Source: LUNA INNOVATIONS INCORPORATED submitted to NRP
PRODUCTION OF RENEWABLE, HIGH PERFORMANCE POLYETHERETHERKETONE (PEEK) RESINS FROM HARDWOOD BIOMASS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
SMALL BUSINESS GRANT
Reporting Frequency
Annual
Accession No.
1019578
Grant No.
2019-33610-29741
Cumulative Award Amt.
$100,000.00
Proposal No.
2019-00701
Multistate No.
(N/A)
Project Start Date
Jul 15, 2019
Project End Date
Dec 14, 2020
Grant Year
2019
Program Code
[8.1]- Forests & Related Resources
Recipient Organization
LUNA INNOVATIONS INCORPORATED
1 RIVERSIDE CIR STE 400
ROANOKE,VA 24016
Performing Department
(N/A)
Non Technical Summary
Increasing legislative, social, and environmental factors are motivating the environmentally responsible use of American energy resources. These carbon feedstocks are finite but critical for production of electrical power, liquid fuels, and chemicals. The development of renewable power, through technologies like wind and solar, has started the process of decarbonizing the energy market, but commodity and specialty chemicals still require a carbon feedstock. The fluctuating price of crude oil in the past decade has resulted in a rise in chemical costs, affecting the price of petroleum-based products, plastics, and specialty polymers. Non-traditional and renewable feedstocks for these industries need to be developed to decrease dependence on petroleum, address economic concerns, and produce materials with little environmental impact. The economic viability of turning woody biomass into useful chemicals may play a critical role in this transition, while protecting forest resources and ensuring the continued existence of productive forest ecosystems.The proposed research program is focused on the production of engineering polymers from woody biomass using catalytic fast pyrolysis (CFP). State-of-the-art CFP produces multiple product streams including fuel vapors, condensed bio-oil, and an aqueous stream that contains valuable oxygenated aromatic compounds. These aqueous waste streams are typically discarded or used to generate process heat; however, value-added chemicals can found in these streams and have an untapped potential for production of new, high performance polymers. In partnership with the National Renewable Energy Laboratory (NREL), the Luna team will separate and recover oxygenated aromatics from a CFP process for the production of a cost-effective, high-performance, and bioderived polymer resin. Unlike petroleum derived equivalents, these materials derived during this program will be highly processable, and will readily dissolve in a variety of solvents. These characteristics, combined with lower costs of bioderived materials vs. petroleum based, are desirable in producing new high performance polymers from forestlands and waste wood feedstocks.
Animal Health Component
50%
Research Effort Categories
Basic
30%
Applied
50%
Developmental
20%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
51106802020100%
Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
0680 - Other products of the forest;

Field Of Science
2020 - Engineering;
Goals / Objectives
The USDA has established endeavors to enhance the productivity of forests by improving efficiency and profitability in environmentally sound ways. In an effort to find alternatives to petroleum products and produce renewables with minimal impact, the USDA has established that the conversion of forest resources to value-added products is a high priority. Technologies to promote energy independence, expand carbon feedstocks, reduce emissions and increase economic growth must be commercialized to meet these goals. Luna Innovations will meet these goals by demonstrating the feasibility of using monomers recovered from the aqueous waste streams of catalytic fast pyrolysis (CFP) thermochemical conversion processes for the production of performance-competitive, engineering polymer resins. This work will build on research in the areas of thermochemical conversion, valorization of CFP waste streams and new polymer development, and will promote bioderived materials and adoption of CFP technologies.The Functional Objectives of the multi-phase SBIR program are: Functional Objective 1: Demonstrate the processing of hardwood biomass into high value products, especially those obtained through petrochemical sources. Functional Objective 2: Improve overall forest productivity by increasing the profitability of biomass conversion through CFP aqueous waste stream valorization. Functional Objective 3: Increase the carbon-to-product efficiency of CFP biomass conversion to produce additional economic returns, promote forest management, increase waste wood utilization, and minimize CO2 emissions. Functional Objective 4: Demonstrate a potential market for the conversion of CFP aqueous waste stream products into high performance polymers.The overall Phase I program goal is to demonstrate the use of recovered monomers from CFP aqueous waste streams for the production of high performance polymer resins from hardwood biomass resources. The specific Phase I technical objectives are: Technical Objective 1: Produce high-value monomers from CFP and expand on previous economic feasibility estimates that evaluated the commercial viability of recovering these monomers from CFP waste streams. Technical Objective 2: Synthesize bioderived, high performance polymer resins from recovered monomer mixtures, produce larger quantities of resin, and characterize their thermal, physical, and mechanical properties. Technical Objective 3: Demonstrate renewable polymer production from recovered CFP aqueous waste stream monomers and compare their properties to petroleum based equivalents.
