Diffusion coefficients of C18 unsaturated fatty acid methyl esters in supercritical carbon dioxide containing 10% mole fraction ethanol as modifier

To determine the molecular diffusion coefficients of C18 unsaturated fatty acid methyl esters in supercritical carbon dioxide (scCO₂) containing 10 mol% ethanol as a modifier, four methyl esters of C18 fatty acids, i.e., methyl oleate, methyl ricinoleate, methyl linoleate and methyl linolenate were selected as the typical solutes. The diffusion coefficients were measured at temperatures from 313.15 to 333.15 K and pressures from 15 to 27 MPa using the Taylor–Aris chromatographic peak broadening (CPB) technique. The influences of temperature, pressure, density and viscosity of the solvent mixture on the diffusion coefficients were examined. The results show that methyl oleate always diffuses faster than methyl ricinoleate at the same operating condition. Moreover, the D₁₂ values in ethanol-modified scCO₂ decrease with the increase of the number of C-C double bonds in C18-methyl ester, which is consistent with the trend reported in pure scCO₂. The diffusivity data are compared with the estimation of eleven predictive models. The modified Wilke–Chang equation is the best purely predictive model and the free volume model of Dymond with two adjustable parameter gives the least errors with average absolute deviations lower than 2.5%.     

Thermal Decomposition of Some Acetoxyoctadecenoates and Acetoxyoctadecadienoates

The rates of the thermal decomposition (dehydroacetoxylation) and the activation energies of the following three samples have been determined: A) acetylated methyl ricinoleate; B) methyl ester mixture of vicinally unsaturated acetoxyoctadecenoates prepared by reacting methyl oleate and mercuric acetate in acetic acid; C) methyl ester mixture of vicinally unsaturated acetoxyoctadecadienoates prepared by reacting methyl linoleate and mercuric acetate in acetic acid. The thermal decomposition is shown to be a first-order reaction.     

Products formed by photosensitized oxidation of unsaturated fatty acid esters

Photosensitized oxidation of unsaturated fatty acid methyl ester was carried out using methylene blue as a sensitizer. Oxidation products, monohydro-peroxides, were identified as trimethylsilyl derivatives. Methyl oleate gave the 9- and 10-isomers; methyl linoleate, the 9-, 10-, 12-, and 13-isomers; and methyl linolenate, the 9-, 10-, 12-, 13-, 15-, and 16-isomers, respectively. The double bond to which the hydroperoxide group attached was shifted to the adjacent position in each isomer. Thus, both conjugated and nonconjugated isomers were present in methyl linoleate monohydroperoxides and methyl linolenate monohydroperoxides. By the inhibition experiment, it was ascertained that the above reaction proceeded via singlet oxygen. The relative rates of methyl oleate, methyl linoleate, and methyl linolenate were 1.0∶1.7∶2.3, respectively. These results obtained from the methyl esters were applied to the photosensitized oxidation of triglycerides purified from vegetable oils, and the reaction mechanism on triglycerides was proposed.     

Dimer acid esters by simultaneous dehydration and polymerization of technical methyl ricinoleate

Filtrol 13 may be used to dehydrate methyl ricinoleate with simultaneous dimerization and polymerization of the linoleate esters formed. Hydrolysis of the ester group is avoided by the use of xylene as an azeotroping solvent and the preferred method of reaction is the dropwise addition of the ester to a stirred suspension of catalyst in xylene. Products prepared by this technique had a dimer/polymer ratio of about 5 when the yield was 50%. The acid value of the polymer was 7 and of the recovered monomer 3–4.     

