Location: Bio-oils Research
2024 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: Biobased epoxy resins from vegetable oils were developed. Commercial epoxy resins are widely utilized as coatings and adhesives, among other important applications. These materials are made from toxic and nonrenewable chemicals obtained from petroleum and do not biodegrade once they have reached the end of their operational lifespans. Because of this, the materials accumulate and persist in the environment as soil and water pollutants, which may cause negative human and wildlife health effects. Thus, ARS researchers in Peoria, Illinois, continued to develop renewable and biodegradable replacements based on vegetable oils and other agricultural chemicals. These biobased polymers are produced using a simple process that avoids the use of toxic materials. Characterization of the properties of the newly developed biopolymers revealed that they are potentially useful in adhesives applications. Future research will further improve properties through feedstock and structural modifications and expand industrial uses into surface coatings applications.
Objective 1: Biobased chewing gum elastomers from vegetable oils were developed. Over 1.7 trillion sticks of chewing gum are produced annually, which equates to a market size of approximately $25 billion. Chewing gum base materials primarily consist of petrochemically-based elastomers. These elastomers proliferate as unsightly waste in public areas due to their nonbiodegradable nature. Therefore, biobased and biodegradable chewing gum base materials were developed by ARS researchers in Peoria, Illinois. Citric acid is commonly found in citrus fruits and is generally regarded as safe for human consumption. Characterization of the properties of the newly developed renewable materials indicated that they are soft and rubbery (as opposed to hard and/or glassy) at room temperature and at body temperature, which is essential for chewing gum.
Objective 2.A: New renewable porous materials were developed. Porous materials have many advantages over nonporous polymers, such as low density, excellent heat and sound insulation, and high strength, which enables their use in structural and construction applications. However, most porous materials are nonrenewable and nonbiodegradable. For example, foam insulation is based on petrochemically-derived polyurethane, which is typically synthesized using a toxic blowing agent such as a chlorofluorocarbon. Therefore, ARS researchers in Peoria, Illinois, developed biobased replacement materials utilizing environmentally friendly materials and methods. The behavior of the reaction was studied to better understand the process and structure of the newly formed biobased materials.
Objective 2.A: A new technology was developed for modification of renewable materials into more useful products. Isomerization is a desirable chemical reaction that leads to products with different properties. A novel process was developed by ARS researchers in Peoria, Illinois. This process uses a common catalyst and an environmentally friendly reaction medium. The usefulness of the new method was demonstrated by converting jojoba oil (a natural material) into a new material. Natural jojoba oil is a liquid at room temperature. Isomerized jojoba oil is a solid with a melting point around the normal human body temperature. Thus, isomerization of jojoba oil and other materials using the newly developed technology offers the following advantages: 1) the ability to transform a liquid into a solid material that may have applications in the cosmetic and food areas due to its higher melting point and 2) the possibility for further modification into other materials.
Objective 2.B: Biodiesel fuels from vegetable oils were studied. The properties of biodiesel made from high oleic soybean oil, jojoba oil, and palm fatty acid distillate were investigated by ARS researchers in Peoria, Illinois. Cold flow properties, oxidative stability, kinematic viscosity (thickness), and lubricity (anti-wear) characteristics were measured. Comparisons were made to important biodiesel fuel standards and the results revealed satisfactory performance in most cases. Biodiesel resulting from palm fatty acid distillate froze at higher temperatures due to its different composition. In addition, a new and reusable catalyst was developed from waste palm leaf biomass. This new catalyst can efficiently convert low-quality, low-cost feedstocks directly into biodiesel. Normally, such feedstocks require an inefficient two-step process that utilizes nonreusable catalysts due to the presence of contaminants that deactivate conventional catalysts. Overall, this work showed that high oleic soybean oil, jojoba oil, and palm fatty acid distillate are suitable for utilization as feedstocks for production of biodiesel and that the new catalyst allows for facile conversion of low-quality feedstocks into biodiesel.
