Non-ionic detergents from wax

Conclusion Non-ionic synthetic detergents having detergent properties similar to those of alkyl phenol polyethylene glycol ethers and alkyl mercapto polyethylene glycol ethers can be prepared by reacting the optimum quantity of ethylene oxide with the composite crude fatty acids made by the air oxidation of low melting chemical grade paraffin wax.     

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.     

Mitochondrial metabolism of (D,L)-threo-9, 10-dibromo palmitic acid

Bromination of palmitoleic or palmitelaidic acid proceeds bytrans addition and yields dibrominated products which cannot undergo β-oxidation when incubated with mitochondria isolated from hamster brown adipose tissue. These mitochondria were selected because they have a high capacity for oxidation of C₁₆ fatty acids and because they are readily uncoupled by an excess of free fatty acids of this chain length. The only metabolites which could be recovered from the incubation mixtures were dibromopalmitoylcarnitine and dibromopalmitoyl CoA. Free fatty acid was also recovered. Addition of synthetic carnitine or CoA esters of brominated fatty acids did not interfere with subsequent oxidation of palmitoylcarnitine. Addition of the free brominated fatty acids did significantly increase the rate of oxidation of subsequent additions of palmitoylcarnitine, as did other known synthetic uncouplers. These results are consistent with observations by others that feeding brominated oils leads to brominated fatty acid incorporation into tissue lipids, and indicate why this is so. They also provide a possible explanation for the hepatic damage noted in feeding experiments.     

New natural antioxidants for protecting omega‐3 rich products

The long‐chain (LC) highly unsaturated omega‐3 fatty acids, EPA (eicosapentaenoic acid, 20:5) and DHA (docosahexaenoic acid, 22:6) are vital for a wide range of biological functions and are implicated in the prevention of numerous diseases. However, these fatty acids are highly susceptible to oxidation because of their unsaturated nature. Addition of antioxidants is one method to prevent lipid oxidation. As synthetic antioxidants may have carcinogenic effects at higher levels, the replacement of synthetic antioxidants with natural antioxidants is now in demand. We have isolated natural antioxidants from yoghurt, potato peel, fish protein hydrolysates and seaweed, which were able to protect highly unsaturated fish oil from oxidation. These antioxidant extracts may have potential for commercial exploitation.     

Historical and marketing trends of natural/synthetic fatty acids

As long as a substantial portion of raw materials for natural fatty acids are relatively inexpensive by-products of other major industries, natural fatty acids should fulfill the world's projected needs at least through 1985. Production of synthetic fatty acids may also increase; however, at the present time the cost of their raw material and processing has made them largely noncompetitive, except in a few cases. Synthetic organic acid manufacturers currently supplying short chain products will continue their efforts to enter the detergent range fatty acid market area. We expect some breakthrough in synthetics during the life of our forecast. However, potential producers have yet to develop an economically competitive synthetic fatty acid as a replacement for natural fatty acids in the U.S. Petroleum-based products include odd, even, and branched chain acids whose performance must be proven. Finally, the petroleum base for synthetic fatty acids no longer has the price stability we have been accustomed to in the past. Recent changes in price of ethylene and forecasts are evidence of this trends for the future.     

New developments in synthetic fatty acids

New developments in synthetic fatty acids have occurred in the last few years in Russia, Japan, the United States and Canada. In 1959 Russia decided to replace 40% of natural fatty acids in soaps with synthetic fatty acids. In 1966, 548 million pounds of C₅–C₃₀ synthetic fatty acids were produced including 288 million pounds of C₁₀–C₂₀ fatty acids. Forty million pounds of fatty acids are converted directly to the fatty alcohols for detergent use. A conservative estimate predicts that one billion pounds of synthetic fatty acids will be produced in Russia by the end of the current five-year program. Reports say that the Japanese have been interested in the oxidation of not only paraffin hydrocarbons but naphthenic petroleum hydrocarbons as well. Production of lower homology fatty acids up to butyric acid is being seriously considered in Japan. In America the most likely syntheses aside from “oxo” syntheses being considered for the manufacture of products like lauric acid is the carboxylation of the Ziegler intermediates prepared from ethylene polymerization. Some data on the current and future coconut oil consumption by major end-use for Canada and the United States are presented. Synthetic lauric acid is predicted for 1970 in the United States. Prepared from an address given at a meeting of the Northeast Section, New York, June 1968.     

