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ARS Home » Midwest Area » Peoria, Illinois » National Center for Agricultural Utilization Research » Bio-oils Research » Research » Research Project #429181

Research Project: Value-added Bio-oil Products and Processes

Location: Bio-oils Research

2016 Annual Report

Objective 1: Enable, from a technological standpoint, new commercial separation processes for the production of marketable low-cost high-purity fatty acids. Objective 2: Enable new commercial products derived from fatty acid esters. Objective 3: Enable new commercial biobased additives for applications in lubricants. • Sub-objective 3.A. Develop novel and cost-competitive structures of biobased additives and base oils. • Sub-objective 3.B. Investigate tribological property of novel biobased additives and base oils and use results to optimize the respective chemical structures. This project is aimed at developing enabling new commercial technologies, processes, and biobased products for various markets including for: remediation (specifically heavy metal remediation to include water treatment/purification); lubricant additives; lubricant base oils; and chemical additives. The technologies and products from this research will be competitive in cost and performance to those currently in the respective markets. The biobased products targeted in this project will result in significant improvements to the U.S. economy and the environment as well as to the safety and health of the American people.

(1) This approach outlines work to be performed related to a) screening of feedstock oil properties and quality; b) design of the membrane-based process Step 1 to remove polyunsaturated fatty acids and enrich saturated fatty acids/ monounsaturated fatty acid (MUFA) concentrations in fatty acid or fatty acid methyl ester (FAME) mixtures; c) evaluate two techniques for the design of process Step 2 to efficiently separate and enrich individual MUFA (oleic and erucic acids) with high yield and purity; and d) integrate designs for Steps 1 and 2 into a single process to fractionate fatty acid mixtures to produce valuable MUFA with high yield and purity. These items present a series of decision points that will be addressed during the course of the research project. (2)Recent research within the unit has shown thioalkyl derivatives of vegetable oils can be used in heavy metal remediation applications with the thioalkyl derivatives acting as metal-coordinating agents for silver ions. Building on these successful findings, new compounds featuring sulfur as the source of binding or chelation will be the primary objective. The initial feedstocks to be examined will be monounsaturated fatty compounds. This will be followed by the more chemically challenging di- and tri-unsaturated fatty compounds and, finally, vegetable oils. Emphasis will be placed on industrial oil feedstocks with enhanced sustainability. Additionally, materials from Objective 1, as they become available, will serve as unique, valuable starting materials. (3a) New biobased additives and base oils will be synthesized from commodity oils and their derivatives. Commodity vegetable oils comprise fatty acids with unsaturation that can be used as reactive sites for chemical modification. In addition to commodity vegetable oils, polymercaptanized soybean oil, which is produced in large quantities from abundant soybean oil and cheap hydrogen sulfide will be used. Other biobased feedstocks to be used in the synthesis include: FAME, obtained from the biodiesel process, especially those with unsaturation on their hydrocarbon chains; esters of fatty acid with various alcohol structures; etc. (3b) The new biobased additives will be first investigated for their compatibility with standard base oils. Additives found to be incompatible will be investigated using various approaches to make them more compatible. Only compatible additives will be allowed into the next phase which involves the investigation of their effectiveness at performing the specific tasks relevant to its application. Additives will be investigated relative to commercial reference additives using established tests for each application. Various concentrations of the additives in each base oil will be prepared and subjected to the respective tests. Based on these results, optimum concentrations of the additives will be determined.

