Improved gas chromatographic analysis of fatty and resin acid mixtures with special reference to tall oil

A gas liquid chromatography system for the analysis of complex mixtures of fatty and resin acids has been developed. On 30–40 m long, 0.3 mm ID glass capillary columns coated with 1,4-butanediol succinate (BDS) and attaining over 90,000 effective theoretical plates, all main fatty and resin acids in wood extractives and various tall oil products can be separated and quantitatively determined without need of any prefractionation of the acids. Also the levopimaric acid is well separated. Retention values, including their temperature dependence, on columns coated with BDS or SE-30 are given for 49 significant fatty and resin acids. Applications on wood extractives, sulfate soaps, and crude and distilled tall oil are presented and discussed.     

Capillary gas chromatography-mass spectrometry of resin acids in tall oil rosin

The resin acid composition of Finnish tall oil rosin was investigated by gas chromatography and mass spectrometry employing open tubular capillary columns. On a column coated with 1,4-butanediol succinate, 16 resin acids found in tall oil rosin samples were well resolved, and mass spectra could be recorded. All resin acids were confirmed to be of the pimaric and abietic types by gas chromatographymass spectrometry. Eight of the acids were not detected in the corresponding crude tall oils and evidently had been formed during the technical distillation process. The presence of 8,15-pimaradien-18-oic and 8,15-isopimaradien-18-oic acids in the rosin, but not in the crude tall oil, indicates that the pimaric type acids also undergo extensive isomerization during tall oil distillation. Additionally, three dihydroabietic acids and two acids with identical mass spectra, tentatively stereoisomers of 7,9(11)-abietadien-18-oic acid, were formed during the distillation process.     

The behavior of resin acids during tall oil distillation

The behavior of resin acids during tall oil distillation was studied by analyzing samples from six industrial-scale processes. The same artifact resin acids were formed in all processes. However, the proportion of artifact resin acids in tall oil rosins varied from 8.3 to 18.3% of the resin acids. The lowest values were found for two processes utilizing thin-film evaporators. The yield of resin acids in the tall oil rosin fraction varied from 62 to 80% of the resin acids in the crude tall oil feeds. Dehydroabietic acid was formed in all processes, the amount in rosin being 14-44% more than in the crude tall oil feed. Of the abietic acid, only 45-82% was recovered in the tall oil rosin fraction. The distribution of various resin acids and their reaction products during distillation was determined. Major resin acid impurities in tall oil fatty acids were 8,15-pimaradien-18-oic acid and 8,15-isoprimaradien-18-oic acid, both formed chiefly during distillation, and two secodehydroabietic acid isomers common in crude tall oils. The reactions of resin acids leading to new isomers or non-acidic products are discussed. Some results of this work were presented at the 173rd American Chemical Society Meeting, New Orleans, March 1977.     

Diterpene resin acids: Major active principles in tall oil against Variegated cutworm,Peridroma saucia (Lepidoptera: Noctuidae)

Tall oil, a by-product of the kraft process for pulping softwood, has been shown to have insecticidal properties. In the present study, the active principles in tall oil against the variegated cutworm,Peridroma saucia Hübner, were investigated. GC-MS analysis showed that abietic, dehydroabietic, and isopimaric acids were major resin acid components of crude tall oil and depitched tall oil. When crude tall oil samples of differing resin acid composition were incorporated into artificial diet at a concentration of 2.0% fresh weight, they suppressed larval growth by 45–60% compared to controls. This suppression was significantly (P0.05) correlated with the equivalent contents of abietic, dehydroabietic, isopimaric, and total resin acids. These results were also evident from a diet choice test, showing that the second-instar larvae obviously selected diets with low levels of resin acids when different diets were randomly arranged in a Petri dish. Bioassays with pure resin acids (abietic, dehydroabietic, and isopimaric acids) demonstrated that all individual chemicals have similar bioactivity against this insect. Comparison of the bioactivities of depitched tall oil and an equivalent mixture of pure resin acids in thePeridroma chronic growth bioassay indicated that pure resin acids and depitched tall oil share a common mode of action to this insect. This study confirms that resin acids are major active principles in tall oil against the variegated cutworm, but other chemicals likely also contribute to the bioactivity of tall oil.     

Tallöl-Fraktionierung als Beispiel der Optimierung konventioneller Füllkörperkolonnen

Fractionation of Tall Oil as an Example of Optimization of Conventional Packed Columns The present communication records a simple calculation for optimization of packed columns in an example of layout of columns for fractional distillation of crude tall oil into the main products, i.e. fatty acids and resin acids. This calculation requires, apart from knowledge on the temperatures stability of the material, only the HETP value, which is the height of chosen packing material equivalent to one theoretical plate. An arrangement of three columns is necessary for complete separation of crude tall oil in continuous manner. In the example shown, calculation of the first column for a capacity of 20 000 t per year is given.     

