2008 Industrial Oil Products
IOP 1.1: Oleochemicals
Chair(s): J. O. Metzger, University of Oldenburg, Germany; and D. Pioch, CIRAD AMIS, France
Plant Oil-Based Building Blocks for Self-Assembly and Soft Materials. George John, The City College of the City University of New York, New York, New York, USA
The self-assembly of low molecular weight building blocks into nanoscale molecular objects has recently attracted considerable interest in terms of the bottom-up fabrication of soft materials. The building blocks currently used in supramolecular chemistry are synthesized mainly from petroleum-based starting materials. However, biobased organic synthesis presents distinct advantages for the generation of new building blocks since they are obtainable from renewable resources. Our research efforts are deeply devoted towards developing building blocks from plant products to generate soft materials such as new surfactants, liquid crystals, lipid nanotubes and molecular gels. Present study illustrates few successful examples of generating self-assembled soft materials from agri-sources, through simple organic transformations and by enzyme catalysis. Also address the advances that have led to the understanding of chiral behaviour and the subsequent ability to control the structure of glycolipid nanostructures-derived from renewable resources-and the resulting impact of this on future material applications.
Novel Drug Delivery Systems from Vernonia Oil. S. Grinberg1, C. Linder1, V. Kolot1, R. Deckelbaum2, E. Heldman1, 1Ben-Gurion University, Beer-Sheva, Israel, 2Columbia University, New-York, USA
Targeted drug delivery is an important goal of pharmaceutical research for optimizing the pharmacokinetic and pharmacodynamic profiles of drugs. We focus on nanovesicles from bolaamphiphiles containing two hydrophilic head groups separated by a hydrophobic chain, aggregating into monolayer membranes. The potential benefits of monolayer vesicles over bilayer liposomes are higher encapsulation capacity and enhanced biological stability. Here we describe the synthesis of new asymmetric bolaamphiphiles from vernonia oil. To study the relationship between bolaamphiphiles and their aggregate nano-scale structures, amphiphiles with different aliphatic chains and head group configurations were synthesized. Critical aggregation concentration (CAC) transmission electron microscopy (TEM) and dynamic light scattering (DLS) were used to characterize the aggregates. Vesicle stability increased with longer aliphatic chains, decreased with introduction of amide, and was dependent on head group orientation. Asymmetric bolaamphiphiles form more stable vesicles than symmetrical bolaamphiphiles due to improved packing parameters.Our novel bolaamphiphiles form cationic nanovesicles with acetylcholine head groups that can be disrupted in a controlled manner when exposed to acetylcholine esterase The combination of cleavable cationic head groups and vesicle stability indicates that these vesicles may be very efficient targeting carriers for drugs.
Novel Monomers and Polymers from Plant Oils. P. Fokou, G. Çaily, A. Rybak, M.A.R. Meier, University of Applied Sciences Oldenburg/Ostfriesland/Wilhelmshaven, Emden, Germany
Within this contribution, the utilization of plant oils as renewable raw materials for monomers and polymers will be discussed. Therefore, the synthesis of novel as well as known monomers from fatty acid derivatives will be described and their subsequent polymerization discussed in detail. We will focus our discussions on the preparation and characterization of linear polymers and block-polymers via controlled and living polymerizations in order to obtain well defined novel materials from plant oils that might show application possibilities as emulsifiers, detergents, stabilizers and others. As an example, the controlled polymerization of lauryl methacrylate and other long chain methacrylates via atom transfer radical polymerization will be described in detail and the properties of the resulting polymers will be discussed. Optimizations of this reaction led, for instance, to the preparation of high molecular weight polymers (number averaged molecular weight > 140.000) with narrow molecular weight distributions (polydisperisty < 1.4) and allowed for the synthesis of well defined amphiphilic block-polymers.
Calendula Oil—A New Oleochemical Feedstock. Ursula Biermann1, Werner Butte1, Ralf Holtgrefe2, Willi Feder2, Jürgen O. Metzger1,3, 1University of Oldenburg, Oldenburg, Germany, 2Bio Pin Processing GmbH, Jever, Germany, 3abiosus e.V., Oldenburg, Germany
Interesting products can be expected by addition reactions to the reactive hexatriene system of octadec-8,10-trans-12-cis-trienoic acid (calendic acid), the main fatty acid (ca. 60%) in the seed oil of calendula officinalis.1 Calendic acid esters were obtained from the native oil by transesterification with alcohols, i.e. methanol. In a patent by DSM methyl calendulate is described as a very efficient reactive diluent.2 The solvent-free Diels-Alder reaction of methyl calendulate and maleic anhydride gave exclusively one highly functionalized cycloaddition product in 78% yield. The endo-8,12-cycloaddition product was formed with high regio- and stereoselectivity. The reaction can be applied to the native oil as well. At 200 – 300°C calendic acid methyl ester reacted in an electrocyclic reaction followed by aromatization to give an ortho-dialkyl substituted aromatic compound. Tung oil – obtained from the nuts of the tung oil tree - is a drying oil and is used for a number of products including varnishes, resins, inks, paints and coatings. In many applications as e.g. paints and coatings the substitution of tung oil should be possible by calendula oil. 1 U. Biermann, W. Butte, T. Eren, D. Haase, J. O. Metzger, "Diels–Alder reactions with Conjugated Triene Fatty Acid Esters", Eur. J. Org. Chem., 2007, 3859–3862. 2 Z. Theodorus, DSM NV (NL): EP0685543, 1995.
Synthesis of Specialty Perfumery and Favour Molecules from Castor and Coconut Oil. Dhananjay Zope, Vinod Kanetkar, Shridhar Patnekar, Perfumery and Flavour Technology Center, Dyestuff Technology Department, Institute of Chemical Technology, University of Mumbai, Matunga, Maharashtra, India
India is the world leader in castor oil and at number three in coconut oil production. 2-Octanol is obtained by the hydrolysis of castor oil and alkali fusion of the resulting ricinoleic acid. Coconut oil contains lauric acid as the main fatty acid and remaining are the other fatty acids like capric acid at 15-20 %. 1-Octanol is obtained by the reduction of the capric acid. The present paper focuses on the synthesis of more than fifteen specialty perfumery and flavour molecules such as dihydrojasmone, methyl dihydrojasmonate, 2-pentyl cyclopentanone, 2,2,5-trimethyl-5-pentyl cyclopentanone, gamma-decalactone, gamma-methyldecalactone etc. starting from 1- and 2-octanol by novel routes. 1- and 2-octanol has functionality suitable for the synthesis of such specialty aroma compounds. We had also prepared some green note aroma moieties from 1- and 2-octanol which may be used as the substitutes for the "Natural Green Note" chemicals. The volatilities and the organoleptic properties of all these molecules have also been discussed.
Design of Solid Catalysts for Selective Conversion of Renewables. J. Barrault, F. Jerome, Y. Gu, Y. Pouilloux, S. Valange, CNRS, Laboratoire de catalyse en Chimie Organique, Poitiers, France
With the aim of finding solutions to the decrease of fossil raw materials scientists focused their attention towards the use of natural products. However their conversions require the close control of the selectivity and catalysis was expected to play a pivotal role by offering tools for performing selective conversions of renewables to high added value chemicals. Recent studies showed that inorganic solid supports can directly and positively impact on the reaction selectivity. Development of mesoporous catalysts with controlled distribution of active sites is probably one of the most fascinating examples. Thanks to their porous framework these solids are able to induce a "shape selectivity" and numerous selective reactions were successfully carried out and performed in a one step process. Control of hydrophilicity of catalytic surfaces is also an important parameter. Playing with the hydrophilic properties of the catalyst surface, it was possible to limit a lot of secondary reactions and to transform carbohydrates, glycerol or hydroxylated fatty acids with yields and selectivities higher than those obtained with homogeneous and usual solid acid catalysts. In the case of synthesis of phytosterol esters dependence of the basic character of the catalysts on their structural and textural properties was emphasized and related to their catalytic properties.
Synthesis and Properties of Isostearic Acids/Esters. H.L. Ngo1, R.O. Dunn2, T.A. Foglia1, 1ERRC, ARS, USDA, Wyndmoor, PA, USA, 2NCAUR, ARS, USDA, Peoria, IL, USA
Isostearic acids are saturated branched-chain fatty acids (sbc-FAs) found in natural fats and oils but for the most part only as minor constituents. In general, sbc-FAs exhibit better low-temperature properties than their linear-chain fatty acid analogs and better oxidative stability than their corresponding unsaturated linear-chain fatty acids (ulc-FAs). Such properties make sbc-FAs ideally suited in such applications as lubricant additives, hydraulic fluids and personal care emollients. The desired sbc-FAs were synthesized by clay- or zeolite-catalyzed isomerization of ulc-FAs to unsaturated branched-chain fatty acids (ubc-FAs), which were subsequently hydrogenated to the desired sbc-FAs. The conversions and selectivities of these catalytic systems, however, were only moderate. Our group has recently found that H-Ferrierite zeolite catalyst isomerized the ulc-FAs at high conversion and selectivity. This talk will discuss the latest efforts in our group on improving the synthesis of sbc-FAs using zeolite catalysts by modification of reaction parameters and catalyst preparation. The solid zeolite catalysts developed can be recycled and reused without the loss of activity and selectivity. The physical properties including cloud and pour points, viscosity, oxidative stability and lubricity of the synthesized sbc-FAs and their esters will be presented.
Biopolymers from Novel Glycerol Polyols. D.R. Kodali1,2, 1Global Agritech Inc., Minneapolis, MN, USA, 2University of Minnesota, St. Paul, MN, USA
Glycerol is a byproduct from fatty acids, soaps, detergents and biodiesel production. Recently, the higher biofuels demand lead to increased biodiesel production doubling the volume of glycerol. This study is focused on the synthesis of new value added symmetrical polyols from glycerol that can be used as building blocks to make polymers such as polyesters, polyurethanes, acrylates and vinylethers. These polyols are symmetrical and contain primary hydroxyls. They react readily in the polymer applications without branching or cross linking. Due to molecular symmetry and steric bulk of alkoxy group the new polymers exhibit different crystallization and physical and functional properties. Due to comparable reactivity the glycerol polyols can be mixed with other polyols to prepare copolymers with unique properties and functionality. The polymers and copolymers made from the condensation of glycerol polyols and mixed polyols with terephthalic acid and their physical and functional properties will be presented. Both flexible and rigid polyurethanes can be readily prepared by reacting the glycerol-polyols with diisocyanates. Polymerization of symmetrical glycerol acrylates gave polymers with pendant hydroxyl groups. In this study, the synthesis, properties and functionality of various polymers made from renewable glycerol-derivatives will be presented.
IOP 1: Alternative Fuels
Chair(s): B. Moser, USDA, ARS, NCAUR, USA; and M. White, Renewable Energy Group Inc., USA
Biodiesel with Optimized Fatty Ester Composition. G. Knothe, USDA, USA
Biodiesel is largely composed of the mono-alkyl esters, usually methyl esters, of vegetable oils or animal fats with its fatty acid profile corresponding to that of the parent oil or fat. The different fatty esters have varying properties of relevance to biodiesel. The feedstock-dependent variations of these esters impart varying properties to biodiesel. Some of these properties of biodiesel from the different feedstocks may impede its use under certain conditions. Properties that are affected include oxidative stability, cold flow as well as cetane number and exhaust emissions. Solving these problems simultaneously has been difficult since improvement of one property often results in aggravating another problem. It is therefore of interest to formulate biodiesel fuels with fatty acid compositions that address these issues simultaneously. While esters of oleic acid are promising candidates for enrichment in biodiesel fuel, esters of other acids, specifically palmitoleic or decanoic acids may offer some advantages compared to oleic acid esters. Properties that were examined include oxidative stability, kinematic viscosity, cold flow, lubricity, heat of combustion, as well as cetane number and exhaust emissions.
