Sustainable Oxidative Cleavage of Vegetable Oils into Diacids by Organo-Modified Molybdenum Oxide Heterogeneous Catalysts

Exploiting vegetable oils to produce industrially valuable diacids via an eco‐friendly process requires an efficient and recyclable catalyst. In this work, a novel catalytic system based on organo‐modified molybdenum trioxide was synthesized by a green hydrothermal method in one simple step, using Mo powder as precursor, hydrogen peroxide, and amphiphilic surfactants cetyltrimethylammonium bromide (CTAB) and tetramethylammonium bromide (TMAB) as capping agents. The synthesized materials were first characterized by different techniques including XRD, SEM, TGA, and FT‐IR. Interestingly, various morphologies were obtained depending on the nature of the surfactants and synthetic conditions. The synthesized catalysts were employed in oxidative cleavage of oleic acid, the most abundant unsaturated fatty acid, to produce azelaic and pelargonic acids with a benign oxidant, H₂O₂. Excellent catalytic activities resulting in full conversion of initial oleic acid were obtained, particularly for CTAB‐capped molybdenum oxide (CTAB/Mo molar ratio of 1:3) that gave 83 and 68% yields of production of azelaic and pelargonic acids, respectively. These are the highest yields that have been obtained for this reaction by heterogeneous catalysts up to now. Moreover, the CTAB‐capped catalyst could be conveniently separated from the reaction mixture by simple centrifugation and reused without significant loss of activity up to at least four cycles.     

Pelargonic acid in enhanced oil recovery

Oxidation of monounsaturated fatty acids, such as erucic and oleic acids, results in the formation of dibasic fatty acids, such as brassylic and azelaic acids. Dibasic acids find many industrial applications. Pelargonic acid is the co-product of the process. Expanded use of dibasic acids would require an expansion in the existing and possibly new uses for pelargonic acid and its derivatives. In this study, the potential for using pelargonic acid in enhanced oil recovery is investigated. Experimental results are presented for the enhanced oil recovery by waterflooding with the aid of a surfactant.In situ formation of surfactant at the oil-water interface vs. the formation of surfactant in the floodwater prior to injection is examined.     

Oxidation of unsaturated and hydroxy fatty acids by ruthenium tetroxide and ruthenium oxyanions

The reactions of ruthenium VIII tetroxide (RuO₄) and the ruthenium VII and VI oxyanions, perruthenate (RuO₄ ⁻) and ruthenate (RuO₄ ⁼) with hydroxy substituted and unsaturated fatty acids have been studied. At a 1:1 molar ratio, ruthenium tetroxide (RuO₄) and both oxyanions (RuO₄ ⁻ and RuO₄ ⁼) oxidized 12-hydroxystearic acid to 12-ketostearic acid. With 9, 10-dihydroxystearic acid, the type of oxidation products obtained depended on the amount of ruthenium oxidant used. At high ratios of oxidant to substrate, cleavage to pelargonic and azelaic acids occurred whereas at lower ratios, partial oxidation to diketo and acyloin derivatives predominated. The oxidation of oleic acid with excess ruthenium tetroxide (RuO₄) or perruthenate anion (RuO₄ ⁻) gave the cleavage products pelargonic and azelaic acid through the intermediate formation of dihydroxy and diketo intermediates. Ruthenate anion (RuO₄ ⁼) did not react with the double bond of oleic acid. Agricultural Research Service, U.S. Department of Agriculture.     

Liquid Phase Selective Catalytic Oxidation of Oleic Acid to Azelaic Acid Using Air and Transition Metal Acetate Bromide Complex

Industrially important di‐carboxylic acids are synthesized from mono‐carboxylic unsaturated and unsaturated fatty acids. In this study, the aim is to perform the simultaneous catalytic oxidative C=C cleavage of oleic acid (OA) to azelaic acid and pelargonic acid, and oxidation of the terminal methyl group in pelargonic acid to azelaic acid using cobalt‐ and manganese‐acetate as catalyst, hydrogen bromide as co‐catalyst and air in acetic acid at elevated pressure (2.8–5.8 barg) and temperature (353–383 K). Oxygen solubility is determined under varying pressure, temperature and OA loading. The effect of OA loading, pressure and temperature on OA conversion and azelaic acid selectivity is studied by varying one variable at a time; however, the presence of the synergistic effect of the catalyst and co‐catalyst is investigated by central composite design assisted response surface methodology. Oxidation of terminal methyl group in saturated fatty acid is also confirmed by the oxidation of stearic acid to octadecanedioic acid using identical oxidation conditions of OA. Oxidation products of fatty acids are quantified by gas chromatographic analysis. The innovation of the work is thus the ability of the catalytic system to perform a total oxidation of a terminal methyl group of the hydrocarbon chain. OA oxidation kinetics relating to catalyst and co‐catalyst concentration along with oxygen solubility at elevated temperature and pressure is established. The frequency factor and activation energy for OA oxidation is determined using the Arrhenius equation.     