Project Methods
The following section outlines the methods to be used in the production of high performance polymers during the Phase I Program. Task 1 - Luna will be to establish the technical and economic success factors to be used throughout the Phase I effort. Discussions with USDA representatives, national laboratory partners, and industrial experts will serve as guidelines for developing a new high performance polymer resin derived from woody resources and the CFP aqueous phase separation process. Task 2 - Luna will demonstrate the commercial viability of viability of using CFP derived monomers in the production of the proposed renewable polymer resin. NREL has demonstrated that CFP aqueous waste streams can be produced from a variety of woody biomass feedstocks, including poplar, oak, and pine. Independent of biomass quality (cellulose, lignin, hemicelluloses content), all CFP aqueous streams contain high value monomers that can be recovered at high yields (>97 %) with NREL's existing separation process. NREL will produce intermittent batches of product over the course of 3-4 months for final demonstration of the renewable high performance polymer resin in later tasks. Compositional analysis will be performed after each batch with gas chromatography (GC-MS) and the resulting data will be provided to Luna. Model mixtures identical to those separated in NREL's product stream will then be prepared at Luna where GC-MS analysis will be used to verify composition. During this task, NREL will also leverage existing CFP aqueous phase carbon processing models, with ASPEN Plus-based material flows and equipment costs, to provide a technoeconomic analysis (TEA) related to this project. This initial TEA will also show potential new routes and process chains for increased recovery from aqueous streams derived from the CFP of hardwood biomass. Task 3: The goal of this task is to optimize the synthesis process for producing polymer resins using model mixtures of the monomer feedstocks produced in Task 2. Luna will purchase high purity, off-the-shelf chemicals to match the composition of the catechol product mixtures and will use GC-MS analysis to verify their composition compared to actual CFP product streams. The model mixtures developed throughout the program will be used to make Luna's new "bioderived" polymer resins that will be compared to final resins produced from actual CFP monomers in Task 5. The synthesis will involve a condensation reaction. Initial polymerization at Luna has shown a lower than expected MW. In Phase I, monomer ratios will be controlled to increase the MW up to 250 kDa with an anticipated polydispersity between 2.5 and 3.0 based on typical condensation polymerizations. The solid polymer products will then be separated and purified, and the molecular weight of the dried resins will be characterized using gel phase chromatography (GPC). The chemical structure of the resin powders will be verified with Luna's Thermo Nicolet IR model 6700 Fourier transform infrared spectroscopy (FTIR) in air on a Germanium plate attenuated total reflectance (ATR) accessory. Glass transition temperatures (Tg), melting points (Tm) and decomposition temperatures (Td) will be measured using Luna's suite of thermal analysis equipment including DSC and TGA. Finally, Luna will investigate the chemical resistance and solubility of the resins in various solvents at high and low temperatures to determine capabilities in harsh applications and to determine suitable solvents for solvent processing, extrusion, and manufacturing. The resulting thermal, physical, and chemical properties of the resins will be recorded over the course of the program with a focus on determining which impurities have the largest effect on resin properties. Luna will prepare additional resins using pure monomers as a control and will investigate the addition of various impurities. The Luna team will focus on developing ideal resin formulations that have high degradation temperatures, possess the ideal molecular weight for melt and solvent processing, and have a high chemical resistance. By actively determining which components have the largest effect on resin properties, Luna can tailor the properties of the resin to increase workability for manufacturing, melt processing, molding, and 3D printing. Task 4: Luna's engineering team will make use of our extensive polymer processing and testing equipment to generate tensile, compressive, and flexural bend samples of the developed resins for mechanical testing. Films, bars, and cylinders will be melt-cast using Luna's high temperature hydraulic press. Tensile testing will be performed in accordance with ASTM D638 (Standard Test Method for Tensile Properties of Plastics) using Type I tensile specimens die pressed from thin sheets. Luna will determine the ultimate tensile strength, elongation at break and tensile modulus. Flexural bend testing will be performed in accordance with ASTM D790 (Standard Test Methods for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Materials) using rectangular bars ( 0.125" x 0.5" x 5.0"). Luna will determine the material's flexural strength and modulus. Compressive strength testing will be performed in accordance with ASTM D695 (Standard Test Method for Compressive Properties of Rigid Plastics) using cylinders with a height to diameter ratio of 2:1. Compression