Biocatalyst and continuous microfluidic reactor for an intensified production of n-butyl levulinate: Kinetic model assessment

Biolubricants, plasticizers, bio-based rigid foams, and nonisocyanate polyurethanes can be made in a green way from epoxidized fatty acids. The classical technology for fatty acid epoxidation requires a reaction carrier, which acts as the real epoxidation agent. The process is complicated and involves a safety risk because of the appearance of percarboxylic acids. Therefore, the direct epoxidation of fatty acids in the presence of an immobilized enzyme is an attractive pathway to epoxidized fatty acids. Oleic acid was used as the model compound is this work, and commercial immobilized lipase Novozym 435 was used as the catalyst and hydrogen peroxide as the epoxidation agent. Batch and semibatch operation modes were tested in a laboratory-scale stirred tank reactor. The experimental results showed that almost complete conversions of the double bonds in oleic acid were achievable under isothermal batch and semibatch operation, with low concentrations of ring-opening byproducts. Semibatch operation gave an improvement of the product yield. Mathematical modeling of the experimental data was based on the reaction stoichiometry OA + HP → POA + W and OA + POA → EOA + OA, where OA = oleic acid, HP = hydrogen peroxide, POA = peroleic acid, W = water, and EOA = epoxized OA. Rate equations for the formation of peroleic acid and epoxide were derived, and the numerical values of the kinetic and adsorption parameters were estimated with nonlinear regression analysis. The reactor models consisted of ordinary differential equations, which were solved numerically during the parameter estimation until the optimal parameter values were reached. The model gave a very good description of the experimental data.

Section: Modeling Of Batch and Semibatch Epoxidation Processesmentioning

confidence: 99%

Fatty Acid Epoxidation on Enzymes: Experimental Study and Modeling of Batch and Semibatch Operation

Wikström

Aguilera

Tolvanen

et al. 2023

“…Triethylammonium hydrogen sulfate, [Et 3 NH][HSO 4 ], has been tested as an inexpensive ionic liquid catalyst for the preparation of alkyl levulinates at 120 °C for 3 h, obtaining the highest yield (84%) using butanol as alcohol; in addition, the ionic liquid can be easily separated from the reaction mixture with a phase separation using chloroform and reused without significant loss of activity . Novozym435 is an immobilized enzyme tested as a biocatalyst in a microfluidic system for the synthesis of n -butyl levulinate, yielding around 70% of conversion after 30 min at 65 °C . Photocatalytic systems have been reported using fluorinated TiO 2 materials and porphyrin-based photocatalysts, promising systems for transforming fatty acids through the esterification route.…”

Section: Introductionmentioning

confidence: 99%

“…In the recent past, pseudohomogeneous kinetic models, ,− enzymatic kinetic studies using models such as Michaelis–Menten and ping-pong Bi–Bi, and activity-based kinetic models have been reported for the production of alkyl levulinates as fuel additives. However, very few studies have been reported using heterogeneous kinetic models , such as Langmuir–Hinshelwood–Hougen–Watson (LHHW) and Eley–Rideal (ER), which are commonly more suitable approaches for modeling the heterogeneous catalytic esterification of fatty acids than the pseudohomogeneous model, which simply assumes a power-law model that considers easy access of active sites by the reactants due to a complete swelling of catalyst and does not give a priority to the adsorption phenomenon .…”

Section: Introductionmentioning

confidence: 99%

“…22 Novozym435 is an immobilized enzyme tested as a biocatalyst in a microfluidic system for the synthesis of nbutyl levulinate, yielding around 70% of conversion after 30 min at 65 °C. 23 Photocatalytic systems have been reported using fluorinated TiO 2 materials 24 and porphyrin-based photocatalysts, 25 promising systems for transforming fatty acids through the esterification route. The literature review showed that heterogeneous catalysts based mainly on Keggin-type heteropolyacids have been studied for esterification of levulinic acid or other fatty acids, as shown in entries 8−17 and 21−25 from Table 1 and additional references.…”

Section: Introductionmentioning

confidence: 99%

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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

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.

“…In recent decades, flow reactions have attracted attention related to the synthesis of pharmaceuticals and fine chemicals. − Compared to a batch reactor, the space–time yield of a flow reaction can be increased and the amount of production can be easily controlled . The heat and mixing efficiency in a flow reactor is better than in a batch reactor .…”

Section: Introductionmentioning

confidence: 99%

Transesterification of Methyl Acetate Using a Flow-Type Membrane Reactor with a Zeolite Membrane

Sakai

Sekine

Matsukata

2023

Continuous-flow reactors used for manufacturing pharmaceuticals and fine chemicals have been investigated because of their advantages of high space−time yield, heat efficiency, mixing efficiency, and selectivity. In this study, we developed a flow-type membrane reactor to perform transesterification, one of the important reactions in synthesizing pharmaceuticals and fine chemicals. We observed that anion exchange ionomer (AEI) membrane exhibited high methanol selectivity because of the molecular sieving effect from the reaction system of transesterification of methyl acetate and i-butyl alcohol. Because the equilibrium level of conversion is shifted by the selective removal of methanol, the yield of i-butyl acetate using the flow membrane reactor with the AEI membrane reached 66.2%, which exceeded the 42.9% level of the equilibrium conversion without membrane. The productivity of ester improved by 54% using the proposed membrane reactor. The flow-type membrane reactor exhibited stable performance for at least 9 h. The effect of residence time in a flow reactor on the yield of ester was also studied. A substantial amount of methanol is removed through the membrane by extending the residence time. A high methanol removal fraction leads to a substantial shift in the equilibrium level, thereby improving the product yield.