Gold‐catalyzed synthesis of dicarboxylic and monocarboxylic acids

Vicinal dihydroxy derivatives of oleic acid, methyl oleate, and erucic acid were converted by oxidative cleavage to the respective di‐ and monocarboxylic acids according to an environmentally benign process carried out in the presence of supported gold catalysts and molecular oxygen as oxidant in an aqueous‐basic medium. Au(0) nanoparticles with particle sizes between 0.5 and 4.1 nm were deposited as catalytically active species on different oxidic supports. The influence of the catalyst composition and morphology as well as of the reaction conditions on conversion of dihydroxy fatty acids and yields of products were investigated. Thus, the reaction of 9,10‐dihydroxystearic acid catalyzed by Au/Al₂O₃ leads to azelaic acid (86% yield) and pelargonic acid (99% yield).     

Periodate-permanganate oxidations for determining location and amount of unsaturation in monounsaturated fatty acids

Conclusions Periodate-permanganate oxidation of three samples of oleic acid considered to be of high purity has given reproducible but less than theoretical amounts of total dibasic acids. Recovery approximated 92% with about 90.3% of the expected azelaic acid. Recovery of other dibasic acids indicated that about 1.5% of the total unsaturation of these samples of oleic acid was present in positions 8 or 10 in the fatty acid molecule. Oxidation of elaidic acid produced from one of the oleic acids has given total dibasic acid yield of about 96%, with a smaller amount of its total unsaturation in the same position as in the parent oleic acid. Oxidation of high purity 9,10-dihydroxystearic acid has given essentially quantitative yield of total dibasic acids. The method described should be useful in determining the composition of similar unsaturated positional isomers. Controls showing the effect of the method on azelaic acid and on a mixture of azelaic acid with pelargonic have shown essentially quantitative recovery of azelaic acid. Failure to establish quantitative recovery on oxidation of oleic acid must be caused by some unknown factor during oxidationper se. The experimental technique described was satisfactory for quantitative studies of the type undertaken. Oxidation of moderate-purity, mono-unsaturated fatty acids, such as erucic, 10-undecenoic, and vaccenic acid, has given mixed dibasic acids corresponding to the respective positions of unsaturation. The data indicate that the method described shows the position of minor unsaturation within about 1%. Presented at meeting of American Oil Chemists' Society, Chicago, Ill., September 24–26, 1956.     

Double bond oxidation of unsaturated fatty acids

Different oxidizing agents for performing the cleavage oxidation of the double bond of the unsaturated fatty acids are presented, and their economic performance is analyzed. Ozone and sodium hypochlorite are the most commercially efficient oxidants. Laboratory work for the oxidation of oleic acid to azelaic and pelargonic acids using hypochlorite as oxidant is described. The advantages of working in an emulsion system and using RuCl₃ as a catalyst are discussed, and a possible mechanism of the reaction is presented. A flow sheet for an industrial process based on this concept is proposed. A simulation of a plant using this technology is made by a computerized model, and the economic parameters obtained permit us to conclude that the sodium hypochlorite can be an interesting reagent for industrial oxidations of double bonds in fatty acids.     

Permanganate oxidation of oleic acid using emulsion technology

Free oleic acid is emulsified in water and oxidized using potassium permanganate, to azelaic and pelargonic acids together with dihydroxy-, ketohydroxy-and diketo-stearic acids at neutral pH. The yield and the products distribution are controlled by: the type of emulsifier and its concentration; the oleic acid concentration in the emulsion; and the oleic acid-oxidant ratio.     

