20 weight percent Zn oxide; (c) about 10 to about 40 weight percent Ti and/or Mn oxide; (d) about 1 to about 5 weight percent K, Rb, and/or Cs oxide; and (e) about 1 to about 10 weight percent Ce oxide, such that where the catalyst contains Fe, the sintered combination comprises a series of Fe, Zn, and/or Ti and/or Mn spinels and oxides of K, Rb and/or Cs, dispersed in a Ce oxide matrix

  8. Fischer-Tropsch Slurry Reactor modeling

    Soong, Y.; Gamwo, I.K.; Harke, F.W. [Pittsburgh Energy Technology Center, PA (United States)] [and others

    1995-12-31

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

  9. Novel inorganic precursors [Co.sub.4.32./sub.Zn.sub.1.68./sub.(HCO.sub.2./sub.).sub.18./sub.(C.sub.2./sub.H.sub.8./sub.N).sub.6./sub.]/SiO.sub.2./sub. and Co.sub.4.32./sub.Zn.sub.1.68./sub.(HCO2).sub.18./sub.(C.sub.2./sub.H.sub.8./sub.N).sub.6./sub.]/Al.sub.2./sub.O.sub.3./sub. for Fischer-Tropsch synthesis

    Saheli, S.; Rezvani, A.R.; Malekzadeh, A.; Dušek, Michal; Eigner, Václav

    2018-01-01

    Roč. 43, č. 2 (2018), s. 685-694 ISSN 0360-3199 R&D Projects: GA ČR(CZ) GA15-12653S; GA MŠk(CZ) LO1603 EU Projects: European Commission(CZ) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : Fischer-Tropsch synthesis * coordination polymers * inorganic precursor * impregnation * catalytic performance Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 3.582, year: 2016

  10. 21 CFR 172.250 - Petroleum naphtha.

    2010-04-01

    ... naphtha is used or intended for use as a solvent in protective coatings on fresh citrus fruit in... CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Coatings...-oxidation, the entire procedure is to be carried out under subdued light. apparatus Separatory funnels. 250...

  11. Peripheral neuropathy following intentional inhalation of naphtha fumes.

    Tenenbein, M; deGroot, W; Rajani, K R

    1984-01-01

    Two adolescent native Canadians who presented with peripheral neuropathy secondary to the abuse of volatile hydrocarbons are described. They were initially thought to have been sniffing leaded gasoline fumes, but public health investigation revealed that they had been sniffing naphtha fumes. Naphtha contains a significant amount of n-hexane, a known inducer of neuropathy. Nerve conduction studies and nerve biopsy confirmed the diagnosis of naphtha abuse. These cases emphasize the need to specifically identify the formulation of hydrocarbons being abused. PMID:6093978

  12. A study on naphtha catalytic reforming reactor simulation and analysis.

    Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei

    2005-06-01

    A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation unit data.

  13. A study on naphtha catalytic reforming reactor simulation and analysis

    Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei

    2005-01-01

    A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation uni...

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

    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.

  15. Attrition resistant Fischer-Tropsch catalyst and support

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

    2004-05-25

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

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

    Adeyiga, Adeyinka

    2010-02-05

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

  17. Steam cracking of hydrocarbons 3. Straight-run naphtha

    Bajus, M.; Vesely, V.; Leclercq, P.A.; Rijks, J.A.

    1980-01-01

    Steam cracking of straight-run naphtha from Romashkino crude oil was investigated in quartz and stainless steel reactors with a relatively large ratio of Inner surface to volume. The experiments were performed at atmospheric pressure at 780-800 OC for starting ratios of steam to naphtha between 0.5

  18. Combustion Stratification for Naphtha from CI Combustion to PPC

    Vallinayagam, R.; Vedharaj, S.; An, Yanzhao; Dawood, Alaaeldin; Izadi Najafabadi, Mohammad; Somers, Bart; Johansson, Bengt

    2017-01-01

    This study demonstrates the combustion stratification from conventional compression ignition (CI) combustion to partially premixed combustion (PPC). Experiments are performed in an optical CI engine at a speed of 1200 rpm for diesel and naphtha (RON

  19. Bacterial degradation of naphtha and its influence on corrosion

    Rajasekar, A.; Maruthamuthu, S.; Muthukumar, N.; Mohanan, S.; Subramanian, P.; Palaniswamy, N.

    2005-01-01

    The degradation problem of naphtha arises since hydrocarbon acts as an excellent food source for a wide variety of microorganisms. Microbial activity leads to unacceptable level of turbidity, corrosion of pipeline and souring of stored product. In the present study, biodegradation of naphtha in the storage tank and its influence on corrosion was studied. The corrosion studies were carried out by gravimetric method. Uniform corrosion was observed from the weight loss coupons in naphtha (0.024 mm/yr) whereas in presence of naphtha with water, blisters (1.2052 mm/yr) were noticed. The naphtha degradation by microbes was characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR). IR study reveals the formation of primary alcohol during degradation process. It was found that microbes degrade (CH 2 -CH 2 ) n to R-CH 3 . Iron bacteria, manganese oxidizing bacteria, acid producers, and heterotrophic bacteria were enumerated and identified in the pipeline. SRB could not be noticed. Since water stratifies in the pipeline, the naphtha-degraded product may adsorb on pipeline, which would enhance the rate of microbial corrosion. On the basis of degradation and corrosion data, a hypothesis for microbial corrosion has been proposed

  20. Catalytic hydrotreatment of coal-derived naphtha using commercial catalysts

    Liaw, S.-J.; Keogh, R.A.; Thomas, G.A.; Davis, B.H. (University of Kentucky, Lexington, KY (United States). Center for Applied Energy Research)

    Naphtha samples derived from the liquefaction of a bituminous Illinois No. 6 and a subbituminous Black Thunder coal were hydrotreated using commercial Co-Mo/Al[sub 2]O[sub 3], Ni-Mo/Al[sub 2]O[sub 3], and Ni-W/Al[sub 2]O[sub 3] catalysts. It was easier to remove the N, O and S heteroatoms from Illinois No. 6 naphtha than from the Black Thunder naphtha. Nitrogen and oxygen were more difficult to remove than sulfur in the temperature range 200-400[degree]C. Considerable differences in catalyst activity for the hydrodenitrogenation (HDN), hydrodeoxygenation (HDO), and hydrodesulfurization (HDS) reactions were observed. The Ni-Mo catalyst was found to be the most active catalyst for the HDN and HDO reactions and the least active catalyst for the HDS. The Co-Mo catalyst was the most active catalyst for the sulfur removal. For the Illinois No. 6 naphtha, a first-order reaction applies for the HDN and HDO reactions for all three catalysts. However, for the Black Thunder naphtha, the first-order reaction applies only at the lower space velocities; a large deviation is observed at higher space velocities. 11 refs., 15 figs., 4 tabs.

  1. Progress in catalytic naphtha reforming process: A review

    Rahimpour, Mohammad Reza; Jafari, Mitra; Iranshahi, Davood

    2013-01-01

    Catalytic naphtha reforming process is a vital process for refineries due to the production of high-octane components, which is intensely demanded in our modern life. The significance of this industrial process induced researchers to investigate different aspects of catalytic naphtha reforming process intensively. Some of the investigators try to improve this process by representing more effective catalysts, while others try to elucidate its kinetic and deactivation mechanisms and design more efficient reactor setups. The amount of these established papers is so much that may confuse some of the researchers who want to find collective information about catalytic naphtha reforming process. In the present paper, the published studies from 1949 until now are categorized into three main groups including finding suitable catalyst, revealing appropriate kinetic and deactivation model, and suggesting efficient reactor configuration and mode of operation. These studies are reviewed separately, and a suitable reference is provided for those who want to have access to generalized information about catalytic naphtha reforming process. Finally, various suggestions for revamping the catalytic naphtha reforming process have been proposed as a guideline for further investigations

  2. Diethyl Ether as an Ignition Enhancer for Naphtha Creating a Drop in Fuel for Diesel

    Vallinayagam, R.

    2016-12-01

    Direct use of naphtha in compression ignition (CI) engines is not advisable because its lower cetane number negatively impacts the auto ignition process. However, engine or fuel modifications can be made to operate naphtha in CI engines. Enhancing a fuel’s auto ignition characteristics presents an opportunity to use low cetane fuel, naphtha, in CI engines. In this research, Di-ethyl ether (DEE) derived from ethanol is used as an ignition enhancer for light naphtha. With this fuel modification, a “drop-in” fuel that is interchangeable with existing diesel fuel has been created. The ignition characteristics of DEE blended naphtha were studied in an ignition quality tester (IQT); the measured ignition delay time (IDT) for pure naphtha was 6.9 ms. When DEE was added to naphtha, IDT decreased and D30 (30% DEE + 70% naphtha) showed comparable IDT with US NO.2 diesel. The derived cetane number (DCN) of naphtha, D10 (10% DEE + 90% naphtha), D20% DEE + 80% naphtha) and D30 were measured to be 31, 37, 40 and 49, respectively. The addition of 30% DEE in naphtha achieved a DCN equivalent to US NO.2 diesel. Subsequent experiments in a CI engine exhibited longer ignition delay for naphtha compared to diesel. The peak in-cylinder pressure is higher for naphtha than diesel and other tested fuels. When DEE was added to naphtha, the ignition delay shortened and peak in-cylinder pressure is reduced. A 3.7% increase in peak in-cylinder pressure was observed for naphtha compared to US NO.2 diesel, while D30 showed comparable results with diesel. The pressure rise rate dropped with the addition of DEE to naphtha, thereby reducing the ringing intensity. Naphtha exhibited a peak heat release rate of 280 kJ/m3deg, while D30 showed a comparable peak heat release rate to US NO.2 diesel. The amount of energy released during the premixed combustion phase decreased with the increase of DEE in naphtha. Thus, this study demonstrates the suitability of DEE blended naphtha mixtures as a

  3. Diethyl Ether as an Ignition Enhancer for Naphtha Creating a Drop in Fuel for Diesel

    Vallinayagam, R.; Vedharaj, S.; Sarathy, Mani; Dibble, Robert W.

    2016-01-01

    Direct use of naphtha in compression ignition (CI) engines is not advisable because its lower cetane number negatively impacts the auto ignition process. However, engine or fuel modifications can be made to operate naphtha in CI engines. Enhancing a fuel’s auto ignition characteristics presents an opportunity to use low cetane fuel, naphtha, in CI engines. In this research, Di-ethyl ether (DEE) derived from ethanol is used as an ignition enhancer for light naphtha. With this fuel modification, a “drop-in” fuel that is interchangeable with existing diesel fuel has been created. The ignition characteristics of DEE blended naphtha were studied in an ignition quality tester (IQT); the measured ignition delay time (IDT) for pure naphtha was 6.9 ms. When DEE was added to naphtha, IDT decreased and D30 (30% DEE + 70% naphtha) showed comparable IDT with US NO.2 diesel. The derived cetane number (DCN) of naphtha, D10 (10% DEE + 90% naphtha), D20% DEE + 80% naphtha) and D30 were measured to be 31, 37, 40 and 49, respectively. The addition of 30% DEE in naphtha achieved a DCN equivalent to US NO.2 diesel. Subsequent experiments in a CI engine exhibited longer ignition delay for naphtha compared to diesel. The peak in-cylinder pressure is higher for naphtha than diesel and other tested fuels. When DEE was added to naphtha, the ignition delay shortened and peak in-cylinder pressure is reduced. A 3.7% increase in peak in-cylinder pressure was observed for naphtha compared to US NO.2 diesel, while D30 showed comparable results with diesel. The pressure rise rate dropped with the addition of DEE to naphtha, thereby reducing the ringing intensity. Naphtha exhibited a peak heat release rate of 280 kJ/m3deg, while D30 showed a comparable peak heat release rate to US NO.2 diesel. The amount of energy released during the premixed combustion phase decreased with the increase of DEE in naphtha. Thus, this study demonstrates the suitability of DEE blended naphtha mixtures as a

  4. Combustion Stratification for Naphtha from CI Combustion to PPC

    Vallinayagam, R.

    2017-03-28

    This study demonstrates the combustion stratification from conventional compression ignition (CI) combustion to partially premixed combustion (PPC). Experiments are performed in an optical CI engine at a speed of 1200 rpm for diesel and naphtha (RON = 46). The motored pressure at TDC is maintained at 35 bar and fuelMEP is kept constant at 5.1 bar to account for the difference in fuel properties between naphtha and diesel. Single injection strategy is employed and the fuel is injected at a pressure of 800 bar. Photron FASTCAM SA4 that captures in-cylinder combustion at the rate of 10000 frames per second is employed. The captured high speed video is processed to study the combustion homogeneity based on an algorithm reported in previous studies. Starting from late fuel injection timings, combustion stratification is investigated by advancing the fuel injection timings. For late start of injection (SOI), a direct link between SOI and combustion phasing is noticed. At early SOI, combustion phasing depends on both intake air temperature and SOI. In order to match the combustion phasing (CA50) of diesel, the intake air temperature is increased to 90°C for naphtha. The combustion stratification from CI to PPC is also investigated for various level of dilution by displacing oxygen with nitrogen in the intake. The start of combustion (SOC) was delayed with the increase in dilution and to compensate for this, the intake air temperature is increased. The mixture homogeneity is enhanced for higher dilution due to longer ignition delay. The results show that high speed image is initially blue and then turned yellow, indicating soot formation and oxidation. The luminosity of combustion images decreases with early SOI and increased dilution. The images are processed to generate the level of stratification based on the image intensity. The level of stratification is same for diesel and naphtha at various SOI. When O concentration in the intake is decreased to 17.7% and 14

  5. Naphtha interaction with bitumen and clays : a preliminary study

    Afara, M.; Munoz, V.; Mikula, R. [Natural Resources Canada, Devon, AB (Canada). CANMET Western Research Centre

    2010-07-01

    This PowerPoint presentation described a preliminary study conducted to characterize naphtha interactions with bitumen and clays. Coarse tailings, fluid-fine tailings, and froth treatment tailings are produced as a result of surface mine oil sands operations. Solvents are used to produce the bitumens, but the actual fraction of the solvent that evaporates and contributes to VOCs from tailing ponds is poorly understood. This study examined the interactions between the solvent, bitumen and mineral components in froth treatment tails. The study was conducted with aim of quantifying the VOC or solvent escaping from the froth treatment tailings. Samples containing bitumen, clay, a bitumen-clay mixture, or MFT were spiked with 3000 ppm of solvent. The amount of naphtha released was monitored by gas chromatography, mass spectrometry, and flame ionization detection of the evolved gases. The results were expressed as a percentage of the total hydrocarbon peak area of the sample versus a control. Results of the study showed that the naphtha interacted more strongly with the bitumen than with kaolinite and the clay minerals from the oil sands. Although initial solvent evaporation was reduced in the presence of bitumens and clays, long-term solvent releases will need to be quantified. tabs., figs.

  6. Compression ignition of light naphtha and its multicomponent surrogate under partially premixed conditions

    Vallinayagam, R.; Vedharaj, S.; An, Y.; Dawood, A.; Izadi Najafabadi, M.; Somers, B.; Chang, J.; Sarathy, M.; Johansson, B.

    2017-01-01

    Light naphtha is the light distillate from crude oil and can be used in compression ignition (CI) engines; its low boiling point and octane rating (RON = 64.5) enable adequate premixing. This study investigates the combustion characteristics of light naphtha (LN) and its multicomponent surrogate

  7. Competitive reaction in hydrodenitrogenation and hydrodeoxygenation of coal-derived naphtha

    Machida, M. (Idemitsu Kosan Co. Ltd., Tokyo (Japan). Central Research Lab.); Sakao, Y.; Ono, S. (Idemitsu Kosan Co. Ltd., Tokyo (Japan))

    1994-03-01

    The naphtha fraction derived from coal is expected to be one of the most suitable blending stocks for motor gasoline because of its high contents of cyclic hydrocarbons. However, since the contents of nitrogen and oxygen are high in the coal naphtha, the amounts of these elements must be reduced to acceptable levels. In this study, aiming to clarify the hydrodenitrogenation (HDN) and hydrodeoxygenation (HDO) performances of practical feed stocks, HDN and HDO of coal-derived naphtha and its model compounds were examined by using a catalyst Ni-Mo/Al2O3 group. There are tree types of nitrogen compounds, pyridine, pyrrole and aniline, in the coal-derived naphtha. Aniline type nitrogen compounds in the coal-derived naphtha are more resistant to HDN than pyridine type compounds, though aniline is more reactive than pyridine when the reaction is carried out individually. 14 refs., 7 figs., 3 tabs.

  8. Improving gasoline quality produced from MIDOR light naphtha isomerization unit

    M.F. Mohamed

    2017-03-01

    Full Text Available Isomerization process became one of the best gasoline production sources, as it gives a high octane product while saving environment from pollution impacts. This paper presents a practical study that aims to improve the gasoline quality and economic income of an existing light naphtha isomerization unit used for octane improvement. The study included selecting the optimum combination of isomerization unit equipment that gives better product specifications for a specified feed. Eight scenarios were studied and simulated to predict the product specs. The original studied unit is MIDOR light naphtha isomerization unit at Alexandria-Egypt that recycles the unconverted hexane (C6. The other studied scenarios were adding fractionators for separating feed iso-pentanes, and recycling unconverted pentanes, hexanes and/or combinations of these fractionators. The results show a change in octane number of gasoline product for a specific feed. Once through process with no extra fractionators has lower octane number of 81 while that with de-iso-pentanizer–de-pentanizer and de-hexanizer produces gasoline with 92.3 octane number. Detailed economic study was done to calculate the return on investment “ROI” for each process option based on equipment, utilities, feed and product prices. Once through simple isomerization unit had the lowest ROI of 14.3% per year while the combination of De-iso-pentanizer with the De-hexanizer had the best ROI of 26.6% per year.

  9. The mutagenic potential of high flash aromatic naphtha.

    Schreiner, C A; Edwards, D A; McKee, R H; Swanson, M; Wong, Z A; Schmitt, S; Beatty, P

    1989-06-01

    Catalytic reforming is a refining process that converts naphthenes to aromatics by dehydrogenation to make higher octane gasoline blending components. A portion of this wide boiling range hydrocarbon stream can be separated by distillation and used for other purposes. One such application is a mixture of predominantly 9-carbon aromatic molecules (C9 aromatics, primarily isomers of ethyltoluene and trimethylbenzene), which is removed and used as a solvent--high-flash aromatic naphtha. A program was initiated to assess the toxicological properties of high-flash aromatic naphtha since there may be human exposure through inhalation or external body contact. The current study was conducted partly to assess the potential for mutagenic activity and also to assist in an assessment of carcinogenic potential. The specific tests utilized included the Salmonella/mammalian microsome mutagenicity assay, the hypoxanthine-guanine phosphoribosyl transferase (HGPRT) forward mutation assay in CHO cells, in vitro chromosome aberration and sister chromatid exchange (SCE) assays in CHO cells, and an in vivo chromosome aberration assay in rat bone marrow.

  10. A novel integrated thermally coupled moving bed reactors for naphtha reforming process with hydrodealkylation of toluene

    Iranshahi, Davood; Saeedi, Reza; Azizi, Kolsoom; Nategh, Mahshid

    2017-01-01

    Highlights: • A novel thermally coupled reactor in CCR naphtha reforming process is modeled. • The required heat of Naphtha process is attained with toluene hydrodealkylation. • A new kinetic model involving 32 pseudo-component and 84 reactions is proposed. • The aromatics and hydrogen production increase 19% and 23%, respectively. - Abstract: Due to the importance of catalytic naphtha reforming process in refineries, development of this process to attain the highest yield of desired products is crucial. In this study, continuous catalyst regeneration naphtha reforming process with radial flow is coupled with hydrodealkylation of toluene to prevent energy loss while enhancing aromatics and hydrogen yields. In this coupled process, heat is transferred between hot and cold sections (from hydrodealkylation of toluene to catalytic naphtha reforming process) using the process integration method. A steady-state two-dimensional model, which considers coke formation on the catalyst pellets, is developed and 32 pseudo-components with 84 reactions are investigated. Kinetic model utilized for HDA process is homogeneous and non-catalytic. The modeling results reveal an approximate increase of 19% and 23% in aromatics and hydrogen molar flow rates, respectively, in comparison with conventional naphtha reforming process. The improvement in aromatics production evidently indicates that HDA is a suitable process to be coupled with naphtha reforming.

  11. Lumping procedure for a kinetic model of catalytic naphtha reforming

    H. M. Arani

    2009-12-01

    Full Text Available A lumping procedure is developed for obtaining kinetic and thermodynamic parameters of catalytic naphtha reforming. All kinetic and deactivation parameters are estimated from industrial data and thermodynamic parameters are calculated from derived mathematical expressions. The proposed model contains 17 lumps that include the C6 to C8+ hydrocarbon range and 15 reaction pathways. Hougen-Watson Langmuir-Hinshelwood type reaction rate expressions are used for kinetic simulation of catalytic reactions. The kinetic parameters are benchmarked with several sets of plant data and estimated by the SQP optimization method. After calculation of deactivation and kinetic parameters, plant data are compared with model predictions and only minor deviations between experimental and calculated data are generally observed.

  12. Surrogate fuel formulation for light naphtha combustion in advanced combustion engines

    Ahmed, Ahfaz; Khurshid, Muneeb; Naser, Nimal; Badra, Jihad; Gaillard, Pattrick; Chung, Suk-Ho; Roberts, William L.; Sarathy, Mani

    2015-01-01

    Crude oil once recovered is further separated in to several distinct fractions to produce a range of energy and chemical products. One of the less processed fractions is light naphtha (LN), hence they are more economical to produce than

  13. Autoignition of straight-run naphtha: A promising fuel for advanced compression ignition engines

    Alabbad, Mohammed

    2017-11-24

    Naphtha, a low-octane distillate fuel, has been proposed as a promising low-cost fuel for advanced compression ignition engine technologies. Experimental and modelling studies have been conducted in this work to assess autoignition characteristics of naphtha for use in advanced engines. Ignition delay times of a certified straight-run naphtha fuel, supplied by Haltermann Solutions, were measured in a shock tube and a rapid comparison machine over wide ranges of experimental conditions (20 and 60 bar, 620–1223 K, ϕ = 0.5, 1 and 2). The Haltermann straight-run naphtha (HSRN) has research octane number (RON) of 60 and motor octane number (MON) of 58.3, with carbon range spanning C3–C9. Reactivity of HSRN was compared, via experiments and simulations, with three suitably formulated surrogates: a two-component PRF (n-heptane/iso-octane) surrogate, a three-component TPRF (toluene/n-heptane/iso-octane) surrogate, and a six-component surrogate. All surrogates reasonably captured the ignition delays of HSRN at high and intermediate temperatures. However, at low temperatures (T < 750 K), the six-component surrogate performed the best in emulating the reactivity of naphtha fuel. Temperature sensitivity and rate of production analyses revealed that the presence of cyclo-alkanes in naphtha inhibits the overall fuel reactivity. Zero-dimensional engine simulations showed that PRF is a good autoignition surrogate for naphtha at high engine loads, however, the six-component surrogate is needed to match the combustion phasing of naphtha at low engine loads.

  14. Autoignition of straight-run naphtha: A promising fuel for advanced compression ignition engines

    Alabbad, Mohammed; Issayev, Gani; Badra, Jihad; Voice, Alexander K.; Giri, Binod; Djebbi, Khalil; Ahmed, Ahfaz; Sarathy, Mani; Farooq, Aamir

    2017-01-01

    Naphtha, a low-octane distillate fuel, has been proposed as a promising low-cost fuel for advanced compression ignition engine technologies. Experimental and modelling studies have been conducted in this work to assess autoignition characteristics of naphtha for use in advanced engines. Ignition delay times of a certified straight-run naphtha fuel, supplied by Haltermann Solutions, were measured in a shock tube and a rapid comparison machine over wide ranges of experimental conditions (20 and 60 bar, 620–1223 K, ϕ = 0.5, 1 and 2). The Haltermann straight-run naphtha (HSRN) has research octane number (RON) of 60 and motor octane number (MON) of 58.3, with carbon range spanning C3–C9. Reactivity of HSRN was compared, via experiments and simulations, with three suitably formulated surrogates: a two-component PRF (n-heptane/iso-octane) surrogate, a three-component TPRF (toluene/n-heptane/iso-octane) surrogate, and a six-component surrogate. All surrogates reasonably captured the ignition delays of HSRN at high and intermediate temperatures. However, at low temperatures (T < 750 K), the six-component surrogate performed the best in emulating the reactivity of naphtha fuel. Temperature sensitivity and rate of production analyses revealed that the presence of cyclo-alkanes in naphtha inhibits the overall fuel reactivity. Zero-dimensional engine simulations showed that PRF is a good autoignition surrogate for naphtha at high engine loads, however, the six-component surrogate is needed to match the combustion phasing of naphtha at low engine loads.

  15. Fabrication of Fischer-Tropsch Catalysts by Deposition of Iron Nanocrystals on Carbon Nanotubes

    Casavola, Marianna; Hermannsdoerfer, Justus; de Jonge, Niels; Dugulan, A. Iulian; de Jong, Krijn P.

    2015-01-01

    The fabrication of supported catalysts consisting of colloidal iron oxide nanocrystals with tunable size, geometry, and loadinghomogeneously dispersed on carbon nanotube (CNT) supportsis described herein. The catalyst synthesis is performed in a two-step approach. First, colloidal iron and iron

  16. Research trends in Fischer-Tropsch catalysis for coal to liquids technology

    Hensen, E.J.M.; Wang, P.; Xu, W.

    2016-01-01

    Fischer–Tropsch Synthesis (FTS) constitutes catalytic technology that converts synthesis gas to synthetic liquid fuels and chemicals. While synthesis gas can be obtained from any carbonaceous feedstock, current industrial FTS operations are almost exclusively based on natural gas. Due to the energy

  17. Synthetic Fischer-Tropsch (FT) JP-5/JP-8 Aviation Turbine Fuel Elastomer Compatibility

    Muzzell, Pat; Stavinoha, Leo; Chapin, Rebecca

    2005-01-01

    ... to seal performance may arise, possibly leading to fuel leakage. The key objective of this study was to compare and contrast the material compatibility of nitrile coupons and O-rings with selected petroleum-derived fuels, Fisher-Tropsch (FT...

  18. Exergetic optimisation of a production process of Fischer-Tropsch fuels from biomass

    Prins, M.J.; Ptasinski, K.J.; Janssen, F.J.J.G.

    2005-01-01

    An exergy analysis of Biomass Integrated Gasification-Fischer–Tropsch process is presented. The process combines an air-blown, atmospheric gasifier, using sawdust as feedstock, with a Fischer–Tropsch reactor and a steam-Rankine cycle for electricity generation from the Fischer–Tropsch tail gas.

  19. On the deactivation of cobalt-based Fischer-Tropsch synthesis catalysts

    Moodley, D.J.

    2008-01-01

    The catalytic conversion of synthesis gas, derived from natural gas, into liquid hydrocarbon fuel via the Fischer–Tropsch synthesis (FTS), is currently receiving much attention due to the demand for environmentally friendly liquid fuel and the rising costs of crude oil. From an industrial

  20. Ultra-Clean Fischer-Tropsch Fuels Production and Demonstration Project

    Steve Bergin

    2005-10-14

    The Report Abstract provides summaries of the past year's activities relating to each of the main project objectives. Some of the objectives will be expanded on in greater detail further down in the report. The following objectives have their own addition sections in the report: Dynamometer Durability Testing, the Denali Bus Fleet Demonstration, Bus Fleet Demonstrations Emissions Analysis, Impact of SFP Fuel on Engine Performance, Emissions Analysis, Feasibility Study of SFPs for Rural Alaska, and Cold Weather Testing of Ultra Clean Fuel.

  1. Enabling electrocatalytic Fischer-Tropsch synthesis from carbon dioxide over copper-based electrodes

    Shibata, H.; Moulijn, J.A.; Mul, Guido

    2008-01-01

    We report on the discovery that paraffins and olefins up to C6 hydrocarbons can be obtained in CO2 electroreduction at room temperature and atmospheric pressure by application of a commercially available Cu-electrode (Eurofysica), provided pretreatment by electropolishing is avoided. The product

  2. CFD analysis of hot spot formation through a fixed bed reactor of Fischer-Tropsch synthesis

    Hamed Aligolzadeh

    2015-12-01

    Full Text Available One of the interesting methods for conversion of synthesis gas to heavy hydrocarbons is Fischer–Tropsch process. The process has some bottlenecks, such as hot spot formation and low degree of conversion. In this work, computational fluid dynamics technique was used to simulate conversion of synthetic gas and product distribution. Also, hot spot formation in the catalytic fixed-bed reactor was investigated in several runs. Simulation results indicated that hot spot formation occurred more likely in the early and middle part of reactor due to high reaction rates. Based on the simulation results, the temperature of hot spots increased with increase in the inlet temperature as well as pressure. Among the many CFD runs conducted, it is found that the optimal temperature and pressure for Fischer–Tropsch synthesis are 565 K and 20 bar, respectively. As it seems that the reactor shall work very well under optimal conditions, the reaction rates and catalyst duration would simultaneously be maximum .

  3. Development of a demonstration reactor using thoria as a Fischer-Tropsch catalyst

    Colmenares, C.A.; McLean, W.

    1981-12-01

    We have demonstrated experimentally that thorium oxide may be used as a catalyst with CO + H 2 mixtures to produce either methanol or a mixture of hydrocarbons from C 1 to C 5 (saturated and unsaturated). The immunity of ThO 2 to poisoning by sulfur compounds makes its use very attractive for industrial applications. We are proposing to optimize the experimental conditions of the catalytic process using a one-inch reactor and to scope and define the experimental conditions for a pilot plant demonstration

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

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

    2014-01-01

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

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

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

    1987-01-01

    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. Iron carbide on titania surface modified with group VA oxides as Fischer-Tropsch catalysts

    Wachs, I.E.; Fiato, R.A.; Chersich, C.C.

    1986-01-01

    A catalyst is described comprising iron carbide supported on a surface modified titania wherein the support comprises an oxide of a metal selected form the group consisting of niobium, vanadium, tantalum or mixture thereof supported on the titania wherein at least a portion of the supported oxide of niobium, vanandium, tantalum or mixture is in a non-crystalline form. The amount of the supported oxide ranges from about 0.5 to 25 weight percent metal oxide on the titania support based on the total support composition and the catalyst contains at least about 2 milligrams of iron, calculated as Fe/sub 2/O/sub 3/, per square meter of support surface

  7. Hydrocarbon synthesis using Iron and Ruthenium/SiO2 with FISCHER-TROPSCH catalysis.

    Y.J. Fonseca

    2007-12-01

    Full Text Available Fe2(CO9, Fe3(CO12 and Ru3(CO12 clusters were used as precursors for silica supported metals. The impregnated silica solids were obtained in organic solvents under inert atmosphere and the adsorbed complexes and reduced metals characterized by FT-IR, SEM EDX and HRTEM. The catalysts showed good Fischer–Tropsch (FT activity; the main products were alkanes, alkenes and medium and higher alcohols as analyzed by GCMS. The Ru catalysts showed higher alcohols selectivity. HRTEM showed Ru nanoparticle size.

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

    Mark C. Thies; Patrick C. Joyce

    1998-04-30

    Further progress in achieving the objectives of the project was made in the period of January I to March 31, 1998. The direct numerical simulation of particle removal process in turbulent gas flows was completed. Variations of particle trajectories are studied. It is shown that the near wall vortices profoundly affect the particle removal process in turbulent boundary layer flows. Experimental data for transport and deposition of fibrous particles in the aerosol wind tunnel was obtained. The measured deposition velocity for irregular fibrous particles is compared with the empirical correlation and the available data for glass fibers and discussed. Additional progress on the sublayer model for evaluating the particle deposition and resuspension in turbulent flows was made.

  9. The reproductive and developmental toxicity of High Flash Aromatic Naphtha.

    McKee, R H; Wong, Z A; Schmitt, S; Beatty, P; Swanson, M; Schreiner, C A; Schardein, J L

    1990-01-01

    Catalytic reforming is a refining process that converts naphthenes to aromatics by dehydrogenation to make higher octane gasoline blending components. A portion of this wide boiling range hydrocarbon stream can be separated by distillation and used for other purposes. One such application is a mixture of predominantly 9-carbon aromatic molecules (C9 aromatics, primarily isomers of ethyltoluene and trimethylbenzene), which is removed and used as a solvent--High Flash Aromatic Naphtha. A program was initiated to assess the toxicological properties of High Flash Aromatic Naphtha since there may be human exposure through inhalation or external body contact. The current study was conducted to assess the potential for developmental toxicity in the mouse and for reproductive toxicity in the rat. In the developmental toxicity study in CD-1 mice, exposure of dams by inhalation to near lethal levels (1500 ppm) resulted in fetal mortality, reduced weight, delayed ossification, and an increased incidence of cleft palate. At 500 ppm, a level at which maternal weight gain was slightly reduced, fetal weight gain was also reduced, but there was no other evidence of developmental effects. The lowest exposure level (100 ppm) did not cause any maternal or developmental toxicity. There was no consistent evidence of reproductive toxicity in rats, even at exposure levels which resulted in significantly reduced parental weight gain. In addition, when parental exposure was stopped on GD (gestation day) 20, birth weights as well as postnatal survival were generally similar to control values, even in the 1500 ppm exposure group. Postnatal weight gain was also similar to controls early in weaning, but, if maternal exposure was reinitiated, weight gain was reduced in the high exposure group. However, when exposure was continued until delivery, pups in the high exposure group exhibited reduced litter size, birth weight and poor survival. Thus it was likely that the reduction in fetal weight

  10. A neurotoxicity assessment of high flash aromatic naphtha.

    Douglas, J F; McKee, R H; Cagen, S Z; Schmitt, S L; Beatty, P W; Swanson, M S; Schreiner, C A; Ulrich, C E; Cockrell, B Y

    1993-01-01

    Catalytic reforming is a refining process that converts naphthenes to aromatics by dehydrogenation to make higher octane gasoline blending components. A portion of this wide-boiling range hydrocarbon stream can be separated by distillation and used for other purposes. One such application is a mixture of predominantly 9-carbon aromatic molecules (C9 Aromatics, primarily isomers of ethyltoluene and trimethylbenzene), which is removed and used as a solvent also known as High Flash Aromatic Naphtha (HFAN). A program was initiated to assess the toxicological properties of HFAN since there may be human exposure, especially in the workplace. The current study was conducted to assess the potential for neurotoxicity in the rat. Adult male Sprague-Dawley rats of approximately 300 grams body weight, in groups of twenty, were exposed by inhalation to HFAN for 90 days at concentrations of 0, 100, 500, and 1500 ppm. During this period the animals were tested monthly for motor activity and in a functional observation battery. After three months of exposure, for 6 hours/day, 5 days/week, 10 animals/group/sex were sacrificed and selected nervous system tissue was examined histopathologically. No signs of neurotoxicity were seen in any of the evaluated parameters, nor was there evidence of pathologic changes in any of the examined tissues.

