Tall Oil Research Articles

Editorial: The innovation engine and the forest products industry value chain

The forest products industry (FPI • pulp, paper, paperboard, building products, allied products, and byproducts) has been continuously innovating as it manufactures and delivers value-added products to consumers worldwide. Integrated pulp and paper mills produce pulp, paper, paperboard, and byproducts like turpentine, tall oil, methanol, lignin, and other chemicals.

Further investigation on fatty acids-based methacrylate monomers: High temperature radical polymerization for obtaining copolymers and their blends with medium-oil alkyd resin for coatings

Fatty acids-based methacrylate monomers have been studied as alternative renewable raw materials for the synthesis of poly(acrylate)s. In this research work, several poly(acrylate)s based on lauric, oleic, linoleic and tall oil fatty acids were obtained by high temperature solution polymerization since it is a process extensively used at industrial scale. The effect of the presence and increase of the aforementioned fatty acids-based methacrylate monomers on the conversion as a function of polymerization time and actual monomer composition in the copolymer were studied, thus inferring that the fatty acid chain length is of paramount importance for the final macromolecular features. The resulting poly(acrylate)s were evaluated as individual and blended with a medium-oil alkyd resin with the aim of balancing the advantages of both, such as low drying, mechanical performance, and chemical resistance, in order to indirectly produce economically viable resins for the industrial coating market.

Study on components selection and performance of bio-oil based asphalt rejuvenator based on softening and asphaltene deagglomeration effect

The bio-oil, with environmental friendliness and good compatibility with asphalt, has been widely used in rejuvenating aged asphalt. In this study, based on the ability of bio-oils to soften aged asphalt and asphaltene deagglomeration on the molecular level, a composite rejuvenator (CD-rejuvenator) was prepared using cardanol and distilled tall oil, and macroscopic rheological properties tests and microscopic tests were used to determine the effectiveness of CD-rejuvenator. According to the outputs of a molecular dynamics simulation, distilled tall oil can shift the peak of the radial distribution function (RDF) of asphaltene back and decrease the aggregation probability of asphaltene. The cardanol's low molecular weight is most helpful in lowering the elastic modulus of aged asphalt molecules. The rheological test results revealed that CD-rejuvenator restored high-temperature rheological properties (G* and δ), and cracking resistance (Glover-Rowe parameter), of aged asphalt more effectively than soybean oil and aromatic oil. The crossover modulus of the rejuvenated asphalt binders shows that the CD-rejuvenator can deagglomerate the asphaltene agglomerates. Additionally, the CD-rejuvenator rejuvenated asphalt exhibited good viscosity behavior and crack resistance after PAV aging. Scanning electron micrographs show that the softening and deagglomeration components of the CD-rejuvenator have a synergistic effect on restoring the microscopic morphology of the aged asphalt surface, with the surface of CD-rejuvenator rejuvenated asphalt exhibiting the least quasi-bee structure and a more uniform surface. The molecular weight of rejuvenated asphalt also demonstrates the effectiveness of the CD-rejuvenator for deagglomerate asphaltene agglomerates. Overall, Regarding rheological characteristics and microstructure recovery effectiveness of aged asphalt, the rejuvenators prepared by using softening and deagglomeration components in blends performed better than the single-component soybean oil or aromatic oil rejuvenators.

Cationic tall oil lignin-starch copolymer as a flocculant for clay suspensions

In this study, a novel cationic tall oil lignin (TOL)-starch copolymer was successfully prepared by the polymerization reaction of TOL, starch and a cationic monomer of (3-acrylamidopropyl) trimethyl ammonium chloride (APTAC) through the free radical chain extension. 1H NMR and 1H–1H COSY studies demonstrated that the TOL and starch were covalently linked by the APTAC to produce the cationic copolymers. The copolymerization reaction reduced the phenolic content of TOL, yielding an increment in the solubility, molecular weight (Mw), and charge density of the cationic copolymer. Moreover, the thermochemical analysis indicated that the obtained copolymer, CR5-pH11, with the largest Mw possessed the highest glass transition temperature (Tg) of 184 °C due to the insertion of a long APTAC chain and the presence of starch and TOL. Owing to its highest charge density (3.6 meq/g) and largest Mw (56,100 kg/mol), CR5-pH11 exhibited the most efficient flocculation behavior in the kaolin suspension under altered agitation and gravitational forces as confirmed by focused beam reflectance measurement and sedimentation techniques. This study provided a new strategy to developing sustainable cationic lignin-starch flocculant for clay suspension systems.

