Tall oil fatty acids

About 1949, with the advent of effective fractional distillation, the tall oil industry came of age, and tall oil fatty acids (TOFA), generally any product containing 90% or more fatty acids and 10% or less of rosin, have grown in annual volume ever since, until they amount to 398.8 million pounds annual production in the U.S. in 1978. Crude tall oil is a byproduct of the Kraft process for producing wood pulp from pine wood. Crude tall oil is about 50% fatty acids and 40% rosin acids, the remainder unsaps and residues; actually, a national average recovery of about 1–2% of tall oil is obtained from wood. On a pulp basis, each ton of pulp affords 140–220 pounds black liquor soaps, which yields 70–110 pounds crude tall oil, yielding 30–50 pounds of TOFA. Separative and upgrading technology involves: (a) recovery of the tall oil; (b) acid refining; (c) fractionation of tall oil; and occasionally (d) conversion to derivatives. TOFA of good quality and color of Gardner 2 corresponds to above 97% fatty acids with the composition of 1.6% palmitic & stearic acid, 49.3% oleic acid, 45.1% linoleic acid, 1.1% miscellaneous acids, 1.2% rosin acids, and 1.7% unsaponifiables.     

Waxes in the candle industry

Summary 1. The waxes in use for candles consist of paraffin and, in special cases, of beeswax. 2. Stearic acid is the only known hardening agent for paraffin. It raises the bending (softening) point and lowers the melting point. It can be used in any quantity without impairing the burning quality of the candle. 3. No other wax, natural or synthetic, can be substituted for stearic acid as a hardening agent for candle stock. Other waxes generally injure the burning quality of the candle or fail to produce any improvement, being at the same time more expensive than stearic acid. 4. The hydrogenated oils and fats serve as hardening agents for paraffin, especially for scale paraffin wax, and are used chiefly for candles which are consumed in glasses. 5. Synthetic or natural resins can be used in form of coatings only and are used chiefly for decorative candles. 6. No known synthetic hardening agent for candle wax can be satis-factorily substituted for stearic acid, even in such a mixture as 95% paraffin (MP 135°) and 5% stearic acid.     

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.     

The importance of glycerol in the fatty acid industry

Historically, glycerol, a valuable by product of the fatty acid insutry, is priced higher in the market-place than any of the common fatty acids. Glycerol “credit” from fat-splitting, frequently in time of economic stress, makes the difference between a profitable stearic acid operation and an economically unsound one. Theoretical yields of glycerol for the common fats and oils range from 9–13.5%; practical plant yields, corrected for FFA and upgrading yield losses, are 9–12.8% on 100% glycerol basis, or 10.3–14.8% on an 88% glycerol basis. Glycerol “credit” per pound of fatty acid ranges from 1 to 3 cents/pound. Upgrading “sweetwaters” from splitting operations in the fatty acid industry requires removal of dissolved salts, elimination of color, and fat and oil impurities, concentration (evaporation of water) and/or distillation. For Twitchellized sweetwaters this generally involves (a.) lime treatment. (b.) filtration, (c.) evaporation to half-crude, (d.) precipitation of excess lime, (e.) filtration, (f.) evaporation to a concentration of 88–90%, and probably, (g.) distillation. For autoclave or continuous process sweetwaters the upgrading includes (a.) light lime treatment, (b.) filtration, (c.) evaporation concentration to 88–90%, and probably, (d.) distillation. Glycerol may also be upgraded by ion-exchange processing followed by evaporation concentration in which distillation may be eliminated. Ion-exclusion (Dow process) is also feasible. Many special triglyceride products are required of different fatty acid homolog distribution than those of the parent or hydrogenated fats and oils. These are prepared by splitting the fats or hydrogenated oils, fractionating the fatty acids, upgrading the glycerol, and recombining the desired fractionated acids with glycerol by reesterification. One example is high lauric triglyceride from coconut oil suited for use as a coco butter substitute.     

