Production of fatty alcohols from fatty acids

Detergent-range alcohols from natural feedstock can be produced by high pressure hydrogenation of either methyl esters or fatty acids. The increasing quantities of fats and oils on the world market secure a reliable and economically priced material. Although fatty acid is an abundant worldwide commodity, most alcohol producers hydrogenate methyl esters, because direct hydrogenation of fatty acids is difficult as the catalyst is sensitive to acid attack. The process described here makes it possible to hydrogenate fatty acids directly to alcohols of high quality without prior esterification. The reaction takes place in the liquid phase over a fine-grained copper chromite slurry in a single reactor vessel. A special reactor design with an optimum arragement of the feeding nozzles causing an appropriate circulation of the reacting components inside the reactor facilitates the rapid “in situ” esterification reaction. This minimizes the free fatty acid concentration in the reactor to nearly zero. This results in a low consumption of catalyst. The most important advantages of the process are: direct feed of fatty acids of various origins, use of reasonably priced raw materials such as soapstock fatty acids and lower grade tallow acids, no process steps with methanol, and excellent economics. The process is industrially proven.     

Efficient synthesis of fatty monoglyceride sulfates from fatty acids and fatty acid methyl esters

An efficient high yield synthesis of fatty monoglyceride sulfates from fatty acids or fatty acid methyl esters, glycerine and chlorosulfuric acid in chloroform using stoichiometric amounts of reagents was developed. Sodium coco monoglyceride sulfate was prepared in 79% yield with 93% purity from coco fatty acids. Similarly, sodium palm kernel monoglyceride sulfate in 57% yield and sodium palm monoglyceride sulfate in 71% yield were obtained from palm kernel fatty acid methyl esters and palm fatty acids, respectively. This new synthetic method produced better quality products with higher active ingredients and improved yields without having to use such cost prohibitive, high purity, fatty acid monoglycerides, and it reduced the undesirable aqueous sodium sulfate by-product by 60% over a current commercial process. The product’s composition and purity were confirmed by cationic titration, infrared and C-13 NMR spectroscopy.     

Determination of fatty alcohols in fatty alcohol sulfates

A simplified procedure for the quantitative determination of very small amts of fatty alcohols in fatty alcohol sulfates has been developed. In the present work this procedure was applied to the determination of lauryl alcohol in lauryl alcohol sulfate.     

Rearrangement of epoxy fatty esters to keto fatty esters

The rearrangement of fatty epoxyesters to ketoesters was studied. The isomerization is carried out in nonaqueous media and is catalyzed by acids. Esters containing one epoxy group per fatty acid chain are isomerized to the corresponding ketones in 70–90% yields using boron fluoride etherate catalyst in boiling dioxane. Conversion to ketonic products is measured either by chromatographic separation followed by IR analysis or by oximation. Principal byproducts are hydroxy derivatives. Fatty esters containing more than one epoxy group/fatty acid chain give low ketone yields. A laboratory of the E. Utiliz. Res. & Dev. Div., ARS, USDA.     

Multivariate fatty acid and fatty alcohol profile of mullet bottarga

Mullet bottarga is a food delicacy obtained by salting and drying the intact roes of mullet (Mugil spp.). The fatty acid and fatty alcohol compositions of different samples of bottarga were studied by means of gas chromatography (GC) and multivariate analysis (MVA). High percentages of beneficial n‐3 PUFA, among which docosahexaenoic acid (DHA) (22:6n‐3, 11.9%) and eicosapentaenoic acid (EPA) (20:5n‐3, 8.6%), were detected. Differences in the concentrations of unsaturated FA and FAL were observed among samples, while saturated components showed little variations. On the other hand, the total contents of saturated, monounsaturated and polyunsaturated components were similar. The principal component analysis loadings bi‐plot showed that n‐6 PUFA concentrations were inversely correlated to those of n‐3 PUFA, except for DHA that showed no correlations. Correlations between FAL concentrations were also observed. Furthermore, integrating our GC data with those from the literature on mullet and tuna bottarga, the MVA showed that both bottarga typologies exhibit a similar trend in the FA distribution and that 16:0 and 16:1n‐7 FA are the variables with the highest discriminant power. In this work, we demonstrated the usefulness of the application of MVA to GC data to extract meaningful information otherwise hidden in the amount of data.     

脂肪酸N-甲基牛磺酸盐对离子脂肪酸皂的开发

1.前言 人类使用肥皂已有2500年的历史.因其成本低廉,尤其是随着近年来人们"回归自然"意识的增强,肥皂又恢复了青春,被广泛地用作皮肤清洁剂.     

Nonvolatilealpha-branched-chain fatty esters

Nonvolatilealpha-branched carboxylic acids and esters have been prepared by a free radical reaction. Various esters of the reaction products of hexadecanoic and octadecanoic acids with the terminal olefins, octene, decene, and dodecene have been synthesized. Fractional crystallization from acetone is a useful method for preparing these compounds in a highly purified state. Mass spectra confirm that branching is found exclusively at thealpha- or 2-position.     