Analyses of lipids and oxidation products by partition chromatography: Hydroxy fatty acids and esters

A liquid-partition chromatographic procedure was used to separate hydroxy fatty acids, their methyl esters, and reduced fatty ester hydroperoxides. Mixtures of methyl stearate, mono- and dihydroxystearate, and mixtures of the corresponding free fatty acids were easily separated. Chromatographic determinations for ricinoleate in castor oils compared favorably with the chemical and infrared analyses. The chromatographic procedure was used to separate hydroxy fatty acids inDimorphotheca andStrophanthus seed oils. The methyl ester of dimorphecolic acid, the principal hydroxy fatty ester ofDimorphotheca oil, behaved like reduced methyl linoleate hydroperoxide and showed a polarity intermediate between methyl 12-hydroxystearate and methyl 9,10-dihydroxystearate. The 9-hydroxy-12-octadecenoic ester ofStrophanthus oil had a larger retention volume than methyl ous hydroxy fatty esters isolated chromatographically. The diene content of the reduced hydroperoxides agrees well with values reported in the literature (1,5,16). The diene content of the chromatographed methyl dimorphecolate is higher than reported by Smithet al. (20) for their preparations but agrees well with the value reported by Chipault and Hawkins (6) for puretrans-trans conjugated methyl linoleate. The extinction coefficient of methyl 12-hydroxystearate at 2.8 μ is higher than that reported for ricinoleate and the absorption band is much sharper. Because of these two conditions no association of the hydroxyl groups is indicated. These results also confirm the purity of the hydroxy fatty esters obtained by LPC. This method has been a valuable adjunct to the study of various oxygen-containing fatty acid and esters and was used to characterize the hydroxy esters obtained from the hydrogenation of methyl linolenate hydroperoxides (9). This work offers a basis for the development of analytical methods to determine the hydroxy and other polar acid content of fatty glycerides and their derivatives.     

Hydrosilylation of long chain unsaturated fatty acid esters

The addition of a series of silicon hydrides: trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyl dichlorosilane, and methyl phenyl chlorosilane to esters of long chain unsaturated fatty acids, such as oleic, linoleic acids, and 10-undecenoic acid, was studied with respect to catalysts, temperature, and solvents. Higher yields were obtained on carrying out the hydrosilylation reactions in the presence of chloroplatinic acid or Pt on C catalysts in bulk without solvent, as compared with peroxide catalysts. The addition reaction with methyl 10-undecenoate, which has a terminal double bond, gave a higher yield than that with methyl oleate. NMR data of the products from methyl 10-undecenoate and methyl oleate, as well as their reduction products with lithium aluminum hydride, have shown that, with the former ester, the silyl moiety added exclusively to the terminal carbon atom, while, with the latter, no migration of the silyl moiety to the terminal carbon atom was observed.     

无毒增塑剂环氧脂肪酸甲酯的合成

采用封闭式冷却循环装置,生物型脂肪酸甲酯为原料,双氧水为给氧体,有机酸作载体,在不使用任何溶剂、稳定剂和酸性催化剂的条件下,一步环氧化反应制得无毒聚氯乙烯(PVC)增塑剂环氧脂肪酸甲酯。实验表明环氧化反应不使用无机中强酸作催化剂,从而降低了所排污水的酸值和COD值。当反应液循环速率为50g/s,搅拌速率为245r/min时,环氧化反应时间为3~3.5h,比传统工艺节省二分之一时间,且产品环氧值高、热稳定性好。     

Structures of ozonolysis products of methyl oleate obtained in a carboxylic acid medium

High-performance liquid chromatography-mass spectrometry (LC-MS) and nuclear magnetic resonance spectrometry (NMR) were applied to the analysis of organic peroxide mixtures, which were labile and tended to decompose during analysis. The ozonolysis reaction of methyl oleate gives a peroxide mixture, and, finally, mono- and dibasic acids are obtained by subsequent oxidation. In this study, methyl oleate was ozonized in a nonanoic acid medium, one of the final reaction products. The reaction products were directly analyzed by LC-MS equipped with a frit-fast atom bombardment interface. The molecular ion peak of each peroxide was clearly observed, and its molecular weight was readily determined. On the other hand, each peroxide was fractionated by high-performance liquid chromatography and submitted to structural analysis by NMR. Both results indicated that the reaction products include four peroxidic species: 1,2,4-trioxolaneI, peroxide oligomerII, 1-acyloxyalkyl-1-hydroperoxideIII, and 1-acyloxyalkyl-1′-hydroxyalkyl peroxideIV, as well as an aldehydeV. Ozonolysis of methyl oleate in the absence of solvent produces mainlyI, while that in the presence of a carboxylic acid solvent characteristically produces mainlyIII andIV derived from the solvent.Bis(1-acyloxyalkyl-1-alkyl) peroxide, which was reported previously as a ozonolysis product of methyl oleate, was concluded to beIV in this study. This work was presented at the 31th Annual Meeting of the Japan Oil Chemists’ Society, 1992, Tokyo, Japan.     