Nitrogen derivatives (Amides,diamides, nitriles,primary amines and oxides)

Without a doubt the nitrogen derivatives are the most broadly diversified family of fatty acid derivatives. Today they account collectively for perhaps 400 million pounds of products per year in the USA alone. Although fatty amides may be produced by a large number of synthetic routes, industrially only two are of any commercial importance. Diamides are the difunctional analogs of simple amides, and a typical one that is in medium scale production volume is ethylene bis(stearamide). Industrially, the production of fatty nitriles in the fatty acid derivative industry is exclusively by ammonolysis of fatty acids at temperatures somewhat above those required to produce amides, or roughly, 300–320 C. Both vapor phase catalytic and liquid phase ammonolysis processes may be employed. Nitriles have limited uses as such, but find their utility as fatty derivative intermediates only. The primary amines, RNH₂, are produced industrially by the catalytic hydrogenation of nitriles. The general conditions for the conversion of nitriles to primary amines with a minimum content of secondary or tertiary amines is with nickel catalyst using an excess of ammonia at relatively low temperatures (130–140 C). Amine oxides are derived from tertiary amines by a controlled reaction with hydrogen peroxide. In addition to tertiary amines, the monoalkyl diethoxylated amines can be considered as in the same class. These are made by the addition of ethylene oxide to primary amine. Two moles of ethylene oxide can be added without catalyst. Additional ethoxylation does require a basic catalyst. These amines, besides having end uses of their own, can be converted to amine oxides or can be converted to ethoxylated quaternary ammonium salts.     

The lipids of the common house cricket,Acheta domesticus L. I. Lipid classes and fatty acid distribution

The lipids of the common house cricket,Acheta domesticus L., have been examined with the following results. The fatty acids associated with the lipid extracts do not change significantly from the third through the eleventh week of the crickets' postembryonic life. The major fatty acids are linoleic (30–40%), oleic (23–27%), palmitic (24–30%), and stearic acids (7–11%). There are smaller amounts of palmitoleic (3–4%), myristic (∼1%), and linolenic acids (<1%). The fatty acid composition of the cricket lipids reflects but is not identical to the fatty acids of the dietary lipids: linoleic (53%), oleic (24%), palmitic (15%), stearic (3%), myristic (2%), and linolenic acid (2%). The amount of triglycerides present in the crickets increases steadily from the second through the seventh or eighth week of postembryonic life, then drops sharply. Other lipid classes, such as hydrocarbons, simple esters, diglycerides, monoglycerides, sterols, and free fatty acids remain about constant. The composition of the fatty acids associated with the tri-, di-, and monoglycerides and the free fatty acid fraction are all about the same. The fatty acids associated with the simple esters are high in stearic acid. Postdoctoral Research Associate, Department of Chemistry, University of Michigan, 1965–1967.     

Low-<Emphasis Type="Italic">trans</Emphasis> Shortening and Spread Fats Produced by Electrochemical Hydrogenation

Partially hydrogenated soybean oils (90–110 IV) were prepared by electrochemical hydrogenation at a palladium/cobalt or palladium/iron cathode, moderate temperature (70–90 °C) and atmospheric pressure. The trans fatty acid (TFA) contents of 90–110 IV products ranged from 6.4 to13.8% and the amounts of stearic acid ranged from 8.8 to 15.4% (the higher stearic acid contents indicated that some reaction selectivity had been lost). The solid fat values and melting point data indicated that electrochemical hydrogenation provides a route to low-trans spreads and baking shortenings. Shortenings produced by conventional hydrogenation contain 12–25% trans fatty acids and up to 37% saturates, whereas shortening fats produced electrochemically had reduced TFA and saturate content. Electrochemical hydrogenation is also a promising route to low-trans spread and liquid margarine oils. Compared to commercial margarine/spread oils containing 8–12% TFA, the use of electrochemical hydrogenation results in about 4% TFA. Names are necessary to report factually an available data: the USDA neither guarantees nor warrants the standard of the product, and the use of the name USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Postparturition changes in the triacylglycerols of cow colostrum

