Theoretical Simulation of n-Alkane Cracking on Zeolites

Swisher, Joseph A.; Hansen, Niels; Maesen, Theo; Keil, Frerich J.; Smit, Berend; Bell, Alexis T.

doi:10.1021/jp101262y

Theoretical Simulation of n-Alkane Cracking on Zeolites

Journal Article · Fri May 14 00:00:00 EDT 2010 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/jp101262y· OSTI ID:1571005

Swisher, Joseph A. ^[1]; Hansen, Niels ^[2]; Maesen, Theo ^[3]; Keil, Frerich J. ^[2]; Smit, Berend ^[1]; Bell, Alexis T. ^[1]

Univ. of California, Berkeley, CA (United States)
Hamburg Univ. of Technology, Hamburg (Germany)
Chevron Energy Technology Company, Richmond, CA (United States)

The kinetics of alkane cracking in zeolites MFI and FAU have been simulated theoretically from first principles. The apparent rate coefficient for alkane cracking was described as the product of the number of alkane molecules per unit mass of zeolite that are close enough to a Brønsted-acid site to be in the reactant state for the cleavage of a specific C-C bond and the intrinsic rate coefficient for the cleavage of that bond. Adsorption thermodynamics were calculated by Monte Carlo simulation and the intrinsic rate coefficient for alkane cracking was determined from density functional theory calculations combined with absolute rate theory. The effects of functional, basis set, and cluster size on the intrinsic activation energy for alkane cracking were investigated. The dependence of the apparent rate coefficient on the carbon number for the cracking of C₃-C₆ alkanes on MFI and FAU determined by simulation agrees well with experimental observation, but the absolute values of the apparent rate coefficients are a factor of 10 to 100 smaller than those observed. This discrepancy is attributed to the use of a small T5 cluster representation of the Brønsted-acid site. Limited calculations for propane and butane cracking on MFI reveal that significantly better agreement between prediction and observation is achieved using a T23 cluster for both the apparent rate coefficient and the apparent activation energy. The apparent rate coefficients for alkane cracking are noticeably larger for MFI than FAU, in agreement with recent findings reported in the experimental literature.

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC); Deutsche Forschungsgemeinschaft (DFG)

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 1571005

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 22 Vol. 114; ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

References (73)

