Tall Oil Research Articles

Hydrogen solubility measurements of analyzed tall oil fractions and a solubility model

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 597K and at pressures from 5 to 10MPa. 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 323.15K.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 323.15K. 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.

Screening of active solid catalysts for esterification of tall oil fatty acids with methanol

The paper is focused on the description of the activity/selectivity of mesoporous silica based materials loaded with various types of active species in the esterification of tall oil free fatty acids. The metals such as aluminium, molybdenum, gallium and zinc, including their combinations were impregnated on the mesoporous silica, which was tested in esterification reaction. All these catalysts preserved its tall oil free fatty conversion in the first and the second catalytic cycles. However, while only insignificant amount of gallium or molybdenum was lost from the solid catalyst into the liquid phases, zinc leached from every studied solid catalyst. In contrast to impregnated gallium on mesoporous silica, which exhibited higher acidity and higher tall oil free fatty acids conversion in the first catalytic cycle, but its value was not preserved in the second catalytic test.

Interactive effects of biochar and an organic dust suppressant for revegetation and erosion control with herbaceous seed mixtures and willow cuttings

AbstractLand reclamation efforts on “non‐soil” substrates frequently involve additions of organic material coupled with soil‐stabilizing dust suppressants to control erosion, but formal experiments, particularly of interactive effects, are lacking. We examined the effects of Entac™, a tall oil pitch emulsion, and pyrolyzed wood waste‐derived biochar on early plant establishment, growth, and survivorship, in 2 factorial greenhouse experiments: 1 using a seed mix widely used for roadside erosion control (the grasses Festuca rubra, Poa pratensis, Lolium perenne, and white clover [Trifolium repens]) and 1 using rooted cuttings of sand bar willow (Salix exigua). Biochar additions of 5, 10, and 20 t/ha enhanced biomass of clover by 14–250%, but had no significant effects on grasses. Entac additions inhibited early establishment and growth of both clover and grasses at all biochar treatment levels. Entac plus biochar treatments significantly enhanced survivorship of willows following a drought treatment in a greenhouse trial. In a field trial, Entac treatments had positive effects on willow diameter growth. Collectively, these results suggest that better soil moisture retention is the principal mechanism responsible for enhanced survivorship and growth of planted willows treated with Entac and biochar on sand substrates. Given Entac's inhibitive effects on early establishment of herbaceous species, and the abilities of Entac and biochar in combination to mitigate drought stress, these treatments may be particularly well suited for ecological restoration efforts using planted tree stock on coarse‐textured substrates and where exposure and ingress of non‐native herbaceous species are of concern.

Utilization of tall oil to enhance natural fibers for composite applications and production of a bioplastic

ABSTRACTTall 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.

Effects of wood-based renewable diesel fuel blends on the performance and emissions of a non-road diesel engine

Renewable fuels form an essential means to reduce greenhouse gas (GHG) emissions emitted by vehicles and non-road machines. Due to the limited production so far, different blends of renewable fuels in fossil fuels are a realistic way to implement the increasing use of renewable fuels. In addition to significant GHG emissions reduction, further benefits can be achieved when high quality renewable fuels are utilized as blending components since the pollutant exhaust emissions, such as unburned hydrocarbons (HC), carbon monoxide (CO), particulate matter mass (PM) and particle number (PN), may also decrease. A global Finnish forestry company has developed an innovative production process from crude tall oil (CTO), a wood-based residue of pulp making process, to renewable diesel. The fuel properties correspond to those of the traditional fossil fuels but the GHG emissions are reduced significantly.

C&EN profiles Ingevity, a new player in the chemical industry

It’s not hard to imagine that D. Michael Wilson’s first thought upon being offered the job as chief executive officer of Ingevity was “Wow, this company is doing pretty well. I better not screw it up.” Ingevity is the former specialty chemical business of the paper company MeadWestvaco. Around in one form or another for more than a century, it converts sawdust into activated carbon and the papermaking by-product crude tall oil into fatty acids, rosin, and downstream chemicals. For most of its history, the business hummed along quietly and profitably within MeadWestvaco. But in mid-2014, an activist investor, Starboard Value, started urging MeadWestvaco’s CEO, John A. Luke Jr., to jettison noncore businesses such as chemicals. In early 2015, Luke finally agreed, announcing plans to spin off the $1 billion-per-year chemical business as a separate company. The name Ingevity was announced in July 2015, and Wilson became CEO two months

