Progress 09/01/23 to 08/31/24

Outputs
Target Audience:In keeping with the strategic goals of the USDA, teh creation of a sustainable bioindustry requires cost-effective, efficient processes for converting wood to biofuels, chemicals and other high-value products while mitigating impact on climate-change. Efficiencies can be achieved by increasing yields derived from biochemical and thermochemical conversion of forest residues, as well as developing new products with enhanced attributes of performance and sustainability from these materials. The goal of this term is to combine our expertise in reactive distillation and selective catalytic processing to demonstrate the viability of converting forest-derived lignocellulosic biomass into high value-added furandicarboxylic acid. This technology would meaningfully contribute towards maximizing the ability of American agricultural producers to prosper, promot American agricultural products and exports, facilitate rural prosperity and economic development and promote the productive and sustainable use of our national forest systems. Our development of FDCA would offer a bio-based plastic in the form of PEF, providing a cleaner, cheaper, healthier plastics solution to underserved communities across the nation. Changes/Problems:We have determined that conversion of FDCA to PEF is a more viable pathway towards commercialization. The end product being more marketable and widening the potential for customer acceptance. As such, we have engaged with University of Massachusetts Polymer Science Department to seek support and education on polymerization of FDCA. Although PEF is beyond the scope of this Phase II project, understanding of the downstream application is critical to incorporate appropriate intermediate processing in the FDCA process. In particular, focus on purification methods which will enable polyester synthesis from the FDCA monomer as described previously. What opportunities for training and professional development has the project provided?We have hired and trained two new engineers and one new intern for our program. In addition, we have attended and presented at a USDA National Poster presentation, sharing our technology and commercialization opportunity with our peers. We have sent our team to the University of Massachusetts to engage in training of technical analysis of results, specifically in the area of Nuclear Magnetic Resonanceand Mass Spectometry to better analyze experimental results and progress against our objectives. How have the results been disseminated to communities of interest?We have sent product for customer acceptance to a major plastics manufacturer. They are evaluating our product for purity and ultimately for acceptance into their manufaturing process. Feedback will be shared with us in the 2nd reporting period. KSE is collaborating with the University of Massachusetts Amherst through the Center for UMass/Industry Research on Polymers (CUMIRP) to establish high yield and scalable protocols for esterification of furan-derived FDCA which will streamline purification in KSE's process scheme to facilitate polyester-grade monomer for demonstration of polyethylene furanoate (PEF) manufacture What do you plan to do during the next reporting period to accomplish the goals?In ouir 2nd reporting period we will focus on Task 1 and Task 4 to conclude our objectives under this award. We continue to scale the entire process, provide product for potential customers for product testing. Our objective is to be readyto scale the process for commercial viability and customer acceptane testing and begin securing customer offtake agreements towards the end of the award period.

Impacts
What was accomplished under these goals? Task Description Objective 1 Lignocellulose biomass pretreatment & fractionation Representative lignocellulosic waste streams will be utilized to generate xylose-rich hydrolysates. Hemicellulose from pretreated timber residue (e.g. sawdust), hydrolysate representative of industrial processing (e.g. pulp manufacture), and furfural will be demonstrated. This task to be accomplished in Year 2 of the program. 2 Dehydration of xylose to furfural & oxidation to furoic acid Conversion of xylose-rich hydrolysates to furfural and furoic acid reactive intermediates at high conversion and selectivity will be scaled to 5L pilot operation. Reactive distillation techniques will be combined with continuous oxidation reaction and closed-loop solvent and catalyst recycle demonstration for incorporation into the economic modelling. Furfural oxidation kinetics have been delineated with further optimization of the process achieving 65% reduction in residence time and 1.5x more concentrated reagent stream with successful demonstration at pilot scale. 3 Furoic acid carboxylation to FDCA, catalyst regeneration, & product purification Furoic acid reactive intermediate will be processed in a suspension carboxylation reaction at pilot scale achieving closed-loop catalyst regeneration, product separation and purification to sample FDCA product for customer acceptance testing & toll manufacturing. Furoic acid carboxylation kinetics have similarly been elucidated with optimization resulting in 70% reduction in residence time and 30% more concentrated reagents. Carboxylation charge has similarly grown 2.5x to comparable pilot scale. In-house oxidation furoate salt has been demonstrated in the carboxylation reaction, eliminating reagent standards, carried through to purified furan dicarboxylic acid (FDCA) product demonstrating integrated process capability. Alkali chloride, a byproduct from post-carboxylation purification has been successfully captured and converted to alkali hydroxide via a pilot bipolar membrane electrodialysis process. The electrodialysis hydroxide has been successfully recycled to the oxidation process for a closed loop recycle. The electrodialysis hydroxide has also been successfully converted to carbonate form via gas absorption process and subsequently demonstrated to catalyze the carboxylation process for complete closed-loop processing. FDCA purification has been demonstrated to >95% purity and an alternative purification process has been demonstrated to the ester of FDCA, dimethyl furandicarboxylate (DMFD). The DMFD monomer has been polymerized to polyethylene furanoate (PEF) key to expanding demonstration products and valuable in commercial development discussions. 4 Cellulose fractionation and selective dehydration of glucose to furfural Glucose will be dehydrated with high selectivity to furfural enabling pretreatment expansion to cellulose recovery and incorporated into the economic modelling for standalone biorefinery application. This task to be accomplished in Year 2 of the program. 5 Techno economic analysis Develop a techno-economic model demonstrating the value-proposition of the KSE process in multiple configurations to advance rapid commercialization of the technology. A robust techno-ecomonic analysis has been developed in anticipation of future investment requests. This analysis is included in our interim technical report. Process simulation has been completed for the proposed FDCA process utilizing open-source CAPE-OPEN compliant software DWSIMto produce material and energy balances. These will be subsequently used in the second reporting period to estimate major process equipment sizing, capital costing, This will continue to evolve over the course of our 2nd period of performance. Detailed process simulation of the envisioned process has been completed providing the capability of sensitivity analysis of process changes as well as the foundation for the techno-economic analysis to be performed in the 2nd reporting period.

Publications