Distillability of extracted mixed-birch tall oil

Chemical and physical properties of tall oil made in the CSR process and distillation results of three different types of distillation plants are presented. Chemically extracted, mixed-birch, tall oil differs remarkably from the normal Scandinavian crude tall oil. The extracted oil deviates from the normal, unextracted, mixed-birch tall oil with respect to the smaller unsaponifiable amount and the fatty acid esters. The amount of resin acid is small in extracted mixed-birch tall oil. The quantity of fatty acids, especially that of saturated fatty acids, is large. Distillation of extracted mixed-birch tall oil is most successful in a distillation plant where thin film evaporators are used.     

A study of the influence of storing wood on the yield and quality of tall oil

In 12 weeks of storage time pine roundwood lost approximately 11% in tall oil yield, while for the same length of time purchased slabwood chips (pine) lost 64%. Most of the loss in yield occurred within six weeks. The purchased chips lost more tall oil yield in one week than the roundwood in 12 weeks. The loss in yield from the roundwood was due entirely to the loss in yield of fatty acids. The loss in yield in the purchased slabwood chips was due predominantly to the loss in yield in fatty acids; however, there was, in addition, a small loss in resin acids, and a very small loss in unsaponifiables. As for tall oil quality, by the end of 12 weeks of storage the acid number of tall oil from both roundwood and purchased chips had dropped below 160. In correlating the yield of tall oil from the wood extractions with the yield of tall oil from the black liquor from digester cooks, it appears that on the average about 80% to 88% of the extracted tall oil can be found in the black liquor.     

Spectrophotometric analysis of tall oil rosin acids

Summary About half of the rosin acids in whole and distilled tall oil consist of abietic and neoabietic acids, as distinguished from hydroabietic acids, dehydroabietic acid, and the pimaric acids. In this respect the tall oil rosin acids are similar to those from gum or wood rosin. This was established by spectrophotometric analysis of the rosin acids from whole tall oil, double distilled tall oil, rosin acids crystallized from tall oil, and rosin acids separated from tall oil by fractional distillation. The rosin acids crystallized from tall oil contained the highest percentage of abietic acid, but the sum of abietic and neoabietic acids was only slightly higher. The rosin acids from acid refined tall oil contained appreciably less abietic and neoabietic acid than the others. Before spectrophotometric analysis the rosin acids were isolated from the tall oils in about 95% yield by cyclohexylamine precipitation.     

Solvent extraction of fatty acids from natural oils with liquid water at elevated temperatures and pressures

The use of liquid water at elevated temperatures and pressures as an extractive solvent for separating mixtures of compounds which occur in natural oils has been studied. A southern pine tall oil and a distillate from the deodorization of soybean oil were extracted with liquid water at temperatures from 298 to 312°C and pressures between 103 and 121 bar. Results indicate that water can be used to extract fatty and resin acids from crude tall oil to obtain a product with a high acid content that produces less pitch during distillation. The process can also be used to extract fatty acids from vegetable oil deodorizer distillate.     

Operating variables in the analysis of tall oil acids by capillary gas chromatography

Factors influencing the analysis of fatty and resin acid methyl esters by capillary gas chromatography have been investigated. Methods to calculate equivalent chain length (ECL) values and their limitations are first discussed. Retention data, expressed as equivalent chain lengths (ECL) were determined on SE-30, SP-2100 and Carbowax 20M columns. The medium length (20–30-m) polysiloxane columns, SE-30 and SP-2100, provided overall better resolution and shorter retention times than the more polar Carbowax 20M column of similar length. The temperature dependence of ECL values was investigated for all three columns in the range 180–210 C. Retention times and ECL values were more temperature-dependent for the Carbowax 20M than for the other two stationary phases. The effects of split ratio and method of injection on the precision and accuracy of the analysis were also examined. Using optimal conditions of analysis established in this paper, the difference between measured and actual weights of an internal standard added to two tall oil samples was determined to be less than 3%.     

