4.7 Article

In-depth understanding of soluble base deactivation during the carbonate transesterification process

Journal

FUEL
Volume 285, Issue -, Pages -

Publisher

ELSEVIER SCI LTD
DOI: 10.1016/j.fuel.2020.119201

Keywords

Dimethyl carbonate (DMC); Ethyl methyl carbonate (EMC); Transesterification; Soluble base; Deactivation mechanism

Funding

  1. National Key Research and Development Plan, China [2018YFB0604500]
  2. Key Task and Local Project in Science & Technology of SYUCT, China
  3. Project for Innovative Talents in Liaoning Province, China [LR2016015]

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This study systematically investigated the influence of various soluble basic catalysts in the production of carbonates, with dimethyl carbonate identified as the cause of catalyst deactivation. The alkali strength, nucleophilicity, and catalyst efficiency were found to increase with decreasing alkalinity coefficient value. The final deactivation species after long-time treatment or recycling was determined to be Na2CO3. The research findings may contribute to the development of more effective homogeneous catalysts for carbonate transesterification processes.
Soluble strong bases such as NaOH or CH3ONa were industrially applied in production of multiple carbonates via the transesterification route. However, the catalytic efficiency decreased significantly after recycling and insoluble solids were formed, leading to a complicated and non-eco-friendly manufacture process. In this study, the influence of Na-based soluble basic catalysts (C4H9ONa, C2H5ONa, CH3ONa, NaOH, Na2CO3, and NaHCO3) structures, amounts, reusability, reaction atmospheres, and different reactants treatment were systematically studied for in-depth understanding the deactivated processes and mechanism. The results indicated dimethyl carbonate (DMC) was responsible for the deactivation and with decreasing the pK(b) (alkalinity coefficient) value, the alkali strength, nucleophilicity, and catalyst efficiency increased. The properties of fresh, DMC-treated and recycled NaOH or CH3ONa samples were characterized by means of XRD, FT-IR, Raman, TG, and SEM. Nearly all the characterizations proved that the final deactivation species was Na2CO3 after long-time treatment or recycle. A possible deactivation mechanism of soluble bases during the transesterification process was proposed. The presence of trace H2O was the induction of CH3ONa deactivation, whereas the interaction between DMC and NaOH led to the formation of Na2CO3. This finding will contribute to the development of strategies to design homogeneous catalysts with high activity and stability for carbonate transesterification.

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