Conversion of Syngas to Fuels

  • Steven S. C. Chuang


This chapter examines the reaction pathways and the selectivity of the catalysts for the conversion of syngas to liquid hydrocarbons and ethanol fuels. Rh is by far the most active catalyst for ethanol synthesis. Co- and Fe-based catalysts exhibit excellent activity for hydrocarbon fuel synthesis from high H2/CO and low H2/CO ratio syngas, respectively. Regardless of the differences in the catalyst selectivity, all of these CO-hydrogenation catalysts produce methane as one of the major products. So far, no approaches are effective in suppressing CH4 formation. Development of a cost-effective liquid-fuel process from syngas with a low net fuel cycle CO2 emission requires consideration of (1) the overall system, including the source of raw materials and by-products and (2) analysis of carbon footprint of each step from raw materials to the desired products and undesired by-products.


Chain Growth Ethanol Synthesis Dissociation Activity Chain Growth Probability Ethanol Selectivity 
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  1. 1.
    Anderson RB (1983) Fischer Tropsch and related synthesis. Academic, New YorkGoogle Scholar
  2. 2.
    Keim W (1983) Catalysis in C1 chemistry: catalysis by metal complexes, vol 4. Springer, BerlinGoogle Scholar
  3. 3.
    Treptow RS (2010) Carbon footprint calculations: an application of chemical principles. J Chem Educ 87(2):168–171CrossRefGoogle Scholar
  4. 4.
    Larson ED et al (2010) Co-production of decarbonized synfuels and electricity from coal + biomass with CO2 capture and storage: an Illinois case study. Energy Environ Sci 3(1):28–42CrossRefGoogle Scholar
  5. 5.
    Wender I (1996) Reactions of synthesis gas. Fuel Process Technol 48(3):189–297CrossRefGoogle Scholar
  6. 6.
    Chuang SC et al (1985) The use of probe molecules in the study of carbon monoxide hydrogenation over silica-supported nickel, ruthenium, rhodium, and palladium. J Catal 96(2):396–407CrossRefGoogle Scholar
  7. 7.
    Chuang SSC (1990) Sulfided group VIII metals for hydroformylation. Appl Catal 66(1):L1–L6CrossRefGoogle Scholar
  8. 8.
    Vannice MA (1975) Catalytic synthesis of hydrocarbons from molecular hydrogen/carbon monoxide mixtures over the group VIII metals. III. Metal-support effects with platinum and palladium catalysts. J Catal 40(1):129–134CrossRefGoogle Scholar
  9. 9.
    Burtron H, Davis MLO (2009) Advances in Fischer-Tropsch synthesis, catalysts, and catalysis. CRC Press, Boca RatonGoogle Scholar
  10. 10.
    Dry ME (1981) The Fischer-Tropsch synthesis. Catal Sci Technol 1:159–255Google Scholar
  11. 11.
    Ertl G, Knözinger H, Schüth F, Weitkamp J (2008) Handbook of heterogeneous catalysis, vol 6. Wiley, WeinheimCrossRefGoogle Scholar
  12. 12.
    Ichikawa M, Fukushima T (1985) Mechanism of syngas conversion into C2-oxygenates such as ethanol catalyzed on a silica-supported rhodium-titanium catalyst. J Chem Soc Chem Commun 6:321–323CrossRefGoogle Scholar
  13. 13.
    Underwood RP, Bell AT (1986) Carbon monoxide hydrogenation over rhodium supported on silicon oxide, lanthanum oxide, neodymium oxide, and samarium(III) oxide. Appl Catal 21(1):157–168CrossRefGoogle Scholar
  14. 14.
    Hedrick SA, Chuang SSC (2003) Modeling the Fischer-Tropsch reaction in a slurry bubble column reactor. Chem Eng Commun 190(4):445–474CrossRefGoogle Scholar
  15. 15.
