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This study investigates the catalytic effects of Nickel-ligated catalysts derived from tall oil (NiTO) and sunflower oil (NiSFO) on the oxidation of heavy oil. Thermogravimetric (TG) analysis were employed to assess the thermal behavior and kinetics of heavy oil degradation. The Friedman isoconversional method provided the activation energies (Ea), which were then used to derive thermodynamic parameters including changes in enthalpy (ΔH), entropy (ΔS), and Gibbs free energy (ΔG). The TG analysis revealed that both NiTO and NiSFO influence the degradation kinetics of heavy oil. Moreover, NiTO exhibited a consistent catalytic effect across a wide range of conversions, lowering the onset temperature of degradation and promoting faster degradation rates, which suggests a rapid breakdown at lower temperatures. Conversely, NiSFO demonstrated a substantial decrease in activation energy at mid-range conversions, indicating a highly efficient catalysis during these stages. In addition, thermodynamic analysis indicated that both catalysts alter the energetic profile of the reaction. Notably, NiSFO reduced ΔG significantly at lower conversions, enhancing the spontaneity of the reaction, while NiTO was associated with lower ΔG values across most conversions, implying a more favorable reaction throughout the process. The findings suggest that the choice of catalyst can be tailored based on the desired conversion range and reaction spontaneity in industrial heavy oil processing. These insights could be crucial for optimizing thermal treatments in heavy oil upgrading, offering potential improvements in the efficiency of in-situ combustion and enhanced oil recovery technologies. [ABSTRACT FROM AUTHOR]

The utilization of polyols derived from renewable sources presents an opportunity to enhance the sustainability of rigid polyurethane (PUR) foams, thereby contributing to the advancement of a circular bioeconomy. This study explores the development of PUR rigid foams exclusively using polyols sourced from second-generation renewable biomass feedstocks, specifically depolymerized birch bark suberin (suberinic acids) and tall oil fatty acids. The polyols achieved a total renewable material content as high as 74%, with a suberinic acid content of 37%. Response surface modeling was employed to determine the optimal bio-polyol, blowing agents, and catalyst content, hence, optimizing the bio-based foam formulations. In addition, response surface modeling was applied to rigid PUR foam formulations based on commercially available petroleum-based polyols for comparison. The results, including apparent density (~40–44 kg/m3), closed cell content (~95%), compression strength (>0.2 MPa, parallel to the foaming direction), and thermal conductivity (~0.019 W/(m·K)), demonstrated that the suberinic acids-based rigid PUR foam exhibited competitive qualities in comparison to petroleum-based polyols. Remarkably, the bio-based rigid PUR foams comprised up to 29% renewable materials. These findings highlight the potential of suberinic acid-tall oil polyols as effective candidates for developing rigid PUR foams, offering promising solutions for sustainable insulation applications. [ABSTRACT FROM AUTHOR]

Cryogenic insulation material rigid polyurethane (PU) foams were developed using bio-based and recycled feedstock. Polyols obtained from tall oil fatty acids produced as a side stream of wood biomass pulping and recycled polyethylene terephthalate were used to develop rigid PU foam formulations. The 4th generation physical blowing agents with low global warming potential and low ozone depletion potential were used to develop rigid PU foam cryogenic insulation with excellent mechanical and thermal properties. Obtained rigid PU foams had a thermal conductivity coefficient as low as 0.0171 W/m·K and an apparent density of 37-40 kg/m3. The developed rigid PU foams had anisotropic compression strength properties, which were higher parallel to the foaming direction. Moreover, the compression strength was also influenced by the type of applied bio-based polyol. The bio-based polyols with higher OH group functionality delivered higher crosslinking density of polymer matrix; thus, the mechanical properties were also higher. The mechanical strength of the foams increased when materials were tested at liquid nitrogen temperature due to the stiffening of the polymer matrix. The thermal properties of the developed materials were determined using differential scanning calorimetry, dynamic mechanical analysis, and thermogravimetric analysis methods. Lastly, the developed rigid PU foams had good adhesion to the aluminium substrate before and after applying cyroshock and an excellent safety coefficient of 4-5. Rigid PU foams developed using Solstice LBA delivered adhesion strength of ~0.5 MPa and may be considered for application as cryogenic insulation in the aerospace industry. [ABSTRACT FROM AUTHOR]

