Cesium partially exchanged heteropolyacid salts: efficient solid catalysts to produce bioadditives from the levulinic acid esterification with alkyl alcohols

Lopes, Neide Paloma Gonçalves; Silva, Márcio José da

doi:10.1007/s11144-022-02310-x

Reac Kinet Mech Cat

2022

DOI: 10.1007/s11144-022-02310-x

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Cesium partially exchanged heteropolyacid salts: efficient solid catalysts to produce bioadditives from the levulinic acid esterification with alkyl alcohols

Neide Paloma Gonçalves Lopes

Márcio José da Silva

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2024

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Cited by 3 publications

References 51 publications

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Kinetic modeling of microwave-assisted esterification for biofuel additive production: conversion of levulinic acid with pentanol using Dowex® 50WX8 catalyst

Gallego-Villada,

Alarcón,

Sathicq

et al. 2024

Reac Kinet Mech Cat

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This study explores the esterification of levulinic acid with 1-pentanol, employing Dowex® 50WX8 as a catalyst under microwave irradiation. Key parameters such as the pentanol/acid molar ratio, temperature, and catalyst loading were evaluated and utilized for kinetic modeling. The kinetic behavior of the reaction was investigated using a dual-model approach: a pseudo-homogeneous model to account for the microwave effect and catalytic contributions modeled through LHHW and Eley–Rideal mechanisms. The best model was chosen based on statistical results obtained from Markov Chain Monte Carlo (MCMC) analysis, which involved an LHHW model with the surface reaction as the limiting step, resulting in an activation energy of 50.6 kJ mol−1 for the catalytic synthesis of pentyl levulinate. The role of the alcohol in the esterification route was explained, and catalytic stability was confirmed, with the catalyst maintaining activity over multiple cycles. The absence of mass transfer limitations was proved using the Weisz–Prater criterion. A plausible reaction pathway was proposed for the levulinic acid esterification over the 50WX8 catalyst. Graphical abstract

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Kinetic modeling of microwave-assisted esterification for biofuel additive production: conversion of levulinic acid with pentanol using Dowex® 50WX8 catalyst

Gallego-Villada,

Alarcón,

Sathicq

et al. 2024

Reac Kinet Mech Cat

View full text Add to dashboard Cite

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Levulinic Acid Esterification with n-Butanol over a Preyssler Catalyst in a Microwave-Assisted Batch Reactor: A Kinetic Study

Gallego-Villada,

Alarcón,

Cerrutti

et al. 2023

Ind. Eng. Chem. Res.

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A Preyssler-type heteropolyacid supported on silica, synthesized and characterized by FTIR, was tested for levulinic acid (LA) esterification with n-butanol under microwave-assisted batch reaction conditions. The optimal conditions were found to be 40 mg of catalyst, a 5:1 n-butanol/LA molar ratio at 160 °C and 3 h, resulting in 77% conversion with 100% selectivity. The catalytic effect was observed at low temperatures (100 °C), and the microwave effect was observed at high temperatures (160 °C). Yield to levulinate was improved (82%) with CuSO 4 as a dehydrating agent. A kinetic study using a pseudohomogeneous reversible model (PH, E Forward = 31.60 kJ mol −1 and E Reverse = 11.53 kJ mol −1 ) and a Eley−Rideal model (ER, E = 31.06 kJ mol −1 ) provided the best fitting to the experimental data. The Preyssler-based catalyst has potential for sustainable synthesis of n-butyl levulinate, a promising fuel additive and can be used at least five times without a loss of activity.

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Cesium Heteropolyacid Salts: Synthesis, Characterization and Activity of the Solid and Versatile Heterogeneous Catalysts

2023

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Keggin-type heteropolyacid cesium salts have been regarded as potential candidates for heterogeneous catalytic reactions. This review describes the success of Keggin-type heteropolyacids cesium salts (Cs-HPA salts) as efficient catalysts in various synthesis processes. The Cs-HPA catalysts can be synthesized as solid salts through the metathesis of a solution containing precursor HPA and another solution containing soluble Cs salt, which will give Cs-HPA salt as a solid precipitate. Alternatively, they can be also obtained from the commercial precursor HPA. In this review, all the routes to prepare the different cesium salts (i.e., saturated, lacunar, metal-doped) were described. These salts can be used in acid-catalyzed reactions (i.e., esterification, etherification, acetalization, dehydration) or oxidative transformations (oxidative esterification, oxidation, epoxidation). All of these reactions were addressed herein. Aspects related to the synthesis and characterization of these catalyst salts were discussed. This review aims to discuss the most pertinent heterogeneous catalytic systems based on Keggin HPA Cs salts. The focus was to correlate the physicochemical properties of these salts with their catalytic activity. Ultimately, the most recent advances achieved in the applications of these Cs-HPA salts as catalysts in the synthesis of industrial interest compounds were discussed. Cesium heteropoly salts are an alternative to the traditional soluble mineral acids as well as to solid-supported catalysts.

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Cesium partially exchanged heteropolyacid salts: efficient solid catalysts to produce bioadditives from the levulinic acid esterification with alkyl alcohols

Cited by 3 publications

References 51 publications

Kinetic modeling of microwave-assisted esterification for biofuel additive production: conversion of levulinic acid with pentanol using Dowex® 50WX8 catalyst

Kinetic modeling of microwave-assisted esterification for biofuel additive production: conversion of levulinic acid with pentanol using Dowex® 50WX8 catalyst

Levulinic Acid Esterification with n-Butanol over a Preyssler Catalyst in a Microwave-Assisted Batch Reactor: A Kinetic Study

Cesium Heteropolyacid Salts: Synthesis, Characterization and Activity of the Solid and Versatile Heterogeneous Catalysts

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