Design of Optimum Zeolite Pore System for Central Hydrocracking of Long-Chain n-Alkanes based on a Single-Event Microkinetic Model

Model based catalyst design is an emerging methodology in the development of new catalytic materials with properties tailored to the needs of specific industrial applications. A Single-Event MicroKinetic model (SEMK) was used to assess the hydrocracking behavior of n-dodecane, 4,4,6-trimethyl nonane and 2,5,8-trimethyl nonane, on a non-selective USY zeolite. The differences in cracking pattern exhibited by the various feed molecules provide guidelines for the control of the cracked product distribution through modifications of the zeolite pore structure. The connection of ZSM-22 type channels to the zeolite Y super cage is considered in this work. The percentage of C6 products obtained by central cracking in the chain can be increased from 25% up to 93% by the design of an appropriate zeolite topology combining USY-like super cages with ZSM-22 like channel segments. This is a promising approach for the development of zeolite catalysts for the selective hydrocracking of Fischer Tropsch waxes into middle distillates.

[1]  J. Martens,et al.  A new overgrowth of mazzite on faujasite zeolite crystal investigated by X-ray diffraction and electron microscopy , 2006 .

[2]  P. A. Jacobs.  Carboniogenic activity of zeolites , 1977 .

[3]  J. Vermant,et al.  Design and synthesis of hierarchical materials from ordered zeolitic building units. , 2005, Chemistry.

[4]  P. Jacobs,et al.  Kinetic modeling of pore mouth catalysis in the hydroconversion of n-octane on Pt-H-ZSM-22 , 2003 .

[5]  Guy Marin,et al.  Single-Event Microkinetic Model for Fischer−Tropsch Synthesis on Iron-Based Catalysts , 2008 .

[6]  Guy Marin,et al.  Alkene Protonation Enthalpy Determination from Fundamental Kinetic Modeling of Alkane Hydroconversion on Pt/H–(US)Y-Zeolite , 2001 .

[7]  Frédéric Clerc,et al.  Development of an integrated informatics toolbox: HT kinetic and virtual screening. , 2007, Combinatorial chemistry & high throughput screening.

[8]  G. Marin,et al.  Pore mouth physisorption of alkanes on ZSM-22: estimation of physisorption enthalpies and entropies by additivity method , 2003 .

[9]  P. Jacobs,et al.  Selective conversion of decane into branched isomers: A comparison of platinum/ZSM-22, platinum/ZSM-5 and platinum/USY zeolite catalysts , 1991 .

[10]  P. Jacobs,et al.  Influence of the zeolite composition on the hydro-isomerisation and hydrocracking of alkanes on Pt/USY zeolites: modelling of the reaction kinetics using an adsorption-reaction approach , 2003 .

[11]  Guy Marin,et al.  Microkinetics of methane oxidative coupling , 2008 .

[12]  E. M. Matos,et al.  Modelling and simulation of the hydrocracking of heavy oil fractions , 2000 .

[13]  G. Marin,et al.  Single-Event Rate Parameters for the Hydrocracking of Cycloalkanes on Pt/US-Y Zeolites , 2001 .

[14]  L. Petzold.  Automatic Selection of Methods for Solving Stiff and Nonstiff Systems of Ordinary Differential Equations , 1983 .

[15]  Gilbert F. Froment,et al.  Fundamental kinetic modeling of hydroisomerization and hydrocracking on noble metal-loaded faujasites. 1. Rate parameters for hydroisomerization , 1989 .

[16]  J. W. Ward.  Hydrocracking processes and catalysts , 1993 .

[17]  Julius Scherzer,et al.  Hydrocracking Science and Technology , 1996 .

[18]  H. Robson,et al.  Synthetic Erionite and Selective Hydrocracking , 1971 .

[19]  Venkat Venkatasubramanian,et al.  An Intelligent System for Reaction Kinetic Modeling and Catalyst Design , 2004 .

[20]  P. Jacobs,et al.  Modeling of adsorption and bifunctional conversion of n-alkanes on Pt/H-ZSM-22 zeolite catalyst , 1999 .

[21]  P. Jacobs,et al.  Acid−Metal Balance of a Hydrocracking Catalyst: Ideal versus Nonideal Behavior , 2005 .

[22]  A. Corma,et al.  Determination of the pore topology of zeolite IM-5 by means of catalytic test reactions and hydrocarbon adsorption measurements , 2000 .

[23]  Effect of confinement on the selectivity of hydrocracking , 2004 .

[24]  B. Smit,et al.  Alkane hydrocracking: shape selectivity or kinetics? , 2004 .

[25]  Shakeel Ahmed,et al.  A comparison between β- and USY-zeolite-based hydrocracking catalysts , 2001 .

[26]  P. Jacobs,et al.  Hydrocracking of n-alkane mixtures on Pt/H-Y zeolite : Chain length dependence of the adsorption and the kinetic constants , 1997 .

[27]  P. Jacobs,et al.  Isomerization and hydrocracking of heptane over bimetallic bifunctional PtPd/H-Beta and PtPd/USY zeolite catalysts , 1997 .

[28]  P. Jacobs,et al.  Attempts to rationalize the distribution of hydrocracked products. I qualitative description of the primary hydrocracking modes of long chain paraffins in open zeolites , 1986 .

