Enhanced yields of diethyl carbonate via one-pot synthesis from ethanol, carbon dioxide and butylene oxide over cerium (IV) oxide

Leino, Ewelina; Mäki‐Arvela, Päivi; Eränen, Kari; Tenho, Mikko; Murzin, Dmitry Yu.; Salmi, Tapio; Mikkola, Jyri‐Pekka

doi:10.1016/j.cej.2011.07.054

Cited by 53 publications

(47 citation statements)

References 32 publications

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“…Analysis of the CO 2 route shows the reaction to be favourable at high temperatures as reported earlier. [35] The equilibrium curve of DMC with temperature was concaved downwards and it can be observed that the maximum value of equilibrium constant was obtained at 423.15 K. The curve of equilibrium constant of EC was somewhat linear with the temperature leaving an impression of endothermic reaction. However, DEC synthesis from DMC and EC is done at a moderate temperature as reported earlier.…”

Section: Effect Of Temperature On Equilibrium Constants and Equilibrimentioning

confidence: 86%

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Synthesis of diethyl carbonate from ethanol through different routes: A thermodynamic and comparative analysis

Shukla

Srivastava

2017

Can J Chem Eng

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In this study, thermodynamic analysis of various possible synthesis routes of diethyl carbonates (DEC), a benign organic carbonate, was carried out and a comparative analysis was performed. Chemical equilibrium constants at standard conditions were calculated using Gibbs free energy of the system. The Benson group contribution method was used to estimate standard heat of formation and standard entropy change of some raw materials/components like dimethyl carbonate. Variation of heat capacity (C p ) with temperature was estimated for different components from the Rozicka-Domalski model. Variation of chemical equilibrium constants with temperature and pressure was studied for various routes. Synthesis of DEC from ethylene carbonate (EC) was also found to be better considering equilibrium constants at room temperature. The CO 2 route was found to be the most unfavourable route for DEC synthesis due to stability of CO 2 molecules. Moreover, DEC synthesis through the urea route was found to be best at high temperatures since the equilibrium constants were found to increase exponentially. Experiments were conducted for DEC synthesis using the EC route at two temperatures. Activity coefficients were calculated using the UNIFAC model. Experimentally and theoretically determined chemical equilibrium constant values were found to be similar. PRO/II was also used to minimize Gibbs free energy of the system and estimate the equilibrium constants and the results were comparable with those obtained by the equilibrium constant method and the trend was found to be the same for both the methods.

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Section: Effect Of Temperature On Equilibrium Constants and Equilibrimentioning

confidence: 86%

“…[41][42][43][44][45] The co-production of water also needs to be dehydrated which increased yield by 9 fold. [35] Synthesis of DEC from DMC is restricted by the formation of azeotropes. To enhance the yield, reactive distillation systems have been reported previously.…”

Section: Comparison Of Experimental Equilibrium Constant and Theoretimentioning

confidence: 99%

Synthesis of diethyl carbonate from ethanol through different routes: A thermodynamic and comparative analysis

Shukla

Srivastava

2017

Can J Chem Eng

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“…This research covers projects involving the synthesis and application of nanomaterials such as carbon nanotubes [16][17][18] ; the production of organic optoelectronic devices [19][20][21] ; synthesis of industrial catalysts [22][23][24] ; fundamental studies on the mechanism of enzymes (such as photosystem II) [9,11,[25][26][27] ; elucidation of the genome sequence, metabolism and biomass formation of various species [28][29][30] ; combustion, gasification and torrefaction of biomass including ash behaviour [31][32][33][34][35][36][37] ; the improvement of biomass (wood) quantity and quality by breeding and genetic modification [38,39] ; and implementation of a biorefinery concept at industrial scale. [40][41][42][43][44][45] For building and maintaining these research facilities and efforts, internal and external funding is required. Umeå University made significant initial investments, which were accompanied by generous support by private foundations (K&A Wallenberg, Kempe).…”

Section: An Institutional Approach To Solar Energy Conversionmentioning

confidence: 99%

An Institutional Approach to Solar Fuels Research

Messinger¹

2012

Aust. J. Chem.

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“…However, the reaction hardly occurs spontaneously, even under harsh conditions, due to the thermodynamic limitations (yield of less than 0.5%) [8]. To address this issue, chemical dehydration reagent was usually involved to shift the reaction forward to the carbonate side.…”

Section: Introductionmentioning

confidence: 99%

“…Diethyl carbonate (DEC) is one of the most important green chemicals among carbonate esters. It is an excellent solvent and an intermediate for various pharmaceuticals, such as antibiotics and phenobarbital [8]. DEC has also been proposed as a replacement for MTBE as an attractive oxygen-containing fuel additive for its high oxygen content (40.6 wt.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Diethyl Carbonate from Carbon Dioxide, Propylene Oxide and Ethanol over KNO3-CeO2 and KBr-KNO3-CeO2 Catalysts

et al. 2016

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Abstract:One-pot syntheses of diethyl carbonate (DEC) from CO 2 , propylene oxide and ethanol were carried out using different solid catalysts. The supercritical CO 2 extraction method was used to separate the liquid products and reactants from the catalysts after reaction. The KNO 3 -CeO 2 and KBr-KNO 3 -CeO 2 were found to be active for the reaction after calcinations. The catalyst was also reusable. The thermodynamic properties of the reaction were also evaluated. The effects of various conditions, such as reaction time, amount of catalysts, molar ratio of the reactants, the composition and calcination temperature of the catalysts on the conversion and yields, were investigated, and the yield of DEC was about 13.0% with a selectivity of 38.5% over KBr-KNO 3 -CeO 2 . The yield of DEC was improved about 10-fold by using KBr-KNO 3 -CeO 2 catalyst compared to CeO 2 .

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Enhanced yields of diethyl carbonate via one-pot synthesis from ethanol, carbon dioxide and butylene oxide over cerium (IV) oxide

Cited by 53 publications

References 32 publications

Synthesis of diethyl carbonate from ethanol through different routes: A thermodynamic and comparative analysis

Synthesis of diethyl carbonate from ethanol through different routes: A thermodynamic and comparative analysis

An Institutional Approach to Solar Fuels Research

Synthesis of Diethyl Carbonate from Carbon Dioxide, Propylene Oxide and Ethanol over KNO3-CeO2 and KBr-KNO3-CeO2 Catalysts

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