The utilization of polyols derived from renewable sources presents an opportunity to enhance the sustainability of rigid polyurethane (PUR) foams, thereby contributing to the advancement of a circular bioeconomy. This study explores the development of PUR rigid foams exclusively using polyols sourced from second-generation renewable biomass feedstocks, specifically depolymerized birch bark suberin (suberinic acids) and tall oil fatty acids. The polyols achieved a total renewable material content as high as 74%, with a suberinic acid content of 37%. Response surface modeling was employed to determine the optimal bio-polyol, blowing agents, and catalyst content, hence, optimizing the bio-based foam formulations. In addition, response surface modeling was applied to rigid PUR foam formulations based on commercially available petroleum-based polyols for comparison. The results, including apparent density (~40–44 kg/m3), closed cell content (~95%), compression strength (>0.2 MPa, parallel to the foaming direction), and thermal conductivity (~0.019 W/(m·K)), demonstrated that the suberinic acids-based rigid PUR foam exhibited competitive qualities in comparison to petroleum-based polyols. Remarkably, the bio-based rigid PUR foams comprised up to 29% renewable materials. These findings highlight the potential of suberinic acid-tall oil polyols as effective candidates for developing rigid PUR foams, offering promising solutions for sustainable insulation applications.

Kraft pulp production generates residues and by‐products of significant importance to the mill. Solid residues from forestry activities are commonly used to generate steam in power boilers. In the recovery cycle, black liquor generates steam (and subsequently energy) by burning in the Tomlinson boiler, while white liquor is regenerated. Well‐developed alternative technologies can use these residues and by‐products to generate different types of biofuels. This review addresses the use of such technologies integrated with Kraft mills, in the concept of biorefineries, showing advantages, disadvantages, and successful examples. Solid residues from forestry can be used to produce bio‐oil through processes such as fast pyrolysis and hydrothermal liquefaction. Bio‐oils are currently used for heating through combustion in commercial/industrial boilers, but greater appreciation occurs if used as biofuels, which is done through catalytic upgrading processes. Black liquor gasification generates synthesis gas, which can be burned for energy co‐generation, used to produce synthetic fuels, or as a hydrogenating agent for bio‐oil or crude tall oil catalytic upgrading. Kraft biorefineries are gradually being implemented, justifying efforts to improve existing and new biomass conversion technologies. [ABSTRACT FROM AUTHOR]

Increasing demand for lithium-ion batteries has led to the development of several new lithium mineral projects around the globe. Some major mineral processing challenges these projects face are similarities in gangue and value mineral behaviour and poor selectivity in froth flotation. Unsaturated anionic fatty acids are the primary spodumene flotation collectors, known to be strong collectors with poor solubility and selectivity. Fundamental flotation research consensus is that spodumene flotation is driven by a fatty acid–anion complex adsorbed at cationic aluminum sites. However, many small-scale studies result in poor recoveries, prompting several researchers to investigate cationic activators or mixed anionic/cationic collectors to improve flotation performance. Testwork with real spodumene ore is rare in recent literature, but older publications from several deposits prove that fatty acids can successfully concentrate spodumene. The process generally includes alkaline scrubbing, high-density fatty acid conditioning, and flotation at pH 7.5–8.5 with 500–750 g/t fatty acid collector. The collector speciation behaviour is notably sensitive to pulp conditions around this pH; possibly resulting in unstable flotation circuits and inconsistent results. This paper reviews fatty acid collector properties and the available industrial and fundamental spodumene flotation research. We aim to provide new insight for understanding particle-collector interactions in spodumene flotation and help bridge the gap between fundamental and industrial processes which will be needed to de-risk projects in the growing lithium mineral industry. [ABSTRACT FROM AUTHOR]

