ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

BIO 1.1 / IOP 1: Biorenewable Polymers Chairs: Richard Ashby, USDA, ARS, ERRC, USA; and Rongpeng Wang, CVC Thermoset Specialties, USA Strategic Planning of Polymeric Materials from Sequential Liquefaction of Nicotiana Tabacum Vegetable Oils Zoran Petrovic*, Pittsburg State Stems Biomass by Crude Polyhydric for University, USA the Production of and Rigid Plant oils are excellent substrates for new Foams Chiragkumar M. Patel*1, Jina R. Patel2, chemistries and design of high value sustainable Amitkumar A. Barot2, and Vijay K. Sinha1, materials. Designing materials must take into 1Industrial Chemistry Dept., V. P. & R. P. T. P. account the structure of lipids. Essential property Science College, India; 2V. P. & R. P. T. P. Science of materials is the cost which imposes limitation on College, India the number of steps for conversion of oils to In this work, Nicotiana tabacum stalks and products. Ideally a product should be made in a -based was synthesized via a two- single step. Direct polymerization of oils was used step process. Preliminarily, stalks were liquefied to prepare liquids of different viscosities useful for using acid catalyst to procure glycol-glycoside and printing inks, plasticizers for rubber, and modifiers the optimized conditions for liquefaction of N. for asphalt etc. For better control of properties tabacum stem’s biomass was 150°C temperature functional groups must be introduced. for 180 min time using PTSA as catalyst. Functionalization of saturated lipids could be Progressively, the glycol-glycoside obtained from carried out by or the former step was further reacted with castor oil transamidation. Unsaturated fatty acids or in the presence of lithium hydroxide to get dark are functionalized by oxidation, brown-coloured polyol with hydroxyl value was epoxidation, , metathesis, running in between 200 and 400 IOH. Glycol- ozonolysis, thio-ene reactions with mercaptans etc. glycoside and polyols were characterized by Thermosetting oil-based polymers are useful for chemical and instrumental methods. Further, by foams, coatings, adhesives and as matrix resins for employing open-cup method involving the mixing fiber-reinforced composites. They are based on of polyol and adducts, the desired poly multifunctional triglycerides and multicomponent urethane rigid foam was obtained. The product curing systems. Thermoplastic polymers and was tested for their physical, mechanical, thermal, elastomers can be made from two-functional fatty and morphological characteristics, while the acids or their fragments. Excellent biodegradable thermal conductivity was in the range of 0.013 to shape memory materials were made from oil- 0.017 kcal/mh AQ1. The performed study may yield based monomers. Direct polymerization of high quality rigid or semi-rigid polyurethane. epoxidized oils leads to pure oil-based polyether foams. The largest outlet for oil-based polyols is in The Effect of Monoglyceride Incorporation on the flexible and rigid polyurethane foams. Solvent Absorption and Mechanical Properties of -based Polymer Films Prince G. Boakye*1, Kerby C. Jones2, Nicholas P. Latona2, Cheng Kung Liu2, Samuel A. Besong3, Stephen E. Lumor3, and

Victor T. Wyatt2, 1Delaware State University, USA;

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

2USDA, ARS, ERRC, USA; 3Dept. of Human Ecology, Fluorescence Emission and Catalyst Effect of College of Agricultural Sciences, Delaware State Precious Metal Nanocomposites Based on University, USA Autoxidized Unsaturated Plant Oils/Fatty Acids Monoglycerides (MGs) have been incorporated Baki Hazer*, Bülent Ecevit University, Turkey into the matrix of poly-(glycerol-co-glutaric acid) Unsaturated plant oils/fatty acids (UPOFA) have films to investigate their effect on the thermal, gained great interest as monomers to produce bio mechanical, and solvent absorption properties of based polymers. UPOFA is prone to react with air these films. MGs were concentrated using a oxygen under daylight at room temperature which combination of molecular distillation and solvent is called “ecofriendly autoxidation”. Eco-friendly extraction, resulting in a concentrate with 99.15% autoxidation process creates peroxide linkages in purity. The MG concentrate was predominantly order to obtain unsaturated plant oil/fatty acid monoolein (92.65%). The films were made by first polymer that can initiate the free radical synthesizing polyester gels from glutaric acid and copolymerization of some vinyl monomers. glycerol with or without the incorporation of MGs. Mixture of salt of silver and soybean oil was spread The polymer gels were then cured at 150°C for 24 out in a glass container and exposed to air oxygen h, forming clear, solid films with a yellow hue. at room temperature to obtain soybean oil Solvent absorption studies revealed that nanocomposite. Similarly, a mixture of salt of gold poly(glycerol-co-glutaric acid-co-MG) films were and soybean oil was spread out in a glass container able to absorb and resorb solvents better than and exposed to air oxygen at room temperature to poly(glycerol-co-glutaric acid) films, albeit they had obtain soybean oil nanocomposite. Catalyst effect higher erosion levels. Thermogravimetric Analysis of gold NPs is dramatically decreased the rate of (TGA) showed that the incorporation MGs did not autoxidation. For example the gold catalyzed remarkably affect the thermal stability of the autoxidized soybean oil polymer was obtained in glycerol-based films. The MG-incorporated films ten days oxidation period while the autoxidation were qualitatively softer than the poly(glycerol-co- time takes nearly one month to obtain oxidized glycerol) films which correlates to the observed 39- soybean oil polymer without Au NPs. In addition, fold reduction in Young’s Modulus and 17-fold high fluorescent emission of silver/oxidized reduction in fracture energy. Mechanical property soybean oil polymer nanocomposite is obtained. studies also revealed that the incorporation of MGs The nanocomposite solutions were analyzed by UV- increased the elongation and reduced the tensile VIS spectrometer in view of the surface plasmon strength of poly(glycerol-co-glutaric acid) films. resonance. TEM was used to characterize size and Correlation analysis revealed a strong linear shape of the metal nano particles embedded into relationship between Young’s Modulus and the copolymer nano composites. fracture energy (R2 = 0.9962), and between Young’s Modulus and tensile strength (R2 = 0.9972). Our Reactivity and Structure-property Performance of study proved that MGs can be successfully Natural Oil Polyols in Ibrahim incorporated in the polymer matrix of Sendijarevic*, Troy Polymers, Inc., USA poly(glycerol-co-glutaric acid) films to produce The key principle in selection of raw materials softer films with increased elongation and in polyurethanes is the understanding of structure- increased solvent absorption capacity. properties relationship, as different building blocks impart different performance characteristics to

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

polyurethane materials. In addition, raw materials of novel waterborne polymeric materials (latexes, are selected to meet the reactivity requirements of dispersions, emulsions etc.) from plant oils for the applications. To meet the performance and coatings, paints, adhesives etc. Due to highly processing requirements, in many applications it is hydrophobic nature of plant oils (triglycerides), common to use a combination of polyols. In some their use for development of such materials has applications, natural oil polyols (NOPs) contribute been challenging. To overcome hydrophobicity, to the performance of polyurethanes, and NOPs converting oils into vinyl monomers to synthesize have been used from early days of polyurethanes latexes via classic radical chain polymerization in industry. A perception exists that NOPs with emulsion was performed. Novel plant oil-based pendant hydroxyls groups in the acrylic monomers are synthesized in a one-step backbone are less reactive compared to the direct transesterification (alcoholysis) of oil conventional polyether polyols with terminal triglycerides. While the vinyl bond of the hydroxyls. However, results of recent kinetic monomers is reactive in radical chain studies demonstrated that the isocyanate reactivity polymerization, the double bonds of the fatty acid of NOPs requires lower activation energy than fragments are unaffected and capable of post- polyether polyols, and under certain conditions polymerization oxidative reactions. New acrylic NOPs are more reactive than polyether polyols. monomers are synthesized from soybean, linseed, Studies of model systems also showed that the sunflower and olive oil, possessing remarkably reaction profiles are not significantly affected by different compositions of fatty acids in drop-in replacement of NOPs in place of polyether triglycerides. While length of fatty acid carbon polyols in elastomers, energy-absorbing and chains is similar (mostly oleic, linoleic and linolenic resilient polyurethane foams. The impact of the acids), average number of double bonds per oil NOPs on physico-mechanical properties of triglyceride (degree of unsaturation) varies polyurethane is more significant. The effect of the significantly. Specifically, degree of unsaturation in NOPs on the hard/soft segment phase separation fatty acids was utilized as a criterion for has been evaluated and correlated with dynamic understanding fundamental behavior of new and mechanical properties of model elastomers, monomers in radical chain (co)polymerization. Key which can be used to guide the selection of NOPs in questions addressed include understanding of i. polyurethane applications. The use of NOPs as how degree of unsaturation impacts new acrylic performance materials will be demonstrated in fatty monomers reactivity in (co)polymerization as energy-absorbing polyurethane foams. well as the resulting latex properties, and ii. do polymer latexes, based on monomers from Free Radical Polymerization of Monomers Based different plant oils, demonstrate different on Plant Oils Zoriana Demchuk1, Kyle Kingsley1, performance in coatings, paints, adhesives, once Oleh Shevchuk1, Ihor Tarnavchik1, Vasylyna they are copolymerized with a variety of Kirianchuk2, Ananiy Kohut2, Stanislav Voronov2, and petroleum-based counterparts? Andriy Voronov*1, 1North Dakota State University, USA; 2Lviv Polytechnic National University, Ukraine Synthesis of a New Generation Biopolyols from Most currently available syntheses of polymers Canola and Other Plant Oils Jonathan M. Curtis*1, from plant oils are limited to polycondensation and Tolibjon S. Omonov2, Ereddad Kharraz2, Xiaohua oxypolymerization. This work targets development Kong2, and M. Hossein Tavassoli-Kafrani2, 1Dept. of

