Source: NORTHERN REGIONAL RES CENTER submitted to
VEGETABLE OIL-BASED ALTERNATIVE DIESEL FUELS, EXTENDERS, AND ADDITIVES
Sponsoring Institution
Agricultural Research Service/USDA
Project Status
TERMINATED
Funding Source
Reporting Frequency
Annual
Accession No.
0404097
Grant No.
(N/A)
Project No.
3620-41000-087-00D
Proposal No.
(N/A)
Multistate No.
(N/A)
Program Code
(N/A)
Project Start Date
Dec 22, 2000
Project End Date
Sep 18, 2004
Grant Year
(N/A)
Project Director
ERHAN S Z
Recipient Organization
NORTHERN REGIONAL RES CENTER
(N/A)
PEORIA,IL 61604
Performing Department
(N/A)
Non Technical Summary
(N/A)
Animal Health Component
20%
Research Effort Categories
Basic
80%
Applied
20%
Developmental
0%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
5111510200010%
5111820200070%
5111841200010%
5111899200010%
Goals / Objectives
Improve the combustion characteristics and fuel properties of vegetable oils (emphasizing soybean oil) and their derivatives as alternative diesel fuels, extenders and additives in the operation of compression-ignition (diesel) engines. Utilize fatty derivatives for performance enhancement and emissions reduction (e.g. nitrogen oxides). The objective will be met by obtaining and applying new knowledge of solubilization, low-temp flow properties, precombustion/combustion chemistry & other fuel characteristics
Project Methods
Modify vegetable oils to provide low emissions biodiesel fuels, extenders and additives with improved viscosity, surface tension, combustion and cold flow properties. Combustion-improving additives will be evaluated as means to reducing harmful exhaust emissions, especially NOx. Winterization, cold solvent extraction, cold-flow improvers and solubilization with surfactants will be evaluated as methods for improving low-temperature properties. Spectroscopic methods will be evaluated for inexpensive and rapid fuel quality testing. Vegetable oil derivatives will be evaluated for developing fuel performance enhancers by testing oxidative stability, lubricity, engine wear, etc. Determine suitability of vegetable oil derivatives for new off-road fuel applications. Identify fuel properties (viscosity, volatility, heat of combustion, density, etc.) that must be modified to meet fuel specifications. Determine how new applications affect problems known from current biodiesel research such as cold-flow, exhaust emissions and oxidative stability. Develop and test fuel formulations.