The development and application of novel vegetable oils tailor‐made for specific human dietary needs

Conventional edible oils, such as sunflower, safflower, soya bean, rapeseed (canola) oils, were modified to obtain high‐oleic, low‐linoleic or even low‐linolenic oils. The aim was to develop salad, cooking and frying oils, that are very stable against lipid peroxidation. They are also suitable for margarine blends, as additives to cheeses and sausages, or even as feed components. Oils containing higher amounts of medium‐chain length or long‐chain polyunsaturated fish oil fatty acids are suitable as special dietetic oils or as nutraceuticals. High‐stearic oils are designed as trans‐fatty acid‐free substitutes for hydrogenated oils. New tailor‐made (designer) oils are thus a new series of vegetable oils suitable for edible purposes, where conventional oils are not suitable.     

Impact of development periods on chemical properties and bioactive components of safflower (Carthamus tinctorius L.) varieties

This study aimed to determine the chemical properties (fatty acid composition, oil content, sterol and tocopherol compositions) of the oils extracted from the seeds of safflower (Dinçer, Remzibey, Balci, Linas, Yenice, Olas) varieties harvested in different periods from flowering to ripening period. In parallel with the increase of harvest time, the humidity rate decreased, while the oil ratios increased. It was determined that palmitic (16:0) and stearic (18:0) acids, which are significant saturated fatty acids, and oleic (18:1) and linoleic (18:2) acids, which are unsaturated fatty acids, are quite high in the oils of all safflower varieties. These fatty acids showed significant changes from the first harvest to the last harvest. The total saturated fatty acid ratios decreased, while the amount of unsaturated fatty acids increased as the maturation progressed. The first and latest harvest samples of Dinçer, Remzibey, Balcı, Linas, Yenice, Olas cultivars were selected and their sterol and tocopherol compositions were examined. The highest level of sterol in all cultivars was β-sitosterol and the amount of sterols decreased towards full maturity. It was determined that α-tocopherol was the dominant tocopherol found in the safflower oils and the amount of tocopherol increased towards full maturity.     

Industrial uses of high erucic oils

Vegetable oils rich in erucic acid have desirable properties for a variety of applications. At present, only a fraction of the potential that exists for commercial exploitation of high erucic oils in the United States is fulfilled with 10 million pounds of rapeseed oil imported annually. Though rape is not a crop in the United States, another member of the mustard family, crambe, has been recommended by the USDA as a practical crop for domestic cultivation. Compared to rapessed oil, crambe oil is more suitable for industrial use because it consistently contains a higher percentage of erucic acid. High erucic oils, as examplified by crambe, can be employed as lubricants in continuous steel casting, in formulated lubricants and in the manufacture of rubber additives. Both the hydrogenated oil and derived wax esters have properties comparable to commercial waxes. Useful nitrogen derivatives can be prepared from either the erucic acid or mixed acids from the oil; behenyl amine is used in a corrosion inhibitor, disubstituted amides are effective plasticizers and erucamide is an excellent slip and antiblocking agent for plastic films. Oxidative ozonolysis of erucic acid produces the dibasic acid, brassylic, and the monoacid, pelargonic. Mixed diacids, mainly brassylic and azelaic, can be obtained by ozonolysis of fatty acids from the oil. Alkyl diesters of brassylic, or of the mixed diacids, are excellent low temperature plasticizers. Two new nylons (13 and 1313), which are derived from C-13 difunctional products of erucic acid ozonolysis, contain repeating units that have longer uninterrupted polymethylene chains than other nylons. Moderate melting points and exceptionally low water absorption are a consequence of this structure. The low-melting characteristic is an advantage in adhesive uses and facilitates fluidized-bed coating, molding and extrusion; low moisture affinity contributes to excellent electrical properties and dimensional stability. One of 9 papers presented at the Symposium, “Cruciferous Oil-seeds”. ISF-AOCS World Congress. Chicago, September 1970. No. and Eastern Utilliz. Rev. Div., ARS, USDA.     

Reactions of ozone. VII. Ozonization of fatty acids and their derivatives

Ozone was a useful tool very early in the history of structural studies involving fatty acids and their derivatives. More recently the productions of azelaic and pelargonic acids by the ozonolysis of oleic acid has become of commercial importance. This paper reviews the chemistry of the ozonolysis of various unsaturated fatty acids and their derivatives. The products can be varied from a single starting material depending on the manner of decomposing the intermediate ozonide. Thus, variations in starting material and variations in procedure make possible a great variety of straight chain products containing one or two functional groups such as carboxyl, aldehyde, hydroxyl, and amino.     

