Recipient Organization
LYNNTECH, INC
7610 EASTMARK DRIVE SUITE 105
COLLEGE STATION,TX 77840
Performing Department
(N/A)
Non Technical Summary
A shift from conventional petrochemical feedstocks towards biomass-based feedstocks is of both environmental and economical importance for the future production of commodity chemicals. 5-hydroxymethylfurfural (HMF) is a versatile biomass-derived platform compound that can be used to synthesize a broad range of chemicals currently derived from petroleum, such as furan-2,5-dicarboxylic acid (FDA). A large-scale, sustainable use of HMF will require cellulosic biomass as feed. Conversion of cellulose to HMF or even glucose has been the primary bottleneck limiting energy-efficient and economical utilization of cellulosic biomass. Lynntech proposes to develop a simple, green, and scalable process to convert cellulose to HMF directly. HMF will be converted to FDA and 5-methoxymethyl-2-vinylfuran (MMVF) and their polymers will be synthesized to demonstrate the feasibility of using lignocellulosic biomass to produce commodity polymers. The Phase I project will establish the proof-of-concept of this approach, including conversion of corn stover to HMF using new low-cost solvents and nontoxic catalysts, production of FDA by aerobic catalytic reactions, and production of a polyamide from FDA and a vinyl polymer from MMVF. In Phase II of the research, Lynntech will optimize the processes for scalable production of HMF, develop a spectrum of polymers (polyesters, polyamides, and PET-like polymers), and partner with a commercial biofuel and bioproduct manufacturer to scale up the processes and produce commercial biomass-based polymers for applications. Biomass-based polymers offering significantly enviromental and economical benefits to our society and human lives.
Animal Health Component
100%
Research Effort Categories
Basic
(N/A)
Applied
100%
Developmental
(N/A)
Goals / Objectives
5-hydroxymethylfurfural (HMF) is a versatile biomass-derived platform compound that can be used to synthesize a broad range of chemicals currently derived from petroleum, such as furan-2,5-dicarboxylic acid (FDA). A large-scale, sustainable use of HMF will require cellulosic biomass as feed. Conversion of cellulose to HMF or even glucose has been the primary bottleneck limiting energy-efficient and economical utilization of cellulosic biomass. Lynntech proposes to develop a simple, green, and scalable process to convert cellulose to HMF directly. HMF will be converted to FDA and 5-methoxymethyl-2-vinylfuran (MMVF) and their polymers will be synthesized to demonstrate the feasibility of using abundant lignocellulosic biomass to produce commodity polymers. The Phase I project will establish the proof-of-concept of this approach, including conversion of corn stover to HMF using new low-cost solvents and nontoxic catalysts, production of FDA by aerobic catalytic reactions, and production of a polyamide from FDA and a vinyl polymer from MMVF. Low-cost ionic liquids as the solvent for direct conversion of corn stover to HMF will be prepared. An alternative low-cost nontoxic catalyst other than chromium for this system will be developed. The target of conversion efficiency of cellulose in corn stover to HMF is greater than 50 percent. Furan-2,5-dicarboxylic acid (FDA) and 5-methoxymethyl-2-vinylfuran (MMVF) from HMF obtained from corn stover will be synthesized. The target yield is greater than 80 percent. A polyamide from FDA and a vinyl polymer from MMVF will be synthesized; the target yield is greater than 98 percent. Structures and mechanical properties of these polymers will be characterized. These polymers are expected to have comparable properties to commercial commodity polymers.
Project Methods
1. Conversion of Lignocellulosic Biomass to 5-hydroxymethylfurfural (HMF). Our approach is to develop low-cost ionic liquids as the solvent to break down lignocellulosic biomass (corn stover) and convert glucose to fructose and HMF efficiently in presence of nontoxic catalysts. These ionic liquids are based on imidazole and hydrochloric acid complex, which has two distinct benefits: 1) low cost starting materials, ease of preparation; 2) addition of Bronsted acids-catalysis capability without compromising weakly ion-paired chloride ions which can form hydrogen bonds with the hydroxyl groups of cellulose, disrupting its extensive network of intra and interchain hydrogen bonds and favor the conversion reactions to HMF. Conversion of lignocellulosic biomass to HMF is the yield determining step for the proposed route. Our approach is to develop alternative nontoxic metal catalysts which can form coordinate complex with glucose for converting ligonocellulosic biomass to HMF and further improve the conversion efficiency. The yield of HMF from glucose is highly correlated with metal coordination. Potential metals include Mn, Fe, Ni, Cu, and Zn. Their ions could be effective catalysts by forming coordinate complexes with glucose and enhancing isomerization for conversion of glucose to fructose. 2. Conversion of HMF to Furan-2,5-dicarboxylic Acid and 5-Methoxymethyl-2-vinylfuran. HMF obtained from lignocellulose can be used to produce furan-2,5-dicarboxylic acid (FDA) and 5-hydroxymethyl-2-vinylfuran (HMVF). Conversion of HMF to FDA is feasible by aerobic HMF oxidation reactions, catalyzed with homogenous metal/bromide systems. HMF can be oxidized to 2,5-furandicarboxylic acid with high selectivity, and 70% conversion of HMF to FDA at 70 bar air has been obtained by using Co/Mn/Zr/Br catalyst at specific molar ratios of these elements. HMVF will be synthesized by converting formyl group in HMF into a vinyl group. Methylated HMF can be synthesized by the Wittig reaction, followed by converting formyl group into vinyl group to form 5-methoxymethyl-2-vinylfuran (MMVF). Polymers from MMVF exhibited much better heat resistance than the corresponding polymer without methoxy group. 3. Synthesis of Polyamide and Vinyl Polymers. Polyamide will be synthesized by condensation reactions from FDA and 1,3-diaminobenzene, which is an analogue of Kevlar and has particularly promising decomposition and glass transition parameters. An inexpensive, commercially available reagent, thionyl chloride, can be used as an activating agent for preparation of polyamide synthesis. Vinyl polymers from HMVF or MMVF could become one of the substitutes for commodity polymers, such as polyethylene, poly(vinyl chloride), and polystyrene, which are used today in large quantities throughout the world. In addition, furan derivatives are flame retardant and heat resistant, vinyl polymers from HMF could be expected to retain these properties even after the polymerization and have similar properties to polystyrene.