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

Agricultural, Food and Nutritional Science, out. Creating model building blocks for University of Alberta, Canada; 2University of epoxy/amine coatings is the first step in carrying Alberta, Canada out these studies. This work demonstrates the Recently, various polyols have been developed synthesis and characterization of model amine from soy and other plant oils, primarily to replace building blocks from saturated fatty acids and polyols used polyurethane diethylenetriamine (DETA) with tunable production. In many cases these biobased polyols hydrophobicity. The glass transition temperature retain aspects of the starting triacylglycerol (Tg) of modified amine samples suffered a 45-50 °C structure, have moderate hydroxyl numbers of Tg reduction, which has been attributed to a loss of 200-250 mg KOH/g and high viscosity that tends to labile available for crosslinking in these increase significantly with increasing hydroxyl samples. It was observed that the fatty acid numbers and oligomeric content. Biobased polyols modified amines exhibited a reduced diffusivity to with high hydroxyl numbers and low viscosities are water of up to 50%. This has been attributed to the highly desirable since these can be functionally increased tortuosity of samples with a pendant incorporated into rigid materials. In a recent patent aliphatic chain in the network. Samples with application we described the process for the modified amines were observed to have lower synthesis of a new class of biobased polyols from a solubility of water of up to 30%. We propose that range of unsaturated plant oils. This comprises the the reduction in solubility can be caused by a sequential reaction steps of (a) epoxidization of the dilution of oxygen in the polymer network caused unsaturated plant oil; (b) transesterification to by the addition of aliphatic pendant chains. produce hydroxyalkyl esters of fatty acid ; and (c) further hydroxylation to obtain polyols. Microwave-assisted Maleation of Tung Oil for Bio- Using this synthetic pathway with canola oil, a based Products Chengguo Liu1, Zengshe Liu*2, polyol with high hydroxyl numbers (i.e. 350-360 mg Brent H. Tisserat3, Rongpeng Wang4, Thomas KOH/g) and with low viscosities (i.e. Schuman5, Yonghong Zhou1, and Lihong Hu1, 1Institute of Chemical Industry of Forestry Products, Synthesis and Characterization of Fatty Acid CAF, China; 2Food and Industrial Oil Research, Modified Amines with Improved Water Barrier NCAUR, ARS/USDA, USA; 3Function Food Research, Properties John H. Vergara*1, Yunze Tian1, John J. NCAUR, ARS/USDA, USA; 4CVC Thermoset La Scala2, Joshua M. Sadler2, and Giuseppe R. Specialties, USA; 5Dept. of Chemistry, Missouri Palmese1, 1Drexel University, USA; 2Army Research University of Science and Technology, USA Laboratory, USA A simple, “green” and convenient chemical Fundamental studies aimed at elucidating the modification of tung oil for maleinized tung oil key contributions to corrosion performance are (TOMA) was developed via microwave-assisted needed to make progress toward effective and one-step maleation. This modifying process didn’t environmentally compliant corrosion control. involve any solvent, catalyst or initiator, but Epoxy/amine systems are typically employed as demonstrated the most efficiency of barrier coatings for corrosion control, however, the functionalizing plant oils: at a reaction time of 4 curing agents used for coating applications can be min, the yield of purified TOMA target product very complex, making fundamental studies of reached 94.5 wt.%. A mechanism of this water and oxygen permeability challenging to carry microwave-assisted maleation was investigated by

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). Moreover, three oil-based epoxides including epoxidized glycidyl ester (EGS), epoxidized soybean oil (ESO), and epoxidized octyl soyate (EOS) as well as hydroxyl-terminated polydimethylsiloxane (PDMS) were employed to react with the optimized TOMA product. Novel fully oil-based epoxy resins and silicon-containing alkyd resins were prepared. Mechanical, thermal, thermo-mechanical, and hydrophobic properties of the as-prepared epoxy and alkyd resins were evaluated.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

BIO 2.1 / IOP 2: Biofuels Chairs: Adeeb Hayyan, University of Malaya, Malaysia; Lieve Laurens, National Renewable Energy Laboratory, USA; and Jun Ogawa, Kyoto University, Japan Recovery of Fatty Acids from Advanced Biofuels: Synthesis and Purification of Polyphenolic Improvement in Acid Number and Value Justice Branched-chain Fatty Acids with Natural Asomaning*, and David C. Bressler, University of Monophenols Helen Ngo Lew*1, Zongcheng Yan2, Alberta, Canada Karen Wagner1, and Robert A. Moreau1, 1USDA, The development of renewable alternatives to ARS, ERRC, USA; 2South China University of fossil derived chemicals and fuels haveattracted a Technology, China significant interest due to socioeconomic and Polyphenolic branched-chain fatty acids (poly- environmental concerns. Advanced biofuels, PBC-FAs) are hybrid compounds produced by particularly from lipids that can be used as drop-in linking electron-rich aromatic rings such as natural fuels, which is directly compatible with current monophenols (i.e., thymol, carvacrol and creosote) petroleum infrastructure has seen considerable with mixed free fatty acids derived from soybean advancements over the last couple of years. One of and safflower oils through a process known as the major drawbacks of advanced biofuels is the arylation. The antimicrobial properties of these high acid number as a result of residual acids, poly-PBC-FAs are similar or better than their parent which necessitates further processing to convert monophenol compounds. This paper will focus on the residual acids hydrocarbons using techniques the continuing development of the arylation such as hydrotreating. The aim of the present study process using mixed fatty acids coupled individually was to develop methods for removing and with thymol, creosote, and carvacrol in the final recovering fatty acids from advanced biofuels products to give poly-PBC-FA yields of 72.4%, thereby reducing the acid number to acceptable 77.2%, and 48.8%, respectively. The difference in level. The recovered fatty acids can then be utilized yields is strongly dependent on the different in high value application such as in the cosmetic functional groups on the three phenolic aromatic and pharmaceutical industries. Various methods rings. Water is a co-catalyst in the reaction and the were used to directly remove the acids from the concentration of water has a significant influence advanced biofuels. The systems were then tested on the arylation reaction by depressing the for their ability to recover the acids and also isomerization reaction. Another aspect of this regenerate the system. Results show that the acids presentation will focus on the development of a can be successfully removed from advanced highly efficient distillation method to clean up the biofuels using these methods providing acid products achieving up to 97% purity, which is numbers below detectable levels. The systems extremely important for evaluating their were then used for ten cycles after regeneration antimicrobial properties. without significant loss in acids removal from the advanced biofuel. This study demonstrated the Animal Fatty Wastewater Sludge recovery by feasibility of improving the quality and value of Acid-catalyzed Esterification into Fatty Acid Butyl advanced biofuel through acid number reduction Esters as Potential Christopher Wallis1, and fatty acids recovery. Muriel Cerny1, Eric Lacroux*2, and Zéphirin Mouloungui1, 1Laboratoire de Chimie Agro-