The Impact of Blending Techniques, Feedstock Choice and Analytical Techniques on Biodiesel Blend Accuracy. S. Rintoul, D. Wilks, Wilks Enterprise, Inc., USA
In a recent paper on biodiesel blend quality submitted by the National Renewable Energy Laboratory, the chief problem found with biodiesel blends was inaccurate blend ratios. Incorrectly blended fuel can result in engine problems and warranty issues. The effect of blending techniques and biodiesel feedstock choice on the final blend ratio was examined and the impacts were assessed. Blending techniques that involve splash blending were found to have some risk of inaccurate blend ratios in cases where the truck has not traveled far enough to provide adequate mixing. Feedstock differences did not result in blend ratio differences, however analysis of some feedstock types were found to require separate analyzer calibration due to differences in chemical makeup in order to accurately determine the blend ratio. Finally, a comparison between the European EN 14078 biodiesel blend ratio analysis method and a low-cost filter based infrared method were compared. The filter based instrument used was a portable device which allowed for blend determination at the fuel source. The filter based infrared method was comparable in accuracy and precision to EN 14078.
Fuel Properties of Biodiesel/Ultra-Low Sulfur Diesel Blends. R. Dunn, B. Moser, National Center for Agricultural Utilization Research, Peoria, IL, USA
Biodiesel is an alternative fuel and fuel extender made from transesterification of vegetable oils or animal fats with methanol or ethanol. The National Biodiesel Board estimated that biodiesel production in the United States increased from 250 million gal in 2006 to 450 million gal in 2007. In 2006, the U. S. Environmental Protection Agency mandated that sulfur content of on-road diesel fuel be limited to a maximum content of 15 ppm to prevent poisoning of exhaust after-treatment devices required in 2007. Hydrotreating fuels to produce this "ultra-low" sulfur diesel fuel (ULSD) alters fuel properties such as lubricity and cold flow. It is known that adding 1-2 vol% biodiesel to ULSD restores the lost lubricity. However, there exists a need to better define the effects of biodiesel on fuel properties in blends with ULSD. This work examines effects of blending fatty acid methyl esters of soybean oil (SME) and used cooking oil (UCOME) on cloud point (CP), kinematic viscosity, specific gravity (SG), and refractive index (RI) in blends with low sulfur (maximum 500 ppm) diesel fuel (LSD) and ULSD. All properties tested increased with respect to increasing blend ratio (vol% biodiesel) for blends with LSD and ULSD. Blends of SME and RME in ULSD from three different sources yielded inconsistent results for CP, viscosity and SG suggesting that the processing steps for ULSD are not consistent. Some properties demonstrated they may be employed to quickly estimate or verify blend ratio in blended fuels. Finally, some SG data were converted into API gravity for biodiesel/diesel fuel blends.
Evaluation of Biodiesel Derived from Camelina Sativa Oil. N. Soriano, G. Kegel, J. Alcorn-Windy Boy, K. Richardson, Bio-Energy Innovation and Testing Center, Montana State University-Northern, Havre, MT, USA
Update on Biodiesel Test Methods and International Standards for Biodiesel and Biodiesel Blends. S. Howell, MARC-IV Consulting, Inc., Kearney, MO, USA
The AOCS Expert Panel on Biodiesel has been extremely active over the past year. Under the leadership of AOCS's Gina Clapper, efforts to conduct round robin testing on acid number analytical methods, develop new test methods for measuring sterol glucosides and mono, di-, and triglycerides in the same test run, and codify other new methods as substitutes for the current GC methods for total glycerin in biodiesel have seen considerable progress. In addition, there have been significant activities with International Biodiesel Standards within ASTM, CEN (Europe), ANP (Brazil), AOCS and ISO. This presentation will provide an update of the latest status of the test methods being address by the AOCS Biodiesel Expert Panel and the latest activity with international biodiesel standards.
The Use of Biodiesel as Blend Component: Emissions and Health Effects. J. Krahl1, A. Munack2, O. Schröder2, Y. Ruschel2, J. Schaak2, L. Schmidt2, J. Bünger3, 1Coburg University of Applied Sciences, Coburg, Germany, 2Johann Heinrich von Thünen Institute, Federal Research Institute for Rural Areas, Forestry and Fisheries (vTI), Braunschweig, Germany, 3University of Bochum, BGFA - Research for Health Protection at Workplace, Bochum, Germany
The German production capacity for biodiesel (B100) has reached almost 5 million tons. Due to the fact that a use of biofuels became mandatory, biodiesel was blended as B5 to common diesel fuel in 2007. In 2008, B7 plus three percent hydrotreated vegetable oil (HVO) has become mandatory in Germany.For the assessment of a fuel the technical and environmental effects must be evaluated.In course of a set of investigations with several engines (Euro <0, 3 and 4) it became obvious that emissions of blends show an approximately linear dependence on the blend composition, in particular when the regulated emissions are considered. However, a strongly negative effect of blends was observed with respect to mutagenic effects of the exhaust gas emissions. In detail, a maximum of the mutagenic potency was found in the range of B20. From this point of view B20 must be considered as a critical blend, in case diesel fuel and biodiesel are used as binary mixture.
Preparation of Biodiesel by Methanolysis of Crude Moringa Oleifera Oil. Umer Rashid1, Farooq Anwar1, Bryan Moser2, Gerhard Knothe2, 1Department of Chemistry, University of Agriculture, Faisalabad, Faisalabad, Punjab, Pakistan, 2NCAUR, ARS, USDA, Peoria, IL, USA
Biodiesel was prepared from the unconventional crude oil of Moringa oleifera by transesterification with methanol and alkali catalyst. Moringa oleifera oil is reported for the first time as potential feedstock for biodiesel. Moringa oleifera oil contains a high amount of oleic acid (> 70%) with saturated fatty acids comprising most of the residual profile. After acid pre-treatment to reduce the acid value of the Moringa oleifera oil, biodiesel was obtained at 6:1 molar ratio of oil to methanol, 60 °C, 1.00% (w/w) sodium methoxide catalyst, and 600 rpm agitation intensity. Fuel properties such as kinematic viscosity, cetane number, cloud point, oxidative stability, and lubricity of the biodiesel derived from Moringa oleifera oil compared well with ASTM D 6751 and EN 14214 specifications. Biodiesel from Moringa oleifera oil exhibited a high cetane number of approximately 67, one of the highest found for a biodiesel fuel. The production of biodiesel from native Moringa oleifera oil may simultaneously reduce dependence on imported fossil fuels and help alleviate the food versus fuel problem that affects rapeseed, soybean, palm, and other oilseed crops that are also traditional food sources.
Separation of Corn Oil in DDGS and Its Conversion to Biodiesel. Hossein Noureddini, Jongwon Byun, Emily Guthrie , Santosh Bandlamudi, University of Nebraska-Lincoln, Lincoln, Nebraska, USA
Fuel ethanol production is one of the fastest growing industries in the US. The annual production of ethanol exceeded 5 billion gallons in 2006. The potential for the starch and sugar-based product as raw material for ethanol production could reach to 9-10 billion gallons per year by the year 2014. In dry milling process for the production of ethanol, for every bushel of corn going into an ethanol plant about 2.65 gallons of ethanol and 16-18 pounds of dried distillers grains with solubles (DDGS) are produced. Based on the current annual ethanol production of 5 billion gallons, the annual production of DDGS was more than 10 million metric tons in 2006. The corn milling and in particular the dry grind processes need to develop technologies to refine and/or separate the unutilized corn kernel which contains significant amount of protein, starch, oil, carbohydrates and minerals into ethanol and other marketable products. This research is focused around one aspect of this perspective on the separation and conversion of oil in DDGS to methyl esters of fatty acids (biodiesel). first, extraction and centrifugation techniques were optimized for the removal of the residual oil from the corn milling by-product. The extracted oil, which contained about 3-5% fatty acids was then converted to biodiesel using a two stage acid/base-catalyzed reactions.
Influence of Minor Components on the Quality of Biodiesel. R. Verhé1, C. Echim1, V. Van Hoed1, W. De Greyt2, 1Ghent University, Faculty of Bioscience Engineering, Gent, Belgium, 2Desmet-Ballestra, Zaventem, Belgium
The biodiesel quality is strictly regulated in specifications such as the European norm EN14214 and ASTM D6751 adopted in the US. These quality parameters are greatly affected by the properties of the used feedstock and the by the technology applied to convert the vegetable oil into (methyl)esters. In this talk, the influence of minor components on the quality of biodiesel is discussed. The unsaponifiable fraction of vegetable oils contains valuable minor components such as phytosterols (free, esterified, or glucosides) and tocopherols. Their content was determined in soybean, rapeseed and corn oil before and after transesterification. The steryl glucosides have an important influence on the cold filter plugging point.Other minor components are not present in the oil but formed during the transesterification process, such as mono-and diglycerides, dimeric and polymeric fatty acids.Processes will be discussed to remove unwanted compounds from biodiesel. Reliable analytical methods are indispensable to monitor the minor components in the oil and understand their influence on the quality of the biodiesel. This knowledge helps in the choice of feedstocks and technologies in order to produce biodiesel fulfilling the quality requirements.
Precipitate Formation above the Cloud Point in Soy-, Cottonseed-, Poultry Fat-, Yellow Grease-, and Palm-Based Biodiesel Blends. Haiying Tang1, Rhet De Guzman1, Steven Salley1, John Wilson2, Simon Ng1, 1Wayne State University, Detroit, MI, USA, 2NextEnergy, Detroit, MI, USA
The formation of precipitates in biodiesel blends may have serious implications for diesel engine fuel delivery systems. Precipitates were observed in soybean oil (SBO-), cottonseed oil (CSO-), poultry fat (PF-), yellow grease (YG-), and palm oil (PO-) based biodiesel blends after storage at 4 ºC. CSO- and PF- based biodiesel had a lower mass of precipitates observed than the SBO-based. Moreover, different rates of precipitate formation were observed for the B20 versus the B100. These suggested that the formation of precipitate during cold temperature storage was dependent on the feedstock and blend concentration. The solvency effects of biodiesel blends were more pronounced at low temperature than at room temperature leading to a higher amount of precipitates formed. Fourier transform infrared (FTIR) spectra, and gas chromatography - flame ionization detector (GC-FID) chromatograms indicated that sterol glucosides are the major cause of precipitate formation in SBO- and CSO- based biodiesel; while for PF-based biodiesel, the precipitates are due to glycerides.
Butter as a Feedstock for Biodiesel Production. Michael J. Haas1, Wes Berry2, Stephen Kasprzyk3, Emily Bockian Landsburg3, Brian Ratigan3, Karen Scott1, Nadia Adawi1, 1Fats, Oils and Animal Coproducts Research Unit, U.S. Department of Agriculture, Agricultural Research Service, Eastern Regional Research Center, Wyndmoor, PA, USA, 2Process Technology Associates, Lakeland, FL, USA, 3Philadelphia Fry-o-Diesel LLC, Philadelphia, PA, USA
The acylglycerides in 348 l of cows milk (Bos taurus) butter were converted to fatty acid methyl esters (FAME) via combined esterification/transesterification in the presence of methanol. The FAME recovery exceeded 99% of maximum theoretical yield. This product was assayed according to the Standard Specification for Biodiesel Fuel Blend Stock (B100) for Middle Distillate Fuels (D 6751) specified by ASTM International. The ester product failed to meet the Standard Specifications for flash point, free glycerin content, total glycerin and total sulfur. However, subsequent analysis indicated that the sample actually deviated from acceptability only in sulfur content. The correct values of the other off-spec readings will be presented, as will a discussion of the reasons for the failure of multiple Standard Specification tests. This work illustrates some potential weaknesses in the accepted methods for biodiesel characterization when employed in the analysis of FAME preparations containing mid- and short-chain fatty acid esters.
Study of Metal Oxides Performance as Heterogeneous Catalyst in Esterification Reactions of Fatty Acids Obtained from Soybean Oil. P.A.Z Suarez, G.P.A.G Pousa, V.M. Mello, I.M. Dias, LMC-IQ-UnB, Brasilia, DF, Brazil
The growing demand for renewable energy sources stimulates the development of new technologies for biofuel production. Biodiesel synthesis by esterification of fatty acids is a favorable route, because, differently from transesterification, it uses cheaper raw material obtained as byproduct of vegetable oil neutralization. In this work the study of metal oxides performance as a Lewis acid catalyst for esterification of fatty acids obtained from soybean oil presented promising results in heterogeneous catalysis, with reaction yields up to 89%. The influence of variables such as temperature, reaction time and the amount of catalyst in the reaction's yield was also evaluated. And a study of tin oxide recycle was made, showing that it is possible to reuse the catalyst up to 10 times without significant losses in its catalytic activity.