  11. Data reconciliation and optimal operation of a Catalytic naphtha reformer

    Tore Lid

    2008-10-01

    Full Text Available The naphtha reforming process converts low-octane gasoline blending components to high-octane components for use in high-performance gasoline fuels. The reformer also has an important function as the producer of hydrogen to the refinery hydrotreaters. A process model based on a unit model structure, is used for estimation of the process condition using data reconciliation. Measurements are classified as redundant or non redundant and the model variables are classified as observable, barely observable or unobservable. The computed uncertainty of the measured and unmeasured variables shows that even if a variable is observable it may have a very large uncertainty and may thereby be practically unobservable. The process condition at 21 data points, sampled from two years of operation, was reconciled and used to optimize the process operation. There are large seasonal variations in the reformer product price and two operational cases are studied. In case 1, the product price is high and throughput is maximized with respect to process and product quality constraints. In case 2, the product price is low and the throughput is minimized with respect to a low constraint on the hydrogen production. Based on the characteristics of the optimal operation, a "self optimizing" control structure is suggested for each of the two operational cases.

  12. Occupational irritant contact dermatitis due to petroleum naphtha

    Aslı Aytekin

    2014-12-01

    Full Text Available Irritant contact dermatitis (ICD is responsible for the vast majority of occupational contact dermatitis and usually seen in professional groups working with wet hand. However, today, with the increasing business lines, employees are exposed to a variety of irritants. Occupational exposure to many chemicals and toxic irritants affect not only the skin, but also the other systems. Therefore, this situation resulting with loss of work and changes in business may become a public health problem. The diagnosis of occupational contact dermatitis should not be limited only with tests for allergens, detailed history of exposure to workplace substances and careful examination of product safety forms are necessary. In addition, by establishing close relationship between occupational physicians and employers, preventive measures should be taken before similar diseases occur in other workers in the same work place. In order to highlight this issue, a 32-year-old male patient working in an invitation card fabric is presented in this case report. Irritant contact dermatitis secondary to “petroleum naphta” was present in the patient’s arms. Another important feature of this case, as far as we know, this is the first case of irritant contact dermatitis due to naphtha in the literature.

  13. Modelling of a Naphtha Recovery Unit (NRU with Implications for Process Optimization

    Jiawei Du

    2018-06-01

    Full Text Available The naphtha recovery unit (NRU is an integral part of the processes used in the oil sands industry for bitumen extraction. The principle role of the NRU is to recover naphtha from the tailings for reuse in this process. This process is energy-intensive, and environmental guidelines for naphtha recovery must be met. Steady-state models for the NRU system are developed in this paper using two different approaches. The first approach is a statistical, data-based modelling approach where linear regression models have been developed using Minitab® from plant data collected during a performance test. The second approach involves the development of a first-principles model in Aspen Plus® based on the NRU process flow diagram. A novel refinement to this latter model, called “withdraw and remix”, is proposed based on comparing actual plant data to model predictions around the two units used to separate water and naphtha. The models developed in this paper suggest some interesting ideas for the further optimization of the process, in that it may be possible to achieve the required naphtha recovery using less energy. More plant tests are required to validate these ideas.

  14. MODELING OF NAPHTHA PYROLYSIS WITH USING GENETIC ALGORITM

    V. K. Bityukov

    2015-01-01

    Full Text Available Summary. In operation of industrial pyrolysis furnaces, the main task is the selection of the optimal mode of thermal decomposition of the feedstock, depending on the yield of the desired products under conditions of technological limitations on the process. To solve this problem for an operating reactor, this paper considers the SRT-VI Large-Capacity industrial Furnace , the mathematical model of the pyrolysis process was constructed, using a kinetic scheme which consists of primary reaction of decomposition of raw materials and secondary elementary reactions of interaction of the considered mixture components, the heat balance equation and hydrodynamics of flow in the coil. The raw material for the selected installation type is naphtha (straight-run petrol. Output parameters of the model are the molar costs of marketable hydrocarbons. The reactor is described by the equation of ideal displacement in the static mode of operation. It is assumed that all reactions have a temperature dependence that follows the Arrhenius law. The activation energies of chemical processes were estimated using the PolanyiSemenov equation and identification of pre-exponential factors was carried out using a genetic algorithm (GA. This task requires solving simultaneous system of differential equations describing the pyrolysis process and a search for a large number of unknown parameters, and therefore it is proposed to modify the GA. Optimal scheme includes Gray encoding arithmetic operators, tournament selection, with tournament ranking more than 4, crossover with partial random choice of alleys, mutations with a high probability of occurring and elitism with competitive global competition. Using the proposed approach, the parametric identification of model process is accomplished. The analysis of the simulation results with the data of operating reactor showed its suitability for use in order to control the pyrolysis process.

  15. Analysis of Optimal Process Flow Diagrams of Light Naphtha Isomerization Process by Mathematic Modelling Method

    Chuzlov, Vyacheslav Alekseevich; Molotov, Konstantin

    2016-01-01

    An approach to simulation of hydrocarbons refining processes catalytic reactors. The kinetic and thermodynamic research of light naphtha isomerization process was conducted. The kinetic parameters of hydrocarbon feedstock chemical conversion on different types of platinum-content catalysts was established. The estimation of efficiency of including different types of isomerization technologies in oil refinery flow diagram was performed.

  16. Analysis of Optimal Process Flow Diagrams of Light Naphtha Isomerization Process by Mathematic Modelling Method

    Chuzlov Vjacheslav

    2016-01-01

    Full Text Available An approach to simulation of hydrocarbons refining processes catalytic reactors. The kinetic and thermodynamic research of light naphtha isomerization process was conducted. The kinetic parameters of hydrocarbon feedstock chemical conversion on different types of platinum-content catalysts was established. The estimation of efficiency of including different types of isomerization technologies in oil refinery flow diagram was performed.

  17. Ignition delay measurements of light naphtha: A fully blended low octane fuel

    Javed, Tamour

    2016-06-15

    Light naphtha is a fully blended, low-octane (RON. = 64.5, MON. = 63.5), highly paraffinic (>. 90% paraffinic content) fuel, and is one of the first distillates obtained during the crude oil refining process. Light naphtha is an attractive low-cost fuel candidate for advanced low-temperature compression ignition engines where autoignition is the primary control mechanism. We measured ignition delay times for light naphtha in a shock tube and a rapid compression machine (RCM) over a broad range of temperatures (640-1250. K), pressures (20 and 40. bar) and equivalence ratios (0.5, 1 and 2). Ignition delay times were modeled using a two-component primary reference fuel (PRF) surrogate and a multi-component surrogate. Both surrogates adequately captured the measured ignition delay times of light naphtha under shock tube conditions. However, for low-temperature RCM conditions, simulations with the multi-component surrogate showed better agreement with experimental data. These simulated surrogate trends were confirmed by measuring the ignition delay times of the PRF and multi-component surrogates in the RCM at . P = 20. bar, . ϕ = 2. Detailed kinetic analyses were undertaken to ascertain the dependence of the surrogates\\' reactivity on their chemical composition. To the best of our knowledge, this is the first fundamental autoignition study on the reactivity of a low-octane fully blended fuel and the use of a suitably formulated multi-component surrogate to model its behavior.

  18. Hydroisomerization of different refinery naphtha streams by using a beta zeolite catalyst

    Ramos, Maria Jesus; de Lucas, Antonio; Jimenez, Vicente; Sanchez, Paula; Valverde, Jose Luis [Departamento de Ingenieria Quimica, Facultad de Ciencias Quimicas, Universidad de Castilla-La Mancha, Avd. Camilo Jose Cela s/n, 13071 Ciudad Real (Spain)

    2008-08-15

    In this work, the evaluation of a catalyst based on beta zeolite agglomerated with bentonite in the hydroisomerization of three feeds obtained by distillation of refinery naphtha streams provided by the petroleum company REPSOL-YPF was considered. These refinery naphthas were different in composition, being constituted mostly by different proportions of paraffin, aromatic and naphthenic compounds. The highest overall paraffin conversion value was obtained with that naphtha with the highest content in linear paraffins. As the classical hydroisomerization mechanism predicts, linear alkanes were transformed into branched isomers. Thus, the relation between branched isomers and linear paraffins (iC6/nC6, iC7/nC7 and iC8/nC8) was higher in the products than in the feed. The presence of the aromatic compounds (benzene and toluene) was detected in the three feeds. In all cases, a complete benzene conversion, leading to naphthenic compounds formation, was reached. Long-term tests showed that, regardless of the type of naphtha fed to the reactor, the research octane number of the products remained practically constant. (author)

  19. Catalytic hydrotreatment of Illinois No. 6 coal-derived naphtha: comparison of molybdenum nitride and molybdenum sulfide for heteroatom removal

    Raje, A.; Liaw, S.J.; Chary, K.V.R.; Davis, B.H. [University of Kentucky, Lexington, KY (United States). Center for Applied Energy Research

    1995-03-16

    The hydrotreatment of naphtha derived from Illinois No. 6 coal was investigated using molybdenum sulfide and nitride catalysts. The two catalysts are compared on the basis of total catalyst weight. Molybdenum sulfide is more active than molybdenum nitride for hydrodesulfurization (HDS) of a coal-derived naphtha. The rate of hydrodeoxygenation (HDO) of the naphtha over both catalysts are comparable. For hydrodenitrogenation (HDN), the sulfide is more active than the nitride only at higher temperatures ({gt}325{degree}C). Based upon conversion data, the naphtha can be lumped into a reactive and a less reactive fraction with each following first-order kinetics for heteroatom removal. The HDS and HDN rates and activation energies of the less reactive lump are smaller for the nitride than for the sulfide catalyst.

  20. Naphtha vs. dieseline – The effect of fuel properties on combustion homogeneity in transition from CI combustion towards HCCI

    Vallinayagam, R.

    2018-03-20

    The scope of this research study pertains to compare the combustion and emission behavior between naphtha and dieseline at different combustion modes. In this study, US dieseline (50% US diesel + 50% RON 91 gasoline) and EU dieseline (45% EU diesel + 55% RON 97 gasoline) with derived cetane number (DCN) of 36 are selected for experimentation in an optical engine. Besides naphtha and dieseline, PRF60 is also tested as a surrogate fuel for naphtha. For the reported fuel with same RON = 60, the effect of physical properties on combustion homogeneity when moving from homogenized charge compression ignition (HCCI) to compression ignition (CI) combustion is studied.The combustion phasing of naphtha at an intake air temperature of 95 °C is taken as the baseline data. The engine experimental results show that higher and lower intake air temperature is required for dieseline mixtures to have same combustion phasing as that of naphtha at HCCI and CI conditions due to the difference in the physical properties. Especially at HCCI mode, due to wider distillation range of dieseline, the evaporation of the fuel is affected so that the gas phase mixture becomes too lean to auto-ignite. However, at partially premixed combustion (PPC) conditions, all test fuels required almost same intake air temperature to match up with the combustion phasing of baseline naphtha. From the rate of heat release and combustion images, it was found that naphtha and PRF60 showed improved premixed combustion when compared dieseline mixtures. The stratification analysis shows that combustion is more stratified for dieseline whereas it is premixed for naphtha and PRF60. The level of stratification linked with soot emission showed that soot concentration is higher at stratified CI combustion whereas near zero soot emissions were noted at PPC mode.

  1. Surrogate fuel formulation for light naphtha combustion in advanced combustion engines

    Ahmed, Ahfaz

    2015-03-30

    Crude oil once recovered is further separated in to several distinct fractions to produce a range of energy and chemical products. One of the less processed fractions is light naphtha (LN), hence they are more economical to produce than their gasoline and diesel counterparts. Recent efforts have demonstrated usage of LN as transportation fuel for internal combustion engines with slight modifications. In this study, a multicomponent surrogate fuel has been developed for light naphtha fuel using a multi-variable nonlinear constrained optimization scheme. The surrogate, consisting of palette species n-pentane, 2-methylhexane, 2-methylbutane, n-heptane and toluene, was validated against the LN using ignition quality tester following ASTM D6890 methodology. Comparison of LN and the surrogate fuel demonstrated satisfactory agreement.

  2. Gauging and Etude Radio exposures in Tartous Cement Factory and Naphtha Strainer of Banias

    Mala, T.; Soufan, A. A.; Bofroud, T.

    2009-01-01

    The radio activity level was measured in both Tartous cement factory and naphtha strainer of Banias by using an electronic strumming EPD produced by E urisy F rance company and digelerat-50 strumming produced by C ope E nglish Company. It was [0.090-0.097]μSv/h that is concert with the background level of radioactivity. Some samples were taken from different places at studying areas and the radioactivity was estimated by using Gamma-ray spectroscopy. (author)

  3. A rapid method for monitoring the hydrodeoxygenation of coal-derived naphtha

    Farnand, B.A.; Coulombe, S.; Smiley, G.T.; Fairbridge, C.

    1988-01-01

    A bonded polar poly(ethylene glycol) capillary column has been used for the identification and quantification of the phenolic components in synthetic crude naphthas. This provides a rapid and routine method for the determination of phenolic oxygen content with results comparable to combustion and neutron activation methods. The method is most useful in monitoring the removal of phenolic oxygen by hydroprocessing. 11 refs., 1 fig. 1 tab.

  4. Infrared spectrophotometry, a rapid and effective tool for characterization of direct distillation naphthas

    Baldrich Ferrer, Carlos A; Novoa Mantilla, Luz Angela

    2005-01-01

    The characterization of naphtha obtained by direct distillation of medium and heavy crude oils is often limited by the low yield of these fractions. Gas chromatography is a technique that allows a complete determination of the chemical composition of this fraction. However, the prediction of properties such as octane rating and RVP from chromatographic data is a difficult task because there are not adequate models to predict the interaction of the different components, and particularly in the case of heavier fractions, there are some problems for the complete separation of components under the gas chromatographic conditions. The IR technology constitutes a rapid and effective tool to predict several properties of naphtha from the correlation of the spectrum in the infrared area and the properties. In this study, prediction models were developed in a Petrospec Cetane 2000 analyzer, in order to predict in a fast and simple way, the density, the antiknock index and the aromatic content of straight run naphtha obtained in a standard crude oil distillation unit. The equipment used was designed in the factory for the exclusive characterization of medium distillation and not for lighter fractions therefore this work constitutes an innovation given the extensive applications of this type of analyzers

  5. Use of Hg-Electroplated-Pt Ultramicroelectrode for Determining Elemental Sulphur in Naphtha Samples

    Carlos Eduardo de Andrade

    2012-01-01

    Full Text Available This paper describes the applicability of a Hg-electroplated-Pt ultramicroelectrode in the quantification of elemental sulphur in naphtha samples by square-wave voltammetry. A reproducible deposition methodology was studied and is reported in this paper. This methodology is innovative and relies on the quality of the mercury stock solution to obtain reproducible surfaces required for the analytical methodology. All analyses were performed using a Hg-electroplated-Pt ultramicroelectrode (Hg-Pt UME due to the low sensibility of such devices to ohmic drops in resistive solutions. The responses of the peak areas in voltammetric experiments were linear in all of the range studied. The method developed here is accurate and reproducible, with a detection limit of 0.010 mg L−1 and a good recovery range for both standard solutions of elemental sulphur (85 to 99% and real naphtha sample (79%. These results attest to the potential for the application of this electroanalytical methodology in determining elemental sulphur in naphtha samples containing mercaptans and disulphides.

  6. Comparison of the composition between coal-liquid naphtha and petroleum gasoline

    Miki, Y.; Sugimoto, Y.; Ono, S.; Machida, M. [National Chemical Laboratory for Industry, Tsukuba (Japan)

    1997-08-01

    Compositional characterization was performed using a gas chromatography-mass spectrometry-atomic emission detector technique on coal-liquid raw naphtha, coal-liquid refined naphtha, coal-liquid reformate and commercial petroleum gasoline. The chemical composition of these oils are divided into five groups: chain hydrocarbons, monocyclic hydrocarbons, bicyclic hydrocarbons, oxygen-containing compounds and other compounds (containing unidentified compounds). Compared to petroleum gasoline, the coal-liquid raw naphtha contains higher concentrations of straight paraffins, cycloparaffins, cycloolefins, bicycloparaffins and oxygen-containing compounds, and contains lower concentrations of brached paraffins and monocyclic aromatic compounds. Phenols and ketones are the major components of oxygen-containing compounds. The total concentration of paraffins and cycloparaffins increased after refining. The hydrogenation of olefins and the hydrodeoxygenation of oxygen-containing compounds are suggested to proceed during the refining process. The reforming treatment increased the concentrations of branched paraffins and monocyclic aromatic compounds; this suggests that coal-liquid reformat could be used as a major blending substance with petroleum gasoline.

  7. Combustion and emission characteristics of Multiple Premixed Compression Ignition (MPCI) fuelled with naphtha and gasoline in wide load range

    Wang, Buyu; Wang, Zhi; Shuai, Shijin; Yang, Hongqiang; Wang, Jianxin

    2014-01-01

    Highlights: • Naphtha MPCI can operate stably in wide load range from 0.4 MPa to 1.4 MPa of IMEP. • Naphtha MPCI can achieve high thermal efficiency due to low exhaust loss. • Gasoline MPCI has low heat transfer loss than CDC and naphtha MPCI. • MPCI can produce low NO x emissions (<0.4 g/kW h) with the EGR ratio less than 30%. - Abstract: This paper investigates the effect of naphtha (RON = 65.6) and commercial gasoline (RON = 94.0) on Multiple Premixed Compression Ignition (MPCI) mode. The experiment is conducted on a single cylinder research diesel engine with compression ratio of 16.7. The engine is operated at an engine speed of 1600 rpm for the IMEP from 0.4 to 1.4 MPa. Commercial diesel (CN = 56.5) is also tested in Conventional Diesel Combustion (CDC) mode as a baseline. At each operating point, the injection strategy and intake conditions are adjusted to meet with the criteria (NO x < 0.4 g/kW h, soot < 0.06 m −1 , MPRR < 1 MPa/deg and CA50 < 20 CAD ATDC). The typical two-stage combustion characteristics of MPCI are obtained in both naphtha and gasoline. Stable combustion is achieved by naphtha in wide load range, while the engine fuelled with gasoline cannot operate stably at 0.4 MPa IMEP. The COV of IMEP of gasoline MPCI is higher than that of naphtha and diesel. However, gasoline has the low MPRR and the retarded CA50 at medium and high loads due to its longest ignition delay. As a result of low exhaust loss for naphtha and low heat transfer loss for gasoline, the thermal efficiencies are higher for both naphtha and gasoline in MPCI mode than diesel in CDC mode, even though diesel has the highest combustion efficiency. The separated combustion in MPCI leads to low cylinder temperature, and moderate EGR ratio (less than 30%) is needed to control NO x emissions under the limit of EURO VI

  8. Model predictive control in light naphtha distillation column of gasoline hydrogenation process

    Kornkrit Chiewchanchairat

    2015-03-01

    Full Text Available The main scope of this research is for designing and implementing of model predictive control (MPC on the light naphtha distillation column of gasoline hydrogenation process. This model is designed by using robust multivariable predictive control technology (RMPCT. The performance of MPC controller is better than PID controllers 32.1 % those are comparing by using as the same of objective function and also in the MPC controller can be used for steam optimization that is shown in this research, stream consumption is reduced 6.6 Kg/ m3 of fresh feed.

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

    None

    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.

  10. Effect of support surface treatment on the synthesis, structure, and performance of Co/CNT Fischer-Tropsch catalysts

    Eschemann, Thomas O.; Lamme, Wouter S.; Manchester, Rene L.; Parmentier, Tanja E.; Cognigni, Andrea; Ronning, Magnus; de Jong, Krijn P.

    We report the preparation of supported cobalt catalysts (9 wt% Co) on untreated (CNT) and surface-oxidized (CNT-ox) carbon nanotube materials by incipient wetness impregnation with solutions of cobalt nitrate in water, ethanol, or 1-propanol. The results show that by a judicious selection of solvent

  11. Iron alloy Fischer-tropsch catalysts--1. Oxidation-reduction studies of the Fe-Ni system

    Unmuth, E.E.; Schwartz, L.H.; Butt, J.B.

    1980-01-01

    Catalysts containing 5% iron, nickel, or 4:1 iron-nickel on silica were hydrogen-reduced at 425/sup 0/C for 12 or 24 hr, reoxidized in air for 2 or 4 hr, reduced again in hydrogen for 12 hr, and studied at each treatment step by Moessbauer spectroscopy, X-ray diffraction, and temperature-programed desorption. The nickel was reduced directly to the metal, redispersed during the oxidation, and gave 20% smaller particles in the second reduction than in the first reduction. The ..cap alpha..-Fe/sub 2/O/sub 3/ reduced via an Fe/sub 3/O/sub 4/ intermediate and yielded approx. 70% metallic iron and the second reduction produced about the same particle size as the first reduction. The alloy catalyst reduced into a mixture of two phases, a face-centered cubic phase containing approx. 37.5% Ni, i.e., the bulk equilibrium value, and a body-centered cubic phase, and the particle sizes obtained in the first and second reductions were similar. The activation energies for the reduction were determined.

  12. Carbon/H-ZSM-5 composites as supports for bi-functional Fischer-Tropsch synthesis catalysts

    Valero-Romero, M.J.; Sartipi, S.; Sun, X.; Rodríguez-Mirasol, J.; Cordero, T.; Kapteijn, F.; Gascon, J.

    2016-01-01

    Mesoporous H-ZSM-5–carbon composites, prepared via tetrapropylammonium hydroxide (TPAOH) post treatment of H-ZSM-5 followed by deposition of pyrolytic carbon, have been used as the support for the preparation of Co-based Fischer–Tropsch catalysts. The resulting catalysts display an improved

  13. Cobalt catalysts, and use thereof for the conversion of methanol and for fischer-tropsch synthesis, to produce hydrocarbons

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

    1988-01-01

    This patent describes a process useful for the conversion of methanol to hydrocarbons which comprises contacting the methanol at reaction conditions with a catalyst which comprises 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 a zirconium, hafnium, cerium, or uranium promoter, the weight ratio of the zirconium, hafnium, cerium, or uranium metal:cobalt being greater than about 0.010:1; the reaction conditions being defined within ranges as follows: Methanol:H/sub 2/ ratio: greater than about 4:1, Space Velocities, Hr/sup -1/:about 0.1 to 10, Temperatures, 0 C.:about 150 to 350, Methanol Partial Pressure, psia: about 100 to 1000

  14. Fischer-Tropsch Synthesis over Iron Manganese Catalysts: Effect of Preparation and Operating Conditions on Catalyst Performance

    Ali A. Mirzaei

    2009-01-01

    molar basis which is the most active catalyst for the conversion of synthesis gas to light olefins. The effects of different promoters and supports with loading of optimum support on the catalytic performance of catalysts are also studied. It was found that the catalyst containing 50%Fe/50%Mn/5 wt.%Al2O3 is an optimum-modified catalyst. The catalytic performance of optimal catalyst has been studied in operation conditions such as a range of reaction temperatures, H2/CO molar feed ratios and a range of total pressures. Characterization of both precursors and calcined catalysts is carried out by powder X-ray diffraction (XRD, scanning electron microscopy (SEM, BET specific surface area and thermal analysis methods such as TGA and DSC.

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

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

    The Fischer–Tropsch synthesis (FTS) reaction is one of the most promising processes to convert alternative energy sources, such as natural gas, coal or biomass, into liquid fuels and other high-value products. Despite its commercial implementation, we still lack fundamental insights into the various

  16. Naphtha vs. dieseline – The effect of fuel properties on combustion homogeneity in transition from CI combustion towards HCCI

    Vallinayagam, R.; An, Yanzhao; S.Vedharaj; Sim, Jaeheon; Chang, Junseok; Johansson, Bengt

    2018-01-01

    The scope of this research study pertains to compare the combustion and emission behavior between naphtha and dieseline at different combustion modes. In this study, US dieseline (50% US diesel + 50% RON 91 gasoline) and EU dieseline (45% EU diesel

  17. Numerical Simulations of Hollow-Cone Injection and Gasoline Compression Ignition Combustion With Naphtha Fuels

    Badra, Jihad A.

    2016-01-29

    Gasoline compression ignition (GCI), also known as partially premixed compression ignition (PPCI) and gasoline direct injection compression ignition (GDICI), engines have been considered an attractive alternative to traditional spark ignition (SI) engines. Lean-burn combustion with the direct injection of fuel eliminates throttle losses for higher thermodynamic efficiencies, and the precise control of the mixture compositions allows better emission performance such as NOx and particulate matter (PM). Recently, low octane gasoline fuel has been identified as a viable option for the GCI engine applications due to its longer ignition delay characteristics compared to diesel and lighter evaporation compared to gasoline fuel (Chang et al., 2012, "Enabling High Efficiency Direct Injection Engine With Naphtha Fuel Through Partially Premixed Charge Compression Ignition Combustion," SAE Technical Paper No. 2012-01-0677). The feasibility of such a concept has been demonstrated by experimental investigations at Saudi Aramco (Chang et al., 2012, "Enabling High Efficiency Direct Injection Engine With Naphtha Fuel Through Partially Premixed Charge Compression Ignition Combustion," SAE Technical Paper No. 2012-01-0677; Chang et al., 2013, "Fuel Economy Potential of Partially Premixed Compression Ignition (PPCI) Combustion With Naphtha Fuel," SAE Technical Paper No. 2013-01-2701). The present study aims to develop predictive capabilities for low octane gasoline fuel compression ignition (CI) engines with accurate characterization of the spray dynamics and combustion processes. Full three-dimensional simulations were conducted using converge as a basic modeling framework, using Reynolds-averaged Navier-Stokes (RANS) turbulent mixing models. An outwardly opening hollow-cone spray injector was characterized and validated against existing and new experimental data. An emphasis was made on the spray penetration characteristics. Various spray breakup and collision models have been

  18. Characteristics of spray from a GDI fuel injector for naphtha and surrogate fuels

    Wang, Libing

    2016-11-18

    Characterization of the spray angle, penetration, and droplet size distribution is important to analyze the spray and atomization quality. In this paper, the spray structure development and atomization characterization of two naphtha fuels, namely light naphtha (LN) and whole naphtha (WN) and two reference fuel surrogates, i.e. toluene primary reference fuel (TPRF) and primary reference fuel (PRF) were investigated using a gasoline direct injection (GDI) fuel injector. The experimental setup included a fuel injection system, a high-speed imaging system, and a droplet size measurement system. Spray images were taken by using a high-speed camera for spray angle and penetration analysis. Sauter mean diameter, Dv(10), Dv(50), Dv(90), and particle size distribution were measured using a laser diffraction technique. Results show that the injection process is very consistent for different runs and the time averaged spray angles during the measuring period are 103.45°, 102.84°, 102.46° and 107.61° for LN, WN, TPRF and PRF, respectively. The spray front remains relatively flat during the early stage of the fuel injection process. The peak penetration velocities are 80 m/s, 75 m/s, 75 m/s and 79 m/s for LN, WN, TPRF and PRF, respectively. Then velocities decrease until the end of the injection and stay relatively stable. The transient particle size and the time-averaged particle size were also analyzed and discussed. The concentration weighted average value generally shows higher values than the arithmetic average results. The average data for WN is usually the second smallest except for Dv90, of which WN is the biggest. Generally the arithmetic average particle sizes of PRF are usually the smallest, and the sizes does not change much with the measuring locations. For droplet size distribution results, LN and WN show bimodal distributions for all the locations while TPRF and PRF shows both bimodal and single peak distribution patterns. The results imply that droplet size

  19. New ANFO explosives made of ammonium nitrate of increased porosity and naphtha

    Kutsarov, B.; Mavrodieva, R.; Ivanov, I.; Stoyanov, V.; Georgiev, N.; Krumov, I.; Katsarski, I.; Vakliev, I.

    1990-01-01

    Discusses results achieved by the KNIIPPI Niproruda Research Institute and the Osogovo enterprise in improving the quality of ANFO explosives. Ammonium nitrate with increased porosity was treated by water steam and wetting agents and then thermally treated. Naphtha in a quantity of up to 8% was then added to the ammonium nitrate to produce a powerful and stable explosive. The quality of explosive cartridges was tested first in the laboratory using the Schaffler apparatus. Test results were very satisfactory (better porosity, higher detonation velocity (2200-3600 m/s), better stability). Industrial experiments carried out in several underground mines also produced satisfactory results (better output in roadway drivage at lower operating cost and better safety). 8 refs.

  20. Stability of cracked naphthas from thermal and catalytic processes and their additive response. Part 1. Evaluation of stability and additive response

    Nagpal, J.M.; Joshi, G.C.; Rastogi, S.N. [Indian Institute of Petroleum, Dehradun (India)

    1995-05-01

    Olefinic naphthas derived from fluid catalytic cracking (FCC) or thermal cracking units are increasingly being used in high-octane motor gasoline with growing concern for resulting fuel quality. Hindered phenols and substituted arylamines are the two classes of antioxidants generally used for improving the stability of gasoline. The olefin types in cracked naphthas depend strongly on the process from which they are derived and hence are expected to show different responses with different antioxidants. However, systematic information on this aspect of antioxidant action is non-existent in the literature. Using two representative commercial antioxidants from each class with representative naphthas (FCC, visbreaking and coker), it was found that phenolic antioxidants gave a better response with thermally cracked naphthas. With amine-type antioxidants no clear preference could be observed. 28 refs., 6 figs., 4 tabs.

  1. Emission Performance of Low Cetane Naphtha as Drop-In Fuel on a Multi-Cylinder Heavy-Duty Diesel Engine and Aftertreatment System

    LeePhD, John [Aramco Services Company; TzanetakisPhD, Tom [Aramco Services Company; Travers, Michael [Aramco Services Company; Storey, John Morse [ORNL; DeBusk, Melanie Moses [ORNL; Lance, Michael J [ORNL; Partridge Jr, William P [ORNL

    2017-01-01

    With higher volatility and longer ignition delay characteristics than typical diesel fuel, low cetane naphtha fuel has been shown to promote partially premixed combustion and produce lower soot for improved fuel economy. In this study, emission performance of low cetane, low octane naphtha (CN 35, RON 60) as a drop-in fuel was examined on a MY13 Cummins ISX15 6-cylinder heavy-duty on-highway truck engine and aftertreatment system. Using the production hardware and development calibrations, both the engine-out and tailpipe emissions of naphtha and ultra-low sulfur diesel (ULSD) fuels were examined during the EPA s heavy-duty emission testing cycles. Without any modification to the calibrations, the tailpipe emissions were comparable when using naphtha or ULSD on the heavy duty Federal Test Procedure (FTP) and ramped modal cycle (RMC) test cycles. Overall lower CO2 emissions and fuel consumption were also measured for naphtha due in part to its higher heating value and higher hydrogen to carbon ratio. Engine-out and tailpipe NOx emissions were lower for naphtha fuel at the same catalyst conversion levels and measured particulate matter (PM) emissions were also lower when using naphtha due to its higher volatility and lower aromatic content compared to ULSD. To help assess the potential impact on diesel particulate filter design and operation, engine-out PM samples were collected and characterized at the B50 operating point. A significant reduction in elemental carbon (EC) within the particulate emissions was found when using naphtha compared to ULSD.

  2. Effect of Feed Composition Changing at Naphtha Catalytic Reforming Unit Due to Involvement of Gasoline Fraction Obtained by Diesel Fuels Hydrodewaxing into the Processing

    Belinskaya, Natalia Sergeevna; Ivanchina, Emilia Dmitrievna; Ivashkina, Elena Nikolaevna; Frantsina, Evgeniya Vladimirovna; Silko, Galina Yurievna

    2014-01-01

    One of the primary products of hydrodewaxing process is stable gasoline, which is characterized by low octane number on the one hand. On the other hand, it contains a significant amount of iso-paraffins (on average 45% wt.) and naphthenes (on average 25% wt.), which are reagents in the naphtha catalytic reforming process primary reactions. Feasibility of stable gasoline obtained by means of diesel fuel catalytic hydrodewaxing process involving into the processing at the naphtha catalytic refo...

  3. Developing a Steady-state Kinetic Model for Industrial Scale Semi-Regenerative Catalytic Naphtha Reforming Process

    Seif Mohaddecy, R.

    2014-05-01

    Full Text Available Due to the demand for high octane gasoline as a transportation fuel, the catalytic naphtha reformer has become one of the most important processes in petroleum refineries. In this research, the steady-state modelling of a catalytic fixed-bed naphtha reforming process to predict the momentous output variables was studied. These variables were octane number, yield, hydrogen purity, and temperature of all reforming reactors. To do such a task, an industrial scale semi-regenerative catalytic naphtha reforming unit was studied and modelled. In addition, to evaluate the developed model, the predicted variables i.e. outlet temperatures of reactors, research octane number, yield of gasoline and hydrogen purity were compared against actual data. The results showed that there is a close mapping between the actual and predicted variables, and the mean relative absolute deviation of the mentioned process variables were 0.38 %, 0.52 %, 0.54 %, 0.32 %, 4.8 % and 3.2 %, respectively.

  4. A surrogate fuel formulation to characterize heating and evaporation of light naphtha droplets

    Kabil, I.

    2018-03-08

    Light naphtha (LN) is gaining interest in internal combustion (IC) engine applications due to its low refining cost and higher heating values compared to commercial gasoline. To properly describe the chemical and physical behavior of the LN fuel under IC engine conditions, a systematic procedure to develop unified physical and chemical surrogates is described. The reduced component models to describe the chemical characteristics of LN are combined with the effective thermal conductivity/effective diffusivity (ETC/ED) model to represent the accurate evaporation behavior. Three surrogate fuels consisting of three to five components are presented and their performance in heating and evaporation of a single LN droplet is compared against the conventional primary reference fuel (PRF65) surrogate which is based on chemical aspects only. Unlike the previous approaches, the new surrogates also target matching the hydrogen-to-carbon ratio and research octane number in order to accurately describe the chemical behavior of the fuel. Subsequently, the performance of the surrogates in describing spray characteristics is tested by computational simulations compared with experimental measurements. The simulations were carried out using CONVERGE CFD package. The ETC/ED model was implemented into CONVERGE using user-defined functions. The predicted spray penetration length for the developed surrogates shows good agreement with the experimental data. At engine-like conditions, the ETC/ED model predicts higher vapor mass than the infinite thermal conductivity/infinite diffusivity model, hence showing the expected trend by incorporating the realistic droplet heating process.

  5. A surrogate fuel formulation to characterize heating and evaporation of light naphtha droplets

    Kabil, I.; Sim, J.; Badra, J.A.; Eldrainy, Y.; Abdelghaffar, W.; Mubarak Ali, M. Jaasim; Ahmed, Ahfaz; Sarathy, Mani; Im, Hong G.; Elwardani, Ahmed Elsaid

    2018-01-01

    Light naphtha (LN) is gaining interest in internal combustion (IC) engine applications due to its low refining cost and higher heating values compared to commercial gasoline. To properly describe the chemical and physical behavior of the LN fuel under IC engine conditions, a systematic procedure to develop unified physical and chemical surrogates is described. The reduced component models to describe the chemical characteristics of LN are combined with the effective thermal conductivity/effective diffusivity (ETC/ED) model to represent the accurate evaporation behavior. Three surrogate fuels consisting of three to five components are presented and their performance in heating and evaporation of a single LN droplet is compared against the conventional primary reference fuel (PRF65) surrogate which is based on chemical aspects only. Unlike the previous approaches, the new surrogates also target matching the hydrogen-to-carbon ratio and research octane number in order to accurately describe the chemical behavior of the fuel. Subsequently, the performance of the surrogates in describing spray characteristics is tested by computational simulations compared with experimental measurements. The simulations were carried out using CONVERGE CFD package. The ETC/ED model was implemented into CONVERGE using user-defined functions. The predicted spray penetration length for the developed surrogates shows good agreement with the experimental data. At engine-like conditions, the ETC/ED model predicts higher vapor mass than the infinite thermal conductivity/infinite diffusivity model, hence showing the expected trend by incorporating the realistic droplet heating process.

