Molar Kinetics in Catalytic Hydrocracking of Asphaltenes

Abstract:

The hydrocracking of a pentane-insoluble asphaltene over NiMo/γ-Al₂O₃ was investigated in a microbatch reactor at 703 K. The cracking kinetics of the asphaltene was analyzed on a total molar basis. The first-order kinetics fits the experimental data in reaction times ≤30 min adequately, to give the rate constant of 0.0498 min^-1. For reaction times over 30 min, however, secondary reactions such as coke formation could become significant. The formation probability of gas products decreases from the initial value of circa 0.8 to a stable level of 0.6 in 30 min, and the formation probability of liquid products increases from 0.2 to 0.4 accordingly.

• Periodical: Advanced Materials Research (Volumes 455-456)
• Pages: 533-539
• DOI: https://doi.org/10.4028/www.scientific.net/AMR.455-456.533
• Online since: January 2012
• Authors: Sheng Jian Zhang, Ying Xian Zhao
• Keywords: Asphaltenes, Hydrocracking, Kinetic, NiMo/γ-Al₂O₃

References

[1] J.C. Ravey, G. Ducouret, and D. Espinant, Asphaltene macrostructure by small angle neutron scattering., Fuel , vol. 67, pp.1560-1567, (1988).

DOI: 10.1016/0016-2361(88)90076-2

[2] D.A. Storm, E.Y. Shue, M.M. DeTar, and R.J. Barresi, A comparison of the macrostructure of Ratawi asphaltenes in toluene and vacuum residue, Energy & Fuels, vol. 8, no. 3, pp.567-569, (1994).

DOI: 10.1021/ef00045a008

[3] B.A. Waston, and M.A. Barteau, Imaging of petroleum asphaltenes using scanning tunneling microscopy, Ind. Eng. Chem. Res., vol. 33, no. 10, pp.2358-2363, (1994).

DOI: 10.1021/ie00034a015

[4] R.M. Balabin, and R.Z. Syunyaev, Petroleum resins adsorption onto quartz sand: Near infrared (NIR) spectroscopy study, J. Colloid and Interface Science, vol. 318, pp.167-174, (2008).

DOI: 10.1016/j.jcis.2007.10.045

[5] E.L. Nordgard, G. Sorland, and J. Sjoblom, Behavior of asphaltene model compounds at W/O interfaces , Langmuir, vol. 26, pp.2352-2360, (2010).

[6] S.E. Moschopedis, J.F. Fryer, and J.G. Speight, Investigation of asphaltene molecular weights, Fuel, vol. 55, pp.227-32, (1976).

DOI: 10.1016/0016-2361(76)90093-4

[7] R.Z. Syunyaev, and R.M. Balabin, Polarization of Fluorescence of asphaltene containing systems, J. Dispersion Science and Technology, vol. 29, pp.1505-1514, (2008).

DOI: 10.1080/01932690802316868

[8] F. Trejo, J. Ancheyta, T.J. Morgan, A.A. Herod, and R. Kandiyoti, Characterization of asphaltenes from hydrotreated products by SEC, LDMS, MALDI, NMR, and XRD , Energy & Fuels, vol. 21, pp.2121-2128, (2007).

DOI: 10.1021/ef060621z

[9] J.G. Speight, and S.E. Moschopedis, On the molecular nature of petroleum asphaltenes, Arab. J. Sci. Eng., vol. 19, pp.335-343, (1994).

[10] A. Marafi, A. Stanislaus, and E. Furimsky, Kinetics and modeling of petroleum residues hydroprocessing, Catalysis Review, vol. 52, pp.204-324, (2010).

DOI: 10.1080/01614941003720167

[11] C.H. Bartholomew, Catalyst Deactivation in Hydrotreating of Residua: A Review, in Catalytic Hydroprocessing of Petroleum and Distillates, M.C. Oballa and S.S. Shih, Eds. New York: Marcel Dekker; 1994, pp.1-32.

DOI: 10.1201/9781003067306-1

[12] J.M. Oelderik, S.T. Sie, and D. Bode, Progress in the catalysis of the upgrading of petroleum residue: A review of 25 years of R&D on Shell's residue hydroconversion technology, Appl. Catal., vol. 47, no. 1, pp.1-24, (1989).

DOI: 10.1016/s0166-9834(00)83258-3

[13] M.R. Gray, Y.X. Zhao, C.M. McKnight, D.A. Komar and J.D. Carruthers, Coking of hydroprocessing Catalyst by Residue Fractions of Bitumen, Energy and Fuels, vol. 13, pp.1037-1045, (1999).

DOI: 10.1021/ef9900076

[14] J.A. Gearhart, and L. Gatwin, ROSE process improve resid feed , Hydrocarbon Process, vol. 55 , no. 5, pp.125-128, (1976).

[15] Y.X. Zhao, and F. Wei, Simultaneous removal of asphaltenes and water from water-in-bitumen emulsionＩ. Fundamental development, Fuel Proc. Tech., vol. 89, pp.933-940, (2008).

DOI: 10.1016/j.fuproc.2008.03.008

[16] I.E. Wiehe, A phase-separation kinetic model for coke formation, Ind. Eng. Chem. Res., vol. 32, no. 11, pp.2447-2454, (1993).

DOI: 10.1021/ie00023a001

[17] M.T. Martinez, A.M. Benito, and M.A. Callejas, Thermal cracking of coal residues: kinetics of asphaltene decomposition, Fuel, vol. 76, no. 9, pp.871-877, (1997).

DOI: 10.1016/s0016-2361(97)00048-3

[18] Y.X. Zhao, and M.R. Gray, Molar kinetics and selectivity in cracking of Athabasca asphaltenes, Energy & Fuels, vol. 15, no. 3, 751-755, (2001).

DOI: 10.1021/ef000286t

[19] K. Usui, K. Kidena, S. Murata, M. Nomura , and W. Trisunaryanti, Catalytic hydrocracking of petroleum-derived asphaltenes by transition metal-loaded zeolite catalyst, Fuel, vol. 83, pp.1899-1906, (2004).

DOI: 10.1016/j.fuel.2003.08.023

[20] T. Takatsuka, R. Kajiyama, H. Hashimoto, I. Matsuo, and S. Miwa, A practical model of thermal cracking of residual, oil J Chem Eng Japan , vol. 22, pp.304-310, (1989).

DOI: 10.1252/jcej.22.304