Direct Production of Propene from Methoxy Species and Dimethyl Ether over H-ZSM-5

The mechanism of the initial C–C bond formation on methanol to olefin (MTO) and/or methanol to hydrocarbon (MTHC) reaction were not clarified. In this paper, the reaction mechanism and the reactivity of methoxy species on H-ZSM-5 zeolite with methanol or dimethyl ether (DME), which is the initial product of MTO and MTHC reactions, were observed by infrared (IR) spectroscopy. The direct production of propene from methoxy groups and DME is evidenced on H-ZSM-5 zeolite by isotopic studies of IR observation of surface species and GC-mass analysis of products. Stepwise reactions of DME to ethene and water followed by methylation of ethene by methoxy groups were negligible during the generation of propene by the reaction of methoxy groups and DME.

[1]  Unni Olsbye,et al.  Mechanistic Aspects of the Zeolite Catalyzed Methylation of Alkenes and Aromatics with Methanol: A Review , 2011 .

[2]  H. Yamazaki,et al.  Evidence for a "carbene-like" intermediate during the reaction of methoxy species with light alkenes on H-ZSM-5. , 2011, Angewandte Chemie.

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

[4]  U. Olsbye,et al.  Methanol to hydrocarbons over large cavity zeolites: Toward a unified description of catalyst deactivation and the reaction mechanism , 2010 .

[5]  K. Lillerud,et al.  The mechanisms of ethene and propene formation from methanol over high silica H-ZSM-5 and H-beta , 2009 .

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

[7]  Weiguo Song,et al.  The Role of Methoxy Groups in Methanol to Olefin Conversion , 2008 .

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

[9]  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.

[10]  J. F. Haw,et al.  Experimental evidence from H/D exchange studies for the failure of direct C-C coupling mechanisms in the methanol-to-olefin process catalyzed by HSAPO-34. , 2006, Angewandte Chemie.

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

[12]  D. Petersen,et al.  The methanol-to-hydrocarbons reaction: insight into the reaction mechanism from [12C]benzene and [13C]methanol coreactions over zeolite H-beta , 2004 .

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

[14]  Philippe Sautet,et al.  Hydroxyl Groups on γ-Alumina Surfaces: A DFT Study , 2002 .

[15]  K. Domen,et al.  Simultaneous Observation of Alkenyl Carbenium Ions and Alkoxy Species on HZSM-5 Zeolite by Adsorption of 1-Methylcyclopentene and 1-Methylcyclopentanol , 2001 .

[16]  Weiguo Song,et al.  Supramolecular origins of product selectivity for methanol-to-olefin catalysis on HSAPO-34. , 2001, Journal of the American Chemical Society.

[17]  J. Nagy,et al.  Generation, Characterization, and Transformations of Unsaturated Carbenium Ions in Zeolites. , 1999, Chemical reviews.

[18]  Michael Stöcker,et al.  Methanol-to-hydrocarbons: catalytic materials and their behavior 1 Dedicated to my wife Wencke Ophau , 1999 .

[19]  V. Santen,et al.  (A,B,C) triplet of infrared OH bands of zeolitic H-complexes , 1995 .

[20]  Ivar M. Dahl,et al.  On the Reaction Mechanism for Hydrocarbon Formation from Methanol over SAPO-34 2. Isotopic Labeling Studies of the Co-reaction of Propene and Methanol , 1994 .

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

[22]  R. Howe,et al.  In situ FTIR studies of methanol and dimethyl ether in ZSM-5 , 1987 .

[23]  T. Mole,et al.  Conversion of methanol to hydrocarbons over ZSM-5 zeolite: An examination of the role of aromatic hydrocarbons using 13carbon- and deuterium-labeled feeds , 1983 .

[24]  T. Mole,et al.  Aromatic co-catalysis of methanol conversion over zeolite catalysts , 1983 .

[25]  C. Chang Hydrocarbons from Methanol , 1983 .

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

[27]  W. J. Reagan,et al.  Evidence of autocatalysis in methanol to hydrocarbon reactions over zeolite catalysts , 1979 .