Influence of environmentally friendly Phytonorman oils on the adhesive properties of frost-resistant rubbers based on nitrile butadiene rubber

The use of plasticizers based on esters of various acids most effectively improves the processing of rubber compounds and the frost resistance of NBR-based rubbers. In this work, as a plasticizer, products based on vegetable raw materials were tested - Phytonorman oils produced by the Biochemical Holding ORGKHIM, which are di- and triglycerides containing fatty acids of tall oil. Model rubber compounds based on BNKS-18AMN contained 10, 20, 30 wt. including eco-oils of the Phytonorman 212 and Phytonorman 213 brands, a mixture without oil and with 10 wt. including dibutyl phthalate (DBPh). To assess the effect of the type and dosage of eco-oils on the properties of rubbers and rubber compounds, methods for studying technological, physical-mechanical and adhesive properties were used. Determination of frost resistance, a comparison was made of methods for determining the glass transition temperature: differential scanning calorimetry (DSC) and thermomechanical analysis (TMA, Fourier). When using vegetable oils Phytonorman -212 and Phytonorman -213, the technological properties of rubber compounds are significantly improved compared to the mixture without oil and are on the same level with DBPH traditionally used in nitrile rubbers. It has been established that the introduction of Phytonorman 213 eco-oil into the formulations of rubber compounds based on BNKS 18AMN up to 10 wt. hours allows you to improve the technological parameters, as well as lower the glass transition temperature of rubber. At the same time, the physical and mechanical parameters and adhesive properties of vulcanizates are reduced by an average of 10%. It is also worth noting that rubbers with Phytonorman 213 oil are not inferior to nitrile rubbers with DBPh in terms of basic characteristics, and they are superior in adhesive properties by 27%.

Wood pulp industry by-product valorization for acrylate synthesis and bio-based polymer development via Michael addition reaction

It is crucial to adapt the processing of forest bio-resources into biochemicals and bio-based advanced materials in order to transform the current economic climate into a greener economy. Tall oil, as a by-product of the Kraft process of wood pulp manufacture, is a promising resource for the extraction of various value-added products. Tall oil fatty acids-based multifunctional Michael acceptor acrylates were developed. The suitability of developed acrylates for polymerization with tall oil fatty acids-based Michael donor acetoacetates to form a highly cross-linked polymer material via the Michael addition was investigated. With this novel strategy, valuable chemicals and innovative polymer materials can be produced from tall oil in an entirely new way, making a significant contribution to the development of a forest-based bioeconomy. Two different tall oil-based acrylates were successfully synthesized and characterized. Synthesized acrylates were successfully used in the synthesis of bio-based thermoset polymers. Obtained polymers had a wide variety of mechanical and thermal properties (glass transition temperature from –12.1 to 29.6 °C by dynamic mechanical analysis, Young's modulus from 15 to 1 760 MPa, and stress at break from 0.9 to 16.1 MPa). Gel permeation chromatography, Fourier-transform infrared (FT-IR) spectroscopy, matrix-assisted laser desorption/ionization-time of flight mass spectrometry, and nuclear magnetic resonance were used to analyse the chemical structure of synthesized acrylates. In addition, various titration methods and rheology tests were applied to characterize acrylates. The chemical composition and thermal and mechanical properties of the developed polymers were studied by using FT-IR, solid-state nuclear magnetic resonance, thermal gravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and universal strength testing apparatus.

Optimizing the Effective Use of Reclaimed Asphalt Pavement in Local Roadways

This study involved the construction of eight test sections in the City of Columbus, Ohio, to evaluate the effects of using different reclaimed asphalt pavement (RAP) contents and types of rejuvenator on the performance and properties of asphalt mixes used for local roads. The first section (control section) had a mix with 20% RAP and PG 64-22 binder. While three sections had mixes with 30%, 40%, 50% RAP, PG 64-22 binder, and Sylvaroad rejuvenator (tall oil), three other sections had mixes with the same RAP percentages and binder but used Hydrolene (aromatic extract) as the rejuvenator. Finally, the last test section was constructed using a mix with a 30% RAP and PG 64-28 binder (softer binder). Specimens were compacted in the laboratory from loose mixes that were obtained during the construction of each test section. Laboratory tests were conducted to evaluate the resistance of the prepared samples to moderate-temperature cracking, low-temperature cracking, rutting, and moisture damage. The test results showed that Hydrolene was more effective than Sylvaroad in improving the moderate-temperature cracking resistance of RAP mixes with more than 30% RAP. In addition, the tests results showed that the 30% RAP, 40% RAP, and 50% RAP mixes had similar low-temperature cracking resistance to that of the control. The laboratory test results also showed that mixes with 30% and 40% RAP had acceptable resistance to moisture damage. Furthermore, all mixes had acceptable rutting resistance. Finally, preliminary field evaluation showed that there were no observed distresses in the test sections after 7 months of construction.

