1a. Objectives (from AD-416):
Objective 1: [addresses NP 307 Action Plan Problem Statements 3(c)(1), 3(c)(2) and 3(a)(4)] Develop new technologies that enable (1) commercial direct (‘in-situ’) production of biodiesel, and (2) commercially-preferred processes for the production of biodiesel from available, low-cost feedstocks. Objective 2: [addresses NP 307 Problem Statements 3(c)(1), 3(c)(2) and 3(a)(4)] Develop technologies that enable commercially-preferred technologies to remove performance-degrading biodiesel contaminants such as catalysts, sterol glucosides and sulfur. Objective 3: [addresses NP 307 Problem Statement 3(c)(5), and NP 306 Problem Statement 2c] Develop technologies that enable; (1) commercial production of hyperbranched polymer products from byproduct glycerol; and (2) commercially-viable and environmentally benign processes for new high-value industrial products made from fatty acids or the combination of fatty acids and lignin derivatives.
1b. Approach (from AD-416):
Develop technologies to use heterogenous catalysts to replace homogenous catalysts in the synthesis of biodiesel from free fatty acids and from glycerides in low quality feedstocks. Improve and scale-up methods newly develop method for biodiesel synthesis from trap grease. Using chromatographic and spectroscopic technologies, identify the structures of sulfur containing species contaminating biodiesel from low quality feedstocks and develop methods for their removal. Using enzymatic catalysis, remove sterol glucoside contaminants from vegetable oil based biodiesels. Develop new methods for the use of novel solid catalysts to modify fatty acids, in some cases through their combination with lignin degradation products generated by the pyroloysis of lignocellulosic feedstocks, to produce lubricants, personal care materials, and other functional lipids. Develop organic chemical methods to produce prepolymers from biodiesel glycerol and organic di-acids and use these to produce hyper-branched polymers. Determine the size and structures of these and determine their physical properties.
3. Progress Report:
A new approach for the removal from biodiesel of performance-degrading contaminants known as monoglycerides was undertaken and shown to be successful. Further development could lead to a technology that improves the reliability of biodiesel by eliminating filter-plugging contaminants. There is great interest in expanding biodiesel supplies. Corn germ is an oil-rich byproduct of corn milling and ethanol production. A direct, or ‘in situ’ method, which increases biodiesel yield and eliminates the use of a toxic solvent, was applied successfully for the conversion of the oil in corn germ to biodiesel. This provides a new source and technology for increased biodiesel production. An economic model to predict the cost of building and operating a large scale facility to produce biodiesel directly from soybeans, without having to isolate and purify the soybean oil within them, was produced. This model both aids further improvement of biodiesel production and helps individuals decide whether to adopt this technology for biodiesel production. There is a strong interest in the development of superior catalysts for the synthesis of biodiesel. This is especially true when using low quality feedstocks such as waste greases (i.e., used cooking oils). Two new catalysts were developed that are active in converting waste grease to biodiesel. Fast-acting and giving high yields, these catalysts can potentially reduce the cost of biodiesel production, enhance rural economic development, and have a positive impact on the environment and public health. Derivatives of fats and oils can be used in cosmetics, paints, lubricants and polymers. To expand the inventory of such derivatives, and in conjunction with colleagues at ARS-Peoria, researchers successfully synthesized and characterized a new modified fatty acid. It is a liquid at room temperature and has an ‘oiliness’ well suited for use as a lubricant. This could lead to new applications employing domestic oils and fats. With the goal of developing commercially viable new materials from glycerol, a co-product of biodiesel production, researchers synthesized highly branched glycerol-based oligomers and polymers. A new assay was developed to determine the extent of reaction by accurately measuring the amounts of unreacted starting material. This was useful in optimizing purification protocols. Modification of the polymer production chemistry led to a 70% reduction in the use of chemical solvents. Films made from these new polymers absorbed as much as 2.5 times their weight of some organic solvents. Synthesis of an initial panel of new, highly branched fatty acid esters has been completed and the determination of their lubricity properties has been initiated. The high degree of branching in these molecules should impart good lubrication properties, with an emphasis on low-temperature performance. Using newly developed methods that are generally applicable to other fats and oils, one of the esters was modified to confer a high degree of resistance to chemical degradation.
Ngo, H., Ashby, R.D., Nunez, A. 2012. Selective microbial degradation of saturated methyl branched chain fatty acid isomers. Journal of the American Oil Chemists' Society. DOI: 10.1007/s11746-012-2092-0 89:1885-1893.