Location: Bio-oils Research
2023 Annual Report
Objectives
Objective 1: Resolving chemical processes advancing high-value polymers from agriculturally based oils and other feedstocks.
Objective 2: Enabling commercially relevant biobased materials and fuels.
Sub-objective 2.A. Transforming cellulose into porous composites used for controlled release or capture of analytes.
Sub-objective 2.B. Use of catalytic technology to synthesize biobased fuels with higher value.
Approach
Alternatives to petroleum-derived products from biobased products has been a research goal of private, university, and government researchers for many years. Although progress toward the goal of a major biobased economy is evident in several commercialized areas, such as biobased fuels, high profile business failures are unfortunately still commonplace in the private sector. The basis for biobased marketplace failures may be due to multiple factors, but enabling more high-value, cutting-edge products that expand the biobased market place is seen as a likely successful solution. This plan utilizes a balanced approach that combines mature technologies, with readily available markets, with newer and less developed areas of research. Existing markets, such as soybean oil-based structural resins and biobased aviation fuels, are targeted for improvements that will increase the biobased content of products that are already available in the marketplace. Entirely new products, such as biobased 3-dimensionally printed films and supercritical solvent-expanded ion absorbing resins, are proposed in this plan. Such an approach reaches across several industries while looking into the future at emerging technologies with market opportunities. More specifically, the first objective is the synthesis of high-value polymers. New reaction technologies and the application of polyfunctional co-reactants will lead to structures that have previously not been possible when starting from vegetable oils. The second objective will develop new materials from cellulosic feedstocks by transforming them into higher surface area polymers that can then be activated with further facile chemical modification. Additionally, newly developed decarboxylation technology will be leveraged to convert fatty acids into a high-value renewable hydrocarbon aviation fuel that mimics the composition of the corresponding petroleum-derived fuel.
Progress Report
Objective 1: Biopolymers from vegetable oils were synthesized using economical catalytic processes. New methods are required to convert vegetable oils into high-performance materials, such as paints, coatings, elastomers, and adhesives. Using fatty acids derived from vegetable oils as chemical building blocks, ARS researchers in Peoria, Illinois, advanced the knowledge and technology required to produce valuable industrial products from vegetable oils. Different chemical processes were employed to transform fatty acid derivatives into polymeric biomaterials. These processes utilized commercially available catalysts to produce renewable and biodegradable polymers with excellent thermal and chemical stability as well as solubility and melting properties needed for target applications. These polymers represent biobased alternatives to existing nonrenewable and nonbiodegradable petrochemically derived materials, which often cause water and soil pollution as well as negative human and wildlife health effects. Thus, this research fulfilled the 36-month milestone for Objective 1 by reporting polymer properties of commercial significance, such as thermal and oxidative behavior.
Objective 2.A: An ion-exchange method for the recovery of lithium from used batteries was developed. To combat global climate change, numerous governments and other entities have pledged to achieve carbon neutrality in the middle to long-term future. A critical step toward reaching that goal is electrified transportation, especially electric vehicles using lithium-ion batteries. However, economical recycling of used batteries remains elusive primarily due to the low value of recovered lithium. Thus, ARS researchers in Peoria, Illinois, in collaboration with university partners, developed a simple, economical, and practical method based on commercially mature ion-exchange technology to recover lithium from spent lithium iron phosphate cathodes. The process produces a potential high-value single or multi-element fertilizer containing potassium and phosphorous in a simple and low-cost way. This research therefore fulfilled the 36-month milestone for Objective 2.A by developing a new resin-based recycling technology for binding lithium from spent battery cathodes.
Objective 2.B: Biodiesel from citrus seed oil was studied. Citrus seed oil, an unutilized waste product of commercial orange juice production, was investigated as a low-cost feedstock for production of biodiesel. The oil, provided by ARS researchers in Fort Pierce, Florida, was converted to biodiesel by ARS researchers in Peoria, Illinois. The fuel properties of the resulting citrus seed oil methyl esters were measured and compared against the same data for biodiesel prepared from other plant seed oil feedstocks as well as against the American biodiesel standard. Findings indicated that the oxidative stability was below the minimum limit in the biodiesel standard, but this could be corrected with antioxidants. However, other important fuel properties were within the limits prescribed in the standard and similar to the properties of soybean oil-based biodiesel. Therefore, this research fulfilled the 36-month milestone for Objective 2.B by reporting the fuel properties of biodiesel prepared from citrus seed oil arising as waste from orange juice production.
Objective 2.B: A biobased anti-mosquito compound was developed. Mosquito-borne diseases continue to pose problems throughout the world, and without effective vaccines for specific diseases, vector control is one of the only practical solutions. Current methods for mosquito control include atmospheric and chemical insecticides, but these pose problems relating to environmental safety and onset of insecticide resistance. Thus, ARS researchers in Peoria, Illinois, developed a vegetable oil-based compound that showed larvicidal activity against Aedes aegypti, a common mosquito that spreads dengue fever, chikungunya, Zika fever, yellow fever, and other diseases. The key synthetic step produced a spin-labelled derivative that allowed for the study of mechanisms of larvicidal effectiveness. Findings indicated that the median lethal concentration (LC50) values for the new compound and a reference comparison were 48 and 55 ppm, respectively, indicating that spin labelling did not negatively affect larvicidal activity.
