THE CHEMISTRY AND PHYSICS OF COKING

Speight JG

Korean Journal of Chemical Engineering, Vol.15, No.1, 1-8, January, 1998

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.

Keywords:Petroleum;Coking;Cracking;Phase Separation

[References]

Bjorseth A, Handbook of Polycyclic Aromatic Hydrocarbons, Marcel Dekker Inc., New York (1983)
Cooper TA, Ballard WP, In Advances in Petroleum Chemistry and Refining K.A. Kobe and J.J. McKetta (Editors). Interscience, New York, Volume 6, Chapter 4 (1962)
Dias JR, Handbook of Polycyclic Hydrocarbons. Part A. Benzenoid hydrocarbons, Elsevier, New York (1987)
Dias JR, Handbook of Polycyclic hydrocarbons. Part B. Polycyclic Isomers and Heteroatom Analogs of Benzenoid Hydrocarbons, Elsevier, New York (1988)
Dickie JP, Yen TF, Anal. Chem., 39, 1847 (1967)
Dolbear GE, In Petroleum Chemistry and Refining, J.G. Speight (Editor), Taylor & Francis Publishers, Washington, D.C., Chapter 7 (1997)
Eliel E, Wilen S, "Stereochemistry of Organic Compounds," John Wiley & Sons Inc., New York (1994)
Fabuss BM, Smith JO, Satterfield CN, In Advances in Petroleum Chemistry and Refining, Volume IX (1964)
Fitzer E, Mueller K, Schaefer W, Chem. Phys. Carbon, 7, 237 (1971)
Gray MR, "Upgrading Petroleum Residues and Heavy Oils," Marcel Dekker Inc., New York (1994)
Hurd CD, "The Pyrolysis of Carbon Compounds," The Chemical Catalog Company Inc., New York (1929)
Kim H, Long RB, Ind. Eng. Chem. Fundam., 18, 60 (1979)
King PJ, Morton F, Sagarra A, In Modern Petroleum Technology, G.D. Hobson and W. Pohl (Editors), Applied Science Publishers, Barking, Essex, England (1973)
Langer AW, Stewart J, Thompson CE, White HT, Hill RM, Ind. Eng. Chem., 53, 27 (1961)
LePage JF, Davidson M, Rev. Inst. Fr. Pet., 41, 131 (1986)
Levinter ME, Medvedeva MI, Panchenkov GM, Aseev YG, Nedoshivin YN, Finkelshtein GB, Galiakbarov MF, Khim. Tekhnol. Topl. Masel., 9, 31 (1966)
Levinter ME, Medvedeva MI, Panchenkov GM, Agapov GI, Galiakbarov MF, Galikeev RK, Khim. Tekhol. Topl. Masel., 4, 20 (1967)
Long RB, Speight JG, In Petroleum Chemistry and Refining., J.G. Speight (Editor), Taylor & Francis Publishers, Washington, D.C., Chapter 1 (1997)
Magaril RA, Aksenova EL, Int. Chem. Eng., 8, 727 (1968)
Magaril RZ, Aksenova EI, Khim. Tekhnol. Topl. Masel., 7, 22 (1970)
Magaril RA, Ramazaeva LF, Izv. Vyssh. Ucheb. Zaved. Neft Gaz., 12(1), 61 (1969)
Magaril RL, Ramazaeva LF, Askenova EI, Khim. Tekhnol. Topliv Masel., 15(3), 15 (1970)
Magaril RZ, Ramazeava LF, Aksenora EI, Int. Chem. Eng., 11, 250 (1971)
Mitchell DL, Speight JG, Fuel, 52, 149 (1973)
Moschopedis SE, Fryer JF, Speight JG, Fuel, 55, 227 (1976)
Mushrush GW, Speight JG, "Petroleum Products: Instability and Incompatibility," Taylor & Francis Publishers, Washington, D.C. (1995)