The changes in the triacylglycerol (TAG) composition of colostrum fat of three cows were studied. In addition to the determination of fatty acid composition by gas chromatography, the distribution of TAG according to the acyl carbon number (ACN) and molecular weight was analyzed utilizing both supercritical fluid chromatography (SFC) and ammonia negative-ion chemical ionization mass spectrometry (MS). Colostrum TAG contained substantially less stearic and oleic acids and more myristic and palmitic acids than the normal Finnish milk fat. The major trends in the changes of fatty acids and TAG were similar for each cow, although clear differences between individuals were found. During the first week of parturition, the proportions of short-chain fatty acids (C₄–C₁₀) typically increased as well as those of stearic and oleic acids, whereas the relative amounts of C₁₂–C₁₆ acids decreased, especially those of myristic and palmitic acids. Distinct changes occurred also in TAG distributions: the proportions of molecules with ACN 38–40 increased and those with ACN 44–48 decreased. Although there were distinct differences between individuals shortly after delivery, both the fatty acid compositions and TAG distributions of the milk samples of the cows started to resemble each other after one week. The theoretical profiles of colostrum TAG calculated based on the fatty acid compositions differed clearly from the ACN distributions analyzed by SFC and MS. Thus, the analysis of TAG is essential, because the changes in molecular species composition of colostrum TAG cannot be estimated according to the fatty acid analysis alone.     

Site-specific differences in the fatty acid composition of human adipose tissue

The fatty acid composition of triacylglycerols from fifteen distinct adipose depots taken from each of seven adult male human subjects was compared. Oleic, palmitic, linoleic, stearic, myristic, palmitoleic and vaccenic acids accounted for more than 90% of the triacylglycerol fatty acids in all sites from all subjects; a number of other fatty acids were also identified and quantified. There were large differences in theaverage fatty acid composition between individual subjects. There were no site-specific differences in the proportions of myristic (3.8–4.7% of triacylglycerol fatty acids), palmitic (23–29%), linoleic (6.7–9.8%) or vaccenic (4.1–4.7%) acids or in the proportions of any of the less abundant fatty acids. There were some significant site-specific differences in the proportions of palmitoleic, oleic and stearic acids. The calf depot contained more palmitoleic acid (6.41±1.09%) than the trapezius (3.12±0.55%), perirenal (3.59±0.50%) and mesenteric (3.70±0.43%) depots, more oleic acid (42.13±1.27%) than the trapezius (36.03±2.18%), perirenal (36.50±1.56%) and breast (37.13±1.55%) depots and less stearic acid (5.18±0.89%) than the trapezius (8.57±0.97%), perirenal (8.49±0.75%), mesenteric (7.87±0.42%), breast (8.02±0.75%) and clavicular (8.34±0.78%) depots. The buttock depot contained less stearic acid (6.06±0.65%) than the perirenal, mesenteric and clavicular depots, while the anterior thigh depot contained less stearic acid (6.07±0.70%) than the perirenal depot. These findings indicate that, while most human adipose depots differ little in fatty acid composition, some sites, in particular the calf, perirenal, trapezius and mesenteric depots, have site-specific properties.     

Positional distribution of the fatty acids in the triglycerides of mango (Mangifera indica) kernel fat

Triglycerides of mango seed kernel fat contain, depending on the variety, 32.4–44.0% of stearic acid and 43.7–54.5% of oleic acid. Palmitic and linoleic acids represent, respectively, 5.9–9.1% and 3.6–6.7% of the fatty acids. The triglycerides also contain minor amounts of arachidic and linolenic acids. Palmitic, stearic and arachidic acids were almost exclusively distributed among thesn-1-andsn-3-positions. Oleic acid represented 85–89% of the fatty acids at thesn-2-position. Oleic acid at thesn-1- andsn-3-positions showed a preference for thesn-1-position. Linoleic acid was mainly esterified at thesn-2-position. The amounts of saturated fatty acids, i.e., palmitic and stearic acids, and of oleic acid, at thesn-1- and sn-3-positions, were linearly related to their respective contents in the total triglycerides.     

