2010 Industrial Oil Products
IOP 1: Alternative Fuels
Chair(s): R.O. Dunn, USDA, ARS, NCAUR, USA; and B.R. Moser, USDA, ARS, NCAUR, USA
Biodiesel from Alternative Oilseed Feedstocks: Production and Properties. B.R. Moser, G. Knothe, S.F. Vaughn, USDA, ARS, NCAUR, Peoria, IL, USA
Fatty acid methyl esters were prepared and evaluated as potential biodiesel fuels from several alternative oilseed feedstocks, which included camelina (Camelina sativa L.), coriander (Coriandrum sativum L.), field mustard (Brassica juncea L.), field pennycress (Thlaspi arvense L.), and meadowfoam (Limnanthes alba L.) oils. Coriander and meadowfoam oil methyl esters were enriched in the unusual fatty esters methyl petroselinate (6Z-octadecenoate) and methyl 5Z-eicosenoate, respectively, whereas field mustard and field pennycress primarily consisted of methyl erucate (13Z-docosenoate). Camelina was comprised primarily of methyl linolenate (9Z,12Z,15Z-octadecatrienoate) and methyl linoleate (9Z,12Z-octadecadienoate). Fuel properties measured using standard methods included oxidative stability, low temperature operability, kinematic viscosity, cetane number, sulfur and phosphorous contents, acid value, free and total glycerol content, iodine value, heat of combustion, lubricity, and Gardner color. Coriander and especially meadowfoam oil methyl esters exhibited excellent oxidative stability, as indicated by induction periods (EN 14112, 110 oC) of 14.6 and 41.5 h, respectively. Lastly, a comparison to biodiesel fuel standards such as ASTM D6751 and EN 14214 was also made.
Biodiesel Derived From a Source Enriched in Palmitoleic Acid, Macadamia Nut Oil. G. Knothe, USDA, ARS, NCAUR, USA
Biodiesel is an alternative diesel fuel commonly produced from commodity vegetable oils such as palm, rapeseed (canola) and soybean. These oils generally have fatty acid profiles that vary within the C16 to C18 range. Thus, biodiesel fuels derived from these oils possess the common problems of poor cold flow and oxidative stability with varying severity. An approach to improving these problems is to utilize feedstocks with inherently different fatty acid profiles. Decanoic acid and palmitoleic acid are candidate fatty acids for enrichment in fatty acid profiles to improve biodiesel fuel properties. In this work, a feedstock moderately enriched in palmitoleic acid, macadamia nut oil, was utilized. Two macadamia oils with slightly varying palmitoleic acid content (15-20%) were used and the properties of the resulting biodiesel fuels determined. Although some differences were observed for biodiesel from the two macadamia feedstocks, at the present levels of palmitoleic acid in macadamia nut oil, enhancement of biodiesel fuel properties compared to biodiesel from commodity oils did not occur, likely due to the slight content of saturated C20 and C22 fatty acids. This highlights the necessity of reducing long-chain fatty acids to small amounts and increasing amounts of desirable fatty acids in order to improve biodiesel fuel properties.
Triacylglyceride as a Feedstock for Jet Fuel Production. P.D. Pansegrau, T. Aulich, C. Wocken, M. Kurz, B. Oster, Energy & Environmental Research Center, Grand Forks, ND, USA
The Energy & Environmental Research Center has developed a catalytic process for the conversion of crop oils, animal fats, algal oils, and waste greases to specification compliant fuels. The conversion process will be discussed, as well as the future production of low cost feedstocks.
Isolation and characterization of Acylated Steryl Glucosides (ASG) in Oil Seed Crops of Pacific Northwest (PNW). K. Duff, J. Van Gerpen, B. He, University of Idaho Biological and Agriculture Engineering, Moscow, Idaho, USA
Acylated steryl glucosides (ASG), a form of phytosterols, have been identified in a variety of agricultural products, including the oilseeds of soybean and rapeseed. Currently, there are limited data available on the quality and quantity of phytosterols in oil seed crops. During biodiesel production the esterification of ASG in oil extracts forms steryl glucosides (SG). These steryl glucosides in low concentrations (less than 50ppm) have been implicated in agglomeration of contaminates leading to subsequent filter clogging in biodiesel applications. Limited methods exist for the direct isolation and characterization of ASG. Methods relay on multistep extraction, saponification, acidification and derivatization for evaluation with GC-MS. The objective of this study is to characterize the ASG in agronomically significant oil seed crops of the Pacific Northwest. In this study HPLC-ESI-MS and HPLC-APCI-MS techniques were evaluated as characterization tools. Oilseeds were solvent extracted; the glycolipid fraction was isolated using a preparatory chromatography, and characterized used using the validated MS techniques. Characterization of these natural products is important to the industry for developing strategies to minimize agglomeration in biodiesel.
Detection and Characterization of Selected Contaminants in Biodiesel. Michael J. Haas1, Stephen Kasprzyk2, Robert A. Moreau1, 1USDA, ARS, Wyndmoor, PA, USA, 2BlackGold Biofuels, Philadelphia, PA, USA
The biodiesel industry is facing new challenges in regard to feedstock and fuel quality: (1) As this fuel has gone been developed from a small-volume research material to a component of the national fuel system it has been subjected to new handling procedures, such as extended low temperature incubations, that have caused new performance problems associated with the presence of previously unappreciated contaminants. Chief among these are the sterol glucosides. (2) Concerns over feedstock cost have recently lead to an increased use of less expensive lipid-rich materials as feedstocks. However, these are often contaminated by species chemical structures not found in the refined and high quality lipids traditionally used in biodiesel production. These materials can complicate biodiesel production and compromise the quality of the product. This presentation will describe our studies on the presence of sterol glucosides in biodiesel samples and associated precipitates that may cause fouling during biodiesel production, storage, and distribution. We will also describe our experiences with the variable composition of trap grease, an extremely low value new feedstock for biodiesel production.
Testing of Biodiesel in Engines with Modern Emission Control Equipment. A. Williams, J. Burton, R.L. McCormick, National Renewable Energy Laboratory, Golden, CO, USA
Tests were conducted to study the impacts of biodiesel on emissions and fuel consumption for a Cummins ISB and an International MaxxForce 10, both 2008 model year. They utilize exhaust gas recirculation (EGR) for NOx emissions reduction and actively regenerated diesel particulate filter (DPF) to reduce PM emissions. The engines were tested over the heavy-duty transient (HDT) test cycle in accordance with the Federal Test Procedure (FTP) for emissions certification on an engine dynamometer. Testing was carried out with various fuels including 2007 certification ULSD as the baseline fuel, B20 biodiesel from four feedstocks, soy, yellow grease, beef tallow, and camelina. In addition, a high-aromatic diesel, a low-aromatic diesel and a winter diesel were tested. Results indicate the DPF and diesel oxidation catalyst eliminated any effect of the fuel on tailpipe out emissions of THC, CO, and PM from both engines. BiodieselÃ¢â‚¬â„¢s effect on NOx ranged from a 0 to 2% increase. The fuel economy penalty while operating with B20 blends was approximately 2% for both engines. When a DPF regeneration event occurred during the heavy-duty transient cycle, NOx emissions increased approximately threefold, independent of fuel type. The fuel economy penalty for DPF regeneration was estimated at 3% to 4%.
The Effects of Illumination Intensity and Period on Growth Rates and Fatty Acid Composition of the Microalgae. Haiying Tang, M. E. Danton Garcia, Ansheng Li, Hongzhi Ma, Meng Chen, Nadia Abunasser, Steven Salley, Simon Ng, Wayne State University, Detroit, MI, USA
Alternative, non-food based biomass fuel feedstock development is vital for our national security, economy and the environment. Microalgae are among the most promising of these alternatives. Microalgal cell growth rates and fatty acid content are affected by a combination of environmental parameters. In this work, the influences of light source, light intensity, CO2 concentration, and photoperiod on the growth of Dunaliella tertiolecta (D. tertiolecta) were studied. Moreover, the fatty acid methyl ester (FAME) content and composition of D. tertiolecta biodiesel was investigated with environmental parameters. Red light-emitting diodes (LEDs), white LEDs, and fluorescent lights all were effective for algal growth. Increasing light intensity significantly resulted in more rapid algal growth, while increasing the period of light also significantly increased biomass productivity. Similar growth rates were observed for 2%, 4%, and 6% CO2 concentrations. Moreover, the different light source and intensity had no significant effect of FAME composition of D. tertiolecta biodiesel. The higher light intensity produced the higher biodiesel yield. The methyl linolenate and methyl palmitate are the major components of D. tertiolecta biodiesel and makes D. tertiolecta biomass a suitable feedstock for biodiesel production, however, a high content of unsaturated chains (such as C18:3) was found in Dunaliella tertiolecta biodiesel.
Low Pressures Catalyst for Deoxygenation of Pyrolysis Oils. W. Holmes, M.G. White, Mississippi State University, Mississippi State, MS USA
A catalyst has been prepared and characterized which will partially remove the oxygen atoms from the liquid phase products of biomass pyrolysis. The results from a model compound study in a micro reactor show that the converted products are alkanes, alkenes, and aromatics. The catalyst from these studies shows a certain amount of coke on the catalyst after brief testing. When these tests were repreated using a real pyrolysis oil very little coking was observed even though the pyrolysis oil had not be filtered or treated in any way. It appeared that the phenolic derivatives in the pyrolysis oil had been converted to substituted benzenes and naphthalenes.
Solubility Limitations of Saturated Monoglycerides in Biodiesel During Cold Weather. R.W. Heiden, Ph.D., R.W. Heiden Associates, LLC, USA
The formation of precipitates that block fuel filters above the cloud point represents an important challenge to the cold weather operability of biodiesel fueled vehicles. Normally, cold weather limitations of biodiesel fuels are predicted by standard cloud point/pour point, and cold soak filtration (CSFT), but these tests fail to predict the impact of the temperature on the solubility of some important impurities. Saturated monoglycerides (SMG's) are identified in previously reported work (1)as the prime factors in incidents of fuel filter blockages that struck fleets of maintenance vehicles using B-20 in the eastern part of the U.S. in 2006. Our initial studies of the temperature dependence of the solubilities of monopalmitin and monostearin in B100 and various blends are reported there. Now, two years later SMG's on filters are an important concern to the biodiesel industry and the solubility of SMG's has come to the forefront. We present here data that defines the magnitude of the SMG challenge. We have systematically studied the effects of various conditions that determine the SMG solubility in B-100 and various blends. The results of these studies are discussed.1) R. W. Heiden, "Impurities In B20 That Cause Filter Plugging In Cold Weather", The International Congress On Biodiesel -The Science and Technology, Vienna, November 5-7, 2007.
Low Temperature Oxidation of Biodiesel Surrogates in a Motored Engine. Y. Zhang, A. Boehman, The EMS Energy Institute, The Pennsylvania State University, University Park, PA 16802, USA
Low temperature oxidation of biodiesel surrogates (i.e., C7, C8 and C10 esters) was studied in a motored CFR engine. Within the test range of this study, pronounced cool flame behavior was observed from the oxidation of saturated esters. The comparison on the ignition behavior between saturated and unsaturated methyl esters revealed that the presence of unsaturation in the aliphatic chain of fatty acid esters inhibits their low temperature reactivity. Furthermore, the inhibition effect becomes more pronounced as the double bond moves toward the center of the aliphatic chain. Qualitative and Quantitative analyses of the reaction intermediates from the low oxidation of saturated esters showed that the aliphatic chain of saturated fatty acid esters experiences paraffin-like low temperature oxidation steps. Moreover, it is observed that the abstraction of H-atoms on the α-carbon of the ester carbonyl group plays an important role in the oxidation of saturated fatty acid esters. In contrast, for unsaturated esters, the autoigniton can undergo olefin ignition pathways.
Study of the Effects on Oxidative Stability Biodiesel Blends Using Synergistic Antioxidants in the Presence of Metallic Prooxidants. R.C. de Guzman, H. Tang, S.O. Salley, K.Y.S. Ng, Wayne State University, Detroit, MI, USA
Biodiesel produced from animal and plant lipids retains the fatty acid profile of the source lipid. As a result, this bio-based fuel also retains its susceptibility to oxygen degradation mediated by air, heat, light and metallic contaminants. Among these factors, metal contaminant catalysis of autoxidation has the potential to be detrimental even at very low levels. This study reports the catalytic activity of Al, Cu, Fe and Zn in their nitrate form in reducing the oxidative stability, as measured by the induction period (IP) of soybean oil (SBO) based biodiesel blends with and without the antioxidant (AOx) tert-Butylhydroquinone (TBHQ). Results indicate that the catalytic effect of the metals follow the hierarchy: Cu >> Fe > Al ≈ Zn. The IP drops resulted mostly from the metals degrading TBHQ followed by the direct attack on the lipid producing radicals and metal transition states that further speed up the chain reaction. In B20, ultra low sulfur diesel (ULSD) proved to be invaluable in maintaining the oxidative stability by minimizing the metal attack on both the SBO component and its AOx.
Degradation of Biodiesel Blends. J. Krahl1,2, A. Munack2, L. Schmidt2, 1Coburg University of Applied Sciences, Coburg, Germany, 2Federal Research Institute for Rural Areas, Forestry and Fishery, Braunschweig, Germany
The degradation of RME and its blends were analyzed. In detail, 250 mL of RME were artificially aged by an ambient air bubble stream (200 mL/min) for 40 h at 110 °C. This aging process was spectroscopically traced by UV-Vis and FTIR. Subsequently the oxidized RME was blended with different diesel fuel components in different concentrations to analyze the appearance and the weight of occurring deposits. UV-Vis and FTIR spectra showed a correlation between the degradation of antioxidants and the formation of oxidation products during the aging process. After 4 hours of aging the antioxidants are mostly degraded and the formation of oxidation products significantly begins in term of deposits. Furthermore deposits of oxidation products accumulate in blends with highly nonpolar diesel fuel components like GtL and HVO. A maximum of deposit mass was found between 5 and 15 volume percent of RME in the blends, depending on the diesel fuel component The interpretation could be made as follows: The antioxidants in RME firstly avoid the formation of oxidation products until they are degraded. Beyond this point the use of oxidized RME in blends forms deposits with nonpolar blend components. This is due to the change of polarity of the blends and the solubility of the polar oxidation products. The reason for the different maxima in deposit formation by the use of different nonpolar mixing components is due to the different polarities of these components.
IOP 2: Bio-based Lubricants, Plasticizers, and Value-added Products
Chair(s): D. Kodali, Global Agritech Inc., USA; and Z. Guo, Aarhus University, Denmark
Sustainable Plasticizers. L. Wiebe, Danisco, Grindsted, Denmark
For the past many years phthalates have been used as plasticisers for PVC, but now recent research has revealed that some of the phthalates can be harmful to human beings.In this context Danisco has developed a plasticiser, which can replace phthalates in a wide range of applications, without possessing these harmful properties. The first generation of a sustainable plasticizer is based on Castor oil â€“ a triglyceride containing ricinoleic oil. This ricinoleic oil is used for the synthesis of a fully acetylated monoglyceride of 12-hydroxystearic acid.The rawmaterial for this plasticiser is Castor oil, which can only be grown in certain geographical regions of the World. The supply is limited and will not allow for a full replacement of phthalates. To overcome this constraint a second generation of sustainable, renewable plasticiser will be developed. The rawmaterial for this will be vegetable oils high in oleic avid. The approach will also include a different, less energy consuming process. Also volatiles solvents will be replaced by ionic liquids.
