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In this study, tall oil fatty acid ester of softwood kraft lignin (TOFA-L) was used to prepare TOFA lignin nanoparticles (TLNP) in water. The average diameters for two prepared TLNPs in 0.1 mg/ml concentration were 140 nm and 160 nm. TLNPs were attached covalently onto modified and unmodified cellulose fibres to form an antimicrobial composite material. The modified cellulose fibres contained reactive allylic double bonds with a degree of substitution of 0.05. The antimicrobial properties of both TLNPs and TLNP coated fibres (TLNP-C) were studied against Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa using silver nanospheres (average size 10 nm) and Lignoboost lignin particles with 300 and 400 nm sizes as references. Antimicrobial activity of the samples was stronger against Gram-positive S. aureus cells than against Gram-negative target microbes E. coli and P. aeruginosa.

In this study, inhibition of tall oil fatty acid hydrodeoxygenation (HDO) activity due to addition of rosin acid over sulfided NiMo/Al2O3 was investigated. Oleic acid and abietic acid were used as model compounds for fatty acid and rosin acid respectively in tall oil. After completion of each HDO experiment, the NiMo catalysts were recovered and used again under the same conditions. The results showed that the oleic acid HDO activity of sulfided catalysts was inhibited by addition of abietic acid due to competitive adsorption and increased coke deposition. The rate of carbon deposition on the catalysts increased when abietic acid was added to oleic acid feed. Moreover, the coke was in a more advanced form with higher stability for the catalysts exposed to both oleic acid and abietic acid. Furthermore, a clear correlation between the rate of coke formation and concentration of abietic acid was observed.

A second-generation bio-based feedstock—tall oil fatty acids—was epoxidised via two pathways. Oxirane rings were introduced into the fatty acid carbon backbone using a heterogeneous epoxidation catalyst-ion exchange resin Amberlite IR-120 H or enzyme catalyst Candida antarctica lipase B under the trade name Novozym® 435. High functionality bio-polyols were synthesised from the obtained epoxidated tall oil fatty acids by oxirane ring-opening and subsequent esterification reactions with different polyfunctional alcohols: trimethylolpropane and triethanolamine. The synthesised epoxidised tall oil fatty acids (ETOFA) were studied by proton nuclear magnetic resonance. The chemical structure of obtained polyols was studied by Fourier-transform infrared spectroscopy and size exclusion chromatography. Average molecular weight and polydispersity of polyols were determined from size exclusion chromatography data. The obtained polyols were used to develop rigid polyurethane (PU) foam thermal insulation material with an approximate density of 40 kg/m3. Thermal conductivity, apparent density and compression strength of the rigid PU foams were determined. The rigid PU foams obtained from polyols synthesised using Novozym® 435 catalyst had superior properties in comparison to rigid PU foams obtained from polyols synthesised using Amberlite IR-120 H. The developed rigid PU foams had an excellent thermal conductivity of 21.2–25.9 mW/(m·K).

Crude tall oil (CTO) is the third largest by-product at kraft pulp and paper mills. Due the large presence of value-added fatty and resin acids, CTO has a huge valorization potential as a biobased, readily available, non-food, and low-cost biorefinery feedstock. The objective of this work was to present a method for the isolation of high-value linoleic acid (LA), an omega (&omega, )-6 essential fatty acid, from CTO using a combination of pretreatment, fractionation, and purification techniques. Following the distillation of CTO to separate the tall oil fatty acids (TOFAs) from CTO, LA was isolated and purified from TOFAs by urea complexation (UC) and low-temperature crystallization (LTC) in the temperature range between &minus, 7 and &minus, 15 &deg, C. The crystallization yield of LA from CTO in that range was 7.8 w/w at 95.2% purity, with 3.8% w/w of &omega, 6 &gamma, linolenic acid (GLA) and 1.0% w/w of &omega, 3 &alpha, linolenic (ALA) present as contaminants. This is the first report on the isolation of LA from CTO. The approach presented here can be applied to recover other valuable fatty acids. Furthermore, once the targeted fatty acid(s) are isolated, the rest of the TOFAs can be utilized for the production of biodiesel, biobased surfactants, or other valuable bioproducts.