Identification of minor cyclic fatty acids in fractionated tall oil

The structure of several minor cyclic fatty acids present in Finnish tall oil fatty acids are elucidated by gas chromatography-mass spectrometry. The origin and mechanism of formation of these cyclic fatty acids are discussed. The cyclic fatty acids identified in tall oil fatty acids are: 4-(5-pentyl-3a,4,7,7a-tetrahydro-4-indanyl)butanoic acid,ω-(o-alkylphenyl)alkanoic acid, 2,6-dimethyl-9-(3-isopropylphenyl)-6-nonenoic acid, 4-(5-pentyl-4-indanyl)butanoic acid, and 4-(2-hexyl-1,2,4a,5,6,7,8,8a-octahydro-1-naphthyl)butanoic acid. In addition, three different branched or cyclic unsaturated C₁₉ fatty acids are reported to be present in tall oil.     

Comparative value of fatty acids and resin acids of tall oil in soaps

Summary A study has been made of the detergency and foaming power of soaps made from a typical acid-refined American tall oil. Sodium soap of tall oil, straight tall oil fatty-acid soap, and straight tall oil resin-acid soap were evaluated. The effect of fatty acid-resin acid ratio was determined by using mixtures of those soaps. Sodium rosinate, sodium oleate, and mixtures of these soaps were used as comparison standards. Curves plotted show wash-test data and foaming values as functions of the ratio of fatty soap to resin soap. The data indicate in terms of detergency: a) tall oil soap has a higher value than sodium rosinate; b) sodium oleate is better than tall oil fatty-acid soap, but the latter is approximately equivalent to soaps from various unsaturated vegetable oils; c) both tall oil resin-acid soap and rosin soap have low detergency on cotton; d) the detergency of most mixtures of tall oil fatty-acid and resin-acid soaps at lower concentrations is greater than would be predicted from the individual soaps, indicating a synergistic effect. As a rough approximation, tall oil soap without unsaponifiables is equivalent to a corresponding mixture of sodium oleate and sodium rosinate. The presence of unsaponifiables lowers both detergency and foaming. Tall oil soap is somewhat less sensitive to hard water than sodium oleate. Significant differences between detergencies of soaps, and especially between soap mixtures, are obscured when launderometer tests are run at moderate soap concentrations. These differences are readily detected at lower concentrations. Presented at 113th meeting of the American Chemical Society, Chicago, Ill., April 14–23, 1948.     

Cyclopropenoid Fatty Acids in Malagasy baobab: Adansonia grandidieri (Bombacaceae) Seed Oil

Adansonia grandidieri (bombacaceae family) seed oil gives a positive Halphen test. Composition analysis of derivatized fatty acid methyl esters, in presence of silver nitrate in anhydrous methanol, after chromatography fractionation on silicagel column, were made by gas-liquid chromatography (GLC) using a packed DEGS column. Presence of malvalic and sterculic acids were detected. GLC analysis using glass capillary columns coated with Carbowax 20 M and BDS shows that A. grandidieri seed oil contains mainly palmitic (41%), oleic (22%) and linoleic (12%) acids. Cyclopropenic fatty acid concentration was 14% with 6% for malvalic and 8% for sterculic acids. A slight proportion of dihydrosterculic acid (1.5%) was observed. GLC fatty acid methyl esters analysis, without derivatization, on the two glass capillary columns coated with Carbowax 20 M and BDS gave the same results for cyclopropenic acids content.     

Separation of fatty acid methyl esters from tall oil by selective adsorption

Fatty acid methyl esters (FAME) and resin acids (RA) were separated from tall oil by selective adsorption. Commercial nonmodified molecular sieve 13X was used as adsorbent. The adsorption isotherms of fatty acids (FA), FAME, and RA on molecular sieve 13X at 25°C were determined using various solvents. The solvents were methanol, ethanol, isopropanol, acetone, benzene, hexane, isooctane, petroleum ether (40–60°C), and petroleum naphtha (80–180°C). With each solvent, FA and RA were adsorbed to a greater extent than FAME. Adsorption isotherms for RA and FAME in binary adsorption systems were also determined using petroleum ether, petroleum naphtha, benzene, and isopropanol. For each component in the binary adsorption, the equilibrium amounts are lower than the values for pure component adsorption. The adsorption of FAME decreased in the presence of RA markedly in petroleum ether and petroleum naphtha. This fact may be the indication of the phenomenon of selective adsorption. Separation was accomplished by adding a solution of esterified tall oil in solvents used in the binary adsorption systems, through a column packed with molecular sieve 13X. With petroleum naphtha, FAME and RA were recovered in yields of 93 and 94%, respectively, from esterified tall oil. Petroleum naphtha gave the best results. The effects of particle size of adsorbent and flow rate of solvent on the efficiency of the separation were also investigated in fixed-bed column studies. The particle size of adsorbent did not apparently alter the results. Changes in the particle size should not significantly change the number of available adsorption sites in a microporous molecular sieve.     