  6. Effect of naphtha diluent on greenhouse gases and reduced sulfur compounds emissions from oil sands tailings.

    Gee, Kathleen F; Poon, Ho Yin; Hashisho, Zaher; Ulrich, Ania C

    2017-11-15

    The long-term storage of oil sands tailings has resulted in the evolution of greenhouse gases (CH 4 and CO 2 ) as a result of residual organics biodegradation. Recent studies have identified black, sulfidic zones below the tailings-water interface, which may be producing toxic sulfur-containing gases. An anaerobic mesocosm study was conducted over an 11-week period to characterize the evolution of CH 4 , CO 2 and reduced sulfur compounds (RSCs) (including H 2 S) in tailings as it relates to naphtha-containing diluent concentrations (0.2, 0.8, and 1.5% w/v) and microbial activity. Our results showed that RSCs were produced first at 0.12μmol°RSCs/mL MFT (1.5% w/v diluent treatment). RSCs contribution (from highest to lowest) was H 2 S and 2-methylthiophene>2.5-dimethylthiophene>3-methylthiophene>thiofuran>butyl mercaptan>carbonyl sulfide, where H 2 S and 2-methylthiophene contributed 81% of the gas produced. CH 4 and CO 2 production occurred after week 5 at 40.7μmolCH 4 /mL MFT and 5.9μmolCO 2 /mL MFT (1.5% w/v diluent treatment). The amount of H 2 S and CH 4 generated is correlated to the amount of diluent present and to microbial activity as shown by corresponding increases in sulfate-reducers' Dissimilatory sulfite reductase (DsrAB) gene and methanogens' methyl-coenzyme M reductase (MCR) gene. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Effect of oxide film of heat resistant alloy on coke formation during naphtha pyrolysis

    Shiratori, Nobuo; Hosoya, Keizo

    2002-01-01

    The coking of cracking furnace tubes has been an important subject of ethylene plants. The coke formations rate on the heat resistant alloys of 20Cr-4.5Al-0.5Y 2 O 3 covered with Al 2 O 3 oxide film and 25Cr-35Ni covered with Cr 2 O 3 oxide film during the thermal cracking of naphtha was quantitatively evaluated at temperatures ranging from 810 to 930 .deg. C. The experimental results showed that the coke formation rate on 20Cr-4.5Al-0.5Y 2 O 3 was lower than that on 25Cr-35Ni because of the difference of a catalytic activity to coke formation, especially in the case of a pre-carburized condition. Namely, the Al 2 O 3 formed on 20Cr-4.5Al-0.5Y 2 O 3 was stable even after carburization treatment and inert for catalytic coke formation, while coke formation on 25Cr-35Ni was under the control of catalytic coke formation, and carburization of 25Cr-35Ni accelerated catalytic coke formation. The stability of Al 2 O 3 and Cr 2 O 3 in a hydrocarbon with steam environment was thermodynamically calculated in 0.1mol of steam, 0.2mol of ethylene and 0.1mol of methane at 1,100 .deg. C. The simulation result shows that Al 2 O 3 is exceedingly stable while Cr 2 O 3 could be decomposed partially into chromium carbide. Therefore, it is concluded that Al 2 O 3 on 20Cr-4.5Al-0.5Y 2 O 3 is more stable than Cr 2 O 3 on 25Cr-35Ni, and 20Cr-4.5Al-0.5Y 2 O 3 is more resistant to coke formation and carburization than 25Cr-35Ni in a hydrocarbon with steam environment at high temperature

  8. Stability of cracked naphthas from thermal and catalytic processes and their additive response. Part II. Composition and effect of olefinic structures

    Nagpal, J.M.; Joshi, G.C.; Rastogi, S.N. [Indian Institute of Petroleum, Dehradun (India)

    1995-05-01

    Olefinic concentrates were separated from two naphthas, one from fluid catalytic cracking (FCC) and one thermal crackate, using column chromatography. The composition and structure of the olefins were determined by a combination of analytical techniques. FCC naphthas contain relatively higher levels of conjugated dienes. The monoolefins are highly branched. The thermal crackates have higher levels of {alpha}-olefins and abound in mono-, di-, tri- and conjugated cyclic olefins. Stability tests on these olefinic concentrates blended in low-S,N straight-run naphtha showed that cyclic olefins are very active gum formers. Representative commercial antioxidants (hindered phenols and phenylenediamines) both gave good responses to different olefin concentrate test blends. Hindered phenols had a marginally better effect. 14 refs., 5 figs., 3 tabs.

  9. Optimization of the reaction parameters of heavy naphtha reforming process using Pt-Re/Al2O3 catalyst system

    Hussien A. Elsayed

    2017-12-01

    Full Text Available One of the most significant procedures in oil refineries is naphtha catalytic reforming unit in which high octane gasoline is gained. Normally, in oil refineries, flow instability in the composition of feedstock can affect the product quality. The aim of the present work was focused on modifications of the final product flow rate and product’s octane number with respect to the modifications of the feedstock composition. The main three reforming reactions investigated, namely; dehydrogenation, dehydrocyclization, and hydrocracking were conducted employing silica supported bimetallic (Pt-Re patented catalyst. Optimization of the catalytic process reaction conditions, i.e.; temperature, hydrogen pressure and liquid hourly space velocity (LHSV was carried out with regard to conversion and selectivity. The optimization results indicated that heavy naphtha component conversion (paraffin’s and naphthenes increases with an increasing in reaction temperature and pressure while decreases with an increase in LHSV. The kinetic study of catalytic reforming reactions reported helped establishing the reaction model explicitly.

  10. Feasibility of the direct generation of hydrogen for fuel-cell-powered vehicles by on-board steam reforming of naphtha

    Darwish, Naif A.; Hilal, Nidal; Versteeg, Geert; Heesink, Bert

    2004-01-01

    A process flow sheet for the production of hydrogen to run a 50 kW fuel-cell-powered-vehicle by steam reforming of naphtha is presented. The major units in the flow sheet involve a desulfurization unit, a steam reformer, a low temperature (LT) shift reactor, a methanation reactor, and a membrane

  11. Heating and Efficiency Comparison of a Fischer-Tropsch (FT) Fuel, JP-8+100, and Blends in a Three-Cup Combustor Sector

    Thomas, Anna E.; Shouse, Dale T.; Neuroth, Craig; Lynch, Amy; Frayne, Charles W.; Stutrud, Jeffrey S.; Corporan, Edwin; Hankins, Terry; Saxena, Nikita T.; Hendricks, Robert C.

    2012-01-01

    In order to realize alternative fueling for military and commercial use, the industry has set forth guidelines that must be met by each fuel. These aviation fueling requirements are outlined in MIL-DTL-83133F(2008) or ASTM D 7566-Annex standards and are classified as drop-in fuel replacements. This paper provides combustor performance data for synthetic-paraffinic-kerosene- (SPK-) type (Fisher-Tropsch (FT)) fuel and blends with JP-8+100, relative to JP-8+100 as baseline fueling. Data were taken at various nominal inlet conditions: 75 psia (0.52 MPa) at 500 aF (533 K), 125 psia (0.86 MPa) at 625 aF (603 K), 175 psia (1.21 MPa) at 725 aF (658 K), and 225 psia (1.55 MPa) at 790 aF (694 K). Combustor performance analysis assessments were made for the change in flame temperatures, combustor efficiency, wall temperatures, and exhaust plane temperatures at 3%, 4%, and 5% combustor pressure drop (% P) for fuel:air ratios (F/A) ranging from 0.010 to 0.025. Significant general trends show lower liner temperatures and higher flame and combustor outlet temperatures with increases in FT fueling relative to JP-8+100 fueling. The latter affects both turbine efficiency and blade/vane life. In general, 100% SPK-FT fuel and blends with JP-8+100 produce less particulates and less smoke and have lower thermal impact on combustor hardware.

  12. Iron Fischer-Tropsch Catalysts Prepared by Solvent-Deficient Precipitation (SDP: Effects of Washing, Promoter Addition Step, and Drying Temperature

    Kyle M. Brunner

    2015-07-01

    Full Text Available A novel, solvent-deficient precipitation (SDP method for catalyst preparation in general and for preparation of iron FT catalysts in particular is reported. Eight catalysts using a 23 factorial design of experiments to identify the key preparation variables were prepared. The catalysts were characterized by electron microprobe, N2 adsorption, TEM, XRD, and ICP. Results show that the morphology of the catalysts, i.e., surface area, pore volume, pore size distribution, crystallite sizes, and promoter distribution are significantly influenced by (1 whether or not the precursor catalyst is washed, (2 the promoter addition step, and (3 the drying condition (temperature. Consequently, the activity, selectivity, and stability of the catalysts determined from fixed-bed testing are also affected by these three variables. Unwashed catalysts prepared by a one-step method and dried at 100 °C produced the most active catalysts for FT synthesis. The catalysts of this study prepared by SDP compared favorably in activity, productivity, and stability with Fe FT catalysts reported in the literature. It is believed that this facile SDP approach has promise for development of future FT catalysts, and also offers a potential alternate route for the preparation of other catalysts for various other applications.

  13. Power to Fuels: Dynamic Modeling of a Slurry Bubble Column Reactor in Lab-Scale for Fischer Tropsch Synthesis under Variable Load of Synthesis Gas

    Siavash Seyednejadian

    2018-03-01

    Full Text Available This research developed a comprehensive computer model for a lab-scale Slurry Bubble Column Reactor (SBCR (0.1 m Dt and 2.5 m height for Fischer–Tropsch (FT synthesis under flexible operation of synthesis gas load flow rates. The variable loads of synthesis gas are set at 3.5, 5, 7.5 m3/h based on laboratory adjustments at three different operating temperatures (483, 493 and 503 K. A set of Partial Differential Equations (PDEs in the form of mass transfer and chemical reaction are successfully coupled to predict the behavior of all the FT components in two phases (gas and liquid over the reactor bed. In the gas phase, a single-bubble-class-diameter (SBCD is adopted and the reduction of superficial gas velocity through the reactor length is incorporated into the model by the overall mass balance. Anderson Schulz Flory distribution is employed for reaction kinetics. The modeling results are in good agreement with experimental data. The results of dynamic modeling show that the steady state condition is attained within 10 min from start-up. Furthermore, they show that step-wise syngas flow rate does not have a detrimental influence on FT product selectivity and the dynamic modeling of the slurry reactor responds quite well to the load change conditions.

  14. Study of selective Fischer-Tropsch catalysts synthesized by the destruction of bimetallic carbonyl complexes on activated γ-Al2O3 support

    Maksimov, Yu.V.; Matveev, V.V.; Suzdalev, I.P.; Khomenko, T.I.; Kadushin, A.A.

    1990-01-01

    The bimetallic catalysts obtained by the deposition of a Fe-Co binuclear cluster on the dehydroxylated γ-Al 2 O 3 are studied and compared to some other relative systems. These bimetallic catalysts are found to be active and selective in olefin synthesis. This is connected with the formation of Fe-Co contact which is detectable by Moessbauer spectroscopy. (orig.)

  15. Impact of H2/CO ratios on phase and performance of Mn-modified Fe-based Fischer Tropsch synthesis catalyst

    Ding, Mingyue; Yang, Yong; Li, Yongwang; Wang, Tiejun; Ma, Longlong; Wu, Chuangzhi

    2013-01-01

    Highlights: ► Decreasing H 2 /CO ratio facilitated the conversion of Fe 3 O 4 to iron carbides on the surface layers. ► The formation of surface carbonaceous species was promoted in higher CO partial pressure. ► The formation of iron carbides on the surface of Fe 3 O 4 provided the FTS active sites. ► Decreasing H 2 /CO ratio promoted the product shifting towards heavy hydrocarbons. - Abstract: Impacts of H 2 /CO ratios on both the bulky and surface compositions of an iron–manganese based catalyst were investigated by XRD, MES, N 2 -physisorption, XPS and LRS. Fischer–Tropsch (F–T) synthesis performances were studied in a slurry-phase continuously stirred tank reactor. The characterization results showed that the fresh catalyst was comprised of the hematite, which was converted firstly to Fe 3 O 4 , and then carburized to iron carbides in both the bulk and surface regions under different H 2 /CO ratios atmosphere. Pretreatment in lower H 2 /CO ratio facilitated the formation of iron carbides on the surface of magnetite and surface carbonaceous species. During the F–T synthesis reaction, the catalyst reduced in lower H 2 /CO ratio presented higher catalytic activity, which is assigned probably to the formation of more iron carbides (especially for χ-Fe 5 C 2 ) on the surface of magnetite. The increase of CO partial pressure promoted the product distribution shifting towards heavy hydrocarbons

  16. Comparison of Cobalt based Catalysts Supported on MWCNT and SBA-15 Supporters for Fischer-tropsch Synthesis by Using Novel Vortex Type Reactor

    Yakubov, A.; Shahrun, M.S.; Kutty, M.G.; Hamid, S.B.A.; Piven, V.

    2011-01-01

    10 and 40 wt% Co/ Multi wall Carbon Nano tubes (MWCNT) and 10 and 40 wt% Co/ Santa Barbara Amorphous-15 (SBA) catalysts were prepared via incipient wetness impregnation and characterized by Scanning Electron Microscopy equipped with Energy Dispersive X-ray Spectroscopy (SEM and EDX), N 2 adsorption-desorption (BET), X-ray Diffractometry (XRD), Transmission Electron Microscopy (TEM) and Temperature- Programmed Reduction and H 2 desorption TPD/RO. Co(NO 3 ) 2 * 6H 2 O was used as a cobalt precursor. 200 ml hastelloy autoclave reactor was implemented to see the performance of the catalysts. This report presents details about the catalyst synthesis and reactor study. (author)

  17. Fundamentals of Melt infiltration for the Preparation of Supported Metal Catalysts.The Case of Co/SiO2 Fischer-Tropsch Synthesis

    Eggenhuisen, T.M.|info:eu-repo/dai/nl/313959498; den Breejen, J.P.|info:eu-repo/dai/nl/304837318; Verdoes, D.; de Jongh, P.E.|info:eu-repo/dai/nl/186125372; de Jong, K.P.|info:eu-repo/dai/nl/06885580X

    2013-01-01

    We explored melt infiltration of mesoporous silica supports to prepare supported metal catalysts with high loadings and controllable particle sizes. Melting of Co(NO3)2 ·6H2O in the presence of silica supports was studied in situ with differential scanning calorimetry. The melting point depression

  18. Potential of the technology gas to liquids -GTL in Colombia

    Perez Angulo, Julio Cesar; Cabarcas Simancas, Manuel E; Archila Castro, Jesus; Tobias, Yamil Yubran

    2005-01-01

    Natural gas has a great potential because of the large reserves that currently exist at a worldwide level and because it is a cleaner source of energy than petroleum, but having the disadvantage of requiring high costs for its transportation. For this reason many alternatives have loomed for the development of reserves. Among these is the conversion of natural gas into synthetic ultra-clean fuels, called GTL, or gas-to-liquids. Through this process, Fischer-Tropsch for the production of diesel, naphtha and specialized products, which are used not only to effectively utilize natural gas reserves, but also, to cover at the need of more environmentally friendly fuels. This article will shed light on GTL technologies, presenting on a first instance an analysis of the different stages of the Fischer-Tropsch process, then the current status of this technology, afterwards the costs of investment and the necessary conditions for a project of this kind to be carried out and finally, and analysis of the applicability or projection for this technology in Colombia. Based on recent studies, it has been observed that is technology has surpassed its demonstrations stage and it is now at a maximum point of interest where companies like Sasol (the largest worldwide company in the area of synthetic carbon-based fuels), Chevron Texaco, Syntroleum, Exxon Mobil, Conoco Phillips, BP Rentech and shell. These companies have performed successful studies for the applicability of the Fischer-Tropsch technology at a large scale, and they will begin to build a number of large plants within the next few years, principally motivated by the low costs of gas and high prices of crude oil

  19. GDI fuel sprays of light naphtha, PRF95 and gasoline using a piezoelectric injector under different ambient pressures

    Wu, Zengyang

    2018-03-20

    This study investigates fuel sprays of light naphtha (LN), primary reference fuel (PRF) and gasoline under different ambient pressures with an outwardly opening piezo gasoline direct injection (GDI) fuel injector. The tested gasoline fuel (regular grade with up to 10% ethanol, E10) was obtained by mixing fuels with AKI (the average of the research octane number (RON) and the motor octane number (MON)) of 87 from three local gas stations. Primary reference fuel (PRF) is commonly used as gasoline surrogate fuel and is blended by iso-octane and n-heptane. PRF95 is the blend of 95% iso-octane and 5% n-heptane by volume. LN fuel was provided by Saudi Aramco Oil Company. Five different ambient pressure conditions varied from 1 bar to 10 bar were tested. The spray was visualized by applying a Mie-scattering technique and a high-speed camera was employed to capture the spray images. The spray structure, spray angle, spray penetration length and spray front fluctuation were analyzed and compared among three fuels. Spray images show that a clear filamentary hollow-cone spray structure is formed for all three fuels at atmospheric conditions, and toroidal recirculation vortexes are observed at the downstream spray edges. A higher ambient pressure leads to a stronger vortex located closer to the injector outlet. Generally speaking, larger spray angles are found under higher ambient pressure conditions for all three fuels. Gasoline fuel always has the largest spray angle for each ambient pressure, while PRF95 has the smallest at most time. For each fuel, the spray front penetration length and spray front penetration velocity decrease with increasing ambient pressure. LN, PRF95 and gasoline show similar penetration length and velocity under the tested conditions. A two-stage spray front fluctuation pattern is observed for all three fuels. Stage one begins from the start of the injection and ends at 450–500 μs after the start of the injection trigger (ASOIT) with a slow

  20. GDI fuel sprays of light naphtha, PRF95 and gasoline using a piezoelectric injector under different ambient pressures

    Wu, Zengyang; Wang, Libing; Badra, Jihad A.; Roberts, William L.; Fang, Tiegang

    2018-01-01

    This study investigates fuel sprays of light naphtha (LN), primary reference fuel (PRF) and gasoline under different ambient pressures with an outwardly opening piezo gasoline direct injection (GDI) fuel injector. The tested gasoline fuel (regular grade with up to 10% ethanol, E10) was obtained by mixing fuels with AKI (the average of the research octane number (RON) and the motor octane number (MON)) of 87 from three local gas stations. Primary reference fuel (PRF) is commonly used as gasoline surrogate fuel and is blended by iso-octane and n-heptane. PRF95 is the blend of 95% iso-octane and 5% n-heptane by volume. LN fuel was provided by Saudi Aramco Oil Company. Five different ambient pressure conditions varied from 1 bar to 10 bar were tested. The spray was visualized by applying a Mie-scattering technique and a high-speed camera was employed to capture the spray images. The spray structure, spray angle, spray penetration length and spray front fluctuation were analyzed and compared among three fuels. Spray images show that a clear filamentary hollow-cone spray structure is formed for all three fuels at atmospheric conditions, and toroidal recirculation vortexes are observed at the downstream spray edges. A higher ambient pressure leads to a stronger vortex located closer to the injector outlet. Generally speaking, larger spray angles are found under higher ambient pressure conditions for all three fuels. Gasoline fuel always has the largest spray angle for each ambient pressure, while PRF95 has the smallest at most time. For each fuel, the spray front penetration length and spray front penetration velocity decrease with increasing ambient pressure. LN, PRF95 and gasoline show similar penetration length and velocity under the tested conditions. A two-stage spray front fluctuation pattern is observed for all three fuels. Stage one begins from the start of the injection and ends at 450–500 μs after the start of the injection trigger (ASOIT) with a slow

  1. Second row transition metal sulfides for the hydrotreatment of coal-derived naphtha. 1. Catalyst preparation, characterization and comparison of rate of simultaneous removal of total sulfur, nitrogen and oxygen

    Raje, A.P.; Liaw, S.-J.; Srinivasan, R.; Davis, B.H. [University of Kentucky, Lexington, KY (United States). Center for Applied Energy Research

    1997-03-13

    Naphtha derived from an Illinois No. 6 coal contains appreciable quantities of sulfur-, nitrogen- and oxygen-containing compounds. The hydrotreatment of this naphtha was evaluated over unsupported transition metal sulfide catalysts (Ru, Rh, Mo, Pd, Zr, Mb). The catalysts were prepared by a room temperature precipitation reaction. Surface areas, crystalline phase and particle size distributions were determined by Brunauer-Emmet-Teller (BET), X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. A comparison of average particle sizes calculated from these three techniques has enable the understanding of the morphology of the transition metal sulfides. The catalysts exhibit a so-called volcano plot for the HDS of dibenzothiophene. Similar so-called volcano plots are also exhibited for the simultaneous hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and the hydrodeoxygenation (HDO) of the coal-derived naphtha containing a mixture of heteroatoms. The order of reactivity of the transition metal catalysts is the same for all three of the processes. Ruthenium sulfide is the most active catalyst for HDS, HDN and HDO of the coal-derived naphtha. 22 refs., 3 figs., 4 tabs.

  2. Modeling of an axial flow, spherical packed-bed reactor for naphtha reforming process in the presence of the catalyst deactivation

    Iranshahi, D.; Pourazadi, E.; Paymooni, K.; Bahmanpour, A.M.; Rahimpour, M.R.; Shariati, A. [Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345 (Iran, Islamic Republic of)

    2010-12-15

    Improving the octane number of the aromatics' compounds has always been an important matter in refineries and lots of investigations have been made concerning this issue. In this study, an axial-flow spherical packed-bed reactor (AF-SPBR) is considered for naphtha reforming process in the presence of catalyst deactivation. Model equations are solved by the orthogonal collocation method. The AF-SPBR results are compared with the plant data of a conventional tubular packed-bed reactor (TR). The effects of some important parameters such as pressure and temperature on aromatic and hydrogen production rates and catalyst activity have been investigated. Higher production rates of aromatics can successfully be achieved in this novel reactor. Moreover, results show the capability of flow augmentation in the proposed configuration in comparison with the TR. This study shows the superiority of AF-SPBR configuration to the conventional types. (author)

  3. Optimization of the vapor/carbon rate in the project of a hydrogen generation unit from naphtha; Otimizacao da relacao vapor/carbono no projeto de uma unidade de geracao de hidrogenio a partir de nafta

    Baleroni, Dirceu; Silva, Mauro [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas

    1993-12-31

    This paper presents a study of the economic optimization of the steam to carbon ratio in the design of a 550,000 Nm{sup 3}/day plant producing hydrogen from naphtha. The effect of the steam to carbon ratio on the production cost and on the plant operational flexibility was taken into account. The process includes feed desulfurization, steal reforming, carbon monoxide conversion and pressure swing adsorption purification. The paper analyzes the influence of the steam to carbon ratio on the purity of the hydrogen product and on the operational cost of an existing 212,000 Nm{sup 3}/day hydrogen from naphtha unit. (author) 17 refs., 2 figs., 11 tabs

  4. Selective Metathesis of α-Olefins from Bio-Sourced Fischer–Tropsch Feeds

    Rouen, Mathieu; Queval, Pierre; Borre, Etienne; Falivene, Laura; Poater, Albert; Berthod, Mikael; Hugues, Francois; Cavallo, Luigi; Basle, Olivier; Olivier-Bourbigou, Helene; Mauduit, Marc

    2016-01-01

    The search for a low-cost process for the valorization of linear alpha-olefins combining high productivity and high selectivity is a longstanding goal for chemists. Herein, we report a soluble ruthenium olefin metathesis catalyst that performs the conversion of linear alpha-olefins to longer internal linear olefins with high selectivity (>99%) under neat conditions at low loadings (50 ppm) and without the need of expensive additives. This robust catalytic process allowed us to efficiently and selectively re-equilibrate the naphtha fraction (C-5-C-8) of a Fischer-Tropsch feed derived from non petroleum resources to a higher-value product range (C-9-C-14), useful as detergent and plasticizer precursors.

  5. Selective Metathesis of α-Olefins from Bio-Sourced Fischer–Tropsch Feeds

    Rouen, Mathieu

    2016-10-14

    The search for a low-cost process for the valorization of linear alpha-olefins combining high productivity and high selectivity is a longstanding goal for chemists. Herein, we report a soluble ruthenium olefin metathesis catalyst that performs the conversion of linear alpha-olefins to longer internal linear olefins with high selectivity (>99%) under neat conditions at low loadings (50 ppm) and without the need of expensive additives. This robust catalytic process allowed us to efficiently and selectively re-equilibrate the naphtha fraction (C-5-C-8) of a Fischer-Tropsch feed derived from non petroleum resources to a higher-value product range (C-9-C-14), useful as detergent and plasticizer precursors.

  6. Multiple response optimization for Cu, Fe and Pb determination in naphtha by graphite furnace atomic absorption spectrometry with sample injection as detergent emulsion

    Brum, Daniel M.; Lima, Claudio F.; Robaina, Nicolle F.; Fonseca, Teresa Cristina O.; Cassella, Ricardo J.

    2011-01-01

    The present paper reports the optimization for Cu, Fe and Pb determination in naphtha by graphite furnace atomic absorption spectrometry (GF AAS) employing a strategy based on the injection of the samples as detergent emulsions. The method was optimized in relation to the experimental conditions for the emulsion formation and taking into account that the three analytes (Cu, Fe and Pb) should be measured in the same emulsion. The optimization was performed in a multivariate way by employing a three-variable Doehlert design and a multiple response strategy. For this purpose, the individual responses of the three analytes were combined, yielding a global response that was employed as a dependent variable. The three factors related to the optimization process were: the concentration of HNO 3 , the concentration of the emulsifier agent (Triton X-100 or Triton X-114) in aqueous solution used to emulsify the sample and the volume of solution. At optimum conditions, it was possible to obtain satisfactory results with an emulsion formed by mixing 4 mL of the samples with 1 mL of a 4.7% w/v Triton X-100 solution prepared in 10% v/v HNO 3 medium. The resulting emulsion was stable for 250 min, at least, and provided enough sensitivity to determine the three analytes in the five samples tested. A recovery test was performed to evaluate the accuracy of the optimized procedure and recovery rates, in the range of 88-105%; 94-118% and 95-120%, were verified for Cu, Fe and Pb, respectively.

  7. Multiple response optimization for Cu, Fe and Pb determination in naphtha by graphite furnace atomic absorption spectrometry with sample injection as detergent emulsion

    Brum, Daniel M.; Lima, Claudio F. [Departamento de Quimica, Universidade Federal de Vicosa, A. Peter Henry Rolfs s/n, Vicosa/MG, 36570-000 (Brazil); Robaina, Nicolle F. [Departamento de Quimica Analitica, Universidade Federal Fluminense, Outeiro de S.J. Batista s/n, Centro, Niteroi/RJ, 24020-141 (Brazil); Fonseca, Teresa Cristina O. [Petrobras, Cenpes/PDEDS/QM, Av. Horacio Macedo 950, Ilha do Fundao, Rio de Janeiro/RJ, 21941-915 (Brazil); Cassella, Ricardo J., E-mail: cassella@vm.uff.br [Departamento de Quimica Analitica, Universidade Federal Fluminense, Outeiro de S.J. Batista s/n, Centro, Niteroi/RJ, 24020-141 (Brazil)

    2011-05-15

    The present paper reports the optimization for Cu, Fe and Pb determination in naphtha by graphite furnace atomic absorption spectrometry (GF AAS) employing a strategy based on the injection of the samples as detergent emulsions. The method was optimized in relation to the experimental conditions for the emulsion formation and taking into account that the three analytes (Cu, Fe and Pb) should be measured in the same emulsion. The optimization was performed in a multivariate way by employing a three-variable Doehlert design and a multiple response strategy. For this purpose, the individual responses of the three analytes were combined, yielding a global response that was employed as a dependent variable. The three factors related to the optimization process were: the concentration of HNO{sub 3}, the concentration of the emulsifier agent (Triton X-100 or Triton X-114) in aqueous solution used to emulsify the sample and the volume of solution. At optimum conditions, it was possible to obtain satisfactory results with an emulsion formed by mixing 4 mL of the samples with 1 mL of a 4.7% w/v Triton X-100 solution prepared in 10% v/v HNO{sub 3} medium. The resulting emulsion was stable for 250 min, at least, and provided enough sensitivity to determine the three analytes in the five samples tested. A recovery test was performed to evaluate the accuracy of the optimized procedure and recovery rates, in the range of 88-105%; 94-118% and 95-120%, were verified for Cu, Fe and Pb, respectively.

  8. Fischer-Tropsch Synthesis: Influence of CO Conversion on Selectivities H2/CO Usage Ratios and Catalyst Stability for a 0.27 percent Ru 25 percent Co/Al2O3 using a Slurry Phase Reactor

    W Ma; G Jacobs; Y Ji; T Bhatelia; D Bukur; S Khalid; B Davis

    2011-12-31

    The effect of CO conversion on hydrocarbon selectivities (i.e., CH{sub 4}, C{sub 5+}, olefin and paraffin), H{sub 2}/CO usage ratios, CO{sub 2} selectivity, and catalyst stability over a wide range of CO conversion (12-94%) on 0.27%Ru-25%Co/Al{sub 2}O{sub 3} catalyst was studied under the conditions of 220 C, 1.5 MPa, H{sub 2}/CO feed ratio of 2.1 and gas space velocities of 0.3-15 NL/g-cat/h in a 1-L continuously stirred tank reactor (CSTR). Catalyst samples were withdrawn from the CSTR at different CO conversion levels, and Co phases (Co, CoO) in the slurry samples were characterized by XANES, and in the case of the fresh catalysts, EXAFS as well. Ru was responsible for increasing the extent of Co reduction, thus boosting the active site density. At 1%Ru loading, EXAFS indicates that coordination of Ru at the atomic level was virtually solely with Co. It was found that the selectivities to CH{sub 4}, C{sub 5+}, and CO{sub 2} on the Co catalyst are functions of CO conversion. At high CO conversions, i.e. above 80%, CH{sub 4} selectivity experienced a change in the trend, and began to increase, and CO{sub 2} selectivity experienced a rapid increase. H{sub 2}/CO usage ratio and olefin content were found to decrease with increasing CO conversion in the range of 12-94%. The observed results are consistent with water reoxidation of Co during FTS at high conversion. XANES spectroscopy of used catalyst samples displayed spectra consistent with the presence of more CoO at higher CO conversion levels.

  9. 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

    Breman, B.B; Beenackers, A.A C M

    1996-01-01

    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

  10. Market competitive Fischer-Tropsch diesel production. Techno-economic and environmental analysis of a thermo-chemical Biorefinery process for large scale biosyngas-derived FT-diesel production

    Van Ree, R.; Van der Drift, A.; Zwart, R.W.R.; Boerrigter, H.

    2005-08-01

    The contents of the presentation are summarized as follows: Introduction of the Dutch policy framework, Biomass availability and contractibility, and Biomass transportation fuels: current use and perspectives; Next subject concerns Large-scale BioSyngas production: optimum gasification technology; slagging EF-gasifier; identification and modelling biomass-conversion chains; overall energetic chain efficiencies, economics, environmental char; and a comparison with fossil-derived diesel. Further subjects are Current technological SOTA and R, D and D-trajectory; Pre-design 600 MWth demonstration plant; and the Conclusions

  11. Rapid Response R&D for the Propulsion Directorate. Delivery Order 0019: Advanced Alternative Energy Technologies, Subtask: Life Cycle Greenhouse Gas Analysis of Advanced Jet Propulsion Fuels: Fischer-Tropsch Based SPK-1 Case Study

    2011-09-01

    and Selection of Equipment.” Ed. Da Silva, S.C. Proceedings of the XIX International Grassland Congress . Sao Paulo , Brazil : 2001. Rotz C.A., and K...compressed CO2 from the CBTL facility to an oil field where it will be used for CO2- flood enhanced oil recovery. 6.2.1 Modeling Approach and Data...under this “best practices” flooding scenario were scaled to the field level and field-level flows were used to estimate surface processing operations

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

    2013-09-01

    environmental standards, and the Department of Energy (DOE) launched several initiatives to develop a new generation of ‘ultra-clean’ transportation fuels...Expanded Mobility Tactical Truck) – A4 HETS (Heavy Equipment Transporter System) – M1070A1 PLS (Palletized Load System) – A1 DDC 8V92TA 12.0 L...Modulus of Compressibility of Diesel/ Biodiesel /HVO Blends. Energy Fuels. 2011, 26, 1336-1343. 578789 Fuels. Coordinating Research Council, Inc. 2009

  13. Techno-Economic Analysis of Biofuels Production Based on Gasification

    Swanson, R. M.; Platon, A.; Satrio, J. A.; Brown, R. C.; Hsu, D. D.

    2010-11-01

    This study compares capital and production costs of two biomass-to-liquid production plants based on gasification. The first biorefinery scenario is an oxygen-fed, low-temperature (870?C), non-slagging, fluidized bed gasifier. The second scenario is an oxygen-fed, high-temperature (1,300?C), slagging, entrained flow gasifier. Both are followed by catalytic Fischer-Tropsch synthesis and hydroprocessing to naphtha-range (gasoline blend stock) and distillate-range (diesel blend stock) liquid fractions. Process modeling software (Aspen Plus) is utilized to organize the mass and energy streams and cost estimation software is used to generate equipment costs. Economic analysis is performed to estimate the capital investment and operating costs. Results show that the total capital investment required for nth plant scenarios is $610 million and $500 million for high-temperature and low-temperature scenarios, respectively. Product value (PV) for the high-temperature and low-temperature scenarios is estimated to be $4.30 and $4.80 per gallon of gasoline equivalent (GGE), respectively, based on a feedstock cost of $75 per dry short ton. Sensitivity analysis is also performed on process and economic parameters. This analysis shows that total capital investment and feedstock cost are among the most influential parameters affecting the PV.

  14. Natural Gas and Cellulosic Biomass: A Clean Fuel Combination? Determining the Natural Gas Blending Wall in Biofuel Production.

    M Wright, Mark; Seifkar, Navid; Green, William H; Román-Leshkov, Yuriy

    2015-07-07

    Natural gas has the potential to increase the biofuel production output by combining gas- and biomass-to-liquids (GBTL) processes followed by naphtha and diesel fuel synthesis via Fischer-Tropsch (FT). This study reflects on the use of commercial-ready configurations of GBTL technologies and the environmental impact of enhancing biofuels with natural gas. The autothermal and steam-methane reforming processes for natural gas conversion and the gasification of biomass for FT fuel synthesis are modeled to estimate system well-to-wheel emissions and compare them to limits established by U.S. renewable fuel mandates. We show that natural gas can enhance FT biofuel production by reducing the need for water-gas shift (WGS) of biomass-derived syngas to achieve appropriate H2/CO ratios. Specifically, fuel yields are increased from less than 60 gallons per ton to over 100 gallons per ton with increasing natural gas input. However, GBTL facilities would need to limit natural gas use to less than 19.1% on a LHV energy basis (7.83 wt %) to avoid exceeding the emissions limits established by the Renewable Fuels Standard (RFS2) for clean, advanced biofuels. This effectively constitutes a blending limit that constrains the use of natural gas for enhancing the biomass-to-liquids (BTL) process.

  15. Refining and end use study of coal liquids I - pilot plant studies

    Erwin, J.; Moulton, D.S.