Combustion characteristics of candles made from hydrogenated soybean oil

Hydrogenated soybean oil, referred to as soywax by candle makers, is a renewable and biodegradable alternative to paraffin wax in candle manufacturing. Soywax was investigated for its tendency to produce soot as well as potentially harmful organic volatiles (acrolein, formaldehyde, and acetaldehyde) during combustion. Beeswax and paraffin candles were used as references. A considerable amount of soot was produced from the combustion of paraffin candles, but little or none was observed from soywax candles. Compared to paraffin candles, soywax candles burned at a significantly slower rate and required less air. Small amounts of formaldehyde were detected and quantified in the fumes of burning paraffin candles. However, formaldehyde, peaks found in the chromatograms of soy- and beeswax candles were similar to or slightly higher than that of the blank. Since soywax candles exhibited burning properties similar to those of beeswax candles, soywax shows promise in candle applications.     

Vegetable oil raw materials

Vegetable oils that are important to the chemical industry include both edible and industrial oils, which contribute 24% and 13.5%, respectively, compared to 55% for tallow, to the preparation of surfactants, coatings, plasticizers, and other products based on fats and oils. Not only the oils themselves but also the fatty acids recovered from soapstock represent a several billion pound resource. Coconut oil is imported to the extent of 700-1,000 million pounds per year. Its uses are divided about equally between edible and industrial applications. Safflower oil has a relatively small production, but 15–25% of the oil goes into industrial products. Soybean oil, the major edible oil of the world, is produced in the United States at the rate of 11,000 million pounds per year with more than 500 million pounds going into industrial uses, representing 5% of the total production. Castor oil is imported to the extent of about 100 million pounds per year. Linseed oil production has declined drastically over the last 25 years but still amounts to about 100 million pounds per year. Oiticica and tung oils are imported in lesser amounts than castor and linseed oils. New crops that have industrial potential, as well as the traditional vegetable oil crops, include seed oils from crambe,Limnanthes, Lesquerella, Dimorphotheca, Vernonia, andCuphea plants. Crambe oil contains up to 65% erucic acid. Oil fromLimnanthes contains more than 95% of fatty acids above C₁₈.Lesquerella oil contains hydroxy unsaturated acids resembling ricinoleic acid from castor oil.Dimorphotheca oil contains a conjugated dienol system.Vernonia oils contain as much as 80% epoxy acids. TheCuphea oils contain a number of short chain fatty acids. Of these, crambe,Limnanthes, andVernonia are probably the most developed agronomically. Competition between vegetable oils and petrochemicals for the traditional fats and oil markets has been marked over the past 25 years, but prices for petrochemicals have accelerated at a greater rate than those for vegetable oils; and, it is now appropriate to reexamine the old as well as the new markets for fatty acids.     

Comparative Evaluation of Physicochemical Properties of Jatropha Seed Oil from Malaysia,Indonesia and Thailand

The jatropha oil was extracted from the jatropha seeds collected from different origins viz., Malaysia, Indonesia and Thailand. The physicochemical properties such as density, viscosity, percentage free fatty acid (FFA), iodine value, saponification value and peroxide value of the extracted jatropha seed oil were evaluated. The evaluation of fatty acid composition using gas chromatography (GC) revealed that, oleic (42.4–48.8%) and linoleic acid (28.8–34.6%) are the dominant fatty acids present in the jatropha seed oil. The saturated fatty acids such as palmitic and stearic acid lie in the range 13.25–14.5 and 7–7.7%, respectively. The observed major triacylglycerol (TAG) composition was OOL (22.94–25.75%) and OLL (15.52–20.77%).     

