Whole Cell Biocatalysis of 5-Hydroxymethylfurfural for Sustainable Biorefineries

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Abstract

The implementation of cost-effective and sustainable biorefineries to substitute the petroleum-based economy is dependent on coupling the production of bioenergy with high-value chemicals. For this purpose, the US Department of Energy identified a group of key target compounds to be produced from renewable biomass. Among them, 5-hydroxymethylfurfural (HMF) can be obtained by dehydration of the hexoses present in biomass and is an extremely versatile molecule that can be further converted into a wide range of higher value compounds. HMF derivatives include 2,5-bis(hydroxymethyl)furan (BHMF), 5-hydroxymethyl-furan-2-carboxylic acid (HMFCA), 2,5-diformylfuran (DFF), 5-formyl-2-furancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid (FDCA), all presenting valuable applications, in polymers, bioplastics and pharmaceuticals. Biocatalysis conversion of HMF into its derivatives emerges as a green alternative, taking into account the high selectivity of enzymes and the mild reaction conditions used. Considering these factors, this work reviews the use of microorganisms as whole-cell biocatalysts for the production of HMF derivatives. In the last years, a large number of whole-cell biocatalysts have been discovered and developed for HMF conversion into BHMF, FDCA and HMFCA, however there are no reports on microbial production of DFF and FFCA. While the production of BHMF and HMFCA mainly relies on wild type microorganisms, FDCA production, which requires multiple bioconversion steps from HMF, is strongly dependent on genetic engineering strategies. Together, the information gathered supports the possibility for the development of cell factories to produce high-value compounds, envisioning economical viable biorefineries.

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Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited

Joseph J Bozell, Gene R. Petersen (2010)

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Production of 2,5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF): recent progress focusing on the chemical-catalytic routes

Muhammad Sajid, Xuebing Zhao, Dehua Liu (2018)

The research progress on the production of 2,5-furandicarboxylic acid by the oxidation of biomass-derived 5-hydroxymethyl furfural has been reviewed, focusing on the chemical-catalytic routes. Furandicarboxylic acid (FDCA) has been considered as a good precursor, instead of petroleum-derived terephthalate acid (TPA), for producing green polymers such as polyethylene 2,5-furandicarboxylate (PEF). The production of FDCA from biomass or its derived sugars or platform chemicals generally involves chemical, biological and electrochemical methods, while the chemical-catalytic way seems to be the most promising in terms of the yield, reaction rate and product purity. The oxidative production of FDCA from bio-based 5-hydroxymethylfurfural (HMF) has attracted the most attention; it can be carried out by electrochemical, catalytic and non-catalytic processes. In the present work, we have comprehensively reviewed the current progress on the production of FDCA from HMF, primarily focusing on the chemical-catalytic approaches. The most frequently used catalysts for the chemical-catalytic methods are oxides of noble metals but their high cost, poor availability and recycling are the major hindrances to their commercial acceptance. Transition metal oxides are good alternatives but they suffer from relatively low FDCA yield. Electrochemical oxidation of HMF can be a good alternative route for FDCA production with simultaneous H 2 production but the yield and product recovery have to be further improved. Biocatalytic processes can produce FDCA with comparative yields under mild conditions but they can only be operated at low concentrations of HMF with much lower productivity. It is recommended that future works should be focused on, but not limited to, the comprehensive evaluation of different routes in terms of catalyst development and characterizations, process parameters, product yield and purity, as well as economic feasibility. The kinetics and reaction mechanisms of the process also need to be more deeply investigated to guide further process intensification.