Review on the synthesis of dimethyl carbonate

Tan, Hai; Wang, Zhiqiao; Xu, Zhusheng; Sun, Jing; Xu, Yu-Ping; Chen, Qingsong; Chen, Yumin; Guo, Guo‐Cong

doi:10.1016/j.cattod.2018.02.021

Cited by 146 publications

(93 citation statements)

References 70 publications

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“…Therefore, DMC comes as a substitute, since, in the concentration of 40% (v/v) in relation to the MTBE concentration achieves the same effectiveness as MTBE reducing waste generation by 50%. [7][8][9][10] Industrial production of DMC is environmentally friendly, however the Gibbs energy for DMC production by direct reaction is greater than zero. Reaction equilibrium constant around 10 À5 indicates that the formation reaction does not occur spontaneously.…”

Section: Introductionmentioning

confidence: 99%

Dehydrating agent effect on the synthesis of dimethyl carbonate (DMC) directly from methanol and carbon dioxide

et al. 2020

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Section: Introductionmentioning

confidence: 99%

Dehydrating agent effect on the synthesis of dimethyl carbonate (DMC) directly from methanol and carbon dioxide

et al. 2020

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“…Dimethyl carbonate (DMC) being environmentally benign chemical has several applications, viz., fuel additives, carbonylation agent, methylation agent, and low toxicity solvent. [1][2][3][4][5] Recently, development of effective catalysts to produce DMC through oxidative carbonylation of methanol, which is thermodynamically favorable has received greater attention. [6][7][8][9][10][11][12][13][14][15][16][17][18] Being, chloride-free, CuY zeolite has shown greate potential to obtain high activity and excellent selectivity for oxidative carbonylation reaction.…”

Section: Introductionmentioning

confidence: 99%

Role of metal co‐cations in improving CuY zeolite performance for DMC synthesis: A theoretical study

Zheng

Narkhede

Zhang

et al. 2020

Applied Organom Chemis

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First principle calculations based on density functional theory are conducted to investigate the influence of metal cations including Mg2+, Ca2+, Sr2+, Ba2+, La (OH)2+ and Ce (OH)2+ in the small cage of zeolite on the electronic environment of adjacent active center, Cu+ in CuY zeolite as well as the process of CO insertion into CH3O to form CH3OCO for oxidative carbonylation of methanol. The study explains the theoretical reasons for the effects of metal cations on the catalytic activity of zeolites. It was found that, the presence of co‐cations in the small cage can affect the electronic properties and also the catalytic activity in two ways. Firstly, the presence of co‐cations, viz., Ca2+, Sr2+, Mg2+, Ba2+ and La species in small cage hinders the migration of active Cu+ cations from the super cage to small cage. Secondly, the co‐cations greatly affect the charge transfer from zeolite framework to Cu+ present in the adjacent super cage, leading to the increase of the net charge and binding energy of Cu+. The findings can improve the CO adsorption and insertion efficiencies, and the stability of transition states, which results in the enhanced catalytic activity of corresponding zeolites.

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“…Until now, several catalytic routes have been applied in order to synthesize DMC, whereby phosgenation, transesterification, oxidative carbonylation, and urea methanolysis have been extensively studied and industrially applied [4][5][6][7]. However, these catalytic routes are accompanied by the use of toxic raw materials or catalytic deactivation, or are less selective and reactive in nature.…”

Section: Introductionmentioning

confidence: 99%

One-Pot, Metal-Free Synthesis of Dimethyl Carbonate from CO2 at Room Temperature

Khokarale

Bui

Mikkola

2020

Sustainable Chemistry

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Herein, we report on the metal-free, one-pot synthesis of industrially important dimethyl carbonate (DMC) from molecular CO2 under ambient conditions. In this process, initially the CO2 was chemisorbed through the formation of a switchable ionic liquid (SIL), [DBUH] [CH3CO3], by the interaction of CO2 with an equivalent mixture of organic superbase 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and methanol. The obtained SIL further reacted with methyl iodide (CH3I) to form DMC. The synthesis was carried out in both dimethyl sulfoxide (DMSO) and methanol. Methanol is preferred, as it not only served as a reagent and solvent in CO2 capture and DMC synthesis, but it also assisted in controlling the side reactions between chemical species such as CH3I and [DBUH]+ cation and increased the yield of DMC. Hence, the use of methanol avoided the loss of captured CO2 and favored the formation of DMC with high selectivity. Under the applied reaction conditions, 89% of the captured CO2 was converted to DMC. DBU was obtained, achieving 86% recovery of its salts formed during the synthesis. Most importantly, in this report we describe a simple and renewable solvent-based process for a metal-free approach to DMC synthesis under industrially feasible reaction conditions.

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Review on the synthesis of dimethyl carbonate

Cited by 146 publications

References 70 publications

Dehydrating agent effect on the synthesis of dimethyl carbonate (DMC) directly from methanol and carbon dioxide

Dehydrating agent effect on the synthesis of dimethyl carbonate (DMC) directly from methanol and carbon dioxide

Role of metal co‐cations in improving CuY zeolite performance for DMC synthesis: A theoretical study

One-Pot, Metal-Free Synthesis of Dimethyl Carbonate from CO2 at Room Temperature

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