Developing Heterogeneous Catalysts for the Production of Value-added Biobased Products from Fats and Oils. H. Ngo, T. Foglia, M. Haas, USDA, ARS, ERRC, Wyndmoor, PA, USA
The development of economically viable technologies for producing lubricating fluids and biofuels from renewable materials is highly desirable from environmental points of view. Lubricating fluids derived from unsaturated fats can, for example, potentially replace non-renewable and poorly degradable petroleum-based products. We have developed new heterogeneous catalysts for the synthesis of a variety of biobased products such as branched-chain fatty acids and fatty acid methyl esters. In this talk, I will discuss our research efforts using microporous and mesoporous solid acid catalysts to convert unsaturated fatty acids into value-added biobased products that can have potentially positive impacts on the US agriculture and industry.
Development of Biodegradable Lubricating Oil Formulations from Non Edible Vegetable Oils. Ponnekanti Nagendramma, Savita Kaul, R.P.S. Bisht, Mange Ram Tyagi, IIP, India
World over , the use of vegetable oils in lubricating oil formulations is increasing due to their origin being from renewable sources,biodegradability and favorable eco-toxic characteristics.In Indian context,the use of non-edible vegetable oils is considered as a potential source in lubricating oil formulations.The fatty acid contents and their chemical structures define the physico-chemical and lubricating characteristics of a vegetable oil. As such they have certain limitations for their use in lubricating oil formulations. Therefore, these oils have to be subjected to chemical transformation to obtain base fluids with satisfactory performance characteristics.Keeping this in view, studies were undertaken at the indian institute of petroleum on this subject.Under these studies, the vegetable oil esters were synthesized using alcohols such as olelyl alcohol and fatty acids from Karanja and Mahua oilks using an indigenous ion-exchange resin catalyst.The synthesized products were characterized for their physico-chemical properties and tribological performance.These were then compared with commercial mineral oil based cutting oil . In the present paper, the results of the above study are presented.
Low VOC Alkyd Paints and Coatings via Sucrose Polyesters. R. Berger1, D. Back1, R. Starghill1, V. Arredondo1, N. Rogers2, D. Eslinger2, D. Ryer2, 1The Procter & Gamble Company, Cincinnati, OH, 45069, USA, 2Cook Composites & Polymers, North Kansas City, MO, 64116, USA
P&G and CCP developed novel alkyd resin technology, Chempol MPS, that enables formulation of paints and coatings with less than half the amount of VOCs while delivering performance advantages as well, such as fast dry, high gloss, film toughness and increased Renewable Content (RC) in a formulated consumer product. Sucrose polyesters made possible the development of this new alkyd resin technology. Derived from sugar and vegetable oils, they are a green chemistry solution to problems associated with both conventional and high-solid alkyd resin systems. For perspective, alkyd resin paints and coatings use large amounts of solvents to solubilize organic components and attain appropriate viscosities. Millions of gallons of these paints/coatings are sold for multiple applications in the U.S. and globally. These solvents are volatile organic compounds (VOCs) that contribute to ground-level ozone formation, a known hazardous gas to humans even at relatively low levels.Several natural vegetable oils such as soybean, linseed, and tung, were used to derive a series of sucrose polyesters. The evaluation and performance of coatings formulations made with sucrose polyester-modified alkyd resins and the potential environmental benefits of this novel alkyd resin technology are discussed.
A Direct Synthesis Route to Soy-based Thiol Oligomers. Zhigang Chen1, Jennifer F. Wu1, Shashi Fernando1, Bret J. Chisholm1,2, Dean C. Webster1,2, 1Center for Nanoscale Science and Engineering, North Dakota State University, Fargo, ND, USA, 2Department of Coatings and Polymeric Materials, Fargo, ND, USA
Utilization of biorenewable chemicals such as seed oil derivatives in Ã¢â‚¬Å“greenÃ¢â‚¬Â coating technologies including UV curable coatings and high solid coatings is a Ã¢â‚¬Å“green+greenÃ¢â‚¬Â solution to future materials need and ever-stricter environmental regulations. Soybean oil based thiol oligomers find potential uses in thiol-ene UV curable coatings, high solid thiol-urethane coatings, and as biobased lubricants. In this work, a novel one-step synthesis route to produce soy-based thiols directly from soybean oil is described. The synthesis reaction conditions were systematically varied and the products characterized by FTIR, NMR, rapid-GPC and viscometry. The effect of reaction time, reactant ratio and functionality, reaction atmosphere, and catalyst amount on the reaction conversion, and the functionality, molecular weight, and viscosity of the synthesized oligomer is illustrated. The direct synthesis route provides a low-cost approach to produce high value-added oil seed derived biochemicals for industry products.
Development of Soybean Oil Derived Plasticizers for PVC. D.R. Kodali, L.J. Stolp, M. Bhattacharya, University of Minnesota, St. Paul, MN, USA
Plasticizers are non-volatile organic liquids that can reduce the glass transition temperature (Tg) of polymers and make them more flexible. Polyvinyl chloride (PVC), due to its unique combination of price, performance and versatile use is the second largest globally produced plastic (36 MMT/year). Plasticizers are an $11 billion/year industry and account for 54% of plastics additives, mostly in PVC. The majority of plasticizers are petroleum derived phthalates which are known to have adverse impact on human health and environment. This prompted the plastic industry to develop bioplasticizers from renewable materials. The required structural features of an effective plasticizer must allow it to fit snugly in long polymer chain matrices and reduce the glass transition (Tg). It should also have reduced tendency to migrate to the surface. The required functionality dictates modification of soybean oil properties like polarity, molecular size, shape and hydrophobicity. We synthesized estolides from soybean oil fatty acid alkyl esters and characterized their structure and functionality. These experimental plasticizers showed reduction of glass transition temperature of PVC and low vapor pressure. The synthesis and functional evaluation of the new plasticizers will be presented.
IOP 3: New Glycerol Uses
Chair(s): J. Kenar, USDA, ARS, NCAUR, USA; and T. Benson, Lamar University, USA
Glycerine as a New Carbon Building Block. D.J. Brown, HBI USA, Portland, OR, USA
Glycerine has been an important ingredient in many products from food and pharmaceuticals to tobacco and industrial uses for many years. In the past it has traded as a normal chemical additive, but with the advent of biodiesel production in Europe, at first, and now the U.S., South America, and South East Asia, its responding by-product glycerine production it is now traded as a general commodity and fallen to the lowest prices in the history of glycerine production. The old school of thought in the oleochemical production of glycerine as a co-product of manufacturing of fatty acids, fatty alcohols, and soap have given way to glycerine as only a by-product with marginal value to the producer. The development of cheap, plentiful glycerine of varying degrees of purity has spawned a new market for glycerine as a raw material in the manufacturing of many carbon-based compounds that previously produced from cheaper carbon sources, including petroleum. This cheap carbon source occurring from low cost glycerine will undoubtedly continue if the extreme overproduction of glycerine as a by-product of biodiesel continues. We will look at this possibility and its ramifications for future, cheaper hydrocarbons from glycerine.
Hydrogen Production from Glycerol: An Update. Sushil Adhikari, Auburn University, Auburn, AL, USA
The production of alternative fuels such as biodiesel and ethanol has increased over the last few years. Such fuels are vital for the reduction of energy dependence on foreign countries and to protect the environmental damage associated with the use of fossil fuels. Due to the increased production of biodiesel, a glut of crude glycerol has resulted in the market and the price has plummeted over the past few years. Therefore, it is imperative to find alternative uses for glycerol. A variety of chemicals and fuels including hydrogen can be produced from glycerol. Hydrogen is being produced by using several processes such as steam reforming, autothermal reforming, aqueous-phase reforming and supercritical water reforming. This paper reviews different generation methods, catalysts and operating conditions used to produce hydrogen using glycerol as a substrate. Most of the studies were focused on hydrogen production via steam reforming process and still less work has been done on producing hydrogen from crude glycerol.
A Biodiesel Feedstock of Microbial Oils from Seafood Processing Waste and Glycerol. Guochang Zhang, Todd French, Rafael Hernandez, Darrell L. Sparks, William E. Holmes, Earl Alley, David C. Swalm School of Chemical Engineering, Mississippi State University, MS State, MS 39762, USA
Biodiesel is a displacement fuel for traditional petroleum-derived diesel. Unfortunately biodiesel is an expensive fuel due in large part to the high cost of feedstocks. Oils derived from byproducts with no value could potentially be a cheap source of biodiesel. Byproducts of glycerol from industrial biodiesel production could be converted into oils by oleaginous microorganism. The byproducts of shrimp processing waste are heads and shells that contain a wealth of carbon (e.g. N-acetylglucosamine) that could be hydrolyzed into organic compounds and used by the oleaginous microorganism for oil production. The objective of this investigation is to determine the feasibility of using oleaginous microorganism to convert these byproducts to triglycerides as a feedstock for biodiesel production.Experiments were conducted using N-acetylglucosamine at a concentration of 50 g/L. C. curvatus mass increased continuously within 118.8 hours to 18.4 g/l while growing on the N-acetylglucosamine. During the growth phase of C. curvatus, the oil content in of the cells was low. Since C. curvatus did not accumulate oil in the growth phase, C. curvatus grown N-acetylglucosamine were tested for the production of oil from glycerol. In this investigation, C. curvatus was first grown with N-acetyl- glucosamine as sole carbon and energy source. Then, the cells of C. curvatus were harvested during the growth phase and transferred to a fresh nitrogen-free media with glycerol as sole carbon and energy source for the oil production. The concentration of glycerol, initial cell mass concentration and the temperature were evaluated for the optimization of the procedure for the oil production from glycerol. The oil content in the cells reached over 30% of the dry cell weight with a 21.8% yield of oils from per gram of glycerol.
Harnessing the Microbial Fermentation of Glycerol for the Production of Fuels and Chemicals. R. Gonzalez, Department of Chemical and Biomolecular Engineering, Rice University, Houston, TX, USA
Given its availability and low prices, glycerol has become an ideal feedstock for fuel and chemical production via microbial fermentation. We recently reported the pathways and mechanisms mediating the metabolism of glycerol in Escherichia coli under anaerobic and micro-aerobic conditions. Following these studies, we have engineered E. coli for the conversion of glycerol to fuels and chemicals. Several biocatalysts have been developed for the production of ethanol, hydrogen, formate, succinate, lactate, and 1,2-PDO from glycerol-rich streams generated during biofuels production (e.g. crude glycerol, thin stillage). This presentation will include the discussion of our latest work related to the harnessing of microbial glycerol fermentation for the production of fuels and chemicals.
Catalytic Conversion of Glycerine to Renewable Amino Alcohol. V. Arredondo, N. Fairweather, P. Corrigan, D. Back, A. Cearley, M. Gibson, D. Kreuzer, The Procter & Gamble Company, Cincinnati, OH, USA
P&G is the world′s largest producer of USP grade glycerine, a material widely used in many market applications. As a key stakeholder, P&G has had for a number of years a very active R&D program in the development of value-added new uses/applications of glycerine. In this paper we report the two-step process for the catalytic transformation of glycerine to 2-amino-1-propanol (2AP), a renewable-based amino alcohol. We will disscuss the evaluation of different catalysts, the impact of impurities in crude glycerine, and the effect of reaction conditions and parameters on conversions and selectivities. This process offers a route to an amino alcohol not readily available in the market place. Biodiesel has experienced an explosive growth in recent years. As a result, the increased supplies of crude glycerine co-product have caused its prices to decline, putting also downward pressure on refined glycerine pricing. The new chemistry/process provides a market opportunity to convert glycerine to a value-added product, 2AP, an amino alcohol with wide-range application potential. It offers a more attractive new outlet for glycerine in a world of supply/demand imbalance and depressed pricing vs. when it is used for animal feed, burn value and other disposal applications.
Microbial Production of Glyceric Acid from Raw Glycerol and Development of Novel Bio-based Polymers. T. Fukuoka, H. Habe, D. Kitamoto, K. Sakaki, National Institute of Advanced Industrial Science and Technology (AIST), Japan
This study deals with the microbial production of glyceric acid (GA) from raw glycerol and the development of GA-based polymers. First, we searched for GA-producing strains among acetic acid bacteria and investigated the productivity of GA by the selected strains. We found that some strains belonging to Gluconobacter frateurii efficiently converted glycerol to GA at a yield of about 137 g/L and Acetobacter tropicalis selectively produced D-GA from glycerol. In addition, we have synthesized branched-type poly(lactic acid)s by polycondensation of lactide in the presence of GA as an initiator. The resulting branched poly(lactic acid)s had lower crystallinity and glass transition temperatures than those of linear poly(lactic acid).
IOP 4: Oleochemicals and Polymers
Chair(s): D. Pioch, CIRAD, France; and J. Metzger, University of Oldenburg, Germany
Oleochemicals Products: Feedstocks and Building Blocks for Polymers. Z. Mouloungui, Université de Toulouse, UMR 1010 INRA/INP-ENSIACET, Toulouse, France
Today’s oleochemicals are substances which are used because of their chemical reactivity by the presence of double-bond functionality, unique properties of long-chain chemicals, special functional groups as hydroxyl and epoxy. A great number of plant oils such as linseed, soybean, sunflower, tall oil fatty acids, dehydrated castor, tung have been used to prepare a variety of bio-based polymers as true drying-oil paint and coatings, resins, adhesives, inks… The production of polymer-grade brassylic acid from high erucic oils as crambe and industrial rapeseed illustrates the potential end products and intermediate products. Pyrolysis of castor oil yields methyl undecylenate which is converted to 11-aminoundecenoic acid and its polymerization gives polyamide11 known commercially as Nylon 11 or Nylsan 11.Castor oil itself is used as a polyol for the production of polyurethane. But the application of natural oil polyols will always be a relatively minor one. Now, new focus is borne to produce the polyurethane-based glycerine without isocyanate and polycarbonate-based glycerine. So, many possibilities exist to move oleochemical products into a larger scale position as feedstocks and building blocks for polymers.
Branched Fatty Acid Esters through Addition of Alcohols Catalyzed by Zeolites. D. Pioch1, A.T. Nguyen1, A. Finiels2, C. Moreau2, 1Process Engineering and Bio-products Development, UMR 016 GPEB, CIRAD, UM1, UM2, Montpellier, France, 2Institut Charles Gerhardt, UMR 5253 CNRS, UM2, ENSCM, UM1, équipe MACS, Ecole Nationale Supérieure de Chimie, Montpellier, France
Low thermal and oxidation stability limits the use of vegetable oils and derived esters because of the presence of C=C double bonds. The reactivity of this double bond has been investigated to perform the addition of alcohols, in the presence of H-form zeolites, thus leading to saturated oxygen-containing side chains.On the chemical side, our previous results relative to the model reaction -addition of methanol to methyl oleate- have shown the influence of key parameters acting on the yield of the target product, methyl methoxy stearate (temperature, methanol excess, Si/Al ratio). The present study deals with an even more complex system: in addition to C=C bond migration and to a thermodynamic limitation related to the reverse reaction (de-methoxylation), already noted, methyl oleate here also undergoes alcoholysis as a parallel reaction, thanks to the acidic properties of the solid catalyst. Selectivity and reaction rates are discussed according to steric and electronic effects, the alcohol being solvent but also reactant upon the case. The initial rate of the alcoholysis being 4 to 10 times faster than the addition to C=C, the reaction medium first contains the ester with the higher alcohol, which is then alkoxylated at almost constant initial rate whatever the chain length from methanol to n-butanol. On the applied side, this work opens the way to a range of oleochemicals under “green” conditions; the catalyst yields C=C free, alkoxylated long chain esters, including di-alkoxylated when starting from linoleate, with selectivity higher than 70 mole%. The adduct is similar to a branched chain wax when starting from a common unsaturated ester, or is a normal chain wax but bearing an oxygen bridge in place of one CH2 when starting from undecylenic ester. All these “new” alcoxylated esters –not yet manufactured at industrial scale but accessible- should bring interesting properties, for example in lubricant and cosmetic formulations, or for upgrading BTL fractions.
