Kinetic model assessment for the synthesis of γ-valerolactone from n-butyl levulinate and levulinic acid hydrogenation over the synergy effect of dual catalysts Ru/C and Amberlite IR-120

Jose Delgado; Wenel Naudy Vasquez Salcedo; Giulia Bronzetti; Valeria Casson Moreno; Mélanie Mignot; Julien Legros; Christoph Held; Henrik Grénman; Sébastien Leveneur

doi:10.1016/j.cej.2021.133053

Kinetic model assessment for the synthesis of γ-valerolactone from n-butyl levulinate and levulinic acid hydrogenation over the synergy effect of dual catalysts Ru/C and Amberlite IR-120

Jose Delgado, Wenel Naudy Vasquez Salcedo, Giulia Bronzetti, Valeria Casson Moreno, Mélanie Mignot, Julien Legros, Christoph Held, Henrik Grénman, Sébastien Leveneur^*

^*Corresponding author for this work

Process- och energiteknik gemensamma

Research output: Contribution to journal › Article › Scientific › peer-review

42 Citations (Scopus)

Abstract

The production of platform molecules from the valorization of lignocellulosic biomass is increasing. Among these plateform molecules, γ-valerolactone (GVL) is a promising one and could be used for different industrial applications. This molecule is synthesized from levulinic acid (LA) or alkyl levulinates (AL) through a tandem hydrogenation/cyclization (lactonization) cascade. A lot of investigations have been carried out to develop the best catalyst for the hydrogenation step by using solely LA or AL. However, one should keep in mind that in the AL production via fructose alcoholysis, there is also LA production, and both are present in the product mixture during the further conversion. To the best of our knowledge, no article exists describing the hydrogenation of LA and AL simultaneously in one-pot. Also, the literature reporting the use of solid catalyst for the second cyclization step is rare. To fill this gap, the hydrogenation of levulinic acid and butyl levulinate (BL) was studied over Ru/C and Amberlite IR-120. Several kinetic models were evaluated via Bayesian inference and K-fold approach. The kinetic assessment showed that a non-competitive Langmuir-Hinshelwood with no dissociation of hydrogen where LA, BL and H₂ are adsorbed on different sites (NCLH1.2) and non-competitive Langmuir-Hinshelwood with dissociation of hydrogen where LA, BL and H₂ are adsorbed on different sites (NCLH2.2) are the best model to describe this system. The presence of LA and Amberlite IR-120 allows to increase the kinetics of cyclization steps, and in fine to accelerate the production of GVL.

Original language	English
Article number	133053
Journal	Chemical Engineering Journal
Volume	430
Early online date	21 Oct 2021
DOIs	https://doi.org/10.1016/j.cej.2021.133053
Publication status	Published - 15 Feb 2022
MoE publication type	A1 Journal article-refereed

Funding

The authors thank the Maîtrise des Risques et Environementaux department, and the Erasmus programme to make the research project of Giulia Bronzetti possible. The authors thank the Ministry of High Education, Science and Technology of Dominican Republic (MESCYT). For the analytical part, the authors thank University of Rouen Normandy, INSA Rouen Normandy, the Centre National de la Recherche Scientifique (CNRS), European Regional Development Fund (ERDF) N° HN0001343, Labex SynOrg (ANR-11-LABX-0029), Carnot Institute I2C, the graduate school for reasearch XL-Chem (ANR-18-EURE-0020 XL CHEM) and Region Normandie for their support. GC/FID was financed by FEDER RIN Green Chem 2019NU01FOBC08 N° 17P04374. This research was funded, in whole or in part, by [ANR-DFG, ANR-20-CE92-0002 Deutsche Forschungsgemeinschaft (DFG) - Project number 446436621]. The authors thank the Ma?trise des Risques et Environementaux department, and the Erasmus programme to make the research project of Giulia Bronzetti possible. The authors thank the Ministry of High Education, Science and Technology of Dominican Republic (MESCYT). For the analytical part, the authors thank University of Rouen Normandy, INSA Rouen Normandy, the Centre National de la Recherche Scientifique (CNRS), European Regional Development Fund (ERDF) N? HN0001343, Labex SynOrg (ANR-11-LABX-0029), Carnot Institute I2C, the graduate school for reasearch XL-Chem (ANR-18-EURE-0020 XL CHEM) and Region Normandie for their support. GC/FID was financed by FEDER RIN Green Chem 2019NU01FOBC08 N? 17P04374. This research was funded, in whole or in part, by [ANR-DFG, ANR-20-CE92-0002 Deutsche Forschungsgemeinschaft (DFG) - Project number 446436621].