United Atom Force Field for Alkanes in Nanoporous Materials Dubbeldam, D.; Calero, S.; Vlugt, T. J. H. The Journal of Physical Chemistry B, Vol. 108, Issue 33 https://doi.org/10.1021/jp0376727	journal	August 2004
The effect of sodium poisoning on dealuminated Y-type zeolites Fritz, P. Journal of Catalysis, Vol. 118, Issue 1 https://doi.org/10.1016/0021-9517(89)90303-5	journal	July 1989
Efficient molecular numerical integration schemes Treutler, Oliver; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 102, Issue 1 https://doi.org/10.1063/1.469408	journal	January 1995
First-principles-based kinetic Monte Carlo simulation of the selective hydrogenation of acetylene over Pd(111) Mei, D.; Sheth, P.; Neurock, M. Journal of Catalysis, Vol. 242, Issue 1 https://doi.org/10.1016/j.jcat.2006.05.009	journal	August 2006
Crystal structure and structure-related properties of ZSM-5 Olson, D. H.; Kokotailo, G. T.; Lawton, S. L. The Journal of Physical Chemistry, Vol. 85, Issue 15 https://doi.org/10.1021/j150615a020	journal	July 1981
The influence of framework and nonframework aluminum on the acidity of high-silica, proton-exchanged FAU-framework zeolites Beyerlein, R. A.; McVicker, G. B.; Yacullo, L. N. The Journal of Physical Chemistry, Vol. 92, Issue 7 https://doi.org/10.1021/j100318a051	journal	April 1988
Observation of a compensation relation for n-hexane adsorption in zeolites with different structures: implications for catalytic activity Ramachandran, C.; Williams, B.; Vanbokhoven, J. Journal of Catalysis, Vol. 233, Issue 1 https://doi.org/10.1016/j.jcat.2005.04.017	journal	July 2005
Prediction of preferred proton locations in HMFI/benzene complexes by molecular mechanics calculations. Comparison with nmr, structural and calorimetric results Mentzen, B. F.; Sacerdote-peronnet, M. Materials Research Bulletin, Vol. 29, Issue 12 https://doi.org/10.1016/0025-5408(94)90159-7	journal	December 1994
A Density Functional That Accounts for Medium-Range Correlation Energies in Organic Chemistry Zhao, Yan; Truhlar, Donald G. Organic Letters, Vol. 8, Issue 25 https://doi.org/10.1021/ol062318n	journal	December 2006
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
The influence of extraframework aluminum on H-FAU catalyzed cracking of light alkanes Narbeshuber, T. F.; Brait, A.; Seshan, K. Applied Catalysis A: General, Vol. 146, Issue 1 https://doi.org/10.1016/0926-860X(96)00289-X	journal	October 1996
RI-MP2: optimized auxiliary basis sets and demonstration of efficiency Weigend, Florian; Häser, Marco; Patzelt, Holger Chemical Physics Letters, Vol. 294, Issue 1-3 https://doi.org/10.1016/S0009-2614(98)00862-8	journal	September 1998
Gaussian basis sets of quadruple zeta valence quality for atoms H–Kr Weigend, Florian; Furche, Filipp; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 119, Issue 24 https://doi.org/10.1063/1.1627293	journal	December 2003
The active site of acidic aluminosilicate catalysts Haag, W. O.; Lago, R. M.; Weisz, P. B. Nature, Vol. 309, Issue 5969 https://doi.org/10.1038/309589a0	journal	June 1984
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Integral approximations for LCAO-SCF calculations Vahtras, O.; Almlöf, J.; Feyereisen, M. W. Chemical Physics Letters, Vol. 213, Issue 5-6 https://doi.org/10.1016/0009-2614(93)89151-7	journal	October 1993
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr Schäfer, Ansgar; Huber, Christian; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 100, Issue 8 https://doi.org/10.1063/1.467146	journal	April 1994
Computational modeling of catalytic reactivity Van santen, R. A.; Offermans, W. K.; Malek, K. Molecular Simulation, Vol. 33, Issue 4-5 https://doi.org/10.1080/08927020601134969	journal	April 2007
Fully optimized contracted Gaussian basis sets for atoms Li to Kr Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 97, Issue 4 https://doi.org/10.1063/1.463096	journal	August 1992
Density Functional Theory Study of Proton Mobility in Zeolites: Proton Migration and Hydrogen Exchange in ZSM-5 Ryder, Jason A.; Chakraborty, Arup K.; Bell, Alexis T. The Journal of Physical Chemistry B, Vol. 104, Issue 30 https://doi.org/10.1021/jp9943427	journal	August 2000