Identification of Optimal Binders for Torrefied Biomass Pellets

The pretreatment of biomass through torrefaction is an effective means of improving the fuel quality of woody biomass and its suitability for use in existing facilities burning thermal coal. Densification of torrefied biomass produces a fuel of similar energy density, moisture content, and fixed carbon content to low-grade coals. Additionally, if the torrefaction conditions are optimized, the produced torrefied pellet will be resistant to weathering and biological degradation, allowing for outdoor storage and transport in a manner similar to coal. In untreated biomass, lignin is the primary binding agent for biomass pellets and is activated by the heat and pressures of the pellet extrusion process. The thermal degradation of lignin during torrefaction reduces its binding ability, resulting in pellets of low durability not suitable for transportation. The use of a binding agent can increase the durability of torrefied pellets/briquettes through a number of different binding mechanisms depending on the binder used. This study gives a review of granular binding mechanisms, as they apply to torrefied biomass and assesses a variety of organic and inorganic binding agents, ranking them on their applicability to torrefied pellets based on a number of criteria, including durability, hydrophobicity, and cost. The best binders were found to be solid lignin by-product derived from pulp and paper processing, biomass tar derived from biomass pyrolysis, tall oil pitch, and lime.

Generation of Sulfonated Lignin-Starch Polymer and Its Use As a Flocculant.

This paper reports the polymerization of tall oil lignin (TOL), starch, and 2-methyl-2-propene-1-sulfonic acid sodium salt (MPSA), a sulfonate-containing monomer, in a three-component system to generate flocculants for colloidal systems. By utilizing the advanced 1H, COSY, HSQC, HSQC-TOCSY, and HMBC NMR techniques, it was confirmed that the phenolic substructures of TOL and the anhydroglucose unit of starch were covalently polymerized by the monomer to generate the three-block copolymer. The molecular weight, radius of gyration, and shape factor of the copolymers were fundamentally correlated to the structure of lignin and starch, as well as the polymerization outcomes. The deposition behavior of the copolymer, studied by a quartz crystal microbalance with dissipation (QCM-D) analysis, revealed that the copolymer with a larger molecular weight (ALS-5) deposited more and generated more compact adlayer than the copolymer with a smaller molecular weight on a solid surface. Owing to its higher charge density, molecular weight, and extended coil-like structure, ALS-5 produced larger flocs with faster sedimentation in the colloidal systems, regardless of the extent of agitation and gravitational force. The results of this work provide a new approach to preparing a lignin-starch polymer, i.e., a sustainable biomacromolecule with excellent flocculation performance in colloidal systems.

Correction: Lipase Catalyzed Self-epoxidation of Tall Oil Fatty Acids in Batch and Continuous Flow Conditions

Correction: Lipase Catalyzed Self-epoxidation of Tall Oil Fatty Acids in Batch and Continuous Flow Conditions

Esters of Inulin and Tall Oil Fatty Acids

Esters of Inulin and Tall Oil Fatty Acids

Thermochemical recycling of tall oil pitch in a dual fluidized bed

Crude tall oil is a by-product obtained from the manufacture of chemical wood pulp. The residue obtained after the distillation of this product is known as tall oil pitch (TOP). This complex fraction is a highly viscous liquid that consists mainly of free fatty acids, fatty acids derivatives, rosin acids and additives. Given its complex composition, it is commonly used as fuel for heat production. In this work, steam cracking is proposed as an alternative treatment for this residue. Steam cracking can convert TOP into a valuable product gas that can be used in different applications including the production of green chemicals, moving towards a carbon circular economy. The experimental tests were performed in the Chalmers pilot scale Dual Fluidized Bed, consisting of a steam cracker and a combustor. For these experiments, the thermochemical decomposition of 150–175 kg/h TOP was performed at the steam cracker at two different temperatures (775 and 825 °C) to evaluate the influence of this parameter on the obtained products. Wood pellets were also tested as reference material for the highest temperature. The distribution of the obtained products was analysed. Results show that TOP can be regarded as a by-product instead of a residue and used as feedstock for the recovery of chemical building blocks and syngas via thermochemical recycling. Between 40 and 50 % of the carbon present in the fuel is kept in the permanent gases, while about 20 % is in aromatic hydrocarbons. Compared to biomass, the aromatics yield obtained for TOP is much higher (190 g/kg for TOP and 13 g/kg for biomass). Among the species found, benzene, toluene and xylene, represent between 62 and 72 % of the total measured aromatics. Regarding the gas fraction, the production of valuable light hydrocarbons (such as ethylene and propylene) is more pronounced in the TOP residue than in the biomass. In addition, an energy balance over the system was estimated and showed that TOP thermochemical recycling can be self-sustained in a Dual Fluidized Bed if the non-valuable products are combusted. The results obtained in this work indicate that this TOP could be an appealing option to consider as a source of biorefinery revenue leading to the circular use of waste.