Keywords

Bayesian statistics
Cross-validation
Kinetic modeling
Levulinic acid
γ-valerolactone

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Delgado, J., Vasquez Salcedo, W. N., Bronzetti, G., Casson Moreno, V., Mignot, M., Legros, J., Held, C., Grénman, H., & Leveneur, S. (2022). Kinetic model assessment for the synthesis of γ-valerolactone from n-butyl levulinate and levulinic acid hydrogenation over the synergy effect of dual catalysts Ru/C and Amberlite IR-120. Chemical Engineering Journal, 430, Article 133053. https://doi.org/10.1016/j.cej.2021.133053

@article{00393858bda94347840a1885ee02bd50,

title = "Kinetic model assessment for the synthesis of γ-valerolactone from n-butyl levulinate and levulinic acid hydrogenation over the synergy effect of dual catalysts Ru/C and Amberlite IR-120",

abstract = "The production of platform molecules from the valorization of lignocellulosic biomass is increasing. Among these plateform molecules, γ-valerolactone (GVL) is a promising one and could be used for different industrial applications. This molecule is synthesized from levulinic acid (LA) or alkyl levulinates (AL) through a tandem hydrogenation/cyclization (lactonization) cascade. A lot of investigations have been carried out to develop the best catalyst for the hydrogenation step by using solely LA or AL. However, one should keep in mind that in the AL production via fructose alcoholysis, there is also LA production, and both are present in the product mixture during the further conversion. To the best of our knowledge, no article exists describing the hydrogenation of LA and AL simultaneously in one-pot. Also, the literature reporting the use of solid catalyst for the second cyclization step is rare. To fill this gap, the hydrogenation of levulinic acid and butyl levulinate (BL) was studied over Ru/C and Amberlite IR-120. Several kinetic models were evaluated via Bayesian inference and K-fold approach. The kinetic assessment showed that a non-competitive Langmuir-Hinshelwood with no dissociation of hydrogen where LA, BL and H2 are adsorbed on different sites (NCLH1.2) and non-competitive Langmuir-Hinshelwood with dissociation of hydrogen where LA, BL and H2 are adsorbed on different sites (NCLH2.2) are the best model to describe this system. The presence of LA and Amberlite IR-120 allows to increase the kinetics of cyclization steps, and in fine to accelerate the production of GVL.",

keywords = "Bayesian statistics, Cross-validation, Kinetic modeling, Levulinic acid, γ-valerolactone",

author = "Jose Delgado and \{Vasquez Salcedo\}, \{Wenel Naudy\} and Giulia Bronzetti and \{Casson Moreno\}, Valeria and M{\'e}lanie Mignot and Julien Legros and Christoph Held and Henrik Gr{\'e}nman and S{\'e}bastien Leveneur",

note = "Funding Information: The authors thank the Ma{\^i}trise des Risques et Environementaux department, and the Erasmus programme to make the research project of Giulia Bronzetti possible. The authors thank the Ministry of High Education, Science and Technology of Dominican Republic (MESCYT). For the analytical part, the authors thank University of Rouen Normandy, INSA Rouen Normandy, the Centre National de la Recherche Scientifique (CNRS), European Regional Development Fund (ERDF) N° HN0001343, Labex SynOrg (ANR-11-LABX-0029), Carnot Institute I2C, the graduate school for reasearch XL-Chem (ANR-18-EURE-0020 XL CHEM) and Region Normandie for their support. GC/FID was financed by FEDER RIN Green Chem 2019NU01FOBC08 N° 17P04374. Funding Information: This research was funded, in whole or in part, by [ANR-DFG, ANR-20-CE92-0002 Deutsche Forschungsgemeinschaft (DFG) - Project number 446436621]. Funding Information: The authors thank the Ma?trise des Risques et Environementaux department, and the Erasmus programme to make the research project of Giulia Bronzetti possible. The authors thank the Ministry of High Education, Science and Technology of Dominican Republic (MESCYT). For the analytical part, the authors thank University of Rouen Normandy, INSA Rouen Normandy, the Centre National de la Recherche Scientifique (CNRS), European Regional Development Fund (ERDF) N? HN0001343, Labex SynOrg (ANR-11-LABX-0029), Carnot Institute I2C, the graduate school for reasearch XL-Chem (ANR-18-EURE-0020 XL CHEM) and Region Normandie for their support. GC/FID was financed by FEDER RIN Green Chem 2019NU01FOBC08 N? 17P04374. This research was funded, in whole or in part, by [ANR-DFG, ANR-20-CE92-0002 Deutsche Forschungsgemeinschaft (DFG) - Project number 446436621]. Publisher Copyright: {\textcopyright} 2021 Elsevier B.V.",

