N-OCTANE HYDROCRACKING KINETIC MODELING BASED ON SINGLE EVENT METHOD

Abstract

Abstract: The n-octane hydrocracking kinetic modeling was studied over a Ni-W catalyst. The kinetic data were obtained in a tubular fixed-bed reactor. The condensed liquids and non-condensable gas components were analyzed by offline and online GCs, respectively. The reaction network was built based on the carbenium-ion mechanism. PCP isomerization and β-scission were assumed as rate determining steps. With the application of Single Event method, the number of independent parameters was reduced. The genetic algorithm and the Marquardt algorithm were used for 12 parameters estimation. The calculated rate values are in agreement with the experimental values. The parameters can be used in kinetic studies of FT wax hydrocracking and other materials with high carbon because of the intrinsic property of the Single Event based values.

References

[1] Froment G F, Kinetics of the hydroisomerization and hydrocracking of paraffins on a platinum containing bifunctional Y-zeolite[J]. Catalysis Today, 1987,1: 455-473.
[2] Froment G F, Fundamental kinetic modeling of catalytic hydrocarbon conversion processes[J]. Reviews in Chemical Engineering, 2013,29: 385-412.
[3] Svoboda G D, Vynckier E, Debrabandere B, Froment G F, Single-event rate parameters for paraffin hydrocracking on a Pt/US-Y zeolite[J]. Industrial & engineering chemistry research, 1995,34: 3793-3800.
[4] Schweitzer J M, Galtier P, Schweich D, A single events kinetic model for the hydrocracking of paraffins in a three-phase reactor[J]. hemical engineering science, 1999,54: 2441-2452.
[5] Martens G G, Thybaut J W, Marin G B, Single-event rate parameters for the hydrocracking of cycloalkanes on Pt/US-Y zeolites[J]. Industrial & engineering chemistry research, 2001,40: 1832-1844.
[6] Guillaume D, Surla K, Galtier P, From single events theory to molecular kinetics—application to industrial process modelling[J]. hemical engineering science, 2003,58: 4861-4869.
[7] Surla K, Vleeming H, Guillaume D, Galtier P, A single events kinetic model: n-butane isomerization[J]. Chem Eng Sci, 2004,59: 4773-4779.
[8] Kumar H, Froment G F, A generalized mechanistic kinetic model for the hydroisomerization and hydrocracking of long-chain paraffins[J]. Industrial & engineering chemistry research, 2007,46: 4075-4090.
[9] Froment G F, Single event kinetic modeling of complex catalytic processes[J]. Catalysis Review, 2005,47: 83-124.
[10] Froment G F, Kinetic modeling of acid-catalyzed oil refining processes[J]. Catalysis Today, 1999,52: 153-163.
[11] Kumar H, Froment G F, Mechanistic kinetic modeling of the hydrocracking of complex feedstocks, such as vacuum gas oils[J]. Industrial & engineering chemistry research,2007, 46: 5881-5897.
[12] 石铭亮, 翁惠新, 单事件方法在酸催化复杂反应动力学领域的研究进展[J]. 化工进展, 2008: 1017-1021.
[13] Baltanas M A, Van Raemdonck K K, Froment G F, Mohedas S R, Fundamental kinetic modeling of hydroisomerization and hydrocracking on noble metal-loaded faujasites. 1. Rate parameters for hydroisomerization[J]. Industrial & engineering chemistry research, 1989,28: 899-910.
[14] Evans M G, Polanyi M, Inertia and driving force of chemical reactions[J]. Transactions of the Faraday Society, 1938,34: 0011-0023.
[15] Martinis J M, Froment G F, Alkylation on solid acids. Part 2. Single-event kinetic modeling[J]. Industrial & engineering chemistry research, 2006,45: 954-967.
[16] Muller C, Scacchi G, C?me G M, A topological method for determining the external symmetry number of molecules[J]. Computers & chemistry, 1991,15: 17-27.
[17] Da?vila G Y O, Martinis J M, Graph-based method for the automated calculation of thermochemical properties of components and intermediate species in the hydroprocessing of light oil fractions[J]. Industrial & engineering chemistry research, 2011,50: 12774-12783.
[18] Park T Y, Froment G F, Kinetic modeling of the methanol to olefins process. 1. Model formulation[J]. Industrial & engineering chemistry research, 2001,40: 4172-4186.