    Balakos MW, Chuang SSC (1995) Dynamic and LHHW kinetic analyses of heterogeneous catalytic hydroformylation. J Catal 151(2):266–278CrossRefGoogle Scholar
  16. 16.
    Dry ME (1981) The Fischer-Tropsch synthesis. In: Anderson JR, Boudart M (eds) Catalysis – science and technology, vol 1. Springer, Berlin/Heidelberg/New York, pp 159–255Google Scholar
  17. 17.
    Soled SL et al (2003) Control of metal dispersion and structure by changes in the solid-state chemistry of supported cobalt Fischer-Tropsch catalysts. Top Catal 26(1–4):101–109CrossRefGoogle Scholar
  18. 18.
    Rao VUS, Gormley RJ (1982) Catalyst for converting synthesis gas to light olefins. (United States Dept. of Energy, USA). Application: US, 5 ppGoogle Scholar
  19. 19.
    Kellner CS, Bell AT (1981) Synthesis of oxygenated products from carbon monoxide and hydrogen over silica- and alumina-supported ruthenium catalysts. J Catal 71(2):288–295CrossRefGoogle Scholar
  20. 20.
    Underwood RP, Bell AT (1988) Lanthana-promoted rhodium/silica. I. Studies of carbon monoxide and hydrogen adsorption and desorption. J Catal 109(1):61–75CrossRefGoogle Scholar
  21. 21.
    Chuang SSC, Pien SI (1992) Role of silver promoter in carbon monoxide hydrogenation and ethylene hydroformylation over rhodium/silica catalysts. J Catal 138(2):536–546CrossRefGoogle Scholar
  22. 22.
    Poels EK, Ponec V (1983) Formation of oxygenated products from synthesis gas. Catalysis 6:196–234CrossRefGoogle Scholar
  23. 23.
    Stroch HH, Golumbic N, Anderson RB (1951) The Fischer-Tropsch and related syntheses. Wiley, New YorkGoogle Scholar
  24. 24.
    Nunan JG et al (1989) Higher alcohol and oxygenate synthesis over cesium-doped copper/zinc oxide catalysts. J Catal 116(1):195–221CrossRefGoogle Scholar
  25. 25.
    Chuang SSC, Pien SI (1991) Synthesis of aldehydes from synthesis gas over sodium-promoted manganese-nickel catalysts. J Catal 128(2):569–573CrossRefGoogle Scholar
  26. 26.
    Chuang SSC et al (1991) Carbon monoxide hydrogenation over sodium-manganese-nickel catalysts: effects of catalyst preparation methods on the C2+ oxygenate selectivity. Appl Catal 70(1):101–114CrossRefGoogle Scholar
  27. 27.
    Tatsumi T et al (1986) Effects of molybdenum precursors on the activity of alkali-promoted molybdenum catalysts for alcohol synthesis from carbon monoxide-hydrogen. Polyhedron 5(1–2):257–260CrossRefGoogle Scholar
  28. 28.
    Li X et al (1998) Higher alcohols from synthesis gas using carbon-supported doped molybdenum-based catalysts. Ind Eng Chem Res 37(10):3853–3863CrossRefGoogle Scholar
  29. 29.
    McCash EM (2001) Surface chemistry. Oxford University Press, New YorkGoogle Scholar
  30. 30.
    Watson PR, Somorjai GA (1982) The formation of oxygen-containing organic molecules by the hydrogenation of carbon monoxide over a lanthanum rhodate catalyst. J Catal 74(2):282–295CrossRefGoogle Scholar
  31. 31.
    Chuang SSC, Stevens RW Jr, Khatri R (2005) Mechanism of C2+ oxygenate synthesis on Rh catalysts. Top Catal 32(3–4):225–232CrossRefGoogle Scholar
  32. 32.
    Watson PR, Somorjai GA (1981) The hydrogenation of carbon monoxide over rhodium oxide surfaces. J Catal 72(2):347–363CrossRefGoogle Scholar
  33. 33.
    Castner DG, Blackadar RL, Somorjai GA (1980) Carbon monoxide hydrogenation over clean and oxidized rhodium foil and single crystal catalysts. Correlations of catalyst activity, selectivity, and surface composition. J Catal 66(2):257–266CrossRefGoogle Scholar