    1995-12-31

    The Office of Fossil Energy, Pittsburgh Energy Technology Center is examining the ways in which coal liquids may best be integrated into the refinery of the 2000-2015 time frame and what performance and emission properties will prevail among the slate of fuels produced. The study consists of a Basic Program administered by Bechtel Group, Inc. to build a linear programming refinery model and provide processing and fuel properties data through subcontractors Southwest Research Institute, Amoco Oil R&D, and M.W. Kellogg Company. The model will be used in an Option 1 to devise a slate of test fuels meeting advanced specifications, which will be produced and tested for physical ASTM-type properties, engine performance, and vehicle emissions. Three coal liquids will be included: a direct liquid from bituminous coal, another from subbituminous, and a Fischer-Tropsch indirect liquefaction product. This paper reports the work to date on fractions of the first direct liquid including naphtha hydrotreating, heavy distillate hydrotreating, FCC of the heavy distillate hydrotreater products. Also reported are the first stages of work on the indirect liquefaction wax including feed preparation and FCC tests of blends with petroleum FCC feed.

  16. Naphtha evaporation from oil sands tailings ponds

    Kasperski, K.; Munoz, V.; Mikula, R. [Natural Resources Canada, Devon, AB (Canada). CANMET Western Research Centre

    2010-07-01

    The environmental impacts of volatile organic compounds (VOCs) from oil sands tailings ponds must be considered when evaluating new oil sands mining and extraction operations. Studies have suggested that only 40 percent of the solvent sent to tailings ponds is available to the environment, while the rest is irreversibly trapped. The recovery of hydrocarbons from oil sands froth process water is low. This PowerPoint presentation discussed a method of distinguishing between water and hydrocarbons at low temperatures. Samples were heated to 246 degrees C at 15 degrees C and held for 10 minutes. Heating was then resumed at 750 degrees C and held for 10 minutes in a pyrolysis phase, then cooled and reheated with an oxygen addition. The method demonstrated that the diluent distribution between the solids and water phases is misinterpreted as diluent that will evaporate, and diluent that will not evaporate. The study concluded by suggesting that the definition of recoverable and unrecoverable hydrocarbon should be re-termed as easily recoverable, and difficult to recover. tabs., figs.

  17. Alternative route of process modification for biofuel production by embedding the Fischer-Tropsch plant in existing stand-alone power plant (10 MW) based on biomass gasification - Part I: A conceptual modeling and simulation approach (a case study in Thailand)

    Hunpinyo, Piyapong; Cheali, Peam; Narataruksa, Phavanee

    2014-01-01

    a base case process model coupled with techno-economic evaluation for the FT synthesis. In particular, the FT process configurations are designed and assessed using current kinetic laboratory data by our research group for modeling specific reactions in PFR reactor. The calculation of equipment sizing......The utilization of syngas shows a highly potential to improve the economic potential of the stand-alone power unit-based gasification plants as well as enhancing the growing demand of transportation fuels. The thermochemical conversion of biomass via gasification to heat and power generations from...... incurred several major unit operations is performed for once-through mode (no recycles of unconverted syngas) with electricity co-production. This study provides a detailed base-case model for the synthesis with the capacities of 1, 2 and 3 MW of syngas technology sharing and the comparison between...

  18. Yosemite Waters Vehicle Evaluation Report: Final Results

    Eudy, L.; Barnitt, R.; Alleman, T. L.

    2005-08-01

    Document details the evaluation of Fischer-Tropsch diesel, a gas-to-liquid fuel, in medium-duty delivery vehicles at Yosemite Waters. The study was conducted by NREL at the company's Fullerton, California, bottling headquarters.

  19. Proceedings of the DGMK-conference 'Synthesis gas chemistry'. Authors' manuscripts

    Hoenicke, D; Kohlpaintner, C; Luecke, B; Reschetilowski, W [eds.

    2000-07-01

    The main topics of the DGMK-Conference ''Synthesis Gas Chemistry'' were: production of synthesis gas from several educts, new catalysts, Fischer-Tropsch synthesis, hydroformylation, steam reforming and carbonylation.

  20. Proceedings of the DGMK-conference 'Synthesis gas chemistry'. Authors' manuscripts

    Hoenicke, D.; Kohlpaintner, C.; Luecke, B.; Reschetilowski, W. [eds.

    2000-07-01

    The main topics of the DGMK-Conference ''Synthesis Gas Chemistry'' were: production of synthesis gas from several educts, new catalysts, Fischer-Tropsch synthesis, hydroformylation, steam reforming and carbonylation.

  1. Multi-Phase Combustion and Transport Processes Under the Influence of Acoustic Excitation

    2014-01-01

    waveguide. Alcohol fuels (ethanol and methonal) as well as aviation fuel replacements ( Fischer -Tropsch (FT) synfuel and an FT blend with JP-8) were studied...replacements ( Fischer -Tropsch (FT) synfuel and an FT blend with JP-8) were studied here. During acoustic excitation, the flame surrounding the droplet was...Wegener is approved. Chris R. Anderson Jeff D. Eldredge Ivett A. Leyva Owen I. Smith Ann R. Karagozian, Committee Chair University of California, Los

  2. Iron on mixed zirconia-titania substrate F-T catalyst

    Dyer, P.N.; Nordquist, A.F.; Pierantozzi, R.

    1988-01-01

    This patent deals with 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

  3. The Comparison of Hydrotreated Vegetable Oils With Respect to Petroleum Derived Fuels and the Effects of Transient Plasma Ignition in a Compression-Ignition Engine

    2012-09-01

    Content per Combustion J FAME Fatty Acid Methyl Ester FMEP Friction Mean Effective Pressure PSI or Bar FT Fischer-Tropsch h Heat...recently, algae-derived oils. Biodiesel has gained popularity in North America over the past decade, but the ester content of Fatty Acid Methyl ... Ester ( FAME ) fuel creates both cold weather and water- based operational issues. The Fischer-Tropsch (FT) process produces liquid fuels from “syngas,” a

  4. Cobalt carbide nanoprisms for direct production of lower olefins from syngas

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

    2016-10-01

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

  5. Occupational irritant contact dermatitis due to petroleum naphtha

    Aslı Aytekin; Arzu Karataş Toğral

    2014-01-01

    Irritant contact dermatitis (ICD) is responsible for the vast majority of occupational contact dermatitis and usually seen in professional groups working with wet hand. However, today, with the increasing business lines, employees are exposed to a variety of irritants. Occupational exposure to many chemicals and toxic irritants affect not only the skin, but also the other systems. Therefore, this situation resulting with loss of work and changes in business may become a public health problem....

  6. Extraction of aromatics from naphtha with ionic liquids

    Meindersma, G.W.

    2005-01-01

    The objective of this study was the development of a separation technology for the selective recovery and purification of aromatic compounds benzene, toluene, ethylbenzene and xylenes (BTEX) from liquid ethylene cracker feeds. Most ethylene cracker feeds contain 10 ¿ 25% of aromatic components,

  7. Extraction of Aromatics from Heavy Naphtha Using Different Solvents

    EI-Bassuoni, A.A.; Esmael, K.K.

    2004-01-01

    Aromatic hydrocarbons are very important to the petrochemical industry. Among these are benzene, toluene and xylene (BTX), which are basic raw materials for the production of a number of important petrochemicals. There are many processes used to separate aromatic from non aromatic such as fractionation, azeotropic distillation and liquid I liquid extraction, etc. Liquid - liquid extraction is unique, efficiently used for heat sensitive, close boiling components and for separation of components not possible by other unit operations and it could be done at ambient temperature makes it more energy efficient. The choice of solvent depends on the properties and boiling range of the feedstock. Through the years, a lot of selective solvents has been proposed and selected for the physical separation of aromatics in liquid liquid extraction. Among the selection criteria are the stability,. chemical compatibility, availability, environmental hazards and price of the solvent. But the basic solvent properties that make it efficient are selectivity and capacity

  8. Combustion stratification for naphtha from CI combustion to PPC

    Vallinayagam, R.; Vedharaj, S.; An, Y.; Dawood, A.; Izadi Najafabadi, M.; Somers, L.M.T.; Johansson, B.H.

    2017-01-01

    This study demonstrated the change in combustion homogeneity from conventional diesel combustion via partially premixed combustion towards HCCI. Experiments are performed in an optical diesel engine at a speed of 1200 rpm with diesel fuel. Single injection strategy is employed and the fuel is

  9. The Eni - IFP/Axens GTL technology. From R and D to a successful scale-up

    Zennaro, R. [Eni S.p.A., Milan (Italy); Hugues, F. [Institut Francais du Petrole, Lyon (France); Caprani, E. [Axens, Paris (France)

    2006-07-01

    Proven natural gas reserves had reached about 184 Tscm in 2006 to which 36% is stranded gas far from the final market. Fischer Tropsch based GtL options today represent a viable route to develop such remote gas resources into high quality fuels and specialties. Thus opening different markets for the gas historically linked to the oil. Thanks to R and D successful improvements in the field of catalysis and reactor technology coupled with optimized integration and economies of scale have reduced the investment cost for building a Fischer Tropsch GtL complex. Basically all major Oil and Gas companies are involved in proprietary GtL development, and today several industrial projects have been announced. The most advanced is the Oryx project (QP-Sasol) which has been inaugurated the 6{sup th} of June '06 and currently in the starting up phase. Eni and IFP-Axens have developed a proprietary GtL Fischer-Tropsch and Upgrading technology in a close collaboration between the two groups. The Eni/IFP-Axens technology is based on proprietary catalysts and reactor, designed according to scale-up criteria defined in ten years of R and D activity. Unique large scale hydrodynamic facilities (bubble columns, loops) bench-scale dedicated pilot units, as well as large scale Fischer-Tropsch pilot plant, have been developed and operated to minimize reactor and ancillaries scale-up risks. The large scale Fischer-Tropsch pilot plant has been built and operated since 2001. The plant, located within the Eni refinery of Sannazzaro de' Burgondi (Pavia, Italy) is fully integrated to the refinery utilities and network. It reproduces at 20 bpd scale the overall Fischer Tropsch synthesis section: from slurry handling (loading, make-up, withdrawal), to reactor configuration and products separation units. Today the scale-up basis has been completed and the technology is ready for industrial deployment. (orig.)

  10. The direct conversion of synthesis gas to chemicals / Ernest du Toit

    Du Toit, Ernest

    2002-01-01

    The catalytic conversion of synthesis gas, obtainable from the processing of coal, biomass or natural gas, to a complex hydrocarbon product stream can be achieved via the Fischer-Tropsch process. The Fischer-Tropsch synthesis process has evolved from being mainly a fuel producing process in the early 1950's to that of a solvent and speciality wax production process towards the end of the 1970's. From the early 1980's there has been a clear shift towards the production of commod...

  11. Development of a novel reactor concept for the partial oxidation of methane to syngas

    Smit, J.; van Sint Annaland, M.; Kuipers, J.A.M.

    2004-01-01

    The gas-to-liquid process, consisting of the partial oxidation of methane (POM) followed by the Fischer-Tropsch reaction, is a promising alternative to conventional oil processing for the production of liquid fuels. The cost of a conventional POM process is mainly determined by cryogenic air

  12. Modelling of a reverse flow catalytic membrane reactor for the partial oxidation of methane

    Smit, J.; van Sint Annaland, M.; Kuipers, J.A.M.

    2003-01-01

    Gas-To-Liquid (GTL) processes have great potential as alternative to conventional oil and coal processing for the production of liquid fuels. In GTL-processes the partial oxidation of methane (POM) is combined with the Fischer-Tropsch reaction. An important part of the investment costs of a

  13. Municipal solid waste conversion to transportation fuels: a life-cycle estimation of global warming potential and energy consumption

    Pressley, Phillip N.; Aziz, Tarek N.; DeCarolis, Joseph F.

    2014-01-01

    This paper utilizes life cycle assessment (LCA) methodology to evaluate the conversion of U.S. municipal solid waste (MSW) to liquid transportation fuels via gasification and Fischer-Tropsch (FT). The model estimates the cumulative energy demand and global warming potential (GWP) associated...

  14. ONLINE SINGLE-COLUMN CAPILLARY GAS-CHROMATOGRAPHIC ANALYSIS OF ALL REACTANTS AND PRODUCTS IN THE SYNTHESIS OF FUEL METHANOL FROM HYDROGEN AND OXIDES OF CARBON

    MARSMAN, JH; BREMAN, BB; BEENACKERS, AACM

    The main problems with complete analysis of the components of fuel methanol, or in Fischer-Tropsch studies, are the several classes of compound present in the sample (permanent gases, water, alcohols, hydrocarbons), its wide range of components, its boiling point range, and the wide range of

  15. Hydrodynamics and mass transfer in slurry bubble columns : scale and pressure effects

    Chilekar, V.P.

    2007-01-01

    Slurry bubble columns (SBC) are widely used in the chemical industry as a multiphase reactor. Applications include oxidation and hydrogenation reactions, fermentation, Fischer-Tropsch synthesis, and waste water treatment. The advantages of a SBC over other multiphase reactors are the simple

  16. Freeze-drying for controlled nanoparticle distribution in Co/SiO 2 Fischer–Tropsch catalysts

    Eggenhuisen, T.M.; Munnik, P.; Talsma, H.; de Jongh, P.E.; de Jong, K.P.

    2013-01-01

    Controlling the nanoparticle distribution over a support is considered essential to arrive at more stable catalysts. By developing a novel freeze drying method, the nanoparticle distribution was successfully manipulated for the preparation of Co/SiO2 Fischer-Tropsch catalysts using a commercial

  17. Two-Dimensional Zeolites: Current Status and Perspectives

    Roth, Wieslaw Jerzy; Nachtigall, P.; Morris, R. E.; Čejka, Jiří

    2014-01-01

    Roč. 114, č. 9 (2014), s. 4807-4837 ISSN 0009-2665 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : zeolites * mesoporous molecular sieves * Fischer-Tropsch synthesis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 46.568, year: 2014

  18. Real-time elucidation of catalytic pathways in CO hydrogenation on Ru

    LaRue, J.; Krejčí, Ondřej; Yu, L.; Beye, M.; Ng, M.L.; Oberg, H.; Xin, H.; Mercurio, G.; Moeller, S.; Turner, J.J.; Nordlund, D.; Coffee, R.; Minitti, M.P.; Wurth, W.; Petersson, L.G.M.; Ostrom, H.; Nilsson, A.; Abild-Pedersen, F.; Ogasawara, H.

    2017-01-01

    Roč. 8, č. 16 (2017), s. 3820-3825 ISSN 1948-7185 Institutional support: RVO:68378271 Keywords : Fischer-Tropsch synthesis * carbone-monoxide * metal-oxide * surface * dissociation * methanol * copper * laser * electroreduction * femtochemistry Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 9.353, year: 2016

  19. Impact of fuel composition on emissions and performance of GTL kerosene blends in a Cessna Citation II

    Snijders, T.A.; Melkert, J.A.; Bogers, P.F.; Bauldreay, J.; Wahl, C.R.M.; Kapernaum, M.G.

    2011-01-01

    International jet fuel specifications permit up to 50% volume Fischer-Tropsch synthetic paraffinic kerosines (FT-SPKs), such as Gas-to-Liquids (GTL) Kerosine, in Jet A-1. Higher SPK-content fuels could, however, produce desirable fuels: lower density, higher SPK-content fuels may have benefits for

  20. Bifunctional catalysts for the direct production of liquid fuels from syngas

    Sartipi, S.

    2014-01-01

    Design and development of catalyst formulations that maximize the direct production of liquid fuels by combining Fischer-Tropsch synthesis (FTS), hydrocarbon cracking, and isomerization into one single catalyst particle (bifunctional FTS catalyst) have been investigated in this thesis. To achieve

  1. Cover Letter Dear Editor, Please find enclosed a paper entitled ...

    Ajamein

    Dear Editor,. Please find enclosed a paper entitled ' Intrinsic Kinetics of Fischer- Tropsch Synthesis Over a. Promoted Iron Catalyst '. I am submitting to your journal to be considered for publication as a research paper in Bulletin of the Chemical Society of Ethiopia. The manuscript has not been previously published, is not ...

  2. CO dissociation on Ni: The effect of steps and of nickel carbonyl

    Engbæk, Jakob; Lytken, Ole; Nielsen, Jane Hvolbæk

    2008-01-01

    The dissociation of CO was investigated on a stepped Ni(141313) crystal. The experiments show that the monoatomic steps completely dominate the dissociation of CO on the nickel surface. The activation energy for dissociation of CO along the steps is measured at 500 K to be 150 kJ/mol in the press...... and in the Fischer-Tropsch synthesis....

  3. Thermodynamic efficiency of biomass gasification and biofuels conversion

    Ptasinski, K.J.

    2008-01-01

    Biomass has great potential as a clean renewable feedstock for producing biofuels such as Fischer-Tropsch biodiesel, methanol, and hydrogen. The use of biomass is accompanied by possible ecological drawbacks, however, such as limitation of land or water and competition with food production. For

  4. Modern bioenergy from agricultural and forestry residues in Cameroon: Potential, challenges and the way forward

    Ackom, Emmanuel; Alemagi, Dieudonne; Ackom, Nana B.

    2013-01-01

    liters of ethanol annually to displace 18–48% of the national consumption of gasoline. Alternatively, the residues could provide 0.08–0.22 billion liters of biomass to Fischer Tropsch diesel annually to offset 17–45% of diesel fuel use. For the generation of bioelectricity, the residues could supply 0...

  5. Toward better understanding of the support effect: test cases for CO dissociation on Fe n /TiO 2 (110), n=4,5

    Jedidi, Abdesslem; Aziz, Saadullah G.; Cavallo, Luigi; Minot, Christian

    2017-01-01

    The Fischer-Tropsch reaction is initiated by direct CO dissociation for Iron catalyst even though a H-assisted mechanism may be easier on other metals. In the gas phase, the CO dissociation is only favorable for Fe-clusters composed by more than 11

  6. EARLY ENTRANCE COPRODUCTION PLANT

    Fred D. Brent; Lalit Shah; Earl Berry; Charles H. Schrader; John Anderson; Ming He; James F. Stevens; Centha A. Davis; Michael Henley; Jerome Mayer; Harry Tsang; Jimell Erwin; Jennifer Adams; Michael Tillman; Chris Taylor; Marjan J. Roos; Robert F. Earhart

    2004-01-27

    The overall objective of this project is the three phase development of an Early Entrance Coproduction Plant (EECP) which uses petroleum coke to produce at least one product from at least two of the following three categories: (1) electric power (or heat), (2) fuels, and (3) chemicals using ChevronTexaco's proprietary gasification technology. The objective of Phase I is to determine the feasibility and define the concept for the EECP located at a specific site; develop a Research, Development, and Testing (RD&T) Plan to mitigate technical risks and barriers; and prepare a Preliminary Project Financing Plan. The objective of Phase II is to implement the work as outlined in the Phase I RD&T Plan to enhance the development and commercial acceptance of coproduction technology. The objective of Phase III is to develop an engineering design package and a financing and testing plan for an EECP located at a specific site. The project's intended result is to provide the necessary technical, economic, and environmental information needed by industry to move the EECP forward to detailed design, construction, and operation. The partners in this project are Texaco Energy Systems LLC or TES (a subsidiary of ChevronTexaco), General Electric (GE), Praxair, and Kellogg Brown & Root (KBR) in addition to the U.S. Department of Energy (DOE). TES is providing gasification technology and Fischer-Tropsch (F-T) technology developed by Rentech, GE is providing combustion turbine technology, Praxair is providing air separation technology, and KBR is providing engineering. Each of the EECP subsystems was assessed for technical risks and barriers. A plan was developed to mitigate the identified risks (Phase II RD&T Plan, October 2000). The potential technical and economic risks to the EECP from Task 2.5 can be mitigated by demonstrating that the end-use products derived from the upgrading of the F-T synthesis total liquid product can meet or exceed current specifications for the

  7. Ignition delay measurements of light naphtha: A fully blended low octane fuel

    Javed, Tamour; Nasir, Ehson Fawad; Ahmed, Ahfaz; Badra, Jihad; Djebbi, Khalil; Beshir, Mohamed; Ji, Weiqi; Sarathy, Mani; Farooq, Aamir

    2016-01-01

    . To the best of our knowledge, this is the first fundamental autoignition study on the reactivity of a low-octane fully blended fuel and the use of a suitably formulated multi-component surrogate to model its behavior.

  8. Numerical Simulations of Hollow Cone Injection and Gasoline Compression Ignition Combustion With Naphtha Fuels

    Badra, Jihad A.

    2016-01-11

    Gasoline compression ignition (GCI), also known as partially premixed compression ignition (PPCI) and gasoline direct injection compression ignition (GDICI), engines have been considered an attractive alternative to traditional spark ignition engines. Lean burn combustion with the direct injection of fuel eliminates throttle losses for higher thermodynamic efficiencies, and the precise control of the mixture compositions allows better emission performance such as NOx and particulate matter (PM). Recently, low octane gasoline fuel has been identified as a viable option for the GCI engine applications due to its longer ignition delay characteristics compared to diesel and lighter evaporation compared to gasoline fuel [1]. The feasibility of such a concept has been demonstrated by experimental investigations at Saudi Aramco [1, 2]. The present study aims to develop predictive capabilities for low octane gasoline fuel compression ignition engines with accurate characterization of the spray dynamics and combustion processes. Full three-dimensional simulations were conducted using CONVERGE as a basic modeling framework, using Reynolds-averaged Navier-Stokes (RANS) turbulent mixing models. An outwardly opening hollow-cone spray injector was characterized and validated against existing and new experimental data. An emphasis was made on the spray penetration characteristics. Various spray breakup and collision models have been tested and compared with the experimental data. An optimum combination has been identified and applied in the combusting GCI simulations. Linear instability sheet atomization (LISA) breakup model and modified Kelvin-Helmholtz and Rayleigh-Taylor (KH-RT) break models proved to work the best for the investigated injector. Comparisons between various existing spray models and a parametric study have been carried out to study the effects of various spray parameters. The fuel effects have been tested by using three different primary reference fuel (PRF) and toluene primary reference fuel (TPRF) surrogates. The effects of fuel temperature and chemical kinetic mechanisms have also been studied. The heating and evaporative characteristics of the low octane gasoline fuel and its PRF and TPRF surrogates were examined. Copyright © 2015 by ASME.

  9. Numerical Simulations of Hollow-Cone Injection and Gasoline Compression Ignition Combustion With Naphtha Fuels

    Badra, Jihad A.; Sim, Jaeheon; Elwardani, Ahmed Elsaid; Jaasim, Mohammed; Viollet, Yoann; Chang, Junseok; Amer, Amer; Im, Hong G.

    2016-01-01

    . An optimum combination has been identified and applied in the combusting GCI simulations. Linear instability sheet atomization (LISA) breakup model and modified Kelvin-Helmholtz and Rayleigh-Taylor (KH-RT) break models proved to work the best

  10. Numerical Simulations of Hollow Cone Injection and Gasoline Compression Ignition Combustion With Naphtha Fuels

    Badra, Jihad A.; Sim, Jaeheon; Elwardani, Ahmed Elsaid; Jaasim, Mohammed; Viollet, Yoann; Chang, Junseok; Amer, Amer A.; Im, Hong G.

    2016-01-01

    identified and applied in the combusting GCI simulations. Linear instability sheet atomization (LISA) breakup model and modified Kelvin-Helmholtz and Rayleigh-Taylor (KH-RT) break models proved to work the best for the investigated injector. Comparisons

  11. Characteristics of spray from a GDI fuel injector for naphtha and surrogate fuels

    Wang, Libing; Badra, Jihad A.; Roberts, William L.; Fang, Tiegang

    2016-01-01

    size distribution were measured using a laser diffraction technique. Results show that the injection process is very consistent for different runs and the time averaged spray angles during the measuring period are 103.45°, 102.84°, 102.46° and 107

  12. Honeycomb supports with high thermal conductivity for the Tischer-Tropsch synthesis

    Visconti, C.G.; Rronconi, E.; Groppi, G.; Lietti, L. [Politecnico di Milano (Italy). Dipt. di Energia; Iovane, M.; Rossini, S.; Zennaro, R. [Eni S.p.A., San Donato Milanese (Italy). Div. Exploration and Production

    2011-07-01

    The potential of multitubular reactors loaded with washcoated structured catalysts having highly conductive honeycomb supports is investigated herein in the low temperature Fischer- Tropsch synthesis by means of a theoretical investigation. Simulation results indicate that extruded aluminum honeycomb monoliths, washcoated with a Co-based catalyst, are promising for the application at the industrial scale, in particular when adopting supports with high cell densities and catalysts with high activity. Limited temperature gradients within the reactor are in fact possible even at extreme process conditions, thus leading to interesting volumetric reactor yields with negligible pressure drop. This result is achieved without the need of cofeeding to the reactor large amounts of liquid hydrocarbons to remove the reaction heat, as opposite to existing industrial Fischer-Tropsch packed-bed reactors. (orig.)

  13. Fuel from the synthesis gas - the role of process engineering

    Stelmachowski, Marek; Nowicki, Lech [Technical Univ. of Lodz, Dept. of Environmental Engineering Systems, Lodz (Poland)

    2003-02-01

    The paper presents the conclusions obtained in the investigations of methanol synthesis, Fischer-Tropsch synthesis, and higher alcohols synthesis from syngas as a raw material in slurry reactors. The overview of the role of process engineering was made on the basis of the experience in optimizing process conditions, modeling reactors and working out new technologies. Experimental data, obtained with a laboratory-stirred autoclave and theoretical considerations were used to develop the kinetic models that can describe the product formation and the model of the simultaneous phase and chemical equilibrium for the methanol and Fischer-Tropsch syntheses in the slurry reactors. These models were employed in modeling of the bubble-column slurry reactor (BCSR). Based on these considerations, a computer simulation of the low-pressure methanol synthesis for the pilot-scale, BCSR, was devised. The results of the calculations and the conclusions could be employed in the process for designing an industrial plant. (Author)

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

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

    1981-05-01

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

  15. Additive Effectiveness Investigations in Alternative Fuels

    2014-05-01

    refers to synthetic paraffinic kerosene generated through the Fischer-Tropsch process. Basically, a carbon source (coal, natural gas, biomass ) is...four cobalt FT process SPKs in that report, two from SASOL and one each from Shell and Syntroleum. SwRI had a good supply of the Shell FT SPK and...guidance material [9] warns that continuous use could result in an incurable biomass accumulation. The active components of this product are a mixture

  16. GLOBAL PROSPECTS OF SYNTHETIC DIESEL FUEL PRODUCED FROM HYDROCARBON RESOURCES IN OIL&GAS EXPORTING COUNTRIES

    Kurevija, Tomislav; Kukulj, Nenad; Rajković, Damir

    2007-01-01

    Production of synthetic diesel fuel through Fischer-Tropsch process is a well known technology which dates from II World War, when Germany was producing transport fuel from coal. This process has been further improved in the South Africa due to period of international isolation. Today, with high crude oil market cost and increased demand of energy from China and India, as well as global ecological awareness and need to improve air quality in urban surroundings, many projects are being planned...

  17. The Simple, Effective Synthesis of Highly Dispersed Pd/C and CoPd/C Heterogeneous Catalysts via Charge-Enhanced Dry Impregnation

    Lawrence D’Souza

    2016-05-01

    Full Text Available Pd/C and CoPd/C heterogeneous catalysts have been synthesized by adopting Charge Enhanced Dry Impregnation (CEDI. The particles size distribution, their high metal surface-to-bulk ratios, and synthesis feasibility are unmatchable to any known noble metal bimetallic heterogeneous catalyst preparation techniques. Next generation Fuel Cells and Fischer-Tropsch catalytic processes economy will be benefited from the proposed methodology.

  18. Wash-oil problem

    Chlosta, J

    1941-01-01

    Meier-Grolman and others have deduced from experimental studies of the vapor pressure of solutions of benzene in paraffin oil and Solway oil-paraffin oil mixtures that the higher the proportion of aliphatic compounds in a wash oil, the less suitable it is for benzene scrubbing. This generalization is not supported. Paraffin oils from brown-coal tar and low viscous oils from the Fischer-Tropsch hydrocarbon synthesis process are both being successfully used for benzene scrubbing.

  19. Alternative Fuels for Military Applications

    2011-01-01

    federal subsidies have promoted produc- tion and use of biodiesel, which is not a hydrocarbon but rather a fatty acid methyl ester ( FAME ) unsuitable for... methyl ester ( FAME ). FAME and blends of FAME with petroleum-derived fuels are currently banned from use in all deployable, tactical DoD military...fatty acid methyl ester FT Fischer-Tropsch FY fiscal year ISBL inside battery limit Navy Fuels Team Naval Fuels and Lubricants Cross-Functional Team

  20. The innovation process : suggestions for improvement in a research and development environment / Friedrich Wilhelm Hein Kruger

    Kruger, Friedrich Wilhelm Hein

    1998-01-01

    Sasol Ltd is regarded as the world leader in Fischer-Tropsch technology and endeavours to reinforce this, not necessarily sustainable, competitive advantage by globalisation. This globalisation strategy reflects the company's commitment to sustainable growth through the development, production, and marketing of new products and processes. Sasol Technology (Pty) Ltd is clearly an important role player in the realisation of this vision, and strives to add optimum value to the tre...

  1. In Vitro Studies and Preliminary Mathematical Model for Jet Fuel and Noise Induced Auditory Impairment

    2015-06-01

    of JP-8 and a Fischer- Tropsch synthetic jet fuel following subacute inhalation exposure in rats. Toxicol Sci 116(1): 239-248. Gallinat, J...AFRL-RH-WP-TR-2015-0084 IN VITRO STUDIES AND PRELIMINARY MATHEMATICAL MODEL FOR JET FUEL AND NOISE INDUCED AUDITORY IMPAIRMENT...April 2014 – September 2014 4. TITLE AND SUBTITLE In Vitro Studies and Preliminary Mathematical Model for Jet Fuel and Noise Induced Auditory

  2. Alternative fuels from forest residues for passenger cars - an assessment under German framework conditions

    Hurtig, O.; Leible, L.; Kälber, S.; Kappler, g.; Spicher, U.

    2014-01-01

    Background Due to the available volumes, biogenic residues are a promising resource for renewable fuels for passenger cars to reduce greenhouse gas (GHG) emissions. In this study, we compare three fuels from forest residues under German framework conditions: biogenic electricity, substitute natural gas (SNG), and Fischer-Tropsch (FT) diesel. Methods Fuels from forest residues are compared with regard to their technical efficiency (here defined as ‘pkm per kg b...

  3. Iron oxides and their applications in catalytic processes: a review

    Oliveira, Luiz C. A.; Fabris, José D.; Pereira, Márcio C.

    2013-01-01

    A review of most of the reported studies on the use of iron oxides as catalyst in specific processes, namely Haber-Bosch reaction, Fischer-Tropsch synthesis, Fenton oxidation and photolytic molecular splitting of water to produce gaseous hydrogen, was carried out. An essential overview is thus presented, intending to address the fundamental meaning, as well as the corresponding chemical mechanisms, and perspectives on new technological potentialities of natural and synthetic iron oxides, more...

  4. An Optical Method for Measuring Injection Timing in Diesel Engines, Using a Single Port

    2014-09-01

    injection, naturally aspirated marine diesel engine with mechanical unit injectors and showed satisfactory results with blends ranging from 25% HRD/75... injector technology, they further concluded that the mechanical unit injectors found throughout the naval fleet and on the Detroit Diesel 3–53 in the...injection timing in a pump-line- nozzle system of blending Fischer- Tropsch derived diesel fuel with low sulfur, ultra-low sulfur and biodiesel fuels. The

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

    None

    1988-02-01

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

  6. The National Nanotechnology Initiative: Research and Development Leading to a Revolution in Technology and Industry. Supplement to the President’s 2012 Budget

    2011-02-01

    waste heat recuperation/fuel efficiency, and electronic device/systems cooling. • The first discrete quaternary nanocrystal based on silver, lead...Fischer-Tropsch based conversion of natural gas to infrastructure-compatible liquid transportation fuels; (c) low-cost and high-performance nanostructured...on a new cathode with 100-nm cesium iodide coating that reduces HPM system size, weight, and power consumption; (2) nanocomposite space system

  7. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    Mala A. Sainna

    2015-09-01

    Full Text Available Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu2(μ2-H (μ2-NHCH3(μ3-CPtCH3(P(CH332](COn+ with n = 0, 2 and Cp = η5-C5(CH35, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes.

  8. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    Sainna, Mala A.; de Visser, Sam P.

    2015-01-01

    Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu)2(μ2-H)(μ2-NHCH3)(μ3-C)PtCH3(P(CH3)3)2](CO)n+ with n = 0, 2 and Cp = η5-C5(CH3)5, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes. PMID:26426009

  9. Characterization of Catalyst Materials for Production of Aerospace Fuels

    Best, Lauren M.; De La Ree, Ana B.; Hepp, Aloysius F.

    2012-01-01

    Due to environmental, economic, and security issues, 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. Additionally, efforts are concentrated on reducing costs coupled with fuel production from non-conventional sources. One solution to this issue is Fischer-Tropsch gas-to-liquid technology. Fischer-Tropsch processing of synthesis gas (CO/H2) produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fisher-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur or aromatic compounds. This process is most commonly catalyzed by heterogeneous (in this case, silver and platinum) catalysts composed of cobalt supported on alumina or unsupported alloyed iron powders. Physisorption, chemisorptions, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) are described to better understand the potential performance of Fischer-Tropsch cobalt on alumina catalysts promoted with silver and platinum. The overall goal is to preferentially produce C8 to C18 paraffin compounds for use as aerospace fuels. Progress towards this goal will eventually be updated and achieved by a more thorough understanding of the characterization of catalyst materials. This work was supported by NASA s Subsonic Fixed Wing and In-situ Resource Utilization projects.

  10. Structural modifications under reactive atmosphere of cobalt catalysts; Modifications structurales sous atmospheres reactionnelles de catalyseurs a base de cobalt

    Ducreux, O.

    1999-11-23

    The purpose of this work was to develop in situ methods under reactive dynamic conditions (XRD and Fourier transform infrared spectroscopy) to describe the active phase structure in order to understand Fischer-Tropsch catalyst behaviour and improve the natural gas conversion process performance. Experiments were designed to correlate structural modifications with catalytic results. The effect of ruthenium used as a promoter has also been studied. The impregnation process increases cobalt-support interaction. The presence of ruthenium promoter reduces this effect. Interactions between Co{sub 3}O{sub 4} oxide and support play an important role in the reducibility of cobalt and in the resulting metal structure. This in turn strongly influences the catalytic behaviour. Our results show a close correlation between structure modification and reactivity in the systems studied. Cobalt metal and CO can react to form a carbide Co{sub 2}C under conditions close to those of the Fischer-Tropsch synthesis. This carbide formation seems to be related to a deactivation process. The presence of interstitial carbon formed by dissociation of CO is proposed as a key to understanding the mechanism of the Fischer-Tropsch reaction. A specific catalyst activation treatment was developed to increase the catalytic activity. This work permits correlation of materials structure with their chemical properties and demonstrates the contribution of in situ physico-chemical characterisation methods to describe solids under reactive atmosphere. (author)

  11. Mg-Fe-mixed oxides derived from layered double hydroxides: A study of the surface properties

    Marinković-Nedučin Radmila P.

