Research Project: Replacement of Petroleum Products Utilizing Off-Season Rotational Crops

Location: Bio-oils Research

2020 Annual Report

Objectives
Objective 1: Enable, from a technological standpoint, the commercial production of off-season oilseed rotational crops. Sub-objective 1.1. Identify and develop winter annuals. Sub-objective 1.2. Identify and develop spring/fall annuals. Sub-objective 1.3. Evaluate and survey new off-season germplasm. Objective 2: Enable processes for the commercial production of oils, meal, gums, and protein from off-season oilseed crops such as pennycress, camelina, and coriander. Sub-objective 2.1. Develop methods for processing and refining of modified oils and waxes from camelina, crambe, and other oilseed crops. Sub-objective 2.2. Develop isolation method, production, and testing application of gums from mucilage-containing Brassica seeds (lesquerella and camelina). Sub-objective 2.3. Develop value-added products from seed meals of off-season oilseed crops for industrial applications. Objective 3: Enable commercial processes for converting the oils from off-season rotational oilseed crops into marketable value-added biobased products. Sub-objective 3.1. Develop biobased estolide lubricants/additives. Sub-objective 3.2. Develop platform chemicals from off-season rotation crops. Sub-objective 3.3. Develop polyketo, polyamines, and corresponding salts as chelating or sequestering agents and plasticizers.

Approach
New off-season crop development is critical to the future sustainability of the United States (U.S.) agriculture by reducing the farmer’s dependence on government subsidies for a select few commodity crops such as corn and soybeans, and by supplementing our need for energy without decreasing food production (food vs. fuel). A number of off-season new crops (pennycress and coriander) will be further developed for the U.S. by developing cost effective industrial products and processes from these agricultural feedstocks. A collaborative effort to the development of pennycress, camelina, and coriander will occur: 1) Off-season germplasm development will be supported through developing analytical methods to rapidly analyze glucosinolates, oil, and seed quality. Additionally, off-season crop germplasm resources will be surveyed and publicly accessible databases generated; 2) Development of chemical and physical processes that enable the commercial production of oils, meal, gums, and proteins in off-season oilseed crops. In order to produce and demonstrate economic data, the new crop raw materials will be produced in pilot scale quantities. 3) Development of novel industrial chemicals and processes through organic synthesis based on off-season crop raw materials derived above. Products to be developed include biodegradable lubricants, biobased viscosity modifiers, lubricant additives, cosmetics, and chelating or sequestering agents. Overall, this research will lead to the development and expansion of off-season oilseed crops which will help diversify the U.S. farm as well as expand the U.S. arsenal of industrial biofriendly chemicals and processes.

Progress Report
This is the final report for this project which terminated in May 2020. See the report for the replacement project, 5010-41000-185-00D, “Development of New Value-Added Processes and Products from Advancing Oilseed Crops” for additional information. Farmers in the United States have seen crop production costs increase with decreases in crop prices. At the same time, farmers are under pressure to reduce their dependence on government support. Additionally, the demand for biobased products continues to increase yet we cannot allow this increase to decrease food production. The main approach to address these problems has been to find logical ways to aid farmers in reducing their production costs by using their land year-round for crop production. Efforts initiated by ARS scientists in Peoria, Illinois, led to the development of pennycress (Thlaspi arvense L.) as an off-season rotation crop for the U.S. Pennycress has allowed farmers to use their land year-round for crop production – summer for food and winter for industrial oils. Pennycress has been commercially grown by a St. Louis, Missouri-based company and acreage has increased yearly. Additionally, ARS scientists in Peoria, Illinois, have released two new pennycress germplasm, Katelyn and Elizabeth, and both were shown to increase germination rates in the crop which aided in its commercialization. Approximately, 22,000 acres of land have been cultivated during the term of this project which is a direct result of more than 18 years of research by ARS scientists. Pennycress oil has been proven as a low carbon feedstock for production of renewable diesel and jet fuels, as a high-quality food oil and meal product to be used in animal feed. Commercialization and collaborative research efforts continue as ARS scientists provide consultative oversight for production and processing the seeds for oil/meal/protein. ARS scientists in Peoria, Illinois, developed a one-of-kind, one stop seed processing, oil processing, and oil modification pilot plant in the United States. The pilot plant gave scientists the ability to process numerous types of seeds from various sources. We have processed numerous seed types including lesquerella, cuphea, coriander, pennycress, soybean and pumpkin for oil and meal over the course of the project. Over the past 10 years, more than 50,000 lbs of seeds have been screw pressed, producing more than 3,000 gallons of crude oil. Samples of crude and refined oils, as well as meal, have been sent out to industrial partners and collaborators interested in utilizing these oils as a feedstock for biodiesel, jet fuel or industrial fluid applications. Another way to address the problems farmers are having is to develop new biobased products utilizing their crops. Biting or blood sucking insects (flies, mosquitos and ticks) can transmit various diseases that cause major health concerns and economic losses for agricultural animals. Currently, there are no effective pesticides available for use against either biting stable flies or biting face flies. ARS scientists in Peoria, Illinois, and Lincoln, Nebraska, through a cross National Program (NP) collaboration (NP306 and NP104) discovered that naturally-derived fatty acids from coconut oil functions as a very effective bio-based repellent having broad repellency and long effectiveness against multiple biting insects. The all-natural aqueous formulation, developed in Peoria, Illinois, provided promising results in field trials conducted on cattle in North Platte, Nebraska. This new finding will aid cattle farmers and ranchers with additional products to address their biting insect issues. Finally, one of the most successful products developed and patented by ARS scientists in Peoria, Illinois, have been estolides, which are a vegetable-based lubricant. Past commercial biobased vegetable engine oils fail to meet the rigorous requirements demanded by the American Petroleum Institute (API). New biobased fluids from vegetable oil sources called estolides have been commercialized as a biobased engine oil. Estolides have excellent physical properties (traits that make them excellent lubricants), such as cold temperature, and outstanding oxidative stability properties with limited additive packages and these performances exceeded other commercially available biobased oils. More importantly, estolides have received certification from the API which allows automobile owners to still receive their engine warranty coverage while using this new biobased material. As a result, two different motor oil formulations (5W-20 and 5W-30) that contain estolides are commercially produced by an Indianapolis, Indiana-based company and are for sale with the world's largest online marketplace. Commercialization efforts continue as ARS scientists provide consultative oversight for scale-up production and with the development of new products and applications.

