Location: Bio-oils Research2021 Annual Report
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.
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.
Under Objective 1, an industrially useful route to a renewable version of p-Cymene, an important industrial chemical currently derived from petroleum, was developed. p-Cymene is usually made from toluene or benzene and is used as a precursor for specialty chemicals like pharmaceuticals and pesticides. It can also be directly used as a solvent or as a component in perfumes. Our method involved catalytic dehydration and isomerization of a natural material, and the proposed mechanism of the transformation was uncovered. This transformation will be useful as a guide to the modification of many similar agricultural materials in support of the industrial utilization of agriculture. Under Objective 2, Sub-objective 2.A, new synthetic porous materials were made from biobased resources. They were characterized via the Brunauer-Emmett-Teller method and results show that they have a large surface area and excellent adsorption properties. Initial studies on absorption of lead using the new materials were done, with further investigations now underway. Because these materials involve the use of chemical catalysis to turn liquid oils into solid polymer resins, these materials are a potential industrial outlet for those agricultural oils. Under Objective 2, Sub-objective 2.B., significant improvements were made in the synthesis of fuels from biological sources. A new catalyst was uncovered that improves the product of the process, allowing a wider range of blending possibilities. This will be a key development in the replacement of petrochemically-based fuels.
1. Improved catalyst for fuel production from vegetable oils. The transformation of a vegetable oil into a material that can be directly used as a replacement for a petroleum oil is a difficult process. ARS researchers at Peoria, Illinois, have developed a new catalyst that is capable of producing a fuel from fatty acids. This new fuel has higher aromatic ring content compared to fuels made using other technologies, which is an advantage in the development of different fuel blends. These aromatic ring structures keep seals in the fuel systems pliable and elastic. They must be included in specified amounts for a fuel to meet standard specifications. The new product is a viable fuel replacement when used alone. Even more, the structures also make it compatible with petroleum fuels so blends of the biobased fuel with conventional fuel are possible. This technology will benefit those producing bio-derived fuels, as well as fuel blenders and end users. It will also enhance agricultural markets and reduce the consumption of petroleum resources.
Moser, B.R., Jackson, M.A., Doll, K.M. 2021. Production of industrially useful and renewable p-cymene by catalytic dehydration and isomerization of perillyl alcohol. Journal of the American Oil Chemists' Society. 98(3):305–316. https://doi.org/10.1002/aocs.12468.
Muturi, E.J., Hay, W.T., Doll, K.M., Ramirez, J.L., Selling, G.W. 2020. Insecticidal activity of Commiphora erythraea essential oil and its emulsions against larvae of three mosquito species. Journal of Medical Entomology. 57(6):1835-1842. https://doi.org/10.1093/jme/tjaa097.
Jin, C., Liu, G., Wu, G., Huo, S., Liu, Z., Kong, Z. 2020. Facile fabrication of crown ether functionalized lignin-based biosorbent for the selective removal of Pb(II). Industrial Crops and Products. 155. Article 112829. https://doi.org/10.1016/j.indcrop.2020.112829.
Xiao, L., Liu, Z., Li, N., Li, S., Fu, P., Wang, Y., Huang, J., Chen, J., Nie, X. 2020. A hyperbranched polymer from tung oil for the modification of epoxy thermoset with simultaneous improvement in toughness and strength. New Journal of Chemistry (RSC). 44:16856-16863. https://doi.org/10.1039/C9NJ06373K.
Sun, T., Zhang, H., Dong, Z., Liu, Z., Zheng, M. 2020. Ultrasonic-promoted enzymatic preparation, identification and multi-active studies of nature-identical phenolic acid glycerol derivatives. RSC Advances. 10:11139-11147. https://doi.org/10.1039/C9RA09830E.
Moser, B.R., Vermillion, K.E., Banks, B.N., Doll, K.M. 2020. Renewable aliphatic polyesters from fatty dienes by acyclic diene metathesis polycondensation. Journal of the American Oil Chemists' Society. 97(5):517-530. https://doi.org/10.1002/aocs.12338.
Muturi, E.J., Selling, G.W., Doll, K.M., Hay, W.T., Ramirez, J.L. 2020. Leptospermum scoparium essential oil is a promising source of mosquito larvicide and its toxicity is enhanced by a biobased emulsifier. PLoS One. 15(2):e0229076. https://doi.org/10.1371/journal.pone.0229076.