Tall Oil Research Articles

Synthesis of new betaine-type amphoteric surfactants from tall oil fatty acid

Two new betaine-type amphoteric surfactants — betaineN,N'-dihydroxyethyl-N-ethyl fatty acid ester and ammoniumN-(fatty acid ester) ethyl-N,N-bis (2-hydroxyethyl)-3-(2-hydroxypropyl) sulfonate — were synthesized using tall oil fatty acids as the raw materials. Processing conditions suitable for synthesizing the intermediates and final products were probed. In addition, the chemical structures of the intermediates and the final products were identified by infrared spectroscopy, hydrogen nuclear magnetic resonance spectroscopy, and elemental analysis.

Mechanism of collector adsorption in fluorite flotation

Fluorite is a strategically important mineral. Commercial deposits of fluorite are widespread throughout the world and its availability is essential to industry.1 The method of concentrating fluorite depends on the final application. Whereas a metallurgical-grade fluorite is obtained by gravity and magnetic separation methods, flotation is the major concentration process for the production of acid-grade fluorite. Selective flotation of fluorite from calcite presents many problems because the two minerals have the same cation, Ca++, in their crystal lattices. As a consequence of their similar physical and chemical surface properties anionic collectors float calcite alongside fluorite, and the depressants used for calcite also inhibit the flotation of fluorite. In the separation of fluorite from calcite by flotation various fatty acids (especially, oleic acid and sodium oleate), oleic acid emulsions with petroleum sulphonates, different mixtures of fatty acids, tall oils, alkyl amino-bis-methylene phosphoric acids, alkyl sulphonates, mixtures of oleic and naphtenic acids and amines are used as collectors. Various regulating agents, such as sodium silicate, sodium silicate–metal salt combinations, phosphates, tannic acid, quebracho, starches and sodium ligno-sulphonates, are used to depress calcite and to increase selectivity.2–5 The adsorption of collectors and depressants is largely controlled by the charge at the particle surface. The results produced by different investigations differ considerably and vary widely with minerals of different origin. The investigations reported here were undertaken with the aim of providing an electrophoretic and infrared spectroscopic characterization of fluorite and calcite as a basis for further flotation studies and for controlling the adsorption of electrolytes by exploiting differences in the surface charge.

Conversion of the Rosin Acid Fraction of Crude Tall Oil into Fuels and Chemicals. 2001, 15, 1166−1172

Conversion of the Rosin Acid Fraction of Crude Tall Oil into Fuels and Chemicals. <b>2001</b>, <i>15</i>, 1166−1172

Effects of modified tall oil and vitamin E on growth performance, carcass characteristics, and meat quality of growing-finishing pigs.