IOP 2: Alternative Feedstocks
Chair(s): R. Hernandez, Mississippi State University, USA; and M. Norris, Agricultural Utilization Research Institute, USA
Conversion of Lignocellulosic Biomass into Triglycerides Using Municipal Wastewater Treatment Infrastructure. T. French, R. Hernandez, J. Hall, A. Mondala, G. Zhang, B. Holmes, E. Alley, H. Toghiani, Mississippi State University, MS State, MS, USA
Oleaginous microorganisms are group of naturally occurring microorganisms that posses the ability to produce up to 80% of their dry cell mass as triglycerides (i.e. biocrude). The substrates from which these microbes can produce the biocrude include, glucose, xylose, ribulose, etc. The objective of this investigation was to optimize a biological process for the conversion of lignocellulosic biomass into biocrude. MSU's research has focused on the oleaginous microorganism Rhodotorula glutinis to accumulate oil using an acid hydrolyzate of switchgrass. The initial sugar concentration of glucose and xylose in the real acid hydrolysate medium were estimated by HPLC to be 2.57 g/l and 2.06 g/l, respectively. In the first 24 hours of oil accumulation process, 78.19% of glucose and only 5.72% of xylose were consumed by the cells. In the following 24 hours, all the remainder of glucose and 77.56% of xylose were metabolized. The lipid content in the cells also increased from 2.15% to 2.70%. MSU has recently developed a consortium of microorganisms to convert lignocellulosic sugars into biocrude using a synthetic municipal wastewater formula as the growth medium. This has the potential of providing an economical means of cultivating these microbes.
Bio-Oils Production and Utilization. Roger R. Ruan, Paul L. Chen, University of Minnesota, St. Paul, MN, USA
Renewable energy is one of the most feasible long-term strategic solutions to energy security and sustainable development. In recent years, tremendous interest and investment have been directed towards production of energy from biomass, which accounts for 47% of all renewable energy or 4% of total energy in the U.S. A 2005 United States Department of Energy (DOE) and United States Department of Agriculture (USDA) report projected that 1.366 billion dry tons of forest and agricultural biomass is available per year. There is an increasing interest in the development of technologies for converting cellulosic biomass to ethanol. Another valid alternative is to convert biomass to bio-oils which can be subsequently processed into liquid fuels and biomaterials. In this presentation, we will talk about new development in thermochemical conversion of bulky biomass to high energy density bio-oils and processes for utilization of the resultant bio-oils. The working principles, process and equipment development, characterization of bio-oils of three conversion techniques, namely microwave assisted pyrolysis, hydrothermal liquefaction, and organosolvent liquefaction will be presented. Bio-oil fractionation, cleanup, upgrading, biomaterial preparation, and syngas reforming will also be discussed.
A Novel Continuous Catalytic System for Biodiesel Production. C. McNeff1, B. Yan1, A. Gyberg2, B. Krohn2, T. Hoye3, 1SarTec Corporation, Anoka, MN, USA, 2Augsburg College, Minneapolis, MN, USA, 3University of Minnesota, Minneapolis, MN, USA
A novel continuous fixed bed reactor process has been developed for the production of biodiesel using a metal oxide-based catalyst. Porous zirconia, titania and alumina micro-particulate heterogeneous catalysts are shown to be capable of continuous rapid esterification and transesterfication reactions under high pressure (ca. 3,000 PSI) and elevated temperature (300-450 °C). The continuous transesterification of triglycerides and simultaneous esterification of free fatty acids with contact times as low as 5.4 seconds is described. Biodiesel produced from a variety of oils and acidulated soapstock using this new process pass ASTM testing specifications. Furthermore the economics of this novel process is much more cost competitive due to the use of inexpensive lipid feedstocks that often contain high levels of free fatty acids.
Cuphea as a Alternative Feedstock. S. Cermak1, T. Isbell1, R. Evangelista1, R. Behle2, R. Gesch3, 1USDA-ARS-NCAUR-NCP, Peoria, IL, USA, 2USDA-ARS-NCAUR-CBP, Peoria, IL, USA, 3USDA-ARS-NCSCRL, Morris, MN, USA
Cuphea (Lythraceae) is an annual plant that produces a small oil seed rich in saturated medium-chain triacylglycerols. The initial oil characterization of a number of cuphea species was done at the USDA Research Center in Peoria, Illinois, in the early 1960's. Oil from cuphea seed consists mainly of medium-chain fatty acids that are used in the formation of lubricants, soaps and detergents. During the past 8 seasons, cuphea has been grown throughout the Midwest by both government labs and a commercial seed producer. Our lab has successfully planted, mechanically harvested, crushed, refined cuphea oil, and created derivatives for cuphea. Some challenges that cuphea has, as a new crop, are an indeterminate growth and a small seed size. With indeterminate growth, the plant flowers continuously throughout the growing season, which is a problem because the early maturing seed pods shatter and drop their seed before harvest. We have recently explored different methods of harvest to help eliminate the green harvest approaches of the past. Seed yields and herbicide types will be addressed as well future planting/harvest conditions and locations. As fuel prices increase, the demand for bio-based products will increase in the U.S. Cuphea will not replace the traditional Midwest crops such as corn and soybeans but rather be grown in areas that cannot support these traditional crops. Potential future markets and productions will be discussed.
Microalgae for Biofuel: The Opportunity and Challenge. Qiang Hu, Arizona State University, USA
Increases in fossil fuel consumption, with the concomitant reduction in national and world oil reserves and the associated environmental impact on global climate change, have stimulated an urgent need for exploration for alternative, renewable, and sustainable sources of oil feedstock for fuel production. Many microalgae can grow rapidly and have demonstrated the ability to synthesize and accumulate substantial amounts (e.g., 20~50% dry weight) of intracellular storage lipid/oil and have been recognized as a promising source of oil feedstock for petroleum replacement. In this presentation, current knowledge related to the synthesis and regulation of storage lipid/oil in oleaginous microalgae, state-of-the-art technologies for microalgae feedstock production, and the extraction and conversion of microalgal oils to liquid fuels (e.g., biodiesel, green diesel, and jet fuel) will be discussed. The major technical hurdles to a cost-affordable and energy-efficient microalgal oil production system and process will be identified and a path forward for ultimate microalgae-based biofuel commercialization will be outlined and discussed.
Development of Transportation Fuels from Algae-Derived Oil Feedstocks. A. Darzins, National Bioenergy Center, National Renewable Energy Laboratory, Golden, CO, USA
Transesterification of triacylglycerols (TAGs) from terrestrial seed crops generates a fuel known as biodiesel that can substitute for petroleum-based diesel fuel. Unfortunately, the current availability of such oils is insufficient to make a truly significant impact on the U.S. diesel market. Microalgae, unicellular, photosynthetic microorganisms, have the potential to directly convert sunlight and CO2 into lipids (i.e., TAGs) that can be can be converted into a variety of biofuels including jet fuel. Per-acre algal productivities have the potential to exceed oilseed crops by more than an order of magnitude. Microalgae, therefore, represent a new feedstock for biofuels. The DOE supported the Aquatic Species Program at the National Renewable Energy Laboratory from 1978-96 to collect and engineer microalgal strains for increased oil production. While recent events in the world energy markets have rejuvenated interest in the development and funding of biofuels research, several technological and economic challenges in microalgal production of diesel fuel substitutes must be first overcome. This talk will provide a brief overview of past algal research at NREL, technology paths leading forward, an evaluation of the potential of microalgae and a discussion of some specific research initiatives currently underway at NREL.
Modeling and Simulation of a Photobioreactor for the Cultivation of Algae to be used as a Feedstock for Renewable Fuels. N. Abunasser2,1, K.Y.S. Ng1,2, S. Salley1,2, J. Wilson3, 1Wayne State University, Detroit, MI, USA, 2National Biofuels Energy Lab, Detroit, MI, USA, 3Next Energy, Detroit, MI, USA
If algae are to be considered an economical alternative feedstock for biodiesel and other renewable fuels, an efficient cultivation method needs to be designed. One method of cultivation currently being considered is the photobioreactor. A complete mathematical model of the system would be useful to analyze and improve the productivity and efficiency and economics of the reactor. In theory, all algae needs to grow are sunlight and carbon dioxide. Unfortunately, the light intensity varies in the reactor both as a function of distance from the source and cell concentration. To date there is no complete mathematical model of the growth kinetics as a function of light intensity. The objective of the current work is to model the algal growth as a function of light intensity to aide in the improvement of the design of the photobioreactor. The photosynthetic factory model proposed by Eilers and Peeters (1988) is used to determine which cells are photosynthetically active. The variation in the light intensity is modeled initially using the Beer-Lambert equation, and then modified using experimental data. The geometry of the system is also considered in the modeling of the growth kinetics. All the equations were solved using Matlab.
IOP 3: Catalysts for Production of Oleochemicals
Chair(s): M. Jackson, USDA, ARS, NCAUR, USA; and T. French, Mississippi State University, USA
Control of Product Selectivity Using Solid Acids for the Catalytic Addition of Phenol to Hydroxy Fatty Acids. M.A. Jackson, S. Cermak, M. Appell, NCAUR, USDA, Peoria, IL, USA
The hydroxyfatty acids found in castor and lesquerella oils are excellent substrates for the study of catalytic conversion of fats and oils to new products. We have studied the addition of phenol and substituted phenols to the methyl esters of ricinoleic and lesquerolic acids over acid-functionalized mesoporous silica. Several products can be formed under the reaction conditions used including dienoic acids resulting from dehydration of the hydroxyfatty acids, Friedel-Crafts adducts formed when the aromatic ring adds to the double bond, and the target ether. Modifications of the catalyst surface have increased the selectivity toward the phenyl ether product. Molecular modeling studies support the influence of pore size on the reaction kinetics; however, effects associated with solvation and physico-chemical properties are also expected.
Efficient Ruthenium Catalyst for Epoxidation of Methyl Esters with Molecular Oxygen. S. Casciato1, V. Dubois1, Y. Pouilloux2, 1Institut Meurice, Bruxelles, Belgium, 2Université de Poitiers, Poitiers, France
Renewable raw materials are environmentally friendly, biodegradable, low cost and readily available. Vegetable oils rich in polyunsaturated chain may be used to introduce functional groups such as epoxide. Epoxidized vegetable oils have many applications as plasticizers and polymer stabilizers. Owing to the high reactivity of oxirane ring, epoxides also act as raw material for a variety of chemicals compounds. Many technologies are used to produce epoxides (percarboxylic acids, peroxides, enzymes) but the most attractive is the epoxidation with molecular oxygen due to the friendly procedure. In this work, we present an efficient green process in which the epoxidation of fatty methyl oleate ester was carried out at 80°C in the presence of molecular oxygen using metal (Ruthenium, cobalt) supported catalyst without sacrificial agent and solvent. The first results show that the catalytic activity and the selectivity to epoxide vary with the nature of metal and support (silica, alumina or charcoal). A side reaction of dimerization of fatty esters was also observed leading to a decrease of epoxide formation. The best yield is obtained over Ru/silica prepared by incipient wetness impregnation. The reaction mechanism was proposed. The influence of temperature, oxygen flow and catalyst weight have been also presented.
