2,5-Furandicarboxylic Acid furfural

Hydroxymethyl furfural. 2,5-diformylfuran (DFF) is a furan derivative that has many uses, including use as a polymer building block. By utilizing a platinum catalyst supported on carbon, and running the reaction in water at high temperatures, DFF is produced as the major product in neutral solution. If low temperatures and high pH are employed, 2,5-furandicarboxylic acid results. 

This chapter provides an industrial perspective on several oxidation routes to new bio-based molecules. In particular, it focuses on the use of Co/Mn/Br catalyst systems in air oxidations, based on the Amoco Mid-Century catalyst system used for / r -xylene oxidation (also see Chapter 4), as an efficient methodology for the conversion of 5-(hydroxymethyl)furfural (HMF) and 5-(methoxymethyl)furfural (MMF) to 2,5-furandicarboxylic acid (FDCA) in Avantium s YXY process. In addition, other less-studied conversions, such as methyl levulinate (ML) to succinic acid (SA), lignin to a variety of aromatic and phenolic carboxylic acids, are discussed as well. 

I 19 From Terephthalic Acid to 2,5-Furandicarboxylic Acid An Industrial Perspective Table 19.3 Oxidation of 5-(methoxymethyl)furfural (MMF). 

The innermost zone covers chemicals for which no petrochemical route exists, and therein lies a great opportunity to produce them from carbohydrate feedstocks (in the case that a market for them is present or arises) gluconic [91,92] and glucaric acids [17], furyl glycolic acid [87], furandicarboxylic acid [85], and fermentation-derived malic, citric, succinic, and itaconic acids [17]. Besides these, the sugar alcohols xylitol [78] and sorbitol [81, 93-95], as well as isosorbide [82, 96, 97], HMF [80,98], and furfural [44,99] are also present, along with tetroses and their derivatives obtained by dehydration [100]. For these molecules, it is virtually certain that no petrochemical-based production will ever be developed. Note that levulinic acid [67, 101-103] is at the border of this zone. 

Abstract 2,5-Furandicarboxylic acid (FDCA) is considered a highly promising bio-based alternative to terephthalic acid for the production of polymers. Wholecell biotransformation of 5-(hydroxymethyl)furfural (HMF) into FDCA is catalyzed by the HMF/furfural oxidoreductase HmfH from Cupriavidus basilensis... 

Chemical Production of 5-(Hydroxymethyl)furfural and 2,5-Furandicarboxylic Acid... 

Fig. 2 Putative subcellular localization of HMF oxidizing reactions in P. putida strains S12 HmfH (a), S12 B38 (b), and S12 B97 (c). ADH aldehyde dehydrogenase from either C. basilensis HMF14 (c) or native to P. putida S12 (p). HMF 5-(hydroxymethyl)furfural, HMF acid 5-(hydroxymethyl)furoic acid, FFA 5-formylfuroic acid, FDCA 2,5-furandicarboxylic acid...

Casanova O, Iborra S, Corma A (2009) Biomass into chemicals aerobic oxidation of 5-hydroxymethyl-2-furfural into 2,5-furandicarboxylic acid with gold nanoparticle catalysts. ChemSusChem 2(12) 1138-1144... 

Koopman F, Wierckx N, deWindeJH, Ruijssenaars HJ (2010b) Identification and characterization of the furfural and 5-(hydroxymethyl)furfural degradation pathways of Cupriavidus basilensis HMF14. Proc Natl Acad Sci USA 107(11) 4919 924 Kroger M, Prusse U, Vorlop KD (2000) A new approach for the production of 2,5-furandicarboxylic acid by in situ oxidation of 5-hydroxymethylfurfural starting from fructose. Top Catal 13(3) 237-242... 

Furan derivatives such as 5-hydroxymethylfurfural (HMF), furfural (FUR), and 2,5-furandicarboxylic acid (FDCA) were listed as the top 10 value-added bio-based chemicals by the US Department of Energy [154]. 

Furfural is one of the members of the Fiuanics class, which also covers a group of molecules, including 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid, and 2,5-dimethylfuran. Furfural is syntiiesized by the chemical dehydration of five carbon carbohydrates such as xylose and arabinose. Furfural is a well-known chemical product with a static market. 

Koopman, R, Merckx, N., de Winde, J.H., Ruijssenaars, H.J., 2010a. Efficient whole-cell biotransformation of 5-(hydroxymethyl) furfural into FDCA, 2,5-furandicarboxylic acid. Bioresource Technology 101,6291-6296. 

Sahu, R., Dhepe, P.L., 2014. Synthesis of 2,5-furandicarboxylic acid by the aerobic oxidation of 5-hydroxymethyl furfural over supported metal catalysts. Reaction Kinetics Mechanisms and Catalysis 112 (1), 173-187. 

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