Progress 12/22/00 to 09/18/04

Outputs
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? What 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), and reduction of harmful exhaust emissions from biodiesel combustion. Additional objectives include the development of analytical methods to assess fuel quality and the development of marketable co-products from biodiesel production, e.g., glycerol. 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 Program 307, Research Component "Biodiesel". 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 creating jobs and economic activity in America, reducing the nation's dependence on foreign oil, and improving the environment by developing alternate energy sources and increasing the use of agricultural crops as feedstocks for biofuels. 2. List the milestones (indicators of progress) from your Project Plan. Combustion chemistry / Reduction of NOx exhaust emissions. 1 year: Investigation of fundamental parameters influencing biodiesel combustion, biodiesel cetane numbers, and the formation of NOx emissions. Establish extramural collaboration for conducting engine tests related to this aspect of the project. 2 years: Develop novel compounds with potential for reducing NOx exhaust emissions. 3 years: Develop fuel formulations containing NOx emissions-reducing additives. Initiate performance and emissions testing (extramural cooperation). 4 years: Engine durability and performance testing; comparative emissions analyses; field operability testing (by extramural cooperation, if appropriate). 5 years: Evaluate results. Recommend promising fuel formulation for field testing. Publication of results. Low-temperature flow properties. 1 year: Develop strategies for modifying compounds with functional moieties designed to inhibit formation of large solid crystals in formulations containing high molecular weight saturated esters. Strategies will primarily be based upon knowledge of nucleation and crystalline growth kinetics acquired from literature and from earlier studies. 2 years: Synthesize and purify new compounds based upon strategies developed above. 3 years: Test new compounds for suitability as cold flow improvers for biodiesel and petroleum diesel/biodiesel blends. Testing will be in accordance with unit-developed protocol, including measuring of cold flow properties and performing thermal analyses on experimental samples. 5 years: Prepare list of most promising cold flow improver additives for treating petroleum diesel/biodiesel blends. This list will provide a basis for subsequent extramural collaboration to conduct field operability tests, engine durability and performance tests, and if necessary comparative emissions analyses of experimental fuel formulations. Publication of results. Fuel quality and process control. 1 year: Evaluate spectroscopic and chromatographic methods for testing biodiesel and monitoring the transesterification reaction in greater detail. Determine parameters that influence storage stability of biodiesel (soyate fatty acid methyl esters) and petroleum diesel/biodiesel blends. Acquire new knowledge of oxidation reaction kinetics under steady-state conditions. 2 years: Extension of results to biodiesel/petrodiesel blends and novel formulations containing vegetable oil-derived components. Develop time- accelerated analytical methods for measuring oxidative stability and screening experimental formulations. Correlate results to allow safe prediction of responses under non-accelerated (real world) conditions. 3 years: Field testing of rapid fuel-quality control methods (by extramural cooperation, if appropriate). 4 years: Evaluate field tests of rapid fuel-quality control methods. Screen commercially available natural and synthetic antioxidants for potential to increase resistance to oxidation of biodiesel. Test physical compatibility of promising antioxidants in petroleum diesel/biodiesel blends. 5 years: Prepare list of most promising antioxidants that increase resistance to oxidation and are physically compatible in blends with petroleum diesel fuel. This list will provide a basis for subsequent extramural collaboration to conduct field operability tests, engine durability and performance tests, and if necessary comparative emissions analyses of experimental fuel formulations. Publication of results. 3. Milestones: A. List the milestones (from the list in Question #2) that were scheduled to be addressed in FY 2004. How many milestones did you fully or substantially meet in FY 2004 and indicate which ones were not fully or substantially met, briefly explain why not, and your plans to do so. All milestones scheduled to be addressed in FY 2004 of the project plan expiring and being replaced with 3620-41000-124-00D (shown following) were fully met. Develop new compounds as cold flow improvers for biodiesel and petro- diesel/biodiesel blends. Action(s): Identified and tested effects of experimental compounds on cold flow properties and performance and melting behavior in blends with biodiesel (methyl soyate). Devised new approaches for identifying freezing point depressants and fractionation of methyl soyate biodiesel. Develop kinetic model for rapid and accurate prediction of oxidative stability of biodiesel under a variety of reaction conditions. Action(s) : Kinetic model developed and ready for application to data collected from thermal analyses of biodiesel. Analyzed resistance to oxidation by oil stability index (OSI) and pressurized-differential scanning calorimetry (P-DSC). Engine durability and performance testing; comparative emissions analyses; field operability testing. Action(s): Combustion parameters were determined in prior years. Comparative emissions analysis, which includes performance testing, is being investigated. Fuel standards and process control. Action(s): This work was largely concluded in prior years. It is currently being expanded to include areas such as monitoring of oxidation as described in the new project plan. B. List the milestones (from the list in Question #2) that you expect to address over the next 3 years (FY 2005, 2006, & 2007). What do you expect to accomplish, year by year, over the next 3 years under each milestone? This is the final Report of Progress (AD-421) for this project, 3620- 41000-087-00D, which is being replaced by 3620-41000-124-00D. The new project plan was certified by the Office of Scientific Quality Review as having completing NP 307 Bioenergy and Energy Alternatives Panel Review on 8/11/04. The milestones for the future project plan are as follows: FY 2005 Develop thermodynamic model based on freezing point depression theory for application to biodiesel formulations. Assemble bench-scale apparatus for optimization of control variables for continuous-flow dry fractionation of biodiesel. Conduct studies on crystallization of methyl stearate and palmitate esters in model solutions. Identify and evaluate compounds and molecular structures that promote crystallization in biodiesel. Identify and evaluate molecular structures that demonstrate good solubility properties. Establish extramural cooperative research and development agreement for developing pilot-scale dry fractionation of biodiesel. Investigate the fundamental parameters influencing biodiesel combustion properties and exhaust emissions, with particular consideration given to fatty acid structure. Establish extramural collaboration for conducting engine tests related to this aspect of the project. 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. Evaluate conversion efficiencies and reaction kinetics of model reactions involving glycerol. FY 2006 Conduct experimental measurements and collect data necessary to support development of thermodynamic models based on freezing point depression theory. Continue studies on crystallization of methyl stearate and palmitate. Develop strategies for synthesizing, purifying and characterizing additive compounds for study as cold flow improver additives for biodiesel. Identify compounds for testing as additives and diluents in solution with biodiesel for measuring solubility curves at varying temperatures. Continue optimization studies on bench-scale continuous-flow dry fractionation apparatus. Develop novel compounds with potential for reducing NOx exhaust emissions. Develop insights on modifying biodiesel fatty ester composition. 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. Synthesize and evaluate a series of glycerol derivatives from reactions identified in previous year. FY 2007 Complete development of thermodynamic models for predicting cold flow properties of biodiesel. Continue testing of compounds as additives and diluents. Complete studies on crystallization kinetics of methyl stearate and palmitate. Compile list of compounds and additives that demonstrate good phase behavior in mixtures with biodiesel. Prepare database for more detailed experimental studies. Synthesize and purify new compounds for testing as cold flow improver additives. Test compounds in neat and blended biodiesel formulations. Complete optimization studies on bench-scale apparatus for continuous- flow dry fractionation of biodiesel. Test the results on larger-scale fractionation equipment. Develop fuel formulations containing NOx emissions-reducing additives and/or changed fatty ester composition. Continue developing time-accelerated analytical methods for determining fuel quality as related to oxidative stability. 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). Develop structure-property relationships for the glycerol derivatives and optimize the synthetic route of most promising compounds. 4. What were the most significant accomplishments this past year? A. Single most significant accomplishment during FY 2004: Identified binary mixtures of oxidation inhibitors (antioxidants) exhibiting synergistic effects when applied to improve oxidative stability of biodiesel. Biodiesel, like many products made from vegetable oils, has relatively poor stability when in contact with air (oxygen). Oxidative degradation of biodiesel during storage can negatively impact fuel quality. Methyl soyate was treated with a series of single and binary antioxidant mixtures and analyzed for relative stability to oxidation at constant temperature. Results showed that combining two antioxidants improved stability to a degree that exceeded either antioxidant acting by itself. Combining two synergistic antioxidants will lower costs of biodiesel by reducing the quantity of antioxidant necessary to protect it from oxidative degradation. B. Other significant accomplishments (if any): Screened solvents for use in solvent fraction of biodiesel to improve its cold flow properties. Though fractionation is a promising technology that can significantly improve cold weather performance of biodiesel, solvent fractionation has advantages such as reduced processing time and increased product yield in comparison to dry fractionation (winterization) . Low concentrated solutions of methyl soyate in organic solvent were analyzed for freezing and related physical behavior. Solvents showing promising results will be employed in bench-scale fractionation experiments and analyses of fractionated methyl soyate. New insights on fuel properties such as viscosity and lubricity were obtained by investigating structure-property relationships. All factors of molecular structure such as presence, nature and number of double bonds, branching and oxygenated moieties affecting viscosity of biodiesel components were determined. Similar investigations are being conducted for lubricity, which has been stated to be one of the major advantages of biodiesel compared to petrodiesel. These results will aid in developing designer fuels with improved properties due to modified fatty ester composition. Building on previous work, new analytical methods and factors affecting oxidative stability are being developed. Improved analytical methods are necessary to provide rapid assessment to producers and users on the quality of biodiesel, especially when it has been stored for some time. A better understanding of factors affecting oxidative stability are significant for developing designer fuels as mentioned above and may also affect the amount and nature of antioxidants needed, leading to further reduction in their use. C. Significant Accomplishments/Activities that Support Special Target Populations. None. D. Progress Report. Collaborated on funded research grant to develop pilot-scale dry fractionation (winterization) process for application to improve cold flow property of biodiesel. Collaborated in cooperative development of grant proposal under USDOE-USDA co-administered Biomass Initiative program. Identified binary mixtures of oxidation inhibitors (antioxidants) exhibiting synergistic effects when applied to improve oxidative stability of biodiesel. Screened solvents for use in solvent fraction of biodiesel to improve its cold flow properties. The evaluation of various analytical methods applied to the oxidation of biodiesel led to the development of a new procedure for determining the fatty acid composition of biodiesel and other fatty materials. Novel fuel property data were collected on the various components of biodiesel as well as related components. New compounds with potential uses as additives were prepared. Investigations associated with trust fund agreement #58-3620-2-0460 (Village Botanica, Inc.) were completed. Details are contained in the Report of Progress (AD-421) for the subordinate project, 3620-41000-087- 02T. 5. Describe the major accomplishments over the life of the project, including their predicted or actual impact. Kinetic models were developed to screen the stability of biodiesel from various lipid feedstocks with respect to exposure to air (oxidative degradation) during long-term storage. Conventional and pressurized- differential scanning calorimetry studies and oil stability index measurements were performed in-house. Results were analyzed to infer activation energies and other parameters associated with oxidation of fatty derivatives. Accurate determination of these kinetic parameters is important because they allow simple and relatively rapid prediction of the oxidative stability of biodiesel samples under various realistic storage conditions even though most conventional industry standard tests generally require days or weeks to complete. Cold fractionation (winterization) of biodiesel can improve its cold flow properties and performance in on- and off-road applications. Laboratory-scale fractionation experiments were performed to improve repeatability and recovery efficiency of winterized material. Cooling curves were determined and winterized products analyzed for yield and relevant cold flow properties. Results from lab-scale experiments including the use of filtering aids will be useful in development of pilot- and commercial-scale process conditions to improve cold flow properties of biodiesel. Effects of oxidative degradation from exposure to air during storage on fuel quality of biodiesel and biodiesel blends is a significant concern. Oil stability index (OSI) and isothermal pressurized-differential scanning calorimetry (P-DSC) measurements on neat biodiesel (100%) and its blends with conventional diesel and aviation fuels were conducted at various temperatures and blend ratios (% biodiesel) in-house. Results were analyzed for effects of temperature and blend ratio. These results will be employed in various kinetic models for predicting performance of biodiesel and other fatty derivatives under realistic storage conditions. The influence of amounts of specific fatty esters, presence of metals and free fatty acids as well as various structural features of fatty esters as they (can) comprise biodiesel were investigated regarding their influence on oxidation of biodiesel using the oil stability index (OSI). Small amounts of more unsaturated fatty compounds have a disproportionately strong effect on oxidation as do metals and free fatty acids. From the results it appears likely that, for example, two lots of biodiesel stored with identical composition and history stored under identical conditions will not necessarily oxidize at the same rate. These results will help biodiesel producers, distributors and users assess the oxidation status of a biodiesel fuel and identify optimal storage conditions. They will also assist in developing designer fuels modified for a more optimal fatty ester composition. Effects of oxidative degradation from exposure to air during storage on fuel quality of biodiesel and biodiesel blends is a growing concern. Oil stability index (OSI) studies on neat biodiesel and blends thereof with conventional diesel fuel were conducted in-house. Results for methyl soyate from five manufacturers were analyzed to determine baseline performance and the effects of temperature with respect to relative resistance to oxidation. These results were used in development of kinetic parameters for predicting performance of biodiesel and other fatty derivatives under realistic (non-accelerated) storage conditions. Winterization processing is effective in improving cold flow properties of biodiesel. Experiments with laboratory-scale continuous equipment were conducted at De Smet (Edegem, Belgium) as part of an informal collaboration with the Food & Industrial Oils research unit. Preliminary results showed that though soybean oil-based biodiesel can effectively be winterized, filtering aids or other modifications to the process equipment or operating procedures will be necessary to improve separation of higher-melting point components. This work may lead to formal collaborations with the ultimate goal of developing a means to winterize biodiesel in bulk quantities for appropriate engine performance and emissions testing. The use of quality parameters derived from general analyses and applications of vegetable oils and derivatives is not always appropriate for biodiesel, although they have been included in some biodiesel standards. A new index that better reflects properties and structure of fatty compounds was developed. Research on oxidative stability of fatty compounds complements this work. This research will enable better prediction of biodiesel properties, may influence standards and also more generally impact analyses and applications of vegetable oils. Cetane tests provide information on the ignition quality of a diesel fuel. Cetane tests of various branched and straight-chain fatty esters as they can be derived from vegetable oils were conducted by extramural collaboration. As cetane test equipment, a newly developed apparatus which permits rapid testing with significantly reduced amounts of test materials was used. This research will provide information on potential tailoring of vegetable oil-derived compounds and additives to enhance fuel properties, such as combustion and reduction of exhaust emissions, of biodiesel and facilitate further investigations. The nitrogen oxides species in exhaust emissions of biodiesel must be reduced in order to meet increasing stringent environmental regulations. Corresponding emissions tests using additives in biodiesel and conducted through extramural collaboration were carried out. Such tests can identify additives which may potentially reduce NOx exhaust emissions from biodiesel use or point in the direction of further promising research in this area. Explored applications for biodiesel in blends with aviation (jet) fuels. Cold flow property, viscosity, and water-compatibility studies with blends containing up to 30 percent by volume soybean oil-based biodiesel in jet fuel were performed in-house. Freezing point studies indicated that blending jet fuel with winterized biodiesel significantly improved flow at low temperatures. This research was conducted to develop technical information in support of stakeholders from government, industry, academia seeking to improve ground level emissions from commercial and military jet aircraft. Developed means to measure effects of oxidative degradation from exposure of biodiesel to air under accelerated conditions. An industry- standard method for determining the oil stability index (OSI) of fats and oils was modified and developed for application to "pure" biodiesel and biodiesel/petrodiesel blends in studies conducted in-house. Optimum experimental conditions were identified for isothermal OSI measurement of biodiesel at temperatures in the range 50-90 degrees C (122-194 degrees F) . Results from this work provided a basis for gathering information on relative resistance to oxidation of various fatty derivatives and for designing studies to support development of various models for oxidation kinetics. Oxidation inhibitor additives (antioxidants) may be useful in protecting fatty derivatives such as biodiesel from exposure to air during long term storage. Natural and synthetic antioxidants were added in very small concentrations (less than 0.1 percent by weight) to soybean oil-based biodiesel and analyzed by oil stability index (OSI) and differential scanning calorimetry (DSC) screening studies performed in-house. Results showed that antioxidants were very effective in protecting biodiesel from oxidation under accelerated conditions. This work showed which antioxidants were most effective and increased the understanding of chemistry associated with inhibition of oxidative degradation in fatty derivatives. A spectroscopic method for determining the blend level of biodiesel in blends with petroleum-derived diesel fuel was developed. An analytical method (near-infrared spectroscopy; NIR) previously developed for monitoring the production and fuel quality of neat biodiesel was applied to solve this problem and work completed using in-house resources. Different blend levels were tested by this method. The procedure is a potential method for fuel producers and distributors to determine blend levels in an easy, cost-efficient manner. A new method for assessing the composition of biodiesel fuel by nuclear magnetic resonance (NMR) spectroscopy was developed which has potential to be correlated to other methods and verify results of those methods. The properties of biodiesel, like those of any fuel, can be positively influenced by compounds termed additives deliberately added to it. Using in-house resources, novel compounds were synthesized with the goal of influencing biodiesel cold-flow or combustion properties. The development additives positively influencing the properties of biodiesel will reduce or remove technological hurdles facing its widespread commercialization. 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), consumers and research scientists and engineers 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. Presented research findings on improvement of cold flow properties of biodiesel, use of biodiesel in aviation fuels, oxidative stability of biodiesel, biodiesel-antioxidant mixtures, fuel properties of biodiesel components such as viscosity and lubricity, rapid and easy-to-use analytical methods for measuring fuel quality of biodiesel, and analytical methods for rapidly assessing the oxidation of biodiesel. These results have the potential for lowering biodiesel production and retail costs. Additional results on NOx exhaust emissions reductions technologies were conveyed to industry and other technical contacts, a material transfer agreement was established with a chemical company to acquire and test possible cold flow improver for biodiesel and biodiesel/petrodiesel blends, and collaborations were made with researchers from academia and industry on a research grant to develop pilot- and industrial-scale dry fractionation (winterization) process to improve cold flow properties of biodiesel (methyl soyate). The grant was funded in April 2004. 7. List your most important publications in the popular press and presentations to organizations and articles written about your work. Interviewed for articles in MONEY and Revista Aera magazines. Topic: Use of biodiesel in aviation fuels. Interviewed by telephone on-the-air on National Public Radio in Baton Rouge, LA. Topic: Introduction of kits for converting vehicles to run on used cooking oils. Knothe, G. 2004. Giants from the past: Wilhelm Normann (1870-1939). INFORM. 15(6):364-365.