A dual catalysis approach enables selective functionalization of unconventional feedstocks composed of complex fatty acid mixtures with highly unsaturated portions like eicosapentaenoate (20:5) along with monounsaturated compounds. The degree of unsaturation is unified by selective heterogeneous hydrogenation on Pd/γ-Al2O3, complemented by effective activation to a homogeneous carbonylation catalyst [(dtbpx)PdH(L)]+ by addition of diprotonated diphosphine (dtbpxH2)(OTf)2. By this one-pot approach, neat 20:5 as a model substrate is hydrogenated to up to 80% to the monounsaturated analogue (20:1), this is functionalized to the desired C21 α,ω-diester building block with a linear selectivity of over 90%. This catalytic approach is demonstrated to be suitable for crude microalgae oil from Phaeodactylum tricornutum genetically engineered for this purpose, as well as tall oil, an abundant waste material. Both substrates were fully converted with an overall selectivity to the linear α,ω-diester of up to 75%.

Knowledge of hydrogen solubility in tall oil fractions is important for designing hydrotreatment processes of these complex nonedible biobased materials. Unfortunately measurements of hydrogen solubility into these fractions are missing in the literature. This work reports hydrogen solubility measured in four tall oil fractions between 373 and 597 K and at pressures from 5 to 10 MPa. Three of the fractions were distilled tall oil fractions their resin acids contents are respectively 2, 20 and 23 in mass-%. Additionally one fraction was a crude tall oil (CTO) sample containing sterols as the main neutral fraction. Measurements were performed using a continuous flow synthetic isothermal and isobaric method based on the visual observation of the bubble point. Composition of the flow was changed step-wise for the bubble point composition determination. We assume that the tall oil fractions did not react during measurements, based on the composition analysis performed before and after the measurements. Additionally the densities of the fractions were measured at atmospheric pressure from 293.15 to 323.15 K. A Henry’s law model was developed for the distilled tall oil fractions describing the solubility with an absolute average deviation of 2.1%. Inputs of the solubility model are temperature, total pressure and the density of the oil at 323.15 K. The solubility of hydrogen in the CTO sample can be described with the developed model with an absolute average deviation of 3.4%. The solubility of hydrogen increases both with increasing pressure and/or increasing temperature. The more dense fractions of the tall oil exhibit lower hydrogen solubility in comparison to the less dense fractions. The increase in the density of a fraction corresponds to an increased resin acid and sterol content of the sample. Sterols and resin acids exhibit lower hydrogen solubility in comparison to fatty acids.

During alkaline pulping significant amounts of lignin, carbohydrates (mostly hemicelluloses), and extractives (tall oil soap and turpentine) are removed from wood feedstock. In this study, the catalytic esterification of fatty acids in tall oil with methanol to produce fatty acid methyl esters under microwave irradiation was performed at 100 °C for 10–60 min. A novel heterogeneous acid catalyst tested for this purpose was synthesized from the hardwood alkali lignin that was precipitated by acidification from the black liquor from soda-AQ pulping. The comparative reaction data were obtained by using other solid catalysts, Amberlyst 15, and p-toluenesulfonic acid. The results showed the highest esterification yields of 93, 88, and 80% with the p-toluenesulfonic acid, lignin-based, and Amberlyst 15 catalysts, respectively, at 100 °C with a reaction time of 60 min, and the corresponding yield without catalyst was 20%. It was also observed that the lignin-based catalyst could be easily recovered and reused without any notable deactivation. peerReviewed

Catalytic hydrodeoxygenation (HDO) of fatty acids has been investigated using different feedstocks for renewable diesel production. Two types of catalysts were studied: sulfur-free nickel supported on H-Y zeolites, γ-Al2O3 and SiO2, and palladium supported on active carbon as a noble metal catalyst. Preliminary HDO experiments were carried out on these catalysts in a semi-batch reactor at 300 °C in H2 under a total pressure of 30 bar for 6 h with stearic acid as a model for fatty acids. An in-depth comparative study of Ni/H-Y and Pd/C was performed in HDO of fatty acid methyl ester (FAME) obtained from the Chlorella microalga, tall oil fatty acids (TOFA) and animal fat. HDO experiments revealed that Ni/H-Y was a better catalyst for this process providing higher activity for different fatty acids. Ni supported on γ-Al2O3 and SiO2 provided complete conversion upon testing in HDO of stearic acid while total HDO over Pd/C was not reached.

Dimer acids are a class of important intermediates that are widely used in many practical applications including polyamides, lubricants, paints, and coatings. They are typically produced through the polymerization (dimerization) of tall oil fatty acids (TOFA) using clays as catalysts. Although this technology is well developed and efficient, the drawback is that the clay catalysts cannot be recycled, generating considerable amounts of hazardous waste. In addition, these products consist of a complex mixture of dimer acids, trimer acids, and polymeric acids. This complexity has limited the ability to thoroughly evaluate their chemical structures. This study reports an advanced recycle zeolite catalysis process using plant-based soybean oil fatty acid (SOFA) which can selectively control the structure formation of the dimer acids and result in yields that are just as efficient as the TOFA technology. The detailed chemical structures of products were thoroughly verified by Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), gas chromatography–mass spectroscopy (GC–MS), and liquid chromatography-mass spectrometry (LC–MS). The reuse process was demonstrated by conducting ten recycle experiments and maintaining high yields, which shows great potential in replacing clay to produce dimer acids. These valuable insights into the structures of the dimer acid products and catalyst reuse results will improve the value and production of dimer acids to meet new industrial uses.

