Soybean Methyl Ester Research Articles

Emission reduction potential from the combustion of soy methyl ester fuel blended with petroleum distillate fuel

Combustion performance of a blend containing 20% soybean methyl ester in heating No. 2 fuel was examined using a residential-scale hot water boiler. The blend burned satisfactorily with no modifications to the appliance and fuel delivery system. SO 2 emissions were 19.7±2.5% lower than that of No. 2 fuel while NO x emissions were similar. Particulate emissions, as determined by a source dilution measurement system, were on average 15.7±7.5% lower than that of No. 2 fuel. The particulate bound sulphates were also lower by 14.1±6.1%. Results indicate potential reductions of PM 2.5, SO 2 and greenhouse gas emissions for the petroleum distillates that can be replaced with biofuels. Reduction of sulphate in PM 2.5, which is associated with adverse health effects, is considered significant.

Soybean oil epoxidation with hydrogen peroxide using an amorphous Ti/SiO2catalyst

We report a study of the epoxidation of soybean oil and soybean methyl esters with hydrogen peroxide in dilute solution (6 wt%) using an amorphous heterogeneous Ti/SiO2 catalyst in the presence of tert-butyl alcohol. The influence of some relevant process variables such as temperature and the hydrogen peroxide-to-double bond molar ratio on performance is examined. The highest yields of epoxidized olefins were obtained upon using a H2O2 ∶ substrate molar ratio of 1.1 ∶ 1. Higher ratios than this were not effective for speeding up the reaction. Under the experimental conditions employed in this work, no degradation of the oxirane ring was observed.

Preparation of long‐chain β‐enaminones and β‐diketones from long‐chain 3,5‐disubstituted isoxazole compounds

AbstractA series of long‐chain compounds containing the β‐enaminone functionality were prepared in yields ranging from 71 to 88% from their corresponding long‐chain 3,5‐disubstituted isoxazole precursors utilizing a Raney nickel‐catalyzed reductive ring‐opening procedure. These newly prepared multifunctional compounds were subsequently hydrolyzed under mild acidic conditions (pH 4–5) to give their corresponding long‐chain β‐diketones in yields ranging from 79 to 98%. Both the β‐enaminone and β‐diketone functionalized compounds were characterized by NMR, IR spectroscopy, GC‐MS, and m.p. The mass spectra for these two classes of compounds, derived by utilizing electron impact ionization, gave distinctive McLafferty rearrangement fragmentation ions that clearly established the newly introduced functionality to reside at the C‐2 and C‐4 positions of the lipid’s alkyl chain. 1H NMR spectra of the pure β‐diketone compounds were complex owing to the keto enol tautomerism displayed by the β‐diketone moiety. In solution the β‐diketone compounds were shown to exist mainly in the enolic tautomeric form. Long‐chain β‐diketone compounds are known to be relatively common constituents of some plant waxes, and the overall procedure starting from soybean methyl esters provides a complementary approach to prepare these types of compounds.

OXIDATION CHARACTERISTICS OF SOYBEAN OILS AS WATER PUMP LUBRICANTS

The use of soybean oil as an alternative lubricant is being investigated extensively, but its relatively rapid thermaland oxidative polymerization restricts its usefulness. Measurement of polymerized oil film thickness and film weight, asmethods for quantifying the degree of polymerization, were investigated. The miscibility and polymerization behavior of crudesoybean oil, proprietary commercial biobased drip oil (BDO), soybean methyl esters, glycerol, and water and their mixtureswere investigated. In a separate study, the antioxidant characteristics of Tenox, 2,2,4,5,5Pentamethyl3imidazoline1oxyl (PMIO), ethylenediaminetetraacetic acid (EDTA), and ionic copper in acidic and alcohol media each in 1% (w/w)concentrations and their formulations mixed with soybean oil were investigated. In the first study, measurement ofpolymerized film weight was preferable to measurement of film thickness for quantifying the extent of polymerization. Soybeanmethyl esters showed the least degree of polymerization. In the next study, ionic copper in acidic media showed the highestresistance to polymerization, followed by the mixture of PMIO and Tenox. The treatments that contained EDTA and Tenoxhad antioxidant properties that were superior to that of the BDO. PMIO tended to promote the polymerization process.