Impacts
(N/A)

Publications

  • Dunn, R.O. 2004. Effect of mixed antioxidants on oxidative stability of biodiesel [abstract]. Annual Meeting and Expo of the American Oil Chemists' Society. p. 77.
  • Knothe, G.H., Steidley, K.R. 2004. Viscosity and lubricity of biodiesel fuel components [abstract]. Annual Meeting and Expo of the American Oil Chemists' Society. p. 77.
  • Holser, R.A., Bost, G., Van Boven, M. 2004. Phytosterol composition of hybrid hibiscus seed oils. Journal of Agricultural and Food Chemistry. 52(9):2546-2548.
  • Knothe, G.H. 2004. Biodiesel fuel properties of soybean oil fatty acid esters. Proceedings of International Soybean Processing and Utilization Conference. p. 1008-1015.
  • Kuo, T., Knothe, G.H. 2004. Production and properties of 7,10,12- trihydroxy-8(e)-octadecenoic acid from ricinoleic acid conversion by pseudomonas aeruginosa. European Journal Lipid Science Technology. 106:405- 411.
  • Kenar, J.A., Knothe, G.H., Copes, A.L. 2004. Synthesis and characterization of dialkyl carbonates prepared from mid-, long-chain, and guerbet alcohols. Journal of the American Oil Chemists' Society. 81(3):285- 291.
  • Knothe, G.H. 2003. Quantitative analysis of mixtures of fatty compounds by 1h-nmr. Lipid Technology. 15:111-114.
  • Knothe, G.H., Kenar, J.A. 2004. Determination of the fatty acid profile by h-nmr spectroscopy. European Journal Lipid Science Technology. 106(2):88- 96.
  • Dunn, R.O., Knothe, G.H. 2003. Oxidative stability of biodiesel/jet fuel blends by oil stability index (osi) analysis. Journal of the American Oil Chemists' Society. 80(10):1047-1048.
  • Knothe, G.H., Dunn, R.O. 2003. Influence of compound structure, concentration and presence of metals on oxidative stability of fatty compounds by the oil stability index method. Journal of the American Oil Chemists' Society. 80(10):1021-1026.