Stereospecific analysis of maize triglycerides

This is the first report of stereospecific analyses of plant triglycerides isolated from seeds of distinct genotypes rather than from commerically refined oils. Triglycerides from six maize inbreds were analyzed. The strains exhibited a wide range of fatty acid compositions (palmitic acid 7.8–19.1%, oleic acid 17.0–43.0%, linoleic acid 41.6–68.3%). The distribution of the fatty acids among the 1, 2 and 3 positions of the triglycerides was clearly nonrandom for all six strains. At the 2 position of the triglycerides over 98% of the fatty acids were unsaturated. More plamitic and stearic acids were found in position 1 than in 3. The general fatty acid pattern of maize triglycerides was similar to that found in most animal triglycerides.     

Cottonseed oil and meal utilization

For five consecutive years world-wide production of cottonseed has set new highs, and cottonseed is more valuable as a source of food, feed, and fiber than ever before. However this paper is primarily concerned with the utilization of cottonseed oil and meal in the United States. During the three-year period, 1963–65, U.S. farmers received about $300 million annually for 6.18 million tons of cottonseed. Annual U.S. crushings were 5.79 million tons, having produced 1.94 billion pounds of crude oil valued at $222 million, 2.72 million tons of meal valued at $174 million, and 1,609,700 running bales of linters valued at $41.2 million. Retail value of cottonseed products is estimated to have been $1.1 billion annually. Changes in the U.S. cottonseed industry include shifts westward, to fewer and larger extraction plants and to the use of new and improved extraction techniques which involve solvents and high-speed expellers. The cottonseed extraction industry has a payroll of $38.2 million and consists of 188 oil mills in about 14 states, employing 8,400 people. Cottonseed oil accounted for 11.5% of total 1965 U.S. factory consumption of 12.7 billion pounds of fats and oils. Some 62% was used in salad or cooking oil, 27% in baking or frying fats, and 8% in margarine. During the 1960–65 period, usage increased in salad or cooking oils, in baking or frying fats, and in inedible products but decreased in margarine, mellorine, and other edible products. Increases exceeded decreases, and total consumption of cottonseed oil in edible and inedible products increased from 1.28 billion lb. to 1.47 billion lb. Practically all of the 2.76 million tons of cottonseed meal produced in the three-year period beginning October 1963 was used for feed. Relatively insignificant amounts were used as fertilizer on farms of cotton growers. Cattle, sheep, horse, and mule rations consumed 1.88 million tons, poultry rations 440 thousand tons, and swine rations 350 thousand tons. Cottonseed meal in cattle rations has had a downward trend since the early 1950’s although usage in poultry and swine rations has increased. It is estimated that 1.52 million tons were used by feed manufacturers in the preparation of mixed feeds during the 1964–65 season, representing a steady increase over the past two decades and a 54% increase over 1962–63. Domestic use of cottonseed flour has not changed appreciably during the past few years.     

Effect of Substitution of High Stearic Low Linolenic Acid Soybean Oil for Hydrogenated Soybean Oil on Fatty Acid Intake

High stearic, low α-linolenic acid soybean oil (HSLL) has been developed via traditional breeding to serve as a substitute for partially hydrogenated soybean oils used in food manufacturing. The purpose of this study was to estimate the impact on fatty acid intake in the United States if HSLL were substituted for partially hydrogenated soybean oils used in several food categories, including baked goods, shortenings, fried foods, and margarines. Using National Health and Nutrition Examination Survey (NHANES) data (1999–2002), baseline intakes of five fatty acids and trans fatty acids (TFA) were determined at the mean and 90th percentile of fat consumption. Then intakes of these fatty acids were determined after HSLL was substituted for 100% of the partially hydrogenated soybean oils used in these four food categories. The results show that baseline intake of stearic acid is 3.0% energy at the mean and 3.3% energy at the 90th percentile. Use of HSLL could increase stearic acid intake to about 4–5% energy. Mean intakes of TFA could decrease from 2.5 to 0.9% energy, and intake of palmitic acid would remain unchanged. Use of HSLL as a substitute for partially hydrogenated soybean oils would result in changes in the fatty acid composition of the US diet consistent with current dietary recommendations.     