Catalytic Mono-Functionalization of Triacylglycerols. M. Rüsch gen. Klaas, R. Wahlandt, T. Vari, Neubrandenburg University of Applied Sciences, Neubrandenburg, Germany
Selective introduction of one functional group in a triglycerol molecule is an important target for the utilization of plant oils for polymer applications, e.g. paints and varnishes.A reported two-step procedure for the introduction of acryl groups in triglycerols consists of the epoxidation of C=C-bonds and the subsequent ring-opening of the epoxide with acrylic acid. Thus, a mono-acrylated triglycerol can be obtained by mono-epoxidation in the first step. This was carried out by the classic Prileshajev-epoxidation with peracetic acid and by the more selective chemo-enzymatic epoxidation.A (statistically) mono-epoxidized oil can also be made by the catalytic randomization of a commercial fully-epoxidized soybean oil with an adequate amount of any other triglycerol. The interesterification is favorably catalyzed by a lipase, because the epoxide-ring might react under standard conditions with a strong base as catalyst. An acryl group can be directly introduced in a triglycerol by lipase-catalyzed interesterification. For that purpose we used trimethylol propane (TMP) triacrylate. Both two-step and one-step reactions were carried out with various unsaturated plant oils like linseed oil, soybean oil and hemp oil. Selectivities and product characteristics will be shown; safety concerns and different problems in downstream-processing will be discussed.
Esters of Calendula Oil and Tung Oil as Reactive Diluents for Alkyd Resins. Ursula Biermann, Werner Butte, Jürgen O. Metzger, University of Oldenburg, Oldenburg, Germany
Presently our interest is focused to plant oils containing unsaturated fatty acids with a highly reactive hexatriene system such as calendula oil and tung oil. The latter is a drying oil and is used for a number of products including varnish, resins and coatings. Tung oil contains about 84% of α-eleostearic acid (9-cis-,11,13-trans-octadecatrienoic acid).Similar properties are expected from calendula oil consisting of octadec-8,10-trans-12-cis-trienoic acid (calendic acid) as main fatty acid (59-65%). A simple protocol for the transesterification of highly unsaturated vegetable oils such as calendula oil with alcohols catalyzed by sodium methoxide to give the respective esters is described.1 The esters were tested as reactive diluents for alkyd resins in coating formulations. Especially ethyl and isopropyl calendula oil esters showed good properties including low viscosity and good drying performance. Furthermore a shortening of the drying time of about 35- 40% compared to conventionally prepared formulations was achieved. Analogously, the respective esters of tung oil were synthesized and used as reactive diluent.1 U. Biermann, W. Butte, R. Holtgrefe, W. Feder, J. O. Metzger, Eur. J. Lipid Sci. Technol. 2010, in press.
Industrial Hydroxylated Fatty Acids—New Opportunities in Polymer and Functional Chemicals. F.H.M. Graichen, M. S. O'Shea, G. Peeters, S. Kyi, CSIRO, Molecular and Health Technologies, Clayton, Victoria, Australia
There is significant global momentum around the (re)emergence of bio-derived feedstock for the chemicals and polymer industries. However, current industrial fatty acid options are limited (in broad terms) to palm, soybean, canola and castor sources. While there are many niche oils (and their associated fatty acids) naturally produced, these are normally unsuitable due to reliability of supply, cost or both. CSIRO’s research in the areas of industrial oils and complex monomers is aimed at the production, evaluation and modification of novel oil and fatty acids for a range of industrial applications including: chemical intermediates, oligomers, cross-linkable polymers, bioactive compounds, fuel additives and thermo/mechano-chromic devices. The currently available plant sourced hydroxyl functional oils and fatty acids, Castor oil and ricinoleic acid respectively have found uses in a wide range of areas. This paper will cover some synthesis methods for the saturated and unsaturated alpha hydroxy fatty acids as well as applications ranging from adhesives to monomers and modifiers for polyurethanes, polyesters and polyamides.CSIRO’s hydroxylated fatty acids program offers a shift in novel oil and fatty acids for industry supply and opens access to new sustainable product platforms.
Hyperbranched Polyols from Hydroformylated Methyl Soyate. Z.S. Petrovic, I. Cvetkovic, D.-P. Hong, I. Javni, Pittsburg State University, Pittsburg, KS, USA
Hydroformylation of methyl soyate produces a mixture of fatty acid methyl esters with zero, one, two and three hydroxyl groups, the major component being with two hydoxyls (around 50%). Polymerization of methyl esters of hydroxy fatty acids gives a hyperbranched product with different content of hydroxyl groups depending on the degree of conversion. At complete conversion total mass becomes a single molecule with infinite molar mass and infinite functionality. In real systems molecular weights have finite values and can be controlled by controlling the degree of conversion but also using monofunctional components. Monte-Carlo simulation of the polymerization of hydroxylated methyl soyate at the highest conversion shows that the products are physical gels, due to very high molecular weights. The simulation results were compared with experimental measurements of molecular weights, OH numbers and acid values. Reducing molecular weight to the workable viscosity range a family of new polyols can be obtained. Analysis of functionality of the polyols was carried out by determining conversion at the gel point when cured with a diisocyanate.
UV-curable Nano-composite Coatings from Soybean Oil: Sustainable Platform for Advanced Materials. Vijay Mannari, Jigarkumar Patel, Eastern Michigan University, Ypsilanti, MI , USA
Over the past several decades, a number of coatings material technologies have evolved that effectively address environmental concerns associated with emission of volatile organic compounds (VOC). Among these, water-borne and radiation-cure technologies have rapidly advanced and commercialized due to a number of technical benefits. At present, however, these technologies heavily rely on petrochemical feedstock as primary source. Material scientists are faced with an important challenge of offering an alternate renewable material platform for sustainable development of these advanced materials. The present research focuses on development of value-added materials form soybean oil for advanced coatings. We report novel UV-curable organic-inorganic hybrid nano-composite coatings and aqueous polyurethane dispersions (PUD) from soy-based intermediates. These coatings, in addition to having low VOC emissions, have high bio-based content and show excellent performance properties for a myriad of potential commercial applications.
Autoxidative Drying Characteristics of Water Borne Coatings from Renewable Resources. Partha Sengupta, Xiao Pan, Thomas Nelson, Adlina Paramarta, Dean Webster, Department of Coatings and Polymeric Materials, North Dakota State University, Fargo, ND, USA.
The three unsaturated fatty acid esters of sucrose used in this research work are sucrose linseedate, sucrose safflowerate and sucrose soyate, with different degree of unsaturation. Water borne dispersions of sucrose esters were prepared using surfactants for dispersion stability and rheology modifier for viscosity modification. For autoxidative curing four drier packages involving cobalt complex and other compounds for partial and total replacement of cobalt were explored. The surface, bulk and depth profiling of the drying characteristics of coatings was done by Drying Recorder, Real time FTIR and Confocal Raman microscopy respectively. Sucrose linseedate shows high surface drying but reduced through drying while sucrose soyate shows the best overall drying process due to higher oxygen permeation. König hardness, impact resistance and MEK double rubs validates the drying characteristics of the three different sucrose esters. Among the four drier packages, cobalt shows poor through drying while tetrafunctional thiol shows better overall curing process. Water uptake of the coatings was determined by Electrochemical Impedance Spectroscopy (EIS) and hardness with depth of coatings on wood was measured by nanoindentation. The high surface drying of sucrose linseedate gave lower water diffusion and higher variation of hardness along the depth of the coating.
Thiol-Ene Reaction of Vegetable Oils with Butyl Thiol: Sulfide Derivatized Vegetable Oils. James A. Kenar1, Grigor Bantchev2, Girma Biresaw2, 1Functional Foods Research Unit, USDA, ARS, NCAUR, Peoria, IL, USA, 2Bio-oils Research Unit, USDA, ARS, NCAUR, Peoria, IL, USA
Vegetable oils and their FA, renewable raw materials, are firmly established components in many industrial products, and their use continues to be of interest to many researchers. The development of new approaches to functionalize vegetable oils to derive novel oleochemicals with unique chemical and physical properties is integral to extend the variety of compounds and uses obtainable from these oils. The carbon-carbon double bonds of vegetable oils were reacted with butyl thiol using a UV initiated thiol-ene reaction. The effects of temperature, reaction time, type of vegetable oil, thiol to vegetable oil ratio were investigated and it was found that both low temperature and high thiol to vegetable oil ratio increased the addition of thiol to the vegetable oil double bonds. Reaction products were analyzed by NMR, IR, and GC-MS methods. Optimized reaction conditions gave up to 90% conversion of soybean oil double bonds into sulfide linkages in isolated yields of 60%. This presentation will present aspects of this work.
Fatty Acid Modified Anhydrides of Hydroxy Carboxylic Acids – Novel Oleochemicals for the Lipid Modification of Renewables. Hans-Josef Altenbach, Rachid Ihizane, Bernd Jakob, Karsten Lange, Sukhendu Nandi, Manfred P. Schneider, Bergische Universität Wuppertal, Germany
Nature, and in this context agriculture, provides a considerable reservoir of useful and low cost raw materials such as fats and oils, plant proteins and carbohydrates. By selective combination of their molecular constituents a wide variety of materials with interesting properties can be prepared, all of them - due to their molecular constitution - being potentially biodegradable.We recently discovered that hydroxy carboxylic acids such as citric, malic and tartaric acid can be converted in one step and quantitatively into the corresponding fatty acid modified, O-acylated anhydrides, excellent electrophiles for ring opening reactions with the above nucleophiles from renewable resources. The title molecules have thus been successfully employed for the lipid modification of various alcohols, including diols, polyols such as glycerol and pentaerythritol, polyethylene glycol and sugar alcohols (e.g.mannitol) and also numerous amino acids. Various monosaccharides such as D-glucose, D-mannose, D-glucosamine, L-ascorbic acid and disaccharides such as α, α-trehalose have also been modified using the title compounds. Next to their surface-active properties (detergents and emulsifiers), many of the thus resulting molecules show additional benefits such as antimicrobial properties, being able to form organogels and films or are oil soluble antioxidants for the stabilization of native oils. They are thus potentially useful for a wide variety of applications such as in cosmetics and food technology.The lecture will describe the syntheses of the title compounds and their use for the preparation of various lipid modified renewables; selected properties of the resulting products will also be discussed.
IOP 5: General Industrial Oil Products
Chair(s): D. Sparks, Mississippi State University, USA; and R. Hernandez, Mississippi State University, USA
Integrated Biorefinery based on Soybeans. D. Graiver1, R. Narayan1,2, K. Farminer2, 1Michigan State University, East Lansing, MI., USA, 2BioPlastics Polymers and Composites, East Lansing, MI., USA
Value-added intermediates and products are prepared from the various parts of the soybean (oil, meal and hulls) by different chemical processes. We have used ozonation under catalytic conditions to oxidize the oil and produce primary polyols, thermally stable lubricants, and fuel additives. The meal was used as a source of amine functional groups to produce aliphatic isocyanates, which could further be polymerized to polyurethane and polyamides. Grafting of reactive silanes onto the unsaturation sites of the fatty acids in the triglycerides yields one-component coating that are vulcanized by atmospheric moisture. These crosslinked coatings have excellent adhesion to metals and can further be formulated as anti-corrosion coatings or as moisture barrier over wood. Allylation of the fatty acids produces monomers that can be polymerized by free radical initiation or sulfonate to yield bio-based detergents. The chemistry and processes of such chemical modifications that are all part of our biorefinary concept will be described.
Effect of Lignocellulosic Inhibitory Compounds on Growth and Lipid Accumulation of Municipal Sewage Activated Sludge Microflora. A. Mondala, R. Hernandez, T. French, L. McFarland, W. Holmes, Mississippi State University, Mississippi State, MS, USA
A biorefinery concept utilizing existing municipal wastewater treatment plant infrastructures, wastewater, and activated sludge will be presented. It was hypothesized that sugars derived from the hydrolysis of lignocellulose biomass can be utilized by activated sludge (AS) microflora as fermentation substrates for biosynthesis of lipids for biofuel applications. However, hydrolysis of lignocellulose yields by-products such as furans and organic acids that may inhibit microbial growth and metabolism. This study then investigated the effects of two representative lignocellulosic inhibitor compounds, furfural and acetic acid, on cell growth, lipid accumulation, and glucose utilization by AS microflora. Batch fermentation experiments were conducted using a 20 % (v/v) inoculum of waste AS in a synthetic wastewater medium. Glucose was supplied as the sole carbon source at an initial C:N ratio of 79. Furfural and acetic acid were tested individually and in binary mixtures to determine their individual and combined effects. Results obtained from these experiments were used to evaluate the inhibitor tolerance capacity of AS microflora and determine if detoxification of lignocellulose hydrolyzate is necessary prior to fermentation.
Sub-critical Water Assisted Biodiesel Production from Activated Sludge. Lien-Huong Huynh, Yi-Hsu Ju, National Taiwan University of Science and Technology, 43, Keelung Rd, Sec.4,Taipei 10607, Taiwan
Faced with environment problem and exhaustion of fossil fuel, the idea of utilizing activated sludge (AS) as a source of renewable energy has attracted many researchers. Methods on the use of AS as an energy source, such as fermentation, pyrolysis and thermal-gasification have been investigated. However, due to the complicate nature of sludge, it is difficult to apply those methods for fuel production. AS has the potential to be used as a raw material for producing biodiese-an environmental friendly and alternative fuel.Sub-critical water (SCW) treatment of sludge has been known as a cheap and effective method for reducing its organic compounds, especially those carcinogenic aromatic PCBs or PAHs. In addition, extractable lipid amount in sludge also increases after SCW treatment. In this study, dry sludge was firstly subjected to SCW treatment. The supernatant after SCW treatment was collected and centrifuged for further analysis whereas the remaining solid sludge was freeze dried and subjected to solvent extraction. Sludge oil (SO) obtained was then dewaxed, degummed to remove wax and phospholipids. Titration and saponification were employed to separate saponifiables lipids from the unsaponifiables in the dewaxed/degummed SO. Composition of the neutral lipids as well as its fatty acid profile were determined and compared to those obtained without SCW treatment.
Solvent Characteristics of Biodiesel Esters and Their Co-Products. J.W. King, K. Srinivas, N.S. Bobbitt, J.D. Vincent, University of Arkansas, Department of Chemical Engineering, Fayetteville, AR 72701, USA
The production of biodiesel ester mixtures and associated co-products such as glycerol in large excess require additional utilization markets be developed, such as their use as solvent or reaction media. To provide an expanded physicochemical data base on their solvent thermodynamic properties, we have employed inverse gas chromatographic (IGC) measurements abetted by miscibility correlations utilizing the solubility parameter – Hansen 3-dimensional sphere approach. IGC measurements of n-alcohol binaries with both soya-derived biodiesel esters and glycerol at near infinite dilution conditions of mole and weight fraction activity coefficients, partition or Henry’s Law coefficients, as well as free energies, enthalpies, and entropies of solution. The mole fraction carbon number activity coefficient trends for methanol to n- butanol increase and decrease, respectively, for their binary solutions with biodiesel and glycerol, respectively – reflective of the alcohol’s cohesive energy densities relative to those for the two solvents. Total and three component solubility contributions derived for soy-biodiesel are very similar whether derived from IGC measurements or Hansen solubility spheres while values reported for glycerol and been found to range from 32 – 40 MPa1/2. The implications of the above data will be discussed in terms of the design of separation processes to separate methyl esters and glycerol as well as their use as solvent media.