Crossbred barrows (n = 72) were used to evaluate effects of diet supplementation with modified tall oil (MTO; 0.0 or 0.50%) and vitamin E (0, 22, or 110 IU/kg) on growth performance, carcass traits, and longissimus muscle (LM) quality traits of finishing pigs. Pigs were blocked by ancestry and initial BW and allotted randomly to treatments in a 2 x 3 factorial. Corn-soybean meal-based diets were fed in two phases: 45.5 to 81.6 (1.00% lysine) and 81.6 to 114.6 (0.75% lysine) kg BW with no added fat. From 45.5 to 81.6 kg, pigs fed MTO had greater ADG (P = 0.03) regardless of added vitamin E; otherwise, treatment did not affect growth performance. Carcasses from pigs fed MTO had reduced (P < 0.05) average backfat (2.76 vs 2.92 cm) and firmer bellies compared to those fed no MTO. Boneless loins were cut into 2.54-cm chops at 7 d postmortem and evaluated for display color, thiobarbituric acid-reactive substance (TBARS), Warner-Bratzler shear force (WBSF), and sensory panel ratings. Visual color was similar (P > 0.05) among treatments at 0 and 1 d of display. At 4 and 6 d of display chops from pigs fed MTO with 110 IU vitamin E/kg had less deterioration (P < 0.05) than chops from pigs fed MTO with 0 IU vitamin E/kg and 0.0% MTO with 22 or 110 IU vitamin E/kg. The CIE L*, a*, b* and spectral values also suggested a delay in color deterioration for chops from pigs fed MTO with 110 IU vitamin E/kg. At 6 and 8 d of display, chops from pigs fed 110 IU vitamin E/kg had lower (P < 0.05) L* values than those from pigs fed 0 or 22 IU vitamin E/kg, and higher (P < 0.05) a* values than those from pigs fed 0 IU vitamin E/kg feed. A higher (P < 0.05) %R630/%R580 (indicator of more oxymyoglobin) was observed for chops from pigs fed MTO with 110 IU vitamin E/kg than those from pigs fed 0.0% MTO with 22 or 110 IU vitamin E/kg and MTO with 0 IU vitamin E/kg. Chops from pigs fed MTO with 110 IU vitamin E/kg had lower (P < 0.05) TBARS values than those from pigs fed MTO with 0 IU vitamin E/kg. No differences (P > 0.05) were detected among treatments for WBSF or sensory evaluations. The addition of MTO in swine diets improved belly firmness and reduced backfat, and feeding MTO with high levels of vitamin E extended display life without affecting palatability of LM chops.

Influence of Adsorption of Lignosulfonates on Kraft Lignin in the Presence of Tall Oil on Separation of Water-Tall Oil Emulsion

The degree of hydrophilicity-oleophilicity of solid lignin recovered from cooking liquors of deciduous and coniferous wood at various pH and its influence on the aggregative stability of water-tall oil emulsion were estimated. The stabilizing effect of lignosulfonates on lignin suspension in aqueous electrolyte solution was studied. The values of absorption of lignosulfonates from aqueous solutions on kraft lignin were determined depending on the molecular weight of lignosulfonates and content of tall oil in the suspension.

Synthesis of new amino acid-type amphoteric surfactants from tall oil fatty acid

Two new amino acid-type amphoteric surfactants — disodiumN-(2-fatty acyl amino) ethyliminodiacetate and disodiumN-(2-fatty acyl amino) ethyl-N,N-bis[3-(2-hydroxy) propylsulfonate] amine — were synthesized using tall oil fatty acids as the raw material. Suitable processing conditions for synthesizing the intermediates and final products were probed. In addition, the chemical structures of the intermediates and the final products were identified by infrared spectroscopy, hydrogen nuclear magnetic resonance spectroscopy, and elemental analysis.

Injected phytosterols/stanols suppress plasma cholesterol levels in hamsters

Although plant sterols are known to suppress intestinal cholesterol absorption, whether plasma and hepatic lipid levels are influenced through non-gut related internal mechanisms has not been established. To examine this question 50 male hamsters were divided into 5 groups and fed semi-purified diets containing 20% energy as fat and 0.25% (w/w) cholesterol ad libitum for 60 days. The control group (i) received diet alone, while four additional groups consumed the diet plus one of four equivalent phytosterol mixtures (5 mg/kg/day) given either as (ii) tall oil phytosterols/stanols mixed with diet (oralSA), (iii) tall oil phytosterols/stanols subcutaneously injected (subSA), (iv) soybean oil phytosterols alone mixed with diet (oralSE), or (v) soybean oil subcutaneous injected phytosterols alone (subSE). The control group and both orally supplemented groups also received placebo subcutaneous sham injections. Neither food consumption, body weight, nor liver weight differed across treatment groups. Subcutaneous administration of SA and SE decreased plasma total cholesterol levels by 21% and 23% (p < 0.0001) and non-apolipoprotein-A cholesterol concentrations by 22% and 15% (p < 0.0002), respectively, compared to control. HDL cholesterol and TG concentrations remained unchanged across all groups, except for a decline of 25% (p < 0.0001) in HDL concentration in the subSE group versus control. Plasma campesterol levels were lower (p < 0.05) in the subSA group relative to all other groups. Plasma campesterol:cholesterol and campesterol:sitosterol ratios were, however, higher (p < 0.0001) for both the oral and subSE groups. Hepatic cholesterol levels were higher (p < 0.0001) in the oral and subSE phytosterol groups by 30% and 31%, respectively, relative to control. We conclude that low doses of subcutaneously administered plant sterols reduce circulating cholesterol levels through mechanisms other than inhibiting intestinal cholesterol absorption.