A side-stream of the cellulose pulping process – tall oil, was valorised for polyol precursor synthesis. The influence of various parameters on the tall oil self-epoxidation method was studied to increase the conversion towards oxirane rings while using a reduced amount of immobilised lipase catalyst – Novozym® 435 and hydrogen peroxide. The influence of synthesis time (0–7 h), process temperature (30–40 ℃), hydrogen peroxide (20–50 wt. %) and Novozym® 435 catalyst concentration (1.5–4.5 wt. % of tall oil mass) on the tall oil fatty acid self-epoxidation process was studied and optimised using response surface method. The shift in relative conversion to oxirane and ethylenic unsaturation was used to track the epoxidation process. The chemical structure change of the epoxidised tall oil was investigated using FTIR, 1H NMR and 13C NMR spectroscopies. The maximum relative conversion to oxirane of 81 % was attained at a relatively high Novozym® 435 catalyst loading of 4.5 wt. %. In comparison, the optimised relative conversion to oxirane of 73 % was achieved at a more feasible catalyst content of 3.2 wt. % after 7 h of synthesis, at hydrogen peroxide and tall oil molar ratios of 2.0/1.0, hydrogen peroxide concentration of 28 wt. % and synthesis temperature of 44 ℃. [Display omitted] • Tall oil fatty acids (TOFA) were used for polyol precursor synthesis. • TOFA epoxidation was done in presence of immobilized lipase catalyst Novozym 435. • Achieved relative conversion to oxirane up to 80.6 %. • Process was optimised to reach minimal catalyst content and minimal synthesis time. [ABSTRACT FROM AUTHOR]

In this study, previously developed acetoacetates of two tall-oil-based and two commercial polyols were used to obtain polymers by the Michael reaction. The development of polymer formulations with varying cross-link density was enabled by different bio-based monomers in combination with different acrylates—bisphenol A ethoxylate diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate. New polymer materials are based on the same polyols that are suitable for polyurethanes. The new polymers have qualities comparable to polyurethanes and are obtained without the drawbacks that come with polyurethane extractions, such as the use of hazardous isocyanates or reactions under harsh conditions in the case of non-isocyanate polyurethanes. Dynamic mechanical analysis, differential scanning calorimetry, thermal gravimetric analysis, and universal strength testing equipment were used to investigate the physical and thermal characteristics of the created polymers. Polymers with a wide range of thermal and mechanical properties were obtained (glass transition temperature from 21 to 63 °C; tensile modulus (Young's) from 8 MPa to 2710 MPa and tensile strength from 4 to 52 MPa). The synthesized polymers are thermally stable up to 300 °C. The suggested method may be used to make two-component polymer foams, coatings, resins, and composite matrices. [ABSTRACT FROM AUTHOR]

Phytosterols (C 29 H 50 O), also known as plant sterols and stanols, are valuable biomolecules with a variety of applications in the pharma, food, and cosmetics industries. Phytosterols are typically manufactured from vegetable oil and tall oil feedstocks through a cooling crystallization process. Depending on the feedstock used, the composition regarding individual phytosterols and phytostanols (saturated analogs of phytosterols), also varies to a large extent. In the current research it was observed that by adding a small amount of water to the organic solvent [i.e., n(water)/n(acetone) of 0.17, n(water)/n(ethanol) of 0.13, and n(water)/n(ethyl acetate) of 0.10], the final phytosterol profile regarding phytosterol and phytostanol concentrations can be modified. This can be explained by the different solubility behavior of phytosterols and phytostanols in the studied solvent systems, based on experimental results obtained from transmissivity measurements. Phytostanols have surprisingly low solubility when compared to phytosterols in all the studied solvent systems. However, in the presence of water, phytosterol solubility decreased more compared to phytostanols. To the best of our knowledge, this is the first time that phytostanol solubility has been systematically studied. Moreover, phytosterol and phytostanol concentrations in a crystallized product with varying binary solvent systems containing water has not previously been reported. The measured experimental solubility data correlated well with the studied solubility models (van't Hoff, modified Apelblat, Buchowski-Ksiazaczak (λh), and polynomial equations). Understanding the solubility behavior of phytosterols and phytostanols allows to optimize the crystallization process itself toward a broader raw material selection, and better yield and quality in the production of phytosterols from plant-based raw materials. In addition, these findings can potentially be further utilized in phytosterol formulations for various applications., Competing Interests: Declaration of competing interest None., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

