Research Project: New High-Value Biobased Materials with Applications Across Industry

Location: Bio-oils Research

2022 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
Under Objective 1, polymers were prepared from biobased products using economical catalytic conversions. New routes are needed to transform natural oils into high-performance materials such as paints, coatings, and adhesives. Using chemical building blocks made from fatty acids, ARS researchers in Peoria, Illinois, are making progress toward those routes. A chemical process called acyclic diene metathesis (ADMET) polymerization was employed to achieve the transformation. The system uses commercially available catalysts and can make products with a wide range of molecular weights needed for advanced materials such as biodegradable medical devices, composite fibers, and adhesives. The products from this work showed good solubility, chemical stability, and melting temperatures. Additionally, the process is such that all atoms from the starting material end up in the products, as it does not produce any unwanted side products, making it highly efficient. These renewable polymers represent biobased alternatives to existing petrochemically-based materials, which often cause water and soil pollution in addition to negative health effects. Under Objective 2, Sub-objective 2.A, a renewable polymer coating system was formulated. Durable coatings are required for many of the items that people use every day. Many of these high-performance coatings, while effective, contain volatile organic chemicals. Conventional coatings that use natural oils are currently not strong enough for applications that require high abrasion resistance such as stair railings, desktops, and other furniture. However, ARS researchers in Peoria, Illinois, are testing a new approach to make a biobased coating that is highly durable. By mixing a natural oil with a biobased additive that is found in apple juice, a new coating material was produced. The product was applied to a surface and then cured by a simple process using ultraviolet light to form a coating with excellent properties. A formulation that is up to 58% biobased was developed. This work will benefit those looking to use safe commodity oils in applications that need new versatile coatings. Additionally, a 3-dimensional print method was also improved, where cellulose was coated with a soybean oil polymer. Under Objective 2, Sub-objective 2.B, a partially biobased electrochemically active material was developed. Materials with electrochemical properties are needed for the next generation of batteries, fuel cells, and active catalysts of the future. Inclusion of biobased materials into these components is not a current practice as conventional petroleum-derived polymers are still the material of choice for these manufacturers. However, ARS researchers in Peoria, Illinois, are investigating a way to incorporate natural materials into these advanced products. Starting from a medium chain length fatty acid, a new electrochemical catalyst in which overall material is approximately 50% comprised of the plant-based fatty acid was produced. This new product was tested in an electrochemical reaction and gave conversion rates similar to the conventional material.

Accomplishments
1. Developed new 3-dimensional printing technology for composite materials. The synthesis of materials that are made from natural products, yet are as useful as conventional materials, is an elusive goal. The starting point toward this goal requires finding natural materials that have characteristics that allow them to be converted into durable goods. A promising candidate for this is vegetable oil. Another candidate is cellulose, the structural part of the cell walls of green plants. Considerable work has been done using each of these, but the results often fall short of the strength and other properties needed. In this research, the two commodities were combined into something that is a stronger and more functional polymer than could be made from either commodity alone. In order to get the reinforcing material where it needs to be, ARS researchers in Peoria, Illinois, developed a new 3-dimensional printing technology. The cellulose component is the core of the new product, which is then coated with a modified vegetable oil, layer by layer. The new composite is then cured with ultraviolet light to form the versatile material. The product, cellulose reinforced-soybean oil polymer, has stronger mechanical properties and performs better in thermal tests, compared to samples made from either material alone. For example, a strength test showed that the material was 37% stronger when a small amount of cellulose filler was added, and it can be twice as strong if even more filler is used. This is approaching the strength of common plastics, such as polypropylene, and with this improved strength, these polymers could be used to build household goods such as furniture. These materials are of great environmental interest not only because they consist of high amounts of agricultural resources, but also because they are mechanically strong.