1. Studies were conducted with tall oil fatty acids (TOFA) to determine their effect on broiler chicken performance and ileal microbiota. TOFA, a product originating from coniferous trees and recovered by fractional distillation of side-streams from pulp production, mainly comprises free long-chain fatty acids (~90%) and resin acids (~8%). Conjugated linolenic acids and pinolenic acid are characteristic fatty acid components of TOFA. 2. TOFA products at 750 mg/kg feed were tested in two 35-day broiler chicken trials, each using a wheat soya-based diet and with 12 replicate pens per treatment. In both trials, TOFA improved body weight gain at all time points (P 0.001) and feed conversion efficiency during the first 21 days (P 0.01). Two different dry TOFA formulations (silica carrier and palm oil coating) were tested and showed performance effects similar to liquid TOFA. 3. Ileal digesta of the broiler chickens was analysed for total eubacteria, Lactobacillus spp., Enterococcus spp., Escherichia coli and Clostridium perfringens on days 14 and 35. TOFA significantly increased total eubacteria and lactobacilli density on day 14 (P 0.05). There was a significant positive correlation between these bacterial groups and broiler body weight on day 14 (P 0.01). 4. A numerical reduction in C. perfringens was observed. In vitro growth inhibition studies showed that C. perfringens was strongly inhibited by 10 mg/l TOFA (P 0.001), while common lactobacilli were resistant to250 mg/l. The in vitro results were thus in line with in vivo observations. 5. The mechanisms behind the bacterial shifts and their role in performance improvement are unknown. Further purification of TOFA components is needed to identify the effective agents.

A method is proposed for producing fatty acid esters of thermomechanical pulp (TMP) using fatty acids of intermediate chain length (C6-C12). The end objective is to use a stream of fatty acids produced via refining tall oil from Alberta's pulping mills. Depending on the degree of modification, these treated materials can serve either as reinforcement or as copolymers in composite applications. The effect of reaction conditions—reaction time, reaction temperature, fatty acyl concentration, and fatty acid chain length—on the degree of substitution of the pulp samples was studied. The reaction conditions were applied for each fatty acyl chloride and the pulp samples were characterized using X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, force tensiometry, time-of-flight secondary ion mass spectroscopy, atomic force microscopy, and thermal gravimetric analysis. The degree of substitution (DS) plateaued after two hours at a concentration of 0.25 M of hexanoyl chloride. These conditi...

All fruits, vegetables, grains and other plant materials contain small amounts of plant sterols, which are essential for the function of the biological membranes in living cells. The average human consumption of plant sterols has been estimated to be about 150–350 mg/day and trace amounts of stanols (which are defined as saturated sterols such as sitostanol), but this number varies regionally and is higher for vegetarians. When consumed in the diet, plant sterols reduce the levels of serum cholesterol. In 1995 the first functional food product, Benecol spread (enriched in plant stanol fatty acid esters), was developed by Raisio and marketed, first in Finland and then globally. Since then many other functional food products have been developed and are now available globally. In addition to stanol esters, other functional food products contain plant sterol esters and/or free (unesterified) plant sterols and stanols. In essentially all of the current functional foods that are enriched in sterols and stanols, the feedstock from which the sterols and stanols are obtained is either tall oil (a byproduct/ coproduct of the pulping of pine wood) or vegetable oil deodorizer distillate (a byproduct/coproduct of the refining of vegetable oils).

Cellulose is mainly utilized by industry for paper and packaging materials. Due to ecological awareness this biopolymer has recently received an increasing amount of attention as a renewable alternative for replacing traditional oil based products. In this work, hydrophobic cellulose based materials were prepared by acylation of cellulose with tall oil fatty acid based saturated, unsaturated and branched fatty acids. Films were prepared by casting, and their oxygen and water vapour permeabilities as well as mechanical and thermal properties were characterized. Unsaturation and branching had a significant effect on the properties of the films. Comparing these materials with already existing commercial products showed that fatty acid modification of cellulose yields films with increased thermal stability, low water vapour transmission rates and enhanced tensile and elastic properties.