    2011-01-01

    Full Text Available The influence of surface properties on the selectivity of the synthesized catalysts was studied, considering that their selectivity towards particular hydrocarbons is crucial for their overall activity in the chosen Fischer- -Tropsch reaction. Magnesium- and iron-containing layered double hydroxides (LDH, with the general formula: [Mg1-xFex(OH2](CO3x/2?mH2O, x = = n(Fe/(n(Mg+n(Fe, synthesized with different Mg/Fe ratio and their thermally derived mixed oxides were investigated. Magnesium was chosen because of its basic properties, whereas iron was selected due to its well-known high Fischer-Tropsch activity, redox properties and the ability to form specific active sites in the layered LDH structure required for catalytic application. The thermally less stable multiphase system (synthesized outside the optimal single LDH phase range with additional Fe-phase, having a lower content of surface acid and base active sites, a lower surface area and smaller fraction of smaller mesopores, showed higher selectivity in the Fischer-Tropsch reaction. The results of this study imply that the metastability of derived multiphase oxides structure has a greater influence on the formation of specific catalyst surface sites than other investigated surface properties.

  12. Economics of gas to liquids manufacture

    Gradassi, M.J.

    1998-01-01

    The last year has seen a great deal in the literature about the rebirth of gas to liquids processes, most notably, Fischer Tropsch processes. This renewed interest has been brought about by a technology that is said to have been so improved that it is now a commercially attractive option for natural gas monetization. No one single reason can be cited for this positive economic change. Rather, it is the result of several technological improvements that together have cut the capital cost of Fischer-Tropsch gas to liquids projects in half. Among these technological improvements are lower cost syngas preparation and lower cost gas to liquids reactors. This paper examines the economics of Fischer-Tropsch gas to liquids manufacture, using recent literature articles to develop process capital costs, operating expenses, liquid product value parameters, and other economic factors, to paint a general picture of the technology's current economic status. While manufacturing economics are reviewed, the answer to the question of gas to liquids project profitability is left to the individual investor whose economic thresholds must, in the final analysis, be met. 15 refs

  13. Carbon monoxide hydrogenation over ruthenium zeolites

    Jacobs, P.A.; Nijs, H.H.; Verdonck, J.J.; Uytterhoeven, J.B.

    1978-03-01

    Ru zeolites are active and stable methanation catalysts. Under Fischer--Tropsch conditions they show a narrow product distribution. Further work is needed to assign this to a possible effect exerted by the zeolite cages. When the size of the Ru particles enclosed in the zeolite cages is increased, a lower methanation activity is found and a higher amount of C/sub 2/ and C/sub 3/ products are formed under Fischer--Tropsch conditions. This effect has not been reported until now on other supports. The less acidic zeolites act as promoters of the CO hydrogenation: under methanation conditions the activity is increased; under Fischer--Tropsch conditions, the selectivity is shifted toward higher hydrocarbons. This is explained by the particular zeolite property that electron deficient metal agglomerates seem to be formed on the acidic zeolites. With respect to kinetic behavior, relative activity of different metals, influence of reaction temperature on product distribution, the zeolite behaves in the same way a conventional alumina support. 4 figs., 4 tables.

  14. Synthetic Or Reformulated Fuels: a Challenge for Catalysis Carburants de synthèse ou reformulés : un défi pour la catalyse

    Courty P.

    2006-12-01

    Full Text Available Despite comparative figures for wordwide crude oil and natural gas proven reserves, present time contribution of syngas chemistry to motorfuels remains marginal when the refining industry is faced to main constraints: market demand evolution, stringent specifications and environmental issues. Actually natural gas upgrading via syngas chemistry yields key products (e. g. methanol among which clean motorfuels (ethers, FT products should develop despite the huge investments required, mostly for syngas production. Main challenges and corresponding issues for catalysts and related technologies are identified for Fischer-Tropsch synthesis and motorfuels long-term reformulation. Among other, mastering the chain-growth (FT synthesis improving the FCC products: gasoline, and LCO for Diesel pool. All these issues need significant progresses in catalyst and technology to be solved. Lastly, our economical study, focused on Diesel-fuel production, shows up that clean diesel (from SR-LCO mixtures and FT Diesel reach similar production costs when cheap NG is available. In the future, FT middle distillates should amount to a few percent (5-150 Mt of the 1700-2000 Mt of transport middle distillates expected from oil refining. However they should more and more be a compulsory part of diesel pool if the level of investment for an FT process continues to decrease significantly. Malgré des réserves prouvées en pétrole et en gaz du même ordre de grandeur, la contribution de la chimie du gaz de synthèse à la production de carburants reste marginale, alors que l'industrie du raffinage est confrontée à des contraintes majeures : évolution de la demande, durcissement des spécifications des produits et contraintes environnementales. Cependant, la conversion chimique du gaz, via la chimie du gaz de synthèse, fournit des produits stratégiques (e. g. méthanol parmi lesquels les carburants propres (éthers, produits Fischer-Tropsch devraient se développer, bien

  15. Project Independence: Construction of an Integrated Biorefinery for Production of Renewable Biofuels at an Existing Pulp and Paper Mill

    Freeman, Douglas

    2012-06-01

    Project Independence proposed to construct a demonstration biomass-to-liquids (BTL) biorefinery in Wisconsin Rapids, isconsin. The biorefinery was to be co-located at the existing pulp and paper mill, NewPage Wisconsin System Incorporated’s Wisconsin Rapids Mill, and when in full operation would both generate renewable energy for Wisconsin Rapids Mill and produce liquid fuels from abundant and renewable lignocellulosic biomass. The biorefinery would serve to validate the thermochemical pathway and economic models for BTL production using forest residuals and wood waste, providing a basis for proliferating BTL conversion technologies throughout the United States. It was a project goal to create a compelling new business model for the pulp and paper industry, and support the nation’s goal for increasing renewable fuels production and reducing its dependence on foreign oil. NewPage Corporation planned to replicate this facility at other NewPage Corporation mills after this first demonstration scale plant was operational and had proven technical and economic feasibility. An overview of the process begins with biomass being harvested, sized, conditioned and fed into a ThermoChem Recovery International (TRI) steam reformer where it is converted to high quality synthetic gas (syngas). The syngas is then cleaned, compressed, scrubbed, polished and fed into the Fischer-Tropsch (F-T) catalytic reactors where the gas is converted into two, sulfur-free, clean crude products which will be marketed as revenue generating streams. Additionally, the Fischer-Tropsch products could be upgraded for use in automotive, aviation and chemical industries as valuable products, if desired. As the Project Independence project set out to prove forest products could be used to commercially produce biofuels, they planned to address and mitigate issues as they arose. In the early days of the Project Independence project, the plant was sized to process 500 dry tons of biomass per day but would

  16. Theoretical characterization of the surface composition of ruthenium nanoparticles in equilibrium with syngas

    Cusinato, Lucy; Martínez-Prieto, Luis M.; Chaudret, Bruno; Del Rosal, Iker; Poteau, Romuald

    2016-05-01

    A deeper understanding of the relationship between experimental reaction conditions and the surface composition of nanoparticles is crucial in order to elucidate mechanisms involved in nanocatalysis. In the framework of the Fischer-Tropsch synthesis, a resolution of this complex puzzle requires a detailed understanding of the interaction of CO and H with the surface of the catalyst. In this context, the single- and co-adsorption of CO and H to the surface of a 1 nm ruthenium nanoparticle has been investigated with density functional theory. Using several indexes (d-band center, crystal overlap Hamilton population, density of states), a systematic analysis of the bond properties and of the electronic states has also been done, in order to bring an understanding of structure/property relationships at the nanoscale. The H : CO surface composition of this ruthenium nanoparticle exposed to syngas has been evaluated according to a thermodynamic model fed with DFT energies. Such ab initio thermodynamic calculations give access to the optimal H : CO coverage values under a wide range of experimental conditions, through the construction of free energy phase diagrams. Surprisingly, under the Fischer-Tropsch synthesis experimental conditions, and in agreement with new experiments, only CO species are adsorbed at the surface of the nanoparticle. These findings shed new light on the possible reaction pathways underlying the Fischer-Tropsch synthesis, and specifically the initiation of the reaction. It is finally shown that the joint knowledge of the surface composition and energy descriptors can help to identify possible reaction intermediates.A deeper understanding of the relationship between experimental reaction conditions and the surface composition of nanoparticles is crucial in order to elucidate mechanisms involved in nanocatalysis. In the framework of the Fischer-Tropsch synthesis, a resolution of this complex puzzle requires a detailed understanding of the interaction

  17. Catalysis. Innovative applications in petrochemistry and refining. Preprints

    Ernst, S.; Balfanz, U.; Jess, A.; Lercher, J.A.; Lichtscheidl, J.; Marchionna, M.; Nees, F.; Santacesaria, E. (eds.)

    2011-07-01

    Within the DGMK conference at 4th to 6th October, 2011 in Dresden (Federal Republic of Germany) the following lectures were held: (1) Developing linear-alpha-olefins technology - From laboratory to a commercial plant (A. Meiswinkel); (2) New developments in oxidation catalysis (F. Rosowski); (3) Study of the performance of vanadium based catalysts prepared by grafting in the oxidative dehydrogenation of propane (E. Santacesaria); (4) Hydrocracking for oriented conversion of heavy oils: recent trends for catalyst development (F. Bertoncini); (5) Acidic ionic liquids for n-alkane isomerization in a liquid-liquid or slurry-phase reaction mode (C. Meyer); (6) Dual catalyst system for the hydrocracking of heavy oils and residues (G. Bellussi); (7) Understanding hydrodenitrogenation on novel unsupported sulphide Mo-W-Ni catalysts (J. Hein); (8) Hydrocracking of ethyllaurate on bifunctional micro-/mesoporous composite materials (M. Adam); (9) Catalytic dehydration of ethanol to ethylene (Ying Zhu); (10) The Evonik-Uhde HPPO process for propylene oxide production (B. Jaeger); (11) A green two-step process for adipic acid production from cyclohexene: A study on parameters affecting selectivity (F. Cavani); (12) DISY: The direct synthesis of hydrogen peroxide, a bridge for innovative applications (R, Buzzoni); (13) Solid catalyst with ionic liquid layer (SCILL) - A concept to improve the selectivity of selective hydrogenations (A. Jess); (14) Co-Zn-Al based hydrotalcites as catalysts for Fischer-Tropsch process (C.L. Bianchi); (15) Honeycomb supports with high thermal conductivity for the Fischer-Tropsch synthesis (C.G. Visconti); (16) How to make Fischer-Tropsch catalyst scale-up fully reliable (L. Fischer); (17) New developments in FCC catalysis (C.P. Kelkar); (18) The potential of medium-pore zeolites for improved propene yields from catalytic cracking (F. Bager).

  18. Holistic analysis of thermochemical processes by using solid biomass for fuel production in Germany

    Henssler, Martin

    2015-01-01

    According to the German act ''Biokraftstoff-Nachhaltigkeitsverordnung'', biofuels must show a CO 2eq -reduction compared to the fossil reference fuel (83.8 g CO 2eq /MJ fuel /Richtlinie 98/70/EG/) of 35 % beginning with 2011. In new plants, which go into operation after the 31.12.2016 the CO 2eq -savings must be higher than 50 % in 2017 and higher than 60 % in 2018 /Biokraft-NachV/. The biofuels (methyl ester of rapeseed, bioethanol and biomethane) considered in this study do not meet these requirements for new plants. To comply with these rules new processes must be deployed. Alternative thermochemical generated fuels could be an option. The aim of this work is to evaluate through a technical, ecological and economic analysis (Well-to-Wheel) whether and under what conditions the thermochemical production of Fischer-Tropsch-diesel or -gasoline, hydrogen (H 2 ) and Substitute Natural Gas (SNG) complies with the targets. Four different processes are considered (fast pyrolysis and torrefaction with entrained flow gasifier, CHOREN Carbo-V registered -gasifier, Absorption Enhanced Reforming (AER-) gasifier). Beside residues such as winter wheat straw and residual forest wood, wood from short-rotation plantations is taken into account. The technical analysis showed that at present status (2010) two and in 2050 six plants can be operated energy-self-sufficient. The overall efficiency of the processes is in the range of 41.5 (Fischer-Tropsch-diesel or -gasoline) and 59.4 % (H 2 ). Furthermore, it was found that for 2010, all thermochemical produced fuels except the H 2 -production from wood from short-rotation plantations in decentralised or central fast pyrolysis and in decentralised torrefactions with entrained flow gasifier keep the required CO 2eq -saving of 60 %. In 2050, all thermochemical produced fuels will reach these limits. The CO 2eq -saving is between 72 (H 2 ) and 95 % (Fischer-Tropsch-diesel or -gasoline). When the production costs of the

  19. Óxidos de ferro e suas aplicações em processos catalíticos: uma revisão

    Luiz C. A. Oliveira

    2013-01-01

    Full Text Available A review of most of the reported studies on the use of iron oxides as catalyst in specific processes, namely Haber-Bosch reaction, Fischer-Tropsch synthesis, Fenton oxidation and photolytic molecular splitting of water to produce gaseous hydrogen, was carried out. An essential overview is thus presented, intending to address the fundamental meaning, as well as the corresponding chemical mechanisms, and perspectives on new technological potentialities of natural and synthetic iron oxides, more specifically hematite (α-Fe2O3, goethite (α-FeOOH, magnetite (Fe3O4 and maghemite (γ-Fe2O3, in heterogeneous catalysis.

  20. Development of CuxFe/Al2O3 catalysts for the hydrogenation of carbon monoxide guided by magnetic methods, Moessbauer and infrared spectroscopy

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

    1993-01-01

    A copper-iron catalyst for the hydrogenation of carbon monoxide has been prepared using a supported stoichiometric cyanide complex. Conversion of the cyanide precursor to a metallic catalyst appeared to be a precious process. Copper and iron in the bimetallic particles easily separate by thermal treatment and upon exposure to carbon monoxide, as revealed from Moessbauer and infrared spectroscopy. During Fischer-Tropsch reaction the catalyst exhibits a rapid decline of activity. Magnetisation measurements on spent catalysts indicate that the deactivation is caused by a fast conversion of metallic iron to initially unstable carbides which transform ultimately to more stable carbides. (orig.)

  1. Biorefineries: Current activities and future developments

    Demirbas, Ayhan [Sila Science, Trabzon (Turkey)

    2009-11-15

    This paper reviews the current refuel valorization facilities as well as the future importance of biorefineries. A biorefinery is a facility that integrates biomass conversion processes and equipment to produce fuels, power, and chemicals from biomass. Biorefineries combine the necessary technologies of the biorenewable raw materials with those of chemical intermediates and final products. Char production by pyrolysis, bio-oil production by pyrolysis, gaseous fuels from biomass, Fischer-Tropsch liquids from biomass, hydrothermal liquefaction of biomass, supercritical liquefaction, and biochemical processes of biomass are studied and concluded in this review. Upgraded bio-oil from biomass pyrolysis can be used in vehicle engines as fuel. (author)

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

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

    2013-03-01

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

  3. Thermochemical Biomass Gasification: A Review of the Current Status of the Technology

    Ajay Kumar

    2009-07-01

    Full Text Available A review was conducted on the use of thermochemical biomass gasification for producing biofuels, biopower and chemicals. The upstream processes for gasification are similar to other biomass processing methods. However, challenges remain in the gasification and downstream processing for viable commercial applications. The challenges with gasification are to understand the effects of operating conditions on gasification reactions for reliably predicting and optimizing the product compositions, and for obtaining maximal efficiencies. Product gases can be converted to biofuels and chemicals such as Fischer-Tropsch fuels, green gasoline, hydrogen, dimethyl ether, ethanol, methanol, and higher alcohols. Processes and challenges for these conversions are also summarized.

  4. Holistic analysis of thermochemical processes by using solid biomass for fuel production in Germany; Ganzheitliche Analyse thermochemischer Verfahren bei der Nutzung fester Biomasse zur Kraftstoffproduktion in Deutschland

    Henssler, Martin

    2015-04-28

    According to the German act ''Biokraftstoff-Nachhaltigkeitsverordnung'', biofuels must show a CO{sub 2eq}-reduction compared to the fossil reference fuel (83.8 g CO{sub 2eq}/MJ{sub fuel} /Richtlinie 98/70/EG/) of 35 % beginning with 2011. In new plants, which go into operation after the 31.12.2016 the CO{sub 2eq}-savings must be higher than 50 % in 2017 and higher than 60 % in 2018 /Biokraft-NachV/. The biofuels (methyl ester of rapeseed, bioethanol and biomethane) considered in this study do not meet these requirements for new plants. To comply with these rules new processes must be deployed. Alternative thermochemical generated fuels could be an option. The aim of this work is to evaluate through a technical, ecological and economic analysis (Well-to-Wheel) whether and under what conditions the thermochemical production of Fischer-Tropsch-diesel or -gasoline, hydrogen (H{sub 2}) and Substitute Natural Gas (SNG) complies with the targets. Four different processes are considered (fast pyrolysis and torrefaction with entrained flow gasifier, CHOREN Carbo-V {sup registered} -gasifier, Absorption Enhanced Reforming (AER-) gasifier). Beside residues such as winter wheat straw and residual forest wood, wood from short-rotation plantations is taken into account. The technical analysis showed that at present status (2010) two and in 2050 six plants can be operated energy-self-sufficient. The overall efficiency of the processes is in the range of 41.5 (Fischer-Tropsch-diesel or -gasoline) and 59.4 % (H{sub 2}). Furthermore, it was found that for 2010, all thermochemical produced fuels except the H{sub 2}-production from wood from short-rotation plantations in decentralised or central fast pyrolysis and in decentralised torrefactions with entrained flow gasifier keep the required CO{sub 2eq}-saving of 60 %. In 2050, all thermochemical produced fuels will reach these limits. The CO{sub 2eq}-saving is between 72 (H{sub 2}) and 95 % (Fischer-Tropsch

  5. Dimethyl Ether (DME); Le Dimethyl Ether (DME)

    NONE

    2006-07-01

    Total is an active participant in research to develop new gas-to-liquids (GTL) processes to obtain automotive fuel, olefins and other liquids from natural gas. Among the various processes for chemical conversion of natural gas, direct synthesis of DME destroys the least amount of gas, making it highly efficient. The thermal efficiency of the process developed by Japan JFE is 65 to 70%, higher than the conventional Fischer Tropsch process. This document presents the researches and the program of Total on this process. (author)

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

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

    2012-01-24

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

  7. Synthesis and structure of the unligated carbene of chromium

    Billups, W.E.; Souchan Chang; Hauge, R.H.; Margrave, J.L. (Rice Univ., Houston, TX (United States))

    1993-04-14

    Complexes with metal-carbon double bonds have found applications as intermediates in many important catalytic reactions including cyclopropanation of alkenes by diazoalkanes, Fischer-Tropsch synthesis, olefin metathesis, Ziegler-Natta polymerization, alkane activation, and in the decomposition of transition metal alkyl complexes. However, complexes with the simplest carbene, CH[sub 2], coordinated to the metal center are relatively rare. In this paper the authors report the synthesis and characterization of the simple unligated carbene of chromium by FTIR matrix isolation spectroscopy. 7 refs., 3 figs., 4 tabs.

  8. Biorefineries: Current activities and future developments

    Demirbas, Ayhan

    2009-01-01

    This paper reviews the current refuel valorization facilities as well as the future importance of biorefineries. A biorefinery is a facility that integrates biomass conversion processes and equipment to produce fuels, power, and chemicals from biomass. Biorefineries combine the necessary technologies of the biorenewable raw materials with those of chemical intermediates and final products. Char production by pyrolysis, bio-oil production by pyrolysis, gaseous fuels from biomass, Fischer-Tropsch liquids from biomass, hydrothermal liquefaction of biomass, supercritical liquefaction, and biochemical processes of biomass are studied and concluded in this review. Upgraded bio-oil from biomass pyrolysis can be used in vehicle engines as fuel.

  9. Fuels from biomass. Potentials, concepts, competitive situation with regard to combustion; Kraftstoffe aus Biomassen. Potentiale, Konzepte, Konkurrenzsituationen zur Verbrennung

    Behrendt, F.; Neubauer, Y. [Technische Univ. Berlin (Germany). Fachgebiet Energieverfahrenstechnik

    2006-07-01

    Liquid fuels are today something of an elixir of life for the industrialised societies and will continue to be so for the foreseeable future. Mobility is dependent on the availability of petrol, diesel and kerosine. Whereas the introduction of alternative vehicle drives is expected to proceed only stepwise over a period of decades, the origin of liquid fuels will change fundamentally. This will involve a shift away from crude oil towards the synthesis of fuels from natural gas, coal and biomass. It will also lead to a revival of long-known technical concepts such as Fischer-Tropsch synthesis or the direct liquefaction of source materials, albeit using significantly refined techniques.

  10. A reaction cell with sample laser heating for in situ soft X-ray absorption spectroscopy studies under environmental conditions.

    Escudero, Carlos; Jiang, Peng; Pach, Elzbieta; Borondics, Ferenc; West, Mark W; Tuxen, Anders; Chintapalli, Mahati; Carenco, Sophie; Guo, Jinghua; Salmeron, Miquel

    2013-05-01

    A miniature (1 ml volume) reaction cell with transparent X-ray windows and laser heating of the sample has been designed to conduct X-ray absorption spectroscopy studies of materials in the presence of gases at atmospheric pressures. Heating by laser solves the problems associated with the presence of reactive gases interacting with hot filaments used in resistive heating methods. It also facilitates collection of a small total electron yield signal by eliminating interference with heating current leakage and ground loops. The excellent operation of the cell is demonstrated with examples of CO and H2 Fischer-Tropsch reactions on Co nanoparticles.

  11. Structure sensitivity of CO dissociation on Rh surfaces

    Mavrikakis, Manos; Baumer, M.; Freund, H.J.

    2002-01-01

    than the flat surface, but the effect is considerably weaker than the effect of surface structure on the dissociation barrier. Our findings are compared with available experimental data, and the consequences for CO activation in methanation and Fischer-Tropsch reactions are discussed.......Using periodic self-consistent density functional calculations it is shown that the barrier for CO dissociation is similar to120 kJ/mol lower on the stepped Rh(211) surface than on the close-packed Rh(111) surface. The stepped surface binds molecular CO and the dissociation products more strongly...

  12. Bifunctional cobalt F-T catalysts

    Miller, J.G.; Coughlin, P.K.; Yang, C.L.; Rabo, J.A.

    1986-03-01

    Results on the catalytic screening of Fischer-Tropsch catalysts containing shape selective components are reported. Catalysts consist of promoted cobalt intimately contacted with Union Carbide molecular sieves and were tested using a Berty type internally recycled reactor. Methods of preparation, promoters and shape selective components were varied and aimed at improving catalyst performance. Catalysts were developed demonstrating high C/sub 5/ + yields with high olefin content and low methane production while maintaining stability under both low and high H/sub 2/:CO ratio conditions.

  13. Ultraclean Fuels Production and Utilization for the Twenty-First Century: Advances toward Sustainable Transportation Fuels

    Fox, Elise B.; Liu, Zhong-Wen; Liu, Zhao-Tie

    2013-11-21

    Ultraclean fuels production has become increasingly important as a method to help decrease emissions and allow the introduction of alternative feed stocks for transportation fuels. Established methods, such as Fischer-Tropsch, have seen a resurgence of interest as natural gas prices drop and existing petroleum resources require more intensive clean-up and purification to meet stringent environmental standards. This review covers some of the advances in deep desulfurization, synthesis gas conversion into fuels and feed stocks that were presented at the 245th American Chemical Society Spring Annual Meeting in New Orleans, LA in the Division of Energy and Fuels symposium on "Ultraclean Fuels Production and Utilization".

  14. Production of Organic Grain Coatings by Surface-Mediated Reactions and the Consequences of This Process for Meteoritic Constituents

    Nuth, Joseph A., III; Johnson, Natasha M.

    2011-01-01

    When hydrogen, nitrogen and CO are 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 reactions. 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.

  15. Production process of the synthetics fuels: technological trajectory analysis; Processos de producao de combustiveis sinteticos: analise das trajetorias tecnologicas

    Dunham, Fabricio B. [Financiadora de Estudos e Projectos (FINEP), Rio de Janeiro, RJ (Brazil)]. E-mail: fbrollo@finep.gov.br; Bomtempo, Jose Vitor [Universidade Federal, Rio de Janeiro, RJ (Brazil). Escola de Quimica]. E-mail: vitor@eq.ufrj.br; Almeida, Edmar Luiz F. de

    2003-07-01

    This paper describes the evolution of the technological trajectories on synthetic fuels. What has influenced on the development of the first production process during the Second World War was analyzed, as well as, the causes of the first technological trajectory ending. It also shows the reasons of returning of the Fischer-Tropsch process to the petroleum companies' and technology licensors' R and D programs. At last, the consequences of the new technological trajectory and its differences regarding to the previous one were analyzed. (author)

  16. Synthetic Natural Gas/ Biogas (Bio-SNG) from Wood as Transportation Fuel

    Biollaz, S.; Stucki, S.

    2004-03-01

    Biofuel production from wood is an interesting option for the energetic use of wood. Various bio fuels could be produced from woody biomass, such as methanol, Fischer-Tropsch (FT) fuels, methane or hydrogen. FT liquids and bio-SNG can be distributed and used via existing infrastructures and therefore fit best today's fossil infrastructure. On an assessment basis from primary to mechanical energy both fuels have pros and cons. For the consolidation of crucial information, i.e. production cost, demonstration plants of transportation fuels are needed. Based on such plants, a detailed evaluation of both fuel chains will be possible. (author)

  17. Coal-related research, organic chemistry, and catalysis

    Anon.

    1980-01-01

    Coal chemistry research topics included: H exchange at 400 0 C, breaking C-C bonds in coal, molecular weight estimation using small-angle neutron scattering, 13 C NMR spectra of coals, and tunneling during H/D isotope effects. Studies of coal conversion chemistry included thermolysis of bibenzyl and 1-naphthol, heating of coals in phenol, advanced indirect liquefaction based on Koelbel slurry Fischer-Tropsch reactor, and plasma oxidation of coal minerals. Reactions of PAHs in molten SbCl 3 , a hydrocracking catalyst, were studied. Finally, heterogeneous catalysis (desulfurization etc.) was studied using Cu, Au, and Ni surfaces. 7 figures, 6 tables

  18. Fischer–Tropsch Synthesis at a Low Pressure on Subnanometer Cobalt Oxide Clusters: The Effect of Cluster Size and Support on Activity and Selectivity

    Lee, Sungsik; Lee, Byeongdu; Seifert, Sönke; Winans, Randall E.; Vajda, Stefan

    2015-05-21

    In this study, the catalytic activity and changes in the oxidation state during the Fischer Tropsch (FT) reaction was investigated on subnanometer size-selected cobalt clusters deposited on oxide (Al2O3, MgO) and carbon-based (ultrananocrystalline diamond UNCD) supports by temperature programmed reaction (TPRx) combined with in-situ grazing-incidence X-ray absorption characterization (GIXAS). The activity and selectivity of ultrasmall cobalt clusters exhibits a very strong dependence on cluster size and support. The evolution of the oxidation state of metal cluster during the reaction reveals that metal-support interaction plays a key role in the reaction.

  19. Óxidos de ferro e suas aplicações em processos catalíticos: uma revisão Iron oxides and their applications in catalytic processes: a review

    Luiz C. A. Oliveira

    2013-01-01

    Full Text Available A review of most of the reported studies on the use of iron oxides as catalyst in specific processes, namely Haber-Bosch reaction, Fischer-Tropsch synthesis, Fenton oxidation and photolytic molecular splitting of water to produce gaseous hydrogen, was carried out. An essential overview is thus presented, intending to address the fundamental meaning, as well as the corresponding chemical mechanisms, and perspectives on new technological potentialities of natural and synthetic iron oxides, more specifically hematite (α-Fe2O3, goethite (α-FeOOH, magnetite (Fe3O4 and maghemite (γ-Fe2O3, in heterogeneous catalysis.

  20. Axial and Radial Gas Holdup in Bubble Column Reactor

    Wagh, Sameer M.; Ansari, Mohashin E Alan; Kene, Pragati T.

    2014-01-01

    Bubble column reactors are considered the reactor of choice for numerous applications including oxidation, hydrogenation, waste water treatment, and Fischer-Tropsch (FT) synthesis. They are widely used in a variety of industrial applications for carrying out gas-liquid and gas-liquid-solid reactions. In this paper, the computational fluid dynamics (CFD) model is used for predicting the gas holdup and its distribution along radial and axial direction are presented. Gas holdup increases linearly with increase in gas velocity. Gas bubbles tends to concentrate more towards the center of the column and follows a wavy path

  1. Sustainable Transportation Fuels from Natural Gas (H{sub 2}), Coal and Biomass

    Huffman, Gerald

    2012-12-31

    This research program is focused primarily on the conversion of coal, natural gas (i.e., methane), and biomass to liquid fuels by Fischer-Tropsch synthesis (FTS), with minimum production of carbon dioxide. A complementary topic also under investigation is the development of novel processes for the production of hydrogen with very low to zero production of CO{sub 2}. This is in response to the nation's urgent need for a secure and environmentally friendly domestic source of liquid fuels. The carbon neutrality of biomass is beneficial in meeting this goal. Several additional novel approaches to limiting carbon dioxide emissions are also being explored.

  2. Dimethyl Ether (DME)

    2006-01-01

    Total is an active participant in research to develop new gas-to-liquids (GTL) processes to obtain automotive fuel, olefins and other liquids from natural gas. Among the various processes for chemical conversion of natural gas, direct synthesis of DME destroys the least amount of gas, making it highly efficient. The thermal efficiency of the process developed by Japan JFE is 65 to 70%, higher than the conventional Fischer Tropsch process. This document presents the researches and the program of Total on this process. (author)

  3. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

    Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI

    2011-01-18

    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  4. Catalysts for conversion of syngas to liquid motor fuels

    Rabo, Jule A.; Coughlin, Peter K.

    1987-01-01

    Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst composition capable of ensuring the production of only relatively minor amounts of heavy products boiling beyond the diesel oil range. The catalyst composition, having desirable stability during continuous production operation, employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component. The latter component is a steam-stabilized zeolite Y catalyst of hydrophobic character, desirably in acid-extracted form.

  5. Investigation of Lubrication Properties of Petroleum Fuel and Biohydrocarbon Blends

    Gawron Bartosz

    2016-07-01

    Full Text Available The paper covers issues regarding lubricity of petroleum fuels used in piston and turbine engines, containing hydrocarbon biocomponents. Basing on available literature it can be said that the most prospective fuel components are biohydrocarbons. The paper describes effect of biohydrocarbons included in aviation fuel and diesel fuel on lubricity of such blends. The analysis covers two processes for obtaining biohydrocarbons, the HVO and the Fischer-Tropsch process. Due to problems with actual products acquiring, biohydrocarbons models representing chemically the actual ones from specific process. Lubricity testing was carried out according to standard test methods.

  6. Development of sustainable coal to liquid processes: Minimising process CO2 emissions

    S. Kauchali

    2017-12-01

    Full Text Available Traditional coal-to-liquid (CTL plants are synonymous with the production of carbon dioxide. Coal may be gasified in the presence of steam and oxygen to produce gas comprising carbon dioxide (CO2, carbon monoxide (CO, methane (CH4, hydrogen (H2 and steam (H2O. The gases can be reacted to a myriad of chemicals and fuels via the Fischer-Tropsch (FT reaction. However, excess carbon dioxide is generated via the Water-Gas-Shift reaction during preparation of CO:H2 ratios for FT. Here, a process development is represented on a CHO phase diagram, where unique regions are identified for autothermal operations for coal conversion. Considerations are given to develop idealised processes for the production of liquid chemicals from coal which emit minimal process CO2, require minimal energy input and do not require steam. This is achieved by co-feeding coal with methane and identifying endothermic-exothermic process pairs for methane-coal dry reforming. Furthermore, it is shown that a preferred method to produce liquid fuels from coal is by first creating dimethyl ether (DME as an intermediate, followed by the dehydration of DME to liquid fuels (gasoline range. For this route, via DME, the CO2 emission was found to be four times less than idealised CTL processes. Keywords: Gasification, Reforming, Coal to liquid, Carbon dioxide, Autothermal, Fischer tropsch

  7. GREET 1.5 - transportation fuel-cycle model - Vol. 1 : methodology, development, use, and results

    Wang, M. Q.

    1999-01-01

    This report documents the development and use of the most recent version (Version 1.5) of the Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation (GREET) model. The model, developed in a spreadsheet format, estimates the full fuel-cycle emissions and energy associated with various transportation fuels and advanced vehicle technologies for light-duty vehicles. The model calculates fuel-cycle emissions of five criteria pollutants (volatile organic compounds, carbon monoxide, nitrogen oxides, particulate matter with diameters of 10 micrometers or less, and sulfur oxides) and three greenhouse gases (carbon dioxide, methane, and nitrous oxide). The model also calculates total energy consumption, fossil fuel consumption, and petroleum consumption when various transportation fuels are used. The GREET model includes the following cycles: petroleum to conventional gasoline, reformulated gasoline, conventional diesel, reformulated diesel, liquefied petroleum gas, and electricity via residual oil; natural gas to compressed natural gas, liquefied natural gas, liquefied petroleum gas, methanol, Fischer-Tropsch diesel, dimethyl ether, hydrogen, and electricity; coal to electricity; uranium to electricity; renewable energy (hydropower, solar energy, and wind) to electricity; corn, woody biomass, and herbaceous biomass to ethanol; soybeans to biodiesel; flared gas to methanol, dimethyl ether, and Fischer-Tropsch diesel; and landfill gases to methanol. This report also presents the results of the analysis of fuel-cycle energy use and emissions associated with alternative transportation fuels and advanced vehicle technologies to be applied to passenger cars and light-duty trucks

  8. Total fuel-cycle analysis of heavy-duty vehicles using biofuels and natural gas-based alternative fuels.

    Meyer, Patrick E; Green, Erin H; Corbett, James J; Mas, Carl; Winebrake, James J

    2011-03-01

    Heavy-duty vehicles (HDVs) present a growing energy and environmental concern worldwide. These vehicles rely almost entirely on diesel fuel for propulsion and create problems associated with local pollution, climate change, and energy security. Given these problems and the expected global expansion of HDVs in transportation sectors, industry and governments are pursuing biofuels and natural gas as potential alternative fuels for HDVs. Using recent lifecycle datasets, this paper evaluates the energy and emissions impacts of these fuels in the HDV sector by conducting a total fuel-cycle (TFC) analysis for Class 8 HDVs for six fuel pathways: (1) petroleum to ultra low sulfur diesel; (2) petroleum and soyoil to biodiesel (methyl soy ester); (3) petroleum, ethanol, and oxygenate to e-diesel; (4) petroleum and natural gas to Fischer-Tropsch diesel; (5) natural gas to compressed natural gas; and (6) natural gas to liquefied natural gas. TFC emissions are evaluated for three greenhouse gases (GHGs) (carbon dioxide, nitrous oxide, and methane) and five other pollutants (volatile organic compounds, carbon monoxide, nitrogen oxides, particulate matter, and sulfur oxides), along with estimates of total energy and petroleum consumption associated with each of the six fuel pathways. Results show definite advantages with biodiesel and compressed natural gas for most pollutants, negligible benefits for e-diesel, and increased GHG emissions for liquefied natural gas and Fischer-Tropsch diesel (from natural gas).