杂多酸催化油酸甲酯环氧化的研究

研究了以磷钨酸-D1821(磷钨酸双十八烷基季铵盐)作催化剂,二氯甲烷作溶剂,30%过氧化氢存在下油酸甲酯的环氧化反应,考察了反应条件对油酸甲酯环氧反应的影响,得到的优化反应条件为:m(30%过氧化氢)∶m(油酸甲酯)=1∶1,m(二氯甲烷)∶m(油酸甲酯)=1.5∶1,m(催化剂)∶m(油酸甲酯)=25‰。在最优条件下得到的环氧油酸甲酯的碘值在4.3 g I2/100 g左右,环氧值在3.95 g/100 g左右,酸值在0.2 mg KOH/g左右,均达到了一等品的要求。     

Solvent extraction of ethanol from aqueous solutions using biobased oils, alcohols, and esters

Distribution coefficients and separation factors were determined for the partitioning of ethanol and water from aqueous mixtures into several vegetable oils and their fatty alcohol and fatty ester derivatives. Castor oil, ricinoleyl alcohol, and methyl ricinoleate all show higher ethanol distribution coefficients, and similar or reduced separation factors, relative to other oils and derivatives studied here or reported by others. Of particular interest, ricinoleyl alcohol has an ethanol distribution coefficient 50% higher than that of oleyl alcohol, a commonly studied solvent for ethanol extraction from fermentation broths.     

Composition of castor oil by optical activity

Summary The optical activity of castor oil and its derivatives has been studied. Pure methyl ricinoleate and methyl acetyl ricinoleate were prepared. The mixed methyl esters and acetylated methyl esters of castor oil were also prepared. By the determination of specific rotation of the pure and technical esters, the percentage of ricinoleate fraction can be deduced. This was calculated to be 93% and 90%, respectively. The esters of castor oil were calculated to contain 91.6% ricinoleate from the chemical hydroxyl value. This was about the average of the two values obtained optically and is believed close to the actual value. A number of castor oils were analyzed by both optical and chemical methods and found to be of nearly constant ricinoleic content. Dehydrated castor oil was found to have a comparative high specific rotation. This was believed due to its estolide content formed during dehydration.     

Analyses of lipids and oxidation products by partition chromatography. Fatty acid hydroperoxides

A liquid partition chromatographic method was developed to isolated and determine hydroperoxides in autoxidized fatty acids or their methyl esters. By the use of benzene containing 2 to 4% methanol as the mobile solvent, the hydroperoxides were separated from unoxidized fatty acids or methyl esters and from secondary and polymeric decomposition products. In the analyses of oxidized fatty acids, diethyl ether was necessary to elute the secondary decomposition products. Saponification of autoxidized fatty esters destroyed the peroxides as determined iodometrically, but the resulting acids contained a fraction which was eluted in the same position as hydroperoxide acids. Evidence showed that this fraction is a monomeric hydroxy fatty acid containing conjugated cis-traux and trans-trans unsaturation. Fatty ester hydroperoxides were isolated chromatographically in yields and purity comparable to those reported in the literature by countercurrent distribution. The concentrations of methyl linoleate hydroperoxide determined chromatographically were smaller than indicated by the peroxide value and diene conjugation of the autoxidized methyl linoleate. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.     

