Sustainable Synthesis of Dimethyl- and Diethylcarbonate from CO2 in Batch and Continuous Flow Lessons from Thermodynamics and the Importance of Catalyst Stability

Matthew F. O'Neill, Meenakshisundaram Sankar, Ulrich Hintermair

Research output: Contribution to journalArticlepeer-review

Abstract

Equilibrium conversions for the direct condensation of MeOH and EtOH with CO2 to give dimethyl- and diethylcarbonate 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 dialkylcarbonates 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.
Original languageEnglish
Pages (from-to)5243-5257
Number of pages15
JournalACS Sustainable Chemisty and Engineering
Volume10
Issue number16
Early online date12 Apr 2022
DOIs
Publication statusPublished - 25 Apr 2022

Keywords

  • COutilization
  • continuous flow processing
  • direct synthesis of dialkyl carbonates
  • supercritical fluids
  • thermodynamics

ASJC Scopus subject areas

  • Chemistry(all)
  • Environmental Chemistry
  • Chemical Engineering(all)
  • Renewable Energy, Sustainability and the Environment

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