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Ab initio molecular dynamics for open-shell transition metals Kresse, G.; Hafner, J. Physical Review B, Vol. 48, Issue 17 https://doi.org/10.1103/PhysRevB.48.13115	journal	November 1993
Some applications of the transition state method to the calculation of reaction velocities, especially in solution Evans, M. G.; Polanyi, M. Transactions of the Faraday Society, Vol. 31 https://doi.org/10.1039/tf9353100875	journal	January 1935
Geometry optimizations with the coupled-cluster model CC2 using the resolution-of-the-identity approximation Hättig, Christof The Journal of Chemical Physics, Vol. 118, Issue 17 https://doi.org/10.1063/1.1564061	journal	May 2003
Treating dispersion effects in extended systems by hybrid MP2:DFT calculations—protonation of isobutene in zeolite ferrierite Tuma, Christian; Sauer, Joachim Phys. Chem. Chem. Phys., Vol. 8, Issue 34 https://doi.org/10.1039/B608262A	journal	January 2006
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Coulombic potential energy integrals and approximations Whitten, J. L. The Journal of Chemical Physics, Vol. 58, Issue 10 https://doi.org/10.1063/1.1679012	journal	May 1973
Monomolecular and bimolecular mechanisms of paraffin cracking: n-butane cracking catalyzed by HZSM-5 Krannila, H. Journal of Catalysis, Vol. 135, Issue 1 https://doi.org/10.1016/0021-9517(92)90273-K	journal	May 1992
Computational Modelling of Nanoporous Materials Vayssilov, Georgi N.; Aleksandrov, Hristiyan A.; Petrova, Galina P. Ordered Porous Solids https://doi.org/10.1016/B978-0-444-53189-6.00008-1	book	February 2009
Benchmark Data for Interactions in Zeolite Model Complexes and Their Use for Assessment and Validation of Electronic Structure Methods Zhao, Yan; Truhlar, Donald G. The Journal of Physical Chemistry C, Vol. 112, Issue 17 https://doi.org/10.1021/jp7112363	journal	May 2008
Distributed memory parallel implementation of energies and gradients for second-order Møller–Plesset perturbation theory with the resolution-of-the-identity approximation Hättig, Christof; Hellweg, Arnim; Köhn, Andreas Physical Chemistry Chemical Physics, Vol. 8, Issue 10 https://doi.org/10.1039/b515355g	journal	January 2006
Hydrocarbon conversion with zeolites — a clair-obscur Rigutto, M. S. Zeolites and related materials: Trends, targets and challenges Proceedings of the 4th International FEZA Conference https://doi.org/10.1016/S0167-2991(08)80150-4	book	January 2008
The Haag–Dessau mechanism of protolytic cracking of alkanes Kotrel, S.; Knözinger, H.; Gates, B. C. Microporous and Mesoporous Materials, Vol. 35-36 https://doi.org/10.1016/S1387-1811(99)00204-8	journal	April 2000
Adsorption Equilibria of C ₁ to C ₄ Alkanes, CO ₂ , and SF ₆ on Silicalite Sun, Matthew S.; Shah, D. B.; Xu, Heather H. The Journal of Physical Chemistry B, Vol. 102, Issue 8 https://doi.org/10.1021/jp9730196	journal	February 1998
Catalytic activity of Brønsted acid sites in zeolites: Intrinsic activity, rate-limiting step, and influence of the local structure of the acid sites Xu, B.; Sievers, C.; Hong, S. Journal of Catalysis, Vol. 244, Issue 2 https://doi.org/10.1016/j.jcat.2006.08.022	journal	December 2006
Ab Initio and Density Functional Study of the Activation Barrier for Ethane Cracking in Cluster Models of Zeolite H-ZSM-5 Zygmunt, S. A.; Curtiss, L. A.; Zapol, P. The Journal of Physical Chemistry B, Vol. 104, Issue 9 https://doi.org/10.1021/jp993194h	journal	February 2000
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions Krishnan, R.; Binkley, J. S.; Seeger, R. The Journal of Chemical Physics, Vol. 72, Issue 1 https://doi.org/10.1063/1.438955	journal	January 1980
Observation of a compensation relation for monomolecular alkane cracking by zeolites: the dominant role of reactant sorption van Bokhoven, Jeroen A.; Williams, Bryce A.; Ji, W. Journal of Catalysis, Vol. 224, Issue 1 https://doi.org/10.1016/j.jcat.2004.02.003	journal	May 2004
Entropy considerations in monomolecular cracking of alkanes on acidic zeolites Bhan, A.; Gounder, R.; Macht, J. Journal of Catalysis, Vol. 253, Issue 1 https://doi.org/10.1016/j.jcat.2007.11.003	journal	January 2008