year = "2022",

month = feb,

day = "15",

doi = "10.1016/j.cej.2021.133053",

language = "English",

volume = "430",

journal = "Chemical Engineering Journal",

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Delgado, J, Vasquez Salcedo, WN, Bronzetti, G, Casson Moreno, V, Mignot, M, Legros, J, Held, C, Grénman, H & Leveneur, S 2022, 'Kinetic model assessment for the synthesis of γ-valerolactone from n-butyl levulinate and levulinic acid hydrogenation over the synergy effect of dual catalysts Ru/C and Amberlite IR-120', Chemical Engineering Journal, vol. 430, 133053. https://doi.org/10.1016/j.cej.2021.133053

Kinetic model assessment for the synthesis of γ-valerolactone from n-butyl levulinate and levulinic acid hydrogenation over the synergy effect of dual catalysts Ru/C and Amberlite IR-120. / Delgado, Jose; Vasquez Salcedo, Wenel Naudy; Bronzetti, Giulia et al.
In: Chemical Engineering Journal, Vol. 430, 133053, 15.02.2022.

Research output: Contribution to journal › Article › Scientific › peer-review

TY - JOUR

T1 - Kinetic model assessment for the synthesis of γ-valerolactone from n-butyl levulinate and levulinic acid hydrogenation over the synergy effect of dual catalysts Ru/C and Amberlite IR-120

AU - Delgado, Jose

AU - Vasquez Salcedo, Wenel Naudy

AU - Bronzetti, Giulia

AU - Casson Moreno, Valeria

AU - Mignot, Mélanie

AU - Legros, Julien

AU - Held, Christoph

AU - Grénman, Henrik

AU - Leveneur, Sébastien

N1 - Funding Information: The authors thank the Maîtrise des Risques et Environementaux department, and the Erasmus programme to make the research project of Giulia Bronzetti possible. The authors thank the Ministry of High Education, Science and Technology of Dominican Republic (MESCYT). For the analytical part, the authors thank University of Rouen Normandy, INSA Rouen Normandy, the Centre National de la Recherche Scientifique (CNRS), European Regional Development Fund (ERDF) N° HN0001343, Labex SynOrg (ANR-11-LABX-0029), Carnot Institute I2C, the graduate school for reasearch XL-Chem (ANR-18-EURE-0020 XL CHEM) and Region Normandie for their support. GC/FID was financed by FEDER RIN Green Chem 2019NU01FOBC08 N° 17P04374. Funding Information: This research was funded, in whole or in part, by [ANR-DFG, ANR-20-CE92-0002 Deutsche Forschungsgemeinschaft (DFG) - Project number 446436621]. Funding Information: The authors thank the Ma?trise des Risques et Environementaux department, and the Erasmus programme to make the research project of Giulia Bronzetti possible. The authors thank the Ministry of High Education, Science and Technology of Dominican Republic (MESCYT). For the analytical part, the authors thank University of Rouen Normandy, INSA Rouen Normandy, the Centre National de la Recherche Scientifique (CNRS), European Regional Development Fund (ERDF) N? HN0001343, Labex SynOrg (ANR-11-LABX-0029), Carnot Institute I2C, the graduate school for reasearch XL-Chem (ANR-18-EURE-0020 XL CHEM) and Region Normandie for their support. GC/FID was financed by FEDER RIN Green Chem 2019NU01FOBC08 N? 17P04374. This research was funded, in whole or in part, by [ANR-DFG, ANR-20-CE92-0002 Deutsche Forschungsgemeinschaft (DFG) - Project number 446436621]. Publisher Copyright: © 2021 Elsevier B.V.

