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Unraveling the Mechanism of the Initiation Reaction of the Methanol to Olefins Process Using ab Initio and DFT Calculations
journal contribution
posted on 2017-10-26, 14:22 authored by Philipp N. Plessow, Felix StudtWe report a theoretical investigation
of the initiation of the
methanol to olefin process, where we study the full reaction mechanism
from methanol to propylene. The zeolite H-SSZ-13 is investigated with
periodic density functional theory (DFT) calculations. These calculations
are corrected with MP2-calculations on large (46T) cluster models,
which is found to be crucial for sufficient accuracy. Our calculations
clearly demonstrate that initiation via the formation of carbon monoxide
is a realistic mechanism and is more likely than the methane–formaldehyde
mechanism or variants thereof. A kinetic model of the autocatalytic
carbon pool mechanism is employed to investigate the initiation kinetics
in more detail, demonstrating that an assessment of the feasibility
of an initiation reaction needs to be based on kinetic modeling of
both the initiation reaction and autocatalysis. This model gives further
evidence that initiation proceeds via oxidation of methanol to carbon
monoxide, which subsequently forms the first carbon–carbon
bond via carbonylation of methanol. The kinetic model also shows that
only extremely small amounts of an olefin need to be formed for autocatalysis
to start, implying that small impurities will dominate over initiation
mechanisms.
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