The esterification of lauric and stearic acids, tall oil fatty acid, and a commercial oleic acid with methanol was investigated using an acid-activated standard montmorillonite (AASM) as a catalyst. Reaction variables such as the methanol:fatty acid molar ratio, catalyst content, and temperature were evaluated. Comparative reactions were performed with K10 catalyst, and similar or even better results were obtained with AASM, indicating that this could be employed as a suitable Lewis/Bronsted esterification catalyst. The experimental results obtained for the esterification of lauric acid with methanol were compared to a thermodynamic model. For this purpose, the UNIFAC model was used for the activity coefficient calculation for components in the nonideal mixture. This model has shown that the catalytic system was able to drive the reaction to equilibrium within 2 h, and this was confirmed by comparing the experimental results with thermodynamic predictions.

Esterification of tall oil fatty acids by neutral components, such as stearyl alcohol and sterols, is an undesired reaction; a potential solution is to eliminate the neutral components by a competing esterification with short-chain carboxylic acids. Esterification of fatty acids and short-chain carboxylic acids with stearyl alcohol and sterols was studied in a laboratory-scale glass reactor in the temperature range of 60–140 °C. Linoleic acid (LA) was used as a model component for fatty acid esterification with stearyl alcohol (StOH) and sitosterol (SitOH). Linoleic acid underwent esterification with stearyl alcohol and sitosterol. In the presence of short-chain carboxylic acids, such as formic and acetic acid, the esterification of linoleic acid by stearyl alcohol was efficiently suppressed because stearyl alcohol reacted with the short-chain carboxylic acid. Formic acid catalyzed the formation of dienes from sitosterol and campesterol. The esterification and dehydration processes were verified by gas ch...

To decrease the combustibility of polyurethanes based on tall oil fatty acids ester, additives of five different halogen- and phosphorus-containing flame retardants were used. The efficiency of the flame retardants was evaluated from the change in the thermal, mechanical and combustibility characteristics of the obtained polyurethanes. It has been found that the phosphorus-containing flame retardant Levagard 4090 N decreases the combustibility of polyurethane to the greatest extent.

The capillary gas chromatographic (GC) separation of complex mixtures of plant steryl and stanyl fatty acid esters was achieved using a medium polar trifluoropropylmethyl polysiloxane as stationary phase. An approach allowing the facile synthesis of steryl/stanyl fatty acid esters was developed, thus creating the basis for a calibration of the method for the different types of ester mixtures to be expected in enriched foods. The usefulness of the approach for the rapid authentication of enriched low-fat products via qualitative and quantitative analysis of intact steryl and stanyl fatty acid esters was demonstrated by analysis of two skimmed milk-drinking yoghurts commercially available on the European market. Combining the extraction of lipids under acidic conditions with the GC separation step showed that one of the products contained a steryl/stanyl ester mixture obtained from long-chain sunflower oil fatty acids and sterols/stanols from tall oil. The other product, however, was shown to contain the rather unusual steryl/stanyl esters of the medium-chain octanoic and decanoic acid as ingredients.

Tall oil fatty acids are a byproduct of the paper industry and consist predominantly of free-fatty acids (FFAs). Although this feedstock is ideal for biodiesel production, there has been relatively little study of its conversion to biodiesel. Thus, the purpose of this study was to investigate the high temperature reaction of methanol with tall oil at subcritical and supercritical pressures to produce fatty acid methyl esters. This study investigates the effects of mixing, pressure, temperature, and methanol to oil molecular ratio in order to determine the potential use of tall oil as a biodiesel feedstock. In this work, tall oil fatty acids were successfully reacted with supercritical and subcritical methanol in a continuous tubular reactor, resulting in a reaction that is primarily temperature dependent. Conversions at subcritical pressures of 4.2 MPa and 6.6 MPa were 81% and 75%, respectively. Pressure seemed to have little correlation to conversion in both regimes, and conversions were comparable between the two. Additionally, it was found that tall oil fatty acids react well with methanol to give comparable conversions at the relatively low molecular flow ratio of 5:1 methanol to tall oil. Both of these observations suggest that hydrolyzed triglycerides or free fatty acid feedstocks would make the primary high temperature biodiesel reaction and the subsequent separation and purification operations less expensive than was previously believed.