Chemistry of Cracking Catalysts Thomas, Charles L. Industrial & Engineering Chemistry, Vol. 41, Issue 11 https://doi.org/10.1021/ie50479a042	journal	November 1949
The Activated Complex in Chemical Reactions Eyring, Henry The Journal of Chemical Physics, Vol. 3, Issue 2 https://doi.org/10.1063/1.1749604	journal	February 1935
Quantum Chemical Modeling of Zeolite-Catalyzed Methylation Reactions: Toward Chemical Accuracy for Barriers Svelle, Stian; Tuma, Christian; Rozanska, Xavier Journal of the American Chemical Society, Vol. 131, Issue 2 https://doi.org/10.1021/ja807695p	journal	January 2009
Intrinsic Catalytic Cracking Activity of Hexane over H−ZSM-5, H−β and H−Y Zeolites Kotrel, S.; Rosynek, M. P.; Lunsford, J. H. The Journal of Physical Chemistry B, Vol. 103, Issue 5 https://doi.org/10.1021/jp982538l	journal	February 1999
Acidity Differences between Inorganic Solids Induced by Their Framework Structure. A Combined Quantum Mechanics/Molecular Mechanics ab Initio Study on Zeolites Brändle, Martin; Sauer, Joachim Journal of the American Chemical Society, Vol. 120, Issue 7 https://doi.org/10.1021/ja9729037	journal	February 1998
The crystal structure of dehydrated NaX Olson, David H. Zeolites, Vol. 15, Issue 5 https://doi.org/10.1016/0144-2449(95)00029-6	journal	June 1995
Density-functional exchange-energy approximation with correct asymptotic behavior Becke, A. D. Physical Review A, Vol. 38, Issue 6 https://doi.org/10.1103/PhysRevA.38.3098	journal	September 1988
Crystal Structure of Dehydrated CsZSM-5 (5.8Al): Evidence for Nonrandom Aluminum Distribution ^† Olson, David H.; Khosrovani, Nazy; Peters, Alan W. The Journal of Physical Chemistry B, Vol. 104, Issue 20 https://doi.org/10.1021/jp000417r	journal	May 2000
High-Temperature Low-Pressure Adsorption of Branched C ₅ −C ₈ Alkanes on Zeolite Beta, ZSM-5, ZSM-22, Zeolite Y, and Mordenite Denayer, Joeri F.; Souverijns, Wim; Jacobs, Pierre A. The Journal of Physical Chemistry B, Vol. 102, Issue 23 https://doi.org/10.1021/jp980674k	journal	May 1998
Applications of molecular modeling in heterogeneous catalysis research Broadbelt, Linda J.; Snurr, Randall Q. Applied Catalysis A: General, Vol. 200, Issue 1-2 https://doi.org/10.1016/S0926-860X(00)00648-7	journal	August 2000
Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18 McLean, A. D.; Chandler, G. S. The Journal of Chemical Physics, Vol. 72, Issue 10, p. 5639-5648 https://doi.org/10.1063/1.438980	journal	May 1980
Analysis of Diffusion Limitation in the Alkylation of Benzene over H-ZSM-5 by Combining Quantum Chemical Calculations, Molecular Simulations, and a Continuum Approach Hansen, N.; Krishna, R.; van Baten, J. M. The Journal of Physical Chemistry C, Vol. 113, Issue 1 https://doi.org/10.1021/jp8073046	journal	December 2008
Ammonia Synthesis from First-Principles Calculations Honkala, K. Science, Vol. 307, Issue 5709 https://doi.org/10.1126/science.1106435	journal	January 2005
An algorithm for the location of transition states Baker, Jon Journal of Computational Chemistry, Vol. 7, Issue 4 https://doi.org/10.1002/jcc.540070402	journal	August 1986
Monomolecular Conversion of Light Alkanes over H-ZSM-5 Narbeshuber, T. F.; Vinek, H.; Lercher, J. A. Journal of Catalysis, Vol. 157, Issue 2 https://doi.org/10.1006/jcat.1995.1304	journal	December 1995
Alkane hydrocracking: shape selectivity or kinetics? Maesen, T. Journal of Catalysis, Vol. 221, Issue 1 https://doi.org/10.1016/j.jcat.2003.07.003	journal	January 2004
Adsorption and cracking of n-alkanes over ZSM-5: Negative activation energy of reaction Wei, James Chemical Engineering Science, Vol. 51, Issue 11 https://doi.org/10.1016/0009-2509(96)00187-X	journal	June 1996
Design of Density Functionals That Are Broadly Accurate for Thermochemistry, Thermochemical Kinetics, and Nonbonded Interactions Zhao, Yan; Truhlar, Donald G. The Journal of Physical Chemistry A, Vol. 109, Issue 25 https://doi.org/10.1021/jp050536c	journal	June 2005
