Location: Bio-oils Research2016 Annual Report
1a. Objectives (from AD-416):
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.
1b. Approach (from AD-416):
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.
3. Progress Report:
This is the first annual report for the project 5010-41000-171-00D, which was certified in March 2015. New off-season crop development is critical to the future sustainability of the United States (U.S.) agriculture by reducing farmer’s dependence on government and by supplementing our need for energy/bio-based products without decreasing food production (food vs. fuel). Two different off-season new crops have been further developed for the U.S. by exploring new agronomical conditions and cost effective industrial products/processes from these crops. One of the most logical ways to help reduce production costs is for farmers to use their land year-round for crop production. The development of pennycress (Thlaspi arvense L.) as an off-season rotation crop continues to be our best new crop candidate. With the help of ARS scientists in Peoria, Illinois, pennycress continued to be commercially grown (by a St. Louis, Missouri based company) during the 2015-2016 season. The commercial production success is more than just a one year effort but rather the result of more than a decade of research efforts by ARS scientists on the production of pennycress. Pennycress has suitable properties useful for development of biofuels – i.e., as an aviation jet fuel drop-in replacement. Commercialization and collaborative research efforts continue as ARS scientists continued to provide consultative oversight for production and processed the seeds for oil/meal/protein, as well as developed other potential industrial products from the oil. Pennycress oil has been successfully converted via a hydrotreated renewable jet (HRJ) process into a suitable aviation and diesel biofuel. Additionally, the oil has been converted into a new estolide based off of pennycress. Estolides were originally developed by ARS scientists, in Peoria, Illinois, as a vegetable-based-type lubricant. The pennycress estolides had physical properties that can make them a leader in fulfilling the demand for increased development of bio-based lubricants in the U.S. Specifically, pennycress estolides proved to have marked viscosity increases over previously used oleic based estolides. These advances have continued to help drive pennycress interest with farmers and other commercial partners. Additional work with other potential industrial crops include lesquerella and camelina. Lesquerella’s (Physaria fendleri) seed coat contains a significant amount of mucilage (gum) which can be separated from the seeds. In the food industry, gums are used as thickening agents, gelling agents, emulsifying agents, and stabilizers. In other industries, gums are used as adhesives, binding agents, crystal inhibitors, clarifying agents, encapsulating agents, flocculating agents, swelling agents, and foam stabilizers. Finally, ARS scientists in Peoria, Illinois, have developed a chemical process to modify vegetable oils into highly functionalized vegetable oils that have the ability to bind to certain heavy metal elements - potential applications include environmental remediation.
1. Development and release of pennycress germplasm, Elizabeth. Pennycress has high dormancy rates which imparts weediness to the crop and makes establishing fields difficult. A non-dormant pennycress germplasm named Elizabeth was developed by ARS scientists in Peoria, Illinois, and publicly released (North Central Regional Plant Introduction Station, Ames, Iowa) in the Fall of 2015. Elizabeth (Temporary Number: Ames 32908) was developed by a selection via three self-pollinated generations from the Katelyn germplasm (PI 673443) which was selected from the wild population Beecher (PI 672505). Elizabeth was selected for its non-dormant characteristic of one day post-harvested seed with 94% germination rate in a 12h day/night protocol and 97% germination rate in complete darkness protocol. The parent Katelyn had 9% and 94% respective germination rates under these two conditions and the wild Beecher population had 0% and 7% germination rates, respectively. The recently released seeds were used as breeding stock by both industry and academia. These new advances will allow for better and higher yield producing pennycress fields, as well as increases in farmer participation in off-season crop rotations.
2. Commercialization/development of estolides as a bio-based engine oil. Current commercial bio-based vegetable engine oils fail to meet the rigorous requirements (thermal oxidative stability and poor low-temperature properties) demanded by the American Petroleum Institute (API). New bio-based fluids from vegetable oil sources called estolides have been commercialized as a bio-based engine oil. Estolides were developed and patented by ARS scientists in Peoria, Illinois. 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 bio-based oils. As a result, estolides were developed on the commercial stage and, to date, two different motor oil formulations (5W-20 and 5W-30) that contain estolides made from high-oleic soybean oil have received certification from the API. The API certification allows automobile owners to still receive their engine warranty coverage for using this new bio-based material. A new type of carbonated estolide was developed as an extension of the original estolide material. The carbonated estolide has higher viscosities than previously developed estolides and will extend the estolide technology platform.
5. Significant Activities that Support Special Target Populations:
Harry-O'kuru, R.E., Gordon, S.H., Klokkenga, M. 2015. Bio-generation of succinic acid by fermentation of Physaria fendleri seed polysaccharides. Industrial Crops and Products. 77:116-122.
Harry-O'kuru, R.E., Biresaw, G., Murray, R.E. 2015. Polyamine triglycerides: Synthesis and study of their potential in lubrication, neutralization and sequestration. Journal of Agricultural and Food Chemistry. 63(28):6422-6429.
Rashid, U., Knothe, G., Yunus, R., Evangelista, R.L. 2014. Kapok oil methyl esters. Biomass and Bioenergy. 66:419-425.
