title: Formation Mechanism of the First Carbon-Carbon Bond and the First Olefin in the Methanol Conversion into Hydrocarbons.
abstract: The elementary reactions leading to the formation of the first carbon-carbon bond during early stages of the zeolite-catalyzed methanol conversion into hydrocarbons were identified by combining kinetics, spectroscopy, and DFT calculations. The first intermediates containing a C-C bond are acetic acid and methyl acetate, which are formed through carbonylation of methanol or dimethyl ether even in presence of water. A series of acid-catalyzed reactions including acetylation, decarboxylation, aldol condensation, and cracking convert those intermediates into a mixture of surface bounded hydrocarbons, the hydrocarbon pool, as well as into the first olefin leaving the catalyst. This carbonylation based mechanism has an energy barrier of 80 kJ mol(-1) for the formation of the first C-C bond, in line with a broad range of experiments, and significantly lower than the barriers associated with earlier proposed mechanisms.
authors.affiliation: Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany.
authors.forename: Yue
authors.initials: Y
authors.lastname: Liu
authors.affiliation: Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Müller
authors.affiliation: Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany.
authors.forename: Daniel
authors.initials: D
authors.lastname: Berger
authors.affiliation: Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany.
authors.forename: Jelena
authors.initials: J
authors.lastname: Jelic
authors.affiliation: Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany.
authors.forename: Karsten
authors.initials: K
authors.lastname: Reuter
authors.affiliation: Clariant Produkte Deutschland GmbH, Waldheimer Strasse 13, 83052, Bruckmühl, Germany.
authors.forename: Markus
authors.initials: M
authors.lastname: Tonigold
authors.affiliation: Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany. m.sanchez@tum.de.
authors.forename: Maricruz
authors.initials: M
authors.lastname: Sanchez-Sanchez
authors.affiliation: Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany. Johannes.lercher@ch.tum.de.
authors.forename: Johannes A
authors.initials: JA
authors.lastname: Lercher
keywords: C−C coupling; carbonylation; methanol-to-hydrocarbons; olefin; zeolites