Solid-acid-catalyzed alkane cracking mechanisms: evidence from reactions of small probe molecules Jentoft, F. C.; Gates, B. C. Topics in Catalysis, Vol. 4, Issue 1/2, p. 1-13 https://doi.org/10.1023/A:1019184004885	journal	November 1997
Monomolecular cracking of n-hexane on Y, MOR, and ZSM-5 zeolites Babitz, S. M.; Williams, B. A.; Miller, J. T. Applied Catalysis A: General, Vol. 179, Issue 1-2 https://doi.org/10.1016/S0926-860X(98)00301-9	journal	April 1999
Correlation of the cracking activity with solid acidity and adsorption property on zeolites Katada, Naonobu; Suzuki, Katsuki; Noda, Takayuki Applied Catalysis A: General, Vol. 373, Issue 1-2 https://doi.org/10.1016/j.apcata.2009.11.022	journal	January 2010
Understanding Diffusion in Nanoporous Materials Beerdsen, E.; Dubbeldam, D.; Smit, B. Physical Review Letters, Vol. 96, Issue 4 https://doi.org/10.1103/PhysRevLett.96.044501	journal	January 2006
Design of Density Functionals by Combining the Method of Constraint Satisfaction with Parametrization for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions Zhao, Yan; Schultz, Nathan E.; Truhlar, Donald G. Journal of Chemical Theory and Computation, Vol. 2, Issue 2 https://doi.org/10.1021/ct0502763	journal	January 2006
H−ZSM-5 Modified Zeolite: Quantum Chemical Models of Acidic Sites Barone, Giampaolo; Casella, Girolamo; Giuffrida, Sergio The Journal of Physical Chemistry C, Vol. 111, Issue 35 https://doi.org/10.1021/jp066652c	journal	August 2007
Self-consistent molecular Hartree—Fock—Slater calculations I. The computational procedure Baerends, E. J.; Ellis, D. E.; Ros, P. Chemical Physics, Vol. 2, Issue 1 https://doi.org/10.1016/0301-0104(73)80059-X	journal	September 1973
Understanding cage effects in the n-alkane conversion on zeolites Maesen, T.; Beerdsen, E.; Calero, S. Journal of Catalysis, Vol. 237, Issue 2 https://doi.org/10.1016/j.jcat.2005.11.007	journal	January 2006
A growing string method for determining transition states: Comparison to the nudged elastic band and string methods Peters, Baron; Heyden, Andreas; Bell, Alexis T. The Journal of Chemical Physics, Vol. 120, Issue 17 https://doi.org/10.1063/1.1691018	journal	May 2004
Adsorption and reaction of organic molecules on solid surfaces – ab-initio density functional investigations Hafner, Jürgen Monatshefte für Chemie - Chemical Monthly, Vol. 139, Issue 4 https://doi.org/10.1007/s00706-007-0828-6	journal	March 2008
Nitrous Oxide Decomposition over Fe-ZSM-5 in the Presence of Nitric Oxide: A Comprehensive DFT Study Heyden, Andreas; Hansen, Niels; Bell, Alexis T. The Journal of Physical Chemistry B, Vol. 110, Issue 34 https://doi.org/10.1021/jp062814t	journal	August 2006
Catalytic and Thermal Cracking of Pure Hydrocarbons: Mechanisms of Reaction Greensfelder, B. S.; Voge, H. H.; Good, G. M. Industrial & Engineering Chemistry, Vol. 41, Issue 11 https://doi.org/10.1021/ie50479a043	journal	November 1949
Alkane sorption in molecular sieves: The contribution of ordering, intermolecular interactions, and sorption on Brønsted acid sites Eder, Florian; Lercher, Johannes A. Zeolites, Vol. 18, Issue 1 https://doi.org/10.1016/S0144-2449(96)00127-3	journal	January 1997
Electronic structure calculations on workstation computers: The program system turbomole Ahlrichs, Reinhart; Bär, Michael; Häser, Marco Chemical Physics Letters, Vol. 162, Issue 3 https://doi.org/10.1016/0009-2614(89)85118-8	journal	October 1989
Density Functionals with Broad Applicability in Chemistry Zhao, Yan; Truhlar, Donald G. Accounts of Chemical Research, Vol. 41, Issue 2 https://doi.org/10.1021/ar700111a	journal	February 2008

Similar Records

Theoretical Analysis of the Influence of Pore Geometry on Monomolecular Cracking and Dehydrogenation of n -Butane in Brønsted Acidic Zeolites

Journal Article · Tue Feb 28 23:00:00 EST 2017 · ACS Catalysis · OSTI ID:1571082

Understanding Brønsted-Acid Catalyzed Monomolecular Reactions of Alkanes in Zeolite Pores by Combining Insights from Experiment and Theory

Journal Article · Wed Dec 13 23:00:00 EST 2017 · ChemPhysChem · OSTI ID:1571097

Theoretical Simulation of n-Alkane Cracking on Zeolites

Citation Formats

References (73)

Similar Records

Related Subjects