Cr(CO)3‐complexed, silica‐bonded polyphenylsiloxane as a stereoselective catalyst for hydrogenation of sorbate and soybean methyl esters

AbstractA silica‐bonded complex was prepared by reacting polyphenylsiloxane with silylated Chromosorb and then with Cr(CO)6. This complex catalyzed stereoselective hydrogenation of sorbate tocis‐3‐hexenoate. Soybean methyl esters were hydrogenated at 210 C in cyclohexane to form products high incis unsaturation. The recovered catalyst could be recycled once with methyl sorbate. IR showed decreased Cr(CO)3 in the recovered catalysts, and the hydrogenation products contained inactive Cr.

Quantitative analyses of hydroxystearate isomers from hydroperoxides by high pressure liquid chromatography of autoxidized and photosensitized‐oxidized fatty esters

AbstractA high pressure liquid chromatography (HPLC) method is described for the determination of the isomeric hydroxysterates from hydroperoxides of oxidized fatty esters. The samples are hydrogenated and the mixtures of hydroxystearates are concentrated by partial removal of unoxidized esters and complete removal of polar materials. Isomeric hydroxystearates are then separated on a porous microparticulate adsorption (10 μ) column and elution with 0.25% isopropyl alcohol inn‐hexane is monitored at 212 nm. The 8‐OH, 9‐OH, 10‐OH, 11‐OH and 16‐OH isomers were completely separated, but the 12‐OH, 13‐OH and 15‐OH were only partly resolved by HPLC. The relative percentages of isomeric hydroxy esters were analyzed quantitatively by a computer integration method. Accuracy of the method was checked with known mixtures of synthetic hydroxystearates. The isomeric hydroperoxide composition of oxidized methyl oleate, linoleate, linolenate and soybean methyl esters determined by HPLC were in good agreement with previous analyses by gas chromatography‐mass spectrometry.

Conjugation of polyunsaturated fats with dimsylsodium

AbstractThe conjugation of polyunsaturated fatty esters, including soybean oil, trilinolein, soybean methyl esters, and methyl linolenate and linoleate, with the sodium salt of dimethyl sulfoxide (dimsylsodium) as catalyst has been investigated. Methyl esters are ca. 95% conjugated within 2 hr. Glycerides react more slowly but are similarly conjugated within 24 hr. The glyceride linkages are not destroyed as they would be with aqueous or alcoholic alkali. Highly conjugated oils can thus be prepared.

Selective hydrogenation catalyzed by polymeric palladium and platinum complexes

AbstractAn organic polymer containing a diphenylbenzyl‐phosphine functional group, combined with PtCl2 or PdCl2, gives a heterogeneous hydrogenation catalyst which is analogous to the homogeneous catalysts PtCl2(Pø3)2 and PdCl2(Pø3)2. In the hydrogenation of soybean methyl ester, this catalyst is highly selective, the products being monoene and diene, with almost no increase in the content of saturated ester.

The selective homogeneous hydrogenation of soybean methyl esters

AbstractSoybean methyl esters are homogeneously, selectively hydrogenated in the presence of a variety of catalysts, of which [Pt(Pph3)2Cl2]+SnCl2·2H2O and [MoCl2(CO)3(Pph3)2]+SnCl2·2H2O are typical. Many variations can be made in these catalysts without destroying their selectivity. All of the catalysts bring about isomerization of the substrate molecules. The role of the solvent and the mechanism of the reaction are discussed.