Preparation of sucrose esters by interesterification

Reactions between sucrose and esters of long chain fatty acids customarily have been conducted in a mutual solvent, such as dimethylformamide. The solvent-free interesterification of molten sucrose and fatty acid esters at temperatures between 170–187 C has now been performed with the aid of lithium, sodium and potassium soaps as catalysts and solubilizers. When the reactants were heated rapidly and then subjected to reduced pressure, the interesterifications could be brought to equilibrium in 12 min or less, including the time necessary to melt the sucrose. The several soaps and combinations of soaps employed differed markedly in their performance. No sucrose esters were obtained with lithium palmitate, while the yield with lithium oleate was among the best, but consisted of over 90% tetra- and higher esters of sucrose. Lower esters were best produced with combinations of lithium oleate with sodium or potassium oleate employed at a level of about 25% total soaps, based on the weight of sucrose. The type of fatty acid ester employed also markedly affected the yield of sucrose esters. Among the esters tested, methyl carbitol palmitate (which could be formed in situ), monopalmitin, distearin and technical grade diglycerides (48% diglycerides) prepared from completely hydrogenated cottonseed oil, interesterified readily. Presented at the AOCS Meeting, Minneapolis, October 1969. So. Utiliz. Res. Dev. Div., ARS, USDA.     

Fractionation of castor oil methyl esters by liquid-liquid extraction

Summary and Conclusions A solubility diagram has been constructed for methanol-castor oil methyl esters-heptane at 8.4°C. and 24°C. A selectivity diagram has been prepared for methanol-castor oil methyl esters-heptane at 8.4°C. and 24°C. Castor oil methyl esters have been fractionated by continuous countercurrent liquid-liquid extraction at 3°C. and at 6°C. with methanol-heptane and heptane-methanol as solvents, using an extraction column containing four equilibrium stages. The methyl ricinoleate fraction produced compared favorably with pure methyl ricinoleate with respect to hydroxyl value and optical activity. It should be noted that there were undoubtedly some mono- and diglycerides in the castor oil methyl esters used in this study. These go along with the methyl ricinoleate and cause discrepancies between hydroxyl value and optical activity (2). The column feeds ranged from 2.9 to 10.3% methyl esters by weight in methanol-heptane. Solvent-feed ratios were from 0.49 to 1.21 lb. per pound. The flow rates were from 706 to 1,020 lb. per hour per square foot of column cross section (based on the cross section of the empty column).     

Oxidation stability of methyl esters studied by differential thermal analysis and rancimat

The oxidation stability of methyl esters derived from fresh rapeseed oil and waste frying oil, used as alternative biodiesel fuels, both distilled and undistilled, unstabilized and stabilized by pyrogallol and BHT, was studied by differential thermal analysis (DTA) under nonisothermal conditions at various heating rates and by the Rancimat test under isothermal conditions at 110°C. The results obtained by both techniques are compared. Both techniques show that oxidation stability increases considerably with the addition of antioxidants and that pyrogallol is very efficient. Distillation of the methyl esters prepared from rapeseed oil decreases their oxidation stability, obviously owing to the removal of natural antioxidants. The stability of methyl esters prepared from the waste frying oil is determined mainly by the history of the oil. From the DTA measurements, the kinetic parameters of an Arrhenius-like equation describing the temperature dependence of the oxidation induction period were obtained. The parameters enable one to assess the protective factor of antioxidants for temperatures outside the measuring region, estimate the residual stability, and model the process of biodiesel oxidation under nonisothermal conditions.     

The oxidation of methyl oleate I. The preparation,properties and reactions of methyl hydroperoxido oleate

Summary Low temperature fractional crystallization from acetone has been applied to the separation of methyl hydroperoxido oleate in 85 to 90 percent purity from partially oxidized methyl oleate. The hydroperoxido ester was subjected to hydrogenation, oxidative fission, and reduction with hydrogen iodide. Certain characteristics of the original hydroperoxide and its reaction products have been described. The results obtained lend definite support to the view that the first oxidation product of methyl oleate is a mixture of 8- and 11-hydroperoxido octadecenoic acids, at least under the conditions employed,i.e., oxidation under the influence of ultraviolet light or reaction temperatures up to 60° C. The spectral absorption of methyl hydroperoxido oleate and some derived products was determined. The hydroperoxide group was shown to have no characteristic absorption in the ultraviolet region. The reactions of the peroxide with alkali, hydroxylamine, lead tetraacetate, and α-tocopherol have been described and discussed. Presented before the 37th Annual Meeting of the American Oil Chemists' Society, New Orieans, Luisiana, May 15–17, 1946. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Analysis of oleate,linoleate and linolenate hydroperoxides in oxidized ester mixtures