[29]  Jean-Marc Schweitzer,et al.  A single events kinetic model for the hydrocracking of paraffins in a three-phase reactor , 1999 .

[30]  P. Galtier,et al.  From single events theory to molecular kinetics—application to industrial process modelling , 2003 .

[31]  S. Ernst,et al.  Factors Influencing the Selectivity of Hydrocracking in Zeolites , 1990 .

[32]  P. Jacobs,et al.  n-Alkane hydroconversion on Zeogrid and colloidal ZSM-5 assembled from aluminosilicate nanoslabs of MFI framework type. , 2003, Chemical Communications.

[33]  P. Jacobs,et al.  Evidence for hypocage catalysis in FAU/ EMT zeolites derived from isomerisation and hydrocracking of heptadecane , 1993 .

[34]  A. Corma,et al.  Hydrocracking catalysts based on the new large-pore ITQ-21 zeolite for maximizing diesel products , 2004 .

[35]  P. Jacobs,et al.  Attempts to rationalize the distribution of hydrocracked products. II. Relative rates of primary hydrocracking modes of long chain paraffins in open zeolites , 1986 .

[36]  M. Ramos,et al.  Hydroisomerization of different refinery naphtha streams by using a beta zeolite catalyst , 2008 .

[37]  P. Jacobs,et al.  Alkylcarbenium Ion Concentrations in Zeolite Pores During Octane Hydrocracking on Pt/H-USY Zeolite , 2004 .

[38]  P. Jacobs,et al.  A fundamental kinetic model for hydrocracking of C8 to C12 alkanes on Pt/US-Y zeolites , 2000 .

[39]  B. Smit,et al.  The Shape Selectivity of Paraffin Hydroconversion on TON-, MTT-, and AEL-Type Sieves , 1999 .

[40]  Rafael Castro-Linares,et al.  Trajectory tracking for non-holonomic cars: A linear approach to controlled leader-follower formation , 2010, 49th IEEE Conference on Decision and Control (CDC).

[41]  P. Jacobs,et al.  Evidences for pore mouth and key–lock catalysis in hydroisomerization of long n-alkanes over 10-ring tubular pore bifunctional zeolites , 2001 .

[42]  G. Froment,et al.  Single-Event Rate Parameters for Paraffin Hydrocracking on a Pt/US-Y Zeolite , 1995 .

[43]  P. Jacobs,et al.  High-Temperature Low-Pressure Adsorption of Branched C5−C8 Alkanes on Zeolite Beta, ZSM-5, ZSM-22, Zeolite Y, and Mordenite , 1998 .

[44]  A. Perrotta,et al.  Selective Hydrocracking with Ferrierite-Based Catalysts , 1975 .

[45]  C. R. Kennedy,et al.  Impact of catalyst acid/metal balance in hydroisomerization of normal paraffins , 1993 .

[46]  Gilbert F. Froment,et al.  Single-event kinetics of catalytic cracking , 1993 .

[47]  L. Pellegrini,et al.  Modelling of hydrocracking with vapour–liquid equilibrium , 2008 .

[48]  P. Galtier,et al.  Single-event microkinetics for coke formation during the catalytic cracking of (cyclo)alkane/1-octene mixtures , 2007 .

[49]  E. Gaigneaux,et al.  Skeletal isomerization of octadecane on bifunctional ZSM-23 zeolite catalyst , 2005 .

[50]  G. Marin,et al.  Pore mouth versus intracrystalline adsorption of isoalkanes on ZSM-22 and ZSM-23 zeolites under vapour and liquid phase conditions. , 2003, Chemical communications.

[51]  M. A. Baltanás,et al.  Modelling of n-hexadecane hydroisomerization and hydrocracking reactions on a Mo/Hβ-alumina Bi-functional catalyst, using the single event concept , 2004 .

[52]  V. Valtchev,et al.  Core–Shell Zeolite Microcomposites , 2005 .

[53]  G. Baron,et al.  Adsorption of normal and branched paraffins in faujasite zeolites NaY, HY, Pt/NaY and USY , 1997 .

[54]  G. Marin,et al.  Kinetic Modeling of the Conversion of Complex Hydrocarbon Feedstocks by Acid Catalysts , 2003 .

[55]  P. Jacobs,et al.  Relumped single-event microkinetic model for alkane hydrocracking on shape-selective catalysts: catalysis on ZSM-22 pore mouths, bridge acid sites and micropores , 2004 .

[56]  Y. Murakami,et al.  A shape-selective platinum-loaded mordenite catalyst for the hydrocracking of paraffins by the chemical vapour deposition of silicon alkoxide , 1985 .

[57]  D. Golden,et al.  Additivity rules for the estimation of thermochemical properties , 1969 .

[58]  E. Gaigneaux,et al.  Formation of ZSM-22 zeolite catalytic particles by fusion of elementary nanorods. , 2007, Chemistry.

[59]  P. Jacobs,et al.  Molecular Shape Selectivity of EuO Zeolites , 1995 .

[60]  G. Froment,et al.  Kinetic Modeling of Paraffins Hydrocracking based upon Elementary Steps and the Single Event Concept. , 1999 .