蒸馏妥尔油改性酚醛树脂的合成与应用

利用造纸厂纸浆废液中分离出的蒸馏妥尔油,合成了改性酚醛树脂,并对反应机理和树脂结构进行了分析。结果表明,当苯酚与甲醛的摩尔比控制为1∶0.6~0.9,蒸馏妥尔油加入量为苯酚的40%~60%时,改性的酚醛树脂性能最佳,与聚合物和溶剂的混溶性得到提高。     

Identification of the less common isologous short-chain triacylglycerols in the most volatile 2.5% molecular distillate of butter oil

The isologous short-chain triacylglycerols of the most volatile 2.5% distillate of butter oil were resolved by reversed-phase high-performance liquid chromatography (HPLC) with mass spectrometry. The molecular species were identified by means of the [MH]⁺ and the [MH-RCOOH]⁺ ions in positive chemical ionization mode. A set of empirically determined incremental elution factors was found that could be used to calculate the accurate elution order of natural butterfat triacylglycerols when analyzed by reversed-phase HPLC. The triacylglycerols were also resolved by temperature-programmed gas-liquid chromatography on capillary columns coated with polar liquid phases. The high polarity of the columns provided separation of triacylglycerols on the basis of the degree of unsaturation, as well as on the nature of the shortest acyl chain, with the isologous species having the shortest chainlength eluting last. Both saturated and unsaturated triacylglycerols containing normal and branched-chain odd-carbon fatty acids in combination with short-chain acids were identified, and over 150 molecular species were quantitated.     

The fat acids of American tall oil

Summary The composition of the fat acids of six samples of American tall oil has been determined. They are all quite similar in fat acid composition. The average values were: linoleic acid 48%; oleic acid 45%; saturated acids 7%. There is present approximately 11% of conjugated linoleic acid, probably formed by the action of alkali and heat during the cooking of the pulp from which the tall oil was formed. Detailed fractional distillation of a sample of the methyl esters of the fat acids showed that the saturated acids are mostly palmitic, that there may be about 1% of palmitoleic, and that the conjugated linoleic acid present can be separated and concentrated by fractional distillation. Paper No. 65, Journal Series, Research Department, General Mills, Inc.     

Biodiesel production from tall oil with synthesized Mn and Ni based additives: Effects of the additives on fuel consumption and emissions

In this study, biodiesel fuel and fuel additives were produced from crude tall oil that is a by-product in the pulp manufacturing by craft or sulphate pulping process. Fatty acids and resinic acids were obtained from crude tall oil by distillation method. Tall oil methyl ester (biodiesel) was produced from fatty acids. Resinic acids were reacted with NiO and MnO₂ stoichiometrically for production of metallic fuel additives. Each metallic fuel additive was added at the rate of 8 μmol/l and 12 μmol/l to make mixtures of 60% tall oil methyl ester/40% diesel fuel (TE60) for preparing test fuels. Metallic fuel additives improved properties of biodiesel fuels, such as pour point and viscosity values. Biodiesel fuels were tested in an unmodified direct injection diesel engine at full load condition. Specific fuel consumption of biodiesel fuels increased by 6.00%, however, in comparison with TE60, it showed trend of decreasing with adding of additives. Exhaust emission profile of biodiesel fuels improved. CO emissions and smoke opacity decreased up to 64.28% and 30.91% respectively. Low NO_x emission was also observed in general for the biodiesel fuels.     

Utilization of tall oil to enhance natural fibers for composite applications and production of a bioplastic

Tall oil is one of the side products from the kraft pulping process of lignocellulosic material. The most abundant acid found in this crude viscous material is abietic acid. Strangely, in the past, the utilization of tall oil has been limited to incineration for cogeneration of power. In this study, tall oil rosin acids (TORAs) were used in two different applications. First, it was used to enhance the hydrophobicity and thermal properties of hemp fibers. Second, TORAs were used to supplement epoxy for the production of a polymeric material. The reaction conditions from a model study were mimicked using a crude tall oil rosin acid mixture to enhance hemp fibers. Treated hemp fibers were characterized with increased surface hydrophobicity and improved thermal properties. Also, IR and X‐ray photoelectron spectroscopy confirmed successful chemical modification and grafting of carbon rich moieties onto the surface of the fibers, respectively. Furthermore, TORAs were used to supplement epoxy resin and produced plastics with comparable properties to pure epoxy based plastics. Specifically, 25% (w/w) replacement exhibited little difference in thermal stability and curing when compared to virgin epoxy plastics. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44327.     

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.