2006 Annual Report 1.What major problem or issue is being resolved and how are you resolving it (summarize project aims and objectives)? How serious is the problem? Why does it matter? This project focuses on improving biodiesel fuel performance properties. This includes cold flow properties, resistance to oxidation during storage (degradation caused by exposure to air), reduction of harmful exhaust emissions from biodiesel combustion and other fuel properties. Additional objectives include the development of marketable co-products from biodiesel production, e.g., glycerol, development of analytical methods to assess fuel quality, and development of property-enhancing additives. Such improvements in fuel properties and related development are necessary to increase the utilization of biodiesel as an alternative fuel source and to improve the economics of biodiesel production. This project is part of National Programs 306, "Quality and Utilization of Agricultural Products" and 307, "Bioenergy & Energy Alternatives". This research is targeted towards removing technological hurdles facing development of alternative diesel fuels from vegetable oils such as soybean oil. Successful completion of this work will significantly advance biodiesel as a renewable alternative fuel that will meet regulatory requirements for protecting the environment and increasing energy security. Completion of this work increases the prospects for widespread commercialization of alternative fuels from vegetable oils. The work is relevant to all entities involved with regulations regarding environmental protection and energy security, producers and processing of vegetable oils including farmers, and biodiesel producers. The general public will benefit from reduced exhaust emissions from the operation of diesel engines as well as enhanced energy security. This research contributes to the ARS goal of sustainable agriculture, creating jobs and economic activity in America, enhancing energy security, and improving the environment by developing alternate energy sources and increasing the use of agricultural crops as feedstocks for biofuels. 2.List by year the currently approved milestones (indicators of research progress) Objective 1. Develop new alternative diesel fuel formulations with improved cold flow properties without compromising fuel quality (defined by American Society for Testing and Materials standard D 6751). Year 1: Develop thermodynamic model based on freezing point depression theory for application to biodiesel formulations. Assemble bench-scale apparatus for conducting investigations on optimizing control variables for dry fractionation of biodiesel. Conduct fundamental studies on crystallization kinetics of compounds that promote crystallization of methyl stearate and palmitate esters in model solutions. Identify molecular structures that demonstrate good solubility properties. Establish cooperative research and development agreement with Alternative Aviation Fuels (AAF)-led consortium for developing pilot-scale dry fractionation process. Year 2: Conduct experimental measurements of variables necessary to develop thermodynamic model based on freezing point depression theory. Continue fundamental studies on crystallization kinetics of methyl stearate and palmitate. Identify compounds for testing as additives and diluents in solution with biodiesel for measuring solubility curves and assembling temperature-composition phase diagrams. Develop strategies for synthesizing, purifying and characterizing additives to be studied as cloud point depressants for biodiesel. Develop results from fundamental studies on nucleators to identify moieties that may be attached to synthesized new additive structures. Continue optimization studies on bench-scale fractionation apparatus. Complete initial cooperative research project with AAF-led consortium. Year 3: Complete experimental measurements of variables for developing thermodynamic models. Continue testing of compounds as additives and diluents. Complete fundamental studies on crystallization kinetics. Synthesize and purify new compounds for testing as cloud point depressants. Test new compounds for suitability as cold flow improvers for biodiesel and petroleum diesel/biodiesel blends. Conduct cloud, pour, cold filter plugging and freezing point and low-temperature flow tests analyses. Compile list of compounds demonstrating eutectic or very good continuous monotectic phase behavior for more detailed studies. Complete optimization studies on bench-scale dry fractionation of biodiesel. Test results from bench-scale optimization studies on larger-scale equipment. Year 4: Apply thermodynamic models to various biodiesel