Fatty acid composition of oil from exotic corn breeding materials

The fatty acid composition of corn oil can be altered to meet consumer demand for “healthful” fats. The first step in altering the oils is to survey existing corn breeding materials for fatty acid composition. The Latin American Maize Project (LAMP), an international program designed to evaluate the agronomic characteristics of maize accessions in Latin American and U.S. germplasm banks for future use, provides useful starting materials. LAMP was based on the cooperative efforts of 12 countries. In a two-stage evaluation, the project identified the highest-yielding open-pollinated top 20% of populations, then approximately the top 5% of those 20%. Twenty of the populations from four countries with temperate climates were randomly selected for fatty acid analysis. The populations were from United States, Chile, Argentina, and Uruguay. Fifty S₁ lines from each population were randomly chosen for analysis for a total of 1,000 genotypes sampled. Statistical differences in fatty acid composition were computed among the 20 populations and among the four countries. The findings showed a wide range of fatty acid profiles present in unadapted, elite corn breeding materials with ranges for each fatty acid as follows: palmitic acid, 6.3–18.2%; stearic acid, 0.9–4.5%; oleic acid, 18.5–46.1%; linoleic acid, 36.6–66.8%; linolenic acid, 0.0–2.0%; and arachidic acid, 0.0–1.4%. Several populations were significantly different from the others. Some lines had unusual fatty acid compositions, including one with 8.3% total saturates and another with 20.2% total saturates. This study shows that existing corn breeding materials could be used to produce high- and low-saturate oils, but other methods would probably be required to produce a high-oleic corn oil.     

Fatty acid composition of Iranian citrus seed oils

Fatty acid compositions of seed oils from eight Iranian citrus fruits were determined. The ranges of values for major fatty acids were 21.8–29.4% palmitic, 3.1–7.60% stearic, 0.3–1.3% palmitoleic, 23.5–32.3% oleic, 33.5–39.8% linoleic, and 3.1–7.6% linolenic. Low amounts (up to 0.1%) of myristic and arachidic acids and traces of a few unidentified ones constituted minor fatty acids.     

The plant geneticist’ contribution toward changing lipid and amino acid composition of safflower

Current research on the fatty acid composition of the seed oil of safflower (Carthamus tinctorius L.) has shown the following: (1) there is a possibility that the oleic acid content can be increased above 80%, though probably not above 85%, by use of modifying genes and the major geneol; (2) wild species do not look very promising as a source of genes for modifying fatty acid composition; (3) commercially grown high linoleic and high oleic types are temperature stable; (4) an experimental type with about equal amounts of oleic and linoleic acids is responsive to temperature, with high temperature increasing oleic acid and low temperature increasing linoleic acid; and (5) stearic acid in another experimental type with higher levels of stearic acid (5–10%) is reduced by low temperatures. One of seven papers presented at the Symposium, “The Plant Geneticist’s Contribution Toward Changing Lipid and Amino Acid Composition of Oilseeds,” AOCS Meeting, Houston, May 1971.     

Hydrogenated vegetable oils as candle wax

Partially hydrogenated soybean oil, referred to as soywax, is gaining attention as a renewable and biodegradable alternative to paraffin wax for use in candles. However, current soywax candles suffer from several problems, especially poor melting and solidification properties. Fully hydrogenated soybean oil exhibits improved melting properties but owing to its fragile texture, it is not yet acceptable in most candle applications. In the present work, KLX^TM (a wax composed of fractionated hydrogenated soy and cottonseed oils) was used as a base material for candles, and the effects of additives such as hydrogenated palm oil (HPO), FFA, and paraffin on the textural and combustion properties were evaluated. Melting and solidification profiles of KLX were better than those of fully hydrogenated soy oil. Adding FFA improved the solidification properties of KLX candles. Adding paraffin improved the compressibility of the wax, while HPO addition decreased hardness and compressibility. Changing the candle diameter and/or wick size along with changing the wax composition resulted in candles with desirable quality attributes.