Mechanistic Aspects of the Zeolite Catalyzed Methylation of Alkenes and Aromatics with Methanol: A Review

Alkylation and methylation are important reactions in industrial zeolite catalyzed hydrocarbon transformation processes. This contribution compiles the present knowledge concerning the reaction mechanism of zeolite catalyzed methylation of alkenes and aromatics, based on insights obtained using spectroscopy, quantum chemistry, and kinetic measurements. A central issue is to discuss the potential role surface bound methoxy group intermediates.

[1]  S. Blaszkowski,et al.  Theoretical Study of the Mechanism of Surface Methoxy and Dimethyl Ether Formation from Methanol Catalyzed by Zeolitic Protons , 1997 .

[2]  G. Marin,et al.  Understanding the failure of direct C-C coupling in the zeolite-catalyzed methanol-to-olefin process. , 2006, Angewandte Chemie.

[3]  G. Ertl,et al.  Handbook of heterogeneous catalysis - second, completely revised and enlarged edition - volume 6 , 2009 .

[4]  K. Lillerud,et al.  Conversion of methanol into hydrocarbons over zeolite H-ZSM-5: ethene formation is mechanistically separated from the formation of higher alkenes. , 2006, Journal of the American Chemical Society.

[5]  A. Bhan,et al.  A link between reactivity and local structure in acid catalysis on zeolites. , 2008, Accounts of Chemical Research.

[6]  J. Lercher,et al.  Coadsorption of toluene and methanol on HZSM-5 zeolites , 1991 .

[7]  Weiguo Song,et al.  The mechanism of methanol to hydrocarbon catalysis. , 2003, Accounts of chemical research.

[8]  M. Payne,et al.  In Situ Study of Reactive Intermediates of Methanol in Zeolites from First Principles Calculations , 1997 .

[9]  M. Payne,et al.  Methanol Adsorption in ZeolitesA First-Principles Study , 1996 .

[10]  T. Romotowski,et al.  Alkylation of benzene with methanol on zeolites: infrared spectroscopy studies , 1993 .

[11]  U. Olsbye,et al.  The conversion of chloromethane to light olefins over SAPO-34: The influence of dichloromethane addition , 2009 .

[12]  B. Arstad,et al.  A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites , 2003 .

[13]  Michel Waroquier,et al.  First principle kinetic studies of zeolite-catalyzed methylation reactions. , 2011, Journal of the American Chemical Society.

[14]  M. Payne,et al.  First principles calculation of the free energy barrier for the reaction of methanol in a zeolite catalyst , 2001 .

[15]  A. Halgeri,et al.  Kinetics of toluene alkylation with methanol on HZSM-8 zeolite catalyst , 1989 .

[16]  S. Al-Khattaf,et al.  Kinetics of Toluene Methylation over ZSM-5 Catalyst in a Riser Simulator , 2008 .

[17]  Wei Wang,et al.  Reactivity of surface alkoxy species on acidic zeolite catalysts. , 2008, Accounts of chemical research.

[18]  A. Jansen,et al.  A DFT study of methanol adsorption in 8T rings of chabazite , 2001 .

[19]  O. Swang,et al.  A Theoretical Investigation of the Methylation of Methylbenzenes and Alkenes by Halomethanes over Acidic Zeolites , 2003 .

[20]  S. Blaszkowski,et al.  Density functional theory calculations of the activation of methanol by a Bronsted zeolitic proton , 1995 .

[21]  J. Weitkamp,et al.  Surface Species Formed during Aniline Methylation on Zeolite H–Y Investigated by in Situ MAS NMR Spectroscopy , 2001 .

[22]  K. Domen,et al.  Activation of hydrocarbons on acidic zeolites: superior selectivity of methylation of ethene with methanol to propene on weakly acidic catalysts. , 2008, Chemical communications.

[23]  M. Payne,et al.  Role of the Zeolitic Environment in Catalytic Activation of Methanol , 1999 .

[24]  K. Lillerud,et al.  Selectivity control through fundamental mechanistic insight in the conversion of methanol to hydrocarbons over zeolites , 2010 .

[25]  X. Jiang,et al.  Methanol to hydrocarbons: spectroscopic studies and the significance of extra-framework aluminium , 1999 .

[26]  J. F. Haw,et al.  Conversion of methyl halides to hydrocarbons on basic zeolites: a discovery by in situ NMR , 1993 .

[27]  S. Svelle,et al.  Kinetic studies of zeolite-catalyzed methylation reactions. 1. Coreaction of [12C]ethene and [13C]methanol , 2004 .

[28]  L. Riekert,et al.  Isomerization of xylene and methylation of toluene on zeolite H-ZSM-5. Compound kinetics and selectivity , 1993 .

[29]  F. Bonino,et al.  Conversion of methanol to hydrocarbons over zeolite H-ZSM-5 : On the origin of the olefinic species , 2007 .

[30]  A. Corma,et al.  Surface Species Formed and Their Reactivity during the Alkylation of Toluene by Methanol and Dimethyl Ether on Zeolites As Determined by in Situ 13C MAS NMR , 1997 .

[31]  Wei Wang,et al.  On the reactivity of surface methoxy species in acidic zeolites. , 2006, Journal of the American Chemical Society.

[32]  First principles location of the transition state for formation of dimethyl ether in a zeolite , 1998 .

[33]  D. B. Ferguson,et al.  Physical Organic Chemistry of Solid Acids: Lessons from in situ NMR and Theoretical Chemistry , 1996 .