testing will be used to determine the material's compressive strength and modulus. All mechanical properties will be compared to commercial polymer resin properties and resins synthesized over the course of the program. In all cases, material synthesized from pure monomer will serve as a control for NREL model mixtures containing impurities. All testing will be conducted on a Luna ADMET universal testing system. Both room and elevated temperature (>100 °C) will be conducted to validate mechanical properties vs. temperature. Additional coupons will be exposed to chemical such as acetone, isopropyl alcohol, methyl ethyl ketone, and various chlorinated solvents for extended periods of time. After soaking, coupons will be tested for tensile, flexural, and compressive properties at both room and elevated temperature to demonstrate chemical resistance. Finally, cyclic abrasion testing and surface analysis will be used to characterize the wear and surface properties. Task 5: The goal of this task is to produce a resin derived from actual CFP monomer product collected during Task 2. NREL will work throughout the Phase I program to collect 500 g or more of product for a final round of thermal, physical, chemical, and mechanical testing. Individual batches of product collected and analyzed by NREL will be combined during this effort to create sufficient quantities for resin synthesis and mechanical test specimen preparation. GC-MS analysis of the final mixture will be used to verify the composition of the mixed product and will be used to create an additional model mixture and model resin as a control. The bioderived resin will be compared to resins produced throughout the program and commercial polymers, and will be used to validate the use of CFP thermochemical conversion for producing renewable, high performance polymer resins with the realization that all biomass sources, catalysts and CFP processes will not produce the same high purity monomer feedstock. The result of this task will be a fully formulated, bioderived material that demonstrates the capabilities of producing high performance polymers from woody biomass resources.

Progress 07/15/19 to 12/14/20

Outputs
Target Audience:Polymeric materials are used in 3D pritning, coatings, adhesives, composites, and lightweight components. Of the most prevalent polymers in high volume consumer applications are those of melt processable thermoplastics. A majority of these thermoplastics are derived from petroleum and natural gas; however, there is growing interest in sustainable generation of polymer feedstock sources through forest resources and other renewable carbon feedstocks. Volatile prices of major raw materials including benzene, ethylene, propylene and styrene coupled with growing environmental concerns regarding their disposal has encouraged the industry to shift towards developing injection molded plastics, 3D printing plastics and compositesusing bio-based or partiall bio-basedthermoplastic counterparts. Major plastic manufacturers have been forming joint ventures with biotechnology companies to synergize their functions to manufacture bioderived plastics. Engineering thermoplastics are a subset of thermoplastics used in applications generally requiring higher performance in the areas of heat resistance, chemical resistance, impact, or mechanical strength. To put in perspective, the global injection molded plastic market size was valued at USD 200 billion in 2015, while comparatively the engineering plastics market is projected to reach over USD 105 Billion by 2026. This represents greater than 40% of the total plastic market value and would be an area for economic growth among forest derived, bioplastic feedstocks. New technologies are therefore needed to introduce cost reductions in the synthesis and manufacturing of engineering thermoplastics. Low-cost or bioderived will result in a more market-tolerable material that will find use in applications including 3D printing, insulation, coatings, films, biomedical implants, and mechanical parts. Monomers produced from the CFP aqueous phase have an untapped potential for production of pesticides, pharmaceuticals, fragrances, flavors and new polymers, and their recovery may be instrumental for improving CFP technologies and efficiently converting woody biomass into high-value engineering polymers. With respect to this SBIR program, the general audience is companies seeking sustaianble thermoplastic materials, companies conducting biomass conversion (especially thermochemcial conversion processes that produce aqueous waste streams), and end-users of thermoplastic who are will to pay premiums on or evaluate materials that are bioderived. During this Phase I program, Luna and NREL seeked to establish partnerships with companies constructing and operating biomass conversion facilities,those buying and utilizing feedstocks from these refineries, and producers and/or end-users of sustainable thermoplastic materials for a vriety of applications.Many of these companies are based in the US and are leading efforts in the production of bioderived polymers and commodity chemicals using forest and agricultural biomass. Many refineries currently use aqueous waste for process heating only. The Luna team's efforts to increase the value of CFP thermochemical conversion may improve adoption of CFP refineries, commercialization of new technologies, and investment from these companies and 3rd party chemical or polymer producers. