2007 Annual Report 1a.Objectives (from AD-416) Expand the use of animal fats, vegetable oils, and their coproducts by developing new and/or alternative processes to exploit the potential of these feedstocks as biobased products and biofuels. Targeted areas include: producing lipids with improved physical and/or nutritional properties; introducing branching into the linear fatty acids common to natural fats and oils; producing polyol fatty acids, amides, as functional or metalworking fluids; using natural and/or modified phospholipids as metalworking fluids and/or lubricant additives; developing alternative processes for producing biodiesel from intact oils and fats and/or less expensive lipid feedstocks; developing methodologies for improving the quality and performance of biodiesel fuels; and developing new uses for glycerol. 1b.Approach (from AD-416) New technologies will be developed for the production of nutraceutical lipids and high-energy lipids or low/zero trans fats using directed enzymatic transesterification and fractionation techniques. Use enzyme immobilization techniques for developing continuous lipid modification processes in bioreactors. Biocatalytic and biomimetic reagents will be applied to produce carbon-carbon and carbon-oxygen branched fatty acids, targeting materials with enhanced lubricity while preserving biodegradability. Incorporate oxygen or phosphate functionalities into fats and oils or their constituent fatty acids to increase their hydrophilic character. Technologies will be optimized to improve the economics of biodiesel from low-cost, agriculturally derived lipid feedstocks using conventional alkali-catalyzed transesterification or alternative methods. Develop an enzymatic/alkali-catalyzed process for the conversion of free fatty acid (FFA) containing feedstocks into biodiesel fuels. Compositional analysis and engine performance studies will be conducted to gather a body of data required to determine: a) the suitability of whole vegetable oils as fuels; and b) the efficacy of additives on the performance of intact oils and biodiesel. Use heterogeneous catalysts to synthesize biodiesel. Produce fuel oxygenates and biodegradable lubricants. Identify origin of sulfur species and develop protocols for their removal from biofuels and/or feedstocks. Produce glycerol-based prepolymers; oligomerize glycerol with itself or other bifunctional monomers to produce hyper-branched polymers. 3.Progress Report Saturated branched-chain fatty acids, or "isostearic acids," are used as biodegradable lubricants, emollients, and hydraulic fluids. CWU researchers developed efficient, high-yield catalytic processes for their synthesis from unsaturated fatty acids using a ferrierite zeolite catalyst. After hydrogenation, the mixture is recrystallized, methylated, and distilled to remove byproducts. Studies continued on the scope, aspects, and optimization of the direct production of biodiesel from lipid-bearing materials. Efforts focused on cost reduction through investigation of the ability of feedstock pretreatment to reduce the amount of alcohol required in the process. CWU scientists continued to collaborate with Philadelphia Fry-O-Diesel, LLC, a research and pilot scale firm investigating biodiesel production from trap grease. Tasks successfully undertaken included refinements to the technologies developed, devising methods to achieve high quality biodiesel, and overcoming issues of contamination of the final product. CWU scientists have responded to requests from industry members, both producers and users, for assistance in helping to determine the causes of sporadic local poor performance with biodiesel. To this end, field samples were forwarded to unit scientists for their assistance in analyzing them. Conveying the results to collaborators and to the biodiesel research community in general has raised industry awareness regarding fuel quality issues. CWU researchers, with on-site engineers, continued their development of quantitative computer-based models for the production of biodiesel from lipid feedstocks. The models provide a baseline against which to compare the results of feedstock cost and alternate conversion technologies. Over 50 copies of the model for biodiesel from refined soybean oil were requested the past year. CWU researchers established the feasibility of synthesizing a series of diacid-glycerol prepolymers. The