  9. Analysis and evalution of selected future biofuel options on the basis of solid biomass; Analyse und Bewertung ausgewaehlter zukuenftiger Biokraftstoffoptionen auf der Basis fester Biomasse

    Mueller-Langer, Franziska

    2011-12-13

    The aim of this work is starting from the investigation of the technical development prospects along the fuel delivery chain to develop a suitable reproducible tool for the analysis and evaluation of future biofuel policies and on selected fuel options from solid biomass (1. bioethanol by biochemical fermentation, 2. Fischer-Tropsch-Diesel by thermochemical gasification, and 3. Bio-Synthetic Natural Gas (Bio-SNG) by thermochemical gasification). For this it is necessary for these biofuels in accordance with the current technology state the essential perspectives for the practical implementation taking into account the short, medium and long term (e.g. time horizon for implementation in up to 5 years, in about 10 to 15 years, or about 20 to 25 years) to identify possible technical options. [German] Ziel dieser Arbeit ist es, ausgehend von der Untersuchung der technischen Entwicklungsperspektiven entlang der Kraftstoffbereitstellungskette ein geeignetes reproduzierbares Werkzeug fuer die Analyse und Bewertung zukuenftiger Biokraftstoffkonzepte zu entwickeln und auf ausgewaehlte Kraftstoffoptionen auf Basis fester Biomasse (hier Bioethanol ueber die biochemische Fermentation, Fischer-Tropsch-Diesel ueber die thermochemische Vergasung und Bio-Synthetic Natural Gas (Bio-SNG) ueber die thermochemische Vergasung) anzuwenden. Dazu gilt es fuer diese Biokraftstoffe unter Beachtung des aktuellen Technikstandes die wesentlichen Perspektiven fuer die praktische Umsetzung unter Beruecksichtigung der kurz-, mittel- bis langfristig (d.h. Zeithorizont fuer die Realisierung in bis zu 5 Jahren, in etwa 10 bis 15 Jahren bzw. in etwa 20 bis 25 Jahren) denkbaren technischen Moeglichkeiten zu identifizieren.

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

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

    2017-03-03

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

  11. Small Molecule Catalysts for Harvesting Methane Gas

    Baker, S. E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ceron-Hernandez, M. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Oakdale, J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Lau, E. Y. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2016-12-06

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

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

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

    1982-01-01

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

  13. Optimal design issues of a gas-to-liquid process

    Rafiee, Ahmad

    2012-07-01

    Interests in Fischer-Tropsch (FT) synthesis is increasing rapidly due to the recent improvements of the technology, clean-burning fuels (low sulphur, low aromatics) derived from the FT process and the realization that the process can be used to monetize stranded natural gas resources. The economy of GTL plants depends very much on the natural gas price and there is a strong incentive to reduce the investment cost and in addition there is a need to improve energy efficiency and carbon efficiency. A model is constructed based on the available information in open literature. This model is used to simulate the GTL process with UNISIM DESIGN process simulator. In the FT reactor with cobalt based catalyst, Co2 is inert and will accumulate in the system. Five placements of Co2 removal unit in the GTL process are evaluated from an economical point of view. For each alternative, the process is optimized with respect to steam to carbon ratio, purge ratio of light ends, amount of tail gas recycled to syngas and FT units, reactor volume, and Co2 recovery. The results show that carbon and energy efficiencies and the annual net cash flow of the process with or without Co2 removal unit are not significantly different and there is not much to gain by removing Co2 from the process. It is optimal to recycle about 97 % of the light ends to the process (mainly to the FT unit) to obtain higher conversion of CO and H2 in the reactor. Different syngas configurations in a gas-to-liquid (GTL) plant are studied including auto-thermal reformer (ATR), combined reformer, and series arrangement of Gas Heated Reformer (GHR) and ATR. The Fischer-Tropsch (FT) reactor is based on cobalt catalyst and the degrees of freedom are; steam to carbon ratio, purge ratio of light ends, amount of tail gas recycled to synthesis gas (syngas) and Fischer-Tropsch (FT) synthesis units, and reactor volume. The production rate of liquid hydrocarbons is maximized for each syngas configuration. Installing a steam

  14. Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals. Technical Progress Report

    Akio Ishikawa; Manuel Ojeda; Nan Yao; Enrique Iglesia

    2006-01-01

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

  15. EARLY ENTRANCE COPRODUCTION PLANT

    Fred D. Brent; Lalit Shah; Earl Berry; Charles H. Schrader; John Anderson; J. Erwin; Matthew G. Banks; Terry L. Ullman

    2004-01-12

    The overall objective of this project is the three phase development of an Early Entrance Coproduction Plant (EECP) which uses petroleum coke to produce at least one product from at least two of the following three categories: (1) electric power (or heat), (2) fuels, and (3) chemicals using ChevronTexaco's proprietary gasification technology. The objective of Phase I is to determine the feasibility and define the concept for the EECP located at a specific site; develop a Research, Development, and Testing (RD&T) Plan to mitigate technical risks and barriers; and prepare a Preliminary Project Financing Plan. The objective of Phase II is to implement the work as outlined in the Phase I RD&T Plan to enhance the development and commercial acceptance of coproduction technology. The objective of Phase III is to develop an engineering design package and a financing and testing plan for an EECP located at a specific site. The project's intended result is to provide the necessary technical, economic, and environmental information needed by industry to move the EECP forward to detailed design, construction, and operation. The partners in this project are Texaco Energy Systems LLC or TES (a subsidiary of ChevronTexaco), General Electric (GE), Praxair, and Kellogg Brown & Root (KBR) in addition to the U.S. Department of Energy (DOE). TES is providing gasification technology and Fischer-Tropsch (F-T) technology developed by Rentech, GE is providing combustion turbine technology, Praxair is providing air separation technology, and KBR is providing engineering. Each of the EECP subsystems was assessed for technical risks and barriers. A plan was developed to mitigate the identified risks (Phase II RD&T Plan, October 2000). Phase II RD&T Task 2.6 identified as potential technical risks to the EECP the fuel/engine performance and emissions of the F-T diesel fuel products. Hydrotreating the neat F-T diesel product reduces potentially reactive olefins, oxygenates, and acids

  16. Bimetallic Catalysts and Platinum Surfaces Studied by X-ray Absorption Spectroscopy and Scanning Tunnelling Microscopy

    Roenning, Magnus

    2000-07-01

    Bimetallic catalyst systems used in Fischer-Tropsch synthesis (Co-Re/Al{sub 2}O{sub 3}) and in the naphtha reforming process (Pt-Re/Al{sub 2}O{sub 3}) have been studied in situ using X-ray absorption spectroscopy (EXAFS). Additionally, the adsorption of ethene on platinum single crystal surfaces has been investigated using scanning tunnelling microscopy. In situ EXAFS at the cobalt K absorption edge have been carried out at 450{sup o}C on the hydrogen reduction of a rhenium-promoted Co{sub 3}O{sub 4}/Al{sub 2}O{sub 3} catalyst. Reductions carried out using 100% hydrogen and 5% hydrogen in helium gave different results. Whereas the reduction using dilute hydrogen leads to bulk-like metallic cobalt particles (hcp or fcc), reaction with pure hydrogen yields a more dispersed system with smaller cobalt metal particles (< 40 A). The results are rationalised in terms of different degrees of reoxidation of cobalt by the higher and lower concentrations of water generated during the reduction of cobalt oxide by 100% and 5% hydrogen, respectively. Additionally, in both reduction protocols a small fraction (3 -4 wt%) of the cobalt content is randomly dispersed over the tetrahedral vacancies of the alumina support. This dispersion occurs during reduction and not calcination. The cobalt in these sites cannot be reduced at 450 {sup o}C. The local environments about the rhenium atoms in Co-Re/{gamma}-A1{sub 2}O{sub 3} catalyst after different reduction periods have been studied by X-ray absorption spectroscopy. A bimetallic catalyst containing 4.6 wt% cobalt and 2 wt% rhenium has been compared with a corresponding monometallic sample with 2 wt% rhenium on the same support. The rhenium L{sub III} EXAFS analysis shows that bimetallic particles are formed after reduction at 450{sup o}C with the average particle size being 10-15 A. Rhenium is shown to be reduced at a later stage than cobalt. The fraction of cobalt atoms entering the support obstructs the access to the support for the

  17. Phase equilibria of toluene/heptane with deep eutectic solvents based on ethyltriphenylphosphonium iodide for the potential use in the separation of aromatics from naphtha

    Kareem, Mukhtar A.; Mjalli, Farouq S.; Hashim, Mohd Ali; Hadj-Kali, Mohamed K.O.; Ghareh Bagh, Fatemeh Saadat; Alnashef, Inas M.

    2013-01-01

    Highlights: • Ionic liquid analogues are introduced as potential replacements for ionic liquids. • Deep eutectic solvents presented in this work were successful for extracting aromatics. • Hand correlation was applied to ascertain the experimental measurements. • The NRTL thermodynamic model was capable for correlating the LLE experimental data. -- Abstract: In this work, the liquid–liquid extraction of toluene from hydrocarbons mixtures (toluene/heptane) was investigated using deep eutectic solvents as solvents. Ethyltriphenylphosphonium iodide as a salt with either ethylene glycol or sulfolane as hydrogen-bond donors (HBDs) were utilized for synthesizing six DESs. (Liquid + liquid) equilibria data were determined experimentally for the ternary system (toluene + heptane + DES) at (30, 40, 50, and 60) °C and atmospheric pressure. Hand correlation was applied to establish the reliability of the experimental data. In many cases the correlation factor is found close to unity which indicates high reliability of the data. The selectivities and distribution coefficients were used to determine the suitability of these DESs as solvents for this extraction process. Higher selectivities than those published for sulfolane as a commercial solvent were observed. The DES made from ethyltriphenylphosphonium iodide and sulfolane at salt:HBD of 1:4 showed the best separation capability at 30 °C. Thus, it was further characterized by measuring its viscosity and refractive index at a range of temperatures to help understand its physical behaviour needed for process design. The non-random two-liquid (NRTL) model was applied successfully to correlate the experimental tie-lines and to calculate the phase compositions of the ternary systems. It has been found that the third non-randomness parameter varies linearly with the HBD number of moles

  18. Life Cycle Assessment Applied to Naphtha Catalytic Reforming Analyse de cycle de vie appliquée au reformage catalytique du naphta

    Portha J.-F.

    2010-10-01

    Full Text Available Facing the increase of environmental concerns in the oil and gas industry, engineers and scientists need information to assess sustainability of chemical processes. Among the different methods available, Life Cycle Assessment (LCA is widely used. In this study, LCA is applied to a catalytic reforming process using the Eco- Indicator 99 as life cycle impact assessment method. The main identified environmental impacts are fossil fuels consumption, climate change and respiratory effects due to inorganics compounds. The influence of different process parameters (feed composition, reaction temperature is determined with respect to environmental impacts. Two allocation methods are analysed (mass and exergetic allocation and two different process versions are compared in order to determine the effect of some improvements on environmental impact. Les considérations liées à l’environnement doivent de plus en plus être prises en compte par les ingénieurs et les scientifiques afin de juger de la durabilité des procédés chimiques dans l’industrie pétrolière et gazière. Parmi les différentes méthodes d’analyse environnementale, l’Analyse de Cycle de Vie (ACV est très utilisée. Dans cette étude, l’ACV est appliquée au procédé de reformage catalytique du naphta en utilisant la méthode Eco-Indicateur 99 comme méthode d’analyse des impacts du cycle de vie. Les principaux impacts environnementaux du procédé sont la consommation de combustibles fossiles, le changement climatique et les effets sur la respiration liés aux composés organiques. L’influence de différents paramètres (composition de l’alimentation, température de réaction sur les impacts environnementaux est testée. Deux méthodes d’allocation sont analysées (allocation massique et énergétique et deux versions du procédé de reformage catalytique sont comparées afin de déterminer les améliorations possibles permettant de minimiser les impacts.

  19. Life Cycle Assessment Applied to Naphtha Catalytic Reforming Analyse de cycle de vie appliquée au reformage catalytique du naphta

    Portha J.-F.; Jaubert J.-N.; Louret S.; Pons M.-N.

    2010-01-01

    Facing the increase of environmental concerns in the oil and gas industry, engineers and scientists need information to assess sustainability of chemical processes. Among the different methods available, Life Cycle Assessment (LCA) is widely used. In this study, LCA is applied to a catalytic reforming process using the Eco- Indicator 99 as life cycle impact assessment method. The main identified environmental impacts are fossil fuels consumption, climate change and respiratory effects du...

  20. Opportunities and challenges at the interface between petrochemistry and refinery. Preprints

    Ernst, S.; Leitner, W.; Lercher, J.A.; Nees, F.; Perego, C.; Rupp, M.; Santacesaria. E. (eds.)

    2007-07-01

    .A. Botavina, P. Pertici, D.V. Trushin, N.V. Nekraskov, C. Evangelisti, N. Panziera, G. Martra, K. Tenchev, L. Petrov, S. Coluccia); (q) Facile synthesis of 2,6-dichlorobenzonitrile by vapour phase ammoxidation (V. Narayana Kalevaru, B. Luecke, A. Martin); (r) Energy efficiency of the cold train of an ethylene cracker (K. Van Geem, N. Hedebouw, J. Grootjans, G.B. Martin); (s) From fuel to wheel: How modern fuels behave in combustion engines (S. Pischinger, M. Muether, F. Fricke, A. Kolbeck); (t) Sulphur poisoning of a Co/Al{sub 2}O{sub 3} Fischer-Tropsch catalyst (C.G. Visconti, L. Lietti, R. Zennaro, P. Forzatti); (u) From Fischer Tropsch raw products to Fischer Tropsch fuels: Development of an upgrading model and application to XtL processes (D. Beiermann).

  1. Simulation of the gasification of animal wastes in a dual gasifier using Aspen Plus®

    Fernandez-Lopez, M.; Pedroche, J.; Valverde, J.L.; Sanchez-Silva, L.

    2017-01-01

    Highlights: • The gasification of manure was evaluated using the software Aspen Plus®. • Composition and LHV of the obtained syngas depends on the operating conditions. • CO 2 net emissions for the steam and CO 2 gasification processes were calculated. • Manure steam gasification can be used as feedstock for Fischer-Tropsch. • Manure CO 2 gasification lead to a syngas suitable for energy production. - Abstract: The gasification of an animal waste biomass (manure) in a dual gasifier was studied using the software Aspen Plus®. For this purpose, a model based on a Gibbs free energy reactor was considered. Effects of the gasification temperature, the gasifying/biomass ratio and the use of steam and CO 2 as the gasifying agents on the composition and the low heating value (LHV) of the produced syngas were evaluated. In this sense, the H 2 /CO ratio and the LHV were the parameters calculated to stablish the best operating conditions for the production of either hydrocarbons via Fischer-Tropsch or energy. Furthermore, the CO 2 net emissions generated by the gasification process were also important in the selection of the best operating conditions from an environmental point of view. The obtained results showed that for both gasifying agents the H 2 and CO production was favoured at high temperatures whereas the production of CH 4 and CO 2 was favoured at low ones. On the other hand, the H 2 production was higher when steam was used as the gasifying agent and the formation of CO was enhanced when CO 2 was considered as gasification agent. An increase of the gasifying agent/biomass ratio had a negatively influence on the production of CH 4 , leading to a decrease of the LHV. Therefore, steam as the gasifying agent and high temperatures favoured the obtaining of a syngas suitable for the Fischer-Tropsch process whereas CO 2 and low gasification temperatures enhanced a syngas with a high LHV which could be used for energy production. Finally, the net CO 2

  2. Gas-to-liquids : who cares?

    Yakobson, D.L.

    1999-01-01

    An overview of gas-to-liquids (GTL) technology was presented along with its capital costs, economics and market niche. GTL technology is a process developed by Fischer-Tropsch in the 1920s, in which carbonaceous feedstock is catalytically converted into synthetic oil. The feedstock can be natural gas, coal, or refinery bottoms, bitumen, Orimulsion TM or biomass. The process involves the making of a gaseous mixture of hydrogen and carbon monoxide and then feeding that mixture into a reactor containing a catalyst. The last step involves the processing of the synthetic oil into fractions for sale. The issue of whether GTL will compete with refinery production or supplement it was also raised. The potential for GTL projects in North America were reviewed. The five companies which have matured GTL technologies are Exxon, Rentech, Sasol, Shell and Syntroleum

  3. Mixed alcohols production from syngas

    Stevens, R.R.; Conway, M.M.

    1988-01-01

    A process is described for selectively producing mixed alcohols from synthesis gas comprising contacting a mixture of hydrogen and carbon monoxide with a catalytic amount of a catalyst containing components of (1) a catalytically active metal of molybdenum or tungsten, in free or combined form; (2) a cocatalytic metal or cobalt or nickel in free or combined form; and (3) a Fischer-Tropsch promoter of an alkali or alkaline earth series metal, in free or combined form; the components combined by dry mixing, mixing as a wet paste, wet impregnation, and then sulfided, the catalyst excluding rhodium, ruthenium and copper, at a pressure of at least about 500 psig and under conditions sufficient to form the mixed alcohols in at least 20 percent CO/sub 2/ free carbon selectivity, the mixed alcohols containing a C/sub 1/ to C/sub 2-5/ alcohol weight ratio of less than about 1:1

  4. Basic nitrogen-heterocyclic compounds in the Murchison meteorite

    Stoks, P.G.; Schwartz, A.W.

    1982-01-01

    A fragment of the Murchison (C2) carbonaceous meteorite was analyzed for basic, N-heterocyclic compounds, by dual detector capillary gas chromatography as well as capillary gas chromatography/mass spectrometry, using two columns of different polarity. In the formic acid extract 2,4,6-trimethylpyridine, quinoline, isoquinoline, 2-methylquinoline and 4-methylquinoline were positively identified. In addition, a suite of alkylpyridines and quinolines and/or isoquinolines was tentatively identified from their mass spectra. The (iso)quinolines were found to contain methyl substituents exclusively. The distribution of the pyridines observed reveals a similarity to that observed from catalytic reactions of ammonia and simple aldehydes under conditions similar to those applied in Fischer-Tropsch type reactions. (author)

  5. CO chemistry/research trends in CO chemistry in the US

    Cantacuzene, M

    1978-10-01

    Research trends in CO chemistry in the U.S. include the development of stable and selective homogeneous catalysts which would facilitate the removal of the heat of reaction and be resistant to sulfur poisoning for the methanation reaction, methanol synthesis, and Fischer-Tropsch synthesis; development of low-temperature homogeneous water gas shift catalysts; and research on the coordination chemistry and photochemical conversions of CO/sub 2/. In 1977, the National Science Foundation awarded 16 contracts for a total of $720,000 to promote the research in this field, including studies on chemisorption and heterogeneous catalysis (four contracts) and on transition metal complexes (ten contracts, of which seven are dedicated to metal clusters). Carbon monoxide-based processes, including water gas shift reactions, CO reduction to alkanes and alcohols, hydroformylation, and homogeneous carbonylation processes, recently developed in the U.S. are listed.

  6. Low temperature hydrogenolysis of waxes to diesel range gasoline and light alkanes: Comparison of catalytic properties of group 4, 5 and 6 metal hydrides supported on silica-alumina

    Norsic, Sébastien

    2012-01-01

    A series of metal hydrides (M = Zr, Hf, Ta, W) supported on silica-alumina were studied for the first time in hydrogenolysis of light alkanes in a continuous flow reactor. It was found that there is a difference in the reaction mechanism between d 0 metal hydrides of group 4 and d 0 ↔ d 2 metal hydrides of group 5 and group 6. Furthermore, the potential application of these catalysts has been demonstrated by the transformation of Fischer-Tropsch wax in a reactive distillation set-up into typical gasoline and diesel molecules in high selectivity (up to 86 wt%). Current results show that the group 4 metal hydrides have a promising yield toward liquid fuels.

  7. Catalysts for synthetic liquid fuels

    Bruce, L.A.; Turney, T.W.

    1987-12-01

    Fischer-Tropsch catalysts have been designed, characterized and tested for the selective production of hydrocarbons suitable as synthetic liquid transport fuels from synthesis gas (i.e., by the reduction of carbon monoxide with hydrogen). It was found that hydrocarbons in the middle distillate range, or suitable for conversion to that range, could be produced over several of the new catalyst systems. The various catalysts examined included: (1) synthetic cobalt clays, mainly cobalt chlorites; (2) cobalt hydrotalcites; (3) ruthenium metal supported on rare earth oxides of high surface area; and (4) a novel promoted cobalt catalyst. Active and selective catalysts have been obtained, in each category. With the exception of the clays, reproducibility of catalyst performance has been good. Catalysts in groups 2 and 4 have exhibited very high activity, with long lifetimes and easy regeneration.

  8. Biomass gasification for liquid fuel production

    Najser, Jan; Peer, Václav; Vantuch, Martin

    2014-01-01

    In our old fix-bed autothermal gasifier we tested wood chips and wood pellets. We make experiments for Czech company producing agro pellets - pellets made from agricultural waste and fastrenewable natural resources. We tested pellets from wheat and rice straw and hay. These materials can be very perspective, because they dońt compete with food production, they were formed in sufficient quantity and in the place of their treatment. New installation is composed of allothermal biomass fixed bed gasifier with conditioning and using produced syngas for Fischer - Tropsch synthesis. As a gasifying agent will be used steam. Gas purification will have two parts - separation of dust particles using a hot filter and dolomite reactor for decomposition of tars. In next steps, gas will be cooled, compressed and removed of sulphur and chlorine compounds and carbon dioxide. This syngas will be used for liquid fuel synthesis

  9. Harnessing biofuels. A global Renaissance in energy production?

    Jegannathan, Kenthorai Raman; Chan, Eng-Seng; Ravindra, Pogaku [Centre of Materials and Minerals, School of Engineering and Information Technology, Universiti Malaysia Sabah, 88999 Kota Kinabalu, Sabah (Malaysia)

    2009-10-15

    Biofuel, peoples' long awaiting alternative fuel, is yet to struggle a long way to reach in retail outlet all over the world as an economical and environmental friendly fuel. Biofuels include bioethanol, biodiesel, biogas, bio-synthetic gas (bio-syngas), bio-oil, bio-char, Fischer-Tropsch liquids, and biohydrogen. Among these bioethanol, biodiesel, biogas are predominant which can be produced either using chemical catalyst or biocatalyst from biomass. At present, the conventional process involves the chemical catalyst while a rigorous research is focused on using a biocatalyst. This review brings out the advantages and disadvantages of using different type of catalyst in biofuel production and emphasis on new technologies as an alternative to conventional technologies. (author)

  10. Methanol and carbonylation

    Gauthier-Lafaye, J.; Perron, R.

    1987-01-01

    The overall focus of the book is on homogeneous catalysed processes which were seen to offer the most promising routes to C/sub 2/ oxygenates. The first three chapters review the industrial synthesis and applications of carbon monoxide such as in the manufacture of gasoline (e.g. Fischer-Tropsch, Mobil processes), organic chemicals (e.g. ethanol, acetic acid, etc.), industrial importance of C/sub 2/ oxygenates, and use of methanol as a future feedstock are discussed. The next six chapters are each concerned with the production of a particular C/sub 2/ oxygenate and a detailed analysis of the methods and catalysts used. The hydrocarbonylation of methanol occupies a large chapter (136 references) with a comparative examination of the catalysts available, and their modification to increase selectivity to either acetylaldehyde or ethanol. Following chapters examine the synthesis of ethyl acetate, acetic acid, acetic anhydride, vinyl acetate, ethylene glycol and oxalic acid.

  11. New syntheses with carbon monoxide

    Falbe, J.

    1980-01-01

    In the chapter of hydroformulation, oxosynthesis ans Roelen reaction the effect of reaction conditions on conversion, selectivity and operation of the oxo synthesis, hydroformulation of particular structures, parallel and consecutive reactions under hydroformulation conditions and process variants and economic background of the industrial oxo synthesis are discussed. The chapter of homologation of alcohols describes reaction mechanism and parallel and secondary reactions. The chapter of Reppe reactions deals with carbonylation of various structures. The chapter of hydrogenation of CO treats methanol, glycol, methane, the Fischer-Tropsch hydrocarbon and polymethylene synthesis. The chapter of Koch reactions treats reaction mechanism and carbonlylation at particular compounds. The last chapter presents ring closure reactions with CO. Separate abstracts were prepared for one chapter in this book.

  12. Revolution in the natural gas industry?

    Thomas, V.

    1999-01-01

    The demand for cleaner automotive fuels has created an opening for converting natural gas to liquid transport fuels and blending agents using Fischer-Tropsch technology. While the technology is well established, it is not yet clear whether the conversion can compete with crude oil refining or with pipelines and liquefied natural gas. Although all the oil giants are interested in the technology, the only commercial-sized plant in the world was the Shell plant in Malaya which had capacity of 12,000 bpd, but the profitability of the plant came from the wax by-products. The plant has been closed since a fire and explosion in 1997. The process chain is described. The gas-to-liquid activities and achievements of Saol, Exxon and Texaco are reported. It was concluded that although there are still some problems to be ironed-out, there is a promising future for gas-to-liquid conversion. (UK)

  13. Development of Hydrogen Electrodes for Alkaline Water Electrolysis

    Kjartansdóttir, Cecilía Kristín

    , production of electricity via fuel cells, fuel for internal combustion engines or gas turbines, or as a raw material for the production of synthetic fuels via Sabatier or Fischer - Tropsch process. In some situations it may be suitable to simply inject hydrogen into the existing natural gas based...... will be needed. Producing hydrogen via water electrolysis using surplus, low cost, power from renewables offers the possibility of increased production capacity and load management with no greenhouse emissions. Hydrogen is a valuable energy carrier, which is able to contribute to various forms of energy, such as...... infrastructure. Alkaline water electrolysis (AWE) is the current standard (stat of the art) for industrial large-scale water electrolysis systems. One of the main criteria for industrial AWE is efficient and durable electrodes. The aim of the present PhD study was to develop electrode materials for hydrogen...

  14. Biofuels 2.0 move to pilot plant

    Dupin, L.

    2010-01-01

    The second generation of biofuels, which use the non-energy parts of plants, do not compete with the food industry. These biofuels have been tried and tested at the laboratory but challenges are occurring with the transition to industrial plants. Demonstrators and prototypes are developing in Germany, Japan, USA and France and bet on two different processes, the biochemical way (enzymatic reaction and fermentation) and the thermochemical way (gasification and Fischer-Tropsch synthesis). Research is in progress on a possible third generation of biofuels which will use micro-algae. The interest of this third way is triple: no competition with the food industry, no land use (production in bioreactors), and enhanced CO 2 capture. (J.S.)

  15. Catalysis by Dust Grains in the Solar Nebula

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

    1996-01-01

    In order to determine whether grain-catalyzed reactions played an important role in the chemistry of the solar nebula, we have applied our time-dependent model of methane formation via Fischer-Tropsch catalysis to pressures from 10(exp -5) to 1 bar and temperatures from 450 to 650 K. Under these physical conditions, the reaction 3H2 + CO yields CH4 + H2O is readily catalyzed by an iron or nickel surface, whereas the same reaction is kinetically inhibited in the gas phase. Our model results indicate that under certain nebular conditions, conversion of CO to methane could be extremely efficient in the presence of iron-nickel dust grains over timescales very short compared to the lifetime of the solar nebula.

  16. Towards Sustainable Production of Formic Acid.

    Bulushev, Dmitri A; Ross, Julian R H

    2018-03-09

    Formic acid is a widely used commodity chemical. It can be used as a safe, easily handled, and transported source of hydrogen or carbon monoxide for different reactions, including those producing fuels. The review includes historical aspects of formic acid production. It briefly analyzes production based on traditional sources, such as carbon monoxide, methanol, and methane. However, the main emphasis is on the sustainable production of formic acid from biomass and biomass-derived products through hydrolysis and oxidation processes. New strategies of low-temperature synthesis from biomass may lead to the utilization of formic acid for the production of fuel additives, such as methanol; upgraded bio-oil; γ-valerolactone and its derivatives; and synthesis gas used for the Fischer-Tropsch synthesis of hydrocarbons. Some technological aspects are also considered. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Size Control of Iron Oxide Nanoparticles Using Reverse Microemulsion Method: Morphology, Reduction, and Catalytic Activity in CO Hydrogenation

    Mohammad Reza Housaindokht

    2013-01-01

    Full Text Available Iron oxide nanoparticles were prepared by microemulsion method and evaluated in Fischer-Tropsch synthesis. The precipitation process was performed in a single-phase microemulsion operating region. Different HLB values of surfactant were prepared by mixing of sodium dodecyl sulfate (SDS and Triton X-100. Transmission electron microscopy (TEM, surface area, pore volume, average pore diameter, pore size distribution, and XRD patterns were used to analyze size distribution, shape, and structure of precipitated hematite nanoparticles. Furthermore, temperature programmed reduction (TPR and catalytic activity in CO hydrogenation were implemented to assess the performance of the samples. It was found that methane and CO2 selectivity and also the syngas conversion increased as the HLB value of surfactant decreased. In addition, the selectivity to heavy hydrocarbons and chain growth probability (α decreased by decreasing the catalyst crystal size.

  18. Functionalized Natural Carbon-Supported Nanoparticles as Excellent Catalysts for Hydrocarbon Production.

    Sun, Jian; Guo, Lisheng; Ma, Qingxiang; Gao, Xinhua; Yamane, Noriyuki; Xu, Hengyong; Tsubaki, Noritatsu

    2017-02-01

    We report a one-pot and eco-friendly synthesis of carbon-supported cobalt nanoparticles, achieved by carbonization of waste biomass (rice bran) with a cobalt source. The functionalized biomass provides carbon microspheres as excellent catalyst support, forming a unique interface between hydrophobic and hydrophilic groups. The latter, involving hydroxyl and amino groups, can catch much more active cobalt nanoparticles on surface for Fischer-Tropsch synthesis than chemical carbon. The loading amount of cobalt on the final catalyst is much higher than that prepared with a chemical carbon source, such as glucose. The proposed concept of using a functionalized natural carbon source shows great potential compared with conventional carbon sources, and will be meaningful for other fields concerning carbon support, such as heterogeneous catalysis or electrochemical fields. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Toward better understanding of the support effect: test cases for CO dissociation on Fe n /TiO 2 (110), n=4,5

    Jedidi, Abdesslem

    2017-06-17

    The Fischer-Tropsch reaction is initiated by direct CO dissociation for Iron catalyst even though a H-assisted mechanism may be easier on other metals. In the gas phase, the CO dissociation is only favorable for Fe-clusters composed by more than 11 atoms. We show here the remarkable effect of the support TiO2(110), making this dissociation exothermic for Fe4 and Fe5 clusters. The main factor for the CO activation is the electron transfer to the reducible support. The role of the TiO2(110) support is to transform the neutral cluster into a positively charged one for which CO dissociation is easier.

  20. Ideas and perspectives: hydrothermally driven redistribution and sequestration of early Archaean biomass - the "hydrothermal pump hypothesis"

    Duda, Jan-Peter; Thiel, Volker; Bauersachs, Thorsten; Mißbach, Helge; Reinhardt, Manuel; Schäfer, Nadine; Van Kranendonk, Martin J.; Reitner, Joachim

    2018-03-01

    Archaean hydrothermal chert veins commonly contain abundant organic carbon of uncertain origin (abiotic vs. biotic). In this study, we analysed kerogen contained in a hydrothermal chert vein from the ca. 3.5 Ga Dresser Formation (Pilbara Craton, Western Australia). Catalytic hydropyrolysis (HyPy) of this kerogen yielded n-alkanes up to n-C22, with a sharp decrease in abundance beyond n-C18. This distribution ( ≤ n-C18) is very similar to that observed in HyPy products of recent bacterial biomass, which was used as reference material, whereas it differs markedly from the unimodal distribution of abiotic compounds experimentally formed via Fischer-Tropsch-type synthesis. We therefore propose that the organic matter in the Archaean chert veins has a primarily microbial origin. The microbially derived organic matter accumulated in anoxic aquatic (surface and/or subsurface) environments and was then assimilated, redistributed and sequestered by the hydrothermal fluids (hydrothermal pump hypothesis).

  1. Manufacture of highly loaded silica-supported cobalt Fischer–Tropsch catalysts from a metal organic framework

    Sun, Xiaohui

    2017-11-16

    The development of synthetic protocols for the preparation of highly loaded metal nanoparticle-supported catalysts has received a great deal of attention over the last few decades. Independently controlling metal loading, nanoparticle size, distribution, and accessibility has proven challenging because of the clear interdependence between these crucial performance parameters. Here we present a stepwise methodology that, making use of a cobalt-containing metal organic framework as hard template (ZIF-67), allows addressing this long-standing challenge. Condensation of silica in the Co-metal organic framework pore space followed by pyrolysis and subsequent calcination of these composites renders highly loaded cobalt nanocomposites (~ 50 wt.% Co), with cobalt oxide reducibility in the order of 80% and a good particle dispersion, that exhibit high activity, C5 + selectivity and stability in Fischer-Tropsch synthesis.

  2. Techno-economic assessment of FT unit for synthetic diesel production in existing stand-alone biomass gasification plant using process simulation tool

    Hunpinyo, Piyapong; Narataruksa, Phavanee; Tungkamani, Sabaithip

    2014-01-01

    For alternative thermo-chemical conversion process route via gasification, biomass can be gasified to produce syngas (mainly CO and H2). On more applications of utilization, syngas can be used to synthesize fuels through the catalytic process option for producing synthetic liquid fuels...... such as Fischer-Tropsch (FT) diesel. The embedding of the FT plant into the stand-alone based on power mode plants for production of a synthetic fuel is a promising practice, which requires an extensive adaptation of conventional techniques to the special chemical needs found in a gasified biomass. Because...... there are currently no plans to engage the FT process in Thailand, the authors have targeted that this work focus on improving the FT configurations in existing biomass gasification facilities (10 MWth). A process simulation model for calculating extended unit operations in a demonstrative context is designed...

  3. Reactions and reaction intermediates on iron surfaces--1. Methanol, ethanol, and isopropanol on Fe(100). 2. Hydrocarbons and carboxylic acids

    Benziger, J.B.; Madix, R.J.

    1980-09-01

    Temperature-programed desorption and ESCA showed that the alcohols formed alkoxy intermediates on Fe(100) surfaces at room temperature, but that the methoxy and ethoxy species were much more stable than the isopropoxy intermediate. The alkoxy species reacted above 400/sup 0/K by decomposing into carbon monoxide and hydrogen, hydrogenation to alcohol, and scission of C-C and C-O bonds with hydrogenation of the hydrocarbon fragments. Ethylene, acetylene, and cis-2-butene formed stable, unidentified surface species. Methyl chloride formed stable surface methyl groups which decomposed into hydrogen and surface carbide at 475/sup 0/K. Formic and acetic acids yielded stable carboxylate intermediates which decomposed above 490/sup 0/K to hydrogen, carbon monoxide, and carbon dioxide. The studies suggested that the alkoxy surface species may be important intermediates in the Fischer-Tropsch reaction on iron.

  4. Indirect coal liquefaction - the first commercial CTL project in the USA

    Radtke, K.; Battensby, D.; Marsico, C.; Hooper, M.; Mather, C. [Uhde GmbH (Germany)

    2006-07-01

    The polygeneration of fuels, chemical and power offers an innovative and economically advantageous way to utilise disadvantaged fuels, such as lignite, waste coal and petroleum coke, in a coal-to-liquids (CTL) plant by means of integration of three main process blocks: gasification island to convert coal into clean synthesis gas; Fischer-Tropsch synthesis to convert synthesis gas into clean liquid fuels and chemicals; and combustion of synthesis gas to produce electric power and steam. This paper describes the process and technology side of this indirect coal liquefaction project with key plant data that has been elaborated for a commercial scale CTL project, which is expected to be the first CTL plant in the USA. The plant will use the Shell Coal Gasification process. 6 figs.