2. New biodiesel catalysts and feedstocks were investigated. Biodiesel, a renewable, environmentally friendly alternative to conventional petroleum diesel fuel, is produced from vegetable oils and animal fats by a process called transesterification. However, conventional transesterification requires high quality oils to be successful. In addition, the most common catalysts are not recyclable and generate large quantities of wastewater during their removal from the biodiesel product. Thus, ARS researchers in Peoria, Illinois, in collaboration with external partners, converted lower-quality feedstocks, such as tallow, Jatropha oil, and others, to biodiesel using new catalyst technologies. The recoverable and recyclable catalysts included one made from calcium and iron oxides, and another that was from a common bacteria found in soil. In addition, their use also reduced the amount of wastewater generated during the process compared to older methods. With this new technology, a variety of low-quality oils were processed, and the fuel property results compared favorably to the fuels from more expensive sources, such as a green algal oil. The improved economic competitiveness of biodiesel with petroleum diesel may result in new possibilities for fuel from agricultural resources. These benefits, such as enhancing vegetable oil supply, reducing wastewater generation, and lowering catalyst costs, will help facilitate the societal transition away from petroleum to mitigate the impact of climate change.

Review Publications
Ibrahim, N.A., Rashid, U., Hazmi, B., Moser, B.R., Alharthi, F.A., Lalthazuala Rokhum, S., Ngamcharussrivichai, C. 2022. Biodiesel production from waste cooking oil using magnetic bifunctional calcium and iron oxide nanocatalysts derived from empty fruit bunch. Fuel. 317. Article 123525. https://doi.org/10.1016/j.fuel.2022.123525.
Fadzilah Abdullah, R., Rashid, U., Lokman Ibrahim, M., NolHakim, M.A.H.L., Moser, B.R., Alharthi, F.A. 2021. Bifunctional biomass-based catalyst for biodiesel production via hydrothermal carbonization (HTC) pretreatment – Synthesis, characterization, and optimization. Process Safety and Environmental Protection. 156:219-230. https://doi.org/10.1016/j.psep.2021.10.007.
Mushtaq, A., Asif Hanif, M., Zahid, M., Rashid, U., Mushtaq, Z., Zubair, M., Moser, B.R., Alharthi, F.A. 2021. Production and evaluation of fractionated Tamarind seed oil methyl esters as a new source of biodiesel. Energies. 14(21). Article 7148. https://doi.org/10.3390/en14217148.
Saeed, A., Asif Hanif, M., Hanif, A., Rashid, U., Iqbal, J., Irfan Majeed, M., Moser, B.R., Alsalme, A. 2021. Production of biodiesel from Spirogyra elongata, a common freshwater green algae with high oil content. Sustainability. 13(22). Article 12737. https://doi.org/10.3390/su132212737.
Hanif, M., Bhatti, H.N., Asif Hanif, M., Rashid, U., Hanif, A., Moser, B.R., Alsalme, A. 2021. A novel heterogeneous superoxide support-coated catalyst for production of biodiesel from roasted and unroasted Sinapis arvensis seed oil. Catalysts. 11(12). Article 1421. https://doi.org/10.3390/catal11121421.
Khan, K., Ul-Haq, N., Ur Rahman, W., Ali, M., Rashid, U., Ul-Haq, A., Jamil, F., Ahmed, A., Ahmed, F., Moser, B.R., Alsalme, A. 2021. Comprehensive comparison of hetero-homogeneous catalysts for fatty acid methyl ester production from non-edible Jatropha curcas oil. Catalysts. 11(12). Article 1420. https://doi.org/10.3390/catal11121420.