The hydroperoxides in oxidized mixtures of methyl oleate, linoleate and linolenate were analyzed by reducing the hydroperoxides to the corresponding hydroxyesters and separating the hydroxyesters from the unoxidized esters by thin layer chromatography (TLC). The hydroxyesters from linolenate were separated from the other hydroxyesters by TLC on silver ion plates. The hydroxyesters were converted to TMS-hydroxy derivatives. The TMS-hydroxyoleate and TMS-hydroxylinoleate were separated by gas chromatography (GC), and all the TMS-derivatives were quantified by GC. The relative rates of oxidation of methyl oleate, linoleate and linolenate in mixtures were ca. 1∶10.3∶21.6. The hydroperoxides formed in the oxidation of soybean and olive oils were similar before and after randomization and similar to corresponding methyl ester mixtures. Journal Paper No. J-9657 of the Iowa Agriculture and Home Economics Experiment Station, Ames. Project 2143.     

Thermochemistry of biodiesel oxidation reactions: A DFT study

Density functional theory (DFT) quantum chemical calculations have been used to evaluate the gas phase electronic and thermochemical properties of fatty acid esters. The calculated low relative energies of the corresponding radicals can explain the large variety of oxidation products observed in experiments. The first oxidation reaction step was determined to be non-spontaneous for all fatty acid esters studied. Ethyl and methyl esters showed similar susceptibilities to oxidation in the gas phase. All subsequent reaction steps leading to the secondary products of oxidation were observed to be spontaneous. The thermochemical stability order of one double bond oxidation in the gas phase was determined to be linoleate < γ-linolenate < α-linolenate < oleate < ricinoleate. Therefore, biodiesel produced from castor oil could be used as an additive to biodiesel produced from other vegetable oil sources in order to improve the oxidation stability properties of the final fuel blend.     

Methods of analysis of mixtures of oleic,linoleic and saturated esters and their application to highly purified methyl oleate and methyl linoleate

Summary Iodine numbers by the Hanus and Wijs methods and thiocyanogen numbers using various absorption periods, were determined on methyl oleate and methyl linoleate and on mixtures of these esters. It is concluded that iodine numbers by the Wijs method and three-hour thiocyanogen numbers are more satisfactory for methyl linoleate and for mixtures containing large amounts of this ester. Small amounts of higher saturated acids were determined with a precision of about 0.1 unit-percent by means of the Bertram procedure. A purified specimen of methyl oleate was found to contain about 0.2 percent of saturated ester by this method. Food Research Division Contribution No. 428.     

Thermal Stability of Rapeseed Oil Fortified with Unsaturated Fatty Acid Sterol Esters

The thermal stability of rapeseed oil fortified with 3 % sterol linolenate, sterol linoleate, and sterol oleate was investigated using the Rancimat accelerated oxidation method. The results indicated that the sterol ester content in fortified oil displayed positive correlations (P < 0.05) with total phenols and tocopherols and significant negative correlations (P < 0.05) with acid value (AV), peroxide value (POV), conjugated diene value, \(\varDelta E\) value, viscosity, and polyphenols and γ-tocopherol levels. The sterol ester content in fortified oil was found to significantly decrease when the oil was heated at 110 °C. The rate of increase of the AV, POV, \(\varDelta E\) value, and viscosity, and the rate of decrease of polyunsaturated fatty acid, tocopherol, and polyphenol contents were accelerated with the increase of the degree of unsaturation of fatty acid sterol esters in rapeseed oil during heating. Therefore, the oxidative stability is further reduced by increasing the degree of unsaturation, as the instability of fortified oil is mainly due to the decomposition of unsaturated fatty acid sterol esters. The addition of lipid-soluble polyphenols is an effective method to improve the stability of rapeseed oil fortified with unsaturated fatty acid sterol esters.