  5. Gasification: in search of efficiency

    Whysall, M. [UOP N.V., Antwerp (Belgium)

    2007-07-01

    Gasification of low cost feed stocks such as coal and heavy residues enables the supply of synthesis gas, hydrogen, power and utilities at a lower cost relative to conventional methodologies. The resulting synthesis gas can be used, after cleaning and sulphur removal, as a fuel or to produce other chemicals such as ammonia, methanol, or Fischer-Tropsch liquids. The paper covers coal and residue upgrading through the use of gasification, conversion and hydroprocessing and its integration with synthesis gas treatment and hydrogen recovery. Residue conversion choices can be influenced by hydrogen cost which can be controlled by integrating hydrogen production, recovery and purification into the gasification complex. Flow-schemes that maximize generation efficiency and minimize capital and operating costs and offer possibilities for CO{sub 2} capture are discussed. 3 figs.

  6. SHS-produced intermetallides as catalysts for hydrocarbons synthesis from CO and H{sub 2}

    Eliseev, O.L.; Kazantsev, R.V.; Davydov, P.E.; Lapidus, A.L. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Institute of Organic Chemistry; Borshch, V.N.; Pugacheva, E.V. [Russian Academy of Sciences, Chernogolovka (Russian Federation). Inst. of Structural Macrokinetics and Materials Science

    2012-07-01

    Raney-type polymetallic alloys were prepared by Self-Propagating High-Temperature Synthesis followed by alkaline treating. Surface morphology and composition of were studied using XRD, BET, SEM and EMPA techniques. The samples were tested in Fischer-Tropsch synthesis demonstrated rather high activity and very high selectivity to heavy paraffins. High selectivity to C{sub 5+} hydrocarbons is attributed to high thermal conductivity of alloys which prevents hot spots formation and therefore suppresses formation of methane and light hydrocarbons. Selectivity can be further improved by adding some d-metals in catalyst composition. Promotion with La seems to be particularly suitable for lowering methane formation while doping with Ni enhances methane yield greatly. (orig.)

  7. Trajetórias Tecnológicas em Combustíveis Sintéticos: Análise dos Mecanismos de Seleção e Indução

    Edmar Luiz Fagundes de Almeida

    2006-01-01

    Full Text Available This article identifies and bounds the existence of two technological trajectories on synthetic liquid fuels. This technological trajectory concept is bounded concerning the selection environment and the programs for technological research. It is applicable at technological levels. The selection environment of the first technological trajectory was bounded by the economical and army limitations observed by the countries that did not produce oil. This situation reached its limit at the beginning of the Second World War. The research programs aimed the development of the Fischer-Tropsch process, high-pressure hydrogenation and low temperature carbonization (LTC. The selection environment of the second technological trajectory is bounded by the increase of natural gas reserves, by the environmental restrictions and by the demand for flexibility in the gas and energy chains. The research programs have as objective the production process for the synthesis gas, which is necessary to the Fischer-Tropsch process. The direct conversion of natural gas into synthetic liquid fuels represents the promise of a radical innovation. Finally, the article compares the two trajectories, identifying similarities and differences between them.O artigo identifica e delimita a existência de duas trajetórias tecnológicas em combustíveis líquidos sintéticos. O conceito de trajetória tecnológica é delimitado em função do ambiente de seleção e dos programas de pesquisa tecnológica, sendo aplicável ao nível das tecnologias. A primeira trajetória tecnológica tem por ambiente de seleção as limitações econômicas e militares observadas pelos países não-produtores de petróleo, o que culminou com os embargos da Segunda Guerra Mundial. Os programas de pesquisa buscavam desenvolver as tecnologias Fischer-Tropsch, hidrogenação em alta pressão e LTC (low temperature carbonization. O ambiente de seleção da segunda trajetória é delimitado pelo aumento

  8. Direct electroreduction of CO2 into hydrocarbon

    Winea, Gauthier; Ledoux, Marc-Jacques; Pham-Huu, Cuong; Gangeri, Miriam; Perathoner, Siglinda; Centi, Gabriele

    2006-01-01

    A lot of methods exist to directly reduce carbon dioxide into hydrocarbons: the photoelectrochemical process is certainly the most interesting, essentially due to the similarities with photosynthesis. As the human activities produce a great quantity of CO 2 , this one can then be considered as an infinite source of carbon. The products of this reaction are identical to those obtained during a Fischer-Tropsch reaction, that is to say hydrocarbons, alcohols and carboxylic acids. These works deal with the electrochemical reduction of CO 2 in standard conditions of temperature and pressure. The photochemical part has been replaced by a current generator as electrons source and a KHCO 3 aqueous solution as protons source. The first catalytic results clearly show that it is possible to reduce CO 2 into light hydrocarbons, typically from C1 to C9. (O.M.)

  9. A criterion for selecting renewable energy processes

    Searcy, Erin; Flynn, Peter C.

    2010-01-01

    We propose that minimum incremental cost per unit of greenhouse gas (GHG) reduction, in essence the carbon credit required to economically sustain a renewable energy plant, is the most appropriate social criterion for choosing from a myriad of alternatives. The application of this criterion is illustrated for four processing alternatives for straw/corn stover: production of power by direct combustion and biomass integrated gasification and combined cycle (BIGCC), and production of transportation fuel via lignocellulosic ethanol and Fischer Tropsch (FT) syndiesel. Ethanol requires a lower carbon credit than FT, and direct combustion a lower credit than BIGCC. For comparing processes that make a different form of end use energy, in this study ethanol vs. electrical power via direct combustion, the lowest carbon credit depends on the relative values of the two energy forms. When power is 70$ MW h -1 , ethanol production has a lower required carbon credit at oil prices greater than 600$ t -1 (80$ bbl -1 ). (author)

  10. Biomass gasification for liquid fuel production

    Najser, Jan, E-mail: jan.najser@vsb.cz, E-mail: vaclav.peer@vsb.cz; Peer, Václav, E-mail: jan.najser@vsb.cz, E-mail: vaclav.peer@vsb.cz [VSB - Technical university of Ostrava, Energy Research Center, 17. listopadu 15/2172, 708 33 Ostrava-Poruba (Czech Republic); Vantuch, Martin [University of Zilina, Faculty of Mechanical Engineering, Department of Power Engineering, Univerzitna 1, 010 26 Zilina (Slovakia)

    2014-08-06

    In our old fix-bed autothermal gasifier we tested wood chips and wood pellets. We make experiments for Czech company producing agro pellets - pellets made from agricultural waste and fastrenewable natural resources. We tested pellets from wheat and rice straw and hay. These materials can be very perspective, because they dońt compete with food production, they were formed in sufficient quantity and in the place of their treatment. New installation is composed of allothermal biomass fixed bed gasifier with conditioning and using produced syngas for Fischer - Tropsch synthesis. As a gasifying agent will be used steam. Gas purification will have two parts - separation of dust particles using a hot filter and dolomite reactor for decomposition of tars. In next steps, gas will be cooled, compressed and removed of sulphur and chlorine compounds and carbon dioxide. This syngas will be used for liquid fuel synthesis.

  11. Lanthanum cobalt oxides as models for La-promoted Co/{gamma}-Al{sub 2}O{sub 3} catalys

    Hansteen, Ole Henrik

    1998-12-31

    Cobalt supported on {gamma}-Al{sub 2}O{sub 3} have for a long time been interesting catalysts for the synthesis of hydrocarbons by hydrogenation of carbonmonoxide, the so-called Fischer-Tropsch synthesis. The reduction and catalytic properties of these catalysts are largely improved by addition of promotors like rhenium and lanthanum. This thesis attempts to provide additional knowledge to the nature of the reduction processes from metal oxides via partially reduced phases into metal and to the large degree of interaction/reaction between the catalyst components. It focuses on detailed studies of model oxides in the La-Co-O and Co-Al-O systems under reducing conditions typically used for the synthesis of the catalysts. 132 refs., 41 figs., 16 tabs.

  12. Synthesis and structures of bimetallic titanium and chromium carbene complexes of the type Cp/sub 2/Ti(Cl)O(CH/sub 3/)CCr(CO)/sub 5/

    Anslyn, E.V.; Santarsiero, B.D.; Grubbs, R.H.

    1988-10-01

    Insertion reactions are some of the most common and important reactions in organometallic chemistry. Aside from being mechanistically interesting, they have proven useful in organic synthesis and have been postulated in catalytic cycles. A subset of the broad group of insertion reactions is the insertion of carbon monoxides of group VIB metal carbonyl complexes into early-transition-metal alkyl, aryl and hydride bonds. Although the coupling of metal alkylidenes with metal carbonyl complexes is rare in monometallic systems, such coupling is frequently postulated in heterogeneous Fischer-Tropsch systems to yield surface-bound ketene fragments. The formation of bound ketene in bimetallic and cluster complexes has been documented. Herein the authors report the coupling of titanocene methylidene with Cr(CO)/sub 6/ to yield a titanocene ketene complex.

  13. Synthesis gas from biomass for fuels and chemicals

    Van der Drift, A.; Boerrigter, H.

    2006-01-01

    Making H2 and CO (syngas) from biomass is widely recognised as a necessary step in the production of various second generation biofuels. There are two major ways to produce a biosyngas: fluidised bed gasification with catalytic reformer or entrained flow gasification. The latter option requires extensive pre-treatment such as flash pyrolysis, slow pyrolysis, torrefaction, or fluidized bed gasification at a low temperature. Cleaned and conditioned biosyngas can be used to synthesize second generation biofuels such as Fischer-Tropsch fuels, methanol, DME, mixed alcohols, and even pure hydrogen. The report describes the different technical options to produce, clean and condition bio-syngas. Furthermore, issues related to scale and biomass transport are covered shortly

  14. Organic molecules in the atmosphere of Jupiter. Final report

    Ponnamperuma, C.A.

    1978-01-01

    Organic synthesis in the primitive solar system was simulated by Fischer Tropsch type experiments. Particular attention was given to the formation of lower molecular weight hydrocarbons. In a gas flow experiment, a gas mixture of H 2 and CO was introduced into a heated reaction tube at a constant flow rate and passed through a catalyst (powdered Canyon Diablo). The products that emerged were directly analyzed by gas chromatography. The results of 21 runs under various gas mixing rations, reaction temperatures, and gas-catalyst contact times showed the predominance of the saturated hydrocarbon formation at C 4 and C 5 over the unsaturated ones. Saturate/unsaturate ratios were mostly less than 0.4 and none showed over 0.7

  15. Towards an atomic level understanding of niobia based catalysts and catalysis by combining the science of catalysis with surface science

    Martin Schmal

    2009-06-01

    Full Text Available The science of catalysis and surface science have developed, independently, key information for understanding catalytic processes. One might argue: is there anything fundamental to be discovered through the interplay between catalysis and surface science? Real catalysts of monometallic and bimetallic Co/Nb2O5 and Pd-Co/Nb2O5 catalysts showed interesting selectivity results on the Fischer-Tropsch synthesis (Noronha et al. 1996, Rosenir et al. 1993. The presence of a noble metal increased the C+5 selectivity and decreased the methane formation depending of the reduction temperature. Model catalyst of Co-Pd supported on niobia and alumina were prepared and characterized at the atomic level, thus forming the basis for a comparison with "real" support materials. Growth, morphology and structure of both pure metal and alloy particles were studied. It is possible to support the strong metal support interaction suggested by studies on real catalysts via the investigation of model systems for niobia in comparison to alumina support in which this effect does not occur. Formation of Co2+ penetration into the niobia lattice was suggested on the basis of powder studies and can be fully supported on the basis of model studies. It is shown for both real catalysts and model systems that oxidation state of Co plays a key role in controlling the reactivity in Fischer-Tropsch reactions systems and that the addition of Pd is a determining factor for the stability of the catalyst. It is demonstrated that the interaction with unsaturated hydrocarbons depends strongly on the state of oxidation.As ciências da catálise e da superfície têm desenvolvido independentemente temas básicos para o entendimento de processos catalíticos. Pode-se até questionar se há ainda algo fundamental para ser descoberto através da interface entre catálise eciência da superfície? Catalisadores mono e bimetálicos de Co/Nb2O5 e Pd-Co/ Nb2O5 apresentaram resultados interessantes de

  16. Seminar 'World CTL 2008'

    Chevalier, B.

    2008-01-01

    'Coal to liquid' (CTL) is a well known technic used since years especially by the Germans during the last world war and South Africa during the oil embargo. The combination of coal gasification and Fischer-Tropsch synthesis allows the production of synthetic diesel and gasoline. Nice alternative for those countries with large reserves of coal (China, South Africa, USA) which want to be more 'oil-free' in the long term, it faces however quite a lot of challenges: Very sophisticated technic, not yet proven for large scale of unit, high investment costs, necessity to add up CO 2 capture and storage (CCS) due to climate change constraints... In any cases this process seems more adequate and competitive to produce electricity and power than to focus on transportation fuels which are more easily manufactured from oil. (author)

  17. Prospects of Fe/MCM-41 as a Catalyst for Hydrocarbon Synthesis

    Cagnoli, Maria V.; Gallegos, Norma G.; Bengoa, Jose F.; Alvarez, Ana M.; Marchetti, Sergio G.; Moreno, Sergio M. J.; Roig, Anna; Mercader, Roberto C.

    2005-01-01

    We report the synthesis of cylindrical nanoparticles of metallic Fe entirely included in MCM-41 pores. Their dimensions are approx.3 nm diameter and approx. 3.8 nm length. We show that a coherent analysis of the results yielded by the various techniques is essential to obtain a catalyst supported on an MCM-41 matrix of ≅ 3 nm average pore diameter, which is active and selective toward olefins. The solids were characterized by low-angle x-ray diffraction, high-resolution transmission electron microscopy, high-resolution scanning transmission electron microscopy equipped with a high-angle annular dark-field, CO chemisorption, volumetric oxidation, and Moessbauer spectroscopy (in controlled atmosphere for the reduced catalysts). Catalytic results in the Fischer-Tropsch synthesis, as well as some unexpected results --like the inhomogeneous pore filling and discontinuous Fe particles-- are also discussed

  18. Valorization of agroindustrial solid residues and residues from biofuel production chains by thermochemical conversion: a review, citing Brazil as a case study

    E. Virmond

    2013-06-01

    Full Text Available Besides high industrial development, Brazil is also an agribusiness country. Each year about 330 million metrics tons (Mg of biomass residues are generated, requiring tremendous effort to develop biomass systems in which production, conversion and utilization of bio-based products are carried out efficiently and under environmentally sustainable conditions. For the production of biofuels, organic chemicals and materials, it is envisaged to follow a biorefinery model which includes modern and proven green chemical technologies such as bioprocessing, pyrolysis, gasification, Fischer-Tropsch synthesis and other catalytic processes in order to make more complex molecules and materials on which a future sustainable society will be based. This paper presents promising options for valorization of Brazilian agroindustrial biomass sources and residues originating from the biofuel production chains as renewable energy sources and addresses the main aspects of the thermochemical technologies which have been applied.

  19. Technical solutions to make biofuels more competitive

    Anon.

    2006-01-01

    With the present day environmental and economical stakes, the French government has announced in 2005 a plan for the accelerated development of biofuels. In France, two traditional ways of biofuel generation exist: the bio-ethanol way and the bio-diesel way (methyl esters of vegetable oils). Two problems limit today the development of biofuels: the available cultivation surfaces and the production costs. The challenge of the next generation of biofuels concerns the better use of the available biomass, with no competition with the food productions, and in particular the development of ethyl esters of vegetable oils or the hydrogen processing of vegetable oils. Other processes are making their way, like the biomass to liquid (BTL) process, based on the Fischer-Tropsch synthesis, which allows to convert any type of biomass source into liquid fuels with a high production rate (about 5000 l/Ha). Short paper. (J.S.)

  20. C1 CHEMISTRY FOR THE PRODUCTION OF ULTRA-CLEAN LIQUID TRANSPORTATION FUELS AND HYDROGEN

    Gerald P. Huffman

    2004-09-30

    The Consortium for Fossil Fuel Science (CFFS) is a research consortium with participants from the University of Kentucky, University of Pittsburgh, West Virginia University, University of Utah, and Auburn University. The CFFS is conducting a research program to develop C1 chemistry technology for the production of clean transportation fuel from resources such as coal and natural gas, which are more plentiful domestically than petroleum. The processes under development will convert feedstocks containing one carbon atom per molecular unit into ultra clean liquid transportation fuels (gasoline, diesel, and jet fuel) and hydrogen, which many believe will be the transportation fuel of the future. Feedstocks include synthesis gas, a mixture of carbon monoxide and hydrogen produced by coal gasification, coalbed methane, light products produced by Fischer-Tropsch (FT) synthesis, methanol, and natural gas.

  1. Bioenergy/Biotechnology projects

    Napper, Stan [Louisiana Tech Univ., Ruston, LA (United States); Palmer, James [Louisiana Tech Univ., Ruston, LA (United States); Wilson, Chester [Louisiana Tech Univ., Ruston, LA (United States); Guilbeau, Eric [Louisiana Tech Univ., Ruston, LA (United States); Allouche, Erez [Louisiana Tech Univ., Ruston, LA (United States)

    2012-06-30

    This report describes the progress of five different projects. The first is an enzyme immobilization study of cellulase to reduce costs of the cellulosic ethanol process. High reusability and use of substrates applicable to large scale production were focus areas for this study. The second project was the development of nanostructured catalysts for conversion of syngas to diesel. Cobalt nanowire catalyst was used in Fischer-Tropsch synthesis. The third project describes work on developing a microfluidic calorimeter to measure reaction rates of enzymes. The fourth project uses inorganic polymer binders that have the advantage of a lower carbon footprint than Portland cement while also providing excellent performance in elevated temperature, high corrosion resistance, high compressive and tensile strengths, and rapid strength gains. The fifth project investigates the potential of turbines in drop structures (such as sewer lines in tall buildings) to recover energy.

  2. Experimental and numerical assessment of on-road diesel and biodiesel emissions

    West, B.H.; Storey, J.M.; Lewis, S.A.; Devault, G.L.; Green, J.B. [Oak Ridge National Lab., TN (United States); Sluder, C.S.; Hodgson, J.W.; Moore, B.L. [Univ. of Tennessee, Knoxville, TN (United States)

    1997-12-31

    The Federal Highway Administration`s TRAF-series of models use modal data to estimate fuel consumption and emissions for different traffic scenarios. A process for producing data-based modal models from road and dynamometer measurements has been developed and applied to a number of light-duty gasoline vehicles for the FHWA. The resulting models, or lookup tables, provide emissions and fuel consumption as functions of vehicle speed and acceleration. Surface plots of the data provide a valuable visual benchmark of the emissions characteristics of the vehicles. Due to the potential fuel savings in the light-duty sector via introduction of diesels, and the concomitant growing interest in diesel engine emissions, the measurement methodology has been extended under DOE sponsorship to include a diesel pickup truck running a variety of fuels, including number 2 diesel fuel, biodiesel, Fischer-Tropsch, and blends.

  3. Antiknock additives for engine fuels

    Poletaeva, O. [Ufa State Petroleum Technological Univ., Ufa (Russian Federation); Movsumzade, E. [Institute of Education of Indigenous Small-Nambered Peoples of the North RAE, Moscow (Russian Federation)

    2013-11-01

    Obtaining gasoline with necessary quality and quantity is an actual problem. To increase fuel resources in the development are involved heavy oil, shale gas with further obtaining synthetic oil. Here is presented an analysis of processing technologies of natural and synthetic oil obtained in the Fischer-Tropsch synthesis, wherein focus is on octane number of gasoline fraction. Due to the low octane number, resolution of questions related to improving the detonation resistance, does not lose its relevance to the present day. Represented a quantum-chemical studies of some antiknock agents in the purpose by quantum chemistry methods to identify trends to increase the octane number of compounds and gasoline when they are added. (orig.)

  4. Analysis of unregulated emissions from an off-road diesel engine during realistic work operations

    Lindgren, Magnus; Arrhenius, Karine; Larsson, Gunnar; Bäfver, Linda; Arvidsson, Hans; Wetterberg, Christian; Hansson, Per-Anders; Rosell, Lars

    2011-09-01

    Emissions from vehicle diesel engines constitute a considerable share of anthropogenic emissions of pollutants, including many non-regulated compounds such as aromatic hydrocarbons and alkenes. One way to reduce these emissions might be to use fuels with low concentrations of aromatic hydrocarbons, such as Fischer-Tropsch (F-T) diesels. Therefore this study compared Swedish Environmental Class 1 diesel (EC1) with the F-T diesel fuel Ecopar™ in terms of emissions under varied conditions (steady state, controlled transients and realistic work operations) in order to identify factors influencing emissions in actual operation. Using F-T diesel reduced emissions of aromatic hydrocarbons, but not alkenes. Emissions were equally dependent on work operation character (load, engine speed, occurrence of transients) for both fuels. There were indications that the emissions originated from unburnt fuel, rather than from combustion products.

  5. Synthesis of high specific activity tritium labelled compounds

    Parent, P.

    1986-01-01

    Tritiated methyl iodide of high specific activity is synthetized by Fischer-Tropsch reaction of tritium with carbon monoxide, tritiated methanol obtained is reacted with hydriodic acid. It is used for the synthesis of S-adenosyl L-methionine 3 H-methyl and of diazepam 3 H-methyl derivatives. Synthesis of 3-PPP 3 H: (hydroxy-3 phenyl)-3N-n propyl [ 3 H-2.3] piperidine [ 3 H-2.3] with a specific activity of 4.25 T Bq/mM (115 Ci/mM) and of baclofene 3 H with a specific activity of 0.925 TBq (25 Ci/mM) are also described [fr

  6. Performance of rotary kiln reactor for the elephant grass pyrolysis.

    De Conto, D; Silvestre, W P; Baldasso, C; Godinho, M

    2016-10-01

    The influence of process conditions (rotary speed/temperature) on the performance of a rotary kiln reactor for non-catalytic pyrolysis of a perennial grass (elephant grass) was investigated. The product yields, the production of non-condensable gases as well as the biochar properties were evaluated. The maximum H2 yield was close to that observed for catalytic pyrolysis processes, while the bio-oil yield was higher than reported for pyrolysis of other biomass in rotary kiln reactors. A H2/CO ratio suitable for Fischer-Tropsch synthesis (FTS) was obtained. The biochars presented an alkaline pH (above 10) and interesting contents of nutrients, as well as low electrical conductivity, indicating a high potential as soil amendment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Gas-to-liquids synthetic fuels for use in fuel cells : reformability, energy density, and infrastructure compatibility.

    Ahmed, S.; Kopasz, J. P.; Russell, B. J.; Tomlinson, H. L.

    1999-09-08

    The fuel cell has many potential applications, from power sources for electric hybrid vehicles to small power plants for commercial buildings. The choice of fuel will be critical to the pace of its commercialization. This paper reviews the various liquid fuels being considered as an alternative to direct hydrogen gas for the fuel cell application, presents calculations of the hydrogen and carbon dioxide yields from autothermal reforming of candidate liquid fuels, and reports the product gas composition measured from the autothermal reforming of a synthetic fuel in a micro-reactor. The hydrogen yield for a synthetic paraffin fuel produced by a cobalt-based Fischer-Tropsch process was found to be similar to that of retail gasoline. The advantages of the synthetic fuel are that it contains no contaminants that would poison the fuel cell catalyst, is relatively benign to the environment, and could be transported in the existing fuel distribution system.

  8. The Analysis of the Experience in Commercialization of Indirect Coal Liquefaction Technologies in the World

    Rudyka Viktor I.

    2017-09-01

    Full Text Available It is substantiated that, taking into account the world trends in the development of fuel and energy complexes, in the near future the most preferable direction in using solid fossil fuels will become not just their burning but advanced thermochemical processing, which will result in obtaining such end products as substitutes for natural gas, electricity, and synthetic analogues of hydrocarbons. There analyzed foreign experience on commercialization of indirect coal gasification technologies, among which the technologies of traditional and plasma gasification are singled out. The advantages and disadvantages of these technologies are systematized, and the hypothesis about better prospects for using the technology of plasma gasification of coal in comparison with the traditional analogues that are based on the Fischer-Tropsch process is put forward.

  9. Synthesis of Organics in the Early Solar Nebula

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

    2007-10-01

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

  10. Coatings of active and heat-resistant cobalt-aluminium xerogel catalysts.

    Schubert, Miriam; Schubert, Lennart; Thomé, Andreas; Kiewidt, Lars; Rosebrock, Christopher; Thöming, Jorg; Roessner, Frank; Bäumer, Marcus

    2016-09-01

    The application of catalytically coated metallic foams in catalytic processes has a high potential for exothermic catalytic reactions such as CO2 methanation or Fischer-Tropsch synthesis due to good heat conductivity, improved turbulent flow properties and high catalyst efficiencies. But the preparation of homogenous catalyst coats without pore blocking is challenging with conventional wash coating techniques. Here, we report on a stable and additive free colloidal CoAlOOH suspension (sol) for the preparation of catalytically active Co/Al2O3 xerogel catalysts and coatings. Powders with 18wt% Co3O4 prepared from this additive free synthesis route show a catalytic activity in Fischer-Tropsch synthesis and CO2 methanation which is similar to a catalyst prepared by incipient wetness impregnation (IWI) after activating the material under flowing hydrogen at 430°C. Yet, the xerogel catalyst exhibits a much higher thermal stability as compared to the IWI catalyst, as demonstrated in catalytic tests after different heat agings between 430°C and 580°C. It was also found that the addition of polyethylene glycol (PEG) to the sol influences the catalytic properties of the formed xerogels negatively. Only non-reducible cobalt spinels were formed from a CoAlOOH sol with 20wt% PEG. Metallic foams with pores sizes between 450 and 1200μm were coated with the additive free CoAlOOH sol, which resulted in homogenous xerogel layers. First catalytic tests of the coated metal foams (1200μm) showed good performance in CO2 methanation. Copyright © 2016 Elsevier Inc. All rights reserved.

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

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

    2017-03-06

    Higher alcohols are important compounds with widespread applications in the chemical, pharmaceutical and energy sectors. Currently, they are mainly produced by sugar fermentation (ethanol and isobutanol) or hydration of petroleum-derived alkenes (heavier alcohols), but their direct synthesis from syngas (CO + H 2 ) would comprise a more environmentally-friendly, versatile and economical alternative. Research efforts in this reaction, initiated in the 1930s, have fluctuated along with the oil price and have considerably increased in the last decade due to the interest to exploit shale gas and renewable resources to obtain the gaseous feedstock. Nevertheless, no catalytic system reported to date has performed sufficiently well to justify an industrial implementation. Since the design of an efficient catalyst would strongly benefit from the establishment of synthesis-structure-function relationships and a deeper understanding of the reaction mechanism, this review comprehensively overviews syngas-based higher alcohols synthesis in three main sections, highlighting the advances recently made and the challenges that remain open and stimulate upcoming research activities. The first part critically summarises the formulations and methods applied in the preparation of the four main classes of materials, i.e., Rh-based, Mo-based, modified Fischer-Tropsch and modified methanol synthesis catalysts. The second overviews the molecular-level insights derived from microkinetic and theoretical studies, drawing links to the mechanisms of Fischer-Tropsch and methanol syntheses. Finally, concepts proposed to improve the efficiency of reactors and separation units as well as to utilise CO 2 and recycle side-products in the process are described in the third section.

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

    Tan, Eric C. D. [National Renewable Energy Laboratory, Golden CO USA; Snowden-Swan, Lesley J. [Pacific Northwest National Laboratory, Richland WA USA; Talmadge, Michael [National Renewable Energy Laboratory, Golden CO USA; Dutta, Abhijit [National Renewable Energy Laboratory, Golden CO USA; Jones, Susanne [Pacific Northwest National Laboratory, Richland WA USA; Ramasamy, Karthikeyan K. [Pacific Northwest National Laboratory, Richland WA USA; Gray, Michel [Pacific Northwest National Laboratory, Richland WA USA; Dagle, Robert [Pacific Northwest National Laboratory, Richland WA USA; Padmaperuma, Asanga [Pacific Northwest National Laboratory, Richland WA USA; Gerber, Mark [Pacific Northwest National Laboratory, Richland WA USA; Sahir, Asad H. [National Renewable Energy Laboratory, Golden CO USA; Tao, Ling [National Renewable Energy Laboratory, Golden CO USA; Zhang, Yanan [National Renewable Energy Laboratory, Golden CO USA

    2016-09-27

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

  13. Optimization of biofuel production from corn stover under supply uncertainty in Ontario

    Jonathan Ranisau

    2017-12-01

    Full Text Available In this paper, a biofuel production supply chain optimization framework is developed that can supply the fuel demand for 10% of Ontario. Different biomass conversion technologies are considered, such as pyrolysis and gasification and subsequent hydro processing and the Fischer-Tropsch process. A supply chain network approach is used for the modeling, which enables the optimization of both the biorefinery locations and the associated transportation networks. Gasification of corn stover is examined to convert waste biomass into valuable fuel. Biomass-derived fuel has several advantages over traditional fuels including substantial greenhouse gas reduction, generating higher quality synthetic fuels, providing a use for biomass waste, and potential for use without much change to existing infrastructure. The objective of this work is to show the feasibility of the use of corn stover as a biomass feedstock to a hydrocarbon biofuel supply chain in Ontario using a mixed-integer linear programming model while accounting for the uncertainty in the availability of corn stover. In the case study, the exact number of biorefineries is left as a policy decision and the optimization is carried out over a range of the possible numbers of facilities. The results obtained from the case study suggests implementing gasification technology followed by Fischer-Tropsch at two different sites in Ontario. The optimal solution satisfied 10% of the yearly fuel demand of Ontario with two production plants (14.8 billion L of fuel and requires an investment of $42.9 billion, with a payback period of about 3 years.

  14. Hydrogenation of carbon monoxide on Co/MgAl2O4 and Ce-Co/MgAl2O4 catalysts

    Kondoh, S.; Muraki, H.; Fujitani

    1986-01-01

    It is well known that various hydrocarbons are obtained by hydrogenation of CO on Fischer-Tropsch catalysts, the products depending on the catalyst components such as Co, Ni, Fe and Ru: and the reaction conditions, particularly, temperature, pressure, space velocity and H 2 /CO ratio. Further, both reactivity and selectivity of catalysts may be improved by suitable selection of support and an additive. The main program of the present work is to develop a catalyst for producing C 5 + liquid hydrocarbons, as an automobile fuel, by the Fischer-Tropsch synthesis. The authors have studied unique CO catalyst systems consisting of various supports - such as Al 2 O 3 (γ, β, α), MgAl 2 O 4 (alumina magnesia spinel), MgO and additives selected from the lanthanoid elements (LE). The composition of spinel-based supports was altered in a range from 28 mol % excess Al 2 O 3 to 28 mol % excess MgO. Particularly, they found that a MgAl 2 O 4 support with 15-18 mol % excess Al 2 O 3 is the most preferable for our purpose and CeO 2 as the additive for Co/spinel catalyst remarkably improves C 5 + yield. Further, it was confirmed that the catalytic activity of Co-base catalysts agree with the oxidation state of Co-oxides on Co and Co-Ce/spinel catalysts. The performance of Co-based catalysts for the production of higher hydrocarbons from syn-gas were described elsewhere. The items described in this report include (a) selection of supports, (b) selection of optimum reaction conditions for Co-Ce/spinel catalyst, (c) redox characteristics of Co-oxides on a spinel surface, and (d) experimental observation of TPD profiles, adsorption capacities and IR spectra relating to adsorbed CO

  15. Catalyst in alternate energy resources for producing environment friendly clean energy

    Hussain, S.T.; Atta, M.A.

    1998-01-01

    Carbon monoxide, a by-product of the Chemical Process Industries, is a deadly poisonous gas; if released into the atmosphere causes irreparable damage to the environment. A bimetallic catalyst system Ru: Mn doped with different concentrations of 'K' (Potassium) and supported on high surface area alumina support was prepared by co impregnation method, dispersed and reduced at 450 deg. C under hydrogen flow using a closed reactor system at atmospheric pressure for the utilization of poisonous CO gas to produce environmental friendly clean energy. Fischer Tropsch catalyst, when subjected to CO/hydrogenation, gives methane and other hydrocarbon products. The main purpose of this research work was two fold: 1. The powder catalyst when dispersed/reduced on a high surface area oxide support spreads on the surface of the system in a different orientations and shapes. The particle size of the prepared catalysts ranges from 5.0-25.0 nm. The whole system forms a complicated mixture of numerous particles and hence becomes very complicated to study. The characterisation of these randomly oriented particles having different sizes and shapes is a difficult job. This required sensitive UHV spectroscopic techniques like SSIMS, XPS, EEls, XRD and TEM. Their operations needs strong skills. Hence the first aim was to utilize these techniques for the characterization of the prepared catalysts and to establish the usefulness of these techniques in studying such complicated systems. 2. Since Ru is a very good Fischer Tropsch catalyst for the production of aliphatic hydrocarbons product. Our other aim was to find out whether if by surface modification through additives or by surface reconstructing through chemical treatment, we could alter the path of this CO/hydrogenation reaction to produce potentially important unsaturated/aromatic hydrocarbon products. This would serve our dual purpose in which we could use poisonous CO for useful purpose. Hence 'K' potassium as surface modifier is

  16. Liquid transportation fuels via large-scale fluidised-bed gasification of lignocellulosic biomass

    Hannula, I.; Kurkela, E.

    2013-04-15

    With the objective of gaining a better understanding of the system design trade-offs and economics that pertain to biomass-to-liquids processes, 20 individual BTL plant designs were evaluated based on their technical and economic performance. The investigation was focused on gasification-based processes that enable the conversion of biomass to methanol, dimethyl ether, Fischer-Tropsch liquids or synthetic gasoline at a large (300 MWth of biomass) scale. The biomass conversion technology was based on pressurised steam/O2-blown fluidised-bed gasification, followed by hot-gas filtration and catalytic conversion of hydrocarbons and tars. This technology has seen extensive development and demonstration activities in Finland during the recent years and newly generated experimental data has also been used in our simulation models. Our study included conceptual design issues, process descriptions, mass and energy balances and production cost estimates. Several studies exist that discuss the overall efficiency and economics of biomass conversion to transportation liquids, but very few studies have presented a detailed comparison between various syntheses using consistent process designs and uniform cost database. In addition, no studies exist that examine and compare BTL plant designs using the same front-end configuration as described in this work. Our analysis shows that it is possible to produce sustainable low-carbon fuels from lignocellulosic biomass with first-law efficiency in the range of 49.6-66.7% depending on the end-product and process conditions. Production cost estimates were calculated assuming Nth plant economics and without public investment support, CO2 credits or tax assumptions. They are 58-65 euro/MWh for methanol, 58-66 euro/MWh for DME, 64-75 euro/MWh for Fischer-Tropsch liquids and 68-78 euro/MWh for synthetic gasoline. (orig.)

  17. Synthesis Gas Purification Purification des gaz de synthèse

    Chiche D.

