Crude Tall Oil Research Articles

Continuous Extraction of Crude Tall Oil

A new continuous extraction method for fatty and resinic acids separation from crude tall-oil sodium salts aqueous solutions by countercurrent contact with n-heptane was developed using a bench-scale multistage mixer-settler plant. The data obtained showed good recoveries and high purities, especially for resinic fraction stream, for which the consumption of chemical reagents is virtually obviated with consequent economic advantages.

Fatty and Resinic Acids Extraction from Crude Tall Oil

Abstract The separation of fatty and resinic acidic fractions from crude tall-oil soap solutions with n-heptane by the technique of dissociation extraction is discussed. The theory of the overall process is supported by a systematic study developed to cover the high selectivity demonstrated in the differential solubility and the aptness between fatty and diterpenic acids to both liquids phases. To study the main factors affecting those liquid-liquid extraction systems and the amphiphilic behavior of such molecules involved, sodium salts aqueous solutions of crude tall oil and synthetic mixtures as molecular acidic models were used.

Refining and Separation of Crude Tall-Oil Components

Abstract Methods for crude tall-oil refining and fractionation involving research studies of long-chain fatty and resinic acids separation are reviewed. Although several techniques have been applied since the 1940s with industrial aims, only distillation under high vacuum is economically practicable for crude tall-oil fractionation. Techniques such as adsorption and dissociation extraction seem to be the most industrially promising for implementation in the future for the separation of long-chain fatty and resinic acids fractions with a high purity level at low cost.

Technology for the beneficiation of graphite-bearing dusts from integrated iron-and-steel works

A combined magnetic separation and flotation technology for the beneficiation of graphite-bearing dusts, in this case wastes from the Krivoy Rog Integrated Iron-and-Steel Works, using high-molecular weight fraction of ‘industrial’ lignosulfonates (a modifier), a mixture of saponified crude tall oil and T-80 frother as a collector, has been developed and tested under pilot-scale conditions. The technique is shown to yield graphite and iron ore concentrates.

Comparison of quantitative methods for analysis of resinic acids in crude Tall-Oil

Currently used analytical methods to quantify resinic acids in crude Tall-Oil (ASTM D 803 and SCAN T 14), have been reviewed and their accuracy and precision ascertained with different samples containing from 30 to 80% of resinic acids. A new method for quantification of resinic acids in crude Tall-Oil samples, using a gas chromatographic method was compared with the standard methods. It provides the same level of precision and accuracy, is much faster and requires smaller samples. Dibuthylphthalate was tested, with good results, as an internal standard.

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 (P≤0.05) 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.

ANTIFEEDANT AND GROWTH INHIBITORY EFFECTS OF TALL OIL AND DERIVATIVES AGAINST THE VARIEGATED CUTWORM, PERIDROMA SAUCIA HÜBNER (LEPIDOPTERA: NOCTUIDAE)

AbstractCrude tall oil and two of its derivatives were assessed for antifeedant and growth inhibitory effects, via incorporation into an artificial diet, in the variegated cutworm (Peridroma saucia Hübner). The substances tested are both toxic to neonate P. saucia and inhibitory to larval growth. The dietary LC50 (lethal concentration for 50% mortality) values are 4.3, 4.7, and 5.3% fresh weight for depitched tall oil (DTO), crude tall oil (CTO), and tall oil pitch (TOP), respectively. These materials significantly reduced growth, feeding, and dietary utilization by first-, second-, third-, and fourth-instar larvae in chronic larval growth bioassays, choice and no-choice feeding tests, and nutritional experiments. The EC50s (effective concentration to inhibit growth by 50% relative to controls) of DTO, CTO, and TOP were 1.4, 2.0, and ≥2.4%, respectively, when first-instar larvae fed on treated diets for 10 days. DTO significantly reduced both growth and consumption rates with corresponding reduction in the efficiency of conversion of food (i.e. nutritional efficiency), suggesting that both antifeedant and toxic effects are involved in larval growth inhibition. DTO and CTO are consistently more biologically active than TOP. Our results suggest that an environmentally sound, low cost natural pest control agent may be developed based on tall oil.

New reagent systems for flotation of low-grade manganese products of combined beneficiation

New reagent systems for flotation of manganese ores have been tested, involving use of a mixture of polyacrylamid (PAA) + carboxymethylcellulose (CXMC) or that of polyacrylamid (PAA) + industrial lignosulphonates (LSP) used as a modifier and a mixture of saponified crude tall oil (SCTO) + amines from nitroparaffin (ANP-2)+ alkali used as a collector. The basic features of the new flotation reagent systems involve the need of using polymers for slime flotation and influence of polymers on flotation results stipulated by their effect on pulp rheology.