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

Industrielle, France; 2Chimie Agro-Industrielle, Ionic Liquids Derived from Amino Acids for France Catalytic Biodiesel Production Jingbo Li* and Animal Fatty Wastewater Sludge (AFWS) Zheng Guo, Aarhus University, Denmark represent a novel source of glyceride and free fatty Ionic liquids (ILs) derived from biomolecules acids (FFA) material for the future. These lost lipids have attracted more and more attention due to were studied for potential conversion into their generally biodegradable, non-toxic, and more biodiesel. Often referred to floatation greases, sustainable properties. Amino acids are a group of AFWS were found to be composed of 20-70% of biomolecules with additional unique property that water, demonstrating the variability in composition they are able to be converted into both cations and that one can expect from such slaughterhouse anions. Herein, we synthesized a series of amino wastes. Generally regarded to be completely acid-based ionic liquids (AAILs) possess either hydrolyzed to FFAs, however, as our analysis shows strong acidic or strong basic properties. Structure they contain up to 20 % of tri-, di- and mono- evolution strategy was adopted to gain the most glycerides. Whilst current technologies employed promising AAILs for catalyzing biodiesel production. for biodiesel production are very effective when The strong acidic AAILs were used to catalyze applied to clean sources of lipids (trans- esterification reaction to convert free fatty acids esterification of glycerides; FFAs esterification), into biodiesel while the strong basic AAILs were they are far less effective when applied to employed to catalyze transesterification reaction to mixtures, or if there is significant amount of water convert acylglycerides into biodiesel. The catalytic present. Fatty acids esters were synthesized in activity of AAILs was strongly correlated to the complex aqueous media. The 4- properties of the side chains of the parental amino dodecylbenzenesulfonic acid catalyzed acids. [Asp+][NO3-] and [Choline+][Arg-] were the esterification of AFWS with 1-butanol was most effective for esterification and performed in a novel batch reactor fitted with a transesterification, respectively due to the strong drying chimney for “in situ” water removal. acidity and basicity of the side chains of aspartic Conversion yield was optimized using a Doehlert acid and arginine. The best catalyst, surface response methodology. Two products that [Tetrabutylammonium+][Arg-], was obtained meet the biodiesel standards (Biodiesel European following structure evolution strategy. Standard EN14214): First type of product Esterification efficiency of 97% was achieved within developed with properties similar to diesel, Fatty 5 h, at 70°C, with 10% [Asp+][NO3-] loading and Acid Butyl Esters (FABEs) were isolated in good 7.5:1 methanol to oleic acid ratio. Complete yields (analysed on CG-FID: 95 %+). The second transesterification of triglycerides was achieved original biodiesel developed is a blend of FABEs within 15 min, at 90°C, with 6% with 1-butanol (16%). These two potential biofuels [Tetrabutylammonium+][Arg-] loading and 9:1 were analyzed in comparison with current methanol to triglyceride ratio without soap analogous biofuels (FAME based biodiesel, FABE formation. The AAILs directly used as catalysts for products from vegetable oils) and were found to both esterification and transesterification reactions exhibit high cetane numbers and flash point values. may result in greener and sustainable biodiesel production processes in the future, which highlights the importance of the current study.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

Grease Formulation Using Post-consumed Clothes: enzymatic processes are only applied to a limited A Sustainable Approach Amitkumar A. Barot*1, extent at industrial scale due to low degrees of Chiragkumar M. Patel2, Tirth M. Panchal3, Jigar V. conversion, typically < 95%, and relatively high Patel3, and Vijay K. Sinha2, 1V. P. & R. P. T. P. costs of current fat-splitting lipases. A protein Science College, India; 2Industrial Chemistry Dept., engineered variant of Thermomyces lanoginosus V. P. & R. P. T. P. Science College, India; 3Dept. of lipase expressed in high yields has been tested at Industrial Chemistry, Institute of Science and 55oC/131oF in 1L-stirred glass reactor system using Technology for Advanced Studies and Research, castor oil as feed-stock, a two-step reaction set-up, India 100% water w/w and 0.6% w/w enzyme solution. Recent scenario demands environmentally The results suggest that the new lipase is superior adaptable routes for recycling synthetic polymeric to traditional lipases and gives both higher degree waste. Also, the demand of bio-based products is of conversion and lower costs. Kinetic studies and increasing due to strict environmental laws. Finding initial engineering assessments of industrial scale a suitable way to recycle polyester is a worldwide applications suggest that enzymatic catalyzed fat- concern due to its environmental impact and splitting technology holds a great potential to increasing volume of these materials produced in replace chemical fat-splitting process within a few society. In the field of lubricants, much effort has years. been spent on substitution of petro-based raw materials by natural-based renewable ones. In this Process Development of a Sustainable Aromatic frame work, current paper shows the utilization of Hydrocarbons Derived from Camelina sativa castor oil as replacement to diols in recycling of Randy L. Maglinao*1, Chazley J. Hulett2, Eleazer P. polyester waste. This in comparison with diols is Resurreccion2, and Alexandra K. Jones1, 1Advanced renewable, easily available, environmental friendly, Fuel Center, Montana State University-Northern, economically cheaper and hence sustainable USA; 2Montana State University Northern, USA indeed. Glycolyzed products were then used as Aromatic compounds in petroleum-based jet base oil in the formulation of grease. Glycolyzed fuels are necessary to give the fuel’s desirable products were characterized by using various lubricity and seal swelling properties. Without chemical and instrumental methods and prepared these compounds in jet fuel, operational problems, greases were evaluated for its tribological such as failure of fuel tank gaskets, could occur and properties. with disastrous consequences. Research on the synthesis of renewable aromatics mostly focused Enzymatic Catalyzed Fat-splitting as Replacement on pyrolysis of lignin coupled with hydrotreating. to Chemical Fat-splitting Process Anders Rancke- We report an alternative feedstock and synthesis Madsen, Hans Christian Holm, Per Munk Nielsen, route for selectively producing renewable aromatic and Simon Emil Lausen*, Novozymes Denmark hydrocarbons, which can be used in both as a Conventional chemical fat-splitting processes blend component for jet fuel. Using fatty acid suffer from environmental problems and methyl esters derived from camelina, renewable equipment corrosion. Enzyme-catalyzed fat- aromatics and straight chain hydrocarbons were splitting is an attractive alternative and lipases produced through a two-step process. Batch offer many advantages such as low CAPEX, high reactor systems (20 – 30 mL) were used to convert quality and environmental safety. However, FAME to hydrocarbons. Results showed that the

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

polyunsaturated fatty acids in camelina FAME yield ethoxylates derived from Elevance Inherent renewable aromatics. It is also found that building blocks exhibited superior cleaning multisubstituted benzenes were produced. performance, foam control, viscosity control and more compact formulations when compared to Novel Building Blocks Designed from standard ethoxylates. Metathesized Vegetable Oils Frederyk Ngantung*, Elevance, USA Sterol Molecular Fingerprinting in Different Algae Elevance produces high-performance, cost- Provide Options for High-value Co-Product advantaged and bio-based chemicals from Development in a Conversion Process Lieve metathesized vegetable oils. The processes use a Laurens*, Oliver Palardy, Keegan Duff, and Stefanie highly efficient, selective catalyst to break down Van Wychen, National Renewable Energy natural oils such as soybean or palm oil and Laboratory, USA recombine fragments. The resulting products are Improving biomass production and utilization is high-value, difunctional chemicals with superior imperative for commercializing a future algae- functional attributes previously unavailable based biorefinery. Sterols are high-value products commercially. These chemicals can be used as that can be isolated from algal biomass and have ingredients and building blocks for detergents, not been studied before in the context of a personal care, oil field and agriculture chemicals. In conversion pathway to biofuels and bioproducts this talk, two industrial examples will be presented and provide value as either nutraceuticals or as to showcase the applicability of Elevance’s feedstocks for novel surfactant production. Mass ingredients and building blocks. Example 1. spectral analysis indicates that there are 11 sterol Hydraulic fracturing chemicals D-limonene when compounds in Chlorella and 16 in Scenedesmus. added as fracking fluid additive has been The compounds we identified fall within two major demonstrated to improve production rate of gas in classes: 28-carbon 4-desmethylsterols and 29- many conventional and unconventional reservoirs carbon 4-desmethylsterols. Within the 28-carbon and basin. The availability and price of d-limonene, group, the spectra either more closely resemble however, have been volatile in the past five-to-six campesterol (MW 472) or ergosterol (MW 468). years. Elevance HFS™ is a high-performing, Within the 29-carbon group, the spectra could be hydraulic fracturing fluid ingredient that can be a grouped into compounds with a MW of 484 (EG cost-effective substitute to d-limonene. In stigmasterol, fucosterol, Δ5-avenasterol) and those independent laboratory tests where Elevance HFS™ with a molecular weight of 486 (sitosterol or Δ7- was blended into hydraulic fracturing fluids and stigmastenol). The commercially available compared to d-limonene- based fluid, Elevance surfactants (e.g. linear alkyl benzene sulfonates) HFS™ clearly outperformed the d-limonene-based are often mixtures of compounds. We demonstrate fluids in enhancing the productivity of oil and gas here that the variety of sterols present is greater in wells. Example 2. Building blocks for surfactants in Scenedesmus than in Chlorella, which seems to be laundry detergents A series of methyl ester almost entirely 28-carbon variants of ergosterol, ethoxylates were prepared from our building block. while the former contains a mixture of both 28 and Their physical properties and efficacy in fabric care 29-carbon sterols. We present data on a new were evaluated and compared to incumbents. It method for sterol characterization in algae and was found that the unsaturated methyl ester highlight the growth phase specific accumulation of

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

this class of compounds along with preliminary operational parameters, and thereby moving a step data on conversion of sterols to non-ionic closer towards implementation of green chemistry surfactants, and surfactant characterization after in the industrial setting. esterification with succinic anhydride and polyethylene glycol.

