Density functional theory study of the reactivity and electronic structure of the transesterification of triacetin in biodiesel production via a sulfated zirconia heterogeneous catalysis

Muñiz, Jesús; Castillo, Roger; Robles, José B.; Sansores, Enrique

doi:10.1002/qua.25116

Cited by 8 publications

(4 citation statements)

References 55 publications

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“…Triacetin was used as a triglyceride model for the kinetic study of this reaction because it has the same chemical functionality as any triglyceride molecule, sharing the same reactivity principles. The transesterification of triacetin with methyl alcohol occurs in three sequential steps, as depicted in Scheme (Muñiz, Castillo, Robles, & Sansores, ).…”

Section: Resultsmentioning

confidence: 99%

A Kinetic Investigation of Triacetin Methanolysis and Assessment of the Stability of a Sulfated Zirconium Oxide Catalyst

Temoteo

Silva

Rodrigues

et al. 2018

J Americ Oil Chem Soc

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In this work, the activity and stability of a sulfated zirconium catalyst in transesterification reactions of triacetin, a model molecule, were investigated. This catalyst has Lewis and Brønsted acid sites and has shown to be highly active in reactions converting triacetin into methyl esters. This catalyst was synthesized using the impregnation method, and systematically characterized using the techniques of x‐rays diffraction (XRD), scanning electron microscopy, Fourier transform‐infrared spectroscopy (FT‐IR), Brunauer, Emmett, and Teller, and thermal gravimetry analysis (TGA). Kinetic studies were carried out to determine the activation energy as well as the reaction order. The effects of the main reaction parameters, such as temperature, the molar ratio, and the catalyst content, were evaluated. The reuse and possible leaching of the catalyst were also investigated. The highest efficiency (ca. 99% of methyl esters) was achieved in the sulfated zirconium oxide‐catalyzed transesterification reaction.

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Section: Resultsmentioning

confidence: 99%

A Kinetic Investigation of Triacetin Methanolysis and Assessment of the Stability of a Sulfated Zirconium Oxide Catalyst

Temoteo

Silva

Rodrigues

et al. 2018

J Americ Oil Chem Soc

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“…The basic knowledge of methanolysis and its competing reaction of triglyceride hydrolysis at the molecular level are of great importance for the development of biodiesel production. A DFT/B3LYP study of glycerol triacetate or triacetin as a model triglyceride compound was conducted in the presence of a sulfated zirconia catalyst and they were detected by the adsorption of triacetin and an alcohol solvent which caused the exchange H of alcohol with the group of triacetin which then causes the transesterification process to produce the experimentally observed methyl acetate (Muniz et al, 2016;Delesma et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

DFT Study of Transesterification and Hydrolysis of the Fatty Acid Triglycerides, Carried Out under Supercritical Fluid Conditions. Analysis of Thermochemistry and Kinetics

Габитова¹,

Kurdyukov²,

Гумеров³

et al. 2019

J. Eng. Appl. Sci.

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By quantum-chemical simulation using DFT method with B3LYP density functional and basis 6-311++g(df, p) in the implementation of the program Gaussian16 and subsequent comparison with calculations data, obtained by using density functional wB97XD/6-311++g(df, p), mechanism of reactions of transesterification and hydrolysis of fatty acid triglycerides, carried out under supercritical fluid conditions has been investigated. The energy characteristics of the elementary acts of potential steps for Supercritical Fluid (SCF) conditions has been calculated, their thermochemical analysis has been given, the rate constants of elementary acts for the temperature range 300-623 K has been investigated. It is shown that under supercritical fluid conditions, transesterification and hydrolysis of fatty acid triglycerides with dimer and trimer associates of alcohol and water in various combinations can proceed by one-step and two-step mechanism.

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“…However, the direct use of solid acid catalysts for the biodiesel production has not been widely explored due to its limitation of a slow reaction rate and the lack of fundamental theoretical studies about dealing with the reaction pathway of triacylglycerols on solid acids (Lam et al, ). Notably, the density functional theory (DFT) study examined the interaction of a sulfated zirconia (SZ) slab model system, estimating that the strong acidic catalyst could effectively reduce Gibbs free energies of the transesterification for triacetin in biodiesel production on the SZ surface (Muñiz et al, ). Augusto et al used DFT to analyze the H + ‐catalyzed ethanolysis of butyric acid monoacylglycerol, and found that the intrinsic H bonds played a key role in stabilizing the tetrahedral intermediate with the solvent effects being taken into account (da Silva et al, ).…”

Section: Introductionmentioning

confidence: 99%

A Density Functional Theory Study on the Acid‐Catalyzed Transesterification Mechanism for Biodiesel Production from Waste Cooking Oils

Tan

Zhang

et al. 2018

J Americ Oil Chem Soc

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The acid-catalyzed transesterification reaction has been one of the most effective methods to produce biodiesel, especially from waste cooking oils (WCO) with high contents of water and free fatty acids (FFA). However, in the acid-catalyzed processes, the H + action mechanism and the controlling step of the reaction rate have been ambiguous. To clearly understand the reaction process, the DMol3 module based on the density functional theory (DFT) was employed to investigate the acid (H + -)-catalyzed transesterification mechanism of methanol and oleic acid monoacylglycerol (OAM). The one step transesterification without a catalyst and the feasible paths of SN2 (substitution nucleophilic bimolecular) and SN1 (substitution nucleophilic unimolecular) reaction mechanisms with H + -based catalysts were built as Path 1, Path 2, and Path 3, respectively. The calculated structures, thermodynamic, and kinetic data revealed that the H + -based catalysts could effectively reduce the activation energy for the transesterification reaction, and the Path 2 based on the SN2 reaction mechanism was the optimal reaction path. A tetrahedral intermediate (IM2-2) could be generated with the highest active energy of 15.383 kcal mol −1 , implying that there was the most stable structure of IM2-2 as the key species in the transesterification process. Hence, the increasing decomposition rate of IM2-2 accelerated the forward reaction in H + -based biodiesel processes. The calculated active energy of 15.383 kcal mol −1 was in good agreement with the kinetic data for the monoacylglycerol transesterification of 15.067 kcal mol −1 . Our calculations should provide basic and reliable theoretical data for further understanding the mechanism of transesterification of WCO to biodiesel products in the future work.

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Density functional theory study of the reactivity and electronic structure of the transesterification of triacetin in biodiesel production via a sulfated zirconia heterogeneous catalysis

Cited by 8 publications

References 55 publications

A Kinetic Investigation of Triacetin Methanolysis and Assessment of the Stability of a Sulfated Zirconium Oxide Catalyst

A Kinetic Investigation of Triacetin Methanolysis and Assessment of the Stability of a Sulfated Zirconium Oxide Catalyst

DFT Study of Transesterification and Hydrolysis of the Fatty Acid Triglycerides, Carried Out under Supercritical Fluid Conditions. Analysis of Thermochemistry and Kinetics

A Density Functional Theory Study on the Acid‐Catalyzed Transesterification Mechanism for Biodiesel Production from Waste Cooking Oils

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