A rapid method for determining the oxidation of n-3 fatty acids

The stability of unsaturated fatty acids to oxidation was monitored by following gas chromatographic (GC) analyses of headspace volatiles in comparison to changes in polyunsaturated fatty acids (PUFA) and increases in malonaldehydevia the 2-thiobarbituric (TBA) assay. Pure standards of linoleic acid (Lo) and n-3 fatty acids [eicosapentaenoic (EPA) and docosahexaenoic acid (DHA)] were added to headspace vials, equilibrated in air for 10 min, followed by heating at 80°C in teflon-capped vials for different time intervals. Headspace analysis showed increases in acetaldehyde, propenal, and propanal, corresponding to the oxidation of n-3 fatty acids, whereas hexanal production corresponded to losses of linoleic acid. The analysis of propanal by GC-headspace after only five minutes of heating appeared to be the most effective method of monitoring the oxidation of n-3 fatty acids, as indicated by correlations between TBA values and loss of PUFA. The oxidation of Lo, EPA and DHA appeared to be a function of the number of double bonds. Correlations between PUFA depletion, TBA values and volatile formation indicate that under the prescribed conditions of this experiment, GC-headspace analysis of propanal and pentane/hexanal is an excellent method for following the oxidation of selected n-3 fatty acids and linoleic acid.     

The free radical oxidation of polyunsaturated lecithins

Two unsymmetric polyunsaturated lecithins were allowed to air oxidize and the primary products of autoxidation were isolated and characterized. 1-Palmitic-2-linoleic-phosphatidylcholine undergoes significant oxidation after 16 hr at room temperature under air. A new phospholipid product may be isolated by reverse phase high pressure liquid chromatography (HPLC) and this HPLC fraction is shown to be made up of lipid hydroperoxides formed by free radical oxidation of the homoconjugated diene of the linoleate component of the lecithin. 1-Stearic-2-arachidonic-phosphatidylcholine undergoes a similar oxidation with the arachidonate polyunsaturated functionality being oxidized. The structure of the oxidation products was established by reduction of hydroperoxide with triphenylphosphine, snake venom hydrolysis of the C-2 ester, and HPLC analysis of the resulting hydroxy fatty acids or their methyl esters.     

Inhibition of hepatic lipogenesis by 2-tetradecylglycidic acid

2-Tetradecylglycidic acid (TDGA), a hypoglycemic agent, has been found to be a very effective inhibitor of de novo fatty acid synthesis by isolated hepatocytes. A comparison was made between the effectiveness of TDGA and 5-(tetradecyloxy)-2-furoic acid (TOFA), a hypolipidemic agent, on the metabolic processes of isolated hepatocytes. These compounds are structurally related and both inhibit fatty acid synthesis; however, they have opposite effects from each other on the oxidation and esterification of fatty acids. TDGA inhibits whereas TOFA stimulates fatty acid oxidation. TDGA stimulates whereas TOFA inhibits fatty acid esterification.     

Use of modified rosins in soap

Summary We have endeavored to show the advantages that rosins modified by hydrogenation, dehydrogenation, or polymerization have over ordinary rosins when used in soap. Ordinary rosin darkens in color upon oxidation. The modified rosins are not as susceptible to oxidation, and, therefore, soaps made using them do not darken in color to any greater extent than is normal for a soap made from the same fat stock but without rosin. The modified rosins when used as a replacement for part of the fat in soap making increase the rate of solubility of soap to a greater extent than do the ordinary rosins. They also show a slight advantage on the amount and stability of the lather. Hydrogenated rosin should be considered wherever germicidal value is desired since it contains a large proportion of tetra- and di-hydroabietic acids which have been shown by other investigators to have greater germicidal activity than the ordinary rosin acids or the fatty acids. The addition of modified rosins increase the wetting action of fatty acid soaps. It is indicated that up to 50% of modified rosin can be added to soap without decreasing detergent action, which, taken together with its other beneficial properties, makes it an ideal extender for fatty soap stocks. Chairman, Committee D-12 on Soap and Other Detergents of the American Society for Testing Materials.     

Composition and related nutritional and organoleptic aspects of palm oil

Palm oil is a fruit-coat fat that is low in sterols and rich in vitamins A and E. Up to 50% of its fatty acids are unsaturated, and linoleic acid constitutes up to 11% of the total acids. Its composition makes it an edible oil of nutritional importance and endows it with an inherent stability to oxidation, which has important organoleptic connotations. Variations in composition can occur for a number of reasons but, in general, oils produced in plantation countries have reasonably consistent properties.     