  34. 34.
    Konishi Y, Ichikawa M, Sachtler WMH (1987) Hydrogenation and hydroformylation with supported rhodium catalysts: effect of adsorbed sulfur. J Phys Chem 91(24):6286–6291CrossRefGoogle Scholar
  35. 35.
    McKee ML, Worley SD (1988) A theoretical study of rhodium/carbonyl species. J Phys Chem 92(13):3699–3700CrossRefGoogle Scholar
  36. 36.
    Biloen P, Sachtler WMH (1981) Mechanism of hydrocarbon synthesis over Fischer-Tropsch catalysts. Adv Catal 30:165–216CrossRefGoogle Scholar
  37. 37.
    Schindeler HD (1989) Coal liquefaction – a research and development needs assessment, vol II. US Department of Energy, McLeanGoogle Scholar
  38. 38.
    Davis BH (2001) Fischer-Tropsch synthesis: current mechanism and futuristic needs. Fuel Process Technol 71(1–3):157–166CrossRefGoogle Scholar
  39. 39.
    Klier K, et al.(1988) Mechanism of methanol and higher oxygenate synthesis. Studies in Surface Science and Catalysis. Methane Conversion, Proceedings of a Symposium on the Production of Fuels and Chemicals from Natural Gas 36:109–125Google Scholar
  40. 40.
    Vannice MA (1975) Catalytic synthesis of hydrocarbons from hydrogen-carbon monoxide mixtures over the group VIII metals. I. Specific activities and product distributions of supported metals. J Catal 37(3):449–461CrossRefGoogle Scholar
  41. 41.
    Nonneman LEY et al (1990) Role of impurities in the enhancement of C2-oxygenates activity: supported rhodium catalysts. Appl Catal 62(2):L23–L28Google Scholar
  42. 42.
    Yoneda Y (1989) Progress in C1 chemistry in Japan. Kodansha/Elsevier, TokyoGoogle Scholar
  43. 43.
    Boffa A et al (1994) Promotion of CO and CO2 hydrogenation over Rh by metal oxides: the influence of oxide Lewis acidity and reducibility. J Catal 149(1):149–158CrossRefGoogle Scholar
  44. 44.
    Underwood RP, Bell AT (1988) Lanthana-promoted rhodium/silica. II. Studies of carbon monoxide hydrogenation. J Catal 111(2):325–335CrossRefGoogle Scholar
  45. 45.
    Ichikawa M et al (1985) Selective hydroformylation of ethylene on rhodium-zinc-silica. An apparent example of site isolation of rhodium and Lewis acid-promoted carbonyl insertion. J Am Chem Soc 107(24):7216–7218CrossRefGoogle Scholar
  46. 46.
    Yin H et al (2003) Influence of iron promoter on catalytic properties of Rh–Mn–Li/SiO2 for CO hydrogenation. Appl Catal A 243(1):155–164CrossRefGoogle Scholar
  47. 47.
    Chuang SC, Goodwin JG Jr, Wender I (1985) The effect of alkali promotion on carbon monoxide hydrogenation over rhodium/titania. J Catal 95(2):435–446CrossRefGoogle Scholar
  48. 48.
    Chuang SSC, Pien SI (1992) Infrared study of the carbon monoxide insertion reaction on reduced, oxidized, and sulfided rhodium/silica catalysts. J Catal 135(2):618–634CrossRefGoogle Scholar
  49. 49.
    Davis BH, Occelli ML (eds) (2009) Advances in Fischer-Tropsch synthesis, catalysts, and catalysis. Chemical Industries, CRC Press, Boca Raton, 2009, Vol 128, 403 ppGoogle Scholar
  50. 50.
    Chuang SSC, Guzmanm F (2009) Mechanistic Investigation of Heterogeneous Catalysis by Transient Infrared Methods. Topic in Catal 52: 1448–1458CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2012

Authors and Affiliations

  1. 1.FirstEnergy Advanced Energy Research Center, Department of Chemical and Biomolecular EngineeringThe University of AkronAkronUSA

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