Composition of neutral fractions in Chinese raw tall oil

Chinese tall oil samples, obtained from pulp and papermaking factories in Qinzhou and Jiamusi of China, were first divided into acidic and neutral fractions by saponification, extraction, and distillation. The obtained neutral fractions were then analyzed by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) after silylation with bis-(trimethylsilyl) trifluoroacetamide. The results obtained show that 10 types of compound (monoterpenes, sesquiterpenes, diterpenes, triterpenes, resin alcohols, resin aldehydes, steroids, fatty alcohols, phenols, stilbenes) exist in the neutral fractions of Chinese raw tall oil. In the neutral fractions from Qinzhou, 55 components were identified, 35 of which were found for the first time in Chinese raw tall oil; 12 components were discovered for the first time in raw tall oil. In the neutral fraction from Jiamusi, 45 components were identified, 9 of which were discovered for the first time in Chinese raw tall oil.

Conversion of the Rosin Acid Fraction of Crude Tall Oil into Fuels and Chemicals

Tall oil rosin acid, a forest product industry residue, has been converted into a diesel fuel additive in a single step process. Fractionation of crude tall oil produces an excess of rosin acids. This material is an abundant, inexpensive and chemically desirable feedstock. Two components, abietic acid and dehydroabietic acid, comprise about 70% of the rosin acid fraction of tall oil. The carboxylic acid functionality of these compounds must be removed and double bonds in the ring structure hydrogenated to obtain diesel fuel additives. Hydrotreatment of the rosin acid fraction achieves both goals. The experiments were performed in a laboratory-scale batch reactor using three commercial sulfided Ni−Mo and Co−Mo catalysts. For each of the catalysts, three different factors were studied: temperature, hydrogen pressure, and reaction time. Experiments probe the effects of these variables on liquid product yield, cetane index, hydrogen-to-carbon ratio, and degree of cracking. The liquid products, mainly saturated tricyclic ring compounds, were analyzed by elemental analysis (C, H, S, and O) and by GC-MS. Boiling point distributions and densities were also determined. From these data, cetane indexes were calculated.

Fatty and resin acid analysis in tall oil products via supercritical fluid extraction-supercritical fluid reaction using enzymatic catalysis.

Supercritical fluid extraction (SFE) is combined with supercritical fluid reaction (SFR) in an analytical mode to assess tall oil products for their fatty or resin acid content or both. The SFR consists of an inline enzymatically catalyzed reaction in which a lipase transesterifies specific lipids with methanol. The SFE-SFR sequence is conducted employing commercially available extractors using supported lipases in the extraction cell to form methyl esters. In this study, six different commercially available lipases are screened for activity. The SFE-SFR extracts are analyzed by capillary gas chromatography and supercritical fluid chromatography and then compared with tall oil products derivatized by conventional chemical derivatization techniques.

The Condition, after 31 Years Exposure, of Pine Stakes Treated with Ammoniacal Copper-Based Preservatives