Czonolysis as a method for establishing the position of olefinic linkages

Summary Ozonolysis and chromatographic procedures as a method for determining the position of double bonds in olefinic acids are not entirely satisfactory. Ozonolysis is seriously limited because of the secondary reactions undergone by the ozonide. Chromatographic resolution of the decomposed ozonides of oleic acid yields the expected pelargonic and azelaic acids but also yields fractions that indicate double bonds which do not exist. Fractions corresponding to pimelic, sebacic, caprylic, suberic, and capric acids appeared. The “pimelic acid” fraction resulted from the reaction of ozone with an oxidizable or hydrolyzable solvent such as acetone, methanol, or tetrachloromethane. The “sebacic” and “caprylic acid” fractions were incompletely decomposed ozonide. The suberic and capric acid fractions however were real and are believed to have resulted from 8-octadecenoic acid present in the oleic acid in amounts too small to be detected by the methods used to establish its purity.     

Impact of Free Fatty Acids and Phospholipids on Reverse Micelles Formation and Lipid Oxidation in Bulk Oil

Association colloids such as phospholipid reverse micelles could increase the rate of lipid oxidation in bulk oils. In addition to phospholipids, other surface active minor components in commercial oils such as free fatty acids may impact lipid oxidation rates and the physical properties of reverse micelles. In this study, the effects of free fatty acids on changes in the critical micelle concentration (CMC) of 1,2-Dioleoyl-sn-glycero-3-phosphocholine (DOPC) in stripped corn oil (SCO) were determined by using the 7,7,8,8-tetracyanoquinodimethane solubilization technique. Different free fatty acids including myristoleic, oleic, elaidic, linoleic and eicosenoic were added at 0.5 % by wt along with the DOPC into the bulk oils. There was no significant effect of free fatty acids with different chain length, configuration and number of double bonds on the CMC value for DOPC in bulk oil. However, increasing concentrations of oleic acid (0.5 to 5 % by wt) caused the CMC value for DOPC in bulk oils to increase from 400 to 1,000 μmol/kg oil. Physical properties of DOPC reverse micelles in the presence of free fatty acids in bulk oils were also investigated by the small angle X-ray scattering technique. Results showed that free fatty acids could impact on the reverse micelle structure of DOPC in bulk oils. Moreover, free fatty acid decreased pH inside reverse micelle as confirmed by the NMR studies. The oxidation studies done by monitoring the lipid hydroperoxide and hexanal formation revealed that free fatty acids exhibited pro-oxidative activity in the presence and absence of DOPC. Different types of free fatty acids had similar pro-oxidative activity in bulk oil.     

Catalytic Oxidation of Oleic Acid in Supercritical Carbon Dioxide Media with Molecular Oxygen

Oxidation of oleic acid was performed over various ordered porous catalysts containing transition metal in supercritical carbon dioxide (scCO₂) media with molecular oxygen. Oleic acid was completely decomposed into mono- and dicarboxylic acids over porous catalysts, viz., mesoporous molecular sieves (CrMCM-41, MnMCM-41, CoMCM-41) and microporous molecular sieves (CrAPO-5, CoMFI, MnMFI) using scCO₂ at 353 K for 8 h. Among the different catalysts studied, microporous and mesoporous catalysts containing chromium, in presence of scCO₂ showed high distribution of azelaic and pelargonic acids as compared to their analogs containing cobalt or manganese. The presence of scCO₂ medium with the catalysts increased the distribution of azelaic and pelargonic acids. The effect of CO₂ pressure, reaction temperature and reaction time on oxidation of oleic acid over CrMCM-41 was also investigated. Additionally it is noticed that the catalyst can be recycled with negligible loss of catalytic activity.     

Preparation of Isocyanates from Linseed,Safflower and Tall Oil Fatty Acids: I

Fatty acids from linseed, safflower and tall oils were converted to the corresponding isocyanates by two methods. In the first method linseed and safflower fatty acids were converted to the acid chloride either with thionyl chloride or oxalyl chloride and the acid chlorides were converted to the azide which was finally decomposed into the isocyanate. Yields of isocyanates were related to the method used to prepare the parent acid chlorides, the oxalyl chloride procedure giving higher yields of isocyanates. Loss in unsaturation from acids to isocyanates was slight. The tall oil isocyanates were prepared in hig yields via the phosgene method, thus, fatty acids to nitriles to amines, to the amine hydrochloride which were then reacted with phosgene. The isocyanates prepared by this procedure contained one more CH₂ group than those prepared via the first mentioned method. The infrared spectra of all isocyanates were essentially identical.     