Heterogeneous modification of various types of cellulose (microcrystalline cellulose, cellulose whiskers and regenerated cellulose) was performed with long-chain fatty acids by an esterification reaction. The differences in reactivity between the celluloses were studied as well as the influences of the chain length and double bond content of the fatty acids. The success of the modification reaction and the structure of modified samples were studied with diverse characterization methods. Surface modification changed the thermal stability of cellulose by decreasing the degradation temperature but also made the pyrolysis curve two-stepped due to the double bonds in the fatty acid chain. It was observed that the nature of the fatty acid affected the degree of substitution (DS). The longer the fatty acid chain was, the lower was the DS. Fatty acids with increased double bond content gave decreased DS. Regenerated cellulose seemed to have the highest surface reactivity due to the distinct morphological structure, which also led to a much lower quantity of fatty acids attached to the structure than for other modified cellulose particles. The mixture of tall oil fatty acids behaved in the same manner as the commercial fatty acids, proving to be an excellent “green” choice for this kind of application.

In the experimental study, tall oil fatty and resinic acids were investigated as alternative diesel fuels. The fatty acids, obtained by distilling the crude tall oil, were esterified with methanol in order to obtain tall oil methyl ester (biodiesel). Blends of the methyl ester, resinic acids and diesel fuel were prepared for test fuels. Performance and emission tests of the test fuels were carried out in an unmodified direct injection diesel engine on full load conditions. The results showed that the specific fuel consumption (SFC) with the blend fuels did not show a significant change. CO emission and smoke level decreased up to 23.91% and 19.40%, respectively. In general, NOx emissions showed on trend of increasing with the blend fuels (up to 25.42%). CO2 emissions did not vary with the blend fuels significantly. (C) 2010 Published by Elsevier Ltd.

This study was conducted to assess the effect of the pulping by-products crude tall oil (CTO), distilled tall oil (DTO), andtall oil fatty acid (TOFA) on dynamic water vapor sorption behavior, inte ...

Esters of tall oil fatty acids and hydroxyl-containing polymers were synthesized in the presence of trichloroacetic acid and pyridine. The surfactant properties of the macromolecular esters obtained were evaluated.

A multiyear, comprehensive study of flotation reagents used in phosphate beneficiation was conducted. The study involved the evaluation of pure fatty acid compounds, comparison of various anionic collectors and testing of iso-acids. Various C12 to C22 fatty acids were tested as Florida phosphate collectors. The saturated fatty acids were found to be very poor collectors when using the standard conditioning procedure, whereas the unsaturated C16 to C22 fatty acids showed fair to good phosphate collecting ability. The C18 fatty acids oleic, impure oleic and linoleic and the C20 eicosenoic acid were shown to be the best phosphate collectors. The best flotation results were obtained using Liqro GA tall oil and oleic acid. Four isostearic/iso-oleic acid type fatty acid collectors were compared with a commercial grade oleic acid and with Liqro GA tall oil as phosphate collectors using standard laboratory conditioning and flotation procedures. The most selective collector evaluated was Century 1108, a high isostearic acid-type reagent. However, it was concluded that this excellent-performing reagent was too expensive for commercial use. Overall, the most promising reagent was probably Century MO-5. This collector is essentially an iso-oleic acid/stearic acid mixture (not isostearic acid), and it costs much less. This program laid a sound foundation for developing single collector, all anionic flotation processes.

Tall oil is a by-product of coniferous wood recovered in the Kraft pulping process. Fatty acids can be recovered from tall oil by vacuum distillation. Biodiesel is becoming a displacement alternative for petroleum diesel. Chemically, biodiesel is a fatty acid (m)ethyl ester. Fatty acid derivatives as alternative fuels have become more attractive recently because of their environmental benefits and the fact that they are made from renewable resources. After saponification, acidulation, and methylation procedures, methyl esters (biodiesel) of the fatty acids were obtained from the tall oil samples. The properties of the various individual fatty esters that comprise biodiesel determine the overall fuel properties of the biodiesel. The kinematic viscosity and density values of biodiesel from tall oil fatty acids were 4.1–5.3 mm2/sec at 311.2 K and 0.878–0.885 kg/L at 288.7 K, respectively.

Four different fatty acid methyl esters (FAMEs): rape seedmethyl ester (RME), tall oil methyl ester (TOME), and two types of linseed oilmethyl ester (Linutin) have been studied as reactive diluents ...

Pinolenic acid (5Z,9Z,12Z-octadecatrienoic acid, 1a), one of the most abundant trienoic fatty acids in nature, is very difficult to obtain in quantity in a pure state from the highly complex mixture of unsaturated tall oil fatty acids. For this reason its chemistry has been little studied when compared to linolenic or linoleic acids. A simple synthesis of esters of 1a and of 12Z,15Z-octadecadienoic acid 3 using the one pot double Wittig procedure is described here. The products of double Wittig reactions were purified by argentation chromatography, and their structural purity was established by 1H-, 13C-NMR and 2D-NMR spectroscopies.