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The Luna and NREL teams utilized thisSBIR program to cross-train staff (both research assistants and PD level personnelin multiple areas of research including biomass conversion, chemical separations, polymer synthesis, polymer processing, data analysis and analytical techniques including thermal analysis, mechanical testing ther materials characterization techniques. Junior researchers at Luna (typically with a bachelors degree) were exposed to unique polymer synthesis procedures that will greatly improve their capatbilities in follow-on programs as well as future polymer related efforst. At NREL, junior researchers (interns and those witha bachelors degree) were trained on biomass conversion processes, gas chromatography, process separations at both small and large scales, and thermal analysis of polymers. Staff at Luna and NREL were encouraged to actively participate in troubleshooting and technology brainstorming, and all program membersparticipated in report writing through the development of data, results, and individual task updates. As a part of this work, Luna trained one junior scientist in program management to help assist this employee in potential running future SBIR programs.NREL also trained research staff and post-doctoral fellows in new areas of research outside of their traditional field of expertise. How have the results been disseminated to communities of interest? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? At the conclusion of the Phase I program, the Luna team demonstrated the properties of a variety of commercial and in-house prepared engineer plastics. Several were commercially available products and others were derivatives of these materials with unique properties. Most importantly, one variant was partially dervied from products separated from typical aqueous waste streams from catalytical fast pyrolysis (CFP) thermochemcial conversion processes.As expected, the commercial engineering plasticmaterials were comparable to or outperformed the Luna prepared engineering plastics as well as those dervide from biomass materials.The commercial engineering plastics derives its excellent mechanical and thermal properties from its linear structure and extensive processing conditions in manufacturing. The Luna team demonstrated the partiallybiodervied engineering plastic variant possessedabove average properties compared to commodity plastics and other engineering properties. These aqueous waste streams of CFP processes are typically discarded or used to generate process heat; however, value-added chemicals like the one used on this program are found in these streams and have an untapped potential for production of new polymers. In partnership with the National Renewable Energy Laboratory (NREL), the Luna team demonstrated a cost-effective, high-performance, and bioderived engineering plasticthat may justify further consideration for processing these aqueous waste streams in commercial CFP processes and provide a cost- and performance-competitive product with unique properties for the aerospace, automotive, 3D printing, composite and coatings industries.Unlike petroleum dervied resins, these mateirals are amorphous, highly processable, and will readily dissolve in a variety of solvents. Their characteristics, combined with the lower costs of bioderived materials vs. petroleum based ones, are desirable in producing engineering plastics from woody biomass conversion processes. They also helpjustify further exploration and adoption of biomass conversion processes like CFP and as well as new processes to valorize aqueous waste streams produced during thermochemcial conversion.The Luna team is now in a position to scale up production of these new materials and further examine important factors that would affect the production of high-performance polymers derived from hardwood biomass. Luna will develop the Phase II work plan to optimize and scale up the production of the partially bioderived engineering plasticresins utilizing the materials derived from CFP aqueous waste streams. Results from the Phase I will be used to develop a detailed technical plan to achieve the Phase II milestones and will include investigations into assessing the cost of materials, scale up to pilot plant CFP production, and their relevance to commercial applications. This plan will also show how Luna, in partnership with NREL, will advance the current technology readiness level (TRL) from 2 (in-house demonstration of material at Luna) through TRL 5 in the Phase II and move rapidly toward a commercial aqueous waste streamrecovery process and cost- and performance-competitive polymer products that could be used in 3D printing, coatings, thermoplastic composites. Phase II planning will involve consultation with USDA personnel, PEEK producers, potential end-users, and other interested parties to further define the end-product specifications and market opportunities for commercial products in these industries. Luna will continue to explore related markets throughout the Phase II, with the intent of building technical interest and a business case to attract the necessary capital to commercialize the technology.

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