2,5-furandicarboxylic acid FDCA

Scheme 1. Oxidation products derived from HMF 2,5-furandicarboxaldehyde (FDC), 5-hydroxymethyl-2-furancarboxylic acid (HFCA), 5-formyl-2-furancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid (FDCA).

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. 

Oxidation reactions play a crucial role in the chemical industry, where >90% of the feedstocks derive from hydrocarbons - the most reduced organic chemicals on the planet. Sustainability concerns are demanding a greater shift toward biomass-derived feedstocks however, oxidation methods will continue to play a major role. For example, even as this book goes to press (March 2016), BASF and Avantium have just announced plans to pursue a joint venture for the production of 2,5-furandicarboxylic acid (FDCA), an important polymer-building block derived from biomass. The proposed 50000 metric tons per year plant will undoubtedly incorporate liquid phase aerobic oxidation chemistry similar to that described in Chapter 19 of this volume. 

A key intermediate in the synthesis of a number of pharmaceuticals, antifungals, and polymer precursors is 5-hydroxymethyl-2-fur-fural (HMF), which is produced by the dehydration of fructose or glucose. Of these applications, the synthesis of polymer precursors is of interest. For example, 2,5-furandicarboxylic acid (FDCA) can replace terephthalic acid commonly used in the manufacture of poly (ethylene terephthalate) (PET). 

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... 

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]. 

Chemical dehydration is employed to syntiiesize HMF using six member carbohydrates. HMF can be converted into a variety of furan derivatives through chemical manipulation (Tong et al., 2010). 2,5-furandicarboxylic acid (FDCA) can be derived from the oxidation of ITMF. In the production of polyester polymers, FDCA is recommended as an alternative to terephthalic... 

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