Styrene–hydroxyethyl acrylate copolymer based alkyd resins with a comb‐type structural morphology obtained with a high solid content

ABSTRACTNowadays, so many studies are being carried out with the goal of obtaining environmentally friendly materials. In this study, styrene–hydroxyethyl acrylate copolymer (St‐co‐HEA) based alkyd resins with high solid contents and comb‐type structural morphologies were synthesized from St‐co‐HEA and macromonomers [MMs; dimethylol propionic acid modified with different proportions of tall oil fatty acids (TOFAs)]. The molar mass and gloss values of St‐co‐HEA were lower than those of the alkyd resins, but the thermal stability, viscosity, and glass‐transition temperature exhibited the opposite behavior. In all cases, the conversion percentage was higher than 80 %. The hydroxyl value and viscosity of the alkyd resins decreased with the TOFA content present in the MMrs, but the molar mass and the thermal stability increased. The rheological behavior of these resins was mainly pseudoplastic. Furthermore, the viscosity values were lower than 10 Pa s. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43996.

Green Diesel from Kraft Lignin in Three Steps.

Precipitated kraft lignin from black liquor was converted into green diesel in three steps. A mild Ni-catalyzed transfer hydrogenation/hydrogenolysis using 2-propanol generated a lignin residue in which the ethers, carbonyls, and olefins were reduced. An organocatalyzed esterification of the lignin residue with an in situ prepared tall oil fatty acid anhydride gave an esterified lignin residue that was soluble in light gas oil. The esterified lignin residue was coprocessed with light gas oil in a continous hydrotreater to produce a green diesel. This approach will enable the development of new techniques to process commercial lignin in existing oil refinery infrastructures to standardized transportation fuels in the future.

Reductive Etherification of Fatty Acids or Esters with Alcohols using Molecular Hydrogen.

In the presence of a catalyst system consisting of a ruthenium/triphos complex and the Brønsted acid trifluoromethanesulfonimide, mixtures of fatty acids and aliphatic alcohols are converted into the corresponding ethers at 70 bar H2 . The protocol allows the sustainable one-step synthesis of valuable long-chain ether fragrances, lubricants, and surfactants from renewable sources. The reaction protocol is extended to various fatty acids and esters both in pure form and as mixtures, for example, tall oil acids or rapeseed methyl ester (RME). Even the mixed triglyceride rapeseed oil was converted in one step.

Microwave-assisted catalytic esterification of α-glucoisosaccharino-1,4-lactone with tall oil fatty acids

Carbohydrates-rich materials are partly degraded during alkaline kraft pulping into a complex mixture of aliphatic carboxylic acids consisting of α-glucoisosaccharinic acid as one of the main acids. On the other hand, crude tall oil, containing significant amounts fatty acids, is obtained as a by-product from kraft pulping. One interesting novel approach is to utilize chemically both these side-streams by producing renewable surfactants from aliphatic carboxylic acids and fatty acids via esterification. In this paper, lauric (C12:0) and oleic (C18:1) acids as well as a mixture of tall oil fatty acids were esterified with α-glucoisosaccharino-1,4-lactone in a microwave-assisted batch reactor using a respective molar ratio of 3:1 in the presence of p-toluenesulfonic acid as a catalyst to obtain a mixture of the corresponding mono- and diesters (nonionic surfactants) at 70–100 °C for 6–24 h. The total yields varied in the range of 40–62 % and the mass ratio of monoesters to diesters (0.4–2.7) was greatly dependent on the fatty acid feedstock. It seems that relatively high yields of mono- and diesters of typical fatty acids can be obtained when they are esterified with one of the most significant lactones (α-glucoisosaccharino-1,4-lactone) in black liquor from kraft pulping. These esters are potential surfactants based on renewable feedstocks.

Investigation of the impacts of aging and RAP percentages on effectiveness of asphalt binder rejuvenators

