2013 Annual Report
1a.Objectives (from AD-416):
Improve the fuel properties and performance of vegetable oils and their derivatives as alternative fuels, extenders, and additives in the operation of compression-ignition (diesel) engines for on-road and off-road applications. Address technical problems identified by stakeholders and customers. Specific objectives for this project are:.
1)Enable new commercially-viable alternative fuel formulations with improved cold weather start-up and operability performance without compromising fuel quality as defined by appropriate standard fuel specifications;.
2)Enable new commercially-viable biodiesel formulations with improved storage stability with respect to oxidative degradation. Develop rapid measurement methods for monitoring effects of degradation on biodiesel fuel quality during storage, as defined by appropriate standard fuel specifications;.
3)Enable new, commercially-viable biodiesel fuels derived from novel oilseed crops (especially inedible plant species), vegetable oils with modified fatty ester composition, and non-traditional feedstocks such as algae and biomass;.
4)Enable new, commercially-viable analytical methods for biodiesel and its minor constituents and other fuel quality issues to enhance market acceptance of biodiesel fuels; and.
5)Develop technologies that expand the markets for glycerol by enabling the commercial conversion of glycerol and its derivatives to chemicals and components in products such as surfactants, emulsifiers, fuel additives, dispersants and/or flocculating agents as well as biodegradable polymer products such as polyesters, polyethers and polyurethanes.
1b.Approach (from AD-416):
Biodiesel is an alternative diesel fuel derived from vegetable oils, animal fats, used oils or algae and other biomass feedstocks. While it is competitive with (in some aspects even technically superior to) petroleum-derived diesel fuel, its use is still affected by technical and supply issues that hinder more widespread commercialization. This project proposes to improve the fuel properties of vegetable oils as well as other feedstocks and their derivatives as alternative diesel fuels, extenders, and additives in the operation of compression-ignition (diesel) engines for on-road and off-road applications. Specific objectives for this project include: .
1)Improve cold weather start-up and operability;.
2)Enhance understanding of oxidative stability and provide methods for its improvement;.
3)Provide novel fuel formulations, including alternative and conventional feedstocks with different fatty acid profiles as well as novel additives;.
4)Develop analytical methods for minor constituents of biodiesel and other fuel quality issues and.
5)Development of specialty chemicals and products such as biodegradable polymers from biodiesel co-products (glycerol). Overall, this research will lead to technically improved biodiesel fuels that are more competitive in the marketplace, enhanced analyses, and new, economically competitive and environmentally friendly products from glycerol.
The influence of minor components of biodiesel relating to cold flow and oxidative stability were investigated as was the effect of the structure of the major components (fatty acid methyl esters) on combustion. ARS scientists in the Bio-Oils Research Unit at the USDA-ARS National Center for Agricultural Utilization Research (NCAUR), Peoria, Illinois, conducted research on various alternative feedstocks for biodiesel with the goal of increasing biodiesel supply and diversity under consideration of low-impact agronomics and sustainable agricultural practices as well as feedstocks with alternative fatty acid profiles to improve biodiesel fuel properties continued. Additives to improve the cold flow of biodiesel were prepared and tested.
Collaborated with 16 various universities (Clemson, Iowa State, Oklahoma State, Western Washington University, University of Wyoming, University of Delaware, University of Idaho, Utah State University, Universidade Federal de Vicosa, Vicosa, Brazil, Universiti Putra Malaysia) and institutions (Argonne National Laboratory, Argonne, Illinois, Illinois Sustainable Technology Center, Urbana-Champaign, Illinois, National Renewable Energy Laboratory, Golden, Colorado, Sandia National Laboratory, Livermore, California, Southwest Research Institute, San Antonio, Texas, and Woods Hole Oceanograpic Institution, Woods Hole, Massachusetts) on combustion, fuel properties, fuel composition, and biodiesel education.
Collaborated with various industrial partners.
Collaborated with the Agricultural Research Service Eastern Regional Research Center on synthesis and testing of new cold flow additives for biodiesel and biolubricants.
Cold flow properties of biodiesel. The effects of storage at low temperature on the formation of solid residues in biodiesel were investigated. ARS scientists in the Bio-Oils Research Unit at the USDA-ARS National Center for Agricultural Utilization Research (NCAUR), Peoria, Illinois, developed an automated test that measured the time required to filter a calibrated volume of biodiesel as its temperature is steadily decreased. At low temperatures, monoglycerides (side products formed during the conversion of vegetable oil into biodiesel) can aggregate together and precipitate to form undesirable solid particles in the fuel. The automated test detects the effects of solid residues by monitoring how much time is necessary to finish the filtration as it increases at lower temperatures. Results from this research will be very useful for biodiesel commercialization because fuel producers, distributors, and terminal operators need to monitor the low temperature stability of biodiesel being stored during cold weather.