Overfield RE, Sheu EY, Sinha SK, Liang KS, Fuel Sci. Technol. Int., 7, 611 (1989)
Rao BML, Serrano JE, Fuel Sci. Technol. Int., 4, 483 (1986)
Roberts I, Prepr. Div. Petrol. Chem. Am. Chem. Soc., 34(2), 251 (1989)
Savage PE, Klein MT, Chem. Eng. Sci., 44, 393 (1989)
Savage PE, Klein MT, Kukes SG, Ind. Eng. Chem. Process Des. Dev., 24, 1169 (1985)
Savage PE, Klein MT, Kukes SG, Energy Fuels, 2, 619 (1988)
Schabron JF, Speight JG, Prepr. Div. Petrol. Chem. Am. Chem. Soc., 42, 386 (1997)
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Schucker RC, Keweshan CF, Prepr. Div. Fuel Chem. Am. Chem. Soc., 25, 155 (1980)
Shiroto Y, Nakata S, Fukul Y, Takeuchi C, Ind. Eng. Chem. Process Des. Dev., 22, 248 (1983)
Speight JG, Fuel, 49, 134 (1970)
Speight JG, "The Desulfurization of Heavy Oils and Residua," Marcel Dekker Inc., New York (1981)
Speight JG, In Catalysis on the Energy Scene, S. Kaliaguine and A. Mahay (Editors), Elsevier, Amsterdam (1984)
Speight JG, Prepr. Div. Petrol. Chem. Am. Chem. Soc., 32(2), 413 (1987)
Speight JG, Neftekhimiya., 29, 723 (1989)
Speight JG, "The Chemistry and Technology of Petroleum," 2nd Edition, Marcel Dekker Inc., New York (1991)
Speight JG, Proceedings 4th International Conference on the Stability and Handling of Liquid Fuels, U.S. Department of Energy (DOE/CONF-911102), 169 (1992)
Speight JG, In Asphalts and Asphaltenes, 1, T.F. Yen and G.V. Chilingarian (Editors), Elsevier, Amsterdam, The Netherlands. Chapter 2 (1994)
Speight JG, In Petroleum Chemistry and Refining, J.G. Speight (Editor), Taylor & Francis Publishers, Washington, D.C., Chapter 5 (1997)
Speight JG, Wernick DL, Gould KA, Overfield RE, Rao BML, Savage DW, Rev. Inst. Fr. Pet., 40, 51 (1985)
Takatsuka T, Kajiyama R, Hashimoto H, Matsuo I, Miwa SA, J. Chem. Eng. Jpn., 22, 304 (1989)
Takatuska T, Wada Y, Hirohama S, Fukui YA, J. Chem. Eng. Jpn., 22, 298 (1989)
Ternan M, Can. J. Chem. Eng., 61(133), 689 (1983)
Thiyagarajan P, Hunt JE, Winans RE, Anderson KB, Miller JT, Energy Fuels, 9(5), 829 (1995)
Valyavin GG, Fryazinov VV, Gimaev RH, Syunyaev ZI, Vyatkin YL, Mulyukov SF, Khim. Tekhol. Topl. Masel., 8, 8 (1979)
Vercier P, In the Chemistry of Asphaltenes J.W. Bunger and N.C. Li (Editors), Advances in Chemistry Series No. 195, American Chemical Society, Washignton, D.C. (1981)
Wiehe IA, Ind. Eng. Chem. Res., 31, 530 (1992)
Wiehe IA, Prepr. Div. Petrol. Chem. Am. Chem. Soc., 38, 428 (1993)
Wiehe IA, Ind. Eng. Chem. Res., 32, 2447 (1993)
Wiehe IA, Energy Fuels, 8(3), 536 (1994)
Yan YT, Prepr. Div. Petrol. Chem. Am. Chem. Soc., 32, 490 (1987)
Yen TF, In the Future of Heavy Crude Oil and Tar Sands, R.F. Meyer, J.C. Wynn, and J.C. Olson (Editors). McGraw-Hill, New York (1984)

[Referenced By]

[1] Bjorseth A, Handbook of Polycyclic Aromatic Hydrocarbons, Marcel Dekker Inc., New York (1983)