Accomplishments
1. Composite polymers with enhanced mechanical strength made from renewable agricultural precursors. Because conventional polymers have excellent durability and mechanical strength for high-performance applications, they have become ubiquitous in modern society. However, these materials are nonrenewable, not biodegradable, and in some cases toxic. Sustainable and biodegradable polymers prepared from renewable resources are attractive alternatives, but often suffer from performance deficiencies relative to conventional polymers. ARS researchers in Peoria, Illinois, developed a biobased composite polymer made from a mixture of cellulose nanofibers and polymerized soybean oil to overcome these deficiencies. Composites are advantageous because they are stronger and more functional than the individual components. The new composites are suitable for packaging, textile, fiber, and rigid plastic applications that non-composites are often unsuitable for. The resulting renewable composites had mechanical strengths that were comparable to nonrenewable conventional plastics like polypropylene. This result is beneficial to the agricultural and polymer industries because it represents a new source of polymer produced from agricultural materials that can potentially replace existing materials derived from petroleum, thereby aiding American farmers by providing additional high-value outlets for soybean oil and residual crop waste (cellulose).
2. Biodiesel made from waste citrus seeds. Worldwide, the citrus industry generates around 50-60 million tons of excess biomass when producing juices, such as orange juice, for human consumption. This underutilized biomass causes environmental issues when discarded, so finding uses for this material reduces food industry waste while potentially generating new revenue streams. ARS researchers in Peoria, Illinois, converted vegetable oil from waste citrus seeds into biodiesel using a well-known process referred to as transesterification. The fuel properties of the biodiesel produced from waste citrus seed oil were within the specifications of the American biodiesel standard. Using a waste oil as a feedstock for production of biodiesel is economically advantageous because feedstock acquisition can approach 80% of the cost to produce biodiesel when refined commodity lipids are utilized as feedstocks. These results are beneficial to the citrus and renewable fuels industries as well as to the public, as an agricultural waste material was utilized to produce an alternative fuel that facilitates the societal transition away from petroleum and its consequent environmental and climatic effects.
Review Publications
Zhang, X., Liu, Z., Qu, D. 2022. Proof-of-Concept study of ion-exchange method for the recycling of LiFePO4 cathode. Waste Management. 157:1-7. https://doi.org/10.1016/j.wasman.2022.12.003.
Doll, K.M., Muturi, E.J., Flor-Weiler, L.B. 2022. Combining TEMPO and methyl undecenoate to produce an effective anti-mosquito compound with convenient spin-labeling. Experimental Parasitology. 244. Article 108440. https://doi.org/10.1016/j.exppara.2022.108440.
Moser, B.R., Doll, K.M., Price, N.P. 2022. Comparison of aliphatic polyesters prepared by acyclic diene metathesis and thiol-ene polymerization of alpha,omega-polyenes arising from oleic acid-based 9-decen-1-ol. Journal of the American Oil Chemists' Society. 100:149-162. https://doi.org/10.1002/aocs.12668
Moser, B.R., Dorado, C., Bantchev, G.B., Winkler-Moser, J.K., Doll, K.M. 2023. Production and evaluation of biodiesel from sweet orange (Citrus sinensis) lipids extracted from waste seeds from the commercial orange juicing process. Fuel. 342. Article 127727. https://doi.org/10.1016/j.fuel.2023.127727.
Moser, B.R., Cermak, S.C., Doll, K.M., Kenar, J.A., Sharma, B.K. 2022. A review of fatty epoxide ring opening reactions: Chemistry, recent advances, and applications. Journal of the American Oil Chemists' Society. 99(10):801-842. https://doi.org/10.1002/aocs.12623.
Kohli, K., Chandrasekaran, S.R., Prajapati, R., Kunwar, B., Al-Salem, S., Moser, B.R., Sharma, B.K. 2022. Pyrolytic depolymerization mechanisms for post-consumer plastic wastes. Energies. 15(23). Article 8821. https://doi.org/10.3390/en15238821.
Winfield, D.D., Moser, B.R. 2023. Selective hydroxyalkoxylation of epoxidized methyl oleate by an amphiphilic ionic liquid catalyst. Journal of the American Oil Chemists' Society. 100(3):237-243. https://doi.org/10.1002/aocs.12672.
Hanif, M., Bhatti, I., Hanif, M., Rashid, U., Moser, B.R., Hanif, A., Alharthi, F. 2023. Nano-magnetic CaO/Fe2O3/Feldspar catalysts for the production of biodiesel from waste oils. Catalysts. 13(6). Article 998. https://doi.org/10.3390/catal13060998.
Shah, S.N., Liu, Z., Sharma, B.K. 2023. Glycerol Monooleate (GMO): a valuable biobased lubricity and pour point enhancer blend component for the ULSD fuel. ACS Omega. 8(22):19503-19508. https://doi.org/10.1021/acsomega.3c00889.