Progress Report
This is the first annual report for the project 5010-41000-175-00D, which was certified in October 2015. This new project aimed at developing new technology for producing high purity fatty acids and their derivatives (methyl esters, etc.) and converting them into value-added products for a variety of applications, including for heavy metal remediation from waste water and for lubrication. In FY16, progress has been made in all key objective areas (listed above) and highlights are given below. A database on the characteristics of membranes for separating fatty acids and esters is being compiled. The contents of the database will be used to evaluate membranes for selectivity in the permeation of different species for separation and purification. Results will then be employed to design and optimize scaled-up membrane-based separation processes. New catalysts and green catalytic procedures were developed for the synthesis of sulfur-containing derivatives of fatty esters. The new materials show promise for heavy metal remediation in aqueous waste streams and/or industrial effluents. In their previous research, ARS researchers in Peoria, Illinois, have shown that furan cyclic structures can be formed from epoxidized vegetable oil. The furan fatty acids potentially can have many useful properties, but their evaluation is hampered by low product yields achieved to date. The researchers continued the work this reporting cycle by evaluating the use of sulfuric acid as a cheap catalyst, and solvents of different polarity. They succeeded in slightly improving the yields (to ~25%). Modified soybean oil, produced commercially from commodity soybean oil, contains sulfur atoms in its structure. As a result, modified soybean oil could have potential application as a biobased multi-functional lubricant additive capable of providing anti-wear, antioxidant, and extreme pressure properties to lubricant formulations. A preliminary investigation of the as-received modified soybean oil samples from a commercial entity was conducted by ARS researchers in Peoria, Illinois. The neat material displayed higher density, higher (> 7-fold) viscosity at 40°C, slightly lower viscosity index, and better oxidation stability and pour point than soybean oil. Modified soybean oil was also investigated as an additive in high oleic sunflower oil (HOSuO) base oil and the property of the blend evaluated as a function of modified soybean oil concentration. It was observed that blending modified soybean oil additive provided improved pour point, improved oxidation stability (at = 10%), lower anti-wear coefficient of friction, wear scar diameter, and almost 3-fold higher extreme pressure weld point than the HOSuO base oil. The result indicates that modified soybean oil, which can be commercially manufactured at low cost, has the potential to be used as low cost biobased additive in lubricant formulations. Further investigation of the as-received, as well as chemically modified soybean oil products is in progress.

1. Vegetable oil-based adsorbents remove mercury and silver ions from wastewater. Heavy metal contamination of natural waters is an emerging environmental problem in the United States. Toxic heavy metals can find their way into lakes and streams from sources such as industrial wastewaters, aging municipal plumbing, or the mining industry. ARS scientists in Peoria, Illinois, developed an adsorbent material from modified corn oil that efficiently removes mercury and silver ions from contaminated water. A very small amount of the modified corn oil was required to reduce mercury concentration by 99.6% and silver concentration by 88.9% after contact with the contaminated water. This research will directly benefit efforts to develop green technologies to clean up wastewater streams without adversely impacting the environment.

2. New heavy metal removal agents based on agricultural products. Removal of heavy metals from aqueous waste streams and/or industrial effluents is a serious environmental and health issue. Compounds containing sulfur are known to often remove such metals. In this connection, a process using new catalysts for making new derivatives of fatty esters containing sulfur were discovered. The fatty esters used for this process can be obtained from common agriculturally-derived plant oils such as soybean oil, corn oil, sunflower oil, or others. The new catalysts have the advantages of easy removal, providing the products in high yield, and enabling facile reaction conditions including no use of solvent which makes the production a truly green procedure. Analytical work on these compounds shows that the products are promising agents for heavy metal remediation in aqueous waste streams or industrial effluents and are competitive or better than existing materials. This work also provides a promising new use of agriculturally-derived products such as plant oils, potentially providing an additional market for farmers.

3. Synthesis of phosphonates from soybean oil (SBO) and high-oleic sunflower oil (HOSO). Previous research has shown that phosphonates synthesized from methyl oleate display anti-wear properties comparable to zinc dialkyldithiophosphate (ZDDP), a commercial anti-wear additive widely used in high volume lubricant formulations such as motor oils, hydraulic fluids, and gear oils. However, methyl oleate is more expensive than vegetable oils since it is obtained by processing vegetable oils. ARS scientists in Peoria, Illinois, have successfully synthesized phosphonates from SBO and HOSO using free radical initiators without solvents. Three different phosphonate structures were used in the synthesis with each vegetable oil. Good conversion of the vegetable oil double bonds to phosphonates was achieved. The reactions were carried out on a few hundred grams scale and can be easily scaled-up further. The phosphonates were characterized by standard methods to confirm their chemical structures. The vegetable oil based phosphonates synthesized in this work can provide a cost-competitive, environmentally friendly, and biobased additive alternative to ZDDP. The later contains metal, is non-biodegradable, and produced from non-renewable petroleum based raw materials.