Bantchev, G.B., Cermak, S.C., Biresaw, G., Appell, M., Kenar, J.A., Murray, R.E. 2015. Thiol-ene and H-phosphonate-ene reactions for lipid modifications. In: Liu, Z., Kraus, G., editors. Green Materials from Plant Oils. 1st edition. Cambridge, UK: RSC Publishing. p. 59-92.
Harry-O'kuru, R.E., Biresaw, G. 2015. Lubricity characteristics of seed oils modified by acylation. In: Liu, Z., Kraus, G., editors. Green Materials from Plant Oils. lst edition. Cambridge, UK: RSC Publishing. p. 242-268.
Beier, R.C., Kubena, L.F., McReynolds, J.L., Byrd II, J.A., Hume, M.E., Evangelista, R.L., Isbell, T., Dierig, D.A. 2014. Evaluation of the safety and efficacy of Lesquerella fendleri seed and oils as poultry feed additives. Clear Blue Knowledge. p. 1-10.
Gordon, S.H., Mohamed, A.A., Harry-O'Kuru, R.E., Biresaw, G. 2015. Identification and measurement of intermolecular interaction in polyester/polystyrene blends by FTIR-photoacoustic spectrometry. Journal of Polymers and the Environment. 23(4):459-469.
Slininger, P.J., Dien, B.S., Kurtzman, C.P., Moser, B.R., Bakota, E.L., Thompson, S.R., O'Bryan, P.J., Cotta, M.A., Balan, V., Jin, M., da Costa Sousa, L., Dale, B.E. 2016. Comparative lipid production by oleaginous yeasts in hydrolyzates of lignocellulosic biomass and process strategy for high titers. Biotechnology and Bioengineering. 113(8):1676-1690. doi: 10.1002/bit.25928.
Harry-O'kuru, R.E., Tisserat, B., Gordon, S.H., Gravett, A. 2015. Osage orange (Maclura pomifera L) seed oil poly(alpha-hydroxydibutylamine) triglycerides: Synthesis and characterization. Journal of Agricultural and Food Chemistry. 63(29):6588-6595.
Cermak, S.C., Durham, A.L., Isbell, T.A., Evangelista, R.L., Murray, R.E. 2015. Synthesis and physical properties of pennycress estolides and esters. Industrial Crops and Products. 67:179-184.
Gesch, R.W., Isbell, T., Oblath, E.A., Allen, B.L., Archer, D.W., Brown, J., Hatfield, J.L., Jabro, J.D., Kiniry, J.R., Long, D.S., Vigil, M.F. 2015. Comparison of several Brassica species in the north central U.S. for potential jet fuel feedstock. Industrial Crops and Products. 75(B):2-7.
Oblath, E.A., Isbell, T.A., Berhow, M.A., Allen, B., Archer, D., Brown, J., Gesch, R.W., Hatfield, J.L., Jabro, J.D., Kiniry, J.R., Long, D.S. 2016. Development of near-infrared spectroscopy calibrations to measure quality characteristics in intact Brassicaceae germplasm. Industrial Crops and Products. 89:52-58.
Moser, B.R., Evangelista, R.L., Isbell, T.A. 2016. Preparation and fuel properties of field pennycress (Thlaspi arvense) seed oil ethyl esters and blends with ultra-low sulfur diesel fuel. Energy and Fuels. 30:473-479.
Gesch, R.W., Royo-Esnal, A., Edo-Tena, E., Recasens, J., Isbell, T., Forcella, F. 2016. Growth environment but not seed position on the parent plant affect seed germination of two Thlaspi arvense L. populations. Industrial Crops and Products. 84:241-247.
Hergert, G.W., Margheim, J.F., Pavlista, A.D., Martin, D.L., Supalla, R.J., Isbell, T.A. 2016. Yield, irrigation response, and water productivity of deficit to fully irrigated spring canola. Agricultural Water Management. 168:96-103.
Hergert, G.W., Margheim, J.F., Pavlista, A.D., Martin, D.L., Isbell, T.A., Supalla, R.J. 2016. Irrigation response and water productivity of deficit to fully irrigated spring camelina. Agricultural Water Management. 177:46-53.
Bredsguard, J.W., Thompson, T.D., Cermak, S.C., Isbell, T.A. 2016. Estolides: Bioderived synthetic base oils. In: Sharma, B.K., Biresaw, G., editors. Environmentally Friendly and Biobased Lubricants. Boca Raton: CRC Press. p. 35-49.
Compton, D.L., Goodell, J.R., Grall, S., Evans, K.O., Cermak, S.C. 2015. Continuous, packed-bed, enzymatic bioreactor production and stability of feruloyl soy glycerides. Industrial Crops and Products. 77:787-794.
Xu, J., Solaiman, D., Ashby, R.D., Garcia, R.A., Gordon, S.H., Harry-O'kuru, R.E. 2016. Properties of starch-polyglutamic acid (PGA) graft copolymer prepared by microwave irradiation - Fourier transform infrared spectroscopy (FTIR) and rheology studies. Starch 68:1-7. doi: 10.1002/star.201600021.