Cross-Metathesis of Unsaturated Fatty Acid Derivatives with Methyl Acrylate and Other Functional Reaction Partners. A. Rybak, M.A.R. Meier, University of Applied Sciences Oldenburg/Ostfriesland/Wilhelmshaven, Emden, Germany
Olefin metathesis, awarded with the Nobel Prize in Chemistry 2005 for Chauvin, Grubbs and Schrock, has emerged as a powerful tool for organic as well as polymer chemistry. Practically, this reaction results in the exchange of substituents of two reacting double bonds, a transalkylidenation. In particular, the metathesis of fatty acid derivatives obtained from plant oils is a promising catalytic route that can be used for the synthesis of chemical intermediates from renewable raw materials.Within this contribution new results on the cross-metathesis of unsaturated fatty acid esters with various functional reaction partners (e.g. methyl acrylate) will be discussed, focussing on a detailed discussion of the use of different metathesis catalysts and reactions conditions. The thus resulting functionalized esters are promising monomers for the synthesis of (novel) polymeric materials, such as polyesters and polyamides, from renewable resources. For instance, our approaches led to the development of reaction conditions for the synthesis of α,ω-diesters requiring reduced amounts of catalyst and shorter reaction times while still providing excellent yields and selectivity.
Pyrolysis of Lipids Using Various Catalysts. D.L. Compton, M.A. Jackson, NCAUR-ARS-USDA, Peoria, IL, USA
Thermochemical conversion of biomass to energy includes the potential of converting lipids to compounds that can be substituted for petroleum-based fuels and chemicals. Arguments for and against the use of agricultural lipids as feed stocks for the production chemicals and fuels lack data from which to add to or detract from either position. Pyrolysis, heating in the absence of oxygen, of lipids results in three product fractions, a trace amount of carbon char, a liquid fraction, and a gas fraction. The liquid fraction represents the majority of the pyrolysis product and consists of mostly long and medium chain alkanes. We developed equipment, instrumentation, and methods for the expedient analysis of pyrolysis reactions. This allowed for relatively high throughput screening and quantitative analysis of char, liquid, and gas fractions. We investigated the use of commercially available catalysts to affect vegetable oil pyrolysis reactions. Preliminary results showed that the use of zeolite catalysts altered the liquid fraction of the pyrolysis, producing more aromatic compounds such as toluene and naphthalene as well as affecting the ratio of the gas species. With the equipment and methods designed for small scale, high throughput analysis we hope to continue the optimization of pyrolysis reactions to yield desired products and value-added coproducts.
Elucidation of Mechanism for the Cracking of Unsaturated Lipids Using a Benchmark Catalyst and Commercial Catalysts. T. Benson, R. Hernandez, T. French, M. White, W. Holmes, Mississippi State University, Mississippi State, MS, USA
Green fuels can be produced from plant, animal, and microbial lipids via heterogeneous catalysis to form green gasoline. This research seeks to develop the cracking mechanisms as acylglycerides are reacted on heterogeneous catalysts. The catalysts used were H-ZSM-5, Zeolite Y, and silica-alumina. H-ZSM-5 is a benchmark catalyst that has been very well characterized and has shown to be an excellent catalyst for studying cracking mechanisms due to its intrinsically high acidity. Zeolite Y and silica-alumina, on the other hand, are two commonly used catalysts within the petroleum industry. Initial studies on the H-ZSM-5 indicated that cracking of the unsaturated acylglycerides (mono-, di-, and triolein) begins at the double bond within the carbon backbone of the fatty acid constituent and proceeds with cyclization to produce a multiplicity of aromatic hydrocarbons and several low molecular weight hydrocarbon gases (C2 – C6). Cracking results using Zeolite Yshowed a shift in the product yield and produced more low molecular weight unsaturated compounds and fewer aromatics. Silica-alumina, an amorphous catalyst, produced chiefly dienes (C5 – C9) and very few aromatic compounds. Also, Zeolite Y and silica-alumina catalysts produced more naphthenic compounds, which are precursors to coke.
Evaluation of Mass Spectrometry Analyzers Coupled to an Online Catalytic Cracking System. W. Holmes, T. Benson, T. French, R. Hernandez, Mississippi State University, MS, State, Mississippi USA
Conversion of lipids into fuels can be accomplished through heterogeneous catalytic cracking to form diesel and gasoline range fuels. However, analysis of cracked products, which are both gases and liquids, can be tedious and cumbersome. In this work, an in-house built reactor/analyzer was constructed using a Varian 3600 GC. This cryogenic capillary catalytic cracker, termed the Quatra C, was used to react and analyze model lipids. In this work, a comparison has been made between different MS analyzers. A benchtop ion trap (Varian Inc., Walnut Creek, CA) and a magnetic sector (Thermo Finnigan, San Jose, CA) were used to perform mass spectral analysis for real-time reactions as lipids were passed over a bed of highly acidic ZSM-5 catalyst. While the standard bench-top MS is capable of most analyses, the magnetic sector allows one to scan a wider range of masses. Product gases as low as hydrogen can be determined and unreacted high molecular weight feedstock can also be quantified for mass balance calculations. Benchtop systems have a limited mass range but have a lower detection limit in scan mode. Spectral quality along with linearity and detection limits were compared for both detectors as applied to this application.
Synthesis of Biodiesel from Greases with Heterogeneous Catalysts. H. Ngo1, N. Zafiropoulos2, T. Foglia1, E. Samulski2, W. Marmer1, W. Lin2, 1USDA-ARS-ERRC, Wyndmoor, PA, USA, 2UNC-Chapel Hill, Chapel Hill, NC, USA
Development of efficient technologies for biodiesel (BD) production is becoming increasingly important in order for BD to be cost-competitive. The established base-catalyzed transesterification procedures work well with refined vegetable oil, but not with less expensive high free fatty acid-containing feedstocks. In this talk, I will discuss the design of new heterogeneous acid and base catalysts for efficient two-step synthesis of BD from free fatty acid (FFA)-containing feedstocks. A series of highly active porous diarylammonium solid catalysts were prepared and examined for BD synthesis. The diarylammonium catalysts supported on highly crosslinked polymers (POP) and mesoporous (MCM-48 and SBA-15) materials were fully characterized by BET surface area measurements, IR, and SEM. The immobilized solid acid catalysts are very active for esterification of FFA in the greases to fatty acid methyl ester (FAME) with a FFA to FAME conversion ranging from 95% to 98.5%. However, the remaining glycerides in the greases require base catalysts to convert to FAME. Thus, we developed a heterogeneous base catalyst for this purpose. In the presence of the new solid base catalyst, the glycerides in the greases were converted to FAME at >99% conversion. The development of these porous catalysts may open up a new avenue for the production of BD from less expensive high free fatty acid-containing feedstocks.
Biodiesel Production by Simultaneous Esterification and Transesterification. Shuli Yan1,2, Manhoe Kim1,2, John Wilson2, Steven O. Salley 1,2, Simon K. Y. Ng1,2, 1Wayne State University, Detroit, MI, USA, 2Next Energy, Detroit, MI, USA
As biodiesel is nontoxic, renewable and beneficial for environmental protection, it is considered as an alternative fuel to traditional petroleum-based fuels. A major barrier to the commercialization of biodiesel is its high production cost, which is primarily related the cost of refined vegetable oils as raw material. Using waste oils is potentially a more economical source for biodiesel production. However waste oils generally contain significant free fatty acids (FFA) and the current catalytic approach is to use a two-step process to handle oils with high FFA content. In this study, we developed a one-step process based on strong cation resin catalysts and ZnO-based catalysts. It is known that solid acids having large pores and moderate to strong acid sites would be active for esterification and transeseterification. Resins with different acidity, pore structure, cross-linking degree and particle size were investigated. It was found that the strong acidic group played an important role in both esterification and transesterification reactions. Moreover, a trace amount of HSO4- in reaction mixtures also had a positive effect on the yield of fatty acid esters. In addition, ZnO-based catalysts with varied surface composition were found to be effective in both esterification and transesterification
A New Catalyst System for Glycerol Hydrogenolysis. J.Y. Bergeron, G. Hersant, Oleotek Inc., Thetford Mines, QC, Canada
This research effort is aimed at the recent challenge of producing commodity chemicals via the catalytic transformation of starting materials from sustainable sources employed as substitutes for petrochemical-based oils and fuels. Due to the fast development of the biodiesel industry, increasingly large amounts of glycerol are available as a reaction by-product. Any attempt to integrate glycerol in the existing chemical production chain must ideally proceed through the controlled deoxygenation of this overfunctionalized molecule.We developped a new catalyst system based on ternary mixed oxides of transition metals and alkaline earth metals, which is used to selectively produce 1,2-propanediol. Concentrated aqueous solutions of glycerol were reacted at temperatures below 250°C and at low H2-pressure in the presence of these catalysts. The composition of the ternary catalyst was finely tuned using statistical methods (Design of Experiment, DoE) in a systematic sequential study.For the best catalyst compositions, the glycerol conversion reached 72% with a selectivity toward 1,2-propanediol production of nearly 95%. Since no optimization was done on the physical properties of the catalyst (cristalline state, porosity, active sites concentration, etc) and only a rough screening of the the reaction parameters was conducted, these results are extremely promising.
Catalytic Transformation of Glycerol to Higher Value Added Chemicals. F. Jérôme, G. Yanlong, A. Karam, J. Barrault, Université de Poitiers CNRS, Poitiers, FRANCE
Since the last ten past years, glycerol has gained considerable attentions. Indeed, glycerol is the main co-product of the vegetable oil industry and the rapid expanding of the biodiesel demand is creating a significant glut of the glycerol market. Transformation of glycerol to higher value added chemicals has become a huge industrial challenge but requires overcoming various obstacles linked to the glycerol viscosity, hydrophilicity and polyfunctionality. Here, we report that organomodified silica catalysts are better adapted than usual solid or homogeneous catalysts for performing efficient and selective transformations of glycerol to higher value added chemicals. Indeed, hydrophilicity of these solid catalysts was favorably used to successfully perform (i) the selective esterification of glycerol with hydroxylated fatty acids and (ii) the selective dehydrative etherification of glycerol with various alcohols including fatty allylic ones. This catalytic route allowed us to selectively synthesize in a one step process various glycerol based structures not accessible by conventional catalytic or organic routes. Particularly, synthesis of new and innovative glycerol-based structures such as elaborated and robust surfactants or monoalkylglycerylethers, which exhibit a wide spectrum of biological applications, are reported.
IOP 4: Lubricants
Chair(s): D. Kodali, Global Agritech Inc., USA, and Department of Bioproducts and Biosystems Engineering, University of Minnesota; and R.B.N. Prasad, Indian Institute of Chemical Technology , India
Development of Biolubricants from Non-Edible Oils. R.B.N. Prasad, Indian Institute of Chemical Technology, Hyderabad, Andhra Pradesh, India
In recent years, concern over the usage of petroleum based products and their impact on environment has created an opportunity to promote environmental-friendly biodegradable lubricants from agricultural feedstocks. Vegetable oils are promising candidates for eco-friendly lubricants as they are derived from renewable resources. In contrast to mineral oil, vegetable oil-based lubricants are environmentally safe, possess good lubricity and viscosity-temperature characteristics and low evaporation loss. The major limitations of vegetable oils as lubricants are oxidative stability and low temperature behavior and need to be improved by a variety of measures like modifying the unsaturated fatty acids present in the oil or to exchange the glycerol moiety by the other polyols like trimethylolpropane or to improve the additive technology. Over the past few years, technological advances have improved the performance of bio-based lubricants, and at the same time, with increasing oil prices and energy security needs, vegetable oils have become cost-competitive with traditional petroleum lubricants. In European countries and USA, oils like rapeseed, soybean, palm and canola are being exploited for lubricants. In India the situation is different as the demand for edible oils is heavy leaving only the non-edible oils as potential source as feed stocks for bio lubricants. The non edible oils currently being available in India include castor, neem, karanja, jatropha mahua etc., Out of these, the chemistry of castor oil centered on its high content of ricinoleic acid (12-hydroxy octadecenoic acid) and this oil has an extraordinary potential for the preparation of variety of lubricant base stocks. The presentation reviews the status of non-edible oil-based lubricants and describes the related work carried out based on castor and karanja oils in the author’s laboratory
Fatty Acid Derivatives as Potential Biolubricants. L. Yao, E.G. Hammond, T. Wang, Iowa State University, Ames, IA, US
The urgent need for replacing petroleum-based lubricants with sustainable and environmental friendly alternatives has encouraged the study of vegetable oil-based materials to make biolubricants. Our studies have focused primarily on molecules that might be made by biosynthesis in genetically altered oilseed plants. Lubricants based on fatty acids often have high melting points if saturated or poor oxidative stability if polyunsaturated. In this study we synthesized fatty acid derivatives by transesterification with sodium alcoxides or Candida antarctica lipase and investigated their properties. The products we studied include:  ricinoleate esters and 12-acetyl ricinoleate esters with normal alcohol moieties of chain lengths 1 to 5 as well as isopropyl esters,  mono- and di-oleates of ethylene glycol, 1,2-propylene glycol, and 2,3-butanediol,  12(decanyl)-methyl ricinoleate, and 12(10-undecenyl)-methyl ricinoleate. Silica gel chromatography and silver ion chromatography were used to attain purities of 95-99%. The melting points and viscosities were measured and some of these compounds showed viscosities and melting points suitable for biolubricants. Ricinoleate esters melted between -3 and -43°C and have viscosities of ~130 to 180 cp at -5°C, and 4 cp at 80°C. 2,3-Butanediol mono-oleate melts at -48°C with viscosities of 237 and 5 cp at -5°C and 80°C, respectively.
