Kinetic study of lipase-catalyzed esterification of furoic acid to methyl-2-furoate

Zhang, Yu; Di, Xiaohui; Wang, Wen; Song, Muping; Yu, Qiang; Wang, Zhongming; Yuan, Zhenhong; Chen, Xiaoyan; Xu, Huijuan; Guo, Ying

doi:10.1016/j.bej.2020.107587

Cited by 19 publications

(16 citation statements)

References 39 publications

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“…A ping‐pong mechanism is widely applied in studying esterification kinetics; 41 however, it is developed based on the Michaelis–Menten equation and cannot hold theoretically in heterogeneous system. Toward this, a mathematical model was developed by our previous report, 12 as shown in Eqn (5):

Y_{M F} = \frac{200 R_{m} k_{1} [1 - \exp (C_{F A_{0}} K t)]}{[k_{1} (R_{m} + 1) - K] - [k_{1} (R_{m} + 1) + K] \exp [C_{F A_{0}} K t]}

K = \sqrt{k_{1}^{2} {(R_{m} - 1)}^{2} + 4 k_{1} k_{2} R_{m}}

R_{m} = C_{M_{0}} / C_{F A_{0}}

where,

Y_{M F}

(%),

R_{M}

k_{1}

(L•h −1 •mol −1 ),

k_{2}

(L•h −1 •mol −1 ),

K

(L•h −1 •mol −1 ),

C_{M_{0}}

(g•L −1 ) and

C_{F A_{0}}

(g•L −1 ) represent the MF yield, the alcohol/acid molar ratio, the esterification rate constant, the hydrolysis rate constant, the apparent rate constant, initial methanol and FA concentration, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…It has been reported previously that unitary regression cannot properly quantify the relationship between

k_{1}

(or

k_{2}

) and

T

42 . To overcome the problem, binary regression was proposed, employing Eqn (4) as the constraint condition 12 . The fitted

E_{a}

for esterification and hydrolysis are 53 and 33 kJ•mol −1 (Table 2), respectively, indicating that the occurrence of esterification is more difficult than hydrolysis.…”

Section: Resultsmentioning

confidence: 99%

“…A ping-pong mechanism is widely applied in studying esterification kinetics; 41 however, it is developed based on the Michaelis-Menten equation and cannot hold theoretically in heterogeneous system. Toward this, a mathematical model was developed by our previous report, 12 as shown in Eqn (5):…”

Section: Enzymatic Esterification Kineticsmentioning

confidence: 99%

“…Methyl‐2‐furoate is a key fine chemical and its use ranges from being an explosion‐proof additive in gasoline to an antitumor drug 11 . It is also an internationally recognized synthetic fragrance 12 . There have been many reports on the synthesis of MF.…”

Section: Introductionmentioning

confidence: 99%

“…11 It is also an internationally recognized synthetic fragrance. 12 There have been many reports on the synthesis of MF. In most of these studies, metal catalysts containing elements such as Au, Pd, and Co have been used widely.…”

mentioning

confidence: 99%

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Chemoenzymatic conversion of furfural to methyl‐2‐furotate

Song

Zhang

et al. 2021

Biofuels Bioprod Bioref

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Furfural (FF) is an important bio‐based platform compound derived from lignocellulose. It can be converted into many industrially valuable chemicals, a typical one being methyl‐2‐furoate (MF). At present, MF production depends largely on vigorous one‐step chemical catalysis (oxidative esterification), in which expensive catalysts (precious metals) and a high temperature (60–120 °C) are required. To reduce the costs of this procedure, a mild, green, and cheap chemoenzymatic process is proposed where FF is initially chemically oxidized to furoic acid (FA), and then FA is enzymatically esterified to MF. Neither step requires an expensive catalyst, and both occur at low temperatures (30–50 °C). For the chemical oxidation process, the optimized FA yield of 83.7% was obtained at 40 °C with an FF/BTIC (1,3‐bis(2,4,6‐trimethylphenyl) imidazolium chloride) molar ratio of 0.18, 10 mL N‐methyl pyrrolidone, and 0.1 MPa oxygen pressure. For the enzymatic esterification, the optimized MF yield reached 80.6% at 50 °C with 50 mg•mL−1 enzyme loading and an alcohol/acid ratio of 7:1. Kinetic studies demonstrated the oxidation to be a sixth‐order reaction, and the esterification to be an endothermic reaction. For both oxidation and esterification reactions, the relationship between the rate constant and temperature agreed well with the Arrhenius equation. For esterification, the relationship between the equilibrium constant and the temperature also agreed with the Van't Hoff equation. A 67.5% MF yield was obtained when sequential oxidation and esterification were initiated from FF. The development of chemoenzymatic processes for MF production from FF is effective and has potential value in decreasing the production cost of MF. © 2021 Society of Chemical Industry and John Wiley & Sons, Ltd