prepolymers were first produced under reduced pressure without solvent using titanium butoxide catalyst, but using a solvent increased the overall yield and molecular weights of the glycerol-based oligomers, facilitated recovery of unreacted acid; increased product yield; and improved the properties of the oligomers. Two acid catalysts (titanium butoxide and dibutyltin oxide) were employed to optimize the synthesis of the oligo(diacid-glycerol) prepolymers. This paragraph serves to document research conducted under Cooperative Agreement #58-1935-7-0748N (1935-41000-066-02N) between ARS and Tuskegee University CWU scientists participated in animal feeding studies conducted at the university. The work seeks to identify at the cellular level the effect of selected fatty acids on cardiovascular disease and type-2 diabetes. This paragraph serves to document research conducted under Cooperative Agreement #58-1935-6-0630N (1935-41000-066-01N) between ARS and the University of Georgia. Trans fatty acids have been implicated as factors in the development of atherosclerotic diseases. To this end CWU researchers collaborated with the university researchers to develop a series of trans free fats from common fats and oils. 4.Accomplishments Synthesis of biodiesel from greases: Biodiesel (BD), a renewable and biodegradable diesel fuel, is primarily synthesized from refined vegetable oils and fats. Their costs add prohibitively to that of the final fuel cost. Greases are lower-cost feedstocks and hence are attractive candidates for producing BD, although their high free fatty acid (FFA) content makes it difficult to produce BD using conventional methods. Unit scientists overcame this hurdle by identifying a series of immobilized acid catalysts, developed in collaboration with a university partner, that are highly efficient in esterifying the FFA in grease to biodiesel. Greases can thus be readily converted to biodiesel via a straightforward simplified process superior to existing approaches. This novel technology has the potential of advancing the use of greases and other second use fats and oils as biodiesel feedstocks. (National Program 307: Bioenergy & Energy Alternatives; Component II. Biodiesel; Problem Addressed: Reduce Cost of Feedstocks) Production of medium-chain fatty acids: There is much interest in the development of environmentally benign and economically viable methods for converting common long-chain-length unsaturated fatty acids of fats & oils into higher-valued medium-chain length fatty acids. To achieve this goal, researchers at the Eastern Regional Research Center, Wyndmoor, PA, are developing new catalytic processes for converting oil-derived fatty acids to high-value biobased intermediates for important consumer products such as detergents. The researchers showed that the common fatty acids can be converted into shorter chain-length fatty acids and hydrocarbons by reaction with ethylene under pressure. The demonstration of the feasibility of such conversions should spur commercial interest in optimizing the process to open new markets for the utilization of agricultural fats & oils. (National Program 306: Quality and Utilization of Agricultural Products; Component 2: New Processes, New Uses, and Value-Added Foods and Biobased Products; Problem Area 2c: New and Improved Processes and Feedstocks) Biodiesel fuel quality: The biodiesel industry continues to seek rapid and universal test methods for monitoring the quality of biodiesel fuels; both neat and as blends in petrodiesel. To this end, unit researchers have expanded their previously developed high performance liquid chromatographic method for measuring bound glycerol in biodiesel fuels to include the determination of free glycerol at the ASTM specified limit of 0.02 wt%. With this newly developed method, the total glycerol in a biodiesel, which is the sum of free and bound glycerol, can be determined in less than one hour. The method has the potential of becoming a standard test method for determining the percentage of biodiesel in a blend. (National Program 307: Bioenergy & Energy Alternatives; Component II. Biodiesel; Problem Addressed: Fuel Quality Testing and On-line Process Control) Emissions properties of biodiesel: Biodiesel has been shown to have emission advantages over petrodiesel with one exception. Some studies have indicated that combustion of biodiesel