Progress 10/01/02 to 09/30/03

Outputs
1. What major problem or issue is being resolved and how are you resolving it? Improving the fuel properties and combustion characteristics of alternative fuels and extenders derived from vegetable oils (biodiesel). Improvements are necessary to create more widespread market opportunities for biodiesel. This project focuses on improving flow properties during cold weather, improving resistance to oxidation (degradation caused by exposure to air) during storage, improving harmful exhaust emissions from combustion of biodiesel, developing rapid and inexpensive analytical methods for assessing fuel quality, and developing improved fuel quality indices. Physical and chemical remedies are being developed to improve flow of biodiesel and diesel/biodiesel blends during cold weather. Physical remedies include removal of higher melting components using a process called winterization. Chemical remedies are focused on synthesis and development of new compounds that may be useful as additives to modify the crystallization properties of biodiesel. Natural and synthetic agents called antioxidants are being developed to increase resistance to oxidation in biodiesel and in biodiesel/conventional diesel fuel blends. This work requires development of accurate and rapid experimental methods to predict resistance to oxidation under expected storage conditions and to screen fuel antioxidants. The use of additives called cetane improvers has been shown to be a possibility for reducing nitrogen oxides exhaust emissions from combustion of conventional diesel fuel. This approach is being developed for biodiesel. Tests have shown that compounds exist that can significantly increase the cetane number of biodiesel (the cetane number is a diesel fuel quality index related to ignition and combustion properties). Higher cetane numbers correlate with reduced nitrogen oxides emissions in conventional diesel fuel. However, combustion and subsequent emissions can depend on fuel composition of biodiesel. Extramural exhaust emissions and combustion testing of biodiesel are under way or under further development. Rapid, easy-to-use, and inexpensive methods for monitoring the conversion of biodiesel from vegetable oils and animal fats and for assessing fuel quality of the products are being developed. A new fuel quality index is being explored which can replace older indices derived directly from the composition of vegetable oils. 2. How serious is the problem? Why does it matter? Improving cold weather flow properties of biodiesel is made by reducing the minimum temperature where overnight exposure does not cause start-up or operability problems the next day. At present, the relatively poor cold flow properties of soybean oil-based biodiesel may limit or prevent its distribution in the northern two-thirds of the United States from October to March. According to average climatic temperature data, reducing the operability temperature limit by just 10 degrees C (18 degrees F) will allow year-round distribution of soybean oil-based biodiesel in 20-percent blends by volume with conventional diesel fuel (B20) in markets such as Denver, CO. Winterization of biodiesel to improve cold flow properties may have unattractive side-effects. One significant side-effect is a reduction in resistance to oxidation. Another effect is a loss in combustion quality that may lead to engine durability problems as well as an increase in harmful exhaust emissions. Thus, there exists a need to develop alternative approaches for improving cold flow properties without compromising fuel quality. One approach under development is synthesis and development of compounds that act as cold flow improver additives or freezing point depressants. Commercial additives developed for improving cold flow of conventional diesel fuels are largely ineffective for biodiesel. Successful development of additives for biodiesel will depend on increasing current levels of fundamental knowledge on mechanisms driving formation of solid crystals at cold temperatures. By nature, biodiesel is more sensitive to oxidative degradation when in contact with oxygen in ambient air than conventional diesel fuels. Should biodiesel undergo extensive degradation it may develop contaminants that retard or cut-off flow through fuel filters and lines or otherwise compromise the fuel with respect to combustion and exhaust emissions. The exact implications of partial (not too extensive) degradation on fuel quality are not readily known and should be determined. Finally, owing to a relative lack of corresponding information for conventional diesel fuels, very little has been developed in standardized test methods for evaluating fuels or hybrid fuel mixtures. Most exhaust emissions are reduced when using biodiesel as a fuel compared to conventional diesel fuel. Nitrogen oxides exhaust emissions are an important exception. These exhaust emissions must be reduced because they are precursors of ozone, which in turn is a major component of health-hazardous urban smog. Consequently, nitrogen oxides and ozone in ambient air are subject to increasingly stringent environmental regulations. Efficient methods for assessing fuel quality will be essential to the production and distribution of biodiesel that meets a provisional American Society for Testing and Materials (ASTM) fuel standard specification. Reliable, rapid and inexpensive monitoring of biodiesel conversion should ease control and reduce processing costs. Fuel test methods that can efficiently and inexpensively monitor conversion processing and assess fuel quality will help control production costs of biodiesel and lead to more consistent fuel quality. These are important because biodiesel is inherently significantly more costly to produce than conventional diesel fuel and because biodiesel needs to meet the provisional ASTM fuel standard. Thus, rapid and reliable test methods should instill confidence in production and help overcome marketing obstacles. Older quality indices based on vegetable oil composition are being applied to biodiesel and have the potential to impede its development by excluding certain feedstocks. A new and improved index with potential to alleviate this problem is being developed. Overall, 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 an renewable alternative fuel that will meet regulatory requirements for protecting the environment and increasing energy security. In a direct sense, 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 which benefits from reduced exhaust emissions from the operation of diesel engines as well as enhanced energy security. 3. How does it relate to the National Program(s) and National Program Component(s) to which it has been assigned? National Program 306 (30%) Quality, and Utilization of Agricultural Products National Program 307 (70%) Bioenergy and Energy Alternatives This research requires expertise in development of new or synthesized materials and in the chemistry of fat- and oil-based products. Its objective is to improve marketability of alternative diesel fuels and extenders from vegetable oil (emphasizing soybean oil) by improving its quality and combustion characteristics. Fuels developed from soybean oil and its derivatives are renewable and inherently more environmentally friendly alternative energy sources. Extramural collaboration is on- going for work on combustion and testing of exhaust emissions. 4. What were the most significant accomplishments this past year? A. Single most significant accomplishment during FY 2003: The fatty acid composition of biodiesel fuel is one of the major factors affecting its fuel properties. A new method for determining the fatty acid composition of biodiesel fuel was developed. A spectroscopic method was correlated with a chromatographic method and the results shown to be in good agreement. The new method will not only help determine fatty acid composition but will also be useful in assessing the fuel quality of biodiesel that has been subjected to deterioration-promoting conditions. B. Other significant accomplishment(s), if any: Kinetic models were developed to screen the stability of biodiesel from various lipid feedstocks with respect to exposure to air (oxidative degradation) during long-term storage. Conventional and pressurized- differential scanning calorimetry studies and oil stability index measurements were performed in-house. Results were analyzed to infer activation energies and other parameters associated with oxidation of fatty derivatives. Accurate determination of these kinetic parameters is important because they allow simple and relatively rapid prediction of the oxidative stability of biodiesel samples under various realistic storage conditions even though most conventional industry standard tests generally require days or weeks to complete. Cold fractionation (winterization) of biodiesel can improve its cold flow properties and performance in on- and off-road applications. Laboratory-scale fractionation experiments were performed to improve repeatability and recovery efficiency of winterized material. Cooling curves were determined and winterized products analyzed for yield and relevant cold flow properties. Results from lab-scale experiments including the use of filtering aids will be useful in development of pilot- and commercial-scale process conditions to improve cold flow properties of biodiesel. Effects of oxidative degradation from exposure to air during storage on fuel quality of biodiesel and biodiesel blends is a significant concern. Oil stability index (OSI) and isothermal pressurized-differential scanning calorimetry (P-DSC) measurements on neat biodiesel (100%) and its blends with conventional diesel and aviation fuels were conducted at various temperatures and blend ratios (% biodiesel) were performed in- house. Results were analyzed for effects of temperature and blend ratio. These results will be employed in various kinetic models for predicting performance of biodiesel and other fatty derivatives under realistic storage conditions. To improve the determination of the oxidation status of biodiesel during long-term storage, reactions conducted under air and accelerated conditions were evaluated. The analysis of the samples by various analytical methods based on spectroscopy and physical properties necessitated the development of a new analytical procedure for fatty acid profile determination. The results and the new method lead to an improved correlation of various analytical methods. This work will help identify the best methods for analyzing the oxidation status of biodiesel, a problem of great concern to biodiesel producers, distributors and users and ultimately will lead to savings in terms of time and expenses for such analyses. Fuel properties of the various individual components of a fuel must be available. For this purpose, various properties such as cetane number and viscosity were determined. The data from these fuel property determinations are being correlated. The results are important as they will aid in defining fuel formulations with improved properties such as oxidative stability and cleaner combustion. The properties of biodiesel, like that of any fuel, can be positively influenced by compounds termed additives deliberately added to it. Using in-house resources, novel compounds were synthesized with the ultimate goal of influencing biodiesel cold-flow or combustion properties. This work on synthesis and characterization of such compounds continued through FY 2003. The development additives positively influencing the properties of biodiesel will reduce or remove technological hurdles facing its widespread commercialization. C. Significant Activities that Support Special Target Populations: None. D. Progress Report: Collaborations were developed by participating in two research grant proposals under the U.S. Department of Energy (DOE) Small Business Innovative Research (SBIR) program and the Biomass Initiative. Oxidation of components of biodiesel and its blends was evaluated by pressurized- differential scanning calorimetry and oil stability index studies. Cold fractionation of biodiesel was improved by using filtering aids and refining the cooling curve. The evaluation of various analytical methods applied to the oxidation of biodiesel led to the development of a new procedure for determining the fatty acid composition of biodiesel and other fatty materials. Novel fuel property data were collected on the various components of biodiesel as well as related components. New compounds with potential uses as additives were prepared. 5. Describe the major accomplishments over the life of the project, including their predicted or actual impact. The influence of amounts of specific fatty esters, presence of metals and free fatty acids as well as various structural features of fatty esters as they (can) comprise biodiesel were investigated regarding their influence on oxidation of biodiesel using the OSI. Small amounts of more unsaturated fatty compounds have a disproportionately strong effect on oxidation as do metals and free fatty acids. From the results it appears likely that, for example, two lots of biodiesel stored with identical composition and history stored under identical conditions will not necessarily oxidize at the same rate. These results will help biodiesel producers, distributors and users assess the oxidation status of a biodiesel fuel and identify optimal storage conditions. Effects of oxidative degradation from exposure to air during storage on fuel quality of biodiesel and biodiesel blends is a growing concern. OSI studies on neat biodiesel and blends thereof with conventional diesel fuel were conducted in-house. Results for methyl soyate from five manufacturers were analyzed to determine baseline performance and the effects of temperature with respect to relative resistance to oxidation. These results were used in development of kinetic parameters for predicting performance of biodiesel and other fatty derivatives under realistic (non-accelerated) storage conditions. Winterization processing is effective in improving cold flow properties of biodiesel. Experiments with laboratory-scale continuous equipment were conducted at De Smet (Edegem, Belgium) as part of an informal collaboration. Preliminary results showed that though soybean oil-based biodiesel can effectively be winterized, filtering aids or other modifications to the process equipment or operating procedures will be necessary to improve separation of higher-melting point components. This work may lead to formal collaborations with the ultimate goal of developing a means to winterize biodiesel in bulk quantities for appropriate engine performance and emissions testing. The use of quality parameters derived from general analyses and applications of vegetable oils and derivatives is not always appropriate for biodiesel, although they have been included in some biodiesel standards. A new index that better reflects properties and structure of fatty compounds was developed. Research on oxidative stability of fatty compounds to complement this research complement this work. This research will enable better prediction of biodiesel properties, may influence standards and also more generally impact analyses and applications of vegetable oils. Cetane tests provide information on the ignition quality of a diesel fuel. Cetane tests of various branched and straight-chain fatty esters as they can be derived from vegetable oils were conducted by extramural collaboration. As cetane test equipment, a newly developed apparatus which permits rapid testing with significantly reduced amounts of test materials was used. This research will provide information on potential tailoring of vegetable oil-derived compounds and additives to enhance fuel properties, such as combustion and reduction of exhaust emissions, of biodiesel and facilitate further investigations. The nitrogen oxides species in exhaust emissions of biodiesel must be reduced in order to meet increasing stringent environmental regulations. Corresponding emissions tests using additives in biodiesel and conducted through extramural collaboration were carried out. Such tests can identify additives which may potentially reduce NOx exhaust emissions from biodiesel use or point in the direction of further promising research in this area. Explored applications for biodiesel in blends with aviation (jet) fuels. Cold flow property, viscosity, and water-compatibility studies with blends containing up to 30 percent by volume soybean oil-based biodiesel in jet fuel were performed in-house. Freezing point studies indicated that blending jet fuel with winterized biodiesel significantly improved flow at low temperatures. This research was conducted to develop technical information in support of stakeholders from government, industry, academia seeking to improve ground level emissions from commercial and military jet aircraft. Developed means to measure effects of oxidative degradation from exposure of biodiesel to air under accelerated conditions. An industry- standard method for determining the OSI of fats and oils was modified and developed for application to pure biodiesel and biodiesel/petro-diesel blends in studies conducted in-house. Optimum experimental conditions were identified for isothermal OSI measurement of biodiesel at temperatures in the range 50-90 degrees C (122-194 degrees F). Results from this work provided a basis for gathering information on relative resistance to oxidation of various fatty derivatives and for designing studies to support development of various models for oxidation kinetics. Oxidation inhibitor additives (antioxidants) may be useful in protecting fatty derivatives such as biodiesel from exposure to air during long term storage. Natural and synthetic antioxidants were added in very small concentrations (less than 0.1 percent by weight) to soybean oil-based biodiesel and analyzed by OSI and differential scanning calorimetry (DSC) screening studies performed in-house. Results showed that antioxidants were very effective in protecting biodiesel from oxidation under accelerated conditions. This work showed which antioxidants were most effective and increased the understanding of chemistry associated with inhibition of oxidative degradation in fatty derivatives. A spectroscopic method for determining the blend level of biodiesel in blends with petroleum-derived diesel fuel was developed. An analytical method (near-infrared spectroscopy [NIR]) previously developed for monitoring the production and fuel quality of neat biodiesel was applied to solve this problem and work completed using in-house resources. Different blend levels were tested by this method. The procedure is a potential method for fuel producers and distributors to determine blend levels in an easy, cost-efficient manner. The properties of biodiesel, like those of any fuel, can be positively influenced by compounds termed additives deliberately added to it. Using in-house resources, novel compounds were synthesized with the goal of influencing biodiesel cold-flow or combustion properties. The development additives positively influencing the properties of biodiesel will reduce or remove technological hurdles facing its widespread commercialization. Accomplishments to December 2000 related to vegetable oil-based diesel fuels can be found in the final Report of Progress for the terminated project 3620-42000-075-00D. 6. What do you expect to accomplish, year by year, over the next 3 years? FY 2004: Collect information on the fuel properties of various biodiesel components and related materials. Synthesize and test new compounds as property-enhancing additives for biodiesel and biodiesel/conventional diesel fuel blends. Develop improved analytical methods for analyzing biodiesel as well as its oxidation status. Complete testing of new compounds as cold flow property enhancers for biodiesel and biodiesel/conventional diesel fuel blends. Identify and test compounds as freezing point depressants for mixtures with biodiesel. Continue development of binary and tertiary mixtures of oxidation inhibitors for treating soybean oil-based biodiesel. Complete development of kinetic model for rapid and accurate prediction of oxidative stability of biodiesel under various conditions. Test promising fuel additive packages for physical and chemical compatibility of individual additives and overall efficacy in improving cold flow properties and inhibiting oxidative degradation. Continue development of information database of lubricity enhancing characteristics of biodiesel from various feedstocks. Establish extramural collaboration(s) supportive to development of biodiesel/jet fuel blends. Develop field studies of biodiesel fuel formulations. FY 2005: Prepare database of fuel properties of various biodiesel components as well as related materials. Prepare database of most promising cold flow property enhancers, freezing point depressants, and oxidation inhibitors for biodiesel and its blends with conventional diesel and other fuels. Develop extramural collaboration(s) to initiate field operability, performance and emissions testing of biodiesel treated for enhanced cold flow properties. Complete testing of promising cold flow property enhancers and antioxidants for compatibility as components in various diesel fuel additive packages. Identify new compounds or methods for reducing the nitrogen oxides exhaust emissions of biodiesel to meet future regulations. FY 2006: Complete studies and initiatives outlined as of previous FY's and report findings. 7. 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. Reported findings on effects of biodiesel on freeze point in blends with jet fuels to military and academic stakeholders. In most cases, 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. Cooperating 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. 8. List your most important publications in the popular press and presentations to organizations and articles written about your work. (NOTE: This does not replace your peer-reviewed publications listed below). Dunn, R.O. Biodiesel in the Wild Blue Yonder. INFORM. 2003. v. 14. p. 36- 37. Knothe, G. Current Perspectives on Biodiesel. INFORM. 2002. v. 13. p. 900-903.