Biodiesel Production via Transmethylation of Triglycerides Using Dimethylcarbonate: A Glycerol-free Biofuel. M.S. Miguez, T.J. Benson, Lamar University, Beaumont, TX, USA
Some biodiesel processing concerns, namely wastewater and byproduct, could have a negative impact on the economic viability of this biofuel. In an effort to alleviate these economic and environmental strains on the biodiesel industry, an alternate process is proposed that uses dimethyl carbonate in place of methanol as the transmethylating agent. The products formed from one triglyceride molecule are two fatty acid methyl ester molecules and a glycerol fatty acid methyl ester that is completely soluble in the FAME’s mixture; thus, eliminating the byproduct glycerol and greatly reducing the amount of wash water. This alternate biodiesel, depending on the feedstock, also meets the ASTM D6751 biodiesel standard. Using model reactant compounds, a screening of acid and bases catalysts was performed, and kinetic studies were carried out on the top-performing catalysts. The selection of catalysts includes alkali base catalysts that are currently used in biodiesel production facilities, as well as, heterogeneous-type catalysts that would be easier and more economical to recover and recycle. The experimental results, along with process modeling using Aspen 7.1, will be presented.
Biodiesel and Biofuel Production from High Acidic Feedstock. R. Verhe1, V. Van Hoed1, C. Echim1,2, J. Maes2, N. Zyaykina2, W. De Greyt2, 1Ghent University, Ghent, Belgium, 2De Smet Ballestra, Zaventem, Belgium
The use of edible vegetable oils as feedstock for the production of biodiesel has led to an increased competition with food and oleochemicals. Alternative resources such as oils and fats with high FFA content and side streams of refining can substitute the refined feedstocks, but require alternative technologies and/or purification steps.Vegetable oils, animal fats and used frying oils with more than 5% FFA can be converted into biodiesel using a two step process involving an acid esterification and alkaline transesterification. If the FFA content is lower than 10% higher yields are obtained by first a transesterification followed by an esterification.Low quality feedstocks need a preliminary refining for the removal of P-compounds (degumming) and metals, ash and S by adsorption.Soap stocks (after acidification) and deodorizer distillates (DOD) are converted into biodiesel and biofuels (CHP) by either a combination of esterification and transesterification with methanol or by esterification with glycerol followed by transesterification.The esterification of high acidic oils with glycerine can be performed either by acid esterification (p-toluene-sulfonic acid) or by heating at 200°C without catalyst.A combination of these various technologies provides excellent procedures for the production of biodiesel and biofuels from high acidic oils.
Using Synthetic Biology to Create Renewable Chemical Building Blocks. N Renninger, D McPhee, E Cratsenburg, Amyris Biotechnologies, Inc., Emeryville, CA, USA
In spite of increasing interest in and demand for sustainable materials, there are limited options available today for renewable raw materials or ingredients that simultaneously meet the requirements of scale, cost-competitiveness, and performance.Industrial biotechnology is poised to shift the paradigm from the traditional petroleum-derived source of carbon to a bio-based renewable source of carbon. Recent advances in synthetic biology now allow us to utilize engineered microbial systems to convert fermentable sugars to molecules previously not made through fermentation. Some of these molecules are interesting and effective chemical building blocks for a variety of novel materials and applications, including, among others, lubricants, cosmetics, polymers, and transportation fuels. Amyris, a renewable product company, will discuss how it is combining advances in synthetic biology with a capital-efficient manufacturing model to commercialize large-scale renewable products in 2011. Amyris will also discuss examples of its product portfolio to demonstrate that by combining the best of biology and chemistry, high-performing and cost-effective sustainable materials will be commercially available in the very near-term.
Fungal Fermentation for Bio-oil Production. D. Mitra, P. Chand, D. Grewell, V. Chintareddy, J. Verkade, J. (Hans) van Leeuwen, Iowa State University, Ames, IA 50011, USA
The biofuels industry is somewhat stagnant and needs to expand opportunities to add value to co-product streams. Expanding the co-product market is essential to offset processing costs. Thin stillage is a leftover stream from corn-to-ethanol plants, while soy whey is a by-product stream from soybean processing. The central hypothesis of this research is that these streams contain important nutrients to support microbial growth. This research paper highlights our success in growing an oil-rich fungus Mucor circinelloides in these substrates, without external nutrient addition or enzymatic modifications. Thin stillage samples from three different corn-ethanol plants: Iowa(LTS), Nebraska(NTS), Minnesota(MTS) were used to evaluate the fungal biomass and oil production. Soy whey was prepared in the lab from defatted soyflakes. Preliminary experiments show the fungal biomass yields were ~16g/L (dry basis) from LTS, NTS & MTS and 4g/L from soy whey. Ultrasonication (20,000Hz, 4min) and an organic solvent were used to extract the oil. The oil yields were 24.3% (g oil per 100g biomass) from NTS & LTS, 12.2% - MTS & 4.9% - soy whey. Further optimizations of the fungal cultivation & oil extraction process are needed. Promising results of our current research indicate higher productions achievable.
Green Diesel from Lipidic Materials obtained from Activated Sludge. Emmanuel Revellame1, Rafael Hernandez1, William French1, Earl Alley2, William Holmes2, 1Swalm School of Chemical Engineering, Mississippi State University, Mississippi State, MS, USA, 2Mississippi State Chemical Laboratory, Mississippi State, MS, USA
Waste activated sludge from municipal wastewater treatment plants is a good source of microorganisms with potential use as feedstock for green diesel production. The lipidic material from the activated sludge was extracted using Bligh and Dyer method. A gravimetric extract yield of 13.00 % (wt.) was obtained using this procedure. The extract was then subjected to solid phase extraction (SPE) using amino-propyl cartridge to determine the amount of lipidic material. Initial results indicated that the extract contains 14.96 % (wt.) free fatty acids, 0.63 % (wt.) triglycerides, 2.01 % (wt.) diglycerides and 2.45 % (wt.) monoglycerides. The fractions collected from the SPE were analyzed to determine their fatty acid profiles, and the results showed that the major fatty acid components of all the fractions are palmitic, palmitoleic, stearic, oleic and linoleic acids. The lipidic materials from the extract was then isolated using gel filtration chromatography utilizing Biobeads SX-1. Then the lipidic material was subjected to catalytic cracking using various catalysts.
Industrial Oil Products Posters
Chair(s): B.R. Moser, USDA, ARS, NCAUR, USA
Cold Flow Properties and Performance of Biodiesel.
Robert O. Dunn, Bryan R. Moser, Bio-Oils Research, USDA, ARS, NCAUR, Peoria, IL, USA
Biodiesel is defined as a fatty acid alkyl ester mixture obtained by reacting vegetable oil or fat with a short chain (C1-C4) alcohol. The cold flow properties of biodiesel depend on the fatty acid composition of its feedstock as well as alcohol chain-length. Increasing biodiesel production in the U.S. depends on development of less expensive lipids such as used cooking oil, waste grease, tallow, inedible oil and high-acid acid oil. Biodiesel from these feedstocks has less advantageous cold flow properties compared to esters from canola, rapeseed or soybean oil. Thus, increased utilization of biodiesel as an alternative fuel or extender for compression-ignition (diesel) engines depends on improving its cold flow properties. Earlier studies reported that decreasing cloud point (CP) is the most practical approach for improving the performance of biodiesel in cold weather. Those conclusions were based on data for biodiesel made from transesterification of soybean oil and methanol (SME). The present work compares results from the earlier studies with data for biodiesel derived from different combinations of lipid and alcohol both in neat (B100) form as well as in blends with petroleum middle distillate fuel (petrodiesel). Linear correlations were observed for pour point (PP), cold filter plugging point (CFPP) and low-temperature flow test (LTFT) with respect to CP. Nearly linear correlations were observed for CP versus biodiesel blend ratio (B0-B50) for blends in ultra-low sulfur petrodiesel (ULSD).
Synthesis and Tribological Properties of Alkyl Succinate Derivatives.
Young-Wun Kim, Keun-Wo Chung, Byeong-Tae Yoon, Seung-Yup Baik, Mi-Hee Kim, Sae-Bom Kim, Korea Research Institute of Chemical Technology, Daejeon, S. Korea
A series of alkyl succinates were synthesized by the reaction of alkyl succinic anhydride and fatty alcohol. The chemical structure of alkyl succinates were confirmed by 1H-NMR and FT-IR spectroscopic technique and the purity of alkyl succinates were also analyzed by GC analysis. The basic properties such as kinematic viscosities (KV), refractive index(RI), TAN, thermal stabilities and corrosion properties were analyzed. As the results of properties, KV and RI depended on the structure of alkyl succinates. And some of alkyl succinate showed good anti-corrosion activity in base oil and vegetable oil. Also, the tribological properties of alkyl succinates were evaluated using a 4-ball tester and SRV tester. As the results of 4-ball WSD, 4-ball property of alkyl succinates depended on the structure of alkyl succinates which showed better antiwear performance than that of commercial additive. And, friction coefficient were ranged from 0.09 to 0.2 which were better than that of base oil (>0.3).
Potential and Prospects of Biodiesel from Seed Oil of Prinsepia utilis.
Savita Kaul, Yogender K. Sharma, IIP, India
Due to wide variation in climatic and soil conditions,India is home of a variety of plants bearing oil and fat. In Himalayan region in general and in the state of Uttarakhand in paticular a large number of such seed oils are totally untapped and can be used as a source for biodiesel production.The paper aimed to investigate potential of seed oil from Princepia seed oil locally named as Bekul for production of biodiesel.The oil content of seed is >35% and transesterification of oil gave a conversionof >90% to biodiesel. The biodiesel produced meets BIS specifications as well as ASTM.
Production of Biodiesel from Brown Indian Mustard (Brassica juncea) Oil.
S. Singh, A. Talebizadeh Rafsanjani, M. Torabi Angaji, University of Tehran, Engineering Faculty, Iran
The reaction was carried out in a 500 millilitre spherical reactor provided with thermostate, mechanical stirring and condensation system.100 millilitre of oil was added to system and then methanol and NAOH as catalyst was added. We heated the mixture until the system reached to 55 celsius degree. The experiment was prolonged for 120 minutes after cooling two layers were formed. The upper phase contains methy ester and the lower phase contains glycerin. After separating the two layers by sedimentation the remaining catalyst was extracted by successive rinses with 50 millilitre of distilled water. The resulting mixture was subjected to a distillation at 55 degrees celsius to recover the excess of methanol. One important property of the resulting biodiesel is the flash point equal to 172 celsius degree.
Determination of Ester Content of Biodiesel Derived from Lauric Oils.
C.L. Yung, Y.M. Choo , A.N. Ma, Malaysian Palm Oil Board (MPOB), 6, Persiaran Institusi, Bandar Baru Bangi, 43000 Kajang, Selangor, Malaysia
The ester content method EN 14103 is derived for fatty acid methyl esters (FAME) with carbon chain length of C14 to C24 and it is not suitable for FAME outside this range e.g. the lauric oils namely palm kernel oil and coconut oil. In this modified method, both methyl undecanoate (C11:0 ME) and methyl heptadecanoate (C17:0 ME) were used as internal standards for the calculation of the ester content. The carbon chain length of lauric oil biodiesels ranges from C8 to C20, with the major component of methyl laurate (C12:0 ME), methyl myristate (C14:0 ME), methyl palmitate (C16:0 ME) and methyl oleate (C18:1). Due to different response factors of FAME with different carbon chain length, methyl heptadecanoate is not suitable to be used for the calculation and will resulting unfavorable low ester content results (<92.0 mass %). However, methyl undecanoate also not suitable for this calculation and will resulting high ester content results of > 100.0 mass %. In the present study, it was shown that the combination of methyl undecanoate and methyl heptadecanoate is a good solution. Methyl undecanoate and methyl heptadecanoate were used to quantify FAME of C8 to C14 and C16 to C20, respectively. Also, the temperature program of gas chromatography has been modified for better separation of individual FAME.
Physical, Chemical and Cold Flow Performance Properties of Triglycerides and Methyl Esters from Canadian Oilseeds.
Sunmin Wang1, Johanna Clancy1, Gordon Rowland2, Kevin C. Falk3, Martin J. Reaney1, 1Department of Food and Bioproduct Sciences, University of Saskatchewan, 51 Campus Drive, Saskatoon, Saskatchewan, S7N 5A8, Canada, 2Department of Plant Sciences, University of Saskatchewan, 51 Campus Drive, Saskatoon, Saskatchewan, S7N 5A8, Canada, 3Agriculture and Agri-Food Canada, Saskatoon Research Centre, 107 Science Place, Saskatoon, Saskatchewan, S7N 0X2, Canada
Seed from six Brassica napus and five Brassica rapa cultivars (canola and rapeseed varieties) were ground and solvent (hexane) extracted to obtain oil. In addition, oil from each of two B. rapa and B. juncea, Sinapis alba, Camelina sativa, and Linum usitatissimum cultivars, were mechanically extracted with a continuous expeller press. Crude oils were filtered and fatty acid profiles (AOCS Method Ce 1b-89) were determined by gas chromatography. The filtered crude oils were converted to methyl esters utilizing a two stage trans-esterification process with methanol. Subsequently all methyl ester products were refined to remove methanol and soaps. Cloud point and pour point were measured for the purified methyl esters. A strong positive linear correlation (r2 = 0.9) was found between the palmitic and stearic acid concentration and pour point in Brassica oils and their methyl esters. Linolenic acid content was negatively correlated with pour point of triglyceride oils and their methyl esters. Oil derived from B. rapa with both very low saturate levels (<3%) and intermediate concentrations of erucic acid exhibited a pour point values below -21oC while methyl esters and ethyl esters derived from these oils had pour points of -24oC and -34oC respectively.
Preparation of Cyclolinopeptide A Analogues as Plausible Drug Candidates.
D. P. Okinyo-Owiti1, P. G. Burnett1, J. Shen1, B. Li1, R. Sammynaiken2, M. J. Reaney1, 1University of Saskatchewan, Department of Food and Bioproduct Sciences, Saskatoon, Saskatchewan, Canada, 2Univesity of Saskatchewan, Saskatchewan Structural Science Centre, Saskatoon, Saskatchewan, Canada
Cyclolinopeptide A (CLP A, 1), which is found in flaxseed oil inhibits T-Cell proliferation at similar concentrations to the drug cyclosporine A (2), which is used to block transplant rejection. While production of analogs of CLP A with improved biological activity is desirable, typical approaches to analog synthesis are difficult if peptide obtained from flax oil is used as a starting material. CLP A lacks reactive amino acids as well as terminal amine and carboxyl groups which are typically targeted in peptide modification. We have prepared novel cyclolinopeptide derivatives through the modification of the amides. The synthesis of peptide CLP A conjugates of folic acid will be described.
Surfactants Using in Agriculture.
