Sustainable synthesis of dimethyl- and diethyl carbonate from CO2 in batch and continuous flow─lessons from thermodynamics and the importance of catalyst stability

O'Neill, Matthew F., Meenakshisundaram, Sankar ORCID: https://orcid.org/0000-0002-7105-0203 and Hintermair, Ulrich 2022. Sustainable synthesis of dimethyl- and diethyl carbonate from CO2 in batch and continuous flow─lessons from thermodynamics and the importance of catalyst stability. ACS Sustainable Chemistry and Engineering 10 (16) , 5243–5257. 10.1021/acssuschemeng.2c00291

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Abstract

Equilibrium conversions for the direct condensation of MeOH and EtOH with CO2 to give dimethyl- and diethyl carbonate, respectively, have been calculated over a range of experimentally relevant conditions. The validity of these calculations has been verified in both batch and continuous flow experiments over a heterogeneous CeO2 catalyst. Operating under optimized conditions of 140 °C and 200 bar CO2, record productivities of 235 mmol/L·h DMC and 241 mmol/L·h DEC have been achieved using neat alcohol dissolved in a continuous flow of supercritical CO2. Using our thermodynamic model, we show that to achieve maximum product yield, both dialkyl carbonates and water should be continuously removed from the reactor instead of the conventionally used strategy of removing water alone, which is much less efficient. Catalyst stability rather than activity emerges as the prime limiting factor and should thus become the focus of future catalyst development.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry Cardiff Catalysis Institute (CCI)
Publisher:	American Chemical Society
ISSN:	2168-0485
Funders:	EPSRC and the Royal Society
Date of First Compliant Deposit:	3 May 2022
Date of Acceptance:	25 March 2022
Last Modified:	24 May 2023 00:28
URI:	https://orca.cardiff.ac.uk/id/eprint/149492

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