Impacts
(N/A)

Publications

  • DUNN, R.O., KNOTHE, G.H. OXIDATIVE STABILITY OF BIODIESEL/JET FUEL BLENDS. Proceedings of the Bioenergy Conference. 2002. Paper No. 2117.
  • DUNN, R.O., KNOTHE, G.H., FOGLIA, T.A., HAAS, M.J., MARMER, W.N. IMPROVING THE FUEL PROPERTIES, EXHAUST EMISSIONS AND ECONOMICS OF BIODIESEL IN THE USA. WORLD CONFERENCE AND EXHIBITION ON OILSEED AND EDIBLE, INDUSTRIAL AND SPECIALTY OILS. 2002. Abstract p. 6.
  • DUNN, R.O., KNOTHE, G.H. OIL STABILITY INDEX (OSI) STUDIES ON THE OXIDATIVE STABILITY OF BIODIESEL. ANNUAL MEETING AND EXPO OF THE AMERICAN OIL CHEMISTS SOCIETY. 2003. Abstract p. 80-81.
  • KNOTHE, G.H. SPECTROSCOPIC METHODS FOR DETERMINING THE OXIDATION OF BIODIESEL FUEL. Proceedings of the Bioenergy Conference. 2002. Paper No. 2121.
  • KNOTHE, G.H. FUEL PROPERTIES AND THE STRUCTURE OF FATTY ESTERS. ANNUAL MEETING AND EXPO OF THE AMERICAN OIL CHEMISTS SOCIETY. 2003. Abstract p. 81.
  • KNOTHE, G.H., KENAR, J.A. SYNTHESIS AND CHARACTERIZATION OF SOME OXYGENATED FATTY COMPOUNDS. World Conference and Exhibition on Oilseed and Edible, Industrial and Specialty Oils. 2002. Abstract p. 14.
  • KNOTHE, G.H. SYNTHESIS, APPLICATIONS, AND CHARACTERIZATION OF GUERBET COMPOUNDS AND THEIR DERIVATIVES. LIPID TECHNOLOGY. 2002. v. 14. p. 101-104.
  • KNOTHE, G.H. INFLUENCE OF STRUCTURE OF ESTERS OF FATTY ACIDS ON BIODIESEL FUEL PROPERTIES. LANDBAUFORSCHUNG VOELKENRODE. 2003. v. 239. p. 115-124.
  • KNOTHE, G.H., MATHEAUS, A.C., RYAN, T.W. CETANE NUMBERS OF BRANCHED AND STRAIGHT-CHAIN FATTY ESTERS DETERMINED IN AN IGNITION QUALITY TESTER. FUEL. 2002. v. 82. p.971-975.


