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Ethylcyclohexane Hydroconversion in EU‐1 Zeolite: DFT‐based Microkinetic Modeling Reveals the Nature of the Kinetically Relevant Intermediates
Author(s) -
GutierrezAcebo Ester,
Rey Jérôme,
Bouchy Christophe,
Schuurman Yves,
Chizallet Céline
Publication year - 2021
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.202100421
Subject(s) - chemistry , density functional theory , catalysis , computational chemistry , catalytic cycle , reaction rate constant , transition state , kinetic energy , elementary reaction , reaction mechanism , zeolite , kinetics , thermodynamics , organic chemistry , physics , quantum mechanics
The transformation of cycloalkanes is a key‐reaction in refining and petrochemistry. Herein, we unravel the mechanism and the kinetics of the transformation of ethylcyclohexane, considering a bifunctional catalyst composed of platinum and of the EU‐1 zeolite, by experiments, density functional theory (DFT) calculations and DFT‐based microkinetic modeling. The simulated mechanisms involve carbenium intermediates. DFT shows the central kinetic role of the π‐complexes corresponding to secondary carbenium ions. Cycle contractions and expansions appear to be rate‐limiting. The DFT‐based microkinetic model includes a limited number of kinetic parameters optimized by regression with respect to the experimental data. The agreement with experimental results is very good, showing that the mechanisms proposed, the nature of the intermediates, and the values of the computed rate constants, are relevant. The reaction starts by the cycle contraction of 1‐ethylcyclohexene, then shifts to a second sequence of cycle expansion‐contraction reactions by intercalated methyl‐shifts.