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In this study, previously developed acetoacetates of two tall-oil-based and two commercial polyols were used to obtain polymers by the Michael reaction. The development of polymer formulations with varying cross-link density was enabled by different bio-based monomers in combination with different acrylates—bisphenol A ethoxylate diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate. New polymer materials are based on the same polyols that are suitable for polyurethanes. The new polymers have qualities comparable to polyurethanes and are obtained without the drawbacks that come with polyurethane extractions, such as the use of hazardous isocyanates or reactions under harsh conditions in the case of non-isocyanate polyurethanes. Dynamic mechanical analysis, differential scanning calorimetry, thermal gravimetric analysis, and universal strength testing equipment were used to investigate the physical and thermal characteristics of the created polymers. Polymers with a wide range of thermal and mechanical properties were obtained (glass transition temperature from 21 to 63 °C; tensile modulus (Young’s) from 8 MPa to 2710 MPa and tensile strength from 4 to 52 MPa). The synthesized polymers are thermally stable up to 300 °C. The suggested method may be used to make two-component polymer foams, coatings, resins, and composite matrices.

The world's rapid energy demand through overpopulation and industrial development, coupled with environmental trends to reduce fossil fuel reliance, has created a global need for renewable and sustainable fuel sources. As researchers, governments, and industries look towards non-edible oils as a source for biofuels, the pulping industry by-product, tall oil, has promise as a feedstock. This review provides an overview of tall oil production from woody biomass, tall oil purification, and treatment of refined tall oil for biochemistry, bioenergy, and miscellaneous applications. Further, this review investigates the recent trends and barriers toward tall oil-derived biofuels. Tall oil and its components currently contribute to the circular bioeconomy through several applications, primarily being biochemicals. Recent commercialization of stand-alone tall oil biorefineries has demonstrated that biodiesel is the main pathway for tall oil-derived fuels, however, experimental gasoline and jet fuel pathways have shown promise in meeting fuel standards. Limited studies have co-processed tall oil biocrude with petroleum intermediates, facing challenges to stay within fuel specifications. Showing technical feasibility as a fuel source, tall oil's by-product nature has an economic and legislature-supported advantage over other biofuel sources, being closer to competing with fossil fuels. Yet tall oil's inflexible global supply as well as demand from biochemical industries may cause future supply chain challenges. The lack of political commitment and scaling uncertainty pose further barriers for tall oil-derived fuels that must be overcome to contribute to biofuel demand in future years. [Display omitted] • Kraft pulping is the primary tall oil production method among developing processes. • Tall oil applications are versatile with globally varying composition and availability. • Bioeconomy opportunities are identified for standalone and co-processed tall oil biofuels. • Despite drivers for tall oil-derived fuels long-term barriers exist in their utilization. [ABSTRACT FROM AUTHOR]

Sodium salt scaling, i. e. the formation of doubles salts comprised of sodium, carbonate and sulphate on the heat transfer surfaces, is a common problem that occurs during black liquor evaporation. In this study, experimental results are presented that provide new insights into the formation and composition of such scales and how they are influenced by the addition of tall oil brine. It was found that increased content of sodium carbonate and sodium sulphate in the black liquor increased scaling, while the ratio between carbonate and sulphate had a lesser influence than reported in other studies. Black liquor created loose clay-like scales comprised of aggregated crystals and black liquor, whereas salt solutions created hard mineral-like scales. The scales formed by both the black liquor and the salt solution showed a tendency to fall off during formation after primary nucleation. It was also found that both tall oil soap and alkalized tall oil brine could inhibit the formation of scales. The inhibition effect is stronger if adding the soap or brine just before scaling starts, but also depends on the amount added, the sodium carbonate and sodium sulphate content in the liquor as well as other factors. [ABSTRACT FROM AUTHOR]