Synthetic fatty acids

Manufacture of fatty acids from petroleum and natural gas is a large industry worldwide and has important implications in the U.S. Eastern Europe produces an estimated 1.2 billion pounds by air oxidation of hydrocarbons compared to an estimated 956 million pounds of natural fatty acids from the U.S., in 1978 (exclusive of tall oil fatty acids). The enormous production of SFA’s in Eastern European countries and in Russia is done by continuous air oxidation of fresh and recycled mixed aliphatic hydrocarbons. Since the products contain proportions of odd-numbered straight chain acids, they have not been used edibly, but have been applied to the manufacture of industrial products such as soap, lubricants, plasticizers and the like. Another European approach (Liquichimica, Italy) for SFA is the caustic fusion (and oxidation) of branched chain alcohols produced by carbonylation and reduction of olefins. American potential technology is diversified but has not yet been translated to production scale, presumably because of the plentiful supply of natural fats and oils that is available.     

Estolides from meadowfoam oil fatty acids and other monounsaturated fatty acids

The formation of estolides was detected during the studies on dimerization of meadowfoam oil fatty acids. By adjusting the reaction conditions, it was possible to produce monoestolides with little dimer or trimer formations. Estolides have potential use in lubricant, cosmetic and ink formulations and in plasticizers. This paper reports the conditions for production of estolides from mixed meadow-foam fatty acids, commercial oleic acid, high-oleic sun-flower oil fatty acids,cis-5,cis-13-docosadienoic acid, petroselinic acid and linoleic acid.     

Influence of fatty alcohol and other fatty acid derivatives on fatty acid uptake into rat intestinal epithelial cells

We investigated the influence of various substrates on the uptake of long-chain fatty acid into IEC-6, rat intestinal epithelial cell line. The uptake of [³H]oleic acid into IEC-6 cells was a saturable function of the oleic acid concentration. Long-chain fatty acids significantly inhibited the oleic acid uptake into IEC-6 cells and shorter-chain fatty acids had little or no effect. Various fatty acid esters suppressed the oleic acid uptake into IEC-6. Fatty alcohols also inhibited oleic acid uptake into IEC-6 and the length of the carbon chain played an important role. These results suggest that long-chain fatty acid uptake was inhibited by the substrates which had a structure similar to long-chain fatty acids, especially those with a long carbon chain. At least two molecules, fatty acid translocase and fatty acid transport protein type 4, which are considered to be involved in the long-chain fatty acid transport into the cell, were expressed on IEC-6 cells, supporting the existence of the carrier-mediated system of long-chain fatty acid transport on IEC-6 cells.     

Polyunsaturated fatty acid concentrates from borage and linseed oil fatty acids

A modified low-temperature solvent crystallization process was employed for the enrichment of polyunsaturated fatty acids (PUFA) in borage and linseed oil fatty acids. The effects of solvent, operation temperature, and solvent to free fatty acid (FFA) ratio on the concentration of PUFA were investigated. The best results were achieved when a mixture of 30% acetonitrile and 70% acetone was used as the solvent. With an operation temperature of −80°C and a solvent to FFA ratio of 30 mL/g, γ-linolenic acid (GLA) in FFA of saponified borage oil can be raised from 23.4 to 88.9% with a yield of 62.0%. At a yield of 24.9%, α-linolenic acid in linseed oil can be increased from 55.0 to 85.7%. The results of this work are comparable to the best results available in the literature.     

Complexation of fatty acids and fatty acid-CoAs with synthetic O-methylated polysaccharides

An experimentally simple, but highly reproducible and reliable method has been developed to follow the complexation event of fatty acid (FA) and FA-CoA with polysaccharides. This method was based on the recent discovery of the unique blue-shifted UV absorption associated with the aggregation of tetraenoic fatty acids (TE-FAs) in aqueous solution. Complexation was monitored by recording the intensity of UV absorption at 250 nm ([free TE-FA]) and 303 nm ([complexed TE-FA]), and the K aggregate of C(20) t,t,t,t-TE-FA exhibited the ideal property for this purpose. Synthetic 3-O-methyl-D-mannose- and 6-O-methyl-D-glucose-containing lipopolysaccharides were found to exhibit a broad range of the binding affinities with C(20) t,t,t,t-TE-FAs as well as saturated FAs/FA-CoAs.     

Selective hydrogenation of fatty acids and methyl esters of fatty acids to obtain fatty alcohols–a review

In this paper, a review is presented of the evolution of different catalytic systems and operating conditions used in the selective hydrogenation of acids and esters of fatty acids to obtain fatty alcohols, which have broad industrial applications in the oleochemical industry. In addition, the current status of the different technologies used industrially (Lurgi, Davy and Henkel) for obtaining fatty alcohols, as well as major global sources of raw materials for the oleochemical industry are put forward. Finally, the reaction mechanisms of the selective hydrogenation process of oleic acid and methyl oleate to obtain the corresponding unsaturated alcohol as well as the new catalysts proposed by researchers are described. © 2016 Society of Chemical Industry     

