Assessing the Industrial Edge of the Lipase-Mediated Oxidation of 2,5-Diformylfuran to 2,5-Furandicarboxylic Acid: Rotating Bed Reactors, an “Acyl-Donor-Free” Oxidation Concept, and Environmental Aspects
Milica Milić, Guillem Vernet, Hai Yen Le, Ningning Zhang, Emil Byström, Pablo Domínguez de María, Selin Kara
{"title":"Assessing the Industrial Edge of the Lipase-Mediated Oxidation of 2,5-Diformylfuran to 2,5-Furandicarboxylic Acid: Rotating Bed Reactors, an “Acyl-Donor-Free” Oxidation Concept, and Environmental Aspects","authors":"Milica Milić, Guillem Vernet, Hai Yen Le, Ningning Zhang, Emil Byström, Pablo Domínguez de María, Selin Kara","doi":"10.1021/acs.oprd.4c00474","DOIUrl":null,"url":null,"abstract":"The lipase-mediated oxidation of 2,5-diformylfuran (DFF) to 2,5-furandicarboxylic acid (FDCA) via peracid formation is a promising alternative to valorizing furans from biorefineries. In this chemoenzymatic reaction, <i>Candida antarctica</i>lipase B (CALB) uses hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) and ethyl acetate as an acyl donor to form peracetic acid <i>in situ</i>, which subsequently performs the oxidation of DFF to FDCA, via the intermediate 5-formyl-2-furancarboxylic acid (FFCA). This study explores the reaction en route to its industrial application, identifying strengths and limitations. First, the origin of DFF is considered since it can proceed from biorefineries either in organic media or in aqueous solutions. The reaction is assessed in ethyl acetate with different water contents, showing that oxidations can be achieved in wet nonaqueous media. Moreover, a mixture of ethyl acetate and <i>tert</i>-butanol improves the FDCA yield 2-fold. Subsequently, the reaction is conducted using a rotating bed reactor (RBR), which may enable straightforward downstream processing while showing hints for future scale-up. Once H<sub>2</sub>O<sub>2</sub> dosage, rotating rate, and enzyme and substrate loadings are optimized, FDCA production of up to ∼27 g/L is achieved, yet still at low DFF selectivity (∼50%). To improve the atom economy of the reaction and enhance the option of organic media recycling, which saves significant CO<sub>2</sub> generation during incineration, an “acyl-donor-free” concept of the lipase-mediated oxidation of DFF to FDCA is proposed, which uses catalytic amounts of FDCA to be taken by the lipase to generate per-FDCA, to oxidize DFF to form the desired product subsequently. Overall, the enzyme-mediated oxidation of DFF to FDCA may become relevant in biorefineries if improvements in the enzyme stability (against H<sub>2</sub>O<sub>2</sub> and peracids), as well as in process conditions (e.g., H<sub>2</sub>O<sub>2</sub> and substrate addition, downstream, etc.) are adequately tuned.","PeriodicalId":55,"journal":{"name":"Organic Process Research & Development","volume":"69 1","pages":""},"PeriodicalIF":3.1000,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Process Research & Development","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.oprd.4c00474","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
引用次数: 0
Abstract
The lipase-mediated oxidation of 2,5-diformylfuran (DFF) to 2,5-furandicarboxylic acid (FDCA) via peracid formation is a promising alternative to valorizing furans from biorefineries. In this chemoenzymatic reaction, Candida antarcticalipase B (CALB) uses hydrogen peroxide (H2O2) and ethyl acetate as an acyl donor to form peracetic acid in situ, which subsequently performs the oxidation of DFF to FDCA, via the intermediate 5-formyl-2-furancarboxylic acid (FFCA). This study explores the reaction en route to its industrial application, identifying strengths and limitations. First, the origin of DFF is considered since it can proceed from biorefineries either in organic media or in aqueous solutions. The reaction is assessed in ethyl acetate with different water contents, showing that oxidations can be achieved in wet nonaqueous media. Moreover, a mixture of ethyl acetate and tert-butanol improves the FDCA yield 2-fold. Subsequently, the reaction is conducted using a rotating bed reactor (RBR), which may enable straightforward downstream processing while showing hints for future scale-up. Once H2O2 dosage, rotating rate, and enzyme and substrate loadings are optimized, FDCA production of up to ∼27 g/L is achieved, yet still at low DFF selectivity (∼50%). To improve the atom economy of the reaction and enhance the option of organic media recycling, which saves significant CO2 generation during incineration, an “acyl-donor-free” concept of the lipase-mediated oxidation of DFF to FDCA is proposed, which uses catalytic amounts of FDCA to be taken by the lipase to generate per-FDCA, to oxidize DFF to form the desired product subsequently. Overall, the enzyme-mediated oxidation of DFF to FDCA may become relevant in biorefineries if improvements in the enzyme stability (against H2O2 and peracids), as well as in process conditions (e.g., H2O2 and substrate addition, downstream, etc.) are adequately tuned.
期刊介绍:
The journal Organic Process Research & Development serves as a communication tool between industrial chemists and chemists working in universities and research institutes. As such, it reports original work from the broad field of industrial process chemistry but also presents academic results that are relevant, or potentially relevant, to industrial applications. Process chemistry is the science that enables the safe, environmentally benign and ultimately economical manufacturing of organic compounds that are required in larger amounts to help address the needs of society. Consequently, the Journal encompasses every aspect of organic chemistry, including all aspects of catalysis, synthetic methodology development and synthetic strategy exploration, but also includes aspects from analytical and solid-state chemistry and chemical engineering, such as work-up tools,process safety, or flow-chemistry. The goal of development and optimization of chemical reactions and processes is their transfer to a larger scale; original work describing such studies and the actual implementation on scale is highly relevant to the journal. However, studies on new developments from either industry, research institutes or academia that have not yet been demonstrated on scale, but where an industrial utility can be expected and where the study has addressed important prerequisites for a scale-up and has given confidence into the reliability and practicality of the chemistry, also serve the mission of OPR&D as a communication tool between the different contributors to the field.