formulations demonstrating changes in cold flow properties after mixing with various additives and diluents. Compare results from thermodynamic models with those from cold flow property measurements. Continue testing of compounds as additives and diluents. Develop strategies based results from fundamental studies on crystallization kinetics. Continue synthesis and testing of new compounds in biodiesel and blends. Begin preparing a list of promising cold flow improver additives for treating biodiesel and biodiesel/conventional diesel blends. Continue optimization of control variables for larger-scale production of fractionated biodiesel. Begin search for partner(s) to enter into cooperative research and development agreement(s) to conduct field operability, engine performance and emissions tests on biodiesel formulations with improved cold flow properties. Year 5: Finish comparison analysis of results predicted by thermodynamic models and those from direct measurement of cold flow properties. Finish testing of compounds as additives and diluents for biodiesel and blends. Complete list of promising cold flow improver additives. Finish optimization studies on larger-scale fractionation equipment. Continue as necessary cooperative research agreements for field operability, engine performance and emissions tests. Publication of results. Objective 2. Develop alternative fuel formulations as combustion promoters that will reduce harmful, regulated exhaust emissions such as nitrogen oxides, carbon monoxide and particulate matter. Year 1: Investigation of fundamental parameters influencing biodiesel combustion properties and exhaust emissions, also under particular consideration of the influence of fatty acid structure. Establish extramural collaboration for conducting engine tests related to this aspect of the project. Year 2: Develop novel compounds with potential for reducing NOx exhaust emissions. Develop insights on modifying biodiesel fatty ester composition. Evaluate how these solutions may affect solutions to Objective 1. Year 3: Develop fuel formulations containing NOx emissions-reducing additives and/or changed fatty ester composition. Year 4: Engine durability and performance testing (extramural cooperation); comparative emissions analyses; field operability testing (by extramural cooperation, if appropriate). Year 5: Evaluate results. Recommend promising fuel formulation for field testing. Publication of results. Objective 3. Develop new biodiesel fuel formulations with improved storage stability with respect to oxidative degradation. Develop instrumental methods rapidly monitor effects of degradation in biodiesel fuel quality during storage. Year 1: Determine quantitatively parameters that influence storage stability of biodiesel and petroleum diesel/biodiesel blends and how they affect monitoring of biodiesel fuel quality by various methods. Acquire new knowledge of oxidation reaction kinetics under steady-state conditions. Year 2: Develop time-accelerated analytical methods for determining fuel quality as related to oxidative stability. Screen experimental formulations, including those that may have modified fatty acid composition. Year 3: Continue screening experimental formulations, including those that may have modified fatty acid composition. Correlate results to allow prediction of responses under non-accelerated (real world) conditions. Year 4: Screen commercially available natural and synthetic antioxidants for potential to increase resistance to oxidation of biodiesel, also under consideration of fatty acid composition. Investigate how this may affect methods developed for monitoring biodiesel oxidation. Test physical compatibility of promising antioxidants in petroleum diesel/biodiesel blends. Year 5: Use most promising antioxidants and/or fuel formulations with changed fatty acid composition to conduct (by extramural collaboration) field operability tests, engine durability and performance tests, and if necessary comparative emissions analyses of experimental fuel formulations. Publication of results. Objective 4. Identify and develop novel specialty chemicals that may be prepared from glycerol, mono-, and diglycerides as marketable co-products of biodiesel production. Year 1: Evaluate conversion efficiencies and reaction kinetics of model reactions. Year 2: Generate series of structural derivatives from candidate reactions identified in first year. Evaluate physical properties. Publish preliminary results. Year 3: Develop structure-property relationships from data collected in second year. Refine synthetic route of most promising compounds. Year 4: Test the range of structure-property relationships. Scale-up reactions to provide larger samples for off-site formulation testing and possible demonstration projects. Year 5: Publish intermediate results. Transfer technology to end-users. 