In this study, the ability of five asphalt binder rejuvenators to restore low and high temperature true performance grades of aged binders was investigated. The rejuvenators considered in this study included a Naphthenic Oil, a Paraffinic Oil, an Aromatic Extracts, a Tall Oil, and an Oleic Acid. Several sets of asphalt mixtures containing different percentages (i.e. 25% and 45%) of RAP materials were prepared using PG 76-22 polymer-modified asphalt binder blended with rejuvenators at manufacturers’ recommended dosage. Control mixtures not including the rejuvenators were also prepared. All mixtures were loose mix aged for two hours and six hours to evaluate the impact of aging on the effectiveness of the different rejuvenators. After aging and compaction, the asphalt binder contained in each of these mixtures was extracted and recovered. The true low and high temperature grades of the extracted binders were determined using the Dynamic Shear Rheometer (DSR) and the Bending Beam Rheometer (BBR) tests. The recovered binders were considered RTFO aged due to the mixture aging used in this study. The DSR shear modulus master curves were also utilized to examine the impact of using different rejuvenators on rutting and fatigue cracking. Furthermore, a multi-factor Analysis of Variance (ANOVA) was conducted to evaluate the statistical significance of the differences between results. The results showed that all rejuvenated binders had lower performance grade than that of the control binder without rejuvenation. In addition, rejuvenator’s effectiveness was not affected by aging (from 2 to 6h) and increasing the amount of RAP materials (up to 45%). The rejuvenators were also found to improve the fatigue resistance without substantially influencing rutting performance.

Flotation of rare earth minerals from silicate–hematite ore using tall oil fatty acid collector

The flotation of rare earth (RE) minerals (i.e. xenotime, monazite-(Nd), RE carbonate mineral) from an ore consisting mainly of silicate minerals (i.e. primary silicate minerals and nontronite clay) and hematite was investigated using tall oil fatty acids (Aero 704, Sylfat FA2) as collector. The RE minerals are enriched with Fe. The effects of tall oil fatty acid dosage, pH, temperature, and conventional depressants (sodium lignin sulfonate, sodium metasilicate, sodium fluoride, sodium metasilicate and sodium fluoride, and soluble starch) were determined at grinding size of P80=63μm. At this grinding size, the grain size of the RE minerals ranges from 2 to 40μm, percentage liberation is 9–22%, and percentage association with nontronite and quartz is 30–35%. Results indicated that Sylfat FA2 at 22450g/t concentration was the more efficient tall oil fatty acid collector at natural pH (pH 7) to basic pH (pH 10.0–11.5). Flotation at the room temperature (25°C) gave higher selectivity than 40°C temperature flotation. The results on the effect of depressants showed similar selectivity curves against the gangues SiO2, Al2O3, and Fe2O3 suggesting that the chemical selectivity of the depressants has been limited by the incomplete liberation of the RE minerals in the feed sample. High recoveries at 76–84% (Y+Nd+Ce)2O3 but still low (Y+Nd+Ce)2O3 grade at 2.1% in the froth were obtained at flotation conditions of 63μm, 25°C, pH 10.5, 1,875g/ton sodium metasilicate and 525g/ton sodium fluoride or 250g/ton soluble starch as depressant for the silicates and hematite, and 22,450g/t Sylfat FA2 as collector for the RE minerals (initial (Y+Nd+Ce)2O3 feed grade=0.77%). The recoveries of gangue SiO2, Al2O3, and Fe2O3 in the froth were low at 25–30%, 30–37%, and 30–36%, respectively. The mineralogical analysis of a high grade froth and its corresponding tailing product showed that the RE minerals have been concentrated in the froth while the primary silicate minerals and hematite have been relatively concentrated in the tailing. However, the clay minerals, primary silicate minerals, and hematite still occupy the bulk content of the froth. This suggests that incomplete liberation of the RE minerals led to the poor grade result, supporting likewise the selectivity curve results by the different depressants. This study showed that liberation is important in achieving selective separation.

Review and experimental study on pyrolysis and hydrothermal liquefaction of microalgae for biofuel production