Feruzan Dane1, Gülden Yılmaz1, Halide Akbaş2, 1Trakya University, Faculty of Science and Arts, Department of Biology, 22030, EDIRNE, Turkey, 2Trakya University, Faculty of Science and Arts, Department of Chemistry, 22030, EDİRNE, Turkey
There are many surfactants used with pesticides to make their effects more. A surfactant is a surface acting agent that reduces the surface tension of a liquid, thereby increasing the spreading, dispersing and wet ability of the spray solution on plant leaf surfaces. There are four basic groups of agricultural surfactants: anionic, cationic, amphoteric and non-ionic. Cationic surfactants are not generally used with selective herbicides because they usually are phytotoxic. Anionic surfactants are most effective when used with contact pesticides. They are sometimes blended with non-ionic surfactants to provide the wetting and emulsifying properties of a herbicide formulation. Amphoteric surfactants may or may not form a charge depending on the acidity of the spray solution. Non-ionic surfactants do not form an electrical charge. Non-ionic surfactants are the type usually used in most herbicide spray solutions. These surfactants are good dispersing agents, stable in cold water and have low toxicity to both plants and animals. Tristyrylphenol, Polyoxyethylene series, Fatty acid methyl ester ethoxylates, Polypropylene Glycols (PPGs), Silicone polyether, Alkylethersulphate sodium salt, Silwet L-77 and Triton X-45 are nonionic surfactants using in agriculture. They are also given as adjuvants. In this rewiew some surfactants used with different pesticides, their effects and the advantages or disadvantages were explained.
Low Field NMR Methods for Measuring Oil Content for the Biofuel and Food Industries.
Alexander Sagidullin1, Kevin Nott1, Debadeep Bhattacharrya2, 1Oxford Instruments Magnetic Resonance, Tubney Woods, Abingdon, Oxfordshire, OX13 5QX, UK, 2Oxford Instruments Magnetic Resonance, 300 Baker Avenue, Suite# 150, Concord, MA 01742, USA
The field of low field Nuclear Magnetic Resonance (NMR) spectroscopy is one of the most widely used techniques for determination of oil in a variety of materials including seeds, snack foods, and textiles. In this study, low field NMR methods were developed and applied for determination of oil in Jatropha seeds and algae, which are considered as possible source of oil in biofuels. We also demonstrate the ability of low field NMR for determination of oil in peanuts. In addition to the bulk analysis of Jatropha, it is important also to measure oil content in single seeds in order to optimise further propagation. Existing extraction methods require at least three seeds for analysis whereas NMR can measure seeds individually using a 100% oil calibration without oven drying. Results agreed with those obtained using the Weibull-Stoldt method for total oil determination. Oil content of peanuts was also measured at different stages of processing using a 100% oil calibration. Oil content in algae was determined using 100% triglyceride as standard. A linear calibration was obtained for the algae at 70°C. The effect of sample homogeneity was tested by carrying out the measurements with whole and separate kernels as well as different sample sizes. Low field NMR is an appropriate analytical method for rapid measurements of oil content in algae, Jatropha seeds and peanuts either for research (to increase yield) or during processing. In addition, it can be successfully applied to analysis of various sample sizes ranging from one seed with mass of a few hundred milligrams up to samples with mass of one hundred grams.
**CANCELED** Bioactivity of Polymer Surfaces Containing α – Hydroxy Fatty Acids.
F.H.M. Graichen, M.S. O'Shea, G. Peeters, S. Kyi, CSIRO, Molecular and Health Technologies, Clayton, Victoria, Australia
A series of polyacetylene substituted 2-hydroxy acids and derivatives were prepared and characterized. Alkylation of butane-2,3-diacetal (BDA) protected glycolic acid with iodoalkyl substituted polyacetylene compounds gave the corresponding diacetal protected polyacetylene substituted 2-hydroxy acids. Diacetal deprotection through acid mediated hydrolysis, transesterification or aminolysis afforded the 2-hydroxy-polyacetylenic acid, ester or amide derivatives. Twenty of these novel compounds were tested against ten microbes of clinical importance. Polyacetylenic lipids and their derivatives have been isolated from a wide variety of species and are known for an array of interesting properties. Compounds containing three conjugated unsaturated moieties, such as yne-ene-,yne, yne-yne-ene and yne-yne-yne polyacetylenics exhibit a diverse range of biological activities including cytotoxicity, antifungal, antimicrobial, herbicidal and antibacterial. There is no doubt, that these compounds and polymers thereof are of great interest for the pharmaceutical industry – for example in the development of novel antimicrobial agents.
Oil Production for Biofuels via Oleaginous Microorganism Consortium.
J.I. Hall, W.T. French, R.A. Hernandez, W. Holmes, D. Sparks, Mississippi State University, Mississippi State, MS, USA
Oleaginous yeasts are a type of microorganism that can produce up to 70 percent of their body weight in oil. By cultivating these microorganisms on municipal wastewater, the wastewater is treated while simultaneously accumulating oil. To achieve significant quantities of intracellular oil additional carbon sources must be supplied. Lignocellulosic sugars are the carbon sources that were used in this investigation. The objective of this study is to determine the inhibition of the growth of an oleaginous microorganism consortium on synthetic wastewater amended with a model lignocellulosic sugar. When hydrolyzing biomass, furfural and acetic acid are known growth inhibitory substances. Results have shown complete inhibition with 5g/L of furfural and 5g/L of acetic acid in the synthetic acid hydrolysate. At 2.5g/L of furfural and 5g/L of acetic acid, the maximum cell mass was 0.34g/L. Without furfural and acetic acid, the maximum cell mass reached 0.66g/L within 24 hours of cultivation. Inhibition models such as Andrews will be used to describe the inhibition effects on the consortium’s growth. These inhibition parameters will enable the estimation of the consortium’s growth and thus the accumulated oil. Future research will include determining whether furfural or acetic acid is the limiting factor on the growth of this consortium.
Biodiesel Production From Algae.
Didem Özçimen, Sevil Yucel, Yildiz Technical University, Bioengineering Department, Istanbul, Turkey
Biodiesel is one of the most important alternative fuels that has proved to be successful in several applications. Biodiesel fuel can be produced from animal fats, waste frying oils and mostly plant oils. Unfortunately, the allocation of land for the production of biodiesel from agricultural crops creates problems. The cultivation of arable land to produce plant oils will eventually compete for land usage of food industry. In this context, the importance of algae for biodiesel production has been increasing recently. Algae can be grown and harvested very quickly and land which isn't suitable for farming can be also used to cultivate algae. In underutilized desert algae can be also cultivated in ponds. The algae contain near 50% natural oil, thus making it a perfect candidate for fuel production and algae can produce more biodiesel than the crops that are currently used. Both microalgae and macroalgae can be used for biodiesel production. Microalgae are widely used in the production of biodiesel compared to macroalgae because of higher oil content. The algae have also some disadvantages besides advantages, such as an intensive care required for algae farming compared to an agricultural farm. Algae cultivation and biofuel process can be expensive. In this study, the current methods used in the biodiesel production from algae and the advantages and disadvantages of algae usage in this perspective will be presented.
Rheological Properties of a Biological Thermo-hydrogel Produced from Soybean Oil Polymers.
J. Xu, Z. Liu, S. Kim, S. Liu, NCAUR, ARS, USDA, Peoria, IL, USA
The rheological properties of a newly developed biological thermo-hydrogel made from vegetable oil were investigated. The material named HPSO-HG is a hydrolytic product of polymerized soybean oil (PSO). HPSO-HG exhibited viscoelastic behavior above 2% (wt.%) at room temperature and viscous fluid behavior at 55°C. The function of thermal assembly-disassembly-reassembly for the HPSO-HG hydrogel was completely reversible. The viscoelastic properties of HPSO-HG were strongly dependent on concentration. The analysis of modulus and concentration dependence and stress relaxation measurement indicated that HPSO-HG was a physical gel meaning the cross-linkers between the molecules were physical junctions. HPSO-HG hydrogel also showed fast initial partially recovery of its viscoelastic properties after being subject to a mechanical shear disruption. The function and behavior of the HPSO-HG hydrogel suggest that this biomaterial be a potential candidate for applications in cosmetic products, drug delivery, and wound skin care products.
Synthesis, Characterization and Industrial Application of Polyalkoxide Base Catalyst.
Felicia H. Y. Gok1, Jian Heng Shen1, Martin J.T. Reaney1, Ramaswami Samminaiken2, Gabriele Schatte2, 1Department of Food and Bioproduct Sciences, University of Saskatchewan, Saskatoon, SK, Canada, 2Saskatchewan Structural Science Centre, University of Saskatchewaan, Saskatoon, SK, Canada
Alkoxide catalysts are extensively used in food and industrial chemistry due to their efficiency at catalysing specific reactions. These strong base catalysts are typically produced by mixing metals or metal hydrides with potentially toxic alcohol. In our study, we describe an alternate route to alkoxide production by reacting alkali hydroxide with a polyalcohol in the presence of water and other solvents. These catalysts may be produced from non-volatile and non-toxic poly-alcohols which are suitable in catalysing transesterification reaction for biodiesel production. This strong base has several advantages. Firstly, the starting materials are easily available and inexpensive to purchase. Secondly, these catalysts are easy to produce and can possibly be prepared on site. Therefore, poly-alkoxide catalysts may lower the manufacturing cost of biodiesel plant. In this presentation, X-ray powder diffraction method is conducted for the catalyst structural characterization. Analysis of their chemical properties such as base strength, hygroscopicity, water content, solvent solubility and shelf life will be discussed. Most importantly, evaluation of the catalytic efficiency in biodiesel production would also be presented.
Compressed Fluid Application in the Extraction of Waxes from Sunflower Seeds.
E.R. Baümler, M.E. Carrin, G.D.B. Mabe, E. Brignole, A.A. Carelli, PLAPIQUI (UNS-CONICET), Bahía Blanca, Buenos Aires, Argentina
Several investigations have been made in recent years on probable industrial applications of the compressed and liquefied fluids to diverse separation problems. Non-toxic gases as dioxide of carbon applied to conditions near to their critical point are able to dissolve non volatile substances at relatively low temperatures.The aim of this work was to investigate the viability of the use of high-pressure liquid solvents as dioxide of carbon, propane and their mixtures (20% CO2 and 80% propane), in the extraction of waxes from whole sunflower seeds. The oils from the treated seeds were extracted by soxhlet extraction using hexane. The oil wax contents were determined by separation with a silicagel chromatographic column and analysis by GC.The extracted oil belonging to the seeds tried with CO2 showed a crystallized wax content (C44-C46-C48) lower than 3 % than the initial content, while the achieved reduction ascended to 31% when propane was used.Propane is considered a green solvent but it is flammable. For this reason, essays using a non-flammable mixture were made; in this case, the reduction in the crystallized wax content was of 6.25%. The removal materials from the different essays were also analyzed. They consisted mainly on C42-C50 waxes with a higher percentage of the crystallized waxes of 44, 46 and 48 carbon numbers.
Different Purification Methods and Quality of Peanut Biodiesel.
Anna Leticia Pighinelli2, Ana Maria Rauen de Oliveira Miguel1, Roseli Aparecida Ferrari1, Kil Jin Park2, 1ITAL Institute of Food Technology, Campinas, São Paulo, Brazil, 2UNICAMP, Campinas, São Paulo, Brazil
Biodiesel is a fuel obtained from triacylglycerides and mostly produced through transesterification, a chemical reaction of vegetable oils with alcohol, methanol or ethanol. Raw material selection should take the costs into account; because 85% of production cost is related to vegetable oil. The objective of this study was to evaluate the transesterification reaction of unrefined peanut oil (Arachis hypogaea L.), in laboratory and pilot scales, and three different biodiesel purification methods. For the best conduction of experiments, an experimental design was used. For biodiesel production at laboratory scale, the best result, 89.2%, was obtained with molar ratio of 3:1 and 3% of catalyst concentration. That experimental condition was applied in bigger scale with a small reactor. For purification with hot water, the biodiesel yield was 43.5%. Purification with silica had a yield of 76.9% and distillation, 85.0%. Distillation of biodiesel produced a biofuel with better quality but that method was the most expensive. Biodiesel production costs for purification with hot water and silica were US$15.00/kg and US$8.40, respectively, and US$9.20/kg for distillation.
Novel Bio-based UV-cure Oligomers for Sustainable Coatings' Applications.
Senthilkumar Rengasamy, Vijay Mannari, Eastern Michigan University, USA
Bio-based coating materials have emerged as environmentally friendly alternatives to petrochemical based ones due to their sustainability, lower carbon footprint and often lower cost. Acrylated vegetable oils and their derivatives are increasingly preferred for advanced photo- curable coatings due to a number of technical and commercial benefits. Novel family of vegetable oils-based acrylate-functional monomers/oligomers has been derived from epoxidized soybean oil and epoxidized soy-methyl ester, using 2- hydroxyethyl acrylate. This research poster will present our novel approach for synthesis of acrylated soy-monomers/ oligomers with low viscosity and high acrylate content. Synthetic strategy and characterization of UV-cured coating systems based on these soy oligomers will be highlighted.
Sterol Glycoside Reduction in Biodiesel using Synthetic Magnesium Silicate and the Effect on Cold Soak and Total Contamination.
Melanie K. Greer, George E. Hicks, Brian S. Cooke, The Dallas Group, USA
Contaminants such as sterol glycosides have been shown to cause filter plugging problems for biodiesel and as such must be removed. Adsorbents, such as synthetic magnesium silicate, have been used for many years to purify biodiesel in order to achieve regulatory specifications. In this study, synthetic magnesium silicate was used to treat three different biodiesel samples in an attempt to remove high levels of sterol glycosides and improve the poor filtration characteristics of the fuel as measured by cold soak filtration and total contamination.Synthetic magnesium silicate was also shown to remove sterol glycosides from biodiesel. The treatments resulted in significant decrease in filtration times and residue remaining after filtration. Furthermore, the biodiesel samples treated with synthetic magnesium silicate passed both the cold soak filtration and total contamination tests. Unlike other post-purification filter treatment systems, the treatment using synthetic magnesium silicate was shown to be efficient at normal process temperatures so there is not a need to chill the biodiesel to remove the contaminants.
Preparation of Omega-3 PUFA Enriched Triglycerides: Esterification vs Transesterification.
W. Wang, R. Townsley , J.A. Kralovec, Ocean Nutrition Canada Ltd., Dartmouth, NS, Canada
The objective of this work was to investigate the use of immobilized lipase B from Candida Antarctica as the catalyst for esterification and transesterification reactions to produce omega-3 PUFA enriched triglycerides (TG). Omega-3 concentrated fish oil free fatty acids (FFA) and ethyl esters (EE) were used to react with glycerol for TG products. Reactions were conducted under solvent-free conditions at 65-90 ºC with 2-3 % immobilized lipase for 5-24 h. Vacuum was applied to remove the co-produced water or ethanol. With FFA or EE to glycerol molar ratio at 3:1, over 90% TG conversions were achieved from both esterification and transesterification reactions, however; higher reaction temperatures were required in the transesterification process. FFA to TG conversion was faster than EE to TG conversion. The immobilized enzyme was found tolerant to the elevated temperatures and could be reused 16 times for EE to TG conversion and over 20 times for FFA to TG conversion in a flask reactor agitated by stir bar.
Production of Biodiesel from Bitter Almond Oil (Prunus dulcis).
S. Singh, S. Ghorbanian, O. Tavakoli, University of Tehran, Engineering Faculty, Iran
the reaction was carried out in a 500 millilitre spherical reactor provided with thermostate, mechanical stirring and condensation system.100 millilitre of oil was added to system and then methanol and NAOH as catalyst was added.we heat the mixture untill the system reached to 55 celsius degree. the experiment was prolonged for 120 minutes after cooling two layers were formed.the upper phase containes methy ester and the lower phase containes glycerin . after separating the two layers by sedimentation the remaining catalyst was extracted by successive rinses with 50 millilitre of distilled water. the resulting mixture was subjedted to a distillation at 55 celsius degree to recover the excess of methanol.