Biolubricants from Novel Glycerol Polyols. D.R. Kodali1,2, 1Globalagritech Inc., Minneapolis, MN, USA, 2University of Minnesota, St. Paul, MN, USA
In the past decade, the biolubricants development to substitute synthetic esters, as alternatives to mineral oil derivatives has intensified. The synthetic lubricants market in US is about a billion dollars per year and synthetic esters comprise one third of this segment. The ester lubricants provide better functionality such as boundary lubrication, high viscosity index and ready biodegradability. The synthetic esters are made from acids and polyols. The preferred polyols used are neopentyl glycol, trimethylolpropane and pentaerythritol. The glycerol and polyglycerols are also used in making ester lubricants. However, there are couple of disadvantages associated with glycerol esters - they being, difficulty to esterify the secondary hydroxyl and the decreased heat stability of products due to the hydrogen atom attached to secondary hydroxyl. In the present study novel glycerol esters are synthesized as better lubricants where these short comings are minimized or eliminated. The structured alkyl glycerol esters of this study contain only primary ester functionality and prepared by esterification or transeserification with acids or esters. Some of the glycerol derivatives made in this study show excellent low temperature properties, fluidity up to -45°C. This presentation will provide synthesis and properties of glycerol esters as lubricants.
Lubricant Properties of Ester Hydroxy Derivatives of Methyl Oleate. S.Z. Erhan1, B.K. Sharma1,2, K.M. Doll1, 1USDA, NCAUR, ARS, Peoria, IL, USA, 2Pennsylvania State University, University Park, PA, USA
The advantages of vegetable oil based products are their eco-friendly and non-toxic nature. The disadvantages of vegetable oils, such as poor oxidation and low temperature properties, can be improved by attaching functional groups at the sites of unsaturation through chemical modifications. In this study, we have shown how functionalization helps overcoming these disadvantages. Five branched ester structures were prepared from commercially available methyl oleate and common organic acids; and their lubricant properties were determined. These branched esters are characterized as a-hydroxy ester derivatives of methyl oleate. These derivatives show improved low temperature properties over olefinic oleochemicals by pour point and cloud point measurements. The derivatization also increased thermo-oxidative stability, measured using both Pressurized Differential Scanning Calorimetry (PDSC) and Thin Film Micro Oxidation (TFMO). Tribological behaviors were evaluated as additives, in soybean oil and polyalphaolefin, using four-ball and ball-on-disk configurations. These derivatives have good anti-wear and friction-reducing properties at relatively low concentrations under all test loads. Overall, the data indicate that some of these derivatives have significant potential to be used as a lubricating base oils or additives.
Derivatives of Alkenyl Succinic Anhydrides as Novel Industrial Agro-Lubricants. F. Stefanoiu, C. Vaca-Garcia, E. Borredon, Université de Toulouse - UMR1010 Chimie Agro-Industrielle, ENSIACET, INPT, INRA, Toulouse Cedex, FRANCE
Alkenyl Succinic Anhydrides (ASA) were synthesized from high oleic sunflower alkyl esters. They were tested as possible biolubricant additives or bases. They showed interesting properties in both domains.Further modification of these ASA molecules were performed with phosphor-containing and nitrogen-containing compounds. The molecules obtained and their performance in the domain of biolubricant additives will be presented.
Lubricants Sourced from Vegetable Sources - An Eco-Friendly Tribological Solution for the Future. R.T. Mookken, Indian Oil Corporation Limited, India
Conventional Lubricants which are based on Group I and Group II / III base oils cause considerable damage to the environment whether they are in fresh or in used condition, mainly because of their high potential of serious water pollution due to toxicity and relatively poor bio-degradability leading to environmental contamination. There is an environmental needto protect the ecology from the pollution of conventional lubricating oils. Vegetable source based lubricants which come under Group-V category will be able to avoid environmental pollution due to their inherent biodegradabiity characteristics. The properties of some of theeco-friendly lubricants specially developed for environment sensitive applications havebeen studied in detail specially their tribological properties. The vegetable sourced base oils are either used as such or in the modified form in these lubricants. Comparative evaluation of thethermo-oxidative stability and hydrolytic stability has also been done among conventional and eco-friendly equivalent formulations in the study.Lubricant formulators are seriously looking into vegetable sourced base materials for incorporating in different type of lubricants.
IOP 5: General Industrial Oils Products
Chair(s): T. Isbell, USDA, ARS, NCAUR, USA; and M. Dasari, Feed Energy Company, USA
Glycerol Use as a Fermentation Feedstock in the Synthesis of New Industrial Biochemicals. R. Ashby, D.K.Y. Solaiman, T.A. Foglia , USDA, ARS, ERRC, Wyndmoor, PA, USA
As the cost of petroleum continues to rise, renewable fuels are becoming more attractive as potential alternatives in the energy arena. Biodiesel (fatty acid alkyl esters) is one such fuel that is derived from the transesterification of animal fats and vegetable oils and is quickly being acknowledged as a safe, reliable alternative in many applications where petroleum has customarily been used. According to the National Biodiesel Board (NBB) in 2007 alone the US produced approximately 450 million gallons of biodiesel which resulted in the simultaneous generation of roughly 45 million gallons of glycerol. The increased availability of glycerol lowers its value and negatively impacts biodiesel economics. As a result, there is a pressing need to discover new outlets for glycerol to help stabilize biodiesel production costs and alleviate potential disposal problems. Our laboratories focus on the research and development of biological processes that utilize glycerol (both pure and crude, derived from the biodiesel industry) as a feedstock for the fermentation-based synthesis of microbial polyesters (e.g, polyhydroxyalkanoates), polyamides (e.g, gamma-polyglutamic acid) and glycolipid surfactants (e.g, sophorolipids). We believe that by expanding the assortment of possible glycerol-based bio-products it will be possible to advance the use of fermentation as an additional outlet for the biodiesel coproduct stream thus helping to improve biodiesel production costs and at the same time make biobased products accessible to the consumer public.
Oil Accumulation by Sewage-Grown Oleaginous Microorganisms. A.T. Ford, W.T. French, R. Hernandez, B. Holmes, Mississippi State University, Mississippi State, MS, USA
The looming energy crisis and recent research in renewable fuels has led to an understanding that any solution will most likely involve many different strategies. The ability of certain microorganisms to accumulate oils utilizing sugars as substrates has long been known. In this paper we examine the potential for using a consortium culture of oleaginous microorganisms along with the current infrastructure of wastewater treatment facilities to provide an inexpensive source for growth media. Previous work has demonstrated sewage wastewater to be an excellent source for inorganic nutrients. Using sewage supplemented with additional carbon sources, greater cell yields than those obtained using commercially available sources were acquired. Next this consortium of oleaginous microorganisms was offered sugars from acid hydrolyzates to begin triglyceride accumulation. Preliminary results show that at least 20% conversion rates of oil from sugar are possible using individual members of the consortium. Thorough examination of optimum sugar concentration and growth conditions is expected to increase these yields. The combination of low cost substrates using the infrastructure already in place (i.e. wastewater treatment facilities) and lignocellulosic sugars strengthens the potential to produce billions of gallons of renewable feedstock for the production of biodiesel or renewable diesel.
Conversion of Wastewater Treatment Facilities into Biorefineries. J. Hall, T. French, R. Hernandez, A. Mondala, M. White, B. Holmes, A. Brown, Mississippi State University, Mississippi State University, MS, USA
Oleaginous microorganisms can produce up to 70 percent of their body weight in oil. The use of these microorganisms as a source of oils for biofuel production is limited by the availability of cost effective carbon and water sources. A growth medium that has not been introduced for cultivating oleaginous microorganisms is municipal and industrial wastewater. This study is designed to determine if a consortium of oleaginous microorganisms can be cultivated on municipal wastewater to produce an abundant amount of oil while treating this water to Environmental Protection Agency (EPA) required levels. These experiments were conducted in a batch process using synthetic wastewater, proposed by LaPara et al. Oil percentage, oil yield, and growth rate are measured using well-established techniques. Also, water quality was measured by determining the biochemical oxygen demand (BOD), the chemical oxygen demand (COD), and the amount of nitrates in the wastewater after the yeast growth stabilizes. These quantities will determine the efficacy of the oleaginous microorganisms assist in removing wastewater contaminants. Preliminary results show that the microorganisms are reaching the oil accumulation stage after 24 hours of cultivation. This modification could potentially generate billions of gallons of oil for producing biofuels.
Fuel Quality Parameters of Functionalized Fatty Acid Methyl Esters. K. Wadumesthrige1, S. Zeng1, M. Winston-Galant1, J Wilson2, S. Salley1, K.Y.S Ng1, 1Department of Chemical Engineering and Materials Science, Wayne State University, Detroit, MI, USA, 2NextEnergy, Detroit, MI, USA
Biodiesel, which is defined as fatty acid methyl esters (FAME) derived from renewable biological sources is considered as a possible substitute of conventional diesel fuels. The fuel quality parameters as described in ASTM D 6751, biodiesel specification, depend on various individual FAME in biodiesel. In fact, the properties of various fatty esters are determined by the chemical structure of the fatty acid chain and that of alcohol part of the ester. Chemical structures that affect the fuel properties of FAME molecule are chain length, degree of unsaturation, branching of the chain and other chemical functional groups such as hydroxyl and epoxide groups. In this work the chemical structure of fatty acid chain was modified by chemical conversions such as catalytic hydrogenation, epoxidation and oxidation under mild conditions. The hydrogenated FAME showed higher oxidation stability but poorer cold flow properties whereas addition of hydroxyl groups in the fatty acid chain yields biodiesel with better cold flow properties and acceptable oxidation stability. Other fuel quality parameters such as cetane number, lubricity, heat of combustion and viscosity of these modified FAMS will be discussed. These results will be helpful to improve better fuel quality additives for both biodiesel and conventional petroleum diesel.
Utilization of a Supercritical Fluid Medium for the Generation of Renewable Chemicals from Oleic Acid. D. Sparks1, R. Hernandez1, A. Estévez2, E. Alley1, T. French1, 1Mississippi State University, Mississippi State, MS, USA, 2University of Puerto Rico at Mayagüez, Mayagüez, Puerto Rico
As petroleum prices continue to increase, alternative sources of fuels and chemicals traditionally derived from petroleum must be identified. For example, many lipid sources contain unsaturated fatty acids, which can be oxidized to form a variety of products such as diacids and epoxides. These chemicals are valuable intermediates for the formulation of pharmaceuticals, herbicides, detergents, plasticizers, lubricants, paints, and other useful products. Oleic acid is one of the most common unsaturated fatty acids found in biomass. In this paper, a kinetic analysis of oleic acid oxidation with potassium permanganate was performed, and the results were compared to carrying out the reaction in sub- and supercritical carbon dioxide. The different solubility of the reaction products in the supercritical mixture can be employed to perform reaction and fractionation in one step. Furthermore, since carbon dioxide is already completely oxidized, reactions in SC-CO2 minimize the production of unwanted reaction by-products.