4a.List the single most significant research accomplishment during FY 2006. Freezing point depression model and biodiesel. A thermodynamic model was developed to predict the cloud point and other cold flow properties of biodiesel. This work relates to improving cold flow properties. The model is based on freezing point depression theory and requires accurate measurement of parameters associated with crystallization of different compounds found in biodiesel from various feedstocks. Once parameters for individual compounds are acquired, the model may be employed to predict cold flow behavior of various compositions of these compounds. Most of the parameters in this work were obtained from analysis of differential scanning calorimetry curves. Results show the model will be useful for screening cold flow additives and for determining influences of various contaminants on the cold flow properties of biodiesel. This accomplishment is under NP 306, Component, "New Processes, New Uses, and Value-Added Foods and Biobased Products" and NP 307, Component "Biodiesel." 4b.List other significant research accomplishment(s), if any. The following accomplishments are under NP 306, Component, "New Processes, New Uses, and Value-Added Foods and Biobased Products" and NP 307, Component, "Biodiesel." Oxidation reaction kinetics of biodiesel. A model was developed describing reaction kinetics associated with the oxidation of biodiesel exposed to air (or oxygen). The model was employed to infer kinetic parameters such as activation energies that may be further applied to determine the rate of oxidative degradation under various reaction conditions. Non-isothermal pressurized-differential scanning calorimetry (P-DSC) heating scans were performed and interpreted in-house with the results being utilized in correlations to infer activation energies and other kinetic parameters. Accurate determination of kinetic parameters will allow easy and relatively rapid determination of the rate of oxidation reaction for setting storage conditions and monitoring of biodiesel quality during storage. Storage and handling of oxidation inhibitors (antioxidants). Effects of storage and handling conditions on antioxidants and biodiesel-antioxidant mixtures were determined. This work relates to fuel quality of biodiesel during long-term storage. Biodiesel made from soybean oil is susceptible to degradation by exposure to airborne oxygen and must be treated with antioxidants to help maintain its resistance to oxidation. In addition, antioxidants are known to lose effectiveness when exposed to air. Trials with individual antioxidants and biodiesel-antioxidant mixtures were conducted under various storage and handling conditions where mixtures were periodically sampled and tested for relative resistance to oxidation. Results provide storage and handling procedures for maintaining the effectiveness of antioxidants. Biodiesel stability by NMR. The oxidative stability of biodiesel was investigated by exposing heated biodiesel to air with varying surface-to-air ratios. This work relates to the general problem of biodiesel stability, especially when stored. Nuclear magnetic resonance spectroscopy was applied for the first time to the analysis of oxidized biodiesel with determination of a residual fatty acid composition and the results compared to viscosity and acid value. The results improve understanding of the oxidation process of biodiesel and aid in devising methods to monitor and maintain its fuel quality. Biodiesel blend ratio test. A method for determining the volume percent biodiesel in blends with conventional diesel fuel (blend ratio) was developed. This work addresses fuel quality concerns voiced by terminal operators and consumers that the actual blend ratios of blended fuels match the stated ratios. Physical properties including cloud point, viscosity, refractive index, relative density, cloud point, and viscosity were measured for a series of blends. Results showed that when accurate data are available for the individual fuels before blending, blend ratio may be determined. This work provides a foundation for development of field tests for evaluating blend ratios. Cold flow properties of biodiesel by automated methods. Automated analytical tools were developed for measurement of cloud point and other cold flow properties of biodiesel and its blends with conventional diesel fuel. This work established two automated and relatively accurate methods for analyzing cold flow properties that are more rapid and