The Synthesis of Poly(diacid-glycerol)s in an Apparent Quazi-Melt Solution with Toluene.
V.T. Wyatt, G. Strahan, ERRC, ARS, USDA, Wyndmoor, PA 19038, USA
Glycerol is the major co-product from the process used to produce biodiesel. Dramatic increases in the production of biodiesel over the past decade have created the need to find new uses for glycerol. In this study, we have synthesized hyperbranched polymers by reacting glycerol with diacids in toluene. These are the first examples of diacid-glycerol hyperbranched polymers produced in a non-polar solvent system. Glycerol-based polymers are of interest for potential uses as cosmetics, food additives, surfactants, and lubricants. Since these polymers have the potential to be used in a variety of applications, it is important to determine how degrees of branching and crosslinking can be controlled. While crosslinked polymers have many applications (i.e. hydrogels and rubbers), they are sometimes undesirable because they cannot be dissolved in solvents, making them less amenable for additional processing into other materials. In this study, we have changed the reaction medium and demonstrated the ability to reduce or avoid crosslinking.
Analysis of Four Specialty Oils of Under-used Forest Species from Benin (Azadirachta indica, Annona squamosa, Carapa procera and Parkia biglobosa).
T. S. Djenontin1,2, V.D. Wotto1, P. Lozano3, D.C.K. Sohounhloué1, D. Pioch3, 1LERCA, Ecole Polytechnique, Université d’Abomey-Calavi, Cotonou, Bénin, 2LBEB, UTER GEI, Fondation 2iE, Ouagadougou, Burkina Faso, 3CIRAD, UMR GPEB, Process Engineering / Water & Bioproducts, Montpellier, France
Oils samples were extracted from seeds of forest species, harvested in Benin: Annona squamosa, Azadirachta indica, Carapa procera and Parkia biglobosa (HAS, HAI, HCP and HPB, respectively). HAI and HCA oils have an acidity of ~6%, due to the fact that seeds are traditionally collected on the ground, contrary to HAS and HPB, having a lower acidity (~2%), thanks to the possibility to harvest directly on the trees. HCP which shows the highest oil content (61.5 % dry weight), is an oleic oil with 59.1% of C18:1, while HPB is the richest in C18:2 (41.2%), but also contains up to 17% of C20-C22. The unsaponifiable extracts are all rich in sterols (1360-2720 ppm), especially HCP, and in addition to β-sitosterol which is the most prominent, this oil contains Δ5-avenasterol (4.8 %) and 8.0 % of uncommon sterols. HPB is particularly doted in tocopherols (880ppm) among which α-tocopherol makes 70%, while γ-tocopherol is the major tocol in HAS et HAI (73 et 67 % respectively), and δ-tocopherol in HPC. Thus the unsaponifiable could be used to identify these specialty oils. Hydratable phospholipids overpass non hydratable phospholipids in HAS, HAI and HPB, thus requiring a water-degumming step to stabilize these oils during storage, while the ratio is about 0.6 for HCP. Regarding the nutritional quality of these oils, the fatty acid balance shows a lack of polyunsaturated acids except for HPB which is close to the suitable value. Our data about fatty acid profile update older reports, sometimes they don’t match early reported values, while phospholipids and unsaponifiable compositions are the first reported to date for these uncommon oils. After having shown the peculiar composition of each oil, a wider range of samples should now be investigated, to check the influence of climate and genotype. These oils could then be exploited according to their properties, either for food or non food uses, including as local renewable fuel, while Benin still relays on oil imports for food supply.
Synthesis of Lipophilic Carboxylic Acid Salts from Oleic Acid, Sunflower Oil and Used Frying Oils in an Original Hydrothermal Reactor Heated by Direct Induction.
E. Lacroux, G. Vaca Medina, J.F. Fabre, R. Valentin, Z. Mouloungui, ENSIACET – Unité Chimie Agro-Industrielle - UMR 1010 INRA/INP-ENSIACET, Toulouse Cedex 4 FRANCE
An original hydrothermal reactor heated by direct induction has been designed and developed for realization of various chemical synthesis in aqueous conductive media. This equipment allows reaction and separation in a single reactor.Such technology has been used for soap production from various raw materials. It has been used successively with oleic acid, oleic sunflower oil and used frying oils.This technology needs to implement electron transfer within emulsified medium. Soaps are obtained using three various methods: fatty acids salification, triacylglycerols saponification and double decomposition. Double decomposition reactions involve an exchange of metallic cation by another on a lipophilic carboxylic acid salt already produced.It was thus possible to obtain sodium, calcium and lithium soaps from each of the three types of raw materials. This original technology permitted to obtain high quality lipophilic carboxylic acid salts even from complex mixtures containing polymers such as used frying oils.
Microwave–assisted Methanolysis of Sunflower Oil.
Sevil Yucel, Isa Rahmanlar, Pinar Terzioglu, Yildiz Technical University, Istanbul, Turkey
Microwaves are a form of electromagnetic energy associated with electric and magnetic fields. Microwave energy having electromagnetic wavelengths with frequencies between 300 MHz and 300 GHz has great potential applications in chemical and food industry. Recently, microwave-assisted esterification method for producing fatty acid esters as an alternative laboratory scale esterification method, which showed less time and more yield.In this study, using microwave assisted method as a rapid and effective method for producing fatty acid methyl esters (FAME) for possible use as biodiesel from sunflower oil was investigated. Molar ratio (methanol: oil), time and concentration of alkaline catalyst were studied as parameters effecting methanolysis reaction. The methanolysis of sunflower oil with 1–2% potassium hydroxide were studied in 3, 5, 8 minutes at 64 °C. The effect of molar ratio, 6:1, 9:1 and 12:1 on ester yield and its quality were investigated. There was no significant difference in the yield of FAME for different reaction times. Catalyst concentration was the most significant factor affecting the yield of FAME. The maximum conversion ratio of 99.5% to FAME is achieved in 3 minutes with % 2 potassium hydroxide and molar ratio 6:1.
Long Term Activity of Modified ZnO Nanoparticles for Oil Transesterification.
Shuli Yan, Siddharth Mohan, Craig DiMaggio, Manhoe Kim, Simon Ng, Steven Salley , Department of Chemical Engineering and Material Science, Wayne State University, Detroit, MI, 48202, USA
Biodiesel can be produced by the transesterification of natural oils with methanol using modified ZnO nanoparticles as catalyst. Crude algae oil, corn oil from DDGs, crude palm oil, crude soybean oil, crude coconut oil, fish oil, waste cooking oil, food grade soybean oil and the food grade soybean oil with 3 % of water and 5 % of FFA addition were converted into FAME within 3 hours using this new catalyst. The ZnO nanoparticles were reused 17 times without any activity loss in a batch stirred reactor and the average yield of FAME was around 93.7 %. ZnO nanoparticles were used continuously for 70 days in a fix bed continuous reactor and the average yield of FAME was around 92.3 %. XRD, ICP, TEM and HRTEM were used to characterize the long term used catalyst structure. Results show that this catalyst is a mixture of wurtzite ZnO nanoparticles and some amorphous materialsand that the used catalysts have similar crystal structure to fresh catalyst. ICP results show that this catalyst does not dissolve in biodiesel, methanol, oil and glycerin-methanol solutions. It has a stable crystal structure under the reaction conditions. The high catalytic activity, long catalyst life and low leaching properties demonstrate these modified ZnO nanoparticles have potential for commercialization in biodiesel production process.
Using Solid Base Containing Ca and La species for Biodiesel Production.
Shuli Yan, Siddharth Mohan, Craig DiMaggio, Manhoe Kim, Steven Salley, Simon Ng, Department of Chemical Engineering and Material Science, Wayne State University, Detroit, MI, 48202, USA
Biodiesel is a mixture of fatty acid esters and can be produced from vegetable oils or animal fats with methanol. In this study, a class of calcium-containing base catalysts was prepared for biodiesel production. Conventional industrial technologies for biodiesel production generally employ homogeneous base catalysts such as NaOH. One disadvantage of such catalysts is that the waste catalysts are difficult to be removed after reaction. Compared to the conventional homogeneous base catalysts, the calcium-containing base catalysts can be easily removed from products by filtering after reactions and can be recycled many times. The effects of metal oxide molar ratio, calcination temperature and catalyst precursors on the yield of FAME were studied. XRD, XPS, BET, FTIR, SEM, EDS and Hammett indicator method were used to characterize the structure of catalysts and the nature of active sites. In comparison with other reported calcium containing catalysts, it shows a higher activity and less leaching of catalyst components. In a fixed bed reactor, it continuously ran for 14 days and maintained the yield of FAME at 94.5 %. In a batch reactor, at the reaction conditions of 65 oC, 20 molar ratio of methanol to oil and 5 % of catalyst dosage, the yield of FAME can reach 96.3 % within 60 minutes.
Novel One-step and Two-step Supercritical Dimethyl Carbonate Process for Non-catalytic Biodiesel Production.
Zul Ilham, Shiro Saka, Graduate School of Energy Science, Kyoto University, Kyoto, Japan
As biodiesel production becomes rapid in years to come, the overproduction of glycerol is expected from the conventional production method. Thus, new production methods of biodiesel without the production of glycerol are therefore worth to be explored. This paper will discuss the potential of non-catalytic supercritical dimethyl carbonate process for production of biodiesel in a one-step and two-step process. Special focus is oriented towards the superiority of this process in producing higher value by-products, than the glycerol produced in the conventional process without tolerating the ability to produce high yield of fatty acid methyl ester. These by-products from this process possess higher value in applications than the abundantly available glycerol. In addition, the two-step process offers milder reaction condition (lower temperature and lower pressure), non-acidic, non-catalytic and applicable to feedstock with high amount of free fatty acidsWithout doubt, these studies on supercritical dimethyl carbonate could charter the path towards exploration of novel and alternative biodiesel production processes for the future.
Properties of Biodiesel Derived from Processed Neem Oil.
J.M. Vargas-Lopez1, D. D. Wiesenborn2, K. K. Tostenson2, N. Chaira-Alcaraz1, 1Universidad de Sonora, Departamento de Investigacion y Posgrado en Alimentos, Hermosillo, Sonora, Mexico, 2North Dakota State University, Department of Agricultural and Biosystems Engineering, Fargo, North Dakota, USA
In recent years, the neem tree (Azadirachta indica A. Juss) has gained the attention of the oleochemical industry throughout the world, including United States and Mexico. The main focus of commercialization has been the limonoids, which are used as pesticides. However, the seed kernels contain up to 50% oil which is rich in oleic acid (68 wt%); this oil has potential industrial application in the preparation of biodiesel. The aim of this work was to evaluate some properties of biodiesel obtained from neem oil after processing for limonoids extraction. Oil was extracted using a Komet S87 screw press; preliminary tests using a combination of seed moisture content (6,8, and 10%) and whole or dehulled (50%) seeds showed particularly good oil yield with 6% seed moisture and 50% dehulled seed. Neem biodiesel properties such as kinematic viscosity, cloud point and glycerol content were compared with ASTM D6751 specifications. Biodiesel from neem oil exhibited high kinematic viscosity (7.0 cS) and high cloud point (14°C), which indicated excessive levels of glycerides. Nevertheless, this study illustrates the potential to produce biodiesel from neem oil, which may simultaneously reduce dependence on food-use oilseed crops. Future research will be directed towards identifying and eliminating neem oil constituents which may interfere with transesterification.
Biojet Production from Vegetable Oil Hydroprocessing Using Supported Noble Metals, and Transition Metal Carbide and Nitride.
Huali Wang, Craig DiMaggio, Manhoe Kim, Steve Salley, Simon Ng, Department of Chemical Engineering and Material Science, Wayne State University, Detroit, MI, USA
In recently years, many researchers are concentrating on developing biofuels from alternative and renewable sources to replace commercial petroleum products in the future. However, there are no known technically and economically feasible processes to produce a stand alone jet fuel from plant oils and animal fats within the scope of catalyst development, especially non-sulfided catalysts. Therefore, the research objective for this study is to synthesize, characterize and test various supported noble metal, metallic nitride and carbide catalysts for their activity in hydroprocessing of vegetable oils to produce jet fuel products. Six different types of supported noble metal, metallic nitride and carbide catalysts were prepared: Mo2N, Mo2C, WN, WC, Ru and Pt supported on ultra-stable Y (USY) zeolite. Transition metal carbides and nitrides of molybdenum and tungsten were prepared by temperature-programmed reaction of the oxide precursor with a reactant gas (20% CH4/H2 for the carbides and 100% NH3 for the nitrides). The phase purity and composition of the samples were established by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The catalysts were tested for their activity in a high-pressure BTRS micro-reactor system using soybean oil as the feedstock.
Improved Coupling Reactions for Production of Kilogram Quantities cis and trans-Vaccenic Acid.
Jianheng Shen1, Spencer Proctor2, Martin J.T. Reaney1, 1Food & Bioproduct Sciences, University of Saskatchewan, saskatoon, SK, Canada, 2Department of Agricultural, Food & Nutritional Science, edmonton, AB, Canada
The major trans-fatty acid found in ruminant meat and milk is trans-vaccenic acid (TVA, trans-11 C18:1) which has been reported to alter lipid lipid metabolism in mammals. Biosynthetic evidence indicates that TVA is readily converted by the bacterial enzyme 9-desaturase into cis-9-trans-11-conjugated linoleic acid. Dietary TVA may affect metabolism after conversion to CLA or it may act directly. Kilogram quantities of stereoisomerically pure forms of TVA were required for nutritional studies but the cost of commercially available reagents was prohibitive. In the current study, we introduce a new methyl ester route to stereoselective preparation of trans -vaccenic acid. The key step involves a Wittig reaction of methyl ester yilid and heptanal. Due to the good solubility of the methyl ester yilid, this reaction is achieved without solvent and thus larger scale reactions are possible. Two kilograms of TVA were prepared using this novel approach.
Identification of Enantioselectivity of Recombinant Candida rugosa Lipase Isozymes for l-Menthyl Acetate Production.
Ying-Ting Luo1, Jei-Fu Shaw2, Shu-Wei Chang3, 1Department of Bioindustry Technology, Dayeh University, 168 University Rd., Dacun, Changhua 51591, Taiwan, R.O.C., 2Department of Food Science and Biotechnology, National Chung Hsing University, 250 Kuo-Kuang Rd. Taichung, 402 Taiwan, R.O.C., 3Department of Medicinal Botanicals and Health, Dayeh University, 168 University Rd., Dacun, Changhua 51591, Taiwan, R.O.C.
l-Menthol, an aromatic compound, was widely used in food, perfume, cosmetics, and pharmaceutical industries. To improve its solubility in water, permanence of refreshing and thermostability for various industrial applications, in this study, we planned to catalyze enantioselective esterificaztion of racemic menthol and ethyl acetate by using recombinant Candida rugosa lipase isozymes (LIP1 ~ LIP4) as biocatalyst. Our aims were to obtain a recombinant isozyme with highest optical specificity and to estimate the effect of various reaction parameters such as reaction time, temperature, enzyme amount, water addition amount and substrate molar ratio on high optical purity of l-menthyl acetate production. The result shows that recombinant LIP4 exhibited a higher enantioselectivity and production yield of menthyl acetate than other isozymes.
The Use of Cadmium Compounds as Catalysts for Biodiesel Production from Low-grade Raw-materials.