Combustion-related fuel properties. The effects of components of biodiesel on combustion in an engine were examined. ARS scientists in the Bio-Oils Research Unit at the USDA-ARS National Center for Agricultural Utilization Research (NCAUR), Peoria, Illinois, established a comprehensive dataset comprising cetane numbers of fatty acid methyl esters that are commonly found in biodiesel. The cetane number is a measure of the ignition quality of a diesel fuel in diesel engines and is also crucial because the cetane number is a prime fuel quality indicator contained in biodiesel standards. For the first time, experimental data were collected on various structural features of these fatty acid methyl esters and how they influence the overall cetane number of a biodiesel fuel. The results of this research are essential to improve our understanding of biodiesel combustion and contribute to formulating biodiesel fuels with improved properties, ultimately enhancing its commercial viability.
A new salt-tolerant biodiesel feedstock. Seashore mallow (Kosteletzkya pentacarpos) is a non-invasive perennial halophytic oilseed-producing shrub indigenous to the Gulf and Atlantic coasts of the U.S. ARS scientists in the Bio-Oils Research Unit at the USDA-ARS National Center for Agricultural Utilization Research (NCAUR), Peoria, Illinois, and a university collaborator investigated seashore mallow's potential as a feedstock for the production of biodiesel. The research demonstrated that oil extracted from seashore mallow seeds could be efficiently converted into biodiesel after pretreatment. The resulting fuel properties of biodiesel derived from seashore mallow oil were within the ranges specified in important biodiesel standards such as the American Society of Testing and Materials (ASTM) standard (D6751) and the European standard (EN 14214) after treatment with antioxidants. These results, together with seashore mallow's compatibility with existing farm infrastructure, relative stress tolerance, and ability to be cultivated on saline or dry land that can be irrigated with brackish or seawater, demonstrate its potential to increase biodiesel feedstock availability utilizing fallow land resources while liberating fresh water and high quality soil for traditional agricultural use.
Rashid, U., Ibrahim, M., Yasin, S., Yunus, R., Taufiq-Yap, Y.H., Knothe, G.H. 2013. Biodiesel from Citrus reticulata (Mandarin orange) seed oil, a potential non-food feedstock. Industrial Crops and Products. 45:355-359.
Knothe, G.H. 2013. Production and properties of biodiesel from algal oils. In: Borowitzka, M.A., Moheimani, N.R., editors. Algae for Biofuels and Energy, Developments in Applied Phycology, Vol. 5. New York, NY: Springer. p. 207-221.
Dunn, R.O. 2012. Thermal-oxidation of biodiesel by pressurized-differential scanning calorimetry: Effects of heating ramp rate. Energy and Fuels. 26:6015-6024.
Dunn, R.O. 2012. Effects of monoacylglycerols on the cold flow properties of biodiesel. Journal of the American Oil Chemists' Society. 89(8):1509-1520.
Moser, B.R., Dien, B.S., Seliskar, D.M., Gallagher, J.L. 2013. Seashore mallow (Kosteletzkya pentacarpos) as a salt-tolerant feedstock for production of biodiesel and ethanol. Renewable Energy. 50:833-839.
Ngo, H., Dunn, R.O., Hoh, E. 2013. C18-unsaturated branched-chain fatty acid isomers: characterization and physical properties. European Journal of Science and Lipid Technology. 115:676-683.
Murray, R.E., Bantchev, G.B., Dunn, R.O., Ascherl, K.L., Doll, K.M. 2013. Thioether-functionalized vegetable oils: Metal-absorbing biobased ligands. ACS Sustainable Chemistry & Engineering. 1:562-565.
Knothe, G.H. 2012. Fuel properties of highly polyunsaturated fatty acid methyl esters: Prediction of fuel properties of algal biodiesel. Energy and Fuels. 26(8):5265-5273.
Moser, B.R. 2014. Impact of fatty ester composition on low temperature properties of biodiesel-petroleum diesel blends. Fuel. 115:500-506.
Knothe, G.H., Razon, L.F., Bacani, F.T. 2013. Kenaf methyl esters. Industrial Crops and Products. 49:568-572.
Knothe, G.H. 2013. Fuel properties of methyl esters of borage and black currant oils containing methyl-gamma-linolenate. European Journal of Lipid Science and Technology. 115:901-908.