Enzymatic Synthesis of Wax Esters from Fatty Acids of Linseed Oil. R. Bernier, J.Y. Bergeron, G. Hersant, OLEOTEK, Thetford Mines, QC, Canada
The main objective of this project was to combine the siccative properties of highly unsaturated oils to the protective properties of the esters of fatty acid and alcohols to obtain an effective protective agent for wood possessing the resistance to the external attacks conferred by drying oil. In this project, fatty alcohols were chosen to give wax its surface pores filling properties whereas polyunsaturated fatty acids (PUFA) content will confer mechanical resistance and good surface protection.To protect the chemical stability of the polyunsaturated fatty acids, the synthesis of wax esters was made by enzymatic way rather than by classic methods requiring higher temperature that degrades PUFA's. Furthermore, synthesis was carried in the absence of solvent which is a technical, economical and environmental advantage. This new protection agent for wood based on wax esters made from highly unsaturated oils should stimulate interest with the concerned industries, such as woodworking industries trying to use bio-based products. This presentation will review the approach and results for the synthesis of wax esters by enzymatic way.
Catalytic Activities of Vanadia Loaded Heterogeneous Catalysts on Transesterification of Soybean Oil with Methanol. Manhoe Kim1,2, Shuli Yan1,2, Huali Wang1,2, John Wilson2, Steven O. Salley1,2, K.Y. Simon Ng1,2, 1Wayne State University, Detroit, MI, USA, 2Next Energy, Detroit, MI, USA
Vanadium oxide was loaded on three different supports including nano ceria, titania, and nano-ZSM-5 using an impregnation method and a grafting method. Catalytic activities of the V-loaded catalysts were evaluated in the transesterification of soybean oil with methanol. The oxidation state was studies by means of X-ray photoelectron spectroscopy for fresh as well as used catalysts. XRD and SEM (w/EDS) were also applied. VOCl3 grafted nano-ZSM-5 was found to be the most promising catalyst, exhibiting the highest ester yields. Experimental parameters such as loading method, amount of loadings, precursor species loaded, supporter species, calcination and reaction temperature effects, and deactivation phenomena were also investigated.
Physical Properties of Polyurethanes Prepared from Erucic Acid Based Aromatic Trialcohol Monomers. M.-J. Dumont, S.S. Narine, University of Alberta, Edmonton, Alberta, Canada
Hexasubstituted benzene of aromatic trialcohols monomers have been synthesized from erucic acid. Their isomers-symmetric and asymmetric benzene- have been separated using a combi-flash apparatus. These isomeric monomers have been polymerized into polyurethanes. The new properties of these polymers have been studied using Fourier transform infrared (FTIR), Wide-angle X-ray diffraction (WAXD), Differential scanning calorimetry (DSC), tensile properties, thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and modulated differential scanning calorimetry (MDSC).
Thermoplastic Elastomers from Vegetable Oils. Z. Petrovic, Y. Xu, Pittsburg State University, USA
Properties of thermoplastic polyurethane elastomers (TPU) are related to their composition. Segmented TPUs were prepared from polyricinoleate diols, MDI and butane diol. The morphology of polyurethanes varied from the dispersed hard domains in the matrix of the soft phase to the co-continuous hard and soft phases, the former giving soft and the latter hard elastomers. Dangling chains in the soft phase prevented crystallization of the soft phase and contributed to the low glass transition. The effect of sample morphology on mechanical properties is discussed.
Industrial Oil Products Posters
Chair(s): R. Dunn, USDA, ARS, NCAUR, USA
Low Temperature Properties and Thermal Stability of Oligomerized Soybean Oil.
Zengshe (Kevin) Liu, Brajendra K. Sharma, Sevim Z. Erhan, FIO, NCAUR/ARS/USDA, Peoria, IL, USA
Soybean oil polymers with lower molecular weight prepared in supercritical carbon dioxide (scCO2) by cationic polymerization were investigated for their applications as lubricants and hydraulic fluids. The low temperature properties were studied by measuring their cloud and pour points, while thermo-oxidative stability of oligomeric soybean oil was studied using pressurized differential scanning calorimetry. Results show that increasing viscosity of soybean oil results in lower oxidation stability, and increased pour and cloud points. These high viscosity soybean oils are desired in formulations of biobased gear oils and greases.
Preparation, Characterization, and Properties of 1,2-Isopropylidene Glycerol Carbonate.
J.A. Kenar, NCAUR, ARS, USDA, Peoria, IL, USA
The utilization of excess glycerol supplies derived from the burgeoning biodiesel industry is of major importance to the oleochemical industry as the economic viability of the biodiesel and oleochemical industries are closely linked to glycerol prices. Carbonate compounds based on glycerol, such as glycerol carbonate, are gaining prominence due to its simple preparation, interesting properties and chemistry. The synthesis, physical properties, and chemistry of an interesting glycerol-based carbonate (4, bis[(2,2-dimethyl-1,3-dioxolan-4-yl)methyl] carbonate) is presented. This carbonate was prepared in 65-70% isolated yields by an interchange reaction between isopropylidene glycerol (solketal) and diethyl carbonate in the presence of sodium methoxide catalyst. The carbonate was characterized using Fourier transform infrared spectroscopy (FTIR), 1 H and 133C nuclear magnetic resonance spectroscopy (NMR), and gas chromatography-mass spectrometry (GC/MS). Physical properties of the carbonate such as kinematic viscosity, refractive index, melting point, as well as the lubricity were determined. Hydrolysis of carbonate's isopropylidene groups gave the corresponding polyol (6, bis(2,3-dihydroxypropyl) carbonate) in yields of 84%. The polyol carbonate was characterized by 1H and 13C NMR and represents a potentially interesting polyol.
Zinc Hydroxide Nitrate as a New Catalyst for Biodiesel Production.
C.S. Cordeiro, G.G.C. Arizaga, F. Wypych, L.P. Ramos, Department of Chemistry, Federal University of Paraná, Curitiba, Paraná, Brasil
The performance of layered double hydroxides (LDH) as heterogeneous catalysts for biodiesel synthesis has been attributed to the alkalinity of its whole outer surface. LDHs are based on the mineral brucite (Mg(OH)2) and are obtained when the M+2 cation is isomorphically substituted by M+3, with the generated excess of layer charge compensated by the intercalation of hydrated anions. One attractive alternative to LDHs are the compounds referred to as layered hydroxide salts (LHS) because they have a pronounced anionic exchange capacity in a structure based in one single metal. The LHS compound zinc hydroxide nitrate (Zn5(OH)8(NO3)2.2H2O, ZHN) was tested for the alcoholysis of triacylglycerols (palm oil) and for the esterification of free fatty acids (lauric acid) using methanol and ethanol (99, 95 and 90% proof). The catalytic activity was higher at 140ºC and catalyst concentrations of 4% were enough to achieve high conversion rates in 2 h. Total ester contents above 95 wt% were obtained in single step esterification and transesterification reactions and glycerin streams up to 94 wt% were recovered as a result of methanolysis. Therefore, ZHN is suitable for processing low cost feedstocks of high acid number and offers several additional advantages as it is totally safe for handling and very easy to synthesize and/or recycle.
Pre-Ozonation of Primary Municipal Wastewater Effluent for the Cultivation of Oleaginous Microorganisms.
A. Mondala1, R. Hernandez1, T. French1, L. Estévez2, J. Hall1, 1Mississippi State University, Mississippi State, MS, USA, 2University of Puerto Rico Mayagüez, Mayaguez, PR, USA
Municipal wastewater treatment facilities have a great potential for oil production in addition to treating wastewater to conform to US Environmental Protection Agency standards by cultivating in the wastewater oleaginous microorganisms. These microorganisms can accumulate 20–70% of their biomass as lipids under excess carbon and nutrient-limited conditions, and can utilize the Biochemical Oxygen Demand (BOD5) of the wastewater for this purpose. To achieve this, elimination of the indigenous microorganisms in the wastewater while improving its biodegradability was necessary.This paper describes the use of ozone to disinfect, improve the biodegradability by increasing the BOD5 , and establish a nitrogen- and phosphorus-limited condition in a primary-treated wastewater. The samples were treated with five different ozone concentrations at a rate of 0.94 Liters per minute. Results show that ozone effectively reduced the indigenous microbial population by as much as 4–log units. Following kinetic analysis, the disinfection data was found to fit m-th (1 ≤ m ≤ 2) order kinetic models satisfactorily (R2 ≥ 0.99). Furthermore, the BOD5 increased and the ammonium and phosphate concentrations were found to have no significant changes.
Canola Oil Ethyl Ester and Canola Oil Ethyl Ester Blended Diesel Fuels as Alternative Fuels.
Asli Isler, Filiz Karaosmanoglu, Istanbul Technical University, Department of Chemical Engineering, Maslak, Istanbul, Turkey
Biofuels are the important biorefinery products of biobased product technology and vegetable oil market. Biofuel industry is gaining one of the most important markets in our century. Biobased industrial products are introducing with increasing rate into our daily life and these occur as "Environmentally Friendly Products" in the forms of biomaterials, biochemicals and biofuels. Today, biodiesel is available as the first generation of biofuels. Biodiesel is one of the most important biofuels, which is used intensively all around the world. In EU, the share of biodiesel in the biofuel sector is 80%. According to the existing standarts biodiesel is defined as fatty acid methyl esters. Also fatty acid ethyl esters can be used as alternative fuels and after 2010 in parallel with the application of vehicles with flexible fuels, it is thought that ethyl esters will take part as diesel fuels, too. Biodiesel and fatty acid ethyl esters can be used directly or they can be appreciated as blends with diesel fuel in the fuel sector. In this study, fuel properties of Turkey originated canola oil ethyl ester and canola oil ethyl ester blended diesel fuel are determined. The fuel properties of Turkey originated canola oil ethyl ester are determined according to the standart TS EN 14214. Furthermore, 2% and 5% v/v canola oil ethyl ester are blended with diesel fuel in order to obtain alternative diesel fuels and fuel properties of these alternative diesel fuels are determined according to the standart TS 3082 (EN 590). Lubricity properties are examined, too. As a result, canola oil ethyl ester and diesel blended with canola oil ethyl ester are presented as alternative diesel fuels.
New Hyperbranched Soybean Polyols.
Mihail Ionescu, Ivana Cvetković, Zoran Petrović, Pittsburg State University, Kansas Polymer Research Center, Pittsburg, Kansas, USA
A new synthetic pathway to hyperbranched soy-polyols by the ring opening polyaddition of cyclic ethers containing hydroxyl groups (glycidol, trimethylol propane oxetane) to the hydroxyl groups of some soy-polyols was investigated. The reaction involves the stepwise addition of the hydroxy-cyclic monomers to the soy polyol in the presence of Brőnsted or Lewis acids as catalysts (HBF4, triflic acid, BF3*Et2O etc.), in mild reaction conditions: 30-60oC and at atmospheric pressure. As a general rule by the addition of one hydroxy-cyclic monomer unit to one hydroxyl group generates a new structure with two hydroxyl groups. The synthesized hyperbranched soy-polyols are very viscous liquids to solids and were characterized by gel permeation chromatography, FT-IR and by determination of Mn, Mw, hydroxyl numbers, acid values, viscosity and density. The hydroxyl numbers of the obtained hyperbranched soy-polyols varied between 300 and 600 mg KOH/g and the functionality between 8 and 40 hydroxyl groups/mol. The hyperbranched soy-polyols have a big potential in various polyurethane formulations to increase the hardness of flexible polyurethane foams, as co-polyols in rigid polyurethane foams or as cross-linking agents.
Evaluation of Myricetin as an Antioxidant Additive in Soybean Oil Methyl Esters.
B. Moser, USDA ARS NCAUR, Peoria, IL, USA
Biodiesel, an alternative fuel obtained by methanolysis of triacylglycerides, is considerably more susceptible to autoxidation than petroleum diesel fuel. Treatment with antioxidant additives is a commonly used strategy to delay oxidative degradation of biodiesel. Flavonoids are previously unexplored with respect to oxidation stability of BD. The current study reports the efficacy of myricetin as an antioxidant additive in soybean oil methyl esters (SME), along with a comparison with a-tocopherol and TBHQ. The Rancimat method, EN 14112, was employed with measurements taken every 30 days over the course of a 90 day period at load levels of 0, 100, 500, and 1000 ppm in SME. It was discovered that the level of effectiveness was TBHQ > myricetin >> a-tocopherol. Also, a-tocopherol was found to have a pro-oxidant effect on SME. As expected, synergy among mixtures of antioxidants were more effective than single antioxidants at delaying oxidative degradation of SME.