Accomplishments
1. New renewable porous materials were developed that will benefit both the environment and agricultural producers. Porous materials are important polymers that contain many small pores. Porous materials have several advantages over nonporous polymers, such as low density, excellent heat and sound insulation, and high strength, which enables their use in structural and construction applications. However, most porous materials are nonrenewable and nonbiodegradable and are synthesized using toxic substances. Therefore, ARS researchers in Peoria, Illinois, developed biobased porous materials from epoxidized vegetable oils using environmentally friendly methods and materials. The behavior of the reaction was studied to better understand both the process and the structure of the newly formed biobased porous materials. This result is beneficial to the agricultural and polymer industries, as well as the environment, because it represents a new source of porous materials produced from agricultural feedstocks that can replace existing materials derived from petroleum, thereby aiding American farmers by providing additional high-value outlets for soybean oil and other agricultural materials.
2. Biodiesel made from jojoba oil will benefit the environment. Biodiesel is normally produced from commodity crops that have competing food related applications. In addition, the cost of commodity oils can account for up to 80% of the cost to produce biodiesel. Therefore, non-food, low-cost feedstocks are needed to augment the supply of alternative fuels, avoid competing food applications, and lower the cost of biodiesel to levels more economically competitive with conventional diesel fuel. Thus, ARS researchers in Peoria, Illinois, investigated inedible jojoba oil as a feedstock for production of biodiesel. Jojoba oil is obtained from the seeds of the jojoba plant, which is native to parts of the United States and elsewhere. Fuel properties of the resulting jojoba oil-based biodiesel were investigated and compared to important fuel standards. The results indicated excellent low temperature performance, which is advantageous in winter months and/or in cold climates. These findings highlight the enormous potential of jojoba oil as an alternative inedible feedstock for biodiesel production, offering favorable fuel properties that can contribute to sustainable and environmentally friendly energy solutions. These results will be beneficial to the renewable fuels industry, jojoba farmers, and the public, as augmentation of alternative fuels facilitates the societal transition away from petroleum and its consequent environmental and climatic impacts.
Review Publications
Doll, K.M., Moser, B.R. 2023. Industrial chemicals via decarboxylation of natural carboxylic acids. In: Liu, Z., Kraus, G., editors. Green Chemistry and Green Materials from Plant Oils and Natural Acids. Vol. 83. Cambridge, UK:Royal Society of Chemistry Publishing. p. 144-158. https://doi.org/10.1039/9781837671595.
Liu, Z., Kraus, G. 2023. Green chemistry and green materials from plant oils and natural acids. Cambridge, UK: Royal Society of Chemistry Publishing. Volume 83, 280 p. https://doi.org/10.1039/9781837671595.
Shah, S.N., Liu, Z. 2023. Natural epoxy oil (Euphorbia oil) polymerization in liquid carbon dioxide-green solvents.In: Liu, Z, Kraus, G., editors. Green Chemistry and Green Materials from Plant Oils and Natural Acids. Volume 83. Cambridge, UK: Royal Society of Chemistry Publishing. p. 23-41. https://doi.org/10.1039/9781837671595.
Liu, Z., Shah, S.N., Vermillion, K., Cheng, H.N., Biswas, A. 2023. Lewis acid catalyzed cis (liquid) to trans (solid) isomerization of Jojoba oil in supercritical CO2. Biocatalysis and Agricultural Biotechnology. 54. Article 102902. https://doi.org/10.1016/j.bcab.2023.102902.
Moser, B.R., Cermak, S.C., Evangelista, R.L. 2023. Fully biobased epoxy resins from ring opening polymerization of epoxidized pennycress (Thlaspi arvense L.) oil with itaconic and citric acids. Industrial Crops and Products. 208. Article 117914. https://doi.org/10.1016/j.indcrop.2023.117914.
Cheng, H.N., Biswas, A., Kuzniar, G., Kim, S., Liu, Z., He, Z. 2024. Blends of carboxymethyl cellulose and cottonseed protein as biodegradable films. Polymers. 16(11). Article 1554. https://doi.org/10.3390/polym16111554.
Aliyu, M., Moser, B.R., Alharthi, F.A., Rashid, U. 2024. Efficient production of biodiesel from palm fatty acid distillate using a novel hydrochar-based solid acid catalyst derived from palm leaf waste. Process Safety and Environmental Protection. 187:1126-1139. https://doi.org/10.1016/j.psep.2024.05.040.