Oxazoline derivatives of the mixture of fatty acids found in tall oil were used as a reactive diluent for two types of alkyd polymers. The polymers had relatively good solubility in the oxazoline and solutions with moderate viscosity were obtained. Films made from the polymer solutions showed little property development at ambient temperatures even after several days. However, films cured at elevated temperatures had good properties in terms of solvent resistance, hardness and gloss. The degree of property development depended on the length of time the films remained at an elevated temperature.

To get insight in the biodegradation and potential read-across of fatty acid amides, N-[3-(dimethylamino)propyl] cocoamide and N-(1-ethylpiperazine) tall oil amide were used as model compounds. Two bacteria, Pseudomonas aeruginosa PK1 and Pseudomonas putida PK2 were isolated with N-[3-(dimethylamino)propyl] cocoamide and its hydrolysis product N,N-dimethyl-1,3-propanediamine, respectively. In mixed culture, both strains accomplished complete mineralization of N-[3-(dimethylamino)propyl] cocoamide. Aeromonas hydrophila PK3 was enriched with N-(1-ethylpiperazine) tall oil amide and subsequently isolated using agar plates containing dodecanoate. N-(2-Aminoethyl)piperazine, the hydrolysis product of N-(1-ethylpiperazine) tall oil amide, was not degraded. The aerobic biodegradation pathway for primary and secondary fatty acid amides of P. aeruginosa and A. hydrophila involved initial hydrolysis of the amide bond producing ammonium, or amines, where the fatty acids formed were immediately metabolized. Complete mineralization of secondary fatty acid amides depended on the biodegradability of the released amine. Tertiary fatty acid amides were not transformed by P. aeruginosa or A. hydrophila. These strains were able to utilize all tested primary and secondary fatty acid amides independent of the amine structure and fatty acid. Read-across of previous reported ready biodegradability results of primary and secondary fatty acid amides is justified based on the broad substrate specificity and the initial hydrolytic attack of the two isolates PK1 and PK3.

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.

Neutralised mixtures of tall oil-derived fatty acids and resin acids were separately pyrolysed (at 750∘C for 20 s) by pyrolysis gas chromatography with mass-selective and flame ionisation detection (Py-GC/MSD/FID) to clarify their thermochemical behaviour. The pyrolysate of fatty acid salts characteristically contained high amounts of unsaturated aliphatic hydrocarbons and minor amounts of monoaromatics, whereas the pyrolysis of resin acid salts mainly resulted in the formation of aromatics with up to three benzene rings and only in very low amounts of aliphatic hydrocarbons. The data obtained are useful when considering the suitability of various tall oil products containing fatty and resin acid fractions for the production of biofuels and chemicals via pyrolysis.

Production of diesel-like hydrocarbons from renewable resources through catalytic deoxygenation is summarized. As a feedstock, fatty acids (C9 - C23) and their derivatives (esters, triglycerides) can be used, as well as tall oil fatty acids (TOFA). The catalytic deoxygenation of fatty acids and their derivatives was typically performed over Pd and Pt catalysts supported on micro- and mesoporous carbon in the temperature and pressure ranges of 270°C – 360°C and 6 – 17 bar, respectively, under inert conditions or in the presence of small amounts of hydrogen. The main liquid phase products were hydrocarbons having one less carbon than in the original fatty acid, whereas CO and CO2 were obtained as major products in the gas phase. n-Heptadecane, with a yield of greater than 90%, was the main product in stearic acid deoxygenation. The feasibility of deoxygenation was demonstrated in both semi-batch and continuous modes. Although no sintering of Pd occurred, which was confirmed by TEM particle size analysis, catalyst deactivation was noticeable due to coking. Overall, deoxygenation can be a viable technology for the upgrading of vegetable oils.

Objective: To test the dose-response effect on low-density lipoprotein cholesterol (LDL-c) of plant sterols (PS) from different sources in a low-fat spread. Methods: Dose responses of soybean oil (BO), tall oil (TO) and a mix of tall oil and rapeseed oil (TO/RP) as fatty acid esters were tested in a parallel design in free-living subjects recruited from the general community who had elevated cholesterol concentrations. Subjects received either control for 6 weeks or 1.6 g PS per day for 3 weeks, then 3.0 g/day for 3 weeks. Results: LDL-c was lowered significantly by consumption of 1.6 g/day of PS ( 10.4%, range 7.3 to 11.4%). Increasing the dose to 3.0 g/day modestly reduced LDL-c concentrations further to 14.7%. TO, containing 78% sitosterol, produced an increase in serum sitosterol of 6.5 nmol/ml, while BO, containing only 27% campesterol, produced an increase in serum campesterol of 9.5 nmol/ml in 6 weeks. After PS withdrawal, serum sterols declined by 50% within 2 weeks. Conclusion: Different PS sources were equally effective in lowering serum LDL-c concentrations. The decrease in absolute concentrations of LDL-c was dependent on the baseline concentrations.