user-friendly than conventional "manual" methods. Light scattering and differential scanning calorimetry (DSC) experiments as well as manual measurements were performed and results interpreted in-house. Both methods may be employed by fuel producers and sellers to easily and rapidly monitor cold flow properties of biodiesel and its blends with conventional fuels. Furthermore, results from DSC scans may be used to infer kinetic parameters such as the latent heat of crystallization. Cold flow properties of biodiesel admixtures. Admixtures of biodiesel derived from soybean oil converted with methyl and other various alcohols (alkyl esters) were studied to determine effects of adding lower-cloud point alkyl soyates on cold flow properties of methyl soyate. This work addresses the need to improve cold flow properties of biodiesel during cool weather. Cold flow properties were analyzed and results interpreted in-house. Results may be employed to determine how much alkyl soyate, which tend to be more expensive than methyl soyate, is needed in these admixtures to significantly improve cold weather performance of biodiesel. New cold flow additives for biodiesel. Several fatty derivatives with bulky moieties were synthesized from technical grade oleic acid by treatment of an assortment of alkyl oleates with a variety of alcohols in the presence of sulfuric acid as catalyst to provide a series of alpha-hydroxy ethers. The materials were analyzed for low temperature behavior through cloud point and pour point determination. Generally, the 2-ethylhexoxy ethers of oleates containing bulky head groups were found to have the best low temperature performance. These results demonstrate that agricultural-based materials have potential as cold flow additives for biodiesel. Effects of biodiesel composition on viscosity. Viscosity is one of the major properties of any fuel and is the major reason why biodiesel is produced from vegetable oils or fats. Individual components of various biodiesel fuels were investigated for their effect on viscosity. The results showed that viscosity of biodiesel depends on individual components and therefore on the fatty acid composition from which the biodiesel is derived. These results may aid in predicting the viscosity of biodiesel from different sources and be useful in formulating "designer" fuels optimized for fatty acid composition. Biodiesel performance in new engine technologies. A comparative investigation and evaluation of the exhaust emissions of biodiesel, petrodiesel and some of their major components in a newer technology diesel engine was carried out and will cause a re-evaluation of this part of the project. This work relates to the problem of exhaust emissions generated by the use of biodiesel, specifically NOx emissions. Under the conditions tested here, some components of biodiesel generated not only less particulate matter but also less NOx emissions than petrodiesel. These results significantly enhance understanding how biodiesel, including versions with modified fatty ester composition, performs in newer-technology engines, also in comparison to petrodiesel, and will aid in meeting upcoming exhaust emissions regulations. Glycerol polymers. Glyceroxides formed by the reaction of glycerol and sodium hydroxide pellets were reacted with chlorinated glycerol to produce short glycerol polymers. The reaction was performed without solvent in excess glycerol. By-products included water and sodium chloride. These polyglycerols represent a marketable product derived from glycerol generated during the production of biodiesel fuels. The polyglycerols are useful in the preparation of non-ionic surfactants and may replace similar materials obtained from petrochemicals. Glycerol co-polymers and blends. Co-polymers and blends of glycerol with citric acid, lactic acid, and starch were prepared by condensation reactions. These materials were shown to have potential in coating applications. Glycerol in UV filters. Glycerol esters were developed that exhibit strong absorption in the ultraviolet region. Such compounds serve as organic UV filters for personnel care formulations. Epoxy esters from vegetable oil. Transesterification of epoxy vegetable oil was demonstrated as a method to prepare epoxy esters. These are useful chemical intermediates to produce the hydroxy, glyceroxy, or carbonated derivative compounds. 