Synthesis of Sodium Cis-12, 13-Epoxy-Cis-9-Octadecenyl Sulfonate from Vernonia Oil.
N.S. Johnson1, D.C. Sutton1, C. Hlongwane1, F.O. Ayorinde1, 1Department of Chemistry, Howard University, Washington, DC, USA, 2Department of Chemistry, Howard Univerisity, Washington, DC, USA, 3Department of Chemistry, Howard University, Washington, DC, USA, 4Department of Chemistry, Howard University, Washington, DC, USA
A water-soluble, foaming epoxyalkene sulfonate, cis-12,13-epoxy-cis-9-octadecenyl sulfonate has been synthesized from vernonia oil (VO) by a series of simple reactions that include transesterification, metal hydride reduction, tosylation. Conversion of VO into vernonia oil methyl esters (VOME) using sodium methoxide was quantitative. Subsequent reduction of VOME with lithium aluminum hydride yielded cis-12,13-epoxy-cis-9-octadecenol (78% yield), along with minor amounts of hexadecenol, octadecenol, cis-9-octadecenol, and cis-9,12-octadecandienol. The cis-12,13-epoxy-cis-9-octadecenol was tosylated with p-toluenesulfonyl chloride to give cis-12,13-epoxy-cis-9-octadecenyl tosylate at 96% yield. Iodination of the tosylate and subsequent substitution reacation with sodium sulfite afforded cis-12,13-epoxy-cis-9-octadecenyl sulfonate (63% yield).This study demonstrates the ability to produce an epoxyalkenyl sulfonate, belonging to a class of anionic surfactants, from vernonia oil without destroying the epoxy functionality in the cis-12,13-epoxy-cis-9-octadecenyl moiety of vernonia oil. Preliminary data suggesting the potential application of the epoxy-sulfonate as a surfactant will also be discussed.
Production of Hydrogen-Rich Gas from Biodiesel By-Products on Ni/Metaloxide-Ceria Based Catalysts.
Gaurav Nahar1,2, Manhoe kim1,2, John Wilson2, Steven O. Salley1,2, K. Y. Simon Ng 1,2, 1Wayne State University, Detroit, MI, USA, 2Next Energy, Detroit, MI, USA
The preparation of Ce0.8Zr0.2O2 and its use as a catalyst support were investigated for the steam reforming of glycerol. The support was prepared by the sol gel-technique and metal loading was carried out by the incipient wetness method. Performance of nickel (5% by weight) loaded Ce0.8Zr0.2O2 was compared to bimetallic Ni-Cu (5% nickel and 1% Cu) and Ni-Re (5% nickel and 1% Re). The Ni-Re catalyst performed well compared to Ni-Cu and Ni supported catalyst in terms of hydrogen selectivity (70% versus 80% and 30%) and conversion (100% versus 30% and 10%). In addition, the catalyst exhibited a good resistance to carbon deposition. Effects of the operating parameters, oxygen to carbon ratio, steam to carbon ratio, and temperature were also studied.
Production of Long Chain Fatty Alcohols Concentrates from Sugarcane Wax.
C.H.R. Rozário, D. Barrera-Arellano, State University of Campinas (UNICAMP), Campinas, SP, Brazil
Brazil, being the world′s greatest sugarcane producer and sugar exporter, represents a potential center for the production of sugarcane wax. This wax is obtained from the filter cake, a sub-product of the sugar and alcohol industry. Sugarcane wax is a natural source of higher primary aliphatic alcohols, with 24 to 34 carbon atoms, with a predominance of octacosanol (28:0 OH). This mixture of high molecular weight alcohols called policosanol, has been investigated due to its pharmacological properties, as an active component in various formulations, with anti-platelet, anti-trombotic and cholesterol-reducing effects. In this work were studied the steps involved in the process to obtain a concentrate of fatty alcohols from sugarcane wax, composed of (a)saponification of the purified wax with alcoholic NaOH solution; (b)separation of the mixture of alcohols in the saponified wax using a salt solution and ethanol to obtain policosanol with 50% long chain fatty alcohols (yield = 55%) and(c) purification with acetone to obtain policosanol with 92% Long chain fatty acohols (yield = 25.7). In both products, octacosanol was the main fatty alcohol (67% of fatty alcohols).
Bioalternatives for Four Stroke Motorcycle Engine Oils.
Asli Isler, Tamer Alyakut, Filiz Karaosmanoglu, Istanbul Technical University, Department of Chemical Engineering, Maslak, Istanbul, Turkey
Biobased industrial products are introducing with increasing rate into our daily life and these occur as "Environmentally Friendly Products" in the forms of biomaterials, biochemicals and biofuels. Today, biobased lubricants, one of the biomaterials, are gaining importance. Over the historical development of lubricants the most important products of lubricant markets are mineral oils and synthetic oils, which are widely used. Using biobased lubricants will have environmental and economical advantages. Mineral oils have limited resources and using environmentally friendly biobased lubricants are also important for utilizing national resources rather than importing crude oils. The main consumption of lubricant market is motor oils. In this study, starting from mineral, synthetic and biobased lubricants; mineral, synthetic, biomineral and biosynthetic based four stroke motorcycle engine oil candidates (10w40) are prepared, then lubricant and lubricity properties of the motor oils are determined. The results show that 5% of biobased lubricants will be suitable for preparing 10w40 motor oils in both mineral and synthetic based motor oils. The lubricity properties of the blends with biobased lubricants have shown also improvements. As a result, biomineral and biosynthetic 10w40 motor oils are presented as alternatives for motorcycle motor oils.
Enzyme- and Lewis Acid-Calalyzed Synthesis of Oligo(Glycerol-Diacid)s.
V. Wyatt, A. Nunez, T.A. Foglia, M.J. Haas, W.N. Marmer, Agricultural Research Service, United States Department Of Agrculture, Eastern Regional Research Center, Wyndmoor, PA, USA
Oligomeric pre-polymers were synthesized by the Lewis acid-catalyzed condensation of glycerol with succinic acid, iminodiacetic acid, glutaric acid or azelaic acid. The reactions were catalyzed with dibutyltin oxide, titanium butoxide or lipase (Novozyme 435) in the presence of solvent (DMSO, DMF, hexane) or under vacuum (neat). All products were characterized by proton NMR, carbon-13 NMR, MALDI-TOF mass spectrometry, and GPC. The prepolymers derived from Lewis catalysis were obtained, on average, in 84% yield and had number-average molecular weights less than or equal to 3245 Daltons, with degrees of polymerization ranging from 2.9 to 13.4 repeat units. The polydispersity was low (average = 1.26). The polymers were also evaluated for degrees of branching, solvent and catalyst effects on elongation, and solubility.
The Use of Hydrolyzed Jojoba Oil in Personal Care Products.
D. Ashley, R. Kleiman, J. Hill, Floratech, Chandler, Arizona, USA
The alkali degradation of jojoba oil results in salts of long chain fatty acids and fatty alcohols. If the reaction is not carried to completion the resulting product includes these two materials along with randomized long chain wax-esters. This mixture of compounds (jojoba hydrolysate) imparts several useful properties when used as a personal care ingredient.One of jojoba hydrolysate′s properties is the ability to adjust pH. In order to provide suitable conditions for formation of polymer gels or neutralization of fatty acids, an appropriate pH must be achieved. PC products may also be adjusted to an appropriate pH to be non-irritating to skin, to optimize the action of detergents, and to optimize the action of some emulsifiers. Triethanolamine (TEA) has often been used to adjust the pH of personal care products. TEA has been implicated in allergic reactions, skin and hair dryness, and systemic toxicity with chronic exposure.We have successfully used jojoba hydrolysate in place of TEA, to adjust pH to form polymer gels, neutralize fatty acids, and merely to attain a desired pH. Because jojoba hydrolysate has much higher molecular weight than TEA, a relatively larger amount of jojoba hydrolysate is needed to achieve the desired pH. Jojoba hydrolysate is superior to TEA in that it provides substantivity and emolliency for both skin and hair.
The Crop Biofactories Initiative (CBI) as a source of novel biotechnological inventions.
F. Graichen1, A. Warden2, S. Kyi1, V. Haritos2, S. Singh3, X. Zhou3, M. O′Shea1, 1CSIRO Molecular and Health Technologies, Melbourne, Victoria, Australia, 2CSIRO Entomology, Canberra, ACT, Australia, 3CSIRO Plant Industry, Canberra, ACT, Australia
The CBI (crop biofactories initiative) is a jointly funded initiative between CSIRO and the Australian GRDC (Grains Research and Development Corporation). The CBI is a 12 year research initiative with the clear aim of adding value to the Australian farmers and economy through the development of technologies to produce novel industrial compounds from genetically modified non-food grains crops. The major drivers for this initiative come from the grains industry (increase of the global competition, increase of the downward pressure on prices and need to capture value on the farm) and the chemical industry (replacement of petrochemical derived monomers and polymers, novel multifunctional materials, biodegradable polymers). To meet these challenges, the CBI is focusing on the following areas:1) Industrial oils2) Complex monomers3) Protein biopolymersThe research in the areas of industrial oils and complex monomers is aimed at the, evaluation and modification of novel oil and fatty acids for a range of industrial applications including: chemical intermediates, crosslinkable polymers, bioactive compounds, fuel additives and thermo/mechano-chromic devices.The research in the protein biopolymers area is aimed at producing novel silk materials with improved toughness compared with existing materials with potential uses as high performance textiles.
Value-Added Co-Products from Corn Dry-Milling Ethanol Plants.
M. Dasari1,2, 1FEC Solutions, Des Moines, IA, USA, 2Feed Energy, Des Moines, IA, USA
Byproducts from dry-mill ethanol production, conventionally sold as bulk livestock feed, are increasing at a significant rate and the supply may soon exceed the feed demand from the livestock industries. Specifically, high value corn fractions containing oil, limit the ability of livestock industries to increase the amounts of byproduct included in feed rations. With the lack of cost effective processes to extract value components from byproduct, an opportunity exists to develop technology to fill this emerging gap. This study will evaluate chemical, physical and enzymatic extraction procedures to extract corn oil, protein and other value added components. Also, this study will determine the most effective process to recover and the quality of various extracted components. The corn oil can be purified further to be used as a feed stock for biodiesel production.
Impurities in B20 That Cause Fuel-Filter Blockages During Cold Weather.
R.W. Heiden, R. W. Heiden Associates LLC, Lancaster, PA, USA
B20 users along the East Coast of the USA experienced numerous incidents of fuel filter plugging during the winter of 2006. These incidents occurred simultaneously with sudden, and then prolonged cold weather patterns, despite underground storage. Build-up of filter debris and the subsequent plugging increased the frequency of vehicle maintenance and unexpected vehicle shutdowns. These plugging incidents received little publicity outside of local user groups.We undertook an in-depth investigation of several of these plugged filter incidents and the lots of B20 used in the regularly maintained affected vehicles. Debris on the filters and impurities in the fuel were analyzed in the laboratory. Precipitates that formed in the B20 at 1-2°C were isolated, identified and their compositions compared to those of precipitates found on the plugged filters. This comparison revealed compositionally distinct similarities.The findings of these studies and their implications for the processing of various feed stocks; biodiesel specifications; and process monitoring are presented and discussed.
A Stability Study of Soybean Oil Feedstocks and Biodiesel.