Progress 10/01/01 to 09/30/02

Outputs
1. What major problem or issue is being resolved and how are you resolving it? Improving the fuel properties and combustion characteristics of alternative fuels and extenders derived from vegetable oils (biodiesel). Improvements are necessary to create more widespread market opportunities for biodiesel. This project focuses on improving flow properties during cold weather, improving resistance to oxidation (degradation caused by exposure to air) during storage, improving harmful exhaust emissions from combustion of biodiesel, developing rapid and inexpensive analytical methods for assessing fuel quality, and developing improved fuel quality indices. Physical and chemical remedies are being developed to improve flow of biodiesel and diesel/biodiesel blends during cold weather. Physical remedies include removal of higher melting components using a process called winterization. Chemical remedies are focused on synthesis and development of new compounds that may be useful as additives to modify the crystallization properties of biodiesel. Natural and synthetic agents called antioxidants are being developed to increase resistance to oxidation in biodiesel and in biodiesel/conventional diesel fuel blends. This work requires development of accurate and rapid experimental methods to predict resistance to oxidation under expected storage conditions and to screen fuel antioxidants. The use of additives called cetane improvers has been shown to be a possibility for reducing nitrogen oxides exhaust emissions from combustion of conventional diesel fuel. This approach is being developed for biodiesel. Tests have shown that compounds exist that can significantly increase the cetane number of biodiesel (the cetane number is a diesel fuel quality index related to ignition and combustion properties). Higher cetane numbers correlate with reduced nitrogen oxides emissions in conventional diesel fuel. However, combustion and subsequent emissions can depend on fuel composition of biodiesel. Extramural exhaust emissions and combustion testing of biodiesel are under way or under further development. Rapid, easy-to-use, and inexpensive methods for monitoring the conversion of biodiesel from vegetable oils and animal fats and for assessing fuel quality of the products are being developed. A new fuel quality index is being explored which can replace older indices derived directly from the composition of vegetable oils. 2. How serious is the problem? Why does it matter? Improving cold weather flow properties of biodiesel is made by reducing the minimum temperature where overnight exposure does not cause start-up or operability problems the next day. At present, the relatively poor cold flow properties of soybean oil-based biodiesel may limit or prevent its distribution in the northern two-thirds of the U.S. from October to March. According to average climatic temperature data, reducing the operability temperature limit by just 10 degrees C (18 degrees F) will allow year-round distribution of soybean oil-based biodiesel in 20- percent blends by volume with conventional diesel fuel (B20) in markets such as Denver, CO. Winterization of biodiesel to improve cold flow properties may have unattractive side-effects. One significant side-effect is a reduction in resistance to oxidation. Another effect is a loss in combustion quality that may lead to engine durability problems as well as an increase in harmful exhaust emissions. Thus, there exists a need to develop alternative approaches for improving cold flow properties without compromising fuel quality. One approach under development is synthesis and development of compounds that act as cold flow improver additives or freezing point depressants. Commercial additives developed for improving cold flow of conventional diesel fuels are largely ineffective for biodiesel. Successful development of additives for biodiesel will depend on increasing current levels of fundamental knowledge on mechanisms driving formation of solid crystals at cold temperatures. By nature, biodiesel is more sensitive to oxidative degradation when in contact with oxygen in ambient air than conventional diesel fuels. Should biodiesel undergo extensive degradation it may develop contaminants that retard or cut-off flow through fuel filters and lines or otherwise compromise the fuel with respect to combustion and exhaust emissions. The exact implications of partial (not too extensive) degradation on fuel quality are not readily known and should be determined. Finally, owing to a relative lack of corresponding information for conventional diesel fuels, very little has been developed in standardized test methods for evaluating fuels or hybrid fuel mixtures. Most exhaust emissions are reduced when using biodiesel as a fuel compared to conventional diesel fuel. Nitrogen oxides exhaust emissions are an important exception. These exhaust emissions must be reduced because they are precursors of ozone, which in turn is a major component of health-hazardous urban smog. Consequently, nitrogen oxides and ozone in ambient air are subject to increasingly stringent environmental regulations. Efficient methods for assessing fuel quality will be essential to the production and distribution of biodiesel that meets a provisional American Society for Testing and Materials (ASTM) fuel standard specification. Reliable, rapid and inexpensive monitoring of biodiesel conversion should ease control and reduce processing costs. Fuel test methods that can efficiently and inexpensively monitor conversion processing and assess fuel quality will help control production costs of biodiesel and lead to more consistent fuel quality. These are important because biodiesel is inherently significantly more costly to produce than conventional diesel fuel and because biodiesel needs to meet the provisional American Society for Testing and Materials (ASTM) fuel standard. Thus, rapid and reliable test methods should instill confidence in production and help overcome marketing obstacles. Older quality indices based on vegetable oil composition are being applied to biodiesel and have the potential to impede its development by excluding certain feedstocks. A new and improved index with potential to alleviate this problem is being developed. Overall, 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 an renewable alternative fuel that will meet regulatory requirements for protecting the environment and increasing energy security. In a direct sense, 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 benefits from reduced exhaust emissions from the operation of diesel engines as well as enhanced energy security. 3. How does it relate to the national Program(s) and National Program Component(s) to which it has been assigned? National Program 306 (70%) Quality and Utilization of Agricultural Products National Program 307 (30%) Bioenergy and Energy Alternatives This research requires expertise in development of new or synthesized materials and in the chemistry of fat- and oil-based products. Its objective is to improve marketability of alternative diesel fuels and extenders from vegetable oil (emphasizing soybean oil) by improving its quality and combustion characteristics. Fuels developed from soybean oil and its derivatives are renewable and inherently more environmentally friendly alternative energy sources. Extramural collaboration is on- going for work on combustion and testing of exhaust emissions. 4. What was your most significant accomplishment this past year? A. Single most significant accomplishment during FY 2002: A kinetic model was developed to screen the stability of biodiesel from various lipid feedstocks with respect to exposure to air (oxidative degradation) during long-term storage. Conventional and pressurized- differential scanning calorimetry studies and oil stability index measurements were performed in-house. Results were analyzed to infer activation energies and other parameters associated with oxidation of fatty derivatives. Accurate determination of these kinetic parameters is important because they allow simple and relatively rapid prediction of the oxidative stability of biodiesel samples under various realistic storage conditions even though most conventional industry standard tests generally require days or weeks to complete. B. Other significant accomplishment(s), if any: To improve the determination of the oxidation status of biodiesel during long-term storage, using in-house resources, reactions under air and accelerated conditions were conducted. Samples were analyzed after specific times by various analytical methods based on spectroscopy and physical properties. The results obtained from the various analytical methods can be correlated. This work will help identify the best methods for analyzing the oxidation status of biodiesel, a problem of great concern to biodiesel producers, distributors and users and ultimately will lead to savings in terms of time and expenses for such analyses. The influence of amounts, presence of metals and free fatty acids as well as various structural features of fatty esters as they (can) comprise biodiesel were investigated regarding their influence on oxidation of biodiesel using the oil stability index (OSI). It was shown that small amounts of more unsaturated fatty compounds have a disproportionately strong effect on oxidation as do metals and free fatty acids. From the results it appears likely that, for example, two lots of biodiesel stored with identical composition and history stored under identical conditions will not necessarily oxidize at the same rate. These results are important as they will help biodiesel producers, distributors and users assess the oxidation status of a biodiesel fuel and identify optimal storage conditions. The properties of biodiesel, like that of any fuel, can be positively influenced by compounds termed additives deliberately added to it. Using in-house resources, novel compounds were synthesized with the ultimate goal of influencing biodiesel cold-flow or combustion properties. This work on synthesis and characterization of such compounds continued through FY 2002. The development additives positively influencing the properties of biodiesel will reduce or remove technological hurdles facing its widespread commercialization. Effects of oxidative degradation from exposure to air during storage on biodiesel fuel quality is a significant concern. Differential scanning calorimetry (DSC) studies under non-isothermal conditions and oil stability measurements under isothermal conditions were performed in- house. Activation energy and other kinetic parameters inferred from DSC results compared well with available literature data. These results served as a basis for developing a kinetic model to rapidly predict oxidative stability of soybean oil-based products including biodiesel under realistic storage conditions. Effects of oxidative degradation from exposure to air during storage on fuel quality of biodiesel and biodiesel blends is a significant concern. Oil stability index (OSI) measurements on "pure" biodiesel and biodiesel/petro-diesel blends conducted isothermally at temperatures in the range 50-90 degrees C (122-194 degrees F) were performed in-house. Results for samples from five manufacturers were analyzed to determine baseline performance for soybean oil-derived biodiesel with respect to relative resistance to oxidation under accelerated conditions. These results will be employed in development of kinetic parameters for predicting performance of biodiesel and other fatty derivatives under realistic (non-accelerated) storage conditions. Effects of oxidative degradation from exposure to air during storage on fuel quality of biodiesel/jet fuel blends is also a significant concern in aviation fuel applications. Oil stability index (OSI) measurements on blends with up to 30 volume percent biodiesel in jet fuel (JP-8), conducted isothermally at temperatures in the range 50-90 degrees C (122- 194 degrees F), were performed in-house. Results confirmed that blends were not as susceptible to oxidative degradation as neat biodiesel and that increasing either temperature or blend ratio reduces resistance to oxidation. These results will contribute significantly towards development of fuel characteristics for biodiesel/jet fuel blends and will be employed in development of various kinetic models for predicting performance under realistic storage conditions. Winterization processing may be effective in improving cold flow properties of biodiesel. Experiments with laboratory-scale continuous equipment were conducted at De Smet (Edegem, Belgium) as part of an informal collaboration with the Food & Industrial Oils research unit. Preliminary results showed that though soybean oil-based biodiesel can effectively be winterized, filtering aids or other modifications to the process equipment or operating procedures will be necessary to improve separation of higher-melting point components. This work may lead to formal collaborations with the ultimate goal of developing a means to winterize biodiesel in bulk quantities for appropriate engine performance and emissions testing. C. Significant Accomplishments/Activities that Support Special Target Populations: none. D. Progress Report: Oxidation of components of biodiesel was evaluated by various analytical methods. A reliable, easy to use method for rapidly determining storage stability of biodiesel fuel formulations was developed. Tests of biodiesel in the presence of additives designed to reduce nitrogen oxides emissions, which are precursors of components of urban smog, are being evaluated. Cetane tests on previously untested fatty compounds were evaluated and a publication prepared. New compounds with potential uses as additives were prepared. A new index for property prediction was developed and research complementing it is in progress. 5. Describe your major accomplishments over the life of the project, including their predicted or actual impact? The use of quality parameters derived from general analyses and applications of vegetable oils and derivatives is not always appropriate for biodiesel, although they have been included in some biodiesel standards. A new index that better reflects properties and structure of fatty compounds was developed. Research on oxidative stability of fatty compounds to complement this research complement this work. This research will enable better prediction of biodiesel properties, may influence standards and also more generally impact analyses and applications of vegetable oils. Cetane tests provide information on the ignition quality of a diesel fuel. Cetane tests of various branched and straight-chain fatty esters as they can be derived from vegetable oils were conducted by extramural collaboration. As cetane test equipment, a newly developed apparatus which permits rapid testing with significantly reduced amounts of test materials was used. This research will provide information on potential tailoring of vegetable oil-derived compounds and additives to enhance fuel properties, such as combustion and reduction of exhaust emissions of biodiesel, and facilitate further investigations. The nitrogen oxides species in exhaust emissions of biodiesel must be reduced in order to meet increasing stringent environmental regulations. Corresponding emissions tests using additives in biodiesel and conducted through extramural collaboration were carried out. Such tests can identify additives which may potentially reduce NOx exhaust emissions from biodiesel use or point in the direction of further promising research in this area. Explored applications for biodiesel in blends with aviation (jet) fuels. Cold flow property, viscosity, and water-compatibility studies with blends containing up to 30 percent by volume soybean oil-based biodiesel in jet fuel were performed in-house. Freezing point studies indicated that blending jet fuel with winterized biodiesel significantly improved flow at low temperatures. This research was conducted to develop technical information in support of stakeholders from government, industry, and academia seeking to improve ground level emissions from commercial and military jet aircraft. Developed means to measure effects of oxidative degradation from exposure of biodiesel to air under accelerated conditions. An industry- standard method for determining the oil stability index (OSI) of fats and oils was modified and developed for application to "pure" biodiesel and biodiesel/petro-diesel blends in studies conducted in-house. Optimum experimental conditions were identified for isothermal OSI measurement of biodiesel at temperatures in the range 50-90 degrees C (122-194 degrees F) . Results from this work provided a basis for gathering information on relative resistance to oxidation of various fatty derivatives and for designing studies to support development of various models for oxidation kinetics. Oxidation inhibitor additives (antioxidants) may be useful in protecting fatty derivatives such as biodiesel from exposure to air during long term storage. Natural and synthetic antioxidants were added in very small concentrations (less than 0.1 percent by weight) to soybean oil-based biodiesel and analyzed by oil stability index (OSI) and differential scanning calorimetry (DSC) screening studies performed in-house. Results showed that antioxidants were very effective in protecting biodiesel from oxidation under accelerated conditions. This work showed which antioxidants were most effective and increased the understanding of chemistry associated with inhibition of oxidative degradation in fatty derivatives. A spectroscopic method for determining the blend level of biodiesel in blends with petroleum-derived diesel fuel was developed. An analytical method (near-infrared spectroscopy, NIR) previously developed for monitoring the production and fuel quality of neat biodiesel was applied to solve this problem and work completed using in-house resources. Different blend levels were tested by this method. The procedure is a potential method for fuel producers and distributors to determine blend levels in an easy, cost-efficient manner. The properties of biodiesel, like that of any fuel, can be positively influenced by compounds termed additives deliberately added to it. Using in-house resources, novel compounds were synthesized with the goal of influencing biodiesel cold-flow or combustion properties. The development additives positively influencing the properties of biodiesel will reduce or remove technological hurdles facing its widespread commercialization. Accomplishments to December 2000 related to vegetable oil-based diesel fuels can be found in the final progress report of the terminated project 3620-42000-075-00D. 6. What do you expect to accomplish, year by year, over the next 3 years? FY 2003: Continue to synthesize and test new compounds as property- enhancing additives for biodiesel and biodiesel/conventional diesel fuel blends. Develop improved chromatographic methods for analyzing biodiesel. Investigate and develop analytical methods for rapidly assessing oxidation status of biodiesel. Determine combustion properties of potential biodiesel fuel components. Complete testing of new compounds as cold flow property enhancing additives for biodiesel and biodiesel/conventional diesel fuel blends. Identify and test compounds as freezing point depressants for mixtures with biodiesel. Continue development of binary and tertiary mixtures of oxidation inhibitors for treating soybean oil-based biodiesel. Complete development of kinetic model for rapid and accurate prediction of oxidative stability of biodiesel under various conditions. Test promising fuel additive "packages" for physical and chemical compatibility of individual additives and overall efficacy in improving cold flow properties and inhibiting oxidative degradation. Develop means for quantitative analyses of lubricity enhancing properties of soybean oil-based biodiesel in blends with petro-diesel. Initiate development of information database of lubricity enhancing characteristics of biodiesel from various feedstocks. Pursue establishment of extramural collaboration(s) supportive to development of biodiesel/jet fuel blends. FY 2004: Prepare database of most promising cold flow property improver additives, freezing point depressants, and oxidation inhibitors for biodiesel and biodiesel/conventional diesel fuel blends. Pursue development of extramural collaboration(s) to initiate field operability, performance and emissions testing of biodiesel treated for enhanced cold flow properties. Complete testing of promising cold flow property improvers and antioxidants for compatibility as components in various diesel fuel additive packages. Identify new compounds or methods for reducing the nitrogen oxides exhaust emissions of biodiesel to meet future regulations. Develop field studies of biodiesel fuel formulations developed by FIO. FY 2005: Complete studies and initiatives outlined as of FY2004 and report findings. 7. What technologies have been transferred and to whom? When is the technology likely to become available to the end user (industry, farmer other scientist)? What are the constraints, if known, to the adoption durability of the technology? 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. Reported findings on effects of biodiesel on freeze point in blends with jet fuels to military and academic stakeholders. 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. Cooperating 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. 8. List your most important publications and presentations, and articles written about your work (NOTE: this does not replace your review publications which are listed below) Knothe, G. Historical Perspectives on Vegetable Oil-Based Diesel Fuels. INFORM. 2001. v. 12. p. 1103-1107.