4c.List significant activities that support special target populations. None. 4d.Progress report. Collaborated with Alternative Aviation Fuels LLC (AAF) on a New York state-funded research project to develop a pilot-scale dry fractionation (winterization) process for improving the cold flow properties of biodiesel. Collaborated with Montana State University on conversion of camelina oil into biodiesel and analyzing the biodiesel for cold flow properties, viscosity, and oxidative stability characteristics. Results were compared with those of biodiesel from soybean oil. Collaborated with the Western Regional Research Center (WRRC) on analysis of cold flow properties, relative density, viscosity, acid value, and oxidative stability characteristics of biodiesel derived from salmon oil, unacidified salmon oil, and corn oil. Results were compared to those of biodiesel from soybean oil. Collaborated with Evergreen Farm Services (FS), (Bloomington, IL) was undertaken to address the storage stability of biodiesel during the winter season. Collaborated with Chemtech Services, Inc. (Joliet, IL) proceeded to develop a modified biodiesel process that produces high purity glycerol and biodiesel without water washing. Collaborated with Southwest Research Institute (SwRI) on emissions testing of biodiesel and components thereof in comparison to petrodiesel and its components. Collaborated with Iowa State University/University of Idaho on biodiesel education courses. Collaborated with Federal Research Institute for Agriculture, Germany, on biodiesel characterization. Collaborated with St. Mary's of the Woods College (Terre Haute, IN) on biodiesel production. In concert with ERRC, collaborated with scientists from the Federal Unitary Enterprise, State Research Institute of Organic Chemistry and Technology (GosNIIOKhT), on preparing a project proposal to develop technology for implentation of biodiesel conversion plants in Russia. This collaboration was coordinated as part of the ARS Former Soviet Union program. Collaborated with Guidry Liason Group, Inc. (Temecula, CA) to develop 1,3- propanediol and similar C3 feedstocks from crude glycerin obtained by conventional biodiesel production. 5.Describe the major accomplishments to date and their predicted or actual impact. Biodiesel made from feedstocks such as soybean, rapeseed, or used cooking oil is composed of varying types of chemical compounds (fatty acid alkyl esters). Consequently, several major accomplishments from this research project have yielded important conclusions on structure-property relationships of these chemicals, including in some cases additives or contaminants. Significant progress has been made in developing models to predict cold flow properties and relative oxidative stability of biodiesel; developing additives and other approaches for improving cold flow properties; and evaluating effects of contaminants such as free fatty acids or monoacylglycerides on biodiesel lubricity and cold flow properties. Other significant progress was made in development of novel polymers and specialty chemicals from glycerol in combination with other agricultural materials. This accomplishment is under NP 306, Component "New Processes, New Uses, and Value-Added Foods and Biobased Products" and NP 307, Component "Biodiesel." 6.What science and/or technologies have been transferred and to whom? When is the science and/or technology likely to become available to the end-user (industry, farmer, other scientists)? What are the constraints, if known, to the adoption and durability of the technology products? Communicated regularly with fuel producers, farmers, original equipment manufacturers (OEMs) and other research scientists through industry trade associations and other contacts. Consulting and advisory activities arising from these activities resulted in a significant impact on negotiations of the biodiesel industry with OEMs on drafting the recently implemented fuel standard for biodiesel. Research findings on cold weather effects improvement of cold flow properties of biodiesel, rapid and easy-to-use analytical methods for biodiesel as well as analytical methods for rapidly assessing the oxidation of biodiesel. These results have the potential for lowering biodiesel production and retail costs. Communicated results on NOx exhaust emissions reductions technologies to industry and other technical contacts. Interested industrial partners have been identified and tech transfer is pending formal agreements with one company to use a biodiesel process and another company to use the conversion of crude glycerin. In most cases, FIO-developed technologies are available for dissemination immediately following peer review, subject to conditions established beforehand regarding the transfer of intellectual properties developed in formal cooperation with stakeholders. Cooperated with researchers from other institutions on a project for developing biodiesel educational tools. This project will educate individuals planning to develop commercial ventures and other interested members of the public on biodiesel. Recent research findings as appropriate are included in the disseminated information. 