Determination of Solubility and Kinetic Parameters for Switchable Solvents Using Microfluidics Ghata M. Nirmal*1, Thomas F. Leary2, and Arun Ramchandran2, 1University of Toronto, St. George, Canada; 2University of Toronto, Canada Current separation processes in the industry involve use of specific solvents at every step, which can be material and energy intensive. An alternative, eco-friendly route is utilization of CO2- triggered switchable solvents. These solvents are capable of switching properties, such as hydrophilicity, polarity or ionic strength, upon reaction with . They revert their property when heated, or in the presence of an inert. Application of these solvents in the current industrial setup entails optimization of operational parameters, for which we use microfluidics. The experiments are carried out in the Taylor flow regime, which involves alternating segments of gas and liquid flowing in a straight circular capillary. The advantage of this setup is the availability of high interfacial areas and well-characterized flow profiles. As the mixture flows through the capillary, the gas segments shrink in size. We provide a systematic framework to interpret this data to extract solubility and kinetic parameters (e.g. diffusivity, reaction rates), supported by scaling analysis and simulations. To demonstrate our experimental method and analysis approach, experiments were carried out in circular, silica capillaries of different radii by generating segmented flow of CO2 in physical solvents such as acetonitrile and propylene carbonate. Our approach can be applied to diverse gas-liquid reaction systems to determine optimum

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

IOP 3: Green Chemistry Chairs: Long Yu, South China University of Technology, China; and Andrew Myers, USA

Lipid Profile of Oklahoma Native Microalgae New Development of Starch-based Materials Long Strains and Chemical Composition of the Bio-oil Yu*, Xioayan Ge, and Ying Chen, South China Produced by Pyrolysis of the Algal Biomass University of Technology, China Nurhan Dunford*, Oklahoma State University, USA The development and production of The objective of this study was to characterize biodegradable starch-based materials have been lipid content, fatty acid profile and biomass spurred by oil shortages and the growing interest in characteristics of seven algae strains isolated from easing the environmental burden of the same environment and grown in standard petrochemically derived polymers. Furthermore, media under similar conditions. Proximate the unique microstructures of different starches composition of the algal biomass was determined and their multiphase transitions during thermal using a thermogravimetric analysis method. Algal processing can be used as an outstanding model biomass was used for bio-oil production via system to illustrate our conceptual approach to microwave assisted pyrolysis, and the effects of understand the structure–processing–property final temperature on the product yields and bio-oil relationships in polymers. Various conventional composition were evaluated. Average biomass processing techniques such as extrusion, injection productivities of SP20, SP46 and SP50 were similar compression molding, and casting, as well as some and significantly higher than the other strains new techniques such as reactive extrusion, have examined in this study. Green algae strains, SP20 been adapted for processing starch-based and SP22, accumulated significantly higher amount polymers. In order to overcome disadvantages of lipids than all the cyanobacteria investigated in pure starch-based materials have, such as poor this study. Saturated fatty acid contents of the algal mechanical properties found in natural polymers; oils varied between 32.5% and 39.9%. The highest or the high price of synthetic polymers, various mono and polyunsaturated fatty acid contents blends and composites have been developed in the were observed in SP46 and SP22, respectively. last decade. The starch-based materials reinforced Total FAME content was highest in SP22 and the with natural fibres and nano-particles have been second highest in SP20. The bio-oil yield from developed to various environmentally friendly microwave assisted pyrolysis of algal biomass composites. The hydrophilic properties of starch produced by SP 46 increased from 4.6% to 22.5% provide the advantage of compatibility with with the increasing final temperature from 450 o C cellulose and nano clay. Compatibilizers and the to 750 o C. The major compounds in the bio-oil technology of reactive extrusion have been used to were acids, aliphatic hydrocarbons, aromatic improve the interface between natural and hydrocarbons, phenols, organic nitrogen synthetic polymers. Various starch-based products compounds. Microwave pyrolysis of algal biomass have been developed and commercialized. did not produce polycyclic aromatic hydrocarbons Examples of commercialized products of starch- at temperatures higher than 450o C. based materials.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

Synthesis and Characterization of Cardanol Based Integrated Methyl Esters Synthesis Technology for Epoxy/Amine System for Corrosion Prevention Multiple Feedstock Oils via Hydrodynamic John J. La Scala1, Giuseppe R. Palmese2, and Emre Cavitation Pilot Scale System Syed Awais Ali Shah Kinaci*2, 1Army Research Laboratory, USA; 2Drexel Bokhari*, Suzana Yusup, and Lai Fatt Chuah, University, USA Universiti Teknologi PETRONAS, Malaysia In this study, a cardanol based mono-epoxy, Methyl ester contributes to environmental cardanol glydcidyl ether (CGE) resins (LITE 2513HP, protection as it is biodegradable, renewable, non- Cardolite®) was epoxidized from the unsaturation toxic, and produces less sulphur oxides emissions sites of the side chain by using peroxide and greenhouse gases. The proposed system is a and formic acid to achieve a cardanol based side pilot scale system developed for semi batch chain epoxidized cardanol glycidyl ether (SCECGE) process capacity of 50 lit/batch. The present work resin with 2.45 epoxy functionality per molecule. highlights the potential of hydrodynamic cavitation This side chain epoxidized resin was incorporated for the methyl ester production from edible and with the synthetic based phenolic resin (DGEBA) non-edible oils. The transesterification process was with different ratios (0-100 wt.%) and thermally conducted under optimised conditions, i.e. oil to cured in the presence of a cyclo-aliphatic curing methanol molar ratio of 1:6 in the presence of 1 agent (PACM). The thermo-mechanical properties wt. % potassium hydroxide as alkali catalyst at of the fully cured formulations were obtained via 60°C. Current innovative method is capable in DMA and DSC methods and mechanical reducing the acid value of the feedstock oil and characterization was achieved via an UTM. Water increasing the purity of the final product of methyl and vapor sorption studies along with the esters, and able to process blended feedstock oil gravimetric water uptake measurements were also and/or produce blended methyl esters. Four newly applied to these fully cured formulations to designed orifice plate geometries induced cavities determine the corrosion coating performance of assisted by a double diaphragm pump in a pilot the polymers. Our findings suggest that; despite a scale hydrodynamic cavitation reactor were significant reduction in the thermo-mechanical investigated. It is shown that the high turbulence properties, addition of cardanol based epoxy resin generated by the cavitating bubbles were effective in to epoxy/amine system is significantly improved reducing the mass transfer resistance between the hydrophobicity and water barrier properties of immiscible reactants during the transesterification the final materials. In addition, the reactivity and reaction due to increased interfacial area. This makes the process more environmentally friendly. In the conversion of the secondary epoxies presented conclusion, methyl ester produced via hydrodynamic on the C15 side chain of the SCECGE resin were cavitation proved to be energy efficiency and time also explored and discussed in this study. Cardanol saving. Technology can be suitable with different types has a growing potential to supply bio-based of orifice plates to produce cavities by regulating flow aromatic building blocks for corrosion prevention rates and adjustable pressure to produce cavities to and composite applications for over 50 years. study its effect on methyl esters conversion. This technology can accommodate various types and blends of oils by varying different catalysts and types.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

IOP 4: New Uses of Glycerine Chairs: Franck Dumeignil, Université de Lille, France; and Xiaofei Ye, University of Tennessee, USA

