Kinetics of the production of glycerol carbonate by transesterification of glycerol with dimethyl and ethylene carbonate using potassium methoxide, a highly active catalyst

Esteban, Jesús; Domı́nguez, Esther; Ladero, Miguel; Garcı́a-Ochoa, Félix

doi:10.1016/j.fuproc.2015.06.012

Cited by 69 publications

(55 citation statements)

References 50 publications

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“…Considering the low rates of reaction in enzymatic reactions in contrast with chemically catalyzed reactions and also the fact that here this reaction has been performed in the presence of a solvent, thus diluting the concentration of the species, it has been decided to make use of larger molar excess of organic carbonate ranging from 3:1 to 9:1. Additionally, the reaction was evaluated at 50, 60, and 70 • C, as this is the temperature range that has been considered in kinetic studies [11,16]. Figure 9 shows that better results are obtained as the molar excess increases from 3:1 to 9:1 at all temperatures, which agrees with the fact that even larger excesses of 17:1 and 21:1 of diethyl carbonate to Gly were reported previously as a strategy to reach conversions of 84% or 97% [40,41].…”

Section: Effect Of the Molar Ratio Of Reactants And Temperaturementioning

confidence: 99%

“…For the latter route, the authors of the present work have conducted extensive research using both dialkyl carbonates like dimethyl carbonate (DMC) [11,12] or cyclic carbonates like ethylene carbonate (EC) [13][14][15][16], or more recently, propylene and butylene carbonate [17]. The advantage of this reaction pathway is that alcohols or glycols can be concomitantly produced when dialkyl or cyclic carbonates, respectively, are used as co-substrates along with Gly.…”

Section: Introductionmentioning

confidence: 99%

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Effect of Operating Variables and Kinetics of the Lipase Catalyzed Transesterification of Ethylene Carbonate and Glycerol

et al. 2018

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Glycerol carbonate (GC) is a value-added product originating from the valorization of widely available glycerol (Gly), a side stream from the production of biodiesel. Here we approach the production of this chemical comparing two reactions based on the transesterification of Gly with dimethyl carbonate (DMC) and ethylene carbonate (EC). When using DMC, it was observed that the free enzyme CALB (lipase B from Candida antarctica) gave the best results, whereas Eversa Transform (a genetic modification of Thermomyces lanuginosus lipase) performed better than the rest if EC was the reagent. With the selected catalysts, their immobilized analogous enzymes Novozym 435 and Lypozyme TL IM, respectively, were also tested. Observing that the yields for the reaction with EC were significantly faster, other operating variables were evaluated, resulting the best performance using a closed system, tert-butanol as solvent, a concentration of enzyme Eversa Transform of 3% w/w, a molar excess of EC:Gly of 9:1 and a temperature of 60 °C. Finally, several runs were conducted at different temperatures and molar ratios of EC:Gly, fitting a kinetic model to all experimental data for the reaction catalyzed with Eversa Transform. This model included the bimolecular transesterification reaction of Gly and EC catalyzed by the lipase and a reversible ring-opening polymerization of EC.

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Section: Effect Of the Molar Ratio Of Reactants And Temperaturementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Effect of Operating Variables and Kinetics of the Lipase Catalyzed Transesterification of Ethylene Carbonate and Glycerol

et al. 2018

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“…[10] Others used other models more containing more equations, which were referred to as simplified model for ethyl ester viscosity. [30][31][32][33][34][35] F is based on a null hypothesis that supports the adequacy of the goodness of the correlation of the model to the experimental values of the measured variable and is defined as follows by Eq. Then, depending on the length of the carbon chain length, the equations used a different amount of parameters.…”

Section: Viscosity Of Pure Fatty Acidsmentioning

confidence: 99%

On the Discrimination of Models for the Viscometric Properties of Myristic, Palmitic and Stearic Acids and Their Binary Mixtures

Esteban

Bakalis

Duckitt

et al. 2018

Euro J Lipid Sci & Tech

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Fatty acids have a great importance in several industrial activities like the manufacture of ingredients for foods, paints, soap, detergents and a wide array of other products in the fast moving consumer goods industry. Processing of fatty acids requires a good knowledge of transport properties, such as viscosity. This work presents a compilation of experimental values of the viscosity of three long‐chain saturated fatty acids, namely: myristic, palmitic and stearic acid. First, a study of the dependence of the viscosity of these fatty acids with temperature is presented comparing results with previously existing data in literature and validating data and models statistically. Then, a thorough analysis of the viscosity of binary mixtures of the aforementioned fatty acids was conducted. To do so, such property was measured over the entire range of compositions in increments of the molar fraction of the components of 0.1 at temperatures ranging from above the melting points of the fatty acids to 373.15 K and correlation with respect to composition and temperature with the Jouyban–Acree model. Last, the so‐called viscosity deviations were computed and correlated with Redlich–Kister equations to explain the variation as a function of the molar composition of the corresponding mixture. Discrimination of different models to correlate the experimental data was made on the basis of different statistical criteria. Practical Application: Good knowledge of transport properties such as viscosity is important to understand the physics and processing of materials. Contrary to simply using a viscometer, here cone and plate rheometry is used to accurately determine the viscosity of myristic, palmitic and stearic acids and their binary mixtures, which have high melting points compared to other liquids. In addition, the presentation of statistical discrimination tools like information criteria is highly relevant to understand the goodness of fit of models and the selection of the most statistically relevant equations without using more parameters than strictly necessary. The viscosities of pure myristic, palmitic and stearic acids as well as their binary mixtures are determined and a discrimination of models is performed to understand the most appropriate number of parameters to describe the behaviour.

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“…Considering the very limited information on the kinetics of the catalytic synthesis of GC available in the literature through this route [39] , the objective of the present work is to obtain a kinetic model as a necessary stage towards process development and reactor design. An assessment is herein made in physicochemical and statistical terms on whether there is a relationship between the kinetics of the reaction and the evolution of the dispersion-like system.…”

Section: Article In Pressmentioning

confidence: 99%

Experimental and modelling approach to the catalytic coproduction of glycerol carbonate and ethylene glycol as a means to valorise glycerol

Esteban

Ladero

Fuente

et al. 2016

Journal of the Taiwan Institute of Chemical Engineers

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Kinetics of the production of glycerol carbonate by transesterification of glycerol with dimethyl and ethylene carbonate using potassium methoxide, a highly active catalyst

Cited by 69 publications

References 50 publications

Effect of Operating Variables and Kinetics of the Lipase Catalyzed Transesterification of Ethylene Carbonate and Glycerol

Effect of Operating Variables and Kinetics of the Lipase Catalyzed Transesterification of Ethylene Carbonate and Glycerol

On the Discrimination of Models for the Viscometric Properties of Myristic, Palmitic and Stearic Acids and Their Binary Mixtures

Experimental and modelling approach to the catalytic coproduction of glycerol carbonate and ethylene glycol as a means to valorise glycerol

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