2007 Annual Report
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.
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)
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. 87:1359-1369.
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.