Summary Pinus sylvestris sapwood stakes were treated with various copper–containing waterborne and oilborne preservatives and exposed in ground for 31 years at Walpeup, Australia. Most of the waterborne preservative treatments contained basic copper carbonate and one or more of the following additives: arsenic pentoxide, pyridine, sodium pentachlorophenate, tannin and benzoic, boric, chromic, salicylic and sorbic acids. Basic copper carbonate and sulphate, at 0.95 kg m−3 of copper, protected the stakes from significant subterranean termite attack at a site in Australia providing a moderate termite hazard. Three additives (arsenic pentoxide at 0.95 kg m−3, sodium pentachlorophenate at 0.93 kg m−3 and fluoride at 0.9 kg m−3) significantly improved the efficacy of basic copper carbonate when used at retentions of 1.7 to 2.0 kg m−3 of copper. The six waterborne preservative combinations that performed best (i.e. rating greater than 6.5 out of 8) against both the termite and decay hazards over the 31 year period contained basic copper carbonate (at least 1.79 kg m−3 of copper) plus arsenic pentoxide (at least 0.92 kg m−3). Three of the six combinations also contained chromic acid. The oilborne preservative combination performing best contained basic copper carbonate (1.33 kg m−3) and pentachlorophenol (6.64 kg m−3) in tall oil. A treatment containing a similar amount of pentachlorophenol in tall oil, but no basic copper carbonate was significantly less effective. Other treatments containing basic copper carbonate and pentachlorophenol in tall oil or the copper compound with sodium pentachlorophenate in oil emulsion performed well. The implications of these results for the current generation of copper-based preservatives are discussed.

Leaching of concrete admixtures containing thiocyanate and resin acids.

There is an increasing concern about the emission of pollutants during the construction and lifetime of buildings. The leaching of concrete admixtures containing thiocyanate and resin acids was studied using standard leaching tests and chemical analysis. Ecotoxicological risk was assessed for each admixture. Thiocyanate leaching from concrete, with a chlorine-free accelerating admixture, was determined by ion chromatography. Of the total amount of thiocyanate added, 6-8% was emitted within 30 d. The thiocyanate diffusion curve indicates a fast dissolution process from the surface layer, followed by a slower continuous diffusion process. Thiocyanate exhibits both acute and chronic toxicity, which makes it of immediate environmental concern. Resin acid leaching from concrete test specimens containing an admixture of air-entraining agents with tall oil was determined by solid-phase extraction, methylation, and GC/MS. Of added resin acids, 10% was emitted over 143 d. The leaching curves for the resin acids indicate a continuous diffusion that is proportional to the square root of time and follows Fick's first law of diffusion. The chemical composition of the resin acids in the leachate demonstrates degradation and rearrangement of the resin acids during diffusion. Resin acids emitted from concrete are of environmental concern because they are persistent and have the ability to bioaccumulate in aquatic organisms.

Modified syntheses of Ca‐resinates by fusion method

AbstractTall oil rosin was modified with fumaric acid or maleic acid anhydride to get fortified rosin. which was used as u raw material in fusion Ca‐resinate syntheses. Two reaction step were observed in the syntheses. A fast resination reaction takes place at 235°C, and a slow decarboxylation of rosin acids forms neutral rosin oil at 265°C. A mechanistic model for the decarboxylation reaction step was derived to explain the effect of fortifying substances on the reaction kinetics. A multivariate calibration method using partial least‐spare (PLS) regression was applied to monitor the acid concentration decrease on the basis of infrared spectroscopic data during the fortified syntheses. A mixture of unmodified rosin and rosin oil (decarboxylated rosin) was used as a raw material in a novel modification of fusion syntheses to increase the mass yield of the resinate. In the modified rosin oil syntheses, decarboxylation of rosin acids is avoided, and recycling the added rosin oil considerably improves the mass yield of the resinate syntheses.

Streamlined LCA of soy-based ink printing

This study provides a benchmark of the life cycle environmental impact characteristics associated with a typical soybased ink used for sheetfed lithographic printing. The scope ineluded a streamlined Life Cycle Inventory (LCI) and Impact Assessment (LCIA). Materials, processes, and life cycle stages that are the same between different printing inks, or were less than one percent by mass of the printing system input materials, were excluded. The LCIA included identification of specific processes in the life cycle of soy-based ink printing that make the greatest contribution to the overall environmental hazard potential in 13 impact categories for the baseline printing system selected. The LCIA approach included both regional scaling for areas that differ in sensitivity to certain impact indicators and normalization against a reference value. Reduction in the use of tall oil rosin and switching from conventional to low or no-till farming appear to be promising opportunities for reducing the environmental hazard potential.