[2] Cooper TA, Ballard WP, In Advances in Petroleum Chemistry and Refining K.A. Kobe and J.J. McKetta (Editors). Interscience, New York, Volume 6, Chapter 4 (1962)

[3] Dias JR, Handbook of Polycyclic Hydrocarbons. Part A. Benzenoid hydrocarbons, Elsevier, New York (1987)

[4] Dias JR, Handbook of Polycyclic hydrocarbons. Part B. Polycyclic Isomers and Heteroatom Analogs of Benzenoid Hydrocarbons, Elsevier, New York (1988)

[5] Dickie JP, Yen TF, Anal. Chem., 39, 1847 (1967)

[6] Dolbear GE, In Petroleum Chemistry and Refining, J.G. Speight (Editor), Taylor & Francis Publishers, Washington, D.C., Chapter 7 (1997)

[7] Eliel E, Wilen S, "Stereochemistry of Organic Compounds," John Wiley & Sons Inc., New York (1994)

[8] Fabuss BM, Smith JO, Satterfield CN, In Advances in Petroleum Chemistry and Refining, Volume IX (1964)

[9] Fitzer E, Mueller K, Schaefer W, Chem. Phys. Carbon, 7, 237 (1971)

[10] Gray MR, "Upgrading Petroleum Residues and Heavy Oils," Marcel Dekker Inc., New York (1994)

[11] Hurd CD, "The Pyrolysis of Carbon Compounds," The Chemical Catalog Company Inc., New York (1929)

[12] Kim H, Long RB, Ind. Eng. Chem. Fundam., 18, 60 (1979)

[13] King PJ, Morton F, Sagarra A, In Modern Petroleum Technology, G.D. Hobson and W. Pohl (Editors), Applied Science Publishers, Barking, Essex, England (1973)

[14] Langer AW, Stewart J, Thompson CE, White HT, Hill RM, Ind. Eng. Chem., 53, 27 (1961)

[15] LePage JF, Davidson M, Rev. Inst. Fr. Pet., 41, 131 (1986)

[16] Levinter ME, Medvedeva MI, Panchenkov GM, Aseev YG, Nedoshivin YN, Finkelshtein GB, Galiakbarov MF, Khim. Tekhnol. Topl. Masel., 9, 31 (1966)

[17] Levinter ME, Medvedeva MI, Panchenkov GM, Agapov GI, Galiakbarov MF, Galikeev RK, Khim. Tekhol. Topl. Masel., 4, 20 (1967)

[18] Long RB, Speight JG, In Petroleum Chemistry and Refining., J.G. Speight (Editor), Taylor & Francis Publishers, Washington, D.C., Chapter 1 (1997)

[19] Magaril RA, Aksenova EL, Int. Chem. Eng., 8, 727 (1968)

[20] Magaril RZ, Aksenova EI, Khim. Tekhnol. Topl. Masel., 7, 22 (1970)

[21] Magaril RA, Ramazaeva LF, Izv. Vyssh. Ucheb. Zaved. Neft Gaz., 12(1), 61 (1969)

[22] Magaril RL, Ramazaeva LF, Askenova EI, Khim. Tekhnol. Topliv Masel., 15(3), 15 (1970)

[23] Magaril RZ, Ramazeava LF, Aksenora EI, Int. Chem. Eng., 11, 250 (1971)

[24] Mitchell DL, Speight JG, Fuel, 52, 149 (1973)

[25] Moschopedis SE, Fryer JF, Speight JG, Fuel, 55, 227 (1976)

[26] Mushrush GW, Speight JG, "Petroleum Products: Instability and Incompatibility," Taylor & Francis Publishers, Washington, D.C. (1995)

[27] Overfield RE, Sheu EY, Sinha SK, Liang KS, Fuel Sci. Technol. Int., 7, 611 (1989)

[28] Rao BML, Serrano JE, Fuel Sci. Technol. Int., 4, 483 (1986)

[29] Roberts I, Prepr. Div. Petrol. Chem. Am. Chem. Soc., 34(2), 251 (1989)