Wood, due to its organic constitution, is highly susceptible to biodeterioration agents, making preservative treatment essential to those with low natural durability. Currently, the main products used in the preservative treatment of wood are CCA and CCB, which because of their constitution, are toxic to the environment and human health. Faced with this situation, it is essential to develop studies on natural products that have a biocidal action and thus can be used in the wood treatment, giving greater protection and increasing the lifespan of the piece. Considering this perspective, the present study aims to assess the quality (penetration and retention) and the efficiency of natural preservatives applied to the treatment of Araucaria angustifolia, Eucalyptus viminalis, and Pinus taeda, subjected to accelerated rotting under laboratory conditions. The woods of the three species were submitted to preservative treatment with tannin, tall oil, and neem oil, using the cold quick immersion method at the concentration of 5% of the product preservative solution for five minutes. In the sequence, they were assessed by the accelerated rotting test under the action of rotting fungi Trametes versicolor and Gloeophyllum trabeum, following the recommendations of ASTM D 2017 (2005) and ASTM D 1413 (1999). Based on the results, it was observed that P. taeda wood showed the best penetration to the neem and tall oil preservatives. The tannin presented vascular penetration for the three species. The best retention values were from A. angustifolia and P. taeda, for all treatments applied. Regarding the efficiency, comparing the results found for the other species, all treatments were efficient for P. taeda wood when in contact with the brown rot fungi (G. trabeum). [ABSTRACT FROM AUTHOR]

Research on decreasing the consumption of coal tar and expanding the range of materials used in binder-pitch production by adding coal extracts and chemical byproducts is reviewed. The liquid byproducts employed are tall oil, semicoking tar, and residues of styrene distillation; the solid byproducts are rubber granules and polycarbonate wastes. [ABSTRACT FROM AUTHOR]

This study presents the development and analysis of rigid polyurethane-polyisocyanurate (PU-PIR) foam synthesized from high functionality tall oil (TO) based polyols. Three PU-PIR formulations with varied high functionality TO based polyol content (45, 75 and 95 pbw) and a different tier of isocyanate (NCO) indexes (110, 150, 200, 300 and 400) for each formulation were compared to a formulation developed using conventional raw materials, mainly obtained from petrochemicals. Using the Fourier transform infrared spectral analysis (FTIR), the chemical structure of the foams was evaluated with emphasis on the characteristic PU-PIR signal ratio and isocyanurate signal peaks. The thermal properties of the PU-PIR polymer matrix were characterized using the thermogravimetric analysis (TGA) method by comparing the thermal degradation temperatures at 5%, 25% and 50% and residual masses. Technological parameters and thermal degradation results indicate that TO is a suitable renewable resource for polyol in a rigid PU-PIR foam formulation, but the results from FTIR analysis suggest that a small optimization in the foam developing process is necessary due to an increasing amount of unreacted NCO groups in samples with the NCO index above 200. • TO polyol gives the foam a renewable material content up to almost 25% of the mass. • TO polyol ensures an improved thermal degradation stability in rigid PU-PIR foams. • The developed formulation is well-suited for rigid PU and rigid PIR foam both. [ABSTRACT FROM AUTHOR]

In recent decades, vegetable oils as a potential replacement for petrochemical materials have been extensively studied. Tall oil (crude tall oil, distilled tall oil, tall oil fatty acids, and rosin acids) is a good source to be turned into polymeric materials. Unlike vegetable oils, tall oil is considered as lignocellulosic plant biomass waste and is considered to be the second-generation raw material, thus it is not competing with the food and feed chain. The main purpose of this review article is to identify in what kind of polymeric materials wood biomass-based fatty acids and rosin acids have been applied and their impact on the properties.

A screening Life Cycle Assessment (LCA) of tall oil-based bio-polyols suitable for rigid polyurethane (PU) foams has been carried out. The goal was to identify the hot-spots and data gaps. The system under investigation is three different tall oil fatty acids (TOFA)-based bio-polyol synthesis with a cradle-to-gate approach, from the production of raw materials to the synthesis of TOFA based bio-polyols at a pilot-scale reactor. The synthesis steps that give the most significant environmental footprint hot-spots were identified. The results showed the bio-based feedstock was the main environmental hot-spot in the bio-polyol production process. Future research directions have been highlighted.

