(19a) Catalytic Reaction Pathways and Process Synthesis for Biomass Conversion to High-Value Chemicals for Organic Dye and Polymer Applications

Decreasing prices of liquid fuels have attracted interest in the production of high-value chemicals from biomass. Biomass-derived 5-(hydroxymethyl) furfural (HMF) can be converted to high-value chemicals with versatile functional groups, and it generates new opportunities for practical applications in organic dye and polymer industries. We have developed an effective process to produce the HMF from glucose by combining catalytic reactions and Simulated-Moving-Bed (SMB) separation. Glucose feed is converted to fructose in acetone/water solvent by an enzymatic isomerization, and fructose is then converted to HMF by acid-catalyzed dehydration. For the modeling of SMB separation, a commercial chromatography resin (DOWEX 99) was examined to measure adsorption equilibrium parameters of glucose, fructose, and HMF. The estimated minimum selling price (MSP) of HMF from glucose was $1461/ton by techno-economic analysis (TEA). Additionally, as-synthesized HMF from sugar feed was reacted with acetone to produce an aldol-condensed product (HAH), where various functional groups can be inserted by using a base catalyst (NaOH) in acetone/water solvent. High purity HAH (>99% purity) was obtained by flowing water over the precipitated product. Finally, selective modifications of functional groups in HAH were investigated by catalytic etherification, reduction, and dimerization to demonstrate the possibility of applications as monomers in organic dyes and polyethers. TEA indicates that the process can produce HAH from fructose at a MSP of $1958/ton, showing its price potential to replace anthraquinone dye and bisphenol-A (BPA)-based polymer markets. The proposed processes with catalytic reaction routes can achieve effective control over functional groups in biomass and provide a facile approach to supply renewable high-value chemicals.