M.B. Alves, F.C.M. Medeiros , P.A.Z. Suarez, University of Brasilia, Brasília, DF, Brazil
Divalent cadmium compounds, particularly CdO, were used as Lewis acid catalysts in the hydrolysis, esterification and transesterification of pure triacylglycerides or fatty acids obtained from neutralized soybean oil, as well as mixtures of these substrates. In more than one step, reaction yields up to 98 % in fatty acids or fatty acid methyl esters were achieved. In order to study the use of these reactions to develop technologies for biodiesel production from low-grade starting materials, it was also carried out a study using a real sample with a high content of free fatty acids from the Brazilian Savanah palm-tree oil called Macauba (Acrocomia sclerocarpa M.). Using multi-step, sequential or combined in one-pot reaction processes it was possible to obtain an overall reaction yield up to 98 % in methyl esters.
New Industrial Technology in Enzymatic Extraction of Vegetable Oils in Czech Republic.
Okoye Urevbu Okwudili, IFRANE s.r.o., Prague, Czech Republic
Enzymatic extraction and degumming of oil seeds have been investigated for some time in the extraction of edible oils from crops such as Rapeseed but more recently new developments in enzyme technology have widened the range of applications. Processes are being proposed for corn and rice bran oil but these are still at an early stage.Enzymatic degumming to remove phosphatide gums has recently been extended through the use of microbial phospholipase. These new enzymes permit degumming to be carried out low water levels and without the use of harsh chemicals, providing a cost effective, environmentally friendly degumming route.In physical degumming which also covers enzymatic treatments, centrifuges are used to separate the aqueous gum fraction from the oil. Recently in Czech Republic we have investigated the use of combined absorbtion and enzymatic hydrolysis of phospholipids to reduce or eliminate the requirement for centrifugation. This process results in a degumming with a reduced energy and water consumption and may be applicable where environmental concerns encourage the reduction of water consumption.This paper will review these developments and report on the results recently obtained on low water degumming.
Synthesis of Ni (II), Sn(II), Co(II) and Fe (II) Carboxilate Complexes and Evaluation of their Catalytic Activity for Polyesterification of Castor Oil (Ricinum communis) with Terephthalic Acid.
E.U.X. Peres, A.P. Umpierre, P.A.Z. Suarez, University of Brasília, Brasília, DF, Brazil
The ricinoleate metal complexes Ni[C17H34(OH)COO]2, Sn[C17H34(OH)COO]2, Co[C17H34(OH)COO]2 and Fe[C17H34(OH)COO]2 have been prepared and used as catalyst precursors for polyesterification of castor oil and terephtalic acid (TFA). The observed catalytic activity decreased in the order: Fe[C17H34(OH)COO]2 > Co[C17H34(OH)COO]2 > Sn[C17H34(OH)COO]2 > Ni[C17H34(OH)COO]2. The new polymeric materials did not show an homogeneity in their chains, as indicated by their high polydispercity. Indeed, the polydispercity value varied from 5.49 for the polymer produced in the presence of the nickel complex to 12.42 for these prepared with the cobalt compound. On the other hand, the chains presented high molecular weight, being the lower value (Mw = 13449) observed for the polymer prepared in the presence of the nickel complex and the highest (Mw = 36446) verified for the one obtained with the cobalt compound. It was observed only a vitreous transition for all the materials, between - 80°C and - 40°C, suggesting an amorphous structure. This work shows that is possible to prepare polymers material with analogous characteristic of synthetic rubbers and resins using renewable raw material, allowing the substitution of petroleum based monomers.
Fats and Oils Hydrocracking Using Noble-metal Magnetic-nanoparticles as Catalysts.
J.P. Rodrigues1, M.J. Jacinto2, H.L. Oliveira1, P.A.Z. Suarez1, L.M. Rossi2, 1University of Brasilia, Brasilia, DF, Brazil, 2University of São Paulo, São Paulo, SP, Brazil
Oil refineries have been developing a process that mixes fats and oils into different currents in refining stations, where the molecules of oil are processed with mineral oil or derivatives. The molecules are cracked at high temperatures and high pressures of H2, in a process called hydrocracking, in order to eliminate oxygen and double bonds. The hydrocracking of fats and oils can be a viable alternative for the production renewable diesel, suitable to be used as diesel-like fuel, since it can be obtained only hydrocarbons as products. In this work, we tested noble metal catalysts (Rh, Ru, and Pt) supported on magnetic particles coated with silica. Using soybean oil, palm-tree oil and castor oil, different reactions were made varying the temperature, pressure of H2 and amount of catalyst. All the metals studied are effective for hydrocracking of the vegetable oils. It should be noted that the best results were found when ruthenium or bimetallic catalyst containing rhodium and ruthenium have been used. It was also observed that the hydrocracking occurs above 400°°C and bellow this temperatures only the hydrogenation of double bonds take place. FAPDF, CNPq, FINATEC, MCT
Methylester Preparation from Brown Grease by Using Heterogeneous Catalysts.
M. Kim1,2, C. DiMaggio1,2, Y. Shuli1,2, S.O. Salley1,2, K.Y. Simon Ng1,2, 1Wayne State University, Detroit, MI, USA, 2Next Energy, Detroit, MI, USA
Biodiesel, a common term for long chain alkyl esters, is a processed fuel derived from the esterificaton and transesterification of free acids (FFAs) and triglycerides, respectively. The current base catalyzed method, which relies on highly refined and expensive oils, is not economically competitive because the feedstock cost is the dominating economic factor. One way to achieve a lower cost product is to use less expensive waste oils (e.g., yellow grease and brown grease) as well as acidulated soapstocks. Brown grease sources, for instance, are low-value lipids containing high concentrations of free fatty acids, waste oils, along with varying amounts of unwanted materials such as sulfur, metals, and water. The main source of brown grease is typically waste cooking grease collected in restaurant grease traps. Because of the wide array of contaminants that accompany the FFA in brown grease, converting brown grease to FAME and purifying the products are challenging processes. To address these challenges, heterogeneous ZnO catalysts supported on ZrO2 (ZnO/ZrO2, ZnO-La2 O3/ZrO2, ZnO-Al2O3/ZrO2, ZnO-NiO/ZrO2, ZnO-La2O3) have been developed which can be easily incorporated into a packed bed continuous flow reactor to produce high FAME yields at the same time as simplifying product separation and purification and reducing waste generation. In addition, the high sulfur (640 ppm) and metal contents (Ca, Mg, Na, Zn, etc.) that are observed in brown grease can be reduced by a factor of two with these catalysts, where traditional sulfuric acid catalysts only slightly decrease these species. The highly oxidized forms of sulfur, sulfonates, and ester-bonded sulfates, which are present as terminal groups, can be released from the lipid molecules via methanolysis. However, the reduced-sulfur structures, organic sulfides, and di- and polysulfides, which are involved in forming intramolecular cross-links, were not removed by esterification or transesterification and remained in the FAME product. Using the ZnO catalysts, the total acid number of the brown grease was reduced from 178 mg KOH/g to near zero by the end of the esterification and transesterification reactions. Among the catalysts developed and tested, the highest FAME yield (78%) was obtained after 2 hours of reaction at 200°C with the ZnO/ZrO2 catalyst.
Preparation of Soypolymers by a Green Processing Method.
Z.S. Liu, NCAUR, ARS, USDA, Peoria, IL, USA
Ring opening polymerization of epoxidized soybean oil (ESO) initiated by boron trifluoride diethyl etherate was conducted in liquid carbon dioxide. The resulting polymers (RPESO) were characterized using Infrared (IR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), 1H NMR, 13C NMR, solid state 13C NMR and gel permeation chromatography (GPC). The results indicated that RPESO materials were highly crosslinked polymers. They had glass transition temperatures ranging from -11.9˚C to -24.1˚C. TGA results showed the RPESO polymers were thermally stable at temperatures lower than 200˚C. Decomposition temperature was found mainly after 340˚C.
Novel Fatty Acid-glycidyl Carbamate Resins for Air Drying Coatings.
Umesh Harkal, Andrew Muehlberg , Dean Webster, Department of Coatings and Polymeric Materials, North Dakota State University, Fargo, ND, USA.
Glycidyl carbamate (GC) resins are produced by reaction of isocyanate functional compounds with glycidol. GC resins contain urethane (-NHCO-) and epoxy functional groups in their structure. The combination of urethane and epoxy functional groups in GC resins imparts an excellent set of properties to GC-based coatings. In this work, GC resin was reacted with linseed oil fatty acid (LOFA) to make a fatty acid functional polyurethane. Formulations of the LOFA functionalized GC resin (GC-LOFA) were developed to produce air drying coatings using several driers and their combinations. Tung oil was also used as a reactive diluent in coating formulations. Air drying coatings made from GC-LOFA resin showed good film formation by autoxidation mechanism and exhibited good coating performance. Hardness of the coatings was found to increase over a period of time.
Thevetia Peruviana Juss: An Unknown Oil Seed Plant Suffering Neglect.
S. Ibiyemi, Biofuel and Alternate Renewable Energy Ltd, Ilorin, Kwara State, Nigeria
Thevetia Peruviana juss is a tropical shrub which hitherto suffers from an almost total neglect because of its high level lethergy of oil toxins.Whereas its seed oil content is 55-62% w/w. the plant in the wild produces about 500 fruits per annum with two peak production periods at start and end of rain. Irradiated seeds produce fruits about four months earlier than plants in the wild. Plants of irradiated seeds produce 700-1000 fruits per annum. Fruits from plants in the wild provide oil rich in oleic acid content.A comparative studies of the physicochemical analysis of biodiesels of eleven seed oils including Jathropha, thevetia neem (non food) soybean, rapeseed, palm oil (food) etc reveal that five(5) of the seven(7) indicate that thevetia seed oil biodiesel performance is better than all others.On-going research: the lipid content of the seed hard coat (equivalent of rice bran). Budding of thevetia at various ages for the effect of branching and performance in fruit yield, Effects of irradiation on the oleic acid content, oil yield, toxins and unsaponifiable/phytostrols of the seeds.Biofuel and Alternate Renewable Energy Ltd (BARE), my consultancy company based in Ilorin, Kwara State, Nigeria, seeks collaborations to promote thevetia as a major oil seed plant.
Degradation and Flammability of Glycerin-based Polyurethane Foams.
I. Javni1, S. Fu1, D.P. Hong1, O. Bilic1, Z. S. Petrovic1, 1Kansas Polymer Research Center, Pittsburg State University, Pittsburg, Kansas, USA, 2Kansas Polymer Research Center, Pittsburg State University, Pittsburg, Kansas, USA, 3Kansas Polymer Research Center, Pittsburg State University, Pittsburg, Kansas, USA, 4Kansas Polymer Research Center, Pittsburg State University, Pittsburg, Kansas, USA, 5Kansas Polymer Research Center, Pittsburg State University, Pittsburg, Kansas, USA
Glycerin, a by-product of the bio-diesel process, is a sustainable, renewable and economical base for the development of a range of useful products. We have developed high glycerin content polyols for rigid polyurethane foams. However, these polyols are rich in oxygen, which contributes to higher flammability. The objective of this work was to find the ways to reduce the flammability and create self-extinguishing rigid polyurethane foams that meet the requirements of current building codes. There are two primary ways to decrease flammability in polyurethanes: by chemical modification of polyols or by additives. In this work we have used flame retardants and studied their effect on physical and burning properties. We prepared self-extinguishing, glycerin based foams using proper flame retardants. These foams did not show a deterioration of structural, mechanical and thermal properties.
Pyrolysis of Palm Biomass.
Soh Kheang Loh, Mohamad Azri Sukiran, Malaysian Palm Oil Board, Kuala Lumpur, Wilayah Persekutuan, Malaysia
Pyrolysis of palm biomass was investigated using a quartz fluidized-fixed bed reactor. The particulate biomass and sand were introduced together into the reactor and pyrolysis was carried out under different pyrolysis temperatures, biomass particle sizes, heating rates and palm biomass feedstock. The temperature of pyrolysis, heating rate and particle size varied in the range of 300-700 °C, 10-100 °C min-1 and <90 µm, 91-106 µm, 107-125 µm and 126-250 µm respectively while the biomass feedstock used were empty fruit bunches (EFB), trunk, frond and fibre. Attempts on the pyrolysis of EFB revealed that the maximum bio-oil, char and gas obtained were 42.28% of bio-oil at 500 °C with a heating rate of 100 °C min-1 and particle size of 91-106 µm, 41.56% of char at 300 °C with heating rate of 30 °C min-1 and particle size of 91-106 µm and 46.00% of gas at 700 °C with heating rate of 30 °C min-1 and particle size of 91-106 µm respectively. The types of gas detected i.e. carbon monoxide, carbon dioxide, methane, ethane and ethylene were dependent on the pyrolysis temperature used.The char and bio-oil were characterized. The calorific values of bio-oil ranged from 20 to 21 MJ/kg. A great range of functional groups of phenol, alcohols, ketones, aldehydes and carboxylic acids were present in the bio-oil as indicated in FTIR and GCMS spectra.
Fuel Properties of Butanol-Diesel-Biodiesel Blends.
K Wadumesthrige, S.O Salley, K.Y.S Ng, Wayne State University, Detroit, MI, USA
The use of butanol (also called bio-butanol when produced biologically) as an alternative biofuel blend component for conventional diesel fuel has been investigated extensivly. However, the limits of some fuel properties such as cetane number and viscosity fall below the accepted values as described by ASTM D 975 diesel specifications. When butanol is blended with #2 ULSD in a 10% blend, the fuel mixture decreases the cetane number by 8% (from 42.6 to 39.0). Also, the addition of butanol decreases the lubricity properties of conventional diesel. Interestingly, blending biodiesel (fatty acid methyl esters) with butanol-diesel mixtures regain the required properties of diesel fuel for compression ignition. Therefore, in this study, biodiesel and butanol were blended with commercial diesel fuel at 5%, 10%, 15%, 20%, 25%, and 30% on a volume basis to characterize the key fuel properties of the blends such as cetane number, viscosity, surface tension, lubricity, flash point, and cold filter plugging point. An optimum ternary mixture of biodiesel-butanol-diesel will be developed based on the physical properties which can be used in compression ignition engines without altering engine parameters or addition of performance enhancers.
Dilute Solution Absorption Isotherm Determination of Biodiesel/n-Alcohol Binary Mixtures by Inverse Gas Chromatography.
N.S. Bobbitt, J.W. King, University of Arkansas, Department of Chemical Engineering, Fayetteville, AR, USA
The determination of absorption isotherms at finite injection size by inverse gas chromatography (IGC) provides additional solution thermodynamic data on the interactions between alcoholic solute probes and soya-derived biodiesel-based esters. Using a modified, inexpensive Gow-Mac Model 580 GC with digital signal amplification, the resultant asymmetric peak profiles and areas have been deconvoluted to allow the determination of sorption isotherms at mole fractions up to 0.1 and partial pressures ratios to 0.5. The resultant isotherms show transitory behavior ranging from Type I behavior for the biodiesel ester – methanol system to anti-Langmuir (Type III) for the biodiesel ester – butanol binary. Over the temperature range of 55 – 85°C, all of the recorded activity coefficients are greater than unity (positive deviation from Raoult’s Law) and they increase with the carbon number of the solute over a range of 1.38 to 3.31, but relative invariant with respect to temperature. These trends are reflected in the trends for the solution thermodynamic parameters, e.g., the excess heats of solution of solution are very close to zero. The activity coefficient values determined at more finite concentrations compare well with previous IGC-determined data and literature-derived- values on model compounds over an expanded temperature range. The reproducibility of the asymmetric peak profiles and hence the isotherm data was excellent.