Tall oil fatty acids (TOFA) consist primarily of oleic and linoleic acids and are obtained by the distillation of crude tall oil. Crude tall oil, a by-product of the kraft pulping process, is a mixture of fatty acids, rosin acids, and unsaponifiables. These components are separated from one another by a series of distillations. Several grades of TOFA are available depending on rosin, unsaponifiable content, color, and color stability. Typical compositions of tall oil fatty acid products are shown. Tall oil fatty acids have a variety of applications. The largest uses of TOFA traditionally have been in coatings, primarily alkyd resins where grades of higher rosin content predominate. Since the 1970s their use as chemical intermediates in applications, which includes manufacture of dimer acids and epoxidized TOFA esters, has exceeded their use in coatings. The more highly refined, low rosin grades are required for their application as intermediates. Other areas of significant use are in soaps, detergents, and ore flotation. Worldwide crude tall oil fractionating capacity and domestic production and prices of TOFA are given. TOFA pricing is strongly dependent on soya fatty acid prices since these materials are often used in the same application. Keywords: Tall oil fatty acids; Oleic acids; Linoleic acids; Crude tall oil

The possibility of preparing amylose and cellulose esters by esterification and acylation with chlorides of tall oil fatty acids was examined.

The possibility of preparing monoesters derived from sucrose and tall oil fatty acids was examined.

The separation of pinolenic acid from distilled tall oil fatty acid by the iodolactonization method was studied. The significance of prefractionation of tall oils and details of the iodolactonization procedure for the pinolenic acid purity achieved is discussed.

Corrosion inhibitors have been prepared by ethoxylation of four commercially available unsaturated fatty acid mixtures: tall oil, soya bean oil, cotton seed oil, and linseed oil. The compounds obtained have the general formula R–COO–(CH2CH2O)n–H, where R is mainly a mixture of C17H29, C17H31, and C17H33 and n equals 20 ethylene oxide moles per mole of fatty acid. They have almost the same hydrophilic-lipophilic balance (HLB), which governs most of their surface activities, but differ in their fatty acid composition. The synthesised compounds provide satisfactory inhibition of steel in hydrochloric acid at temperatures up to 80°C. The ethoxylate of linseed oil is the most efficient inhibitor on account of its high content of linolenic acid, which has three double bonds. Polarisation measurements indicate that the additives act as mixed type inhibitors.

Die Sulzer-Mellapak als Kolonnenfullung fur die Destination von Tallol und Fettsauren hat sich industriell mehrfach bewahrt und ist heutzutage die bevorzugte Packung im Fettsaurebereich. Dank ihr ist der Einsatz von Treibdampf nicht mehr notig. Ein kleiner Druckverlust und ein kleiner Hold-up schonen die empfindlichen Produkte. Im Vergleich zu Bodenkolonnen ergibt sich eine Kapazitatssteigerung um das Doppelte und ein um ca. 40 % kleineres Rucklaufverhaltnis. Fur die Ermittlung spezifischer Trennaspekte fuhrt Sulzer Destillationsversuche in einer Pilotanlage unter industriellen Bedingungen durch, und zwar mit dem Produkt des Kunden. Versuche mit Mellapak in der Pitch-Kolonne ergaben dank der besseren Pechabtrennung eine Erhohung der Ausbeute an destilliertem Tallol um ca. 10 % mit hoherer Saurezahl. Pilotversuche ohne Treibdampf in der Rosinkolonne fuhrten zu einer besseren Trennung zwischen Harzsaure und Roh-Fettsaure im Vergleich zu einer Bodenkolonne gleicher Hohe. Bei der eigentlichen Fettsaurekolonne konnte die Ausbeute an Fettsaure von 66% auf uber 70% erhoht werden, bei gleichzeitiger Qualitatssteigerung. Aufgrund der umfangreichen Versuchsergebnisse konnen industrielle Anlagen mit Durchsatz- und Reinheitsgarantie angeboten werden. Das bekannte Scale-up-Verhalten der Mellapak und Betriebsresultate aus industriellen Fettsaurekolonnen erlauben eine sichere Auslegung. Fatty Acid Separation by Sulzer-Mellapak®-Columns - Trials, Layout and Industrial Experience The Sulzer-Mellapak as column filling for the distillation of tall oil and fatty acids has proved true in industry for many times; nowadays it is the favoured package in the range of fatty acids. Thanks to it the application of propellent steam is no longer necessary. A small pressure loss and a little holdup preserve the delicate products. In comparison to the stage columns there is a twofold increase in capacity and a reflux ratio which is about 40 % lower. Distillation tests are carried out in a pilot plant under industrial conditions by Sulzer to detect specific separation aspects. The tests are made with the customer's product. Tests with Mellapak in the Pitch-column showed, due to the better pitch separation an increase of the yield of distillated talloil of about 10 % with higher acid factor. Pilot tests without propellent steam in the rosin column led to a better separation between rosin acid and raw fatty acids in comparison to a stage column of the same height. The yield of fatty acid in the real fatty acid column could be increased from 66 % to more than 70% at simultaneous quality increase. Industrial plants with throughput- and purity guarantee can be offered because of extensive test results. The well-known scale-up behaviour of Mellapak and working results from industrial fatty acid columns allow a reliable layout.