7.List your most important publications in the popular press and presentations to organizations and articles written about your work. (NOTE: List your peer reviewed publications below). Delafontaine, M.J., Dunn, R.O., Hubert, M., Krishna, C.R. 2005. B-Jet project: Crystallization of fatty acid methyl esters using a scraped surface heat exchanger - monitored by focus beam reflectance and particle measurement probes. Proceedings of the 9th International Conference on Stability, Handling and Use of Liquid Fuels. IASH 2005. Dunn, R.O. 2006. Written interview in biodiesel industry poll. Biorenewable Resources No. 1: Building Biodiesel. Supplement to Inform. p. 5. Dunn, R.O. 2006. Oxidation reaction kinetics of biodiesel by pressurized-differential scanning calorimetry. Proceedings of the Annual Meeting of the North American Thermal Analysis Society. Holser, R.A. 2006. Exploring glycerin uses. Biofuels Journal. 2:12-16. Knothe, G. 2005. Comments on the biodiesel energy balance study by Pimentel and Patzek. Lipid Technology. 17(9):198. Knothe, G. 2005. Book review: The Chemistry of Oils and Fats. Journal of the Science of Food and Agriculture. 85:2325. Knothe, G. 2005. The lubricity of biodiesel. SAE Technical Paper. 2005-01-3672. Knothe G., Dunn, R.O. 2005. Biodiesel: An alternative diesel fuel from vegetable oils or animal fats. In Erhan, S.Z., editor. Industrial Uses of Vegetable Oil. Champaign, IL: AOCS Press, Academic Press. p. 42-89. Knothe, G. 2006. Biodiesel and the issue of petrodiesel lubricity. Lipid Technology. 18(5):105-108. Knothe, G. 2006. Written interview in biodiesel industry poll. Biorenewable Resources No. 1: Building Biodiesel. Supplement to Inform. p. 6. Knothe, G. 2006. 1H-NMR spectroscopy of fatty acids and their derivatives. Available: http://www.lipidlibrary.co.uk. Knothe, G. 2006. Oxidative stability of biodiesel and NMR. ACS Division of Fuel Chemistry 51(1):16-17. Review Publications Dunn, R.O. 2005. Cold flow properties of biodiesel: Admixtures of soybean oil fatty acid esters of methyl and branched-chain alcohols [abstract]. PacifiChem 2005. p. 43. Dunn, R.O. 2006. Crystallization behavior of fatty acid methyl esters [abstract]. 97th American Oil Chemists' Society Annual Meeting and Expo. p. 68. Dunn, R.O. 2006. Oxidative stability of biodiesel by non-isothermal pressurized-differential scanning calorimetry in dynamic mode [abstract]. 97th American Oil Chemists' Society Annual Meeting and Expo. p. 76. Dunn, R.O. 2006. Oxidation kinetics of biodiesel by non-isothermal pressurized-differential scanning calorimetry. In: Proceedings of the 34th Annual Conference of the North American Thermal Analysis Society, August 7-9, 2006, Bowling Green, Kentucky. p. 12-14. Holser, R.A. 2006. Transesterified milkweed (asclepias) seed oil as an alternative diesel fuel [abstract]. 97th American Oil Chemists' Society Annual Meeting and Expo. p. 67. Holser, R.A. 2006. Characterization of starch-modified glycerol citrate polymers [abstract]. 97th American Oil Chemists' Society Annual Meeting and Expo. p. 72. Holser, R.A., Doll, K.M., Erhan, S.Z. 2006. Metathesis of vegetable oil esters for improved fuel properties. Fuel. 85(3):393-395. Holser, R.A., Harry-O'Kuru, R.E. 2006. Transesterified milkweed (asclepias) seed oil as a biodiesel fuel. Fuel. 85(14/15):2106-2110. Knothe, G.H. 2006. Oxidative stability of biodiesel assessed by various methods [abstract]. 97th American Oil Chemists' Society Annual Meeting and Expo. p. 69. Knothe, G.H. 2006. Research on biodiesel and vegetable oil fuels - Then and now [abstract]. 97th American Oil Chemists' Society Annual Meeting and Expo. p. 66. Knothe, G.H. 2006. Analysis of oxidized biodiesel by 1H-NMR and effect of contact area with air. European Journal of Science and Lipid Technology. 108:493-500. Knothe, G.H. 2006. NMR characterization of dihydrosterculic acid and its methyl ester. Lipids. 41:393-396. Knothe, G.H., Sharp, C.A., Ryan, III, T.W. 2005. Exhaust emissions of biodiesel, petrodiesel, neat methyl esters, and alkanes in a new technology engine. Energy and Fuels. 20(1):403-408. Moser, B.R., Erhan, S.Z. 2006. Synthesis and evaluation of a series of oleate derivatives as potential biodiesel value-added products [abstract]. 97th American Oil Chemists' Society Annual Meeting and Expo. p. 76-77. Wyatt, V.T., Hess, M.A., Dunn, R.O., Foglia, T.A., Haas, M.J., Marmer, W.N. 2005. Fuel properties and nitrogen oxides emissions levels of biodiesel produced from animal fats. Journal of the American Oil Chemists' Society. 82(8):585-591.