Shabbir, A., Mukhtar, H., Waseem Mumtaz, M., Rashid, U., Abbas, G., Moser, B.R., Alsalme, A., Touqeer, T., Ngamcharussrivichai, C. 2022. Lewatit-immobilized lipase from Bacillus pumilus as a new catalyst for biodiesel production from tallow: Response surface optimization, fuel properties and exhaust emissions. Process Safety and Environmental Protection. 160:286-296. https://doi.org/10.1016/j.psep.2022.02.032.
Doll, K.M., Moser, B.R., Knothe, G. 2021. Decarboxylation of oleic acid using iridium catalysis to form products of increased aromatic content compared to ruthenium systems. International Journal of Sustainable Engineering. 14(6):2018-2024. https://doi.org/10.1080/19397038.2021.1978589.
Liu, Z., Knetzer, D.A., Wang, J., Chu, F., Lu, C., Calvert, P.D. 2021. 3D printing acrylated epoxidized soybean oil reinforced with functionalized cellulose by UV curing. Journal of Applied Polymer Science. 139(4):e51561. https://doi.org/10.1002/app.51561.
Liu, Z., Vermillion, K., Jin, C., Wang, X., Zhao, W. 2021. NMR study on the oxidation of vegetable oils for assessing the antioxidant function of trehalose. Biocatalysis and Agricultural Biotechnology. 36. Article 102134. https://doi.org/10.1016/j.bcab.2021.102134.
Perveen, S., Hanif, M.A., Nadeem, R., Rashid, U., Azeem, M.W., Zubair, M., Nisar, N., Alharthi, F.A., Moser, B.R. 2021. A novel route of mixed catalysis for production of fatty acid methyl esters from potential seed oil sources. Catalysts. 11(7). Article 811. https://doi.org/10.3390/catal11070811.
Liu, Y., Zhou, X., Jin, C., Liu, G., Liu, Z., Kong, Z. 2022. Efficient and rapid removal of typical phenolic compounds from water with biobased porous organic polymers. Industrial Crops and Products. 184. Article 114971. https://doi.org/10.1016/j.indcrop.2022.114971.
Li, Q., Zhang, Y., Liu, Z., Liu, S., Huang, F., Zheng, M. 2022. Novel bacterial cellulose-TiO2 stabilized pickering emulsion for photocatalytic degradation. Cellulose. 29:5223-5234. https://doi.org/10.1007/s10570-022-04604-8.
Zhang, J., Huang, J., Zhu, G., Yu, X., Cheng, J., Liu, Z., Hu, Y., Shang, Q., Liu, C., Hu, L., Zhou, Y. 2021. Self-healing, recyclable, and removable UV-curable coatings derived from tung oil and malic acid. Green Chemistry. 23(16):5875-5886. https://doi.org/10.1039/d1gc01726h.
Doll, K.M., Cermak, S.C. 2022. Selective electrochemical oxidation of alcohols catalyzed by partially biobased TEMPO analogs. ChemistrySelect. 7(29). Article e202201736. https://doi.org/10.1002/slct.202201736.
Li, W., Xiao, L., Wang, Y., Huang, J., Liu, Z., Chen, J., Nie, X. 2022. Thermal-induced self-healing bio-based vitrimers: Shape memory, recyclability, degradation, and intrinsic flame retardancy. Polymer Degradation and Stability. 202. Article 110039. https://doi.org/10.1016/j.polymdegradstab.2022.110039.
Hazmi, B., Rashid, U., Kawi, S., Mokhtar, W.N.A.W., Yaw, T.C.S., Moser, B.R., Alsalme, A. 2022. Palm fatty acid distillate esterification using synthesized heterogeneous sulfonated carbon catalyst from plastic waste: Characterization, catalytic efficacy and stability, and fuel properties. Process Safety and Environmental Protection. 162:1139-1151. https://doi.org/10.1016/j.psep.2022.05.001.
Xiao, L., Li, W., Liu, Z., Zhang, K., Li, S., Wang, Y., Chen, J., Huang, J., Nie, X. 2022. Tung oil-derived epoxy vitrimers with high mechanical strength, toughness, and excellent recyclability. ACS Sustainable Chemistry & Engineering. 10(30):9829-9840.
Ro, K.S., Jackson, M.A., Szogi, A.A., Compton, D.L., Moser, B.R., Berge, N.D. 2022. Sub- and near-critical hydrothermal carbonization of animal manures. Sustainability. 14(9). Article 5052. https://doi.org/10.3390/su14095052.