Plant sterol precipitation in system composed by fatty acids using in-situ synthesized ionic liquids

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.

Asymptotic distribution of the eigenvalues of the bending‐torsion vibration model with fully nondissipative boundary feedback

AbstractAsymptotic and spectral results on the initial boundary‐value problem for the coupled bending‐torsion vibration model (which is important in such areas of engineering sciences as bridge and tall building designs, aerospace and oil pipes modeling, etc.) are presented. The model is given by a system of two hyperbolic partial differential equations equipped with a three‐parameter family of non‐self‐adjoint (linear feedback type) boundary conditions modeling the actions of self‐straining actuators. The system is rewritten in the form of the first‐order evolution equation in a Hilbert space of a four‐component Cauchy data. It is shown that the dynamics generator is a matrix differential operator with compact resolvent, whose discrete spectrum splits asymptotically into two disjoint subsets called the α‐branch and the β‐branch, respectively. Precise spectral asymptotics for the eigenvalues from each branch as the number of an eigenvalue tends to ∞ have been derived. It is also shown that the leading asymptotical term of the α‐branch eigenvalue depends only on the torsion control parameter, while of the β‐branch eigenvalue depends on two bending control parameters.

ИНГИБИТОРЫ СЕРОВОДОРОДНОЙ КОРРОЗИИ НА ОСНОВЕ ОКСИЭТИЛЬНЫХ ПРОИЗВОДНЫХ ПИПЕРАЗИНА

The effect of the composition of the reaction mass of esterification of distilled tall oil with oxyethylated piperazine derivatives on the protective effect in hydrogen sulfide-containing media was studied. The reaction product is a mixture of complex mono- and diesters. Statistical processing of the results showed that the protective effect is mainly determined by the content of esterification products for one hydroxyl group. The maximum protective effect is achieved when the conversion of tall oil acids is not lower than 98 %.

Low-carbon footprint diluents in solvent extraction for lithium-ion battery recycling.

This study investigated the influence of the diluent on the extraction properties of three extractants towards cobalt(ii), nickel(ii), manganese(ii), copper(ii), and lithium(i), i.e. Cyanex® 272 (bis-(2,4,4-trimethylpentyl)phosphinic acid), DEHPA (bis-(2-ethyl hexyl)phosphoric acid), and Acorga® M5640 (alkylsalicylaldehyde oxime). The diluents used in the formulation of the extraction solvents are (i) low-odour aliphatic kerosene produced from the petroleum industry (ELIXORE 180, ELIXORE 230, ELIXORE 205 and ISANE IP 175) and (ii) bio-sourced aliphatic diluents (DEV 2138, DEV 2139, DEV 1763, DEV 2160, DEV 2161 and DEV 2063). No influence of the diluent and no co-extraction of lithium(i), nickel(ii), cobalt(ii), manganese(ii) and aluminum were observed during copper(ii) extraction by Acorga M5640. The nature of the diluent influenced more significantly the extraction properties of manganese(ii) by DEHPA as well as cobalt(ii) and nickel(ii) by Cyanex® 272. Life cycle assessment of the diluents shows that the carbon footprints of the investigated diluents followed the following order: (ELIXORE 180, ELIXORE 230, ELIXORE 205) from petroleum industry > kerosene from petroleum industry > diluent produced from tall oil (DEV 2063) > diluents produced from recycled plastic (DEV 2160, DEV 2161) > diluents produced from used cooking oil (DEV 2138, DEV 2139). By taking into account the physicochemical properties of these diluents (viscosity, flashpoint, aromatic content), the extraction properties of Acorga® M5640, DEHPA, Cyanex® 272 in these diluents and the CO2 footprint of the diluents, this study showed DEV2063 and DEV2139 were the best diluents. A low-carbon footprint solvent extraction flowsheet using these diluents was proposed to extract selectively cobalt, nickel, manganese, lithium and copper from NMC black mass of spent lithium-ion batteries.