Metabolism of odd-numbered fatty acids and even-numbered fatty acids in mouse

Fatty acids are converted into energy via beta-oxidation. Although almost all natural occurring fatty acids are even-numbered, there are some odd-numbered fatty acids too. The details of the metabolism rate of odd-numbered fatty acids, however, are not clear. In the present study, we simultaneously administered a triacylglycerol containing four types of labeled even-numbered (palmitic acid and stearic acid) and odd-numbered (pentadecanoic acid and heptadecanoic acid) fatty acids to mice to compare the rates of their metabolism. The rates of metabolism were evaluated based on the accumulation of the labeled fatty acids in the small intestine epithelium, liver, and epididymal fat. Odd-numbered fatty acids accumulated mainly in the epididymal fat. In contrast, there was no accumulation of even-numbered fatty acids observed in the small intestine epithelium, liver, or epididymal fat. These results suggest that odd-numbered fatty acids might not be favorable substrates for beta-oxidation-related enzymes.     

Synthesis of fatty 2-oxazolines from fatty methyl 2,3-epoxy ester

Reaction of methyltrans-2,3-epoxyhexadecanoate (I) with benzonitrile in presence of boron trifluoride-etherate (BF₃-etherate) as catalyst has yieldedcis-2-phenyl-4-tridecyl-5-carbomethoxy-2-oxazoline (II), methyl 2-hydroxy-3-benzamidohexadecanoate (IV) and methyl 2,3-dihydroxyhexadecanoate (III). On the other hand, reactions of I with acetonitrile and acrylonitrile have resulted in the formation of their corresponding hydroxyamides, methyl 2-hydroxy-3-acetamidohexadecanoate (VI) and methyl 2-hydroxy-3-acryloamido hexadecanoate (VII), respectively, along with the product (III) only. Pyrolysis of hydroxyamides (IV), (VI) and (VII) afforded their corresponding 2-oxazolines,cis-2-phenyl-4-tridecyl-5-carboxy-2-oxazoline (V),cis-2-methyl-4-tridecyl-5-carboxy-2-oxazoline (VIII) andcis-2-vinyl-4-tridecyl-5-carboxy-2-oxazoline (IX), respectively, in good yields. The products have been characterized with the help of spectral and microanalyses. Presented at the 4th Annual Convention of the Indian Council of Chemists held in December 1984 at Gorakhpur University, India.     

Homogeneously catalysed hydrogenation of unsaturated fatty acids to unsaturated fatty alcohols

The use of copper and cadmium oxides or soaps as catalysts for the hydrogenation of unsaturated fatty acids to unsaturated fatty alcohols has been investigated. It is shown that copper soaps homogeneously activate hydrogen. When copper and cadmium oxides are used as catalysts, they react with the acid under formation of a homogeneous soap solution. A continuous reaction system for the preparation of unsaturated fatty alcohols by hydrogenation under the influence of copper and cadmium soaps is described.     

Hydrogenation of fatty acid methyl esters to fatty alcohols at supercritical conditions

Extremely rapid hydrogenation of fatty acid methyl esters (FAME) to fatty alcohols (FOH) occurs when the reaction is conducted in a substantially homogeneous supercritical phase, using propane as a solvent, over a solid catalyst. At these conditions, the limitations of hydrogen transport are eliminated. At temperatures above 240°C, complete conversion of the starting material was reached at residence times of 2 to 3 s, which is several orders of magnitude shorter than reported in the literature. Furthermore, formation of by-products, i.e., hydrocarbons, could be prevented by choosing the right process settings. Hydrogen concentration turned out to be the key parameter for achieving the above two goals. As a result of the supercritical conditions, we could control the hydrogen concentration at the catalyst surface independently of the other process parameters. When methylated rapeseed oil was used as a substrate, the hydrogenation catalyst was deactivated rapidly. However, by using methylated sunflower oil, a catalyst life similar to that obtained in industrial processes was achieved. Our results showed that the hydrogenation of FAME to FOH at supercritical conditions is a much more efficient method than any other published process.     

Useful direct conversion of tetrahydropyranyl ethers of fatty alcohols into fatty acids

Tetrahydro-2-pyranyl ethers from fatty primary alcohols can be converted in a one-step procedure into the corresponding carboxylic acids in high yields. This process avoids the synthesis of symmetrical esters, particularly for long-chain compounds. This reaction proved to be useful, for instance, to produce polyunsaturated fatty acids immediately before their biological testing.     

铜铬催化剂催化脂肪酸甲酯加氢制备脂肪醇的研究

采用共沉淀法制备了铜铬催化剂并用于催化脂肪酸甲酯加氢反应制备脂肪醇。考察了催化剂种类和用量、反应温度、反应时间和反应压力等因素对反应结果的影响。确定了最佳实验条件,脂肪酸甲酯2.5g,m(铜铬催化剂)∶m(原料)=3∶200,反应温度230℃,氢气压力6MPa,反应时间6h。在该条件下,产物脂肪醇羟值186mgKOH/g,碘值22I2g/100g。另外,该催化剂回收重复利用5次后,脂肪醇的羟基值没有明显降低,具有较好的重复使用性能。