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Y_{M F} = \frac{200 R_{m} k_{1} [1 - \exp (C_{F A_{0}} K t)]}{[k_{1} (R_{m} + 1) - K] - [k_{1} (R_{m} + 1) + K] \exp [C_{F A_{0}} K t]}

K = \sqrt{k_{1}^{2} {(R_{m} - 1)}^{2} + 4 k_{1} k_{2} R_{m}}

R_{m} = C_{M_{0}} / C_{F A_{0}}

where,

Y_{M F}

(%),

R_{M}

k_{1}

(L•h −1 •mol −1 ),

k_{2}

(L•h −1 •mol −1 ),

K

(L•h −1 •mol −1 ),

C_{M_{0}}

(g•L −1 ) and

C_{F A_{0}}

Section: Resultsmentioning

confidence: 99%

“…It has been reported previously that unitary regression cannot properly quantify the relationship between

k_{1}

(or

k_{2}

) and

T

42 . To overcome the problem, binary regression was proposed, employing Eqn (4) as the constraint condition 12 . The fitted

E_{a}

for esterification and hydrolysis are 53 and 33 kJ•mol −1 (Table 2), respectively, indicating that the occurrence of esterification is more difficult than hydrolysis.…”

Section: Resultsmentioning

confidence: 99%

Section: Enzymatic Esterification Kineticsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Chemoenzymatic conversion of furfural to methyl‐2‐furotate

Song

Zhang

et al. 2021

Biofuels Bioprod Bioref

Self Cite

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A review of synthesis of esters with aromatic, emulsifying, and lubricant properties by biotransformation using lipases

Bôas

Castro

2022

Biotech & Bioengineering

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The esterification reactions catalyzed by lipases are among the most significant biochemical processes of industrial relevance. The lipases have the function of versatility by catalyzing a diversity of reactions with extreme ease, obtaining quality products with high yield. Therefore, enzyme-catalyzed esterification has gained increasing attention in many applications, due to the importance of derived products.More specifically, lipase-catalyzed esterification reactions have attracted interest in research over the past decade, due to the increased use of organic esters in the chemical and biotechnology industry. These esters can be obtained by three techniques: extraction from natural sources, chemical and enzymatic syntheses. Biotechnological processes have offered several advantages and are shown as a competitive alternative to chemical methods due to high catalytic efficiency, mild operating conditions, and selectivity of natural catalysts. These an industrial point of view, reactions catalyzed by enzymes are the most economical approach to achieve green products with no toxicity and no harm to human health. Thus, this review presents a descriptive evaluation of the trends and perspectives applied to enzymatic esterification, mainly for the synthesis of esters with different properties, such as aromatics, emulsifiers, and lubricants using the esterification process. An emphasis is given to essential factors, which affect the lipase-catalyzed esterification reaction. In which, the parameters are dependent on the lipase source, a form of the biocatalyst (free or immobilized), the polarity of the reaction medium, the molar ratio between alcohol and acid, among other variables, are also discussed.

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Nano‐Au Anchored in Organic Base Group‐Grafted Silica Aerogel: A Durable and Robust Catalysts for Green Oxidative Esterification of Furfural

et al. 2022

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Inorganic metal (hydro)oxide supports with appropriate basicity or acid-base properties can promote oxidative esterification of furfural over Au-based catalysts, however, they suffer the problems of easy inactivation induced by the leaching of the components in this water-producing reaction and the shield of catalytic sites by product adsorption. In this work, we report efficient and stable oxidative esterification of furfural over Au nanoparticles anchored in aminopropyl-grafted silica aerogel. The support is insoluble and possesses no strong Lewis acid sites to adsorb oxygen-containing products or intermediates, reducing the probability of catalyst deactivation induced by adsorption. In 7 cycles of reactions, the catalyst maintained the initial activity without any treatments, the yields of alkyl furoate kept above 98 %, and no agglomeration and leaching of Au occurred. Moreover, the roles of Au, alkyl chain, À NH 2 group and Au-activated O species in reactions were clarified, and accordingly, a possible catalytic mechanism involving oxidative dehydrogenation was given.

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Kinetic study of lipase-catalyzed esterification of furoic acid to methyl-2-furoate

Cited by 19 publications

References 39 publications

Chemoenzymatic conversion of furfural to methyl‐2‐furotate

Chemoenzymatic conversion of furfural to methyl‐2‐furotate

A review of synthesis of esters with aromatic, emulsifying, and lubricant properties by biotransformation using lipases

Nano‐Au Anchored in Organic Base Group‐Grafted Silica Aerogel: A Durable and Robust Catalysts for Green Oxidative Esterification of Furfural

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