Quality Survey of Biodiesel Blends in Michigan.
Rhet de Guzman, Haiying Tang, Sachintha Wadumesthrige, Tim Zhou, Danton Garcia, Steven Salley, Simon Ng, Wayne State University, Detroit, MI,USA
The quality of biodiesel blends in the retail market is of importance to biodiesel producers, automotive manufacturers, fuel delivery components suppliers, as well as the general public. In order to compare the quality of biodiesel blends before and after the approval of ASTM specifications (D7467-09a) for biodiesel blends (B-6 to B-20), twenty-eight biodiesel blend samples were collected from retail merchants throughout the State of Michigan in 2009. The following properties were evaluated: kinematic viscosity, acid number, Rancimat induction period, water content, cloud point, pour point, cold filter plugging point, Cetane number, flash point, biodiesel blend level, and fatty acid methyl ester (FAME) composition profile. Variations in fuel quality across the state will be discussed as well as survey results on user satisfaction. Comparison of the Michigan biodiesel fuel quality in 2009 with a similar biodiesel survey in 2007 will be made.
Interesterification of Camelina and Castor Oil: Analysis and Optimization of the Reaction.
J. Garcia, J.Y. Bergeron, A. Tremblay, G. Hersant, J. Labrecque, Oleotek Inc., Thetford Mines, QC, Canada
Interesterification is one of the most important processes for modifying both composition and physical properties of oils. During interesterification, fatty acids (FA) are exchanged within (intraesterification) and among (interesterification) triacylglycerols (TAG) until a thermodynamic equilibrium is reached. The aim of this research is the synthesis and production of structured TAG enriched with ricinoleic acid (C18 :1-OH) in order to improve the properties of target oils. Chemical interesterification occured between Camelina sativa oil and Castor oil. Oil extrated from Camelina seeds contains high levels of polyunsaturated fatty acids (linolenic and linoleic acid) up to 40-60% of total fatty acids. Castor oil is very rich (about 90%) in ricinoleate and it is the only commercial source. The operating condition (duration, temperature, vacuum, concentrations of the reactants, etc.) of the interesterification reaction was optimized in order to maximize yields, properties and quality of the produced structured oil. The interesterified oils were analyzed by a non-aqueous reverse-phase HPLC method and the major TAG were identified by comparison with literature data and standard TAG.
Effect of Acid and Base Catalysts in Alcoholysis of Waste Oil from Activated Bleaching Earth.
Omer Faruk Gul1, Melek Tuter2, 1TUBITAK, Gebze, Kocaeli, Turkey, 2Istanbul Technical University, Chemical Engineering Department, Maslak, 34469, Istanbul, Turkey
Biodiesel produced by alcoholysis of vegetable oils holds promise as a clean, renewable energy source and has become increasingly important. Waste activated bleaching earths from crude oil refining process containing up to 40% waste oil are potential raw material for biodiesel production.The waste oil adsorbed on activated bleaching earth (ABE), which was waste material in sunflower oil refining process, was evaluated as a raw material for biodiesel production. The waste ABE oil contained 10.3% free fatty acid. After extraction oil from waste ABE with hexane, alcoholysis reactions were conducted by NaOH, KOH and sodium methoxide as base catalysts and H2SO4 as acid catalyst. Reaction time with H2SO4 catalyst was much longer than that of all basic catalysts, other drawback of H2SO4 catalyst, higher molar ratio of alcohol:oil was used (75:1-200:1). The best conditions for the reaction catalyzed by H2SO4 were 60 ï‚°C, 1.5% catalyst load, 175:1 alcohol:oil molar ratio and 240 min. Molar conversion of oil was 96.5%. Among base catalysts, sodium methoxide was determined as suitable catalyst. The best condition for the reaction catalyzed by sodium methoxide were found to be 60 ï‚°C, 2% catalyst load, 6:1 alcohol:oil molar ratio, and 120 min. Molar conversion of oil was 97.1 %.
Fuel Properties of a Novel Plant-based Biofuel from Copaifera reticulata.
B.L. Joyce2, B.G. Bunting1, S. Lewis1, J.S. Choi1, J. Storey1, F. Chen2, C.N. Stewart2, 1Oak Ridge National Laboratory, Oak Ridge, TN, USA, 2The University of Tennessee, Knoxville, TN, USA
Biofuels have become a source of interest for replacing, at least in part, petroleum-based fuels. This would allow countries throughout the world to become producers of energy needed for transportation, infrastructure, and economic growth. We have identified several novel plant-based fuels whose chemistry does not consist of methyl esters from fatty acids. Specifically, the sesquiterpene-rich oleoresin from Copaifera reticulata was investigated as a potential fuel source. As the usefulness of these chemistries for biofuels is unknown, functional screening of these fuels are required to decide which are of interest for future characterization. Two oleoresins, one being a crude extract direct from the tree and the other processed by steam distillation, had their ASTM biodiesel fuel properties determined. These oleoresins were then blended with #2 diesel fuel (80:20 diesel fuel/Copaifera oleoresin) and run on a homogenous charge compression ignition (HCCI) engine to determine combustion and emission properties.
Ethyl Ester Obtained from Turkish Originated Safflower Oil and Fuel Ethanol as an Alternative Diesel Fuel.
Asli Isler, Filiz Karaosmanoglu, Istanbul Technical University, Chemical Engineering Department, Maslak, Istanbul, Turkey
Biofuels,as a clean alternative to the fossil fuels,are of wide interest at the time of high fossil fuel prices,increasing world energy demand and environmental burdens. Based on production type and feedstock choice,biofuels are classified as first,second,third and fourth generation biofuels. It is expected that second generation biofuels will take part after 2010 and will be used in flexi-fuel vehicles. Such fuels are produced from non-food crops in order to be considered more sustainable. Fatty acid ethyl ester is one of the second-generation biofuels,which provides many environmental and economical advantages by using ethanol for biodiesel production. Safflower,which is one of the humanity′s oldest crops,is one of the non-food oil seed resources which can be used as one of the perfect candidates for biodiesel production in Turkey. Safflower agriculture is suitable in Anatolia with higher yields even in the drought prone regions. The objective of this study is to investigate the appropriate reaction conditions for Turkey originated safflower oil-bioethanol transesterification reaction and to determine fuel properties for the ester product according to the EN standards. Safflower oil ethyl ester as a biofuel,which is introduced for the first time to the literature,is presented as an alternative diesel fuel candidate.
Photo-curable Advanced Nano-composite Coatings from Soybean Oil: Sustainable Hybrids.
Jigarkumar Patel, Dr. Vijaykumar Mannari, Eastern Michigan University, Coatings Research Institute, Ypsilanti, Michigan, USA
Organic-inorganic hybrid (OIH) nanocomposite materials have become increasingly important due to their remarkably improved performance properties for a myriad of applications. In the recent years our ability to manipulate OIH structures at nanoscale has enabled us to design and fabricate materials with well defined properties. Use of vegetable oils and their derivatives to fabricate advanced OIH materials may be very useful route for sustainable development. This poster will present development and application of photo-curable materials derived from soybean oil and their applications in advanced UV-curable OIH coatings.
Effect of Water on Esterification of Free Fatty Acids using Zeolite Catalysts.
A. Coker, A. Iretski, R. Hernandez, M. White, T. French, Mississippi State University, Starkville, MS, USA
Due to the high cost of separating water from algal oil before processing this oil into biodiesel (by esterification of the organic acids contained in the algal oil), a study to determine the maximum concentration of water that the esterification reaction would tolerate, and the influence of the acidity (Si:Al) ratio in zeolite catalysts on the reaction was conducted.In this work, esterification was completed using three surrogates to represent the free fatty acids present in the algal oils: Palmitic acid, Stearic acid, and Oleic acid. Two types of zeolite catalysts (Zeolyst International) were tested: Zeolite Y and Zeolite CBV 3024E with Si:Al ratio of 80:1 and 30:1 respectively. The reactants included 0.25 g fatty acid, 5 ml methanol, and 10 mass % catalyst, with reaction temperature of 65°C, and a duration of 3 hours. The effects of varying the concentrations of water and compositions of catalyst are discussed.Small amounts of water seem to benefit production of FAME (fatty acid methyl esters) and the yield of FAME shows nonlinear dependency on water concentration.
Fatty Acid Monoglyceride Synthesis from Palm oil by Transesterification with 1,2-O-isopropylideneglycerol.
K. Makkam1, B. Kitiyanan1,2, 1The Petroleum and Petrochemical College, Chulalongkorn University, Patumwan, Bangkok, Thailand, 2Center for Petroleum, Petrochemicals, and Advanced Materials, Chulalongkorn University, Bangkok, Thailand
The global production of biodiesel has been dramatically increased in the last few years. As a result, a large surplus of glycerol causes a decreasing in glycerol price making the entire biodiesel production process to be less competitive. Therefore, many researchers are finding the way to increase the use of glycerol by transforming it to other useful chemicals. In this work, the fatty acid monoglycerides from transesterification of palm oil and protected glycerol is studied. The high selectivity toward monoglycerides, in particular 1-monoglyceride is expected to obtain by using protected glycerol with isopropylidene group as protecting group. Initially, two adjacent OH groups in glycerol will be first protected by converting OH groups to isopropylidene group, then the protected glycerol will be used in transesterification with triglycerides. Subsequently, the resulting monoglycerides will be deprotected. The products are identified by Fourier-Transform Infrared Spectroscopy (FT-IR) and High Performance Liquid Chromatography (HPLC). We have simultaneously protected the hydroxyl groups of glycerol at the 1- and 2- positions. As expected, the results have revealed that the very high selectivity toward monoglycerides is obtained and the protecting group is also successfully removed.
Solvent Characteristics of Biodiesel Esters and Their Co-Products.
J.W. King, K. Srinivas, N.S. Bobbitt, and J.D. Vincent, University of Arkansas, Dept. of Chemical Engineering, USA
Textural Properties of Biorenewable Waxes Containing Partial Acylglycerides.
Linxing Yao, Tong Wang, Iowa State University, IA, USA
Vegetable oil-based waxes are a promising alternative to both beeswax and paraffin wax, which are largely used in traditional candles and encaustic painting, as they are environmentally friendly, biorenewable, and with low cost. In this study, MDwax made from mono- and diacylglycerides (DAG) of fully hydrogenated vegetable oil were formulated and their textural properties were compared to beeswax. It was found that MDwax having 30 to 40% of DAG had better texture than MDwax having other proportions of DAG in terms of hardness and cohesiveness, and the values were closer to those of beeswax than others. Various additives including free fatty acid, fatty alcohol, OHwax (hydroxyl TAG), and acetylated monoglycerides (AM) were added to MDwax (with 30% DAG) in order to reproduce a texture like beeswax as these additives may provide similar chemical composition thus interaction to the minor constituents in beeswax. Demar resin was also included as an additive since it was commonly used by the artists to improve the wax hardening properties. We found that the texture of MDwax and AM equal mixture was very similar to that of beeswax. A sensory evaluation showed that the surface buffability of selected waxes was in an ascending order of MDwax+10% demar mixture, MDwax, MDwax+50% AM mixture, paraffin wax, and beeswax. Thus, it is possible to produce a beeswax like wax with vegetable oil based materials.
Phenolation of Vegetable Oils.
Mihail Ionescu, Zoran Petrovic, Pittsburg State University, Kansas Polymer Research Center, 1701 South Broadway,Pittsburg, Kansas, 66762, USA
Based on the principles of Friedel Crafts alkylation of phenols with olefines, the alkylation of various phenols (phenol, m-cresol, guajacol) with the double bonds of vegetable oils, in acidic catalysis, has been studied. The reaction between phenols and vegetable oils, mainly soybean oil, was carried out at 90 oC, in the presence of a superacid as catalysts (HBF4). Simultaneous with the alkylation of phenols two side reactions take place: cationic polymerization of oils and formation in a small extent of phenyl esters of fatty acids. The product of reaction of phenol with soybean oil is a polymerized oil with phenol rings chemically linked to the fatty acid chains. The alkylated products were characterized by, FT-IR, 1H NMR, 13C NMR, by GPC and by the determination of viscosity, content of phenols chemically linked to the fatty acid chains, iodine value. The products of reaction of phenols with vegetable oils are promissing new raw materials for the synthesis of new hybrid aromatic-aliphatic polyols for polyurethanes and for the synthesis of new biobased phenolic resins.
Production and Enrichment of Conjugated Linoleic Acid from Corn Oil.
Seren Eryilmaz Kar, Guldem Ustun, Istanbul Technical University, Chemical Engineering Department, Istanbul, Turkey
Conjugated linoleic acid (CLA) which is a mixture of geometric and positional isomers of linoleic acid (C 18:2) has nutritional and health benefits. CLA decreases the risk of atherosclerosis and cancer and lowers the insulin resistance and body fat. Ruminant animals produce CLA naturally in their rumen from linoleic and vaccenic acids. The CLA concentrates can be produced by several methods, including alkali isomerization of linoleic acid, dehydration of ricinoleic acid, and microbial synthesis from linoleic acid using cultures of different microorganisms. In this study, the CLA concentrate was prepared from corn oil fatty acids by alkali isomerization reaction. To optimize reaction conditions, reactions were conducted at 100-160 °C, using 3-9M of KOH for 1-8h. Optimal temperature, KOH concentration and time were determined as 140 ºC, 5M and 4h, respectively. At optimal conditions, reaction product was obtained with 50.1% CLA content. Later the CLA content of the product was increased by urea fractionation studies. When the urea fractionation reaction carried out at +4 ºC using a urea-to-fatty acids ratio of 2.5 (w/w) and an ethanol-to-urea ratio of 7.0 (v/w) for 2h, the CLA concentrate containing 68.0% CLA was obtained which is to be used for food and pharmaceutical purposes.
Prevention and Elimination of Pathogens from Cooling Towers by Hydrofugation of Surfaces by Pure Short Chain Polymorphic Glycerol and Carbonic Fatty Acids Esters.
Romain Valentin1, Géraldine Giacinti1, Marion Alignan1, François Renaud3, Bernard Raymond2, Zéphirin Mouloungui1, 1ENSIACET – Unité Chimie Agro-Industrielle - UMR 1010 INRA /INP-ENSIACET, Toulouse, France, 2BR Consultant, Ondres, France, 3NOSOCO.Tech Laboratoire de microbiologie-Unité biomatériaux, dispositifs médicaux et remodelages matriciels, EA 3090 ISPB, Lyon Cedex 08, France
Manufacturing industries are constantly faced with the risk of contamination by pathogens (Legionella) in water of their cooling towers.Currently most of them use environmental non friendly curative treatments. If they have a bactericidal action, they have no action on the fixation of biofilms and constitute a dynamic reservoir of pathogens. An effective solution to this problem would be to make the wall surfaces anti-adhesive and/or bactericidal.In this study, we synthesized various highly pure glycerol and carbonic fatty acids esters. These molecules present different polar function with free polar head or locked polar head and variable hydrophobic chain lengths (7-18 carbons) giving them an amphiphilic character and polymorphic properties. Four of these esters have been selected by their biocide potential against bacterial models (low IMC <10%, mg/mL). A physico-chemical study of these bioactive biomolecules demonstrated that they present good adhesive properties for the coating of various surfaces of industrial interest. We demonstrated that a mixture of pure esters of different short chain lengths develop permanent water repellent properties because of their autoorganization in ternary aqueous system and a marked action against biofilm development.