Remote Sensing Application for Tall Oil Palm Harvester

Oil palm is the primary source of economic gain and the community's primary need for palm oil and other daily necessities. In order to maximise the yield and benefits of oil palm, it is very difficult to do so with ordinary labour, and even if it is possible, it takes a long time to produce. Therefore, by adopting new technology, it is possible to overcome the challenges posed by tall oil palm harvesting. The application of remote sensing on tall oil palms will facilitate the harvesting procedure. With advancements in technology, such as remote sensing, it will be possible to achieve better results in less time and with fewer people. This pole has been equipped with multiple functionalities, such as a camera, to facilitate harvesting. This is because the height of the oil palm prevents workers from seeing the condition of the fruit and fronds that will be dropped. This paper also explains the use of remote sensing and its applications to the monitoring of oil palm plantations.

Lipase Catalyzed Self-epoxidation of Tall Oil Fatty Acids in Batch and Continuous Flow Conditions

Lipase Catalyzed Self-epoxidation of Tall Oil Fatty Acids in Batch and Continuous Flow Conditions

Pinoresinol stimulates keratinocyte proliferation and downregulates TNF-α secretion in peripheral blood mononuclear cells: An experimental in vitro study.

Natural coniferous resins are used in traditional medicine for the treatment of skin wounds. Coniferous wood resins ("callus" resin) are a mixture of abietic (resin) acids, lignans such as pinoresinol, and p-coumaric acid. The wound-healing properties of resins are thought to be related to their antimicrobial properties, but also to their effects on cell proliferation and inflammation. The purpose of this study was to identify and investigate the effects of novel aqueous dispersions of resin and its main components in the proliferation of human primary keratinocytes in vitroand in the expression of proinflammatory cytokines in human peripheral blood mononuclear cells. The proliferation studies were performed under low and high calcium conditions with or without added growth stimulators at the time points of 2and 6 days using AlamarBlue Cell Viability Reagent. The cytokine release assay was carried out by incubating the cells with the test articles for 18 h, after which the levels of tumor necrosis factor-α(TNF-α),interleukin-1β (IL-1β), IL-6, and IL-8 were measured in the supernatant by enzyme-linked immunosorbent assay. Resin and the purified lignan PINO, but not p-coumaric acid or abietic acid (industrial tall oil rosin), enhanced the proliferation of human keratinocytes in vitroand inhibited the expression of TNF-α, and to a lesser extent the expression of IL-1β in peripheral blood mononuclear cells. In this study, novel aqueous dispersions of spruce resin were used to investigate the effects of main resin components on keratinocyte proliferation and on the expression of key proinflammatory cytokines known to be associated with chronic wounds. The observations suggest that lignans, such as PINO, but not resin acids, are the components of resins that mediate the proliferative and TNF-α-suppressing effects. Lignans including PINO were identified as novel potential compounds in the treatment of chronic skin ulcers.

Performance of warm asphalt mixtures containing reclaimed asphalt pavement, an anti-stripping agent, and recycling agents: A study using a balanced mix design approach

This research aims to use a balanced mix design (BMD) approach to investigate the effect of recycling agents (RAs) and an anti-stripping agent on the mechanical properties of warm-mix asphalt (WMA) containing different levels of reclaimed asphalt pavement (RAP). The BMD used three RAs (aromatic extract, triglycerides and fatty acids, and tall oil), an amidoamine WMA additive (PAWMA®), and an anti-stripping agent (Zycotherm®). The Dynamic Creep (DC), Indirect Tensile Strength (ITS), and Semi-Circular Bending (SCB) fracture tests were respectively used to evaluate the rutting, moisture susceptibility, and cracking resistance of mixtures. In addition, two-dimensional and three-dimensional (2-D and 3-D) performance interaction diagrams were developed as typical approaches for the BMD of asphalt mixtures. For mixtures with RAP, the results indicated that the aromatic extract and tall oil RAs decreased the moisture susceptibility, while triglycerides and fatty acids increased the moisture susceptibility. In addition, the RAs generally decreased the rutting resistance of mixtures while they increased the cracking resistance. This effect was more noticeable in the mixtures treated with triglycerides and fatty acids. The results also showed that introducing PAWMA® and Zycotherm® to the mixtures improved their resistance to moisture damage, cracking, and rutting.