MRA microeactions for lipid analysis

AbstractMany types of reactions have been performed on a microscale with the microreactor apparatus (MRA) system, which incorporates a modified soldering gun. Specific procedures developed for some typical reactions include bromination of olive methyl esters, silylation of castor methyl esters, homogeneous reduction of oleic acid, heterogeneous reduction of soybean methyl esters, several methods of methyl ester preparation from soybean fatty acids and saponification of soybean triglycerides followed by esterification. The reaction chamber of the MRA has been redesigned to increase its versatility and to reduce explosion hazards when diazomethane is used. Advantages of the MRA over other systems are less handling of sample, minimum hazards due to small sample size and direct injection of products into analytical instruments, such as a gas chromatograph or mass spectrometer.

Homogeneous catalytic hydrogenation of unsaturated fats: Metal acetylacetonates

AbstractHydrogenation of linseed and soybean methyl esters was achieved at 100舑180C, 100舑1000 psi H2 and 0.05舑0.25 moles catalyst per mole of ester. The relative activity of metal acetylacetonates in decreasing order was: nickel (III), cobalt (III), copper (II) and iron (III). Reduction occurred readily in methanol solution but only slowly in dimethylformamide and acetic acid. No reduction occurred in the absence of solvents. Soybean oil was also hydrogenated rapidly with nickel (III) acetylacetonate in methanol, but in this system the triglycerides were converted to methyl esters. Nickel (III) acetylacetonate was the most selective catalyst toward linolenate hydrogenation. Methyl linoleate and linolenate hydrogenated with nickel(III) acetylacetonate were fractionated into monoenes, dienes and trienes. Thecis monoenes separated in 62 to 68% yield had double bonds in the original position. The remainingtrans monoenes had extensively scattered unsaturation. The dienes and trienes showed no conjugation, but some of the double bonds in the dienes were not conjugatable with alkali. Little stearate was formed.

Homogeneous catalytic hydrogenation of unsaturated fats: Cobalt carbonyl

AbstractHomogeneous hydrogenation of unsaturated fats by cobalt carbonyl has been compared with the previously reported catalysis by iron carbonyl. Soybean methyl esters, methyl linoleate and linolenate have been hydrogenated at 75舑180C, 250舑3,000 psi H2 and 0.02 molar concn of catalyst. The cobalt carbonyl catalyst is more active at lower temp than iron carbonyl. The partially reduced products are similar to those observed with iron carbonyl, but the reaction differs in showing much less accumulation of conjugated dienes, no selectivity toward linolenate, almost complete absence of monoene hydrogenation to saturates, less double bond migration and moretrans isomerization. No evidence was found for a stable complex between cobalt carbonyl and unsaturated fats as previously observed with iron carbonyl. The rates of hydrogenation/double bond were the same for linoleate and linolenate on one hand, and for alkali‐conjugated linoleate and nonconjugated linoleate on the other.

Countercurrent distribution of soybean fatty acid methyl esters biosynthetically labeled with H3 and C14

Fatty acids randomly labeled with C14 and with H3 were prepared by culturing soybean plants (a) in the presence of C14O2, and (b) with H3OH in the nutrient medium. After maturation of the beans, extraction of the oils, and transesterification of the glycerides with methanol, the methyl esters were readily separated by countercurrent distribution to yield fractions of pure linoleate (7 g and 469 μc of Cl4-labeled esters), 97% linolenate, a 2:1 mixture of oleate and palmitate, 83% stearate, and concentrates of C20, and higher acid esters. Over-all recoveries of 90% may be expected from countercurrent distribution.

Reactions of conjugated fat acids

1. Addition products of ethyl crotonate and crotononitrile with conjugated methyl linoleate, derived from soybean methyl esters conjugated with a nickelcarbon catalyst, were prepared. 2. The addition product of ethyl crotonate and nonconjugated methyl linoleate was prepared and compared with that from conjugated methyl linoleate. 3. The addition product of ethyl crotonate and conjugated methyl linoleate was saponified to a dibasic acid which was used to prepare a decamethylene glycol polyester and an ethylene diamine polyamide. 4. The compatibility of the addition product of ethyl crotonate and conjugated methyl linoleate with various synthetic resins was determined.