Solvent effect investigation on the acid-catalyzed esterification of levulinic acid by ethanol aided by a Linear Solvation Energy Relationship

Baco, Sindi; Klinksiek, Marcel; Zakaria, Rashid Ismail Bedawi; Garcia-Hernandez, Elizabeth Antonia; Mignot, Mélanie; Legros, Julien; Held, Christoph; Moreno, Valeria Casson; Leveneur, Sébastien

doi:10.1016/j.ces.2022.117928

Cited by 14 publications

(17 citation statements)

References 74 publications

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“…To summarize the results, we found that these ions only contribute to < 1 mol% of the overall acid concentration at the initial reaction conditions. This result is in agreement what we found in previous work on ePC-SAFT predicted pK a values in different solvents compared to experimental data [13] . The ability to predict the solvent-dependent acid dissociation over the reaction coordinate then allowed us modeling the activity coefficients of the reacting agents including interactions to the catalyst species.…”

Section: Kinetic Model II -Influence Of Ions On Reactantssupporting

confidence: 93%

“…The detailed methodology is described in the literature [13] . Further, also the K th values of LA esterification for each temperature were determined using Eq.…”

Section: Reaction Equilibriamentioning

confidence: 99%

“…( 8), and the result is shown in Figure 1. values from Baco et al [ 13] with activity coefficients predicted by ePC-SAFT advanced using parameters summarized in Tables S1 -S3. Right: Natural logarithmic function of 𝐾 𝑡ℎ according to the Van't Hoff equation (Eq.…”

Section: Esterification Equilibriummentioning

confidence: 99%

“…The detailed methodology is described in the literature. [13] Further, also the K th values of LA esterification for each temperature were determined using Eq. ( 8) by using equilibrium mole fractions of all listed experiments in Table S4 and the respective activity coefficients using ePC-SAFT advanced.…”

Section: Reaction Equilibriamentioning

confidence: 99%

“…Further, within the esterification reaction the protonation of the carboxyl group is the rate-determining step and needs activation either by temperature or by a catalyst. [10] The kinetics of an acid-catalyzed esterification of LA to ELA in a temperature range of 50 to 80 °C was investigated in batch reactor by Baco et al [13] Although that study explored several conditions on kinetics, still it lacks in knowledge on the catalyst properties during the reaction coordinate, such as catalyst dissociation and molecular interactions of the catalyst. Activity-based approaches from Lemberg and Sadowski [14] allow predicting solvent effects on the reaction equilibrium and kinetics of esterification, but this model was limited to one catalyst concentration as catalyst effects on the kinetics were neglected.…”

Section: Introductionmentioning

confidence: 99%

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Activity‐Based Models to Predict Kinetics of Levulinic Acid Esterification

et al. 2022

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The solvent is of prime importance in biomass conversion as it influences dissolution, reaction kinetics, catalyst activity and thermodynamic equilibrium of the reaction system. So far, activity-based models were developed to predict kinetics and equilibria, but the influence of the catalyst could not be predicted by thermodynamic models. Thus, in this work, the thermodynamic model ePC-SAFT advanced was used to predict the activities of the reactants and of the catalyst at various conditions (temperature, reactant concentrations, γ-valerolactone GVL cosolvent addition, catalyst concentration) for the homogeneously acid-catalyzed esterification of levulinic acid (LA) with ethanol. Different kinetic models were applied, and it was found that the catalyst influence on kinetics could be predicted correctly by simultaneously solving the dissociation equilibrium of H2SO4 catalyst along the reaction coordinate and the relating reaction kinetics to proton activity. ePC-SAFT advanced model parameters were only fitted to reaction-independent phase equilibrium data, but the key reaction properties were determined by one experimental kinetic curve for a set of temperatures, yielding the reaction enthalpy at standard state ∆ 𝑅 𝐻 0 = 11.48 𝑘𝐽 𝑚𝑜𝑙 −1 , activation energy 𝐸 𝐴 = 30.28 𝑘𝐽 𝑚𝑜𝑙 −1 and the intrinsic reaction rate constant k = 0.011 s -1 at 323 K, which is independent of catalyst concentration. The new procedure allowed an a-priori identification of the effects of catalyst, solvent and reactant concentration on LA esterification.

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Section: Kinetic Model II -Influence Of Ions On Reactantssupporting

confidence: 93%

“…The detailed methodology is described in the literature [13] . Further, also the K th values of LA esterification for each temperature were determined using Eq.…”

Section: Reaction Equilibriamentioning

confidence: 99%

Section: Esterification Equilibriummentioning

confidence: 99%

Section: Reaction Equilibriamentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Activity‐Based Models to Predict Kinetics of Levulinic Acid Esterification

et al. 2022

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Unveiling Stereo‐Electronic Effects in Homogeneous Catalysis Integrating Theory and Experiments: the Potential of Dimeric Iron(III) Salen Complexes in Methyl Levulinate Transesterification

Perrella,

Langellotti,

Buttarazzi

et al. 2024

ChemCatChem

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Biomass represents an abundant and renewable source of raw materials that can be effectively converted into intermediates and base chemicals. Among these, levulinic acid has garnered significant attention due to its direct derivation from lignocellulosic biomass and the presence of two functional groups, a carboxylic acid, and a ketone, enabling diverse transformations into valuable products. Levulinic acid esters have already found applications in various industrial sectors such as cosmetics, plasticizers, and solvents. In this study, a broad array of alkyl levulinates has been successfully synthesized through homogeneous transesterification catalyzed by Lewis acids. A systematic screening of a library of μ‐oxo‐dinuclear Fe(III) salen complexes has been conducted, aiming to elucidate the impact of steric and electronic properties of their substituents. A complementary theoretical‐computational study based on quantum mechanics calculations and machine learning regression techniques has been employed to unravel the relationship between the structure of the catalysts and their corresponding properties, shedding light on the key factors influencing their catalytic performance.

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Efficient synthesis of acetylsalicylic acid over Y-immobilized cation exchange resin conjoined ultrasonic collaborative method under mild conditions

Yan,

Chen,

et al. 2024

Res Chem Intermed

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Solvent effect investigation on the acid-catalyzed esterification of levulinic acid by ethanol aided by a Linear Solvation Energy Relationship

Cited by 14 publications

References 74 publications

Activity‐Based Models to Predict Kinetics of Levulinic Acid Esterification

Activity‐Based Models to Predict Kinetics of Levulinic Acid Esterification

Unveiling Stereo‐Electronic Effects in Homogeneous Catalysis Integrating Theory and Experiments: the Potential of Dimeric Iron(III) Salen Complexes in Methyl Levulinate Transesterification

Efficient synthesis of acetylsalicylic acid over Y-immobilized cation exchange resin conjoined ultrasonic collaborative method under mild conditions

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