Accomplishments
1. New engine oil additive. There is a great demand in the United States and the world to find new biobased engine additives to help improve lubricant issues found in petroleum oils. The goal of an oil is to provide lubrication between two moving metal surfaces. The oil must be of sufficiently low viscosity (water-like) to pass into the contact areas yet be viscous enough to provide separation between the moving surfaces at all operating temperatures. The problem is as oils heat up in engines, their viscosities (how thick an oil is) change and they are unable to maintain good lubricity. ARS scientists in Peoria, Illinois, previously developed a class of biobased materials called estolides which are commercially available in engine oil formulations and make a great starting material for other products. ARS scientists used these estolides (made from sunflower and soybean oils) to develop a type of new engine oil additive to help solve lubrication engine problems. When small amounts of these materials are added to an engine oil, the oil’s viscosity remain nearly constant over a broad temperature range. These new materials are beneficial to farmers, consumers, and retailers because they are environmentally friendly, improve utilization of soybean and sunflower production, and enhance economic security for rural communities.

Review Publications
Isbell, T.A., Lowery, B.A., Vermillion, K., Cermak, S.C. 2020. Synthesis and characterization of polyethylene glycol diesters from estolides containing epoxides and diols. Journal of the American Oil Chemists' Society. 97(4):409-423. https://doi.org/10.1002/aocs.12336.
Isbell, T., Lowery, B.A., Cermak, S.C. 2020. Viscometric properties of polyethylene glycol di-esters of estolides. Journal of the American Oil Chemists' Society. 97(4):425-435. https://doi.org/10.1002/aocs.12334.
Zanetti, F., Isbell, T.A., Gesch, R.W., Evangelista, R.L., Alexopoulou, E., Moser, B.R., Monti, A. 2019. Turning a burden into an opportunity: Pennycress (Thlaspi arvense L.) a new oilseed crop for biofuel production. Biomass and Bioenergy. 130:105354. https://doi.org/10.1016/j.biombioe.2019.105354.
Gesch, R.W., Long, D.S., Palmquist, D.E., Allen, B.L., Archer, D.W., Brown, J., Davis, J.B., Hatfield, J.L., Jabro, J.D., Kiniry, J.R., Vigil, M.F., Oblath, E.A., Isbell, T. 2019. Agronomic performance of Brassicaceae oilseeds in multiple environments across the Western USA. BioEnergy Research. 12(3):509-523. https://doi.org/10.1007/s12155-019-09998-1.
Roh, G., Zhou, X., Wang, Y., Cermak, S.C., Kenar, J.A., Lehmann, A.T., Han, B., Taylor, D.B., Zeng, X., Park, C., Brewer, G.J., Zhu, J.J. 2020. Spatial repellency, antifeedant activity and toxicity of three medium chain fatty acids and their methyl esters of coconut fatty acid against stable flies. Pest Management Science. 76(1):405-414. https://doi.org/10.1002/ps.5574.
Qureshi, N., Saha, B.C., Liu, S., Harry O Kuru, R.E. 2019. Production of acetone-butanol-ethanol (ABE) from concentrated yellow top presscake using Clostridium beijerinckii P260. Journal of Chemical Technology & Biotechnology. 95(3):614-620. https://doi.org/10.1002/jctb.6242.
Gazave, E., Tassone, E.E., Baswggio, M., Cyder, M., Byrel, K., Oblath, E.A., Lueschow, S.R., Poss, D.J., Hardy, C.D., Wingerson, M., James, D.B., Abdel-Haleem, H.A., Grant, D.M., Hatfield, J.L., Isbell, T., Vigil, M.F., Dyer, J.M., Jenks, M.A., Brown, J., Gore, M.A., Pauli, D. 2020. Genome-wide association study identifies acyl-lipid metabolism candidate genes involved in the genetic control of natural variation for seed fatty acid traits in Brassica napus L. Industrial Crops and Products. 145. https://doi.org/10.1016/j.indcrop.2019.112080.
Tisserat, B., Harry-O'kuru, R.E. 2019. Osage orange, honey locust and black locust seed meal adhesives employed to fabricate composite wood panels. Fibers. 7(10):91. http://doi.org/10.3390/fib7100091.
Chen, Y., Biresaw, G., Cermak, S.C., Isbell, T., Ngo, H.L., Chen, L., Durham, A.L. 2020. Fatty acid estolides: A review. Journal of the American Oil Chemists' Society. 97(3)231-241. https://doi.org/10.1002/aocs.12323.
Biresaw, G., Bantchev, G.B., Lansing, J., Harry-O'kuru, R.E., Chen, Y. 2020. Sulfurized methyl esters of soya fatty acids: Synthesis and characterization. Tribology Letter. 68. Article 61. https://doi.org/10.1007/s11249-020-01292-y.
Biswas, A., Cheng, H.N., Evangelista, R.L., Hojilla-Evangelista, M.P., Boddu, V.M., Kim, S. 2020. Evaluation of composite films containing poly(vinyl alcohol) and cotton gin trash. Journal of Polymers and the Environment. 28:1998-2007. https://doi.org/10.1007/s10924-020-01742-7.