4. Biobased phosphonates derived from methyl lionoleate displayed superior anti-wear properties. Biobased lubricants provide numerous economic, environmental, safety, and health benefits. However, to get the maximum benefits from application of biobased lubricants, they must be formulated with biobased base oils and biobased additives. Unfortunately, there are no commercial biobased additives and current formulators have to use petroleum-based additive to produce biobased lubricants. ARS scientists in Peoria, Illinois, investigated biobased dialkyl phosphonates derived from methyl linoleate (MeLin) for antiwear additive properties. MeLin is obtained from vegetable oils using the biodiesel process. Blends of three different phosphonates (dimethyl, diethyl, di-n-butyl) with high oleic sunflower oil as the biobased base oil were investigated. The results showed superior anti-wear and anti-friction properties by the biobased phosphonates relative to the commercial anti-wear additive zinc dialkyldithiophosphate (ZDDP). The results indicate that biobased anti-wear additives have the potential for replacing ZDDP, which is currently applied in many commercial lubricants including engine oil, hydraulic fluids, and gear oils. ZDDP is not environmentally friendly because it contains heavy metal, is non-renewable because it is produced from petroleum based raw materials, and not biodegradable.


Review Publications
Biresaw, G., Compton, D., Evans, K., Bantchev, G.B. 2016. Lipoate ester multifunctional lubricant additives. Industrial and Engineering Chemistry Research. 55(1):373-383.
Knothe, G.H. 2014. Biodiesel lubricity and other properties. In: Biresaw, G., Mittal, K.L., editors. Surfactants in Tribology. Vol. IV. Boca Raton, FL: CRC Press: Taylor & Francis Group. p. 483-500.
Knothe, G.H. 2016. Biodiesel and its properties. In: McKeon, T.A., Hayes, D.G., Hildebrand, D.F., Weselake, R.J., editors. Industrial Oil Crops. 1st edition. Urbana, IL: AOCS Press. p. 15-42.
Bantchev, G.B., Biresaw, G., Palmquist, D.E., Murray, R.E. 2016. Radical-initiated reaction of methyl linoleate with dialkyl phosphites. Journal of the American Oil Chemists' Society. 93(6):859-868.
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.
Dunn, R.O. 2015. Cold flow properties of biodiesel: A guide to getting an accurate analysis. Biofuels. 6(1-2):115-128. doi: 10.1080/17597269.2015.1057791.
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.
Sutivisedsak, N., Leathers, T.D., Biresaw, G., Nunnally, M.S., Bischoff, K.M. 2016. Simplified process for preparation of schizophyllan solutions for biomaterial applications. Preparative Biochemistry and Biotechnology. 46(3):313-319.
Doll, K.M., Walter, E.L., Bantchev, G.B., Jackson, M.A., Murray, R.E., Rich, J.O. 2016. Improvement of lubricant materials using ruthenium isomerization. Chemical Engineering Communications. 203(7):901-907.
Biresaw, G., Bantchev, G.B. 2015. Tribological properties of limonene bisphosphonates. Tribology Letters. 60(11). doi: 10.1007/s11249-015-0578-2.
O'Neil, G.W., Knothe, G., Williams, J.R., Burlow, N.P., Reddy, C.M. 2016. Decolorization improves the fuel properties of algal biodiesel from Isochrysis sp. Fuel. 179:229-234.
Liu, Z., Chen, J., Knothe, G., Nie, X., Jiang, J. 2016. Synthesis of epoxidized cardanol and its antioxidative properties for vegetable oils and biodiesel. ACS Sustainable Chemistry & Engineering. 4(3):901-906.
Bantchev, G.B., Doll, K.M., Biresaw, G., Vermillion, K. 2014. Formation of furan fatty alkyl esters from their bis-epoxide fatty esters. Journal of the American Oil Chemists' Society. 91:2117-2123.
Knothe, G.H., Razon, L.F., Madulid, D.A., Agoo, E.M., De Castro, M.E. 2016. Fatty acid profiles of some Fabaceae seed oils. Journal of the American Oil Chemists' Society. 93:1007-1011.
O'Neil, G.W., Williams, J.R., Wilson-Peltier, J., Knothe, G., Reddy, C.M. 2016. Experimental protocol for biodiesel production with isolation of alkenones as coproducts from commercial Isochrysis algal biomass. Journal of Visualized Experiments. 112:e54189. doi: 10.3791/54189.
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.
Knothe, G. 2016. Biodiesel: A fuel, a lubricant, and a solvent. In: Sharma, B.K., Biresaw, G., editors. Environmentally Friendly and Biobased Lubricants. Boca Raton: CRC Press. p. 391-405.