Lipid changes in maturing oil-bearing plants. II. Changes in fatty acid composition of flax and safflower seed oils

Changes in the fatty acids composition of the oil in flax and safflower seed that occur during the seed-ripening period have been measured. Concentrations of lipid or of specific fatty acid, expressed on a weight-per-seed basis, have been plotted as functions of days after fertilization and of percentage of oil development. Relations between these two independent variables have been established, and limitations to the unsefulness of the latter variable have been pointed out. Days after fertilization proved to be the more useful abscissa. Nonpolar solvents were used to remove free lipid from the tissue, and the total extractable matter was separated into true lipid and nonlipid components. With both flax and safflower, weight of true free lipid per seed and total unsaturation increased during the same period of growth. Nonlipid extractable matter was an inverse function of the extent of development. In developing flax seed, oleic, linoleic, and linolenic acids all increased continuously; oil in immature seed however was more saturated than oil in more mature seed. Nevertheless the ratio of linolenic acid to linoleic acid that characterizes linseed oil was established by the 20th day after fertilization during a normal growing season. In developing safflower seed, oleic acid concentration increased slowly during the first 30 days after fertilization and then appeared to level off in some cases as maturity was approached. Initially linoleic acid was present in almost the same amount as oleic acid, but by the 20th day after fertilization its concentration was three times that of oleic acid. This ratio of linoleic to oleic acid tended to increase steadily during the latter part of seed development.     

Structure of unsaturated vegetable oil glycerides: Direct calculation from fatty acid composition

Composition and structure of unsaturated glycerides of vegetable oils can be calculated directly from the fatty acid composition of the oil. Fatty acid distribution on the 2 position as normally determined by lipase hydrolysis is calculated from the composition of the whole oil by applying the following three rules in their respective order: Saturated fatty acids and those with chain length greater than 18 carbons are first distributed equally and randomly on the 1 and 3 position of the glycerol moiety; oleic and linolenic acids are treated equally, or as a unit, and distributed equally and randomly on all three glyceride positions with any excess from the 1 and 3 position being added to the 2 position; and all remaining positions are filled by linoleic acid. Remarkably good agreement between the calculated and experimentally determined fatty acid distributions is shown for soybean, linseed, safflower and many other vegetable oils whose compositions are reported in the literature. An association between oleic and linolenic acid within the glyceride structure of some vegetable oils is evident. Presented in part at the T. P. Hilditch Symposium Annual Meeting AOCS, Houston, Texas, 1965. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Specificity of a lipase fromGeotrichum candidum forcis-octadecenoic acid

A lipase fromGeotrichum candidum released mostly oleic acid from glyceryl 1-elaidate-2,3-dioleate and very littletrans fatty acid from margarine. When cod liver, Macadamia nut, peanut and safflower oils were substrates, the oleic acid content of the free acids was always in excess of the amount of the acid in the intact triglycerides. Congo palm oil was digested by bothG. candidum and pancreatic lipases and the fatty acid compositions of the products of hydrolysis compared. The results obtained with the aid ofG. candidum lipase tend to substantiate existence of some of the triglyceride isomers predicted from pancreatic lipase data. Scientific contribution No. 134, Agricultural Experiment Station, University of Connecticut, Storrs.     

Current advances in sunflower oil and its applications

The fatty acid and triacylglycerol composition of a vegetable oil determine its physical, chemical and nutritional properties. The applications of a specific oil depend mainly on its fatty acid composition and the way in which fatty acids are arranged in the glycerol backbone. Minor components, e. g. tocopherols, also modify oil properties such as thermo‐oxidative resistance. Sunflower seed commodity oils predominantly contain linoleic and oleic fatty acids with lower content of palmitic and stearic acids. High‐oleic sunflower oil, which can be considered as a commodity oil, has oleic acid up to around 90%. Additionally, new sunflower varieties with different fatty acids and tocopherols compositions have been selected. Due to these modifications sunflower oils possess new properties and are better adapted for direct home consumption, for the food industry, and for non‐food applications such as biolubricants and biodiesel production.