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Kinetic study for the direct synthesis of dimethyl carbonate from methanol and CO2 over CeO2 at high pressure conditions

Paper ID Volume ID Publish Year Pages File Format Full-Text
40367 45851 2013 8 PDF Available
Title
Kinetic study for the direct synthesis of dimethyl carbonate from methanol and CO2 over CeO2 at high pressure conditions
Abstract

The kinetics for the direct synthesis of dimethyl carbonate was studied over CeO2 at high pressure conditions in a batch reactor. Langmuir–Hinshelwood and Eley–Rideal mechanisms were proposed and compared by the performance of the respective reaction rate expression in fitting to the experimental kinetic data. The reactions were held at different temperatures (378–408 K), CO2/methanol molar ratios (1.1–4.0) and pressures (15–20 MPa) in order to adjust the kinetic parameters. An activation energy of 106 kJ mol−1, as well as the standard enthalpy and Gibbs energy of reaction (−20.10 and 31.50 kJ mol−1) were calculated from experiments. Furthermore, the changes in pressure revealed an effect on the kinetic constant, with an activation volume equal to −0.208 cm3 mol−1.

Graphical abstractFigure optionsDownload full-size imageDownload high-quality image (169 K)Download as PowerPoint slideHighlights► The kinetics for direct synthesis of DMC over CeO2 at high pressure is studied. ► Model based on Langmuir–Hinshelwood mechanism fits our data. ► ΔrH° and ΔrG° were estimated to be −20.10 and 31.50 kJ mol−1. ► The activation energy was estimated to be 106 kJ mol−1. ► An activation volume was estimated to be −0.209 cm3 mol−1.

Keywords
DMC, dimethyl carbonate; MeOH, methanol; mHV2, modified Huron–Vidal second order mixing rule; MC, methyl carbonate; NC, number of compounds; NP, number of points; SEM, scanning electron microscope; SRK, Soave–Redlich–Kwong equation of stateDimethyl carbon
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Kinetic study for the direct synthesis of dimethyl carbonate from methanol and CO2 over CeO2 at high pressure conditions
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Publisher
Database: Elsevier - ScienceDirect
Journal: Applied Catalysis A: General - Volume 455, 30 March 2013, Pages 219–226
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Catalysis
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Price was $35.95
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Price after discount Only $4.95
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