Thirteen aromatic carboxylic acids in Finnish tall oil fatty acids were identified and quantified by gas chromatography-mass spectrostereoisomeric secodehydroabeitic acids secoditerpene and dehydroabeitic acids. The other aromatic acids were various secoditerpene ando- alkyl- phenylalkanoic acids. A number of minor nonaromatic acids with mono- and bicyclic, and branched chain structures were also identified and quantified.

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.

A method is described which permits ready and complete separation of the unsaponifiable constituents from the fatty acids contained in the tall oil head fraction. The fatty acids are converted to zinc soaps which are essentially non-volatile and surprisingly heat stable. They form a low viscosity, homogeneous solution in the unsaponifiable components. The latter are then removed by distillation in vacuo leaving zinc soaps as a low melting residue. These soaps are readily decomposed by mineral or organic acids to fatty acids and an aqueous solution of the appropriate zinc salt which is re-cycled for further preparations of zinc soaps.

A series of homologousn-alkylbenzenes and ω-phenylcarboxylic acids were detected and identified from the pyrolysis reaction of tall oil fatty acids and several pure fatty acids, respectively, with kraft lignin. Different reaction conditions (e.g., varying amounts of lignin) and different reaction times were applied. Temperatures were kept constant at 280 C. Products were distilled at 0.1 Pa and 150 C. After methylation, the distilled fractions were analyzed by gas chromatography-mass spectrometry (GC-MS). The method of detection and identification of the different substances by GC-MS is described. Pure singly and double unsaturated fatty acids (99.9% gas chromatographic purity) showed reactions to the title products (up to 4% total amount), whereas saturated fatty acids did not react at all. A possible reaction scheme taking quantitative parameters into account is suggested.

An analytical procedure is presented for determination of the rosin and fatty acid contents of tall oil products. Rosin acids are determined by titration after selective esterification of the fatty acids at room temperature with anhydrous methanolic hydrochloric acid reagent. The fatty acid content is calculated by difference from acid number and rosin acid determinations. The method presented has smaller sample requirements, shorter analysis time, greater selectivity, and improved precision above 15% rosin acid compared to standard procedures. The standard deviations for the determination of percent rosin and fatty acids have been found to be 0.30 and 0.34, respectively, over the entire concentration range. The reaction mechanism of acid catalyzed esterification is discussed with respect to the reaction rates and selectivity. The esterification variables which were investigated include catalyst concentration, sample size, reaction time, selectivity, and effect of water.

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.

Minor constituents in high quality tall oil fatty acids have been isolated successfully by liquid column chromatography, using silicic acid as the adsorbent. The minor constituents contained two types of compounds: those which were noneffective and those which were effective in causing the darkening of tall oil fatty acids during heating. The former consisted oftrans-3,5-dimethoxystilbene and rosin acids. The latter was separated into numerous fractions by the combination of chemical methods, silicic acid column chromatography, and low temperature fractional crystallization. The fractions were characterized by functional group analyses, chemical reactions, and UV and IR spectrometric methods. Most of the fractions contained two-three times as much oxygen in the molecule as the original sample and were highly oxidized fatty acids. They had mol wt ranging 300–551 and contained double bonds, carbonyl, ester, peroxide, and hydroxyl groups. The effect of these minor constituents upon the color stability of tall oil fatty acids during heating was postulated as being due to the hydroxyl groups located in the α-position to the double bond in the molecule.

Once 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.