Catalytic conversion of crude tall oil to fuels and chemicals over HZSM-5: Effect of co-feeding steam

The catalytic conversion of crude tall oil to fuels and chemicals was studied at atmospheric pressure over HZSM-5 in a fixed bed microreactor. The oil was diluted with tetralin in all experiments and in addition, steam was co-fed in some runs. The experiments were carried out at 370, 380, 390 and 405°C using space velocities of 2.5 and 3.6 h −1. The addition of steam led to a substantial reduction in coke formation with the result that at 390°C, only 0.5 wt.% of the tall oil was converted to coke. Although the conversion to gaseous hydrocarbons remained mostly between 15 and 23 wt.%, the olefin/paraffin ratio increased dramatically in the presence of steam from around 0.2–0.4 to values in the range 1.3–15.

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.

Tall oil fatty acids

AbstractAbout 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.

Distillability of extracted mixed‐birch tall oil

AbstractChemical 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.

The behavior of resin acids during tall oil distillation

AbstractThe 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.

Tall oil fatty acid marketing

Abstract and SummaryOnce considered a low cost by‐product of crude tall oil fractionation, tall oil fatty acids are now being used for their own distinctive and specific properties in special applications. Consumption of tall oil fatty acids in protective coatings, soaps, and ore flotation has declined in recent years, however, usage in chemical intermediates has increased significantly in the past 10 years. These intermediates are dimer acids, oleic and linoleic acids, epoxidized esters, amidoamines, and diacids. Static tall oil production during the mid 1970s caused by changes in paper mill operations (i.e., continuous digestion, waste recycling, increased usage of chips and hard wood) has increased the demand for higher priced oleic acid and other unsaturated fatty acids.

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

AbstractThe 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.

Air and water pollution control in crude tall oil manufacture in the pulp and paper industry.

AbstractPollution preventive measures should be built into the process when a new mill is designed; corrective measures must be taken on existing mills. For air pollution control, these measures consist essentially of enclosing all vessels that contain the black liquor from which the tall oil is recovered. Hoods are placed over storage tanks, sumps, heat exchangers, and other liquor‐containing vessels. The hoods must be vented to a ductwork system that brings the off‐gases to a central point for disposition. Typical devices to remove the offensive odors and particulate matter in the off‐gases are wet scrubbers and incinerators. Evaporation can be used to concentrate liquids containing small amounts of contaminants to much smaller volumes and to concentrations that permit incineration. The lime kiln and recovery boiler of the typical Kraft mill commonly are used to burn the odorous gases, thus destroying the odors completely. Sometimes a separate incinerator is required. Water pollution is best prevented by careful design and operation of the various tall oil removal equipment, such as soap skimmers, level controls, and valving systems. In spite of great care in design and operation, some tall oil will enter the wastewater stream. The effluent treatment plant must be designed to take care of this residual biochemical oxygen demand load and, in some cases, provide for color reduction in the treated effluent.

Modern techniques for the production of crude tall oil

AbstractA short background of the methods for the production of crude tall oil is given.A simplified flow sheet of the continuous acidulation proces is shown and a new type centrifuge is introduced for the continuous separation of the various components of the acidulated sulfate reaction mixture.The separation section of the process is described with particular emphasis given to the operation of the centrifuge.Performance of the process is discussed with respect to yield and quality of the crude tall oil.

Rigid Urethane Foams Derived from Crude Tall Oil

Rigid Urethane Foams Derived from Crude Tall Oil

Production methods for the manufacture of crude tall oil and its subsequent processing

SummaryThe source of crude tall oil and methods to produce the oil have been described. These include acidulation of sulfate pulp, black liquor skimmings, and gravity settling as well as centrifugal means of separation to reduce the lignin content of the product.Subsequent processing of the crude tall oil into fractionated fatty acids and rosin has been outlined with suggestions for consideration in all stages of the distillation section of the plant.

Studies on the Utilization of Tall Oil II.

In the previous paper, preparation of the mixed methyl esters, consisted of fatty and rosin esters, was discussed. In this paper, these esters were converted into mixed alcohols, consisted of fatty and rosin alcohol, by Bouvealt-Blanc reaction. The kind, amount of reduced alcohol, amount of sodium in the reduction and the distillation of produced crude alcohol were discussed. Tertiary butyl alcohol was most suitable for reduction in the case of all esters. Because saponification value of the esters containing rosin ester can not be accurately determined, theoretical requirement for sodium and reducing alcohol could not be calculated. However, excess sodium and reducing alcohol seems to increase the yield of mixed alcohol. Against author's expectation, these esters have a saponifying tendencies, when excess sodium is present. Methyl ester from distilled tall oil is less saponifiable than that from crude tall oil in the reduction reaction. When distilled the crude alcohols produced, under reduced pressure, fatty alcohols are distilled out firstly and the rosin alcohol subsequently. Distillation residue is considered to be a polymerized rosin esters, the rotation property of which is extremely changed owing to the isomerization caused by heating.