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

Esteban, Jesús; Ladero, Miguel; Fuente, Elena; Blanco, Ángeles Blanco; Garcı́a-Ochoa, Félix

doi:10.1016/j.jtice.2016.03.031

Cited by 23 publications

(20 citation statements)

References 47 publications

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“…The smectite clay under study was contacted with HCl for different lengths of time, from 0.5 to 20 h, and several key features were measured to select the most adequate contacting time. In Table 1, the yields after 24 h of reaction to solketal (ketal 1) and the ketal from cyclohexanone ( [1,4] dioxaspiro [4,5]decane-2-methanol or ketal 3), together with the specific surface (S BET ) and the Brönsted acidity are displayed, while Table 2 depicts the mineralogical data of these clays treated during different times with HCl 3 N. Finally, Figure 5 shows the initial reaction rate for the obtention of ketals 1 and 3 with fresh and used catalysts for the two reaction systems (systems 1 and 3). Activity and stability tests were performed using acetone and cyclohexanone as ketones to obtain the corresponding ketals 1 and 3.…”

Section: Catalyst Selectionmentioning

confidence: 99%

“…Thereby, the proper choice of heterogeneous catalyst constitutes a major scientific challenge in organic chemistry, in particular for glycerol recycling and upgrading. Several studies have focused on the valorization of glycerol as a byproduct in biodiesel industry [4,5], as it has attracted an appreciable attention.…”

Section: Introductionmentioning

confidence: 99%

“…Additionally, large quantities of glycerol are available as a reaction byproduct because of the development of biodiesel production by transesterification of vegetable oils [7]. Numerous main pathways of glycerol transformation have been reported in literature involving hydrogenolysis [8], dehydration [9], oxidation [10], carbonation [5,11], etherification [12,13], esterification [14,15], acetalization [14,16] and ketalization [17,18]. Therefore, a considerable number of chemical intermediates and commodities can be obtained from glycerol through optimized catalytic routes, as shown in Figure 1 [19].…”

Section: Introductionmentioning

confidence: 99%

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Green Production of Glycerol Ketals with a Clay-Based Heterogeneous Acid Catalyst

et al. 2019

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Glycerol remains a bottleneck for the biodiesel industry as well as an opportunity from the biorefinery perspective, having a notable reactivity as a platform chemical. In particular, glycerol ketals can be envisaged as oxygenates for fuel formulation. In this study, we have focused on the green synthesis of glycerol ketals by reacting glycerol with acyclic (acetone, butanone) and cyclic (cyclohexanone) ketones in the presence of an acid activated clay Tunisian AC in homogeneous systems under quasi-solventless conditions. These reactions were followed by on-line Fourier Transform Infrared Spectroscopy (FTIR) (namely, ReactIR 10). Firstly, the contacting time was selected studying the activity, stability and chemical characteristics of a set of catalysts. The 1-h activated clay AC was further characterized by X-Ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electronic Microscopy with Energy Dispersive Spectroscopy (SEM/EDS). Finally, the effect of the main operational variables (catalyst concentration, reagents molar ratio, time and temperature) were checked and we reflected on adequate second-order kinetic models with partial first-order deactivation.

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Section: Catalyst Selectionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Green Production of Glycerol Ketals with a Clay-Based Heterogeneous Acid Catalyst

et al. 2019

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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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“…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%

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

Cited by 23 publications

References 47 publications

Green Production of Glycerol Ketals with a Clay-Based Heterogeneous Acid Catalyst

Green Production of Glycerol Ketals with a Clay-Based Heterogeneous Acid Catalyst

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

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

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