Glycerol: A C3 Bio-based Platform Intermediates versatile intermediate or building block for the for Value-added Products Christophe Len*, production of methionine and plastics and Université de Technologie de Compiegne, France polymers that are environmentally friendly with The design of environmentally friendly wide applications in such as superabsorbent methodologies has been the driving force of polymers, textile treating agents, and adhesives. scientists in recent years. In particular, the use of Despite their industrial values and intensive effort biomass-derived materials, green solvents and to convert glycerol to acrolein/acrylic acid in recent alternatives techniques has been investigated. In years, quick catalyst deactivation in the conversion this regards, glycerol has the potential to be both of glycerol remains as a major technical obstacle an excellent renewable solvent in modern chemical hindering the commercial production of acrolein processes and a versatile building block in and acrylic acid from glycerol. In this study, biorefineries. In this conference, several green supercritical carbon dioxide (SC-CO2) was used for chemistry approaches that target advanced the first time as reaction medium for the synthesis and processes using glycerol will be dehydration of glycerol to acrolein catalyzed by presented. Few approaches will be described: (i) solid acids. Unprecedented catalyst stability over green synthesis of quinoline and phenanthroline 500 hours of time-on-stream was achieved and the derivatives in sole water using microwave rate of coke deposition on the catalysts is the irradiation and high temperature/pressure;[1] (ii) lowest compared to the extensive literature data, production of oligomer of glycerol for showing potential for industrial application. The polymerisation.[2] Conception, synthesis and coking pathways in SC-CO2 were also elucidated physico-chemical properties will be detailed. [1] (a) for future development. The results should also H. Saggadi, D. Luart, N. Thiebault, I. Polaert, L. have implications for other dehydration reactions Estel, C. Len, Catal. Commun. 2014, 44, 15; (b) H. catalyzed by solid acids. Saggadi, D. Luart, N. Thiebault, I. Polaert, L. Estel, C. Len, RSC Adv. 2014, 4, 21456; (c) H. Saggadi, I. New Catalytic Process for Highly Efficient Polaert, D. Luart, C. Len, L. Estel. Today Conversion of Glycerol to Allyl Alcohol Yoshihiro 2015, 255, 66. [2] M. Kumari, M. Billamboz, E. Kon1, Marcia Araque2, Benjamin Katryniok2, Takuya Leonard, C. Len, C. Böttcher, A.K. Prasad, R. Haag, Nakashima1, Joëlle Thuriot2, Sébastien Paul2, and S.K. Sharma. RSC Adv. 2015, 5, 48301. Franck Dumeignil*3, 1AIST, Japan; 2Unite de Catalyse et Chimie du Solide, Université de Lille, Overcoming Catalyst Deactivation in Glycerol France; 3Université de Lille, France Dehydration to Enable Sustainable Production of Allyl alcohol is known as a valuable starting Acrolein and Acrylic Acid Shoujie Ren1, Bin Zou1, material for the chemical industry. We have and Xiaofei P. Ye*2, 1Biosystems Engineering, developed a Re-based reusable catalyst, which, in University of Tennessee, USA; 2University of the presence of a sacrificial alcohol, enables a yield Tennessee, USA of 91 % of allyl alcohol from glycerol. This process Acrolein and acrylic acid are promising could significantly increase the economical viability derivatives of glycerol holding important status as of the biodiesel value chain by proposing a high - 13 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

value-added / high volume application for the by- produced glycerol. Moreover, this new methods reduces the environmental impact of allyl alcohol production, currently petro-sourced.

Reactive Distillation: Exploring Process Intensification Routes for the Oil Products Industry Tracy Benson* and Obakore Agbroko, Lamar University, USA Combining reaction engineering and distillation into a single unit operation presents some interesting challenges, yet, reduces the operational footprint as well as the operating and capital costs of manufacturing. Operational and design challenges include mismatched temperatures between the separating components and the reacting components, unfavorable volatilities, and slow reaction rates generally due to poor reactant/catalyst/product mass transfer rates. Reactive distillation is a likely pathway towards process intensification to minimize overall energy consumption, particularly since distillation accounts for 20 % of total energy used within the U.S. manufacturing sector. Increased reflux ratios typically yield higher product In this study, Aspen was used to model the conversion of glycerol to 1,3-propranediol and 1,2-propanediol while being separated from methanol, water, and other inorganic components that are commonly found in waste glycerol from biodiesel production processes. Using the Non-Random Two Liquid activity coefficient model, the number of trays, conversion, and product selectivities were estimated. To verify simulation results, laboratory experiments were conducted using a 1-inch ID, 32- tray glass distillation column. Column temperature profiles and reboiler heat duties were determined. The complete reactive distillation analysis will be presented as well as the extension of this technology into other areas of the oil products industry.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

IOP 5: Oleochemicals Chairs: Eric Cochran, Iowa State University, USA; and Guoqin Liu, South China University of Technology, China Oleosomes: Isolation and Commercial Use of were grafted onto epoxidized soybean oil (ESO) to Nature’s Oil-storage Vesicles James V. Gruber*, produce a liquid rubber modifier superior to Botaneco Inc., USA traditional butadiene-acrylonitrile copolymers for Nature has a way of perfecting the storage of toughening thermosets. FTIR and 1H NMR were large amounts of important materials into very employed to understand the chemical structure of small spaces. The storage of starch in corn kernels, the bio-rubber (BR). The composition of grafted the storage of DNA in a cell’s nucleus, and the ESO can be tuned to work with the many storage of triglyceride oils in oleosomes all are formulations of available thermoset resins. It was elements of Nature’s way of perfecting storage of demonstrated that significant improvement in fragile things in unique storage vesicles. Normal fracture toughness is achieved with a minimal commercial oil isolation processes typically reduction of Tg. Scanning electron microscopy squeeze oil from oil body structures or employ (SEM) of the fracture surfaces shows the harsh organic solvents like hexane to enhance appearance of a discontinuous rubber phase recovery of desired oil. However, under more resulting from chemically induced phase separation controlled and unique aqueous isolation mechanism. The size of the phase-separated conditions, it is possible to commercially recover oil domains can be varied from tens of nm to several seed oleosomes in their native state. As such, these µm by changing the composition of the BR and the products do not appear as normal refined oils, but processing conditions. Particle cavitation along the rather as creamy emulsions held intact by the crack was clearly observed rand is believed to unique emulsifying properties of the non- account for the greatly enhanced fracture denatured oleosome surface proteins. Commercial toughness. Dynamic mechanical thermal analysis use of oleosomes has expanded significantly in the (DMA) provides additional verification of the cosmetic arena where such emulsions are a natural existence of a prominent rubbery second phase and sustainable substitute for many synthetically- that does not result in significant loss of Tg. derived emulsifiers. This talk will focus on Moreover, the low viscosity associated with the BR commercial mechanisms of oleosome isolation provides ease of processing compared to common including how they differ from standard oil liquid and particulate rubber modifiers. recovery operations. In addition, the talk will focus on current uses of oleosomes based on safflower Structure Function Correlation of Bioplasticizers in and almond oil seeds and how they are finding PVC Dharma R. Kodali*, and Lucas J. Stolp, unique spaces in cosmetic ingredients. University of Minnesota, USA Plasticizers, the largest class of plastic additives, Toughening Thermoset Resins Using Grafted impart flexibility and improve the functionality of Epoxidized Soybean Oil Santosh K. Yadav1, John J. plastics. The currently used phthalate plasticizers La Scala2, and Giuseppe R. Palmese*3, 1Dept. of have EHS concerns. Bioplasticizers with various Chemical Engineering, Drexel University, USA; functional groups such as epoxy, acetoxy, methoxy, 2Army Research Laboratory, USA; 3Drexel thiirane, aziridine on the acyl chain and/or head University, USA group of soy fatty acid esters have been In this study, fatty acid/fatty anhydride residues synthesized and evaluated as plasticizers in poly - 15 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

