Advertisement

Korean Journal of Chemical Engineering

, Volume 15, Issue 1, pp 1–8 | Cite as

The chemistry and physics of coking

  • James G. Speight
Featured Review

Abstract

The causes of coke formation during petroleum refining are only now beginning to be understood. They are closely related to the mechanism of the thermal decomposition of the petroleum Constituents and to changes in the character of the liquid medium. It was formerly believed that coke formation was, a polymerization reaction whereupon the chemical precursors to coke immediately formed macromolecules when subject to the processing temperatures. This is not so. And it is the initial stages of the thermal decomposition which determine the ultimate path of the reaction. Coke formation is a complex process involving both chemical reactions and thermodynamic behavior. Reactions that contribute to this process are cracking of side chains from aromatic groups, dehydrogenation of naphthenes to form aromatics, condensation of aliphatic structures to form aromatics, condensation of aromatics to form higher fused-ring aromatics, and dimerization or oligomerization reactions. Loss of side chains always accompanies thermal cracking, and dehydrogenation and condensation reactions are favored by hydrogen deficient conditions.

Key words

Petroleum Coking Cracking Phase Separation 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Bjorseth, A., Handbook of Polycyclic Aromatic Hydrocarbons, Marcel Dekker Inc., New York (1983).Google Scholar
  2. Cooper, T. A. and Ballard, W. P., In Advances in Petroleum Chemistry and Refining K. A. Kobe and J. J. McKetta (Editor). Interscience, New York, Volume 6, Chapter 4 1962.Google Scholar
  3. Dias, J. R., Handbook of Polycyclic Hydrocarbons. Part A. Benzenoid Hydrocarbons, Elsevier, New York, 1987.Google Scholar
  4. Dias, J.R., Handbook of Polycyclic Hydrocarbons. Part B. Polycyclic Isomers and Heteroatom Analogs of Benzenoid Hydrocarbons, Elsevier, New York, 1988.Google Scholar
  5. Dickie, J. P. and Yen, T. F.,Anal. Chem.,39, 1847 (1967).CrossRefGoogle Scholar
  6. Dolbear, G. E., In Petroleum Chemistry and Refining, J. G. Speight (Editor), Taylor & Francis Publishers, Washington, DC, Chapter 7, 1997.Google Scholar
  7. Eliel, E. and Wilen, S., “Stereochemistry of Organic Compounds”, John Wiley & Sons Inc., New York, 1994.Google Scholar
  8. Fabuss, B. M., Smith, J. O. and Satterfield, C. N., In Advances in Petroleum Chemistry and Refining, Volume IX, 1964.Google Scholar
  9. Fitzer, E., Mueller, K. and Schaefer, W.,Chem. Phys. Carbon,7, 237 (1971).Google Scholar
  10. Gray, M. R., “Upgrading Petroleum Residues and Heavy Oils”, Marcel Dekker Inc., New York, 1994.Google Scholar
  11. Hurd, C. D., “The Pyrolysis of Carbon Compounds”, The Chemical Catalog Company Inc., New York, 1929.Google Scholar
  12. Kim, H. and Long, R. B.,Ind. Eng. Chem. Fundam.,18, 60 (1979).CrossRefGoogle Scholar
  13. King, P. J., Morton, F. and Sagarra, A., In Modern Petroleum Technology, G. D. Hobson and W. Pohl (Editor), Applied Science Publishers, Barking, Essex, England, 1973.Google Scholar
  14. Langer, A. W., Stewart, J., Thompson, C. E., White, H. T. and Hill, R. M.,Ind. Eng. Chem.,53, 27 (1961).CrossRefGoogle Scholar
  15. LePage, J. F. and Davidson, M.,Rev. Institut Francais du Petrole.,41, 131 (1986).Google Scholar
  16. Levinter, M. E., Medvedeva, M. I., Panchenkov, G. M., Aseev, Y. G., Nedoshivin, Y. N., Finkelshtein, G. B. and Galiakbarov, M. F.,Khim. Tekhnol. Topl. Masel,9, 31 (1966).Google Scholar
  17. Levinter, M. E., Medvedeva M. I., Panchenkov, G. M., Agapov, G. I., Galiakbarov, M. F. and Galikeev, R. K.,Khim. Tekhol. Topl. Mosel.,4, 20 (1967).Google Scholar
  18. Long, R. B. and Speight, J. G., In Petroleum Chemistry and Refining., J. G. Speight (Editor), Taylor & Francis Publishers, Washington, DC, Chapter 1, 1997.Google Scholar
  19. Magaril, R. A. and Aksenova, E. L.,Int. Chem. Eng.,8, 727 (1968).Google Scholar
  20. Magaril, R. Z. and Aksenova, E. I.,Khim. Tekhnol Topl Masel,7, 22 (1970).Google Scholar
  21. Magaril, R. A. and Ramazaeva, L. F.,Izv. Vyssh. Ucheb. Zaved. Neft Gaz.,12(1), 61 (1969).Google Scholar
  22. Magaril, R. L., Ramazaeva, L. F. and Askenova, E. I.,Khim. Tekhnol Topliv Masel,15(3), 15 (1970).Google Scholar