D. Root, R. Jorgenson, M. Norris, Agricultural Utilization Research Institute, Marshall, MN, USA
Oxidative changes of soybean oil and biodiesel (B100) were monitored during storage at 40°F, 75°F, and 110°F. The observed changes were moderated by the addition of tert-butyl-hydroquinone, TBHQ, as an antioxidant. In general, biodiesel changed more rapidly than refined, bleached (RB) soybean oil and was less well protected by the addition of TBHQ. The most sensitive indicator of oxidative change and shelf life was the Oxidative Stability Index (OSI). The OSI provided a useful tool for tracking changes during storage for "as produced" B100 and distilled samples of biodiesel. Calculated iodine values, free fatty acid values, and acid values that biodiesel samples stored in sealed containers undergoes measureable oxidation within six months at ambient temperatures. This occurs with or without the addition of TBHQ. The observed changes in the OSI during storage allow the prediction of a "shelf-life" for commercial use of biodiesel. The utility of antioxidants as stabilizers for extending the shelf-life of biodiesel is also apparent in the results of this stability study.
Effect of Temperature on Filter Performance of Biodiesel Fuel.
M. Winston-Galant1, P. Dingle2, H. Tang1, T. Commons2, S. Salley1, J. Wilson1, S. Ng1, 1Wayne State University, Detroit, MI, USA, 2Delphi Diesel Systems, Troy, MI, USA
Biodiesel presents numerous possibilities as an alternative, renewable fuel. Produced from the transesterifcation of methyl esters from vegetable oils or animal fats, biodiesel offers lower carbon emissions, better lubrication, and lower dependence on foreign oil than current diesel fuel does. However, biodiesel is limited by its poor cold flow properties, the formation of precipitates in biodiesel blends may have serious implications for the automotive fuel delivery system in terms of filter plugging and deposits on injectors and critical fuel pump components. The objective of this study is to determine the effect of temperature (above and below the cloud point) on flow rate and pressure of different blends of biodiesel fuel with a graphical correlation, and in turn investigate the effectiveness of different types of commercial filters. Soybean oil, rapeseed oil, poultry fat, and yellow grease derived biodiesel and blends will be used in this study. An electric pump and a motorized pump will be installed in order to simulate the flow methods from vehicles in different parts of the world. The ASTM D 2068-04 testing will also be implemented for biodiesel and blends to do a comparison of test results from the customized design. These results will supply information regarding the life of the commercial filter.
Quantification of Minor Components in Biodiesel Using GC-MS, FTIR, and HPLC.
Huali Wang1,2, Haiying Tang1,2, John Wilson2, Steven Salley1,2, Simon Ng1,2, 1Department of Chemical Engineering and Material Science, Wayne State Univeristy, Detroit, MI, USA, 2Next Energy, Detroit, MI, USA
Biodiesel is produced from the transesterification of vegetable oils with short chain alcohols in the presence of an alkali catalyst. Minor components in biodiesel exist as a result of the unreacted feedstock components, reaction by-products, additives, and autoxidation products, such as water, free glycerin, bonded glycerin, free fatty acids, catalyst, residue alcohol, unsaponifiable matter (plant sterols, antioxidants and hydrocarbons), soaps, polymers, etc. Biodiesel properties, such as cold flow property, acid number, cetane number, oxidative stability, etc., may be affected by these minor components and ASTM limitations have been specified on many minor component levels. Thus, the determination of minor component concentrations and understanding their effects on biodiesel properties are very important. For example, one minor component, steryl glycosides, can form precipitates in biodiesel due to its high melting point and insolubility in biodiesel. The presence of steryl glycosides will accelerate the precipitate formation even at room temperature and block the fuel filter. However, a quantification technique for steryl glycosides is still not fully developed. In this study, we use HPLC, FTIR and GC-MS to qualify and quantify the contents of sterol glycosides in biodiesels from soy oil, palm oil and cotton seed oil.
Extraction of Fish Oil from Salmon Processing Discards for Biodiesel Production: Influence of Solvent Extraction Methods on Oil Yield and Quality.
Albertan. A. Aryee, Benjamin K. Simpson, McGill University, STE. ANNE-DE-BELLEVUE, QUEBEC, CANADA
The main drawback to the full commercialization of biodiesel is production cost which is contributed to a large extent by the feedstock. Oil was extracted from the discards of salmon processing and analyzed in terms of the efficiency of various extraction methods on oil yield and quality. The extraction methods compared were; Folch, Bligh and Dyer, Radin, Soxhlet, and Soxtec, using chloroform, methanol, isopropanol, hexane or petroleum ether (PE) as solvents. Salmon skin oil (SSO) yield was appreciably lower with the hexane-isopropanol solvent system than either of the chloroform-methanol systems; 32.21% d.b against 35.15% d.b and 43.82% d.b. respectively. The yield of SSO from Soxhlet-hexane compared favourably with Soxhlet-PE at all the extraction times investigated. Soxtec-hexane gave the highest oil yield of ca 62%; however both hexane and PE were suitable solvents in the Soxtec extraction. Hexane is preferred over PE because the former is cheaper, has comparably lower B.P. and safer to handle. Regardless of the method used and oil yield, free fatty acid (FFA) was substantially low. A choice between the methods investigated can be made on the basis of oil yield, extraction ease and time, cost of solvents and safety of each technique. Fish skin from salmon processing was a good source of oil.
Metal Organic Frameworks as Heterogeneous Catalysts for Transesterification of Vegetable Oils.
V. Durand, D. Bazer-Bachi, V. Lecocq, N. Bats, IFP, Lyon, France
Today, biofuels are front-page news. Environmental constraints and political determination to promote the emergence of alternative energy resources are just two of the factors that have brought them back into the limelight. Biodiesel, consisting of monoalkyls esters, is a fuel obtained from renewable biomass feedstocks. Most of the commercial biodiesel is produced using homogenous basic catalysts. This process has the drawbacks to produce high amounts of wastewaters and low-quality glycerine. These problems can be overcome with the use of an heterogeneous catalyst. Thus the Axens process Esterfip-H, based on a zinc aluminate catalyst, allows the production of monoalkyls esters from vegetable oils and methanol, with high purity glycerine in a continuous mode. Metal Organic Frameworks (MOF) have been explored as a new kind of high surface zeolite analogs .Their metallic nodes and organic linkers allow these materials tunable topologies and physico-chemical properties so that they can be envisaged for heterogeneous catalysis.These work presents the synthesis of some MOF materials based on Zn, their characterization (SBET, XRD, IR, TGA) and their use in the reaction of transesterification (influence of temperature, methanol/oil ratio and nature of the alcohol).
Alkyd Resin from Crude Glycerol and Sunflower Oil.
Rosana de Cassia de Souza Schneider1, Henrique Hesse1, Ezequiel Bavaresco1, Diana Pagliochi Bottega2, 1Universidade de Santa Cruz do Sul, Santa Cruz do Sul, RS, Brazil, 2Universidade Federal do Rio Grande do Sul, Porto Alegre, RS, Brazil
Alkyd resins are used in surface treatment. They are product of the glycerolysis followed of polymerization. In this work were studied methods of alkyd resin production from crude glycerol compared with resin produced with pure glycerol. This glycerol corresponds 10% of the final products in the biodiesel production. The crude glycerol was partially purified with neutralization, flotation and adsorption. The experiments were accomplished with temperature control, inert atmosphere and with several quantities of the sunflower oil and glycerol. For characterization of the products were used physic-chemistry methods, infrared spectroscopy and hydrogen nuclear magnetic resonance. As observed results the resins obtained with crude glycerol presented similar properties of the classic alkyd resin produced with pure glycerol. The exploitation of the crude glycerol reduces the stages and costs of process. The differences of the energy of the process with crude or pure glycerol were evaluated.
Rates of Homogeneous and Heterogeneous Acid Catalyzed Transesterification Reactions of Tri-, Di- and Mono-Glycerides.
Earl G. Alley1, Rafael Hernandez1, Todd French1, Jimmy Cain1, Bill Holmes2, 1Dave C. Swalm School of Chemical Engineering, Miss State University, Miss. State, MS, USA, 2Miss. State Chemical Laboratory, Miss. State, MS, USA
We have determined rate constants for the sulfuric acid catalyzed methanolysis of C12:0,C14:0, C16:0, C18:1, C18:2 and C18:3 triglycerides diglycerides, and monoglycerides. These reactions were all conducted at concentrations that allowed complete solubilization at 60º C in methanol. The analyses were performed with high temperature GC/FID. MSTFA derivatization was employed in order to allow for the analysis of triglyceride, the two diglycerides, and the two monoglycerides in one operation. Kinetics were also determined on selected members of these 18 compounds at concentrations that were about ten times the saturation limit in methanol in order to study these reactions under heterogenous conditions.
Process Development to Reduce Sterol Glucosides Content in Biodiesel.
Haiying Tang1, Huali Wang1, Steven Salley1, John Wilson2, Simon Ng1, 1Wayne State University, Detroit, MI, USA, 2NextEnergy, Detroit, MI, USA
Biodiesel is a renewable and environmentally friendly alternative fuel. However, filter plugging and engine failure have taken place in vehicles using biodiesel blends due to precipitate formation at low-temperature. The majority of these precipitates can be attributed to sterol glucosides found in vegetable oil-based biodiesel. These dispersed sterol glucoside particles increased the filtration time, and also promoted the crystallization of other compounds. Up until now, no ASTM standard analytical methods to determine sterol glucosides in biodiesel exist. The objective of this work is to evaluate and develop processing strategies to reduce sterol glucoside content in soybean oil based biodiesel, and develop a robust analytical method to determine sterol glucoside content in biodiesel. A number of processing techniques will be discussed: 1. ambient filtering; 2. cold filtering; 3. water degumming; 4. absorbent treatment; and 5. vacuum distillation. In each of the processing technique, the amount of sterol glucosides in soybean oil based biodiesel before and after the processing treatment was determined by three different analytical approaches: Fourier transform infrared (FTIR) spectroscopy, gas chromatography - flame ionization detector (GC-FID) and high pressure liquid chromatography (HPLC).
Characterization of Jatropha curcas Crude and Transesterified Seeds Oil from Benin: a Potential Source of Fuel
T.K. Tovignan1, S.T. Djenontin1, I.Y. Bokossa2, V.D. Wotto1, D. Pioch3[*], and D.C.K. Sohounhloue4 1Laboratoire d’Etude et de Recherche en Chimie Appliquée (LERCA), Ecole Polytechnique d'Abomey-Calavi (EPAC), Université d'Abomey-Calavi (UAC), République du Bénin; 2Laboratoire de Microbiologie et des Technologies Alimentaires (LAMITA), Faculté des Sciences et Techniques (FAST), Université d’Abomey-Calavi (UAC), République du Bénin; and 3UMR CIRAD 016 Génie de Procédés Eau-Bioproduits (GPEB), France
Jatropha curcas, a bush widely spread in Africa and elsewhere for enclosing cattle fields is now being considered as a potential fuel source in several tropical countries. Benin, a small West African country, is launching a program for evaluating its potential for the same purpose. However, there a no reports on chemical composition of Beninese Jatropha curcas oil. This preliminary work is a contribution to the program, focusing on possible variation between various locations and including determination of minor components, like sterols and tocopherols, that could be useful as food ingredients, as well as physical and chemical characteristics of oil and derived ethyl ester.
Seeds were harvested in three areas of Benin (Calavi-South: JCA; Savalou-center: JCS and Penessoulou-North: JCP), having different climates. Oil content of seeds is 46-49w% dry nut. Results show that the three oils have a relatively good quality (acidity < 3%; peroxide value < 2 meq O2/Kg), excepted JCP which has a peroxide value of 6,3 meq O2/Kg. Unsaturated fatty acids accounts for ~80%, mainly oleic (41 - 48%) and linoleic (30-37%) acids. Sterols (mainly β-sitosterol) and tocopherols (mainly γ-tocopherol) are respectively in the range of 1270 - 1440ppm and 186 – 247ppm; although highest values are shown by samples from the same region (JCP) this should be considered only as an indication to be confirmed by further work. The potential of Jatropha curcas oil and derived ethyl ester from Benin as fuel is rather interesting, based on relevant parameters, either from our preliminary results and as expected from literature data : high energetic value (50mJ/Kg), cetane number 49,5.
In terms of chemical composition, we did not note significant regional variations of oil composition neither discrepancy with available data for J. curcas oil from other countries.