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Formation Mechanism of the First Carbon–Carbon Bond and the First Olefin in the Methanol Conversion into Hydrocarbons
Author(s) -
Liu Yue,
Müller Sebastian,
Berger Daniel,
Jelic Jelena,
Reuter Karsten,
Tonigold Markus,
SanchezSanchez Maricruz,
Lercher Johannes A.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201511678
Subject(s) - chemistry , carbonylation , methanol , carbon–carbon bond , catalysis , aldol condensation , decarboxylation , olefin fiber , hydrocarbon , organic chemistry , photochemistry , bond cleavage , acetic acid , double bond , carbon monoxide
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.