Synthesis of diethyl carbonate from urea and ethanol over lanthanum oxide as a heterogeneous basic catalyst

Xin, Shumin; Wang, Liguo; Li, Huiquan; Huang, Kelin; Li, Fengjiao

doi:10.1016/j.fuproc.2014.05.029

Cited by 41 publications

(29 citation statements)

References 31 publications

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“…The lanthanum oxide catalyst prepared by the precipitation method exhibited the highest catalytic activity among various metal oxide catalysts, such as MgO, Al 2 O 3 and ZnO. The characterization results indicated that the basic sites were responsible for the catalytic activity and the medium strength of the basic sites was thought to further enhance the catalytic activity . It was reported that transition metal‐modified mesoporous Mg‐Al hydrotalcites presented much higher base‐catalytic performance than the corresponding pure hydrotalcites in the synthesis of DEC from ethyl carbamate and ethanol.…”

Section: Synthesis Of Organic Carbonates From Ureamentioning

confidence: 99%

“…The characterization results indicated that the basic sites were responsible for the catalytic activity and the medium strength of the basic sites was thought to further enhance the catalytic activity. 120 It was reported that transition metal-modified mesoporous Mg-Al hydrotalcites presented much higher base-catalytic performance than the corresponding pure hydrotalcites in the synthesis of DEC from ethyl carbamate and ethanol. Characterization results indicated that there was a close correlation between EC conversion and the numbers of moderate and strong basic sites.…”

Section: Synthesis Of Dec From Urea and Ethanolmentioning

confidence: 99%

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Incorporation of CO₂ into carbonates through carboxylation/hydration reaction

Zhao

Liu

et al. 2018

Greenhouse Gases

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In recent years increasing attention has been given to the efficacious synthesis of organic carbonates from sustainable CO2. The carboxylation/hydration reaction of alcohols with CO2 stands out for its environmentally friendly and economic features. However, it faces several substantial challenges such as thermodynamic limitations, low catalytic efficiency, and product selectivity. In this article, recent advances in the development of catalytic methods for the synthesis of organic carbonates through carboxylation/hydration reaction of alcohols with CO2 are summarized. Catalytic schemes (metal and metal‐free catalysis), water‐dehydration strategies, and catalytic mechanisms are also discussed in detail. The review covers the carbonylation cyclization of various alcohols and the equivalent of CO2, i.e. urea. Finally, an overview is provided of the recent breakthrough in the development of thermodynamically favorable processes involving alcohols and CO2. © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd.

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Section: Synthesis Of Organic Carbonates From Ureamentioning

confidence: 99%

Section: Synthesis Of Dec From Urea and Ethanolmentioning

confidence: 99%

Incorporation of CO₂ into carbonates through carboxylation/hydration reaction

Zhao

Liu

et al. 2018

Greenhouse Gases

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“…The second step, involving adsorption of EEC and ethanol at catalyst surface requires a mildly basic catalyst which has been reported in past studies as well. [40] Dialkyl carbonates synthesis from CO 2 is a thermodynamically unfavourable route. However, this route is most green as it involves direct utilization of CO 2 .…”

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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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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“…1). Moreover, differently from other traditional synthesis routes such as ethanolysis of phosgene [5], oxidative carbonylation of ethanol [6], carbonylation of ethyl nitrite [7], ethanolysis of urea [8], ethanol and dimethyl carbonate transesterification [9], ethanolysis of ethtylene carbonate [10], and decarbonylation of diethyl oxalate [11], which use toxic, flammable, and corrosive compounds (e.g., phosgene, hydrogen chloride, ethyl nitrite, and carbon monoxide), the direct synthesis may be regarded as ''green'' chemical process. K 2 CO 3 [12], CeO 2 [13], Ce x Zr 1-x O 2 [14,15], and CeO 2 -Al 2 O 3 [16] catalysts have been reported for the direct synthesis of DEC in liquid phase under high pressure, but deactivation of the catalyst has been observed due to dissolution of the solid.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Conversion in the Direct Synthesis of Diethyl Carbonate from Ethanol and CO₂ by Process Intensification

et al. 2019

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To overcome the low equilibrium conversion in the direct synthesis of diethyl carbonate from ethanol and CO 2 under moderate reaction conditions, the reaction was conducted in a membrane reactor packed with pelletized Cu-Ni:3-1 supported on activated carbon. A SiO 2 /g-Al 2 O 3 commercial membrane and zeolite A membranes synthesized on commercial Al 2 O 3 supports were evaluated in the membrane reactor. Although characterization of the membranes by X-ray diffraction confirmed the presence of a zeolite A layer on the supports, gas permeation and permselectivity tests of ethanol and water evidenced some defects of the synthesized membranes. An increase in conversion with respect to a conventional packed-bed reactor was observed in the membrane reactors prepared on Al 2 O 3 , but equilibrium conversion was not attained. However, with the commercial membrane, the ethanol conversion was higher than the equilibrium conversion.

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Synthesis of diethyl carbonate from urea and ethanol over lanthanum oxide as a heterogeneous basic catalyst

Cited by 41 publications

References 31 publications

Incorporation of CO₂ into carbonates through carboxylation/hydration reaction

Incorporation of CO₂ into carbonates through carboxylation/hydration reaction

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

Enhanced Conversion in the Direct Synthesis of Diethyl Carbonate from Ethanol and CO₂ by Process Intensification

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Synthesis of diethyl carbonate from urea and ethanol over lanthanum oxide as a heterogeneous basic catalyst

Cited by 41 publications

References 31 publications

Incorporation of CO2 into carbonates through carboxylation/hydration reaction

Incorporation of CO2 into carbonates through carboxylation/hydration reaction

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

Enhanced Conversion in the Direct Synthesis of Diethyl Carbonate from Ethanol and CO2 by Process Intensification

Contact Info

Product

Resources

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Incorporation of CO₂ into carbonates through carboxylation/hydration reaction

Incorporation of CO₂ into carbonates through carboxylation/hydration reaction

Enhanced Conversion in the Direct Synthesis of Diethyl Carbonate from Ethanol and CO₂ by Process Intensification