Thermal oxidation of synthetic triglycerides. II. Analysis of the volatile condensable and noncondensable phases

Tripalmitin, 1-lauryl dipalmitin, 2-lauryl dipalmitin, 1-oleyl dipalmitin and 2-oleyl dipalmitin were subjected to thermal oxidation at 200 C in the presence of air. The volatile consensable products of oxidation collected after 3 and 24 hours were analyzed for carbonyl and carboxyl compounds. The volatile non-condensable products were quantitatively examined for carbon monoxide, carbon dioxide, and hydrogen. The results indicated that long chain carbonyls were formed in the initial stages of oxidation. When the oxidation was allowed to proceed for 24 hours, saturated aldehydes from C₁ to C₁₆, methyl ketones, and other ketones were found in the volatile oxidation products. A variety of fatty acids from C₄ to C₁₆ were identified in the volatile fatty acids. The presence of dicarboxylic acids indicated that oxygen attacked the double bond of oleic acid in 1-oleyl dipalmitin. Possible mechanisms for the formation of the decomposition products were discussed. Portion of a thesis presented by Joseph G. Endres as partial fulfillment of the requirements for the degree of Doctor of Philosophy in Food Technology. Funds for the partial support of these studies were made available by the National Institute of health Grant A-1671.     

Thermal oxidation of synthetic triglycerides I. composition of oxidized triglycerides

Tripalmitin, 1- and 2-lauryl dipalmitin and 1- and 2-oleyl dipalmitin were subjected to thermal oxidation at 200C in the presence of air for various lengths of time. The triglycerides showed a loss in weight, and an increase in carbonyl hydroxyl and acid values. The I.V. increased in the case of saturated triglycerides and decreased in the case of unsaturated triglycerides. Hydrolysis of the ester linkage between glycerol and fatty acid was found to occur during thermal oxidation of the type and position of the fatty acid in the triglyceride molecule. The fatty acids released from the triglyceride by hydrolysis were found either to be oxidized further to short chain fatty acids, or were oxygenated with the introduction of a carbonyl or hydroxyl group in the molecule. Moreover, the unsaturated fatty acid in the triglyceride molecule was found to be oxidized more readily than the saturated fatty acid. A hydroxy fatty acid with a carbon number of 13.5 on a diethylene glycol succinate column was isolated from oxidized tripalmitin and was also found to occur in the free fatty acid fraction of oxidized tripalmitin, 1-lauryl, 2–3 dipalmitin, and 1-oleyl, 2–3 dipalmitin. The presence of laurie or oleic acid in the 2-position of the triglyceride prevented the formation of this acid, which suggested that it is an oxidation product of palmitic acid. Portion of a thesis presented by J. G. Endres as partial fulfillment of the requirements for the degree of Ph.D. in food technology. Funds for partial support of these studies were made available by the National Institute of Health, Grant A-1671.     

Verfahren und Anlagen zur Fraktionierung von synthetischen Fettsäuren

Processes and Plants for the Fractionation of Synthetic Fatty Acids Synthetic fatty acids, prepared by oxidation of paraffins, can be used to save valuable edible fats. Fractional distillation of these fatty acids enable their manifold application. For this, the paraffins have to fulfil certain criteria of quality. In a multiple stage vacuum fractionation process provided with material balance regulator, high boiling complex mixtures can be processed to distillates of high purity. Such a multi-column plant is equipped with stills, fractional columns and rectifying columns, and the plant is controlled by feeding machines. Many years of experience and production data have shown that synthetic fatty acid distillates can be produced economically and these products meet the technical requirements of soap and detergent industry.     

Effects of milk fat replacement by PUFA enriched fats on n‐3 fatty acids,conjugated dienes and volatile compounds of fermented milks

A study was carried out to determine the profiles of fatty acids in fermented milks and dairy derivatives made with milk fat substituted by polyunsaturated fatty acid (PUFA)‐enriched fat. In order to improve the organoleptic properties of those products, whey protein concentrates (WPC) were added during the manufacturing process. Interest was focused during manufacturing and storage period on the contents of “healthy” fatty acids, mainly conjugated linoleic acid and n‐3 PUFA. Contents of these fatty acids were not affected by the manufacture practices and neither did addition of WPC during manufacturing nor cold storage cause their decrease. Percentages of total n‐3 fatty acids in fat from dairy derivatives enriched in PUFA after 21 d of storage (1.45%) were very close to those obtained before processing (1.39%). Contents did not differ either substantially when WPC were added during manufacturing (1.46%). The increase of volatile compounds was also examined. Although a slight decrease in the total volatile content was observed, percentages of different compounds were not modified when milk fat was substituted by PUFA enriched fat.     

The Free Fatty Acid Content of Fish Oil-An Analysis of Anchovy Lipids at Different Stages in the Manufacture of Anchovy Meal and Oil

The quality of fish oil, as reflected by its free fatty acid (FFA) content, was studied in relation to the processing conditions of fish meal manufacture from anchovy (Engraulis capensis). Six samples of anchovy lipids were isolated from consecutive stages of the process and analysed for fatty acid composition, FFA, phosphorus and choline content. Results indicated that no significant oxidation of polyunsaturated fatty acids takes place in the fish meal manufacturing process. Only minimal amounts of FFA, generated as a result of chemical breakdown, are accumulated in the fish meal, rather than the press oil.     

