Mechanism of CaO catalyst deactivation with unconventional monitoring method for glycerol carbonate production via transesterification of glycerol with dimethyl carbonate


Glycerol carbonate (GC) was synthesized by transesterification of glycerol with dimethyl carbonate (DMC) using calcium oxide (CaO) derived from eggshell as a catalyst. The best results of 96% glycerol conversion and 94% GC yield were achieved under the following reaction conditions: 0.08 mole ratio of CaO to glycerol, 1:2.5 mole ratio of glycerol to DMC, 60°C reaction temperature, and 3 hours reaction time. As expected, CaO showed deteriorated catalytic performance when recycling as observed by a rapid decrease in GC yield. This research showed that the active CaO phase first was converted to calcium methoxide (Ca[OCH3]2) and calcium diglyceroxide (Ca[C3H7O3]2) and finally to carbonate phase (CaCO3) which can be confirmed by XRD patterns. According to the phase transformation, the basicity decreased from 0.482 mmol/g to 0.023 mmol/g, and basic strength altered from strong basic strength (15.0 < H_ < 18.4) to weak basic strength (7.2 < H_ < 9.8), resulting in the lower catalytic activity of the consecutive runs. Despite the fact that the GC selectivity was almost 100%, the reaction products (methanol and GC) were not obtained in their stoichiometric ratio and their extents corresponded with that of the catalyst phase transformation to CaCO3. The mechanism of CaO catalyzed transesterification based on the condensation reaction of glycerol and catalyst was proposed, and in situ formation of water-derivative species was hypothesized as a cause of CaO transformation. CaO could react with DMC and water, generating methanol and CaCO3. This enabled unconventional monitoring of catalyst deactivation by checking if the mole ratio of methanol to GC was higher than 2:1 of its reaction stoichiometric ratio. It was also demonstrated that calcination of post-run catalyst at 900°C to CaO exhibited almost constant catalytic activity, and the mole ratio of methanol to GC was constant at its reaction stoichiometry (2:1) for at least 4 times use.

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Divisions: College of Engineering & Physical Sciences
College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
Additional Information: This is the peer reviewed version of the following article: Praikaew, W, Kiatkittipong, W, Aiouache, F, et al. Mechanism of CaO catalyst deactivation with unconventional monitoring method for glycerol carbonate production via transesterification of glycerol with dimethyl carbonate. Int J Energy Res. , which has been published in final form at  This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving. Funding: Thailand Science Research and Innovation; Research and Researchers for Industrials PhD Program, Grant/Award Number: PHD 57I0078; National Science and Technology Development Agency.
Uncontrolled Keywords: biomass waste derived catalyst,catalyst deactivation,catalytic activity,deactivation mechanism,fatty acid methyl ester,glycerol carbonate production,Renewable Energy, Sustainability and the Environment,Nuclear Energy and Engineering,Fuel Technology,Energy Engineering and Power Technology
Publication ISSN: 1099-114X
Last Modified: 27 May 2024 07:35
Date Deposited: 20 Sep 2021 09:04
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Related URLs: https://onlinel ... 10.1002/er.7281 (Publisher URL)
http://www.scop ... tnerID=8YFLogxK (Scopus URL)
PURE Output Type: Article
Published Date: 2021-09-15
Published Online Date: 2021-09-15
Accepted Date: 2021-08-31
Authors: Praikaew, Wanichaya
Kiatkittipong, Worapon
Najdanovic, Vesna (ORCID Profile 0000-0002-1035-0982)
Aiouache, Farid
Termtanun, Mutsee
Lim, Jun Wei
Lam, Su Shiung
Kiatkittipong, Kunlanan
Laosiripojana, Navadol
Boonyasuwat, Sunya
Assabumrungrat, Suttichai



Version: Accepted Version

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