vinyl chloride (PVC) applications. Synthetic performance liquid chromatography method procedures such as epoxidation, methoxylation, developed in our laboratory that utilizes an acetylation, thiiration, and aziridination were used evaporative light-scattering detector for for synthesizing multifunctional soy fatty acid quantification and mass spectrometer for chemical esters. Epoxidized soybean oil fatty acid esters identification. The results showed that the average served as the key intermediate to incorporate most amount of wax extracted from the surface of intact of the functional groups on the fatty acid sorghum kernels was about 0.3% weight percent backbone. The physical and analytical properties of using hexane at temperatures between 25-120 °C bioplasticizers such as acid and saponification and 1000 psi. The yield of wax varied among values are acceptable for plasticizer applications. common sorghum hybrids and cell lines and ranged The high viscosity and darker color of aziridine and from about 0.1 to 0.5 wt %. For sorghum bran, the thiirane derivatives limit their usefulness, whereas yield of wax was about 1% and the yield of oil was the physical properties of the other derivatives about 7-10%. For both whole grain sorghum and were acceptable for PVC applications. The bran, extraction with more polar solvents resulted plasticizer evaluation of epoxy, acetoxy soy fatty in higher yields of extracts, but after fractionation, acid ester derivatives demonstrated excellent the weight percent of waxes remained the same. compatibility with PVC, high efficiency (Shore Hardness), thermal stability and gelling properties. Animal Fats as Oleochemicals: Nitrogen The functional properties were comparable to Containing Contaminants Martin Mittelbach*, commercial plasticizer, diisononylphthalate (DINP). Sigurd Schober, and Tamara Ruprecht, Institute of Chemistry, University of Graz, Austria Extraction, Fractionation, and Characterization of Waste animal fats are an important feedstock Waxes from Sorghum Megan E. Hums*1, Jonathan for the oleochemical industry. A series of L. Hoyt1, Michael J. Powell1, and Robert A. contaminants restrict conventional conversion Moreau2, 1US Department of Agriculture, USA; processes. Impurities like sulfur, phosphorus, 2USDA, ARS, ERRC, USA calcium as well as polyethylene residues can have a Sorghum has potential as a domestic source of negative impact on the conversion itself, like wax for applications in the food and non-food poisoning heterogeneous catalysts, or remain industries. The waxes extracted from sorghum within the end product leading to quality problems. have similar physical properties to those of The composition of these impurities depends on Carnauba wax, a common imported commercial the source of the material and the treatment of wax. This work focused on the extraction, animal waste fat during the rendering process. In fractionation, and characterization of waxes from recent time also nitrogen containing impurities sorghum kernels and sorghum bran (obtained by were identified to influence the production of abrading the surface layers of the kernel, ~ 10% by biodiesel, leading to separation problems during mass). Extraction was performed using various the transesterification process or to precipitation in types of extractors and solvents, including hexane, the final product. One compound group could be ethanol, and methanol. A fractionation technique identified as primary fatty acid amides. Because of was developed to separate and quantify waxes the relatively high melting points of those from non-waxes. The fractions were then compounds they could separate after longer characterized using a reverse phase high storage of biodiesel, together with steryl glycosides

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

or saturated monoglycerides. We want to present Center, City University of New York, USA; 3The City an analytical approach for quantitative College of New York, USA determination of fatty acid amides in animal fats as Oleogels are supramolecular soft materials, in well as in biodiesel, based on GC as well as HPLC which gelator molecules self-assemble to form 3-D including SPE for sample treatment. The results network through weak intermolecular forces in based on spiking with synthesized C-19 fatty acid vegetable oils. Although an extensive research has amide as ISTD were compared with the been done on oleogels for various applications measurement of total nitrogen in the samples. It (pharmaceutical, food, cosmetics, petrochemical, can be seen that only a part of nitrogen could be environmental, tissue engineering, and art), their assigned to fatty acid amides, the origin of the industrial usage is still in the budding stage. One remaining nitrogen is still unclear. Possible sources major foreseeable constraint for the industrial of fatty acid amides and other nitrogen containing application of oleogels is how to maintain compounds are discussed. consistent physical properties during scale up. It has been discovered in this study that, when Application of Low Cost Ionic Liquids Analogues different sizes (1g, 5g, 10g, 15g, and 20g) of for Removal of Free Fatty Acid from Sludge Palm oleogels were prepared, the minimum gelation Oil Adeeb Hayyan*1, Shahidah N. Rashid2, Maan concentration of the gelators (sorbitol dioctanoate Hayyan3, M. Y. Zulkifli3, and Mohd A. Hashim2, (S8), mannitoal dioctanoate (M8), and 12-hydroxy 1University of Malaya, Malaysia; 2University of stearic acid (12-HSA)) varied when tested by the Malaya Centre for Ionic Liquids (UMCiL), Kuala inverted tube method and rheological studies. Lumpur, Malaysia; 3Institute of Halal Research Efforts to address this problem, including even University of Malaya, Malaysia after maintaining a constant aspect ratio (height: Sludge palm oil (SPO) low grade industrial oil diameter ratio) for all sizes, proved futile. Through generated from oil palm mills. SPO has high free a rigorous investigation, it was subsequently found fatty acid and therefore deep eutectic solvents that, when surface area to volume (S/V) ratio of (DES) was used as catalyst for reduction of FFA of the gels was kept constant, MGC and other physical SPO. This DES was made from ammonium acetate properties of the gel remained consistent (AmAc) and tolune-4-sulfonic monohydrate acid regardless of the sizes of the gel prepared; the (PTSA). Different operating conditions were other physical properties were solid phase content optimized such as catalyst dosage, molar ratio and (SPC), oil binding capacity (OBC), melting reaction temperature. FFA was reduced from 10% temperature (Tm), melting enthalpy (ΔHm), and to less than 2% under optimum conditions. This rheological properties (yield stress, Ys). Based on study revealed that DES made from AmAc and these findings, it could be inferred that S/V ratio of PTSA has high catalytic activity for FFA removal. the oleogels seems crucial in understanding and modulating the properties of the oleogels during An Investigation to Achieve Physical Consistency scale up studies. of Oleogels During Scale up Sai S. Sagiri*1, Malick Samateh2, and George John3, 1Center for Discovery and Innovation, Dept. of Chemistry, The City College of New York, USA; 2The City College of New York & Ph.D. Program in Chemistry at Graduate

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

IOP-P: Industrial Oil Products Poster Session Chair: Tracy Benson, Lamar University, USA 1. Edible Oleogels: Viable Alternative toward development of eco-friendly food processing Healthier Solid Fat Food Products D. Pulido*1, technologies. Malick Samateh2, Sai S. Sagiri3, Nannette 2. Starch Derivative to Emulsify Cedarwood Oil Hernadez1, Riliwan Sanni1, and George John4, and Pressure Treat Wood Fred J. Eller*1, William 1Dept. of Chemistry & Center for Discovery and Hay1, Grant Kirker2, and Mark Mankowski2, 1USDA, Innovation (CDI), The City College of New York, ARS, NCAUR, USA; 2USDA, FS, FPL, USA USA; 2The City College of New York & Ph.D. Previously, we demonstrated that CO2-derived Program in Chemistry at Graduate Center, City cedarwood oil has a range of bioactivities, including University of New York, USA; 3Center for Discovery insect repellency and toxicity as well as conferring and Innovation, Dept. of Chemistry, The City resistance to termites and wood-rot fungi. In the College of New York, USA; 4The City College of New earlier pressure treatment work, ethanol was used York, USA as the diluent/carrier. However, it is preferable to Gelation is a favorable alternative to the use a water-based carrier for several reasons. current methods of edible oil hardening Because water and cedarwood are immiscible, an (structuring): , interesterification, emulsifier was used to prepare a stable mixture of and addition of saturated fat. These traditional the materials. This research reports the use of a hardening methods have been associated with starch derivative to prepare a cedarwood oil-water syndromes such as obesity, coronary heart disease, emulsion and its use for treating wood against and diabetes. As an alternative, gelation of liquid termites and wood-rot fungi. oils into semisolids (oleogels) is a viable option for the future. Consequently, molecular gels are being 3. Waste Eggshell Catalyzed Conversion of explored due to their biodegradability, Jatropha Oil to Biodiesel Under an Ultrasonication biocompatibility and verse number and diversity of Jitenkumar C. Patel*, Gaurav K. Patel, and applications. In this study, low calorific sugars Hasmukh S. Patel, Dept. of Chemistry, Sardar Patel (sorbitol and mannitol) are converted to University, India amphiphilic molecules with gelation ability for Jatropha oil consisting of saturated and edible oil hardening. The gelators were synthesized unsaturated fatty acids was extracted from the in a single step from the respective raw materials seeds of Jatropha curcas using petroleum ether. using and capitalizing on the regiospecificity of The extracted oil was further utilized for lipase enzyme. The gelators were well transestrification process catalyzed by CaO characterized (TLC, 1H-NMR and 13C-NMR), procured from the waste egg shell leading to followed by gelation studies. Minimum gelation biodiesel under ultrasonic irradiation as energy concentration (MGC) and gel-to-sol transition source. The pure CaO was obtained by calcination temperature (Tg) studies have confirmed the of egg shell at 900 °C for a period of around 3 gelation efficiency of the sugar derivatives towards hours. The catalyst was characterized by X-ray the oils. In the nearby future, the as-synthesized diffraction, FT-IR and DT-TGA studies. Various molecules and structured oils may lead to the parameters like methanol to oil ratio, reaction time and quantity of the catalyst were considered to - 18 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