produces elevated amounts of oxides of nitrogen (NOx) compared to the combustion of petroleum diesel. This perception can impede the widespread adoption of biodiesel. To address this concern, CWU researchers produced biodiesels whose molecules had been chemically modified, and conducted engine testing to determine if NOx emissions were reduced. One modified fuel, containing an increased number of hydroxyl groups, exhibited a 4.5% reduction in output compared to the unmodified biodiesel from which it was obtained. This offers a route to reduce the NOx emissions of biodiesel. (National Program 307: Bioenergy & Energy Alternatives; Component II. Biodiesel; Problem Addressed: Combustion and Exhaust Emissions) Reducing emissions, improving stability, and also improving the suitability of soy biodiesel for non-U.S. use: The content of double bonds in a biodiesel directly increases its output of NOx while also reducing its field stability. This has led some countries to limit the content of unsaturated fatty acids in this fuel. Soy biodiesel slightly exceeds these limits. An industrially common and chemically minor chemical modification (partial hydrogenation) was applied to soy oil and its effect on the properties and performance in specification tests of biodiesel made from this oil was determined. The modified fuel met the desired specifications and exhibited desirable fuel properties. This work offers a means of overcoming possible export barriers to the wider use of biodiesel, potentially expanding the global market for soy-based biodiesel. (National Program 307: Bioenergy & Energy Alternatives; Component II. Biodiesel; Problem Addressed: Combustion and Exhaust Emissions) 5.Significant Activities that Support Special Target Populations None. 6.Technology Transfer Number of new CRADAs and MTAs 1 Number of active CRADAs and MTAs 1 Number of invention disclosures submitted 1 Number of patent applications filed 2 Number of web sites managed 1 Number of non-peer reviewed presentations and proceedings 18 Number of newspaper articles and other presentations for non-science audiences 14 Review Publications Ngo, H., Jones, K.C., Foglia, T.A. 2006. Metathesis of unsaturated fatty acids: synthesis of long chain unsaturated alpha, omega-dicarboxylic acids. Journal of the American Oil Chemists' Society. 83(7)629-634. Piazza, G.J., Foglia, T.A. 2006. One-Pot Synthesis of Fatty Acid Epoxides from Triacylglycerols Using Enzymes Present in Oat Seeds. Journal of the American Oil Chemists' Society. 83(12):1021-1025. Ngo, H., Nunez, A., Lin, W., Foglia, T.A. 2007. Zeolite-Catalyzed Isomerization of Oleic Acid to Branched-Chain Isomers. European Journal of Lipid Science and Technology. 108:214-224. Zafiropoulos, N.A., Ngo, H., Foglia, T.A., Samulski, E.T., Lin, W. 2007. Catalytic synthesis of biodiesel from high free fatty acid-containing feedstocks. Journal of the Chemical Society Chemical Communications. 3670-3672. Moser, B.R., Haas, M.J., Winkler, J.K., Jackson, M.A., Erhan, S.Z., List, G.R. 2007. Evaluation of partially hydrogenated methyl esters of soybean oil as biodiesel. European Journal of Lipid Science and Technology. 109:17-24. Haas, M.J., Scott, K.M. 2007. Moisture removal substantially improves the efficiency of in situ biodiesel production from soybeans. Journal of the American Oil Chemists' Society. 84(2):197-204. Wyatt, V.T., Nunez, A., Strahan, G.D. 2010. The Lewis acid catalyzed synthesis of hyperbranched Oligo(glycerol-diacid)s in aprotic polar media. Journal of the American Oil Chemists' Society, 87(11):1539. Lee, J., Jones, K.C., Foglia, T.A., Nunez, A., Lee, J., Kim, N., Vu, P., Lee, K. 2007. Separation of Triacylglycerol Species from Interesterified Oils by High Performance Liquid Chromatography. Journal of the American Oil Chemists' Society. 84(3):211-217. Hess, M.A., Haas, M.J., Foglia, T.A. 2007. Attempts to Reduce NOx Exhaust Emissions by Using Reformulated Biodiesel. Fuel Processing Technology. 88(7):693-699. Piazza, G.J., Marmer, W.N. 2007. Conversion of Phosphatidylcholine to Posphatidylglycerol with phospholipase D and Glycerol. Journal of the American Oil Chemists' Society. 84(7):645-651. Haas, M.J., Scott, K.M., Foglia, T.A., Marmer, W.N. 2007. The general applicability of in situ transesterification for the production of fatty acid esters from a variety of feedstocks. Journal of the American Oil Chemists' Society. 84(10):963-970.