Advanced Biofuels steadily developed during recent year, with several highly innovative processes and technologies explored at various scales: among these, lignocellulosic ethanol and CTO (Crude Tall Oil)-biofuel technologies already achieved early-commercial status, while hydrotreating of vegetable oils is today fully commercial, with almost 3.5Mt/y installed capacity worldwide. In this context, microalgae grown in salt-water and arid areas represent a promising sustainable chain for advanced biofuel production but, at the same time, they also represent a considerable challenge. Processing microalgae in an economic way into a viable and sustainable liquid biofuel (a low-cost mass-product) is not trivial. So far, the most studied microalgae-based biofuel chain is composed by microorganism cultivation, lipid accumulation, oil extraction, co-product valorization, and algae oil conversion through conventional esterification into Fatty Acids Methyl Esters (FAME), i.e. Biodiesel, or Hydrotreated Esters and Fatty Acids (HEFA), the latter representing a very high quality drop-in biofuel (suitable either for road transport or for aviation). However, extracting the algae oil at low cost and industrial scale is not yet a mature process, and there is not yet industrial production of algae-biofuel from these two lipid-based chains. Another option can however be considered: processing the algae through dedicated thermochemical reactors into advanced biofuels, thus approaching the downstream processing of algae in a completely different way than separation. The present work examines the possible routes for thermochemical conversion of microalgae into liquid biofuels, distinguishing between dry-processes (namely Pyrolysis, PO) and wet-processes (near critical-water HydroThermal Liquefaction, HTL). A literature review on algae-HTL was carried out, distinguishing between batch and continuous experiments, and compared to original results from algae pyrolysis. In particular, pyrolysis was carried out on both starved (lipid-accumulated) and non-starved microalgae. Typical composition of major products is given for both PO and HTL, comparing the main characteristic of the products.Major engineering advantages and challenges in thermochemical conversion of algae into liquid biofuels were identified and discussed for both processes, in view of the production of a transport biofuel and the full exploitation of this renewable feedstock in energy and biorefinery complexes.

Sub/supercritical water oxidation of high concentration wastewater from tall oil rosin production base

The sub/supercritical water oxidation (SCWO) of wastewater with high concentrations of pollutants from tall oil rosin production base was studied under the temperature range of 320°C–420°C and the pressure range of 11–25 MPa. The results showed that after pretreatment with Ca(OH)2 for ions removal, around 385 mg/L remained which inhibited the oxidation activity by reducing the concentration of hydroxyl radicals (•OH). Since the wastewater compounds were mainly cyclic organic materials, higher O2 contents (stoichiometric ratio over 2.5) and temperatures (over 380°C) are favorable for TOC removal. With O2 SR = 2.5 and T = 420°C, the TOC removal reached almost 100% (99.89%) in 30 min. A global kinetic model for TOC removal during SCWO treatment was built during the research. The kinetic data acquired through the model were fitted to a power‐law function, and the data correlated well with the experimental data. © 2016 American Institute of Chemical Engineers Environ Prog, 35: 975–981, 2016

Effect of weathering on wood treated with tall oil combined with some additives

Growing interest on bio-based material has led to focus on environmentally benign wood treatment systems because of the environmental concerns. Tall oil is a by-product from pulp and paper industry, contains resin and fatty acids, and is biodegradable. Tall oil treated wood can provide some reduction in water uptake and increase in decay resistance. In this research crude tall oil was dissolved in ethanol at 5, 10 and 15 % concentrations in the treatment of Scots pine according to full cell process. Dyestuff, iron oxide and sodium ascorbate were used an additive as 0,5 %. Weathering performance of tall oil and tall oil combined with additives were investigated in accelerated weathering chamber by application of ultraviolet irradiation and water spray. It is taken for granted that increasing concentration results in higher weight percent gain in treated samples. The best results were obtained with 10 % tall oil and iron oxide which indicated minimum total color changes. Colour measurements and visual examination revealed that iron oxide was the most effective additive in reducing weathering effect and lowering the total colour change.

Dimensional stabilization of wood treated with tall oil dissolved in different solvents

Many water repellents, such as classic wood preservatives have the disadvantage of being harmful to the environment. Therefore, interest increased even eco-friendly, or of biodegradable material. Natural oils (tallow, linseed oil), appears to be capable of preventing the wood water uptake. However, the total amount of oil required to achieve a high penetration of the sapwood. The aim of this study was to investigate the water repellent efficiency of tall oil dissolved in different solvents. As solvents ethanol, methanol, acetone and tall oil water emulsions were used. Scots pine and Uludag fir sapwood samples were impregnated with tall oil formulations. For this purpose we used tall oil/solvents (W/W) at the concentrations of 10% and 20% respectively. Test samples cut into small sizes (20 x 20 x 10 ± 0,2 mm) for water uptake and tangential swelling tests. The tests were carried out based on American Wood Protection Association (AWPA) standard E4 (2003).

Effect of melamine phosphate on the thermal stability and flammability of bio-based polyurethanes

The effect of melamine phosphate (MP) on the thermal stability of bio-based polyurethane and the flammability parameters of wood samples with polyurethane coatings was studied. Thermogravimetric analysis and cone calorimeter test at a heat flux of 35 kW/m2 were used for this purpose. The main characteristics of the thermal stability and flammability of the coating with addition of MP were compared with the characteristics of analogous coatings with addition of ammonium polyphosphate (APP), as well as APP in combination with melamine. It was found that the use of MP as an intumescent additive allows a considerable decrease of most of the flammability parameters of the polyurethane based on tall oil fatty acids, like APP. To reach the maximum effect, it is enough to load in the polyurethane 20% of MP. In contrast to APP, MP reduces also the smoke release of the samples. Using MP in combination with APP at definite weight ratios, it is possible to essentially reduce the flammability parameters of polyurethane coatings, such as PHRR, THR and MARHE.

ВЗАИМОДЕЙСТВИЕ СУЛЬФИДА НАТРИЯ И ОКТАДЕКАНТИОЛА С СОЛЯМИ СМОЛЯНЫХ И НЕПРЕДЕЛЬНЫХ ЖИРНЫХ КИСЛОТ

In order to study attachment of hydrogen sulfide and methyl mercaptan to the double bonds of unsaturated fatty acids and rosin acids during kraft pulping and isolation The interaction sulfate soap and sodium oleate, sodium salts of resin acids from gum rosin aqueous-alkaline solution of sodium sulphide and 1-oktadekantiola at 160-165 °С. The formation of organic sulfides and thiols due to hydrogen sulfide and oktadekantiola connection respectively to the double bonds of the fatty acids and resin does not occur. It has been found that the washing-treatment of the reaction mass saline alkaline solution (sodium chloride + sodium hydroxide) containing copper metal after reaction with sodium sulfide or 1 oktadekantiolom prevents residual connection thiol and hydrogen sulfide to the double bonds of fatty and rosin acids by treatment 30% aqueous sulfuric acid. Maximum total sulfur content measured by two methods (energy dispersive x-ray fluorescence spectroscopy and UV-oxidation products of the high temperature), in this case in the final products of interaction of sodium oleate and sodium salts of rosin acids, sulfur compounds was 55 ppm. Known patterns may be used in the preparation of sulfate soap and tall oil and its fractions (fatty acids, rosin, pitch) with a low total sulfur content, which will expand the field of their application.

Rheological properties of inverse emulsions stabilized by ethanolamides of tall oil fatty acids

The paper presents the comparative analysis of inverse emulsion rheological behavior stabilized by monoethanolamide and diethanolamide of tall oil fatty acids, which are promising reagents for petroleum engineering. Flow curves of emulsions and volume ratio of dispersed phase have been obtained. The analysis of the dependence of Herschel–Bulkley model parameters on concentration of emulsifiers has been carried out. It is proved that emulsifiers affect weakly on the rheological parameters in high water phase content emulsions, while in cut-back emulsions their impact is registered to be stronger. It has been found that rheological parameters of the emulsions stabilized by monoethanolamide throughout the range of concentration are considerably higher than the samples on the base of diethanolamide. The experimental data proved the key impact of viscosity of dispersion medium on rheological behavior of cut-back emulsions.

Greenhouse Gas and Energy Life Cycle Assessment of Pine Chemicals Derived from Crude Tall Oil and Their Substitutes

SummaryPine chemicals are co‐products of papermaking that are upgraded into diverse products from inks to adhesives. They can also be utilized for energy purposes. This research investigates the carbon and energy life cycle assessment (LCA) of pine chemicals derived from crude tall oil (CTO). The study goals are to determine the cradle‐to‐gate carbon and energy footprint for CTO‐derived chemicals, compare CTO‐derived chemicals to their likely substitutes, and calculate the carbon and energy effects of shifting CTO resources from current chemical production to biodiesel production. The data collected represent 100% of the U.S. and 90% of the European CTO distillation industry for 2011. This analysis is the first industry‐level LCA of pine chemicals. The carbon footprint for CTO‐derived pine chemical products is 50% lower than the likely mix of alternative products, including hydrocarbon resins for rubber, ink, and adhesive, alkyl succinic anhydride for paper size, and heavy fuel oil for heat. Current and proposed European policies could result in CTO being classified as renewable biomass for energy production, creating incentive to convert CTO into fuel rather than chemicals. The differences in the carbon and energy footprints of utilizing CTO for biodiesel versus chemicals are not meaningful when comparing European CTO biodiesel, which displaces conventional diesel, to European CTO‐derived chemicals, which displace the previously discussed substitutes. Therefore, there is no additional carbon or energy benefit that accrues by diverting CTO from current chemical feedstock applications to use for biodiesel production in Europe.