obtain biodiesel in high yields. The catalyst was quality mung bean cakes with higher quality could recycled and reused for over 5 reaction cycles. be produced by partially replacing SBO with palm Diverse physical and chemical properties like oil fractions. density, kinematic viscosity, etc. were also studied. 5. New Bis (Alkylthio) Fatty Acid Methyl Esters 4. Palm-based Mung Bean Cakes: Production via Gerhard Knothe*, USDA, ARS, NCAUR, USA Blending Three Different Palm Fractions with The addition reaction of dimethyl disulfide Soybean Oil Jun Jin*1, Yinhui Ma2, Liyou Zheng3, (DMDS) to mono-unsaturated fatty acid methyl Cheng Keat Ooi2, Xingguo Wang1, and Qingzhe Jin1, esters is well-known for analytical purposes to 1Jiangnan University, China; 2Palm Oil Research and determine the position of double bonds by mass Technical Service Institute of Malaysian Palm Oil spectrometry. In this work, the classical iodine- Board, China; 3CAAS, China catalyzed reaction is expanded to other dialkyl Objective: Mung bean cake is one of the most disulfides (RSSR), including diethyl disulfide (DEDS), famous soybean oil (SBO)-containing snacks in dipropyl disulfide (DPDS), dibutyl disulfide (DBDS), China. But the short shelf life and high cost di-iso-propyl disulfide (DiPDS) and di-tert-butyl dramatically reduce its market competitiveness, disulfide (DtBDS). Yields decrease with increasing which needs to be improved. Methods Used: Super length or branching of the alkyl moieties in the olein (SO), palm olein (PO) and palm stearin (PS) RSSR. While MS analysis is straightforward for the were selected respectively to partially replace the new derivatives, similar to the derivatization with SBO in ratios of 20%, 40%, 60% and 80%. The slip DMDS, 1H- and 13C-NMR spectroscopy is now also melting points, triacylglycerols and compatibilities extensively applied. The compounds exhibit various of the oil blends were analyzed to determine the interesting effects in NMR, including the possibility best blending ratios and additive amounts of the to distinguish erythro- and threo diastereomers, cake oils. Then the sensory, textural (gumminess, Besides this, initial investigations indicate chewiness and resilience) and oxidative stability potentially interesting properties of these indexes (OSIs) tests were carried out on the final compounds for a variety of applications. products: the cakes. Results: No eutectic effects occurred at 0-40 °C when 20%-80% SO, 60%-80% 6. Studies on Modulating Aesthetic and PO and 40%-60% PS were separately blended with Mechanical Properties of Molecular Gels Riliwan SBO. The best conditions for manufacturing the Sanni*1, Malick Samateh2, Sai S. Sagiri3, Raul Rivas1, cakes based on the compatibilities of the cake oils and George John4,1Dept. of Chemistry & Center for as follows: SO-cake, containing 20% cake oil that Discovery and Innovation (CDI), The City College of consisted of 80% SO and 20% SBO; PO-cake, New York, USA; 2The City College of New York & containing 20% cake oil that consisted of 80% PO Ph.D. Program in Chemistry at Graduate Center, and 20% SBO; and PS-cake, containing 15% cake oil City University of New York, USA; 3Center for that consisted of 60% SO and 40% SBO. These Discovery and Innovation, Dept. of Chemistry, The cakes demonstrated better quality compared to City College of New York, USA; 4The City College of the soybean-based cake in terms of sensory scores New York, USA and textural profiles. Furthermore, they showed Molecular gels are being designed as functional longer oxidation time (SO- and PO- and PS-cake: soft materials for food and personal care 0.66, 0.73 and 0.83 h, respectively) than the applications. There has been a need to develop soybean-based cake (0.51 h). Conclusions: High- them as structured oils that are solid-like as fats - 19 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

but are healthier than the current solid fats (trans- which may affect the properties of polyurethanes. fat and saturated fat). The mechanistic Algae are a future potential renewable source that resemblance of molecular gels to solid fats has can be manipulated by genetic modification to made them promising healthier alternatives. In this make desired oleochemicals for the use in regard, our research focuses on developing green, polyurethanes. New algal oils have been developed sustainable molecular gels. The gels are prepared with very regular structure which can be used for using low molecular weight gelators (LMWGs) that polyols and polyurethanes with improved are derived from abundant, green and inexpensive properties. Polyols prepared by epoxidation/ring biomass. The LMWGs are hence rendered opening and hydroformylation were made from renewable, eco-friendly, sustainable, algal oil with structure close to triolein. Novel biodegradable and producing less carbon print. polyurethanes were tried in foams for surfboards, From our previous studies, two sugar alcohol based flotation devices, elastomers for boot soles and LMWGs, mannitol and sorbitol derivatives, have adhesives. Mechanical properties of new materials shown great potential to structure vegetable oils. were excellent. However, while the gel of sorbitol derivative is translucent, it is weak; on the other hand, while 8. Evaluation of Octane Number Property of the gel of mannitol derivative is strong, it is Renewable Hydrocarbons Synthesized from opaque. Here we show how a gel with optimal Camelina sativa Randy L. Maglinao1, Chazley J. properties could be formulated by using a mixture Hulett*2, Eleazer P. Resurreccion2, and Alexandra K. of the two LMWGs. The results have shown that Jones1, 1Advanced Fuel Center, Montana State 2:8 ratio of the mannitol and sorbitol derivatives University-Northern, USA; 2Montana State gave the most efficient (lowest minimum gelation University Northern, USA concentration) gel that was most translucent. The Currently, the most widely used piston engine results have also indicated a correlation between aircraft fuel is 100 low lead aviation gasoline. It the composition of gelator-mixture and other contains lead which is used to boost octane properties like microstructure, oil binding capacity, number of the fuel. Although, its lead toxicity and gel-to-sol transition temperature, rheology, opacity contribution to air pollution have been long been and solid fat content. Thus, aesthetic and desirable realized and finding a replacement is imperative. physical properties of the oleogels may be Camelina sativa, a good rotational crop for wheat, achieved by a simple physical mixture of the can be processed to produce renewable gelators. hydrocarbons with desirable octane number rating. The novel conversion technology is a two-step 7. High Oleic Algal Oil Polyurethanes Olivera process, wherein the fatty acid moieties are split Bilic*1, Zoran Petrovic2, Jian Hong1, and Scott and refined to renewable hydrocarbons of varying Franklin3, 1Kansas Polymer Research Center/PSU, carbon lengths and medium-chain fatty acids. This USA; 2Pittsburg State University, USA; 3Checkerspot, study evaluates the prospect of utilizing the Inc., USA renewable hydrocarbon fraction derived from Polyurethanes are among the most widely used camelina processing as a blend component for classes of polymers due to their excellent physical unleaded aviation gasoline. Results of the study and mechanical properties. polyols includes detailed hydrocarbon analyses of have usually very heterogeneous composition distillates and combustion and physico-chemical

