Process Intensification for the Production of Furandicarboxylic Acid

Terephthalic acid is large volume global commodity chemical used in the production of polyester polymers for applications such as polyester fibers, beverage bottles, and specialty polymers and resins. Terephthalic acid (PTA) is currently produced from hydrocarbon feedstocks by a complex, inefficient, energy intensive process, resulting in poor utilization of hydrocarbon resources, high energy consumption, and substantial greenhouse gas emissions. FDCA, 2,5-furandicarboxylic acid, a furan analog of terephthalic acid, may be utilized in place of terephthalic acid for the production of commodity polyester polymers. FDCA is derived from biomass carbohydrates, specifically fructose, with 5-hydroxymethylfurfural (HMF) as a key intermediate. The synthesis of the key HMF intermediate by conventional technology for the catalytic dehydration of fructose exhibits unacceptably poor selectivity. Commercial production of FDCA, and commodity polyester polymers based on FDCA, is currently hindered by poor selectivity for the catalytic dehydration of fructose to form the key HMF intermediate. The overall goal of this Small Business Innovation Research Phase I project is to establish the technical and economic feasibility of an innovative application of process intensification techniques to manufacture 2,5-furan dicarboxylic acid (FDCA) from fructose. The novel technology is based on renewable lignocellulosic biomass feedstock, and will result in substantial reduction in consumption of scarce hydrocarbon resources, reduction in greenhouse gas emissions, and support for the growth, productivity, and profitability of biorefineries. The key HMF intermediate for the synthesis of FDCA is produced by the catalytic dehydration of fructose. Substantial amounts of water are produced as a byproduct of the dehydration reaction. The presence of water in the dehydration reaction provokes numerous side reactions, resulting in the poor HMF selectivity. Improved selectivity to FDCA will be achieved by: (1) the utilization of process intensification techniques, specifically reactive distillation, to remove the byproduct water as it is generated by the reaction, thereby suppressing water-driven degradation reactions and increasing the rate of dehydration; (2) the development of novel catalysts, specifically designed for use in a reactive distillation environment, for the dehydration of fructose to an HMF ester with very high selectivity; (3) the utilization of an alternative reaction pathway, through an HMF ester, that further suppresses byproduct formation; and (4) the demonstration of the catalytic oxidation of HMF esters to FDCA at exceptionally high yield. The Phase I program will demonstrate the technical and economic feasibility of the novel reactive distillation technology through demonstration of the performance of the reactive distillation system, the evolution of new catalyst compositions designed specifically for use in reactive distillation, and will provide process design, energy usage, and life cycle cost comparisons to existing technologies. This program will be conducted with a subcontract to the Department of Chemical Engineering at the University of Massachusetts. Commercial Applications and Other Benefits: Selective catalytic dehydration of fructose by reactive distillation will allow commercial production of 2,5-furandicarboxylic acid (FDCA) from renewable lignocellulosic biomass feedstocks for the production of large volume commodity products, such polyester fibers, beverage bottles, and other products, resulting in reduced consumption of scarce hydrocarbon resources, supporting the growth of biorefineries, and improving long term U.S. competitiveness in global markets. Reactive distillation represents a new integrated process technology that can potentially be applied to the conversion of a wide range of commodity chemical products and intermediates to biomass based feedstocks.