  23. Magaril, R. Z., Ramazeava, L. F. and Aksenora, E. I.,Int. Chem. Eng.,11, 250 (1971).Google Scholar
  24. Mitchell, D. L. and Speight, J. G.,Fuel,52, 149 (1973).CrossRefGoogle Scholar
  25. Moschopedis, S. E., Fryer, J. F. and Speight, J. G.,Fuel,55, 227 (1976).CrossRefGoogle Scholar
  26. Mushrush, G. W. and Speight, J. G., “Petroleum Products: Instability and Incompatibility”, Taylor & Francis Publishers, Washington, DC, 1995.Google Scholar
  27. Overfield, R. E., Sheu, E. Y., Sinha, S. K. and Liang, K. S.,Fuel Sci. Technol. Int.,7, 611 (1989).Google Scholar
  28. Rao, B. M. L. and Serrano, J. E.,Fuel Sci. Technol. Int.,4, 483 (1986).Google Scholar
  29. Roberts, I.,Preprints. Div. Petrol Chem. Am. Chem Soc.,34 (2), 251 (1989).Google Scholar
  30. Savage, P.E. and Klein, M. T.,Chem. Eng. Sci.,44, 393 (1989).CrossRefGoogle Scholar
  31. Savage, P. E., Klein, M. T. and Kukes, S. G.,Ind. Eng. Chem. Process Des. Dev.,24, 1169 (1985).CrossRefGoogle Scholar
  32. Savage, P. E., Klein, M. T. and Kukes, S. G.,Energy & Fuels,2, 619 (1988).CrossRefGoogle Scholar
  33. Schabron, J. F. and Speight, J. G.,Preprints Div. Petrol Chem. Am. Chem. Soc,42, 386 (1997a).Google Scholar
  34. Schabron, J. F. and Speight, J. G.,Revue Institut Francais du Petrole.,52, 73 (1997b).Google Scholar
  35. Schucker, R. C. and Keweshan, C. F.,Preprints Div. Fuel Chem. Am. Chem. Soc,25, 155 (1980).Google Scholar
  36. Shiroto, Y., Nakata, S., Fukul, Y. and Takeuchi, C.,Ind. Eng. Chem. Process Design Dev.,22, 248 (1983).CrossRefGoogle Scholar
  37. Speight, J. G.,Fuel,49, 134 (1970).CrossRefGoogle Scholar
  38. Speight, J. G., “The Desulfurization of Heavy Oils and Residua”, Marcel Dekker Inc., New York, 1981.Google Scholar
  39. Speight, J. G., In Catalysis on the Energy Scene, S. Kaliaguine and A. Mahay (Editor), Elsevier, Amsterdam, 1984.Google Scholar
  40. Speight, J. G.,Preprints. Div. Petrol. Chem. Am. Chem. Soc,32(2), 413 (1987).Google Scholar
  41. Speight, J. G.,Neftekhimiya.,29, 723 (1989).Google Scholar
  42. Speight, J. G., “The Chemistry and Technology of Petroleum”, 2nd Edition, Marcel Dekker Inc., New York, 1991.Google Scholar
  43. Speight, J. G., Proceedings 4th International Conference on the Stability and Handling of Liquid Fuels, US. Department of Energy (DOE/CONF-911102), 169 (1992).Google Scholar
  44. Speight, J. G., In Asphalts and Asphaltenes, 1, T. F. Yen and G.V. Chilingarian (Editor), Elsevier, Amsterdam, The Netherlands. Chapter 2, 1994.Google Scholar
  45. Speight, J. G., In Petroleum Chemistry and Refining, J.G. Speight (Editor), Taylor & Francis Publishers, Washington, DC, Chapter 5, 1997.Google Scholar
  46. Speight, J. G., Wernick, D. L., Gould, K. A., Overfield, R. E., Rao, B. M. L. and Savage, D. W.,Rev. Inst. Francais du Petrole,40, 51 (1985).Google Scholar
  47. Takatsuka, T., Kajiyama, R., Hashimoto, H., Matsuo, I. and Miwa, S.A.,J. Chem. Eng. Japan,22, 304 (1989a).CrossRefGoogle Scholar
  48. Takatuska, T., Wada, Y., Hirohama, S. and Fukui, Y. A.,J. Chem. Eng. Japan,22, 298 (1989b).CrossRefGoogle Scholar
  49. Ternan, M.,Can. J. Chem. Eng.,61, 133, 689 (1983).CrossRefGoogle Scholar
  50. Thiyagarajan, P., Hunt, J. E., Winans, R. E., Anderson, K. B. and Miller, J. T.,Energy & Fuels,9, 829 (1995).CrossRefGoogle Scholar
  51. Valyavin, G. G., Fryazinov, V. V., Gimaev, R. H., Syunyaev, Z. I., Vyatkin, Y. L. and Mulyukov, S. F.,Khim. Tekhol. Topl. Masel.,8, 8 (1979).Google Scholar
  52. Vercier, P., In the Chemistry of Asphaltenes J. W. Bunger and N. C. Li (Editor), Advances in Chemistry Series No. 195, American Chemical Society, Washington, DC (1981).Google Scholar
  53. Wiehe, I. A.,Ind. Eng. Chem. Res.,31, 530 (1992).CrossRefGoogle Scholar
  54. Wiehe, I. A.,Preprints. Div. Petrol Chem. Am. Chem. Soc,38, 428 (1993a).Google Scholar
  55. Wiehe, I. A.,Ind. Eng. Chem. Research,32, 2447 (1993b).CrossRefGoogle Scholar
  56. Wiehe, I. A,Energy & Fuels,8, 536 (1994).CrossRefGoogle Scholar
  57. Yan, T. Y.,Preprints Div. Petrol. Chem. Am. Chem. Soc.,32, 490 (1987).Google Scholar
  58. Yen, T. F., In The Future of Heavy Crude Oil and Tar Sands, R. F. Meyer, J. C. Wynn, and J. C. Olson (Editor). McGraw-Hill, New York (1984).Google Scholar

Copyright information

© Korean Institute of Chemical Engineering 1998

Authors and Affiliations

  1. 1.Western Research InstituteLaramieUSA

Personalised recommendations