Impacts
(N/A)

Publications

  • Dunn, R.O. Alternative Jet Fuels from Vegetable Oils. Transactions of the American Society of Agricultural Engineering. 2001. v. 44. p. 1751-1757.
  • Dunn, R.O. Low-Temperature Flow Properties of Vegetable Oil / Cosolvent Blend Diesel Fuels. Journal of the American Oil Chemists' Society. 2002. v. 79. p. 709-715.
  • Dunn, R.O., Knothe, G. Predicting the oxidative stability of biodiesel. 93rd American Oil Chemists' Society Annual Meeting & Expo. 2002. Abstract p. S105.
  • Knothe, G. Monitoring of Biodiesel Oxidation. 93rd American Oil Chemists' Society Annual Meeting & Expo. 2002. Abstract p. S105.
  • Knothe, G. Analytical Methods Used in the Production and Fuel Quality Assessment of Biodiesel. Transactions of the American Society of Agricultural Engineers. 2001. v. 44. p. 193-200.
  • Knothe, G. Determining the Blend Level of Mixtures of Biodiesel with Conventional Diesel Fuel by Fiber-Optic NIR Spectroscopy and 1H-NMR Spectroscopy. Journal of the American Oil Chemists' Society. 2001. v. 78. p. 1025-1028.
  • Krahl, J., Bunger, J., Schroder, O., Munack, A., Knothe, G. Exhaust Emissions and Health Effects of Particulate Matter from Agricultural Tractors Operating on Rapeseed Oil Methyl Ester. Journal of the American Oil Chemists' Society. 2002. v. 79. p. 717-724.
  • Knothe, G. Synthesis and Characterization of Long-chain 1,2-Dioxo Compounds. Chemistry and Physics of Lipids. 2002. v. 115. p. 85-91.