The purpose of this work was to verify the binders available on the Polish market due to their physical features and effectiveness of building permanent active carbon granules. The conducted tests concerned a comparison of sorption properties and strength of activated carbon formed from hard coal depending on the type of binder used. Raw material preparation, granulation, drying and carbonization, as well as activation processes were carried out. The results obtained are presented in the form of tables. Based on the reached results, one of the most important effects in terms of operating conditions is the greatest advantage of the aqueous glycocell solution as a binder.

High-quality rigid polyurethane (PU) foam thermal insulation material has been developed solely using bio-polyols synthesized from second-generation bio-based feedstock. High functionality bio-polyols were synthesized from cellulose production side stream—tall oil fatty acids by oxirane ring-opening as well as esterification reactions with different polyfunctional alcohols, such as diethylene glycol, trimethylolpropane, triethanolamine, and diethanolamine. Four different high functionality bio-polyols were combined with bio-polyol obtained from tall oil esterification with triethanolamine to develop rigid PU foam formulations applicable as thermal insulation material. The developed formulations were optimized using response surface modeling to find optimal bio-polyol and physical blowing agent: c-pentane content. The optimized bio-based rigid PU foam formulations delivered comparable thermal insulation properties to the petro-chemical alternative.

Este trabalho descreve o desempenho de um reator Fenton em grande escala usado para remoção de fenol em uma planta de valorização dos resíduos da indústria de papel e celulose. O efluente consiste em óleo vegetal e fenol. A estação de tratamento objetiva tratar 4 m3 h-1 e é constituída por um pré-tratamento para remoção de óleo, reator Fenton, Flotador de Ar Dissolvido - FAD e uma lagoa de aeração. Para a avaliação da estação de tratamento foram comparadas análises próprias do efluente com análises feitas em laboratório certificado. A eficiência global de remoção de fenol é maior do que 99,7%. Foi demonstrado que a combinação do processo de oxidação avançada com o biológico constitui-se em um sistema de tratamentos interessante a fim de remover contaminantes recalcitrantes.

Tall Oil is considered one of the cheapest natural oils in the world, since it is an industrially generated by-product, not dependent on climatic and soil weather, but on the production of cellulose and kraft paper. The yield and composition of Tall Oil can vary, as they are influenced by the quantity of extractives, the quality and species of the wood, and the time of storage before cooking. The objective of this work was to determine the chemical composition, that is, to quantify the fatty acids, resin and unsaponifiable acids (neutral), and the acidity and saponification indexes of the Brazilian CTO sample. And, additionally, compare to the composition of CTO's from different locations in the world. It can be concluded that the composition of the CTO can vary because they are influenced by the quantity of extractives, the quality, age and species of the wood, the storage time before cooking and the soil and climate conditions in which the wood was developed. Studying the chemical composition of the CTO is very important because this study determines the applications of the refined CTO and the performance of the fractionation process, as well as the quantities and qualities of the products obtained. [ABSTRACT FROM AUTHOR]

Black liquor soap is used to produce tall oil with subsequent fractionation. The main distilled products are tall oil rosin and fatty acids, as well as pitch. The presence of sulfur compounds in tall products limits the number of their end-use applications. The existing methods for tall oil and tall oil-derived products desulfurization are expensive, time-consuming and non-universal. Desulfurization of sulfate soap can solve the problem of reducing the sulfur content in the tall oil and its fractions. By treatment with sodium hydroxide + sodium chloride aqueous solution and copper, the total sulfur content of softwood black liquor soap was reduced from 3120 to 197 ppm, and in the case of softwood + hardwood black liquor soap-from 2960 to 423 ppm. Minimum total sulfur contents of the tall oils obtained from desulfurized sulfate soaps were 165 and 410 ppm, respectively. [ABSTRACT FROM AUTHOR]