[34]  Adrian J Mulholland,et al.  High-accuracy computation of reaction barriers in enzymes. , 2006, Angewandte Chemie.

[35]  J. Sauer,et al.  Interaction of methanol with Broensted acid sites of zeolite catalysts: an ab initio study , 1995 .

[36]  S. Al-Khattaf,et al.  Kinetics of toluene methylation over USY-zeolite catalyst in a riser simulator , 2008 .

[37]  J. Sauer,et al.  Ab initio molecular dynamics simulation of methanol interacting with acidic zeolites of different framework structure , 2000 .

[38]  José Luis Valverde,et al.  Kinetics of toluene alkylation with methanol over magnesium-modified ZSM-5 , 1993 .

[39]  F. Salehirad,et al.  Solid-State13C MAS NMR Study of Methanol-to-Hydrocarbon Chemistry over H-SAPO-34 , 1996 .

[40]  Tomoyuki Mori,et al.  Mechanism of methanol conversion into hydrocarbons over ZSM-5 zeolite , 1981 .

[41]  Wei Wang,et al.  Evidence for an initiation of the methanol-to-olefin process by reactive surface methoxy groups on acidic zeolite catalysts. , 2003, Journal of the American Chemical Society.

[42]  Unni Olsbye,et al.  Kinetic studies of zeolite-catalyzed methylation reactions. Part 2. Co-reaction of [12C]propene or [12C]n-butene and [13C]methanol , 2005 .

[43]  K. Lillerud,et al.  Thermochemistry of organic reactions in microporous oxides by atomistic simulations: benchmarking against periodic B3LYP. , 2010, The journal of physical chemistry. A.

[44]  S. Kolboe,et al.  H-[B]-ZSM-5 as catalyst for methanol reactions , 1995 .

[45]  J. Lercher,et al.  Production and reactions of xylenes over H-ZSM5 , 1991 .

[46]  Ø. Mikkelsen,et al.  Use of isotopic labeling for mechanistic studies of the methanol-to-hydrocarbons reaction. Methylation of toluene with methanol over H-ZSM-5, H-mordenite and H-beta , 2000 .

[47]  F. Figueras,et al.  Terminal and bridging methoxyls on zeolites detected by 13C magic angle spinning NMR spectroscopy , 1999 .

[48]  J. Hafner,et al.  A theoretical study of the alkylation reaction of toluene with methanol catalyzed by acidic mordenite. , 2001, Journal of the American Chemical Society.

[49]  Glenn J. Sunley,et al.  Selective carbonylation of dimethyl ether to methyl acetate catalyzed by acidic zeolites. , 2006, Angewandte Chemie.

[50]  In situ FTIR studies of methanol and dimethyl ether in ZSM-5 , 1987 .

[51]  S. Blaszkowski,et al.  The mechanism of dimethyl ether formation from methanol catalyzed by zeolitic protons , 1996 .

[52]  Glenn J. Sunley,et al.  Site requirements and elementary steps in dimethyl ether carbonylation catalyzed by acidic zeolites , 2007 .

[53]  Ayman D. Allian,et al.  Specificity of sites within eight-membered ring zeolite channels for carbonylation of methyls to acetyls. , 2007, Journal of the American Chemical Society.

[54]  J. Sauer,et al.  Quantum chemical modeling of zeolite-catalyzed methylation reactions: toward chemical accuracy for barriers. , 2009, Journal of the American Chemical Society.

[55]  K. Lillerud,et al.  The methyl halide to hydrocarbon reaction over H-SAPO-34 , 2006 .

[56]  C. Naccache,et al.  Kinetics of methanol dehydration on dealuminated H-mordenite: Model with acid and basic active centres , 1991 .

[57]  S. Moon,et al.  A simple-design high vacuum infrared cell for in situ studies of supported metal catalysts , 1981 .

[58]  P. Geerlings,et al.  Reactivity Descriptors and Rate Constants for Electrophilic Aromatic Substitution: Acid Zeolite Catalyzed Methylation of Benzene and Toluene , 2002 .

[59]  V. Bosacek,et al.  Formation of surface-bonded methoxy groups in the sorption of methanol and methyl iodide on zeolites studied by carbon-13 MAS NMR spectroscopy , 1993 .

[60]  B. Arstad,et al.  A theoretical investigation on the methylation of methylbenzenes on zeolites , 2002 .

[61]  Younan Xia,et al.  Cover Picture: Shape‐Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics? (Angew. Chem. Int. Ed. 1/2009) , 2009 .

[62]  Enrique Iglesia,et al.  Selective homologation routes to 2,2,3-trimethylbutane on solid acids. , 2009, Angewandte Chemie.

[63]  M. Hunger,et al.  Adsorption of Methanol on Brønsted Acid Sites in Zeolite H-ZSM-5 Investigated by Multinuclear Solid-State NMR Spectroscopy , 1996 .

[64]  M. Probst,et al.  Reaction Mechanisms of the Methylation of Ethene with Methanol and Dimethyl Ether over H-ZSM-5: An ONIOM Study , 2009 .

[65]  O. Swang,et al.  Methylation of alkenes and methylbenzenes by dimethyl ether or methanol on acidic zeolites. , 2005, The journal of physical chemistry. B.

[66]  S. Wong,et al.  In situ Fourier transform i.r. observation of methylating species in ZSM-5 , 1986 .

[67]  Paolo Pollesel,et al.  A priori selection of shape-selective zeolite catalysts for the synthesis of 2,6-dimethylnaphthalene , 2003 .