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

properties (e.g., distillation, viscosity, acidity, (2-MAG) rich in DHA through a three-step process octane number, etc.). The novel and patented is performed: 1) synthesis of 2-MAG by ethanolysis process to selectively convert camelina to aviation of tuna oil, 2) 2-MAG purification by liquid-liquid gasoline is also discussed. extraction, 3) 2-DHA-MAG purification by low temperature crystallization. The effects of enzyme 9. Starch-lipid Complexes for Aerogel Formation type, reaction time, reaction temperature, reactant Jim A. Kenar*, Fred J. Eller, Frederick C. Felker, radio and lipase amount were investigated. Under George F. Fanta, Michael A. Jackson, and Jeffrey A. the optimized conditions (ethanol/tuna oil=4:1 Byars, USDA, ARS, NCAUR, USA (w/w), 8% Lipozyme 435 from Candida Antarctica), Recently, we have reported that aqueous there was about 26.5% (area/area) 2-MAG slurries of starch can be excess steam jet-cooked produced in the crude mixture with 78.6% yield in and blended with aqueous solutions of fatty acid 3 h. Subsequently, 2-MAGs were purified by liquid- salts to produce inclusion complexes between liquid extraction. Using hexane and 85% ethanol amylose and the fatty acid salt. These complexes aqueous solution, there was 95.0% 2-MAG can be simply prepared on large scale using obtained with 87.2% yield. Finally, 2-DHA-MAG was commercially available steam jet cookers. The concentrated by low solvent crystallization. physical interaction between the fatty acid salt and Hexane, acetone, ethanol and acetonitrile were the amylose component of the starch confer used to enrich 2-DHA-MAG. The highest content of unique polyelectrolytic and physicochemical 2-DHA-MAG (70.3%) was purified by acetonitrile in properties to the bulk material not inherent to -40 °C for 5 h. The remaining MAGs content in the either the native starch or fatty acid salt alone. product was 94% and PUFA-MAGs was more than Aqueous dispersions of inclusion complexes were 87%. Compared to previous methods, our method used to form hydrogels between pH 5.5-6.5. for preparation of 2-DHA-MAG is more economical Subsequent, solvent exchange with ethanol and easier to scale up. In addition, the method followed by supercritical carbon dioxide (SC-CO2) conducted in low temperature is good for stability drying of these gels preserved the structure of the of PUFA and also avoids acyl migration of 2-MAG. gels and yielded the corresponding aerogels. This Keywords: 2-monoacylglycerol, DHA, enzymatic study describes recent results concerning the ethanolysis, low temperature crystallization characterization and properties of these starch- fatty acid salt inclusion complexes and their 11. A Sustainable Process for the Synergy corresponding aerogels. Between Petroleum and Biofuels Industries in Nigeria Chika S. Ezeanyanaso*, Gloria N. Elemo, 10. Preparation of 2-Monoacylglycerol Rich in Viola A. Nwachukwu, Segun Munir, and Chima C. DHA by Enzymatic Ethanolysis and Crystallization Igwe, Federal Institute of Industrial Research Yu Zhang*1, Xiaosan Wang1, Ruijie Liu2, Qingzhe Oshodi, Nigeria Jin1, and Xingguo Wang1, 1Jiangnan University, Fossil fuels are globally consumed commodities China; 2Jiangnan University, China; Cornell and the world is facing acute peaking problems due University, USA to the ever increasing demand in the face of It has been reported that 2-monoacylglycerol dwindling production rate and very serious rich in DHA exhibits various biological functions. In environmental challenges. In Nigeria, the this paper, the preparation of 2-monoacylglycerol dependence on imported petroleum products for

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

meeting local demands coupled with the while others provide all three of these benefits and instabilities in the centers of petroleum production more. The flexibility of tall oil based chemistry has resulted in fluctuations in oil price and allows for a wide range of products providing an destabilizing the nation economies. Our near total array of additive benefits to lubricant reliance on petroleum to fuel transportation manufacturers. This presentation sheds some light threatens our economy, causes devastating effects on how tall oil is made, the multi-functional nature of climate change that threatens man’s existence, of tall oil based chemistry, and the unique and poses a unique threat to our energy security. characteristics that make these additives a good fit Combination of these factors has renewed the for such a wide range of applications. interest in finding alternate sustainable fuels such 13. Synthesis and Characterization of as biofuels to augment energy-security and at the Phosphonates from Methyl Linoleate and same time maintain food security. Hence, this Vegetable Oils Grigor Bantchev*, Bio-oils Research paper highlights the opportunities and challenges Unit, NCAUR, ARS, USDA, USA of a synergy between petroleum and biofuels Phosphonates were synthesized at medium industries in Nigeria for sustainable energy scale (~200 g) from three lipids – methyl linoleate security. In conclusion, the paper recommends (MeLin), high-oleic sunflower oil (HOSO) and efficient policy implementation as a pathway of soybean oil (SBO), and three dialkyl phosphites – ensuring a sustainable petroleum and biofuels methyl, ethyl and n-butyl, using radical initiator. synergy, especially with large availability of arable Staged addition of the lipid and the initiator to the land and varieties of bio-resources for biofuel dialkyl phosphite was needed to achieve good production. yields. Good results were observed with MeLin and

HOSO using tert-butyl perbenzoate as initiator. 12. The Benefits, Uses, and Future of Pine With SBO, benzoyl peroxide was used as initiator, Chemistry for Lubricant Applications Monica A. due to its capability to generate radicals at higher Ford*, Eric J. Olivier, Nicholas Kob, and Aaron rate at slightly lower temperature and thus to Engel, Ingevity, USA shorten the reaction time. The progress of the Tall oil based products have historically been reaction was monitored with GC-MS. The products used in the lubricant industry for a wide range of were characterized using 1H, 13C and 31P NMR, IR applications, and they are used as additives to and gel permeation chromatography. Prolonged boost the performance of many different lubricant reaction led to some transesterification between systems from metalworking fluid formulations to the carboxylic and dialkyl phosphite ester groups. fuel additives. This variety of applications is made Higher reaction rate led to formation of more possible by the chemical nature of the products; all oligomers and benzoate fatty ester byproducts. tall oils are naturally occurring mixtures of The benzoate fatty ester byproducts were formed monomer fatty acids and tricyclic diterpene acids. by attack of a benzoate radical on a double bond. Each grade of tall oil has it's own unique mixture of fat and rosin isomers, and the ratio of these 14. Designing Multifunctional Sugar Alcohol- molecules dictates the performance of each based Oleogels as Solid Fat Substitutes Malick product. Not all tall oil based products are created Samateh*1, Sai S. Sagiri2, and George John3, 1The equal. Some tall oil based products only provide City College of New York & Ph.D. Program in emulsification, lubrication or corrosion inhibition; Chemistry at Graduate Center, City University of

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

New York, USA; 2Center for Discovery and 15. Analysis of Phorbol Ester of Jatropha Curcas L. Innovation, Dept. of Chemistry, The City College of by HPLC with UV-VIS and ToF-MS Detection New York, USA; 3The City College of New York, USA Philipp M. Neu*1, Sigurd Schober2, and Martin The use of vegetable oils, instead of solid fats, Mittelbach2, 1University of Graz, Austria; 2Institute has been receiving special attention due to their of Chemistry, University of Graz, Austria nutritional and health benefits associated with The oil of the seeds from Jatropha curcas L. is a unsaturated fatty acids (UFAs). However, efforts to promising biodiesel feedstock which gets trans- incorporate the oils in food products are esterificated to obtain biodiesel. The remaining challenged by lack of similar organoleptic press cake contains proteins and other nutritional properties and oxidative stability as those of fat- compounds which makes it as ideal source for structured food materials; the oils are prone to animal feed supply. However, most of the oxidation due to the presence of UFAs. The harvested Jatropha products are toxic to humans techniques adapted to solve these issues include and animals due to the natural ingredients partial hydrogenation and addition of solid fat and toxalbumin curcin and the group of diterpenester: synthetic antioxidants. However, the limitations phorbol esters . These phorbol esters show skin include, for instance, catalytic hydrogenation leads irritant, inflammatory and carcinogenic promotor to trans fats, which are being restricted owing to activity. Analytic procedures were established for growing health concerns. To address these the phorbol esters content like HPLC-UV at a challenges, multifunctional low molecular weight wavelength at 280 nm and comparison with gelators (LMWGs) are hereby proposed to impart phorbol myristat acetate as internal standard. The both mechanical and oxidative stability to oils. difference in the fatty acid sidechains leads to Selecting optimal precursors form plant sources different absorption effects at the detected and combining the capabilities of biocatalysis in a wavelength and cause problems for exact GRAS protocol, we have successfully designed and quantitative measurements. Furthermore, the lack demonstrated an array of simple sugar alcohols of commercial available standards hinders deeper (mannitol, sorbitol, and xylitol) based LMWGs as investigations. In this work we want to focus on a multifunctional structuring agents, exploiting their fast identification and precise measurement of low-/non-caloric and antioxidant properties. phorbol ester content. This is performed on an Structuring ability was systematically tested in Agilent 6200 Series HPLC-ToF-MS. We use a RP-C18 edible oils such as canola, soybean, olive and corn column to separate the analytes of a methanolic oil oils, which created excellent oil gels (oleogels) with extract chromatographically and with the help of minimal gelator concentration. The nature and the high resolution mass spectrometry focused on aesthetic value (transparency/opaqueness) of the the formic-PE analyte adducts the interfering oleogels can be tuned by gelator concentration, matrix e.g. free fatty acids is reduced. The results nature of oil, etc. The study also aims at finding the were measured by standard addition method with correlation between textural and organoleptic a three step purified PE and PMA as internal properties against the nanostructure and rheology standard. The LOQ of the used method was 50 µg of the oleogels for future food applications. PE/ g Oil. Tested Jatropha oils had a PE content of approximately 1 mg/g oil coming from different origins.

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