Numerical Simulation of Reaction Mechanism of Ethane Pyrolysis to Form Benzene and Styrene

Document Type : Research Article

Authors

1 Provincial Key Laboratory of Oil & Gas Chemical Technology, College of Chemistry & Chemical Engineering, Northeast Petroleum University, Daqing 163318, Heilongjiang, P.R. CHINA

2 China National Petroleum Corporation, Daqing Chemical Research Center, Daqing 163714, Heilongjiang, P.R. CHINA

3 State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, P.R. CHINA

Abstract

Based on Materials Studio and Aspen Plus, the reaction mechanism of producing benzene and styrene from ethane steam heat lysis was investigated through the addition reaction of free radicals + alkenes or free radicals + alkynes to form large free radicals and then through the cyclization and dehydrogenation of large free radicals to form aromatic hydrocarbons. It was found the thermal cracking of ethane had 2 paths to form benzene and 1 path to form styrene. The 1st path to form benzene is that the product ethylene form C2H3• through a chain transfer, then C2H3• and ethylene additively react to form 1-C4H7•-4, which then reacts with ethylene to form C6H11•, and finally, benzene is produced by dehydrogenation and transfer of C6H11•. The 2nd path to form benzene is that acetylene is produced by dehydrogenation of C2H3•, and then acetylene reacts via two sub-paths to form 1,3-C4H5•-4, which is cyclized to form C6H9•, and finally, benzene is formed through dehydrogenation and transfer. The path to form styrene is that 1,3-C4H5•-4 and 1,3-butadiene are cyclized to form C8H11•, and styrene is finally formed through dehydrogenation and chain transfer. Comparative analysis with industrial data showed there were 3 cycles in the ethane thermal cracking reaction network. The simulation data were well consistent with the industrial production data.

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References

[1] Rice F.O., The Thermal Decomposition of Organic Compounds from the Standpoint of Free Radicals (IV): the Dehydrogenation of Paraffin Hydrocarbons and the Strength of The C—C Bond, American Chemical Society, 55(10): 4245- 4247 (1933).
[2] Rice F.O., The Thermal Decomposition of Organic Compounds from The Standpoint of Free Radicals (III): the Calculation of the Products Formed from Paraffin Hydrocarbons, American Chemical Society, 55(1): 3035-3040 (1933).
[3] Yoshiakai H., Shoichi S., Thermal Decomposition of Ethane in Shock Waves, International Journal of Chemical Kinetics, 17(4): 441-453 (1985).
[4] Wang K., Villano S.M., Dean A.M., Fundamentally-Based Kinetic Model for Propene Pyrolysis, Combustion & Flame, 162(12): 4456-4470 (2015).
[5] Wang K., Villano S.M., Dean A.M., Experimental and Kinetic Modeling Study of Butene Isomer Pyrolysis(I): 1- and 2-Butene, Combustion & Flame, 173: 347-369 (2016).
[6] Wang K., Villano S.M., Dean A.M., Experimental and Kinetic Modeling Study of Butene Isomer Pyrolysis(II): Isobutene, Combustion & Flame, 176: 23-37 (2017).
[7] Jan N., Iftikhar A.A., Kinetics of the Gas-Phase Thermal Decomposition of 3-Chloropropene, Chemical Physics Letters, 661: 200–205 (2016).
[8] Jan N., Rameez R., Kinetics of the Uninhibited Reaction of 2-Chloropropene-Part II: Comparison With Inhibited Reaction, Journal of Chemical Society of Pakistan, 37: 649-652 (2015).
[9] Jan N., Iftikhar A.A., Kinetics of the Gas-Phase Thermal Decomposition of 3-Bromopropene, Kinetics and Catalysis, 52: 487-492 (2011).
[10] Ibrahim A.S., Asma A.A., Mathematical Model of Biomass Product Using Gasification Reactor, Iranian Journal of Chemistry and Chemical Engineering (IJCCE), 37(5): 235-246 (2018).
[11] Camp C.E.V., Damme P.S.V., Willems P.A., Clymans P.J., Froment G.F.. Severity in the Pyrolysis of Petroleum Fractions. Fundamentals and Industrial Application, Ind. Eng. Chem. Process Des. Dev., 24(3): 561-570 (1985).
[12] Guillaume D., Vakery E., Verstraete J.J., Surla K., Galtier P., Schweich D. Single Event Kinetic Modelling Without Explicit Generation of Large Networks: Application to Hydrocracking of Long Paraffins, Oil & Gas Science & Technology, 66(3): 399-422 (2011).
[13] Becker P.J., Celse B., Guillaume D., Costa V., Bertier L., Guillon E., Pirngruber G., A Continuous Lumping Model for Hydrocracking on a Zeolite Catalysts: Model Development and Parameter Identification, Fuel, 164: 73-82 (2016).
[14] Gao H., Wang G., Li R., Xu C.M., Gao J.S., Study on the Catalytic Cracking of Heavy Oil by Proper Cut for Higher Conversion and Desirable Products, Energy & Fuels, 26(3): 23275-84 (2012).
[15] Becker P.J., Celse B., Guillaume D., Dulot H., Costa V., Hydrotreatment Modeling for a Variety of VGO Feedstocks: a Continuous Lumping Approach, Fuel, 139(139): 133-143 (2015).
[16] Maarten K.S., Kevin M.V.G., Reyniers M., Marin G.B., First Principle-Based Simulation of Ethane Steam Cracking, American Institute of Chemical Engineers Journal, 57(2): 482-496 (2011).
[17] Goethem M.W.M.V., Barendregt S., Grievink J,
Verheijen P.J.T., Dented M., Ranzid E., A Kinetic Modelling Study of Ethane Cracking for Optimal Ethylene Yield, Chemical Engineering Research & Design, 91(6): 1106-1110 (2013).
[18] Zhang H.M., Lin F., Ren M.Q., Li J.L., Free Radical Models of Small Molecular Alkane Pyrolysis, CIESC Journal, 68(4): 1423-1433 (2017).
[19] Li J.L., Zhang H.M., Li C.X., Et Al. Numerical Simulation on Reaction Mechanism of 1-Butene Pyrolysis, Acta Petrolei Sinica (Petroleum Processing Section), 32(5): 1055-1061 (2016).
[20] Fu X.C., Shen W.X.,” Physical Chemistry”, Higher Education Press, Beijing China (1990).
Iranian Journal of Chemistry and Chemical Engineering
Volume 39, Issue 6 - Serial Number 104
November and December 2020
Pages 9-18

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