Oxidative stability of conjugated linoleic acids relative to other polyunsaturated fatty acids

Contrary to current opinion, conjugated linoleic acids (CLA) as a mixture of several isomers have been previously shown to function as prooxidants in the form of free fatty acids and methyl esters in heated canola oil. Furthermore, CLA oxidizes considerably faster than linoleic acid. However, stability of CLA relative to other polyunsaturated fatty acids remains undetermined. The present study was therefore undertaken to examine the relative oxidation rate of CLA compared with that of linolenic acid (LNA), arachidonic acid (AA), and docosahexaenoic acid (DHA) in air at 90°C. CLA, both in the form of free fatty acids and triacylglycerols, were extremely unstable to the same extent as DHA, but they oxidized considerably faster than LNA and AA. The mechanism by which CLA were readily decomposed was probably due to formation of the unstable free-radical intermediate.     

Fatty alcohols

“Fatty” or higher alcohols are mostly C₁₁ to C₂₀ monohydric compounds. In probably no other homologous aliphatic series is the current balance between natural and synthetic products so vividly evident. Natural sources, such as plant or animal esters (waxes), can be made to yield straight chain (normal) alcohols with a terminal (primary) hydroxyl, along with varying degrees of unsaturation. In the past, socalled fatty alcohols were prepared commercially by three general processes from fatty acids or methyl esters, occasionally triglycerides. Fatty acids add hydrogen in the carboxyl group to form fatty alcohols when treated with hydrogen under high pressure and suitable metal catalysts. By a similar reaction, fatty alcohols are prepared by the hydrogenation of glycerides or methyl esters. Fatty alcohols are also prepared by the sodium reduction of esters of fatty acids in a lower molecular weight alcohol. The sodium reduction method was ordinarily too expensive; it was displaced early by the other methods; finally most unsaturated alcohols made by this route were largely replaced. Methyl ester reduction continues to provide perhaps 20% of the saturated fatty alcohols, and selective hydrogenation with the use of special catalysts such as copper or cadmium oxides was developed for the production of oleyl alcohol. Synthetic or petroleum technology for long chain alcohols include the Ziegler process, useful for straight chain, even-numbered saturated products. A second is the carbonylation and reduction of olefins affording medium or highly branched chain alcohols. Paraffin oxidation affords mixed primary alcohols. Fatty alcohols undergo the usual reactions of alcohols. They may be reacted with ethylene oxide to yield a series of polymeric polyoxyethylene alcohols or with acetylene under pressure to yield vinyl ethers or with vinyl acetate to give vinyl ethers.     

Partial hydrothermal oxidation of unsaturated high molecular weight carboxylic acids for enhancing the cold flow properties of biodiesel fuel

Biodiesel fuel has become more attractive recently because of its environmental benefits and the fact that it is a product made from renewable resources. However the less favorable cold flow properties or the low temperature operability of biodiesel fuel compared to conventional diesel is a major drawback limiting its use. The poor flow properties of biodiesel at cold temperatures are mainly due to biodiesel fuel being composed of long-chain fatty acids with an alcohol molecule attached. If the double bond of unsaturated fatty acids in these long-chain fatty acids could be ruptured selectively, then the cold flow properties of biodiesel fuel would be enhanced by reducing its viscosity.In this study, the selective hydrothermal oxidation of oleic acid, as a model compound of unsaturated high molecular weight carboxylic acids, was studied experimentally. The objective was to use this as a model to investigate whether the double bond of unsaturated fatty acids can be ruptured selectively by partial hydrothermal oxidation. Demonstration of this method could then be used to show the potential to improve the cold flow properties of biodiesel. Results showed that the amount of mono-carboxylic acids, aldehyde, di-carboxylic acids, and aldehyde-acids with a carbon number of 9 was significantly higher than other oxidative products. This suggests that the oxidative cleavage may principally occur at the double bond in hydrothermal conditions. The cloud and pour points for biodiesel fuel (B100) and B100 blend with a mixture of methyl esters or acetals were measured. These are the most important indicators for the cold flow properties of biodiesel fuel. The methyl esters or acetals used were made from the esterification of carboxylic acids or aldehydes by simulating the major oxidation products. These were obtained from the hydrothermal oxidation of oleic acid at different oxygen supply rates. Results showed that the cloud and pour points of the blend were significantly enhanced compared to those of B100.     

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.