Due to its toxic effect on fungi, for the last 50 years copper has been one of the most widely used materials in the impregnation industry. The ban on CCA (copper-chrome-arsenic), known as an effective deterrent against fungi and insects, has led to the development of new and environmentally-friendly alternatives. Copper-azole (CuA), which is one of the most widely used of the newly-developed materials, is very effective against fungi and insects. However, one of its most serious problems is the fact that copper is leached from the wood. Various factors affect the leaching of copper from wood. One of the most important effects is the duration of fixation. In this study, samples impregnated with copper azole were exposed to a secondary impregnation process using tall oil and linseed oil 24 hours and 5 days, respectively, after the first impregnation. The effects of different fixation durations and oiled impregnation procedures on Scotch pine were investigated. For this purpose, biological, physical and chemical analyses of the wood were performed. Moreover, the amount of copper residual after leaching was also examined. According to the results obtained, it was observed that the duration of fixation had no significant effect on the physical properties and that the linseed oil improved the physical properties of the wood. Through the copper and oil combination, an improvement in the physical and biological properties of the wood was observed, as well as a decrease in the amount of copper leached out. [ABSTRACT FROM AUTHOR]

Tall oil is an important by-product of Kraft pulping processes. One possibility to improve the economic feasibility of Kraft pulp mills is to consider tall oil production from their wasted tall oil soaps. This review paper describes the current technology practiced to produce tall oil from the black liquor of Kraft pulping processes. Moreover, alternative processes to separate tall oil soap from black liquor, produce tall oil from the separated soap, purify tall oil, and to produce value-added products from tall oil are reviewed. The main perspectives and challenges associated with each process are comprehensively described. Currently, soap is separated from black liquor via decantation. To improve the efficiency of this separation, the application of neutral soluble colloids in dilute black liquor reported to be promising. Tall oil soap is converted to crude tall oil in the acidulation process via treating with sulfuric acid. However, the use of sulfuric acid forms calcium sulfate as a by-product of the process. The replacement of sulfuric acid with a sodium sesquisulfate solution is beneficial for decreasing the direct use of sulfuric acid in the tall oil production process. Crude tall oil can be used without purification as fuel. Its purification and subsequent reaction with methanol can lead to biodiesel production. However, this process may be complicated to implement in industry. The production of valuable lignin-based products from the tall oil production process may have benefits for the mills as these processes can be fully integrated into the Kraft pulping and tall oil production processes. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

• Plant sterols can be precipitated from fatty acid based ionic liquids. • Over 80% of plant sterols recovery and over 90% purity can be obtained. • Plant sterol precipitation is only slightly affected by the fatty acid used. • Plant sterol precipitation is strongly inhibited by other molecules. • Recovery of 79.4% and purity of 991% plant sterols are reached from tall oil. Plant sterols and stanols are bio-derived compounds used in functional foods because of their hypocholesterolemic effect. Currently, plant sterols and stanols are recovered from tall oil and vegetable oil waste streams by using high vacuum distillation and crystallization. The aim of this work was to explore the recovery and purification of plant sterols and stanols using ionic liquids. Particularly, in-situ protic ionic liquids were synthesized by mixing an amine and fatty/resin acids as a model system of tall oil and vegetable oil waste streams, then an anti-solvent precipitation was performed using alcohols and water. Precipitation temperature, alcohol concentration, water concentration, type of alcohol (methanol and ethanol) and structure of amine (triethylamine, butylamine, and methyldiethanolamine) strongly affect the precipitation from model systems. On the other hand, precipitation time (3–12 h) and type of fatty/resin acid (myristic acid, oleic acid, abietic acid) only slightly influence the precipitation. Results show that when myristic acid was used, the best combination of recovery and purity is reached using triethylamine and methanol with maximum experimental values of 79.9 % of purity and 99.4 % of recovery at 5 °C, 120 % alcohol, 30 % water, and 12 h. Unfortunately, the precipitation performance of plant sterols and stanols from tall oil (5.3 %) using triethylamine and methanol is significantly worse than the performance observed in model systems, achieving maximum experimental values of 70.5 % of recovery of and 76.5 % of purity. However, it was found that saponifying the tall oil before the precipitation significantly improve plant sterols and stanols recovery and purity. [ABSTRACT FROM AUTHOR]

ABSTRACT 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. [ABSTRACT FROM AUTHOR]