[30] Savage PE, Klein MT, Chem. Eng. Sci., 44, 393 (1989)

[31] Savage PE, Klein MT, Kukes SG, Ind. Eng. Chem. Process Des. Dev., 24, 1169 (1985)

[32] Savage PE, Klein MT, Kukes SG, Energy Fuels, 2, 619 (1988)

[33] Schabron JF, Speight JG, Prepr. Div. Petrol. Chem. Am. Chem. Soc., 42, 386 (1997)

[34] Schabron JF, Speight JG, Revue Inst. Francais Petrole, 52, 73 (1997)

[35] Schucker RC, Keweshan CF, Prepr. Div. Fuel Chem. Am. Chem. Soc., 25, 155 (1980)

[36] Shiroto Y, Nakata S, Fukul Y, Takeuchi C, Ind. Eng. Chem. Process Des. Dev., 22, 248 (1983)

[37] Speight JG, Fuel, 49, 134 (1970)

[38] Speight JG, "The Desulfurization of Heavy Oils and Residua," Marcel Dekker Inc., New York (1981)

[39] Speight JG, In Catalysis on the Energy Scene, S. Kaliaguine and A. Mahay (Editors), Elsevier, Amsterdam (1984)

[40] Speight JG, Prepr. Div. Petrol. Chem. Am. Chem. Soc., 32(2), 413 (1987)

[41] Speight JG, Neftekhimiya., 29, 723 (1989)

[42] Speight JG, "The Chemistry and Technology of Petroleum," 2nd Edition, Marcel Dekker Inc., New York (1991)

[43] Speight JG, Proceedings 4th International Conference on the Stability and Handling of Liquid Fuels, U.S. Department of Energy (DOE/CONF-911102), 169 (1992)

[44] Speight JG, In Asphalts and Asphaltenes, 1, T.F. Yen and G.V. Chilingarian (Editors), Elsevier, Amsterdam, The Netherlands. Chapter 2 (1994)

[45] Speight JG, In Petroleum Chemistry and Refining, J.G. Speight (Editor), Taylor & Francis Publishers, Washington, D.C., Chapter 5 (1997)

[46] Speight JG, Wernick DL, Gould KA, Overfield RE, Rao BML, Savage DW, Rev. Inst. Fr. Pet., 40, 51 (1985)

[47] Takatsuka T, Kajiyama R, Hashimoto H, Matsuo I, Miwa SA, J. Chem. Eng. Jpn., 22, 304 (1989)

[48] Takatuska T, Wada Y, Hirohama S, Fukui YA, J. Chem. Eng. Jpn., 22, 298 (1989)

[49] Ternan M, Can. J. Chem. Eng., 61(133), 689 (1983)

[50] Thiyagarajan P, Hunt JE, Winans RE, Anderson KB, Miller JT, Energy Fuels, 9(5), 829 (1995)

[51] Valyavin GG, Fryazinov VV, Gimaev RH, Syunyaev ZI, Vyatkin YL, Mulyukov SF, Khim. Tekhol. Topl. Masel., 8, 8 (1979)

[52] Vercier P, In the Chemistry of Asphaltenes J.W. Bunger and N.C. Li (Editors), Advances in Chemistry Series No. 195, American Chemical Society, Washignton, D.C. (1981)

[53] Wiehe IA, Ind. Eng. Chem. Res., 31, 530 (1992)

[54] Wiehe IA, Prepr. Div. Petrol. Chem. Am. Chem. Soc., 38, 428 (1993)

[55] Wiehe IA, Ind. Eng. Chem. Res., 32, 2447 (1993)

[56] Wiehe IA, Energy Fuels, 8(3), 536 (1994)

[57] Yan YT, Prepr. Div. Petrol. Chem. Am. Chem. Soc., 32, 490 (1987)

[58] Yen TF, In the Future of Heavy Crude Oil and Tar Sands, R.F. Meyer, J.C. Wynn, and J.C. Olson (Editors). McGraw-Hill, New York (1984)