PY - 2022/2/15

Y1 - 2022/2/15

N2 - The production of platform molecules from the valorization of lignocellulosic biomass is increasing. Among these plateform molecules, γ-valerolactone (GVL) is a promising one and could be used for different industrial applications. This molecule is synthesized from levulinic acid (LA) or alkyl levulinates (AL) through a tandem hydrogenation/cyclization (lactonization) cascade. A lot of investigations have been carried out to develop the best catalyst for the hydrogenation step by using solely LA or AL. However, one should keep in mind that in the AL production via fructose alcoholysis, there is also LA production, and both are present in the product mixture during the further conversion. To the best of our knowledge, no article exists describing the hydrogenation of LA and AL simultaneously in one-pot. Also, the literature reporting the use of solid catalyst for the second cyclization step is rare. To fill this gap, the hydrogenation of levulinic acid and butyl levulinate (BL) was studied over Ru/C and Amberlite IR-120. Several kinetic models were evaluated via Bayesian inference and K-fold approach. The kinetic assessment showed that a non-competitive Langmuir-Hinshelwood with no dissociation of hydrogen where LA, BL and H2 are adsorbed on different sites (NCLH1.2) and non-competitive Langmuir-Hinshelwood with dissociation of hydrogen where LA, BL and H2 are adsorbed on different sites (NCLH2.2) are the best model to describe this system. The presence of LA and Amberlite IR-120 allows to increase the kinetics of cyclization steps, and in fine to accelerate the production of GVL.

AB - The production of platform molecules from the valorization of lignocellulosic biomass is increasing. Among these plateform molecules, γ-valerolactone (GVL) is a promising one and could be used for different industrial applications. This molecule is synthesized from levulinic acid (LA) or alkyl levulinates (AL) through a tandem hydrogenation/cyclization (lactonization) cascade. A lot of investigations have been carried out to develop the best catalyst for the hydrogenation step by using solely LA or AL. However, one should keep in mind that in the AL production via fructose alcoholysis, there is also LA production, and both are present in the product mixture during the further conversion. To the best of our knowledge, no article exists describing the hydrogenation of LA and AL simultaneously in one-pot. Also, the literature reporting the use of solid catalyst for the second cyclization step is rare. To fill this gap, the hydrogenation of levulinic acid and butyl levulinate (BL) was studied over Ru/C and Amberlite IR-120. Several kinetic models were evaluated via Bayesian inference and K-fold approach. The kinetic assessment showed that a non-competitive Langmuir-Hinshelwood with no dissociation of hydrogen where LA, BL and H2 are adsorbed on different sites (NCLH1.2) and non-competitive Langmuir-Hinshelwood with dissociation of hydrogen where LA, BL and H2 are adsorbed on different sites (NCLH2.2) are the best model to describe this system. The presence of LA and Amberlite IR-120 allows to increase the kinetics of cyclization steps, and in fine to accelerate the production of GVL.

KW - Bayesian statistics

KW - Cross-validation

KW - Kinetic modeling

KW - Levulinic acid

KW - γ-valerolactone

UR - https://www.scopus.com/pages/publications/85118187574

U2 - 10.1016/j.cej.2021.133053

DO - 10.1016/j.cej.2021.133053

M3 - Article

AN - SCOPUS:85118187574

SN - 1385-8947

VL - 430

JO - Chemical Engineering Journal

JF - Chemical Engineering Journal

M1 - 133053

ER -

Delgado J, Vasquez Salcedo WN, Bronzetti G, Casson Moreno V, Mignot M, Legros J et al. Kinetic model assessment for the synthesis of γ-valerolactone from n-butyl levulinate and levulinic acid hydrogenation over the synergy effect of dual catalysts Ru/C and Amberlite IR-120. Chemical Engineering Journal. 2022 Feb 15;430:133053. Epub 2021 Oct 21. doi: 10.1016/j.cej.2021.133053

Kinetic model assessment for the synthesis of γ-valerolactone from n-butyl levulinate and levulinic acid hydrogenation over the synergy effect of dual catalysts Ru/C and Amberlite IR-120

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