Progress 10/01/00 to 09/30/01

Outputs
1. What major problem or issue is being resolved and how are you resolving it? Improving the fuel properties and combustion characteristics of alternative fuels and extenders derived from vegetable oils (biodiesel). Improvements are necessary to create more widespread market opportunities for biodiesel. This project focuses on improving flow properties during cold weather, improving resistance to oxidation (degradation caused by exposure to air) during storage, improving harmful exhaust emissions from combustion of biodiesel, developing rapid and inexpensive analytical methods for assessing fuel quality, and developing improved fuel quality indices. Physical and chemical remedies are being developed to improve flow of biodiesel and diesel/biodiesel blends during cold weather. Physical remedies include removal of higher melting components using a process called winterization. Chemical remedies are focused on synthesis and development of new compounds that may be useful as additives to modify the crystallization properties of biodiesel. Natural and synthetic agents called antioxidants are being developed to increase resistance to oxidation in biodiesel and in biodiesel/conventional diesel fuel blends. This work requires development of accurate and rapid experimental methods to predict resistance to oxidation under expected storage conditions and to screen fuel antioxidants. The use of additives called cetane improvers has been shown to be a possibility for reducing nitrogen oxides exhaust emissions from combustion of conventional diesel fuel. This approach is being developed for biodiesel. Tests have shown that compounds exist that can significantly increase the cetane number of biodiesel (the cetane number is a diesel fuel quality index related to ignition and combustion properties). Higher cetane numbers correlate with reduced nitrogen oxides emissions in conventional diesel fuel. However, combustion and subsequent emissions can depend on fuel composition of biodiesel. Extramural exhaust emissions and combustion testing of biodiesel are under way or under Rapid, easy-to-use, and inexpensive methods for monitoring the conversion of biodiesel from vegetable oils and animal fats and for assessing fuel quality of the products are being developed. A new fuel quality index is being explored which can replace older indices derived directly from the composition of vegetable oils. 2. How serious is the problem? Why does it matter? Improving cold weather flow properties of biodiesel is made by reducing the minimum temperature where overnight exposure does not cause start-up or operability problems the next day. At present, the relatively poor cold flow properties of soybean oil-based biodiesel may limit or prevent its distribution in the northern two-thirds of the U. S. from October to March. According to average climatic temperature data, reducing the operability temperature limit by just 10 degrees C (18 degrees F) will allow year-round distribution of soybean oil-based biodiesel in 20-percent blends by volume with conventional diesel fuel (B20) in markets such as Denver, CO. Winterization of biodiesel to improve cold flow properties may have unattractive side-effects. One significant side- effect is a reduction in resistance to oxidation. Another effect is a loss in combustion quality that may lead to engine durability problems as well as an increase in harmful exhaust emissions. Thus, there exists a need to develop alternative approaches for improving cold flow properties without compromising fuel quality. One approach under development is synthesis and development of compounds that act as cold flow improver additives or freezing point depressants. Commercial additives developed for improving cold flow of conventional diesel fuels are largely ineffective for biodiesel. Successful development of additives for biodiesel will depend on increasing current levels of fundamental knowledge on mechanisms driving formation of solid crystals at cold temperatures. By nature, biodiesel is more sensitive to oxidative degradation when in contact with oxygen in ambient air than conventional diesel fuels. Should biodiesel undergo extensive degradation it may develop contaminants that retard or cut-off flow through fuel filters and lines or otherwise compromise the fuel with respect to combustion and exhaust emissions. The exact implications of partial (not too extensive) degradation on fuel quality are not readily known and should be determined. Finally, owing to a relative lack of corresponding information for conventional diesel fuels, very little has been developed in standardized test methods for evaluating fuels or hybrid fuel mixtures. Most exhaust emissions are reduced when using biodiesel as a fuel compared to conventional diesel fuel. Nitrogen oxides exhaust emissions are an important exception. These exhaust emissions must be reduced because they are precursors of ozone, which in turn is a major component of health- hazardous urban smog. Consequently, nitrogen oxides and ozone in ambient air are subject to increasingly stringent environmental regulations. Efficient methods for assessing fuel quality will be essential to the production and distribution of biodiesel that meets a provisional American Society for Testing and Materials (ASTM) fuel standard specification. Reliable, rapid and inexpensive monitoring of biodiesel conversion should ease control and reduce processing costs. Fuel test methods that can efficiently and inexpensively monitor conversion processing and assess fuel quality will help control production costs of biodiesel and lead to more consistent fuel quality. These are important because biodiesel is inherently significantly more costly to produce than conventional diesel fuel and because biodiesel needs to meet the provisional American Society for Testing and Materials (ASTM) fuel standard. Thus, rapid and reliable test methods should instill confidence in production and help overcome marketing obstacles. Older quality indices based on vegetable oil composition are being applied to biodiesel and have the potential to impede its development by excluding certain feedstocks. A new and improved index with potential to alleviate this problem is being developed. Overall, this research is targeted towards removing technological hurdles facing development of alternative diesel fuels from vegetable oils such as soybean oil. Successfull completion of this work will significantly advance biodiesel as an renewable alternative fuel that will meet regulatory requirements for protecting the environment and increasing energy security. In a direct sense, 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 which benefits from reduced exhaust emissions from the operation of diesel engines as well as enhanced energy security. 3. How does it relate to the National Program(s) and National Component(s)? National Program 306 (70%) Quality and Utilization of Agricultural Products. National Program 307 (30%) Bioenergy and Energy Alternatives. This research requires expertise in development of new or synthesized materials and in the chemistry of fat- and oil-based products. Its objective is to improve marketability of alternative diesel fuels and extenders from vegetable oil (emphasizing soybean oil) by improving its quality and combustion characteristics. Fuels developed from soybean oil and its derivatives are renewable and inherently more environmentally friendly alternative energy sources. Extramural collaboration is on-going for work on combustion and testing of exhaust emissions. 4. What were the most significant accomplishments this past year? A. Single most significant accomplishment during FY 2001 year: The use of quality parameters derived from general analyses and applications of vegetable oils and derivatives is not always appropriate for biodiesel, although they have been included in some biodiesel standards. A new index that better reflects properties and structure of fatty compounds was developed in the Food and Industrial Oil research unit. Research on oxidative stability of fatty compounds to complement this research are under way. This research will enable better prediction of biodiesel properties, may influence standards and also more generally impact analyses and applications of vegetable oils. B. Other significant accomplishment(s), if any: To develop rapid, accurate laboratory test methods for screening biodiesel fuel samples and measure their propensity to degrade due to exposure to air during long- term storage. Oxidation reaction kinetics were studied by differential scanning calorimetry (DSC) using personnel, facilities and equipment of the Food and Industrial Oils research group. Activation energy and other parameters were measured from DSC-analysis and employed in development of a kinetic model that could be applied to determine extent of oxidative degradation of soybean oil-based products under a variety of experimental conditions. This work ultimately will lead to the accurate determination in minutes the response of biodiesel to oxidative degradation under "real world" storage conditions, information that through current industry standard methods generally requires days or weeks to develop. To confirm validity of kinetic model developed from differential scanning calorimetry-analyses (see above) and to develop an isothermal (constant-temperature) laboratory method for determining relative resistance to oxidation of soybean oil-based products. The American Oil Chemists' Society standard test method for determining the oil stability index (OSI) of vegetable oils and fats was modified and developed for application to biodiesel and biodiesel/conventional diesel fuel blends using personnel, facilities and equipment of the Food and Industrial Oil research group. In this rating period, optimum experimental conditions were identified for measurement of OSI of biodiesel isothermally at temperatures between 50 and 90 degrees C (122 and 194 degrees F). Measurement of OSIs of biodiesel may provide important information on relative resistance to oxidation under isothermal conditions with results being acquired in less than one day instead of weeks or months normally required for industry standard methods. To identify potential of oxidation inhibitor additives (antioxidants) for improving relative resistance of biodiesel to oxidation. Antioxidants were added in very small concentrations (less than 0.1 percent by weight) to soybean oil-based biodiesel and tested by differential scanning calorimetry-analyses and measurement of oil stability index (see above) using personnel, facilities and equipment of the Food and Industrial Oil research group. Predominantly, one natural and one synthetic antioxidant were extensively tested and shown to be very effective in protecting soybean oil-based biodiesel. This work increased the understanding of chemical mechanisms associated with inhibition of oxidative degradation in fatty derivatives. To explore the application of biodiesel in blends with aviation jet fuels. Cold flow properties, oxidative stability, and salt-water-compatibility properties of biodiesel/jet fuel blends containing up to 30 percent by volume soybean oil-based biodiesel were measured using personnel, facilities and equipment of the Food and Industrial Oil research group. Freezing point studies indicated that blending jet fuel with winterized biodiesel significantly improved cold flow properties of the blends. This research was conducted to increase the experimental basis for cooperative grant proposals sponsored by stakeholders from federal agencies, industry, academia seeking to develop biodiesel/jet fuel blends to reduce ground level emissions from commercial and military jet aircraft. Previously, the problem of determining the blend level of biodiesel in conventional diesel fuels when using such blends had not been investigated. An analytical method (near-infrared spectroscopy; NIR) previously developed for monitoring the production and fuel quality of neat biodiesel was applied to solve this problem and work completed using resources of the Food and Industrial Oil research unit. Different blend levels were tested by this method. The procedure is a potential method for fuel producers and distributors to determine blend levels in an easy, cost- efficient manner. The properties of biodiesel, like that of any fuel, can be positively influenced by compounds termed additives deliberately added to it. Using resources of the Food and Industrial Oil research unit, novel compounds were synthesized with the goal of influencing biodiesel cold-flow or combustion properties. This work continued through FY 2001 through synthesis and characterization of such compounds. The development additives positively influencing the properties of biodiesel will reduce or remove technological hurdles facing its widespread commercialization. C. Significant Accomplishments/Activities that Support Special Target Populations: None. D. Progress report: A reliable, easy to use method for rapidly determining storage stability of biodiesel fuel formulations was developed. Tests of biodiesel in the presence of additives designed to reduce nitrogen oxides emissions, which are precursors of components of urban smog, are being evaluated. Cetane tests on previously untested fatty compounds were carried out. A method used for monitoring biodiesel production and fuel quality adapted to determine the level of blends of biodiesel in conventional diesel fuel was completed. A new index for property prediction was developed and research complementing it is in progress. Enhanced cold flow properties of winterized biodiesel/jet fuel blends were evaluated by freezing point measurements. 5. Describe the major accomplishments over the life of the project including their predicted or actual impact. This project plan has been certified 12/00 by the Office of Scientific Quality Review as having completed the peer review process. The history of this research can be found in the final progress report of the terminated project 3620- 42000-075-00D. 6. What do you expect to accomplish, year by year, over the next 3 years? FY 2002: Synthesize and test new compounds as cold flow property enhancers for biodiesel and biodiesel/conventional diesel fuel blends. Identify and test compounds as freezing point depressants in mixtures with biodiesel. Refine kinetic model for rapid and accurate prediction of oxidative stability of biodiesel from various feedstocks under "real world" storage conditions. Identify and screen binary and tertiary mixtures of oxidation inhibitors for effectiveness in treating soybean oil-based biodiesel and biodiesel/conventional diesel fuel blends. Pursue establishment of cooperative research project on development of biodiesel/jet fuel blends. Develop methods and apparatus for quantitative analyses of lubricity enhancing properties of biodiesel from several feedstocks including soybean oil in blends blends with "ultra-low sulfur" conventional diesel fuel. Develop experiments that will yield additional information on the formation of ozone-forming nitrogen oxides emissions with regard to biodiesel fuel composition. Determine cetane numbers of compounds not previously tested for this property. Conduct extramural cooperation needed to carry out the experiments. Develop additional methods for more easily and more rapidly assessing biodiesel fuel quality. Develop additional data to support new fuel quality parameters. FY 2003: Complete testing of new compounds as cold flow property enhancers and/or freezing point depressants for biodiesel and biodiesel/conventional diesel fuel blends. Identify promising cold flow property improvers and oxidation inhibitors and test for physical and chemical compatibility in various diesel fuel additive packages. Develop information database of lubricity enhancing characteristics of biodiesel from various feedstocks. This work will determine minimum blend-level of biodiesel necessary to sufficiently enhance lubricity in blends with conventional diesel fuels. Develop new correlations for predicting cetane numbers from the chemical composition of biodiesel. Continue investigations on formation of nitrogen oxides exhaust emissions which will include significant extramural cooperation. Continue work on developing biodiesel additives that have the potential to improve cold- flow properties. Continue to develop rapid test methods for assessing fuel quality and production monitoring. FY 2004: Prepare database of most promising cold flow property improver additives, freezing point depressants, and oxidation inhibitors for biodiesel and biodiesel/conventional diesel fuel blends. Pursue development of extramural collaboration(s) to initiate field operability, performance and emissions testing of biodiesel treated for enhanced cold flow properties. Complete testing of promising cold flow property improvers and antioxidants for compatibility as components in various diesel fuel additive packages. Identify new compounds or methods for reducing the nitrogen oxides exhaust emissions of biodiesel to meet future regulations. Develop field studies of biodiesel fuel formulations developed by FIO. These studies will likely require extramural collaboration. 7. 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 & durability of the technology product? Communicated regularly with fuel producers, farmers, original equipment manufacturers (OEMs) and other research scientists through industry trade associations and other contacts. Representatives from the NBB and the Illinois Soybean Association visited the CRIS facilities. 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 provision fuel standard for biodiesel. One impact of communications with the biodiesel industry resulted in dissemination of findings from research on the effects of cold weather and improvement of cold flow properties of biodiesel. Another impact was the distribution of information on an analytical method for rapid, easy and cost-efficient determination of biodiesel fuel quality and monitoring of biodiesel production. This has the potential for lowering biodiesel production and thus retail costs. Communicated results on NOx exhaust emissions reductions technologies to industry and other technical contacts. Reported findings on effects of biodiesel on freeze point in blends with jet fuels to military and academic stakeholders. This work has led to submission of two independent research proposals from FIO research to participate in multi-party cooperative effort to develop biodiesel/jet fuel blends as alternatives with improved air quality characteristics. 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. Information on research and development of alternative diesel fuels from vegetable oils, emphasizing soybean oil, is available and periodically updated on the FIO research unit's website. Despite recent fuel price trends, biodiesel remains too expensive to compete economically with conventional diesel. The U.S. Congress has recently empowered USDOE to add a 20 percent by volume biodiesel in diesel blend (B20) to its list of "alternative" fuels under the Energy Policy Act (EPACT) a move that should ease distribution of biodiesel into the regulated fleets market. However, much of the technology developed or under development is not expected to greatly impact economics. 8. List your most important publications in the popular press (no abstracts) and presentations to non-scientific organizations and articles written about your work (NOTE: this does not replace your peer-reviewed publications which are listed below) Work on the biodiesel/jet fuel blends was featured in articles published in Agricultural Research magazine (July 2001) and Lipid Technology Newsletter (August 2001).

Impacts
(N/A)

Publications

  • Dunn, R.O., Bagby, M.O. Low-temperature phase behavior in vegetable oil/co-solvent blends as alternative diesel fuel. Journal of the American Oil Chemists' Society. 2000. v. 77. p. 1315-1323.
  • Dunn, R.O., Knothe, G. Alternative diesel fuels from vegetable oils and animal fats. Journal of Oleo Science. 2001. v. 50. p. 415-426.
  • Dunn, R.O., and Knothe, G. Alternative diesel fuels from vegetable oils and animal fats. Japan Oil Chemists' Society/American Oil Chemists' Society World Congress, Tyoto, Japan. 2000. p. 172.
  • Dunn, R.O. Low-temperature flow properties of biodiesel/jet fuel (BioJet) blends. 92nd American Oil Chemists' Society Annual Meeting & Expo. Special Supplement to Inform. 2001. v. 12. p. S74.
  • Knothe, G. Characterization of esters of fatty acids and dicarboxylic Acids with Guerbet alcohols. Journal of the American Oil Chemists' Society. 2001. v. 78. p. 537-540.