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
Demonstrated that fatty acid methyl esters for potential use as biodiesel can be produced directly from oil-bearing algae. Identified the amounts of feedstock water level and reaction components, as well as the duration and reaction temperature parameters giving maximum yields. In partnership with a private sector collaborator, collaborated on the design and blueprint layout of a demonstration scale facility implementing a new process for biodiesel production, especially from low quality feedstocks. Oversaw construction of the corresponding plant by a private sector contractor. Analyzed the resulting biodiesel; developed methods for contaminant removal. Continuing collaboration with a university partner, applied a new family of solid catalysts to convert trap grease, an inexpensive but very contaminated fat, into biodiesel. Identified reaction conditions giving high yield conversion. Project scientists previously developed novel environmentally friendly methods to synthesize renewable, biodegradable materials branched-chain fatty acid isomers from fats and oils. These are potential replacement for analogues produced from petroleum. Project researchers, in conjunction with process engineers at this site, developed a technoeconomic model for the conduct of the new methodologies. The model predicted that the new technology is economically feasible at the industrial level, and identified cost centers where further efforts could achieve significant cost reduction. To better mimic the performance of some petroleum-based products, and thus promote the displacement of petroleum derivatives in industrial applications, Project scientists developed an efficient means of linking a class of organic molecules known as alkoxy phenols to fatty acids isolated from fats and oils. The new process gave up to 70% yield of the desired product, the highest yield known today. Ongoing efforts are aimed at increasing production so as to allow physical property studies. Having synthesized highly branched polymers from glycerol and various diacids using an organic solvent as part of the reaction mixture, it was determined that the solvent had participated in the reaction, terminating the growth of the polymers. Methods were also identified to synthesize such polymers in the absence of catalyst, thereby reducing cost while increasing product purity. Project scientists have prepared new compounds by linking fatty acids, which are obtained from oilseeds, to a chemical unit (phenol) generated by the pyrolysis of woody biomass in a sister project Distributed-Scale Pyrolysis of Agricultural Biomass for Production of Refinable Crude Bio-Oil and Valuable Coproducts,(1935-41000-082). These new compounds also contain chemical groups that are known to impart toughness and UV-resistance to polymers, and could lead to a new group of high performance biobased coatings, films, and molded solids.
1. Biodiesel from waste greases: The high cost of the refined oils typically used as the starting materials for biodiesel production can render the final fuel economically uncompetitive with petrodiesel. In addition, the single-use features of the alkaline catalysts currently employed in biodiesel synthesis from refined vegetable oil adds cost to the production process. The use of waste greases as biodiesel feedstocks could substantially reduce production costs. Since these greases are not used as human or animal foods their use as fuel feedstocks does not jeopardize food supplies. In partnership with a university collaborator ARS researchers at Wyndmoor, PA have obtained solid, multiple-use catalysts and shown them to be highly active in converting waste grease to biodiesel using an environmentally friendly and economically competitive approach. This process has the potential of reducing the cost of biodiesel, thereby increasing its use and displacing petroleum, as well as reducing engine emissions and their impact on global climate change.
2. Industrially-relevant polymers produced from glycerol byproduct of biodiesel production: With the increased production of coproduct glycerol by the growing biodiesel industry has come a need for new value-added materials synthesized from glycerol. ARS researchers at Wyndmoor, PA have demonstrated that polymers of glycerol and organic acids can be produced by reactions conducted in selected non-water solvent systems. The advantage of making polymers from glycerol in such systems are two-fold: it addresses the need for glycerol utilization while also producing polymers that have the ability to be further processed for many applications, e.g., additives for paints and varnishes and starting materials for adhesives, rubbers, and foams. To the best of our knowledge, this is the first example of glycerol polyesters being produced in a solvent system.
Ngo, H., Zafiropoulos, N.A., Foglia, T., Samulski, E.T., Lin, W. 2010. Mesoporous Silica-Supported Diarylammonium Catalysts for Esterification of Free Fatty Acids in Greases. Journal of the American Oil Chemists' Society. 87:445-452.