    2013-10-01

    Full Text Available Fischer-Tropsch (FT based B-XTL processes are attractive alternatives for future energy production. These processes aim at converting lignocellulosic biomass possibly in co-processing with petcoke, coal, or vacuum residues into synthetic biofuels. A gasification step converts the feed into a synthesis gas (CO and H2 mixture , which undergoes the Fischer-Tropsch reaction after H2/CO ratio adjustment and CO2 removal. However synthesis gas also contains various impurities that must be removed in order to prevent Fischer-Tropsch catalyst poisoning. Due to the large feedstocks variety that can be processed, significant variations of the composition of the synthesis gas are expected. Especially, this affects the nature of the impurities that are present (element, speciation, as well as their relative contents. Moreover, due to high FT catalyst sensitivity, severe syngas specifications regarding its purity are required. For these reasons, synthesis gas purification constitutes a major challenge for the development of B-XTL processes. In this article, we focus on these major hurdles that have to be overcome. The different kinds of syngas impurities are presented. The influence of the nature of feedstocks, gasification technology and operating conditions on the type and content of impurities is discussed. Highlight is given on the fate of sulfur compounds, nitrogen compounds, halides, transition and heavy metals. Main synthesis gas purification technologies (based on adsorption, absorption, catalytic reactions, etc. are finally described, as well as the related challenges. Les procédés de synthèse de biocarburants par voie Fischer-Tropsch (FT, voies B-XTL, représentent des alternatives prometteuses pour la production d’énergie. Ces procédés permettent la conversion en carburants de synthèse de biomasse lignocellulosique, éventuellement mise en oeuvre en mélange avec des charges fossiles telles que petcoke, charbons ou résidus sous vide. Pour

  18. Catalytic conversion of CO2 into valuable products

    Pham-Huu, C.; Ledoux, M.J.

    2008-01-01

    Complete text of publication follows: Synthesis gas, a mixture of H 2 and CO, is an important feed-stock for several chemical processes operated in the production of methanol and synthetic fuels through a Fischer- Tropsch synthesis. Synthesis gas is produced via an endothermic steam reforming of methane (CH 4 + H 2 O → CO + 3H 2 , ΔH = +225.4 kJ.mol -1 ), catalytic or direct partial oxidation of methane (CH 4 + (1/2)O 2 → CO + 2H 2 , ΔH -38 kJ.mol -1 ) and CO 2 reforming of methane (CH 4 + CO 2 → 2CO + 2H 2 , ΔH= +247 kJ.mol -1 ). The main disadvantage of these processes is the high coke formation, essentially in the nano-filament form, which may cause severe deactivation of the catalyst by pore or active site blocking and sometimes, physical disintegration of the catalyst body causing a high pressure drop along the catalyst bed and even, in some cases, inducing damage to the reactor itself. Previous results obtained in the catalytic partial oxidation of methane have shown that due to the hot spot and carbon nano-filaments formation, especially in the case of the CO 2 reforming, the alumina-based catalyst in an extrudate form was broken into powder which induces a significant pressure drop across the catalytic bed. In the case of endothermic reactions, steam and CO 2 reforming, the temperature drop within the catalyst bed could also modified the activity of the catalyst. Silicon carbide (SiC) exhibits a high thermal conductivity, a high resistance towards oxidation, a high mechanical strength, and chemical inertness, all of which make it a good candidate for use as catalyst support in several endothermic and exothermic reactions such as dehydrogenation, selective partial oxidation, and Fischer-Tropsch synthesis. The gas-solid reaction allows the preparation of SiC with medium surface area, i.e. 10 to 40 m 2 .g -1 , and controlled macroscopic shape, i.e. grains, extrudates or foam, for it subsequence use as catalyst support. In addition, due to its chemical

  19. Design Concepts for Co-Production of Power, Fuels & Chemicals Via Coal/Biomass Mixtures

    Rao, A. D.; Chen, Q.; Samuelsen, G. S.

    2012-09-30

    The overall goal of the program is to develop design concepts, incorporating advanced technologies in areas such as oxygen production, feed systems, gas cleanup, component separations and gas turbines, for integrated and economically viable coal and biomass fed gasification facilities equipped with carbon capture and storage for the following scenarios: (i) coproduction of power along with hydrogen, (ii) coproduction of power along with fuels, (iii) coproduction of power along with petrochemicals, and (iv) coproduction of power along with agricultural chemicals. To achieve this goal, specifically the following objectives are met in this proposed project: (i) identify advanced technology options and innovative preliminary design concepts that synergistically integrate plant subsections, (ii) develop steady state system simulations to predict plant efficiency and environmental signature, (iii) develop plant cost estimates by capacity factoring major subsystems or by major equipment items where required, and then capital, operating and maintenance cost estimates, and (iv) perform techno- economic analyses for the above described coproduction facilities. Thermal efficiencies for the electricity only cases with 90% carbon capture are 38.26% and 36.76% (HHV basis) with the bituminous and the lignite feedstocks respectively. For the coproduction cases (where 50% of the energy exported is in the form of electricity), the electrical efficiency, as expected, is highest for the hydrogen coproduction cases while lowest for the higher alcohols (ethanol) coproduction cases. The electrical efficiencies for Fischer-Tropsch coproduction cases are slightly higher than those for the methanol coproduction cases but it should be noted that the methanol (as well as the higher alcohol) coproduction cases produce the finished coproduct while the Fischer-Tropsch coproduction cases produce a coproduct that requires further processing in a refinery. The cross comparison of the thermal

  20. Exploring the Perspectives of Alternative Fuels Production. Towards alternative fuels with zero, or negative greenhouse gas emissions, considering coal, biomass and carbon capture and storage

    Eerhart, A.J.J.E.

    2009-05-01

    In this report it is shown that future improvements in the production process of Fischer-Tropsch fuels can reduce costs and produce CO2 neutral gasoline and diesel. Major benefits lie in the improvement of the overall temperature profile of the plant at higher temperatures and carbon capture and storage. Based on literature studies, it was found that future technologies can operate at higher temperatures, and thus a better integration of heating and cooling. It was found that the future model of a CBTL (Coal and Biomass To Liquids) plant can produce liquids at a break-even oil price (BEOP) of 58.60 USD/barrel at 100% coal, with similar greenhouse gas emissions compared to liquids produced by conventional means today. However, once biomass is introduced at a ratio of 33% - 67% biomass, a CBTL plant becomes neutral in terms of GHG emissions. The BEOP for this neutral scenario is 69.60 USD/barrel. Looking at the 100% biomass scenario, the BEOP becomes 82.77 USD/barrel. The greenhouse gas emissions at this point are negative, meaning that more CO2 is captured during the process than is needed to grow biomass. This in effect makes a CBTL plant a carbon sink. By introducing future technologies and improvements, such as membrane technology for CCS (Carbon dioxide Capture and Storage), higher FTS (Fischer-Tropsch Synthesis) catalyst selectivities and an overall better temperature profile, the BEOP for the 100% coal scenario drops from 58.60 to 45.27 USD/barrel. The BEOP for the neutral scenario drops from 69.60 to 57.99 USD/barrel. The BEOP for the 100% biomass scenario drops from 82.77 to 69.07 USD/barrel. For the neutral scenario, the BEOP drops from 69.60 to 57.99 USD/barrel. If one assumes that a BEOP of 60 USD/barrel is economically reasonable, one can calculate the level of a carbon tax, once a carbon tax regime is imposed. For SOTA (state-of-the-art) 100% coal, FS (Future Scenario) 100%, FS 50% coal and FS 33% coal, there is no need for a carbon tax to reach 60 USD

  1. Two-phase characteristics of the feeding fluid of Cerro Prieto IV wells (Mexico) obtained by gas equilibrium; Caracteristicas bifasicas del fluido de alimentacion de pozos de Cerro Prieto IV (Mexico), obtenidas por equilibrio gaseoso

    Barragan-Reyes, Rosa Maria; Arellano-Gomez, Victor Manuel; Portugal-Marin, Enrique [Instituto de Investigaciones Electricas (Mexico); De Leon-Vivar, Jesus [Comision Federal de Electricidad, Residencia General de Cerro Prieto, B.C (Mexico)

    2008-10-15

    The gas composition of fluids produced by CP IV geothermal wells from the Cerro Prieto field was studied in order to identify different types of fluids entering the wells by estimating their temperature and excess steam. A method based on the Fischer Tropsch reaction and H2S equilibrium with pyrite-pyrrhotite as mineral buffer (FTHSH3) was used. The results for the reservoir natural state indicated the presence of fluids with heterogeneous reservoir temperature (between 275 and 310 degrees Celsius) and excess steam values, which were found from negative (boiled liquid that has lost steam when flowing to the well) to one (steam phase with zero liquid saturation). The study for individual wells in which boiling processes were identified, showed that through time, the feeding fluids consist of a two-phase mixture with different liquid/steam proportions. Also, the results suggested that a steam phase could occur at CP IV which is added to the feeding fluid, depending on the operation conditions of the wells. The origin of this steam could be the boiling of the deeper liquid due to a pressure drop. [Spanish] Se estudio la composicion gaseosa de los fluidos producidos por pozos geotermicos del sector CP IV del campo de Cerro Prieto para tratar de distinguir aportes de fluidos diferentes mediante la estimacion de su temperatura de yacimiento y del exceso de vapor. Se utilizo un metodo de equilibrio gaseoso basado en la reaccion de Fischer Tropsch y el equilibrio combinado pirita-pirrotita (FT-HSH3). Los resultados obtenidos indican que en el estado inicial del yacimiento existen fluidos que muestran heterogeneidad en los valores de temperatura de yacimiento (entre 275 y 310 grados Celsius), asi como en el exceso de vapor con valores desde negativos (liquido que despues de ebullir ha perdido vapor en su trayecto hacia el pozo) hasta uno (vapor con cero saturacion de liquido). El estudio individual de los pozos con fenomenos de ebullicion muestra que a traves del tiempo

  2. Life Cycle Analysis of the Production of FT-Fuels. 4 Different Scenarios

    Blinge, M. [Chalmers University of Technology (Sweden); Rehnlund, B. [Atrax Energi AB (Sweden); Larsen, U.; Lundorf, P.; Ivarsson, A.; Schramm, J. [Technical University of Denmark (Denmark)

    2006-11-15

    This paper deals with aspects concerning the life cycle aspects regarding Fischer-Tropsch (FT) fuels. Four different scenarios are being analysed based on Life Cycle Assessment (LCA) figures. The results etc presented below emanates from a project undertaken by the International Energy Agency's (IEA) Implementing Agreement on Advanced Motor Fuels (IEA/AMF). The project has been carried out as an IEA/AMF annex, number XXXI, with financial support from the USA, Finland and Denmark. Some important results from the scenario studies based on the evaluated LCA data are: Production and use of GTL fuel has the potential of contributing about the same or slightly less greenhouse gas to the atmosphere than production and use of conventional diesel; Production and use of CTL emits more than twice as much greenhouse gases compared to traditional fuels; Production and use of BTL reduces the emissions of greenhouse gases by 60-90 %; To substitute 15 % of the EU 15 countries fuel consumption would an area of 310 000 km2 be cultivated with Salix. This corresponds to an area of the size of Poland. It would also require 122 FTplants of 1,6 GW; Theoretically, it is possible supply the worlds need for energy with biomass. However, planning the production, the localization of plants, building the infrastructure, this will take time and requires heavy long-term investments; The demand for Natural gas is increasing and there is no way for the US to meet an increased demand from supplying the vehicle fleet with F-T fuels from domestic reserves. With the political situation in the Middle East and in Venezuela, it doesn't seem likely that this solution will ease the US problems with reducing their oil dependences. The IEA/AMF project has also included emission tests on road vehicles fuelled by FT-Gasoline. These tests have been performed by The Technical University of Denmark and will be presented in another presentation at the ISAF XVI, 'Emissions from Road Vehicles Fuelled

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

    Ghampson, Isaac Tyrone

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

  4. Advanced computational model for three-phase slurry reactors

    Goodarz Ahmadi

    2001-10-01

    In the second year of the project, the Eulerian-Lagrangian formulation for analyzing three-phase slurry flows in a bubble column is further developed. The approach uses an Eulerian analysis of liquid flows in the bubble column, and makes use of the Lagrangian trajectory analysis for the bubbles and particle motions. An experimental set for studying a two-dimensional bubble column is also developed. The operation of the bubble column is being tested and diagnostic methodology for quantitative measurements is being developed. An Eulerian computational model for the flow condition in the two-dimensional bubble column is also being developed. The liquid and bubble motions are being analyzed and the results are being compared with the experimental setup. Solid-fluid mixture flows in ducts and passages at different angle of orientations were analyzed. The model predictions were compared with the experimental data and good agreement was found. Gravity chute flows of solid-liquid mixtures is also being studied. Further progress was also made in developing a thermodynamically consistent model for multiphase slurry flows with and without chemical reaction in a state of turbulent motion. The balance laws are obtained and the constitutive laws are being developed. Progress was also made in measuring concentration and velocity of particles of different sizes near a wall in a duct flow. The technique of Phase-Doppler anemometry was used in these studies. The general objective of this project is to provide the needed fundamental understanding of three-phase slurry reactors in Fischer-Tropsch (F-T) liquid fuel synthesis. The other main goal is to develop a computational capability for predicting the transport and processing of three-phase coal slurries. The specific objectives are: (1) To develop a thermodynamically consistent rate-dependent anisotropic model for multiphase slurry flows with and without chemical reaction for application to coal liquefaction. Also establish the

  5. Societal lifecycle costs of cars with alternative fuels/engines

    Ogden, Joan M.; Williams, Robert H.; Larson, Eric D.

    2004-01-01

    Effectively addressing concerns about air pollution (especially health impacts of small-particle air pollution), climate change, and oil supply insecurity will probably require radical changes in automotive engine/fuel technologies in directions that offer both the potential for achieving near-zero emissions of air pollutants and greenhouse gases and a diversification of the transport fuel system away from its present exclusive dependence on petroleum. The basis for comparing alternative automotive engine/fuel options in evolving toward these goals in the present analysis is the 'societal lifecycle cost' of transportation, including the vehicle first cost (assuming large-scale mass production), fuel costs (assuming a fully developed fuel infrastructure), externality costs for oil supply security, and damage costs for emissions of air pollutants and greenhouse gases calculated over the full fuel cycle. Several engine/fuel options are considered--including current gasoline internal combustion engines and a variety of advanced lightweight vehicles: internal combustion engine vehicles fueled with gasoline or hydrogen; internal combustion engine/hybrid electric vehicles fueled with gasoline, compressed natural gas, Diesel, Fischer-Tropsch liquids or hydrogen; and fuel cell vehicles fueled with gasoline, methanol or hydrogen (from natural gas, coal or wind power). To account for large uncertainties inherent in the analysis (for example in environmental damage costs, in oil supply security costs and in projected mass-produced costs of future vehicles), lifecycle costs are estimated for a range of possible future conditions. Under base-case conditions, several advanced options have roughly comparable lifecycle costs that are lower than for today's conventional gasoline internal combustion engine cars, when environmental and oil supply insecurity externalities are counted--including advanced gasoline internal combustion engine cars, internal combustion engine

  6. Applications of density functional theory calculations to selected problems in hydrocarbon processing

    Nabar, Rahul

    Recent advances in theoretical techniques and computational hardware have made it possible to apply Density Functional Theory (DFT) methods to realistic problems in heterogeneous catalysis. Hydrocarbon processing is economically, and strategically, a very important industrial sector in today's world. In this thesis, we employ DFT methods to examine several important problems in hydrocarbon processing. Fischer Tropsch Synthesis (FTS) is a mature technology to convert synthesis gas derived from coal, natural-gas or biomass into liquid fuels, specifically diesel. Iron is an active FTS catalyst, but the absence of detailed reaction mechanisms make it difficult to maximize activity and optimize product distribution. We evaluate thermochemistry, kinetics and Rate Determining Steps (RDS) for Fischer Tropsch Synthesis on several models of Fe catalysts: Fe(110), Fe(211) and Pt promoted Fe(110). Our studies indicated that CO-dissociation is likely to be the RDS under most reaction conditions, but the DFT-calculated activation energy ( Ea) for direct CO dissociation was too large to explain the observed catalyst activity. Consequently we demonstrate that H-assisted CO-dissociation pathways are competitive with direct CO dissociation on both Co and Fe catalysts and could be responsible for a major fraction of the reaction flux (especially at high CO coverages). We then extend this alternative mechanistic model to closed-packed facets of nine transition metal catalysts (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt). H-assisted CO dissociation offers a kinetically easier route on each of the metals studied. DFT methods are also applied to another problem from the petroleum industry: discovery of poison-resistant, bimetallic, alloy catalysts (poisons: C, S, CI, P). Our systematic screening studies identify several Near Surface Alloys (NSAs) that are expected to be highly poison-resistant yet stable and avoiding adsorbate induced reconstruction. Adsorption trends are also correlated with

  7. Biomass-derived Syngas Utilization for Fuels and Chemicals - Final Report

    Dayton, David C

    2010-03-24

    Executive Summary The growing gap between petroleum production and demand, mounting environmental concerns, and increasing fuel prices have stimulated intense interest in research and development (R&D) of alternative fuels, both synthetic and bio-derived. Currently, the most technically defined thermochemical route for producing alternative fuels from lignocellulosic biomass involves gasification/reforming of biomass to produce syngas (carbon monoxide [CO] + hydrogen [H2]), followed by syngas cleaning, Fischer-Tropsch synthesis (FTS) or mixed alcohol synthesis, and some product upgrading via hydroprocessing or separation. A detailed techno-economic analysis of this type of process has recently been published [1] and it highlights the need for technical breakthroughs and technology demonstration for gas cleanup and fuel synthesis. The latter two technical barrier areas contribute 40% of the total thermochemical ethanol cost and 70% of the production cost, if feedstock costs are factored out. Developing and validating technologies that reduce the capital and operating costs of these unit operations will greatly reduce the risk for commercializing integrated biomass gasification/fuel synthesis processes for biofuel production. The objective of this project is to develop and demonstrate new catalysts and catalytic processes that can efficiently convert biomass-derived syngas into diesel fuel and C2-C4 alcohols. The goal is to improve the economics of the processes by improving the catalytic activity and product selectivity, which could lead to commercialization. The project was divided into 4 tasks: Task 1: Reactor Systems: Construction of three reactor systems was a project milestone. Construction of a fixed-bed microreactor (FBR), a continuous stirred tank reactor (CSTR), and a slurry bubble column reactor (SBCR) were completed to meet this milestone. Task 2: Iron Fischer-Tropsch (FT) Catalyst: An attrition resistant iron FT catalyst will be developed and tested

  8. BioTfueL Project: Targeting the Development of Second-Generation Biodiesel and Biojet Fuels Le projet BioTfueL : un projet de développement de biogazole et biokérosène de 2 génération

    Viguié J.-C.

    2013-10-01

    Full Text Available 2nd generation biofuels will have an important part to take in the energy transition as far as fuels are concerned. Using non edible biomass, they will avoid any direct competition with food usage. Within 2nd generation biofuels, the BTL route consists in the production of middle distillates (Diesel and jet fuel via gasification and Fischer-Tropsch (FT synthesis. These fuels are called “drop in” fuels; this means that to be used they technically do not request any modification in the vehicle whatever the blending rate with conventional fuels. This route is currently at the pre-industrial phase where demonstration is required. This article presents the BioTfueL project which has been created by Axens, CEA, IFP Energies nouvelles, Sofiprotéol, ThyssenKrupp Uhde and Total. This project is focused on the original concept of co-processing (biomass can be gasified together with fossil feedstock and proposes to develop and demonstrate a full process chain to be commercialized worldwide via licensing. Les biocarburants de 2e génération ont un rôle important à jouer en ce qui concerne le pool carburant dans le cadre de la transition énergétique. Utilisant comme matière première de la biomasse non comestible, ces carburants éviteront toute compétition directe avec un usage alimentaire de cette ressource. Parmi les biocarburants de 2e génération, la voie BTL consiste en la production de distillats moyens (gazole moteur et carburéacteur via gazéification et synthèse Fischer-Tropsch (FT. Ces carburants sont communément appelés des « drop in fuels », ce qui signifie que techniquement ils ne nécessitent aucune modification du véhicule quelque soit leur taux d’incorporation dans les carburants traditionnels. Cette voie entre actuellement en phase préindustrielle pour laquelle une démonstration est nécessaire. Cet article présente le projet BioTfueL qui est porté par Axens, le CEA, IFP Energies nouvelles, Sofiprotéol, Thyssen

  9. Preprints of the DGMK-Conference - Future feedstocks for fuels and chemicals. Author's manuscripts

    Ernst, S.; Jess, A.; Nees, F.; Peters, U.; Ricci, M.; Santacesaria, E. (eds.)

    2008-07-01

    Within the conference,Future Feedstocks for Fuels and Chemicals, of the German Society for Petroleum and Coal Science and Technology at 29th Spetember to 1st October, 2008, in Berlin (Federal Republic of Germany), the following lectures were held: (a) New technologies in Biodiesel production (E. Santacessari, M. Di Serio, R. Tesser, L. Casale); (b) A new heterogeneous process catalyst for the Biodiesel production (O. Meyer, F. Roessner, R.A. Rakoczy, R.W. Fischer); (c) Vegetable oil hydrotreating for production of high quality diesel Components (M. Endisch, U. Balfanz, M. Olschar, Th. Kuchling); (d) Hydrocracking of vegetable oil using bifunctional, porous catalyst systems (O. Busse, K. Raeuchle, H. Toufar, W. Reschetilowski); (e) Raw material change in the chemical industry (R. Diercks); (f) Fundamentals of the oxidative conversion of methane to ethylene, methanol and formaldehyde (E. Kondratenko); (g) The dehydroalkylation of toluene with ethane - an example for the non-oxidative activation of light alkanes (Y. Traa); (h) Isoprene - Applications beyond polymers (S. Reyer, A. Behr); (i) The gas-phase ammocidation of n-hexane to unsaturated 1,6-C{sub 6} dinitriles, intermediates for 1,6-hexamethylenediamine synthesis (N. Ballarini, A. Battisti, A. Castelli, F. Cavani, C. Lucarelli, P. Marion, P. Righi, A. Turrini); (j) Chemicals from Biomass (T. Tacke); (k) Coal Processing and Fuels from Coal - State of the Art (R. Abraham); (l) Energy from aquatic biomass: an integrated approach to biodiesel and hydrogen production (M. Aresta, A. Dibenedetto); (m) High throughput catalyst optimization program for the gas-to-liquids (GTL) technologies Methanol-to-Gasoline (MTG), higher alcohol synthesis (HAS) and Fischer-Tropsch-Synthesis (FTS) (H. Dathe, K.-F. Finger, A. Haas, P. Kolb, A. Sundermann, G. Wasserschaff); (n) Diesel yield according to Fischer-Tropsch process conditions (M.-C. Marion, F. Hugues); (o) Glycerol derivatives as fuel components (D. Bianchi, E. Batistelle

  10. Advanced computational model for three-phase slurry reactors

    Goodarz Ahmadi

    2000-11-01

    In the first year of the project, solid-fluid mixture flows in ducts and passages at different angle of orientations were analyzed. The model predictions are compared with the experimental data and good agreement was found. Progress was also made in analyzing the gravity chute flows of solid-liquid mixtures. An Eulerian-Lagrangian formulation for analyzing three-phase slurry flows in a bubble column is being developed. The approach uses an Eulerian analysis of gas liquid flows in the bubble column, and makes use of the Lagrangian particle tracking procedure to analyze the particle motions. Progress was also made in developing a rate dependent thermodynamically consistent model for multiphase slurry flows in a state of turbulent motion. The new model includes the effect of phasic interactions and leads to anisotropic effective phasic stress tensors. Progress was also made in measuring concentration and velocity of particles of different sizes near a wall in a duct flow. The formulation of a thermodynamically consistent model for chemically active multiphase solid-fluid flows in a turbulent state of motion was also initiated. The general objective of this project is to provide the needed fundamental understanding of three-phase slurry reactors in Fischer-Tropsch (F-T) liquid fuel synthesis. The other main goal is to develop a computational capability for predicting the transport and processing of three-phase coal slurries. The specific objectives are: (1) To develop a thermodynamically consistent rate-dependent anisotropic model for multiphase slurry flows with and without chemical reaction for application to coal liquefaction. Also to establish the material parameters of the model. (2) To provide experimental data for phasic fluctuation and mean velocities, as well as the solid volume fraction in the shear flow devices. (3) To develop an accurate computational capability incorporating the new rate-dependent and anisotropic model for analyzing reacting and

  11. Analysis and identification of gaps in the research for the production of second-generation liquid transportation biofuels

    Schwietzke, S.; Ladisch, M.; Russo, L.; Kwant, K.; Maekinen, T.; Kavalov, B.; Maniatis, K.; Zwart, R.; Shahanan, G.; Sipila, K.; Grabowski, P.; Telenius, B.; White, M.

    2008-08-01

    Research gaps were found in cellulosic ethanol, Fischer-Tropsch liquids and green diesel, dimethyl ether and P-Series fuels. Lignocellulosic ethanol is derived from pre-treatment, hydrolysis, and fermentation of the resulting sugars from cellulosic sources such as wood chips, agricultural residues, and grasses. Green diesel is a high boiling component, not derived from vegetable oil, obtained either from Fischer-Tropsch synthesis or through pyrolysis of biomass. Dimethyl ether has potential as a high quality fuel for diesel engines and is produced by converting syngas into methanol followed by dehydration of methanol to dimethyl ether. P-Series fuel is a mixture of ethanol, methyltetrahydrofuran, pentanes and higher alkanes, and butane. Methyltetrahydrofuran may be produced from dehydration of pentose and glucose sugars to form furfural and levulinic acid respectively, which when hydrogenated result in methyltetrahydrofuran. Common denominators in gaps for these different fuels and the biochemical or thermochemical processes used to produce them are given by three main areas. These are: catalysts and biocatalysts; feedstock preparation and bioprocessing; and systems integration. In the biocatalyst (or catalyst) area research is needed to achieve more robust, versatile, and cost-effective catalysts. The catalytic systems must be less subject to inhibition and more stable in the presence of chemically complex feedstocks derived from biomass materials. With bioprocessing, the gaps lie in economic enzyme production, reduction of enzyme inhibition, development of pentose utilising and cellulase producing micro-organisms, feedstock preparation (pre-treatment), and inhibitor removal. For thermochemical systems, the list is analogous except the term 'catalyst' replaces 'enzyme' or 'microorganism'. Gaps were identified in feedstock preparation, with this term being broadly defined. Feedstocks are defined as biomass materials entering the process, as well as gases derived

  12. 78 FR 36041 - Regulation of Fuels and Fuel Additives: RFS Pathways II and Technical Amendments to the RFS 2...

    2013-06-14

    ... Production, Transport and Tailpipe Emissions for Renewable Diesel and Naphtha C. Proposed Regulatory... and diesel fuel, or renewable fuels such as ethanol and biodiesel. Regulated categories and entities...

  13. Solar kerosene from H2O and CO2

    Furler, P.; Marxer, D.; Scheffe, J.; Reinalda, D.; Geerlings, H.; Falter, C.; Batteiger, V.; Sizmann, A.; Steinfeld, A.

    2017-06-01

    The entire production chain for renewable kerosene obtained directly from sunlight, H2O, and CO2 is experimentally demonstrated. The key component of the production process is a high-temperature solar reactor containing a reticulated porous ceramic (RPC) structure made of ceria, which enables the splitting of H2O and CO2 via a 2-step thermochemical redox cycle. In the 1st reduction step, ceria is endo-thermally reduced using concentrated solar radiation as the energy source of process heat. In the 2nd oxidation step, nonstoichiometric ceria reacts with H2O and CO2 to form H2 and CO - syngas - which is finally converted into kerosene by the Fischer-Tropsch process. The RPC featured dual-scale porosity for enhanced heat and mass transfer: mm-size pores for volumetric radiation absorption during the reduction step and μm-size pores within its struts for fast kinetics during the oxidation step. We report on the engineering design of the solar reactor and the experimental demonstration of over 290 consecutive redox cycles for producing high-quality syngas suitable for the processing of liquid hydrocarbon fuels.

  14. Dry reforming of methane with CO{sub 2} at elevated pressures

    Milanov, A.; Schwab, E.; Wasserschaff, G. [BASF SE, Ludwigshafen (Germany); Schunk, S. [hte AG, Heidelberg (Germany)

    2013-11-01

    The indirect conversion of natural gas into higher value chemicals and fuels via syngas is superior with regard to efficiency compared to the currently available direct conversion technologies and remains the industrially preferred route. Typically the syngas production route is generally dictated by the H{sub 2}/CO ratio requirements of the downstream synthesis process. Processes such as direct DME synthesis, high-temperature Fischer-Tropsch and acetic acid synthesis require CO rich syngas that is not readily accessible by established technologies like steam methane reforming (SMR) and autothermal reforming of methane (ATR). The CO{sub 2} reforming of methane, also known as dry reforming (DRM), is an attractive alternative technology for the production of CO-rich syngas. This paper gives an overview of the current joint research activities at BASF and hte AG aiming to develop suitable catalysts for CO{sub 2} reforming of methane at elevated pressures with minimized input of process steam. The performance profiles of two newly developed base metal catalysts are presented and discussed. The catalysts exhibit high degrees of methane and CO{sub 2} conversion in combination with an extraordinary coking resistance under high severity process conditions. (orig.)

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

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

    2011-01-01

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

  16. EARLY ENTRANCE CO-PRODUCTION PLANT--DECENTRALIZED GASIFICATION COGENERATION TRANSPORTATION FUELS AND STEAM FROM AVAILABLE FEEDSTOCKS

    John W. Rich

    2001-03-01

    Waste Processors Management, Inc. (WMPI), along with its subcontractors Texaco Power and Gasification (now ChevronTexaco), SASOL Technology Ltd., and Nexant Inc. entered into a Cooperative Agreement with the USDOE, National Energy Technology Laboratory (NETL) to assess the techno-economic viability of building an Early Entrance Co-Production Plant (EECP) in the US to produce ultra clean Fischer-Tropsch (FT) transportation fuels with either power or steam as the major co--product. The EECP design includes recovery and gasification of low-cost coal waste (culm) from physical coal cleaning operations and will assess blends of the culm with coal or petroleum coke. The project has three phases: Phase 1 is the concept definition and engineering feasibility study to identify areas of technical, environmental and financial risk. Phase 2 is an experimental testing program designed to validate the coal waste mixture gasification performance. Phase 3 updates the original EECP design based on results from Phase 2, to prepare a preliminary engineering design package and financial plan for obtaining private funding to build a 5,000 barrel per day (BPD) coal gasification/liquefaction plant next to an existing co-generation plant in Gilberton, Schuylkill County, Pennsylvania. The current report is WMPI's third quarterly technical progress report. It covers the period performance from October 1, 2001 through December 31, 2001.

  17. A comprehensive combustion chemistry study of 2,5-dimethylhexane

    Sarathy, Mani

    2014-06-01

    Iso-paraffinic molecular structures larger than seven carbon atoms in chain length are commonly found in conventional petroleum, Fischer-Tropsch (FT), and other alternative hydrocarbon fuels, but little research has been done on their combustion behavior. Recent studies have focused on either mono-methylated alkanes and/or highly branched compounds (e.g., 2,2,4-trimethylpentane). In order to better understand the combustion characteristics of real fuels, this study presents new experimental data for the oxidation of 2,5-dimethylhexane under a wide variety of temperature, pressure, and equivalence ratio conditions. This new dataset includes jet stirred reactor speciation, shock tube ignition delay, and rapid compression machine ignition delay, which builds upon recently published data for counterflow flame ignition, extinction, and speciation profiles. The low and high temperature oxidation of 2,5-dimethylhexane has been simulated with a comprehensive chemical kinetic model developed using established reaction rate rules. The agreement between the model and data is presented, along with suggestions for improving model predictions. The oxidation behavior of 2,5-dimethylhexane is compared with oxidation of other octane isomers to confirm the effects of branching on low and intermediate temperature fuel reactivity. The model is used to elucidate the structural features and reaction pathways responsible for inhibiting the reactivity of 2,5-dimethylhexane. © 2014 The Combustion Institute.

  18. The recent development of efficient Earth-abundant transition-metal nanocatalysts.

    Wang, Dong; Astruc, Didier

    2017-02-06

    Whereas noble metal compounds have long been central in catalysis, Earth-abundant metal-based catalysts have in the same time remained undeveloped. Yet the efficacy of Earth-abundant metal catalysts was already shown at the very beginning of the 20th century with the Fe-catalyzed Haber-Bosch process of ammonia synthesis and later in the Fischer-Tropsch reaction. Nanoscience has revolutionized the world of catalysis since it was observed that very small Au nanoparticles (NPs) and other noble metal NPs are extraordinarily efficient. Therefore the development of Earth-abundant metals NPs is more recent, but it has appeared necessary due to their "greenness". This review highlights catalysis by NPs of Earth-abundant transition metals that include Mn, Fe, Co, Ni, Cu, early transition metals (Ti, V, Cr, Zr, Nb and W) and their nanocomposites with emphasis on basic principles and literature reported during the last 5 years. A very large spectrum of catalytic reactions has been successfully disclosed, and catalysis has been examined for each metal starting with zero-valent metal NPs followed by oxides and other nanocomposites. The last section highlights the catalytic activities of bi- and trimetallic NPs. Indeed this later family is very promising and simultaneously benefits from increased stability, efficiency and selectivity, compared to monometallic NPs, due to synergistic substrate activation.

  19. Overview of biomass conversion technologies

    Noor, S.; Latif, A.; Jan, M.

    2011-01-01

    A large part of the biomass is used for non-commercial purposes and mostly for cooking and heating, but the use is not sustainable, because it destroys soil-nutrients, causes indoor and outdoor pollution, adds to greenhouse gases, and results in health problems. Commercial use of biomass includes household fuelwood in industrialized countries and bio-char (charcoal) and firewood in urban and industrial areas in developing countries. The most efficient way of biomass utilization is through gasification, in which the gas produced by biomass gasification can either be used to generate power in an ordinary steam-cycle or be converted into motor fuel. In the latter case, there are two alternatives, namely, the synthesis of methanol and methanol-based motor fuels, or Fischer-Tropsch hydrocarbon synthesis. This paper deals with the technological overview of the state-of-the-art key biomass-conversion technologies that can play an important role in the future. The conversion routes for production of Heat, power and transportation fuel have been summarized in this paper, viz. combustion, gasification, pyrolysis, digestion, fermentation and extraction. (author)

  20. Selective transformation of syngas into gasoline-range hydrocarbons over mesoporous H-ZSM-5-supported cobalt nanoparticles.

    Cheng, Kang; Zhang, Lei; Kang, Jincan; Peng, Xiaobo; Zhang, Qinghong; Wang, Ye

    2015-01-26

    Bifunctional Fischer-Tropsch (FT) catalysts that couple uniform-sized Co nanoparticles for CO hydrogenation and mesoporous zeolites for hydrocracking/isomerization reactions were found to be promising for the direct production of gasoline-range (C5-11 ) hydrocarbons from syngas. The Brønsted acidity results in hydrocracking/isomerization of the heavier hydrocarbons formed on Co nanoparticles, while the mesoporosity contributes to suppressing the formation of lighter (C1-4 ) hydrocarbons. The selectivity for C5-11 hydrocarbons could reach about 70 % with a ratio of isoparaffins to n-paraffins of approximately 2.3 over this catalyst, and the former is markedly higher than the maximum value (ca. 45 %) expected from the Anderson-Schulz-Flory distribution. By using n-hexadecane as a model compound, it was clarified that both the acidity and mesoporosity play key roles in controlling the hydrocracking reactions and thus contribute to the improved product selectivity in FT synthesis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.