Effects of feeding modified tall oil and supplemental potassium and magnesium on growth performance, carcass characteristics, and meat quality of growing-finishing pigs

Eighty crossbred gilts (initially 45.9 kg) were allotted randomly to one of four dietary treatments by weight and ancestry. The trial was arranged as a 2 × 2 factorial with two levels of modified tall oil (MTO) (0 or 0.50%) and added K2SO4-2MgSO4 (0 or 2%), equating to daily K and Mg intakes of 10.84 and 7.75 g, respectively. The corn-soybean meal diets were fed in two phases [45.9 to 76.2 and 76.2 to 118.1 kg body weight (BW)], and supplemental K/Mg was added in place of corn for the final 7 d preslaughter (starting at 114.1 kg BW). Dietary treatment did not affect (P &gt; 0.10) average daily gain (ADG), average daily feed intake (ADFI), or gain to feed ratio (G/F). Feeding MTO decreased average backfat (P = 0.05) and increased intramuscular marbling (P = 0.04). Modified tall oil increased (P = 0.02) percentage lean, and K/Mg supplementation lowered (P = 0.04) longissimus muscle glycogen content. Dietary treatment did not affect (P &gt; 0.10) other carcass characteristics or measures of meat quality. Feeding MTO increased plasma glucose (P = 0.05) and decreased (P = 0.10) base excess in the extracellular fluid. Feeding K/Mg decreased (P &lt; 0.10) plasma pH, BUN, and base excess in the whole-blood and extracellular fluid and increased (P &lt; 0.10) ionized Mg++ and lactate. These results support earlier research identifying MTO as a carcass modifier and contributor to meat composition and quality. Potassium and Mg supplementation altered whole-blood profiles and longissimus muscle glycogen content in a manner expected to improve pork quality, although not observed. Key words: Swine, modified tall oil, potassium, magnesium, meat quality

Daily consumption of non-esterified phytosterols from tall oil (Phytrol™) in a chocolate matrix significantly lowers LDL cholesterol in moderately hypercholesterolemic individuals

Daily consumption of non-esterified phytosterols from tall oil (Phytrol™) in a chocolate matrix significantly lowers LDL cholesterol in moderately hypercholesterolemic individuals

Phytosterols from tall oil (Phytrol™) prove very effective for cholesterol reduction in gerbils fed various diets

Phytosterols from tall oil (Phytrol™) prove very effective for cholesterol reduction in gerbils fed various diets

Effects of combination of tall oil sterols and n-3 fatty acids on atherosclerotic lesion development in cholesterol-fed (0.2% w/w) apo E-KO mice

Effects of combination of tall oil sterols and n-3 fatty acids on atherosclerotic lesion development in cholesterol-fed (0.2% w/w) apo E-KO mice

Comparison of cholesterol-lowering effects of hydrogenated vs unhydrogenated tall oil phytosterols in apo E-KO mice

Comparison of cholesterol-lowering effects of hydrogenated vs unhydrogenated tall oil phytosterols in apo E-KO mice

Composition of acidic components in Chinese raw tall oil

Chinese raw tall oil samples, which were obtained from pulp and papermaking factories in Qingzhou and Jiamusi, were first divided into acidic and neutral parts with a diethylaminoethyl-Sephadex (DEAE-Sephadex) gel column. The acidic components were then analyzed qualitatively and quantitatively by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). The results obtained are as follows: Most of the compounds that comprised 0.1% or more of the components were identified. Secodehydroabietic, 8,15-pimaradienoic, 8,15-isopimaradienoic, 7,13,15-abietatrien-18-oic acid, and others were found for the first time in Chinese tall oil; they have not been found in Chinese fatty rosin. Docosan-1,22-dioic acid was also found in tall oil for the first time.