EFFICIENCY OF TRADITIONAL SHOU SUGI BAN WOOD PROTECTION TECHNIQUE IN ASSOCIATION WITH VEGETABLE OILS AGAINST ROTTING FUNGI ACTION ON PINUS WOOD

The main objective of this study was to evaluate the feasibility of conversion of crude tall oil and tall oil fatty acids into biodiesel. During the Kraft pulping process, Crude Tall Oil originates as tall oil soap, which is separated from recovered black liquor. The soap is then converted to Crude Tall Oil by acidulation with sulphuric acid. The Crude Tall Oil is then fractionated by distillation to produce tall oil fatty acids (TOFA), rosin and pitch. There were a number of conversional methods that were considered but proved to be inappropriate. A base-catalyzed method was inappropriate with due to the high free fatty acid content on the feedstock, and the acid-base catalyzed method was inappropriate due to the long reaction times and large excess of methanol required. An enzyme based conversion method was also found to be inappropriate because of the high price attached to the purchasing of the enzymes and the stability of the enzyme. A procedure of choice was the supercritical methanol treatment, due to the fact that it requires no separate catalyst. A procedure was developed for both the feedstocks (i.e. crude tall oil and tall oil fatty acids) using the supercritical methanol treatment. In supercritical methanol treatment, feedstock and methanol were charged to a reactor and were subjected to temperatures and pressures beyond the critical point of methanol (Tc = 240 °C, Pc = 35 bar). The maximum biodiesel yield obtained from Crude tall oil was 66% and was 81% for the tall oil fatty acids that was produced in a single stage process. The temperature and methanol to feedstock ratio effects was also found to yield a maximum biodiesel yield at 325°C and 40:1 respectively. A 20 minutes reaction time was found to be appropriate for the maximum yield of biodiesel. The final biodiesel produced was also evaluated against a commercial biodiesel product and its parameters measured. The biodiesel resulting from the tall oil fatty acid yielded parameters that were acceptable according to ASTM D6751 specifications for biodiesel. The biodiesel produced from the crude tall oil did not meet the ASTM D6751 specification, and this was mostly attributed to the presence of unsaponifiables which hindered the conversion of oil into biodiesel.

The synthesis technology of polyol from crude deciduous tree tall oil was developed, the structure of obtained polyol was analyzed using FTIR spectroscopy. Compositions of rigid polyurethane (PUR) foams were formulated using polyol from crude deciduous tree tall oil, Isocyanate indexes varied in wide range from 150 to 300. The densities of obtained rigid polyurethane foams was in range from 44-101 kg/m3. Produced rigid PUR foams were characterized by good compression characteristics and low water absorption. The optimal water absorption was achieved at density lower than 50 kg/m3 and Isocyanate index lower than 175. Thus the obtained PUR foams have the potential to be used for boat construction or for production of life-saving equipment.

In 2011, the Swedish coastline suffered a major oil spill of about 800 tonnes of CTO (crude tall oil) from a land based tank farm on the east coast, into the Söderhamn archipelago in the brackish Baltic Sea. The impacted area exhibit a high ecological value and is frequently used for outdoor recreation and a large number of private properties. There are very few incidents reported on CTO spills. CTO is a viscous yellow-black odorous liquid obtained as a by-product in the kraft pulping process. Sometimes the general notion is that it is harmless to the environment since it origins from coniferous trees. The name originated as an anglicization of the Swedish “tallolja” (“pine oil”).Tall oil is the third largest chemical by-product in a Kraft mill after lignin and hemicellulose. Although CTO is less harmful compared to mineral oil, release of CTO, especially large quantities, may also cause severe environmental damage to aquatic systems and to impacted shores. CTO may also cause allergic reactions to humans and mammals. The shores of the Söderhamn Bay consist mainly of rocky beaches, large rocks as well as very small pebble stones. Since the oil also got into jetties, the entire clean-up process has been difficult and time consuming, also due to the cold weather conditions in the north. Remediation of the shores and stone coffins, inside the jetties, has been made through manual labor. The impacts to the bird population were minimal since most birds had migrated for the winter. The incident happened during late fall, when the biological activity in marine organisms is low; hence low impact on the marine organism's active reproductive periods. In Söderhamn, fatty acids, recin acids and sterols have been sampled in sediments, fish muscle, and mussels. Limited impact could be noted, however, established test methods are missing for CTO. Degradation time of the CTO was longer than expected. Extensive and hardcore cleanup usually causes more damage to nature; removal of important microorganisms, increased soil erosion and diminishes the possibilities for the vegetation recovery. It is crucial to start the communication process with public and property owners as early as possible to set expectations on “how clean is clean”. The clean-up process in Söderhamn has been very successful and is coming to an end in the spring of 2016. The status and conclusions after five years of remedial actions will be presented.

The primary objective of this work was to investigate the thermal and rheological properties of crude tall oil (CTO), a low-cost by-product from the Kraft pulping process, as a potential feedstock for biodiesel production. Adequate knowledge of CTO properties is a prerequisite for the optimal design of a cost-effective biodiesel process and related processing equipment. The study revealed the correlation between the physicochemical properties, thermal, and rheological behavior of CTO. It was established that the trans/esterification temperature for CTO was greater than the temperature at which viscosity of CTO entered a steady-state. This information is useful in the selection of appropriate agitation conditions for optimal biodiesel production from CTO. The point of interception of storage modulus (G′) and loss modulus (G′′) determined the glass transition temperature (40 °C) of CTO that strongly correlated with its melting point (35.3 °C). The flow pattern of CTO was modeled as a non-Newtonian fluid. Furthermore, due to the high content of fatty acids (FA) in CTO, it is recommended to first reduce the FA level by acid catalyzed methanolysis prior to alkali treatment, or alternatively apply a one-step heterogeneous or enzymatic trans/esterification of CTO for high-yield biodiesel production.

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

It is believed that several global policies incentivising the energetic utilisation of Crude Tall Oil (CTO) might have had an impact on the demand for CTO from its competing and emerging end-use application in biofuels in the recent years. Hence, this study performed a methodological and structural analysis of the global CTO chain to assess the availability of the CTO (supply) and its demand in the respective end-use markets globally. The overarching goal was to examine whether market distortions occur when CTO is diverted from its historical utilisation in the production of bio-chemicals to the production of biofuels. The methodology consisted of collecting and analysing primary data from currently operating as well as upcoming softwood kraft pulp mills, CTO fractionators and refiners. Additionally, present day as well as upcoming CTO-based biofuel capacities were also collected. The geographical scope covered the following five regions: (1) North America, (2) Europe, (3) Russian region and the common wealth of independent states (CIS) (4) South America (5) Rest of the World. The analysis shows that since 2009 there is a steady rise in the global CTO supply, with a 16% increase in supply until 2018 compared to 2009 levels, with supply and demand in balance. However, this balance is expected to shift after the year 2020, where a tipping point could be reached, since the global CTO demand may exceed the global CTO supply for the first time. This shift in balance can primarily be attributed to the continuously growing demand for biofuels (capacity expansions and new capacities), and will – at least on short term – be reflective of the European legislation and its national implementation by member states. In particular, the estimations project a supply deficit of CTO of 0.6% in 2020. This deficit will rise to 8% or 0.18 million tonnes by 2030 globally, and is driven primarily by the increase in demand for CTO-based biofuels for transportation. The supply-demand imbalance for CTO might grow further unless alternative raw materials become available or corrective legislative measures are taken.

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.

Quantifying the impact of cascading use: A comparative integrated assessment of the European pine chemicals industry

A new polymer composite material based on furfural-acetone monomer, crude tall oil and its fatty acids, which are waste from the pulp and paper industry, was obtained. In this paper, the effect of crude tall oil and its fatty acids on furfural-acetone monomer binder in a composite material is considered. The composition for the composite material, consisting of FA monomer, filler and catalyst p-toluenesulfonic acid, was modified with crude tall oil additives or tall oil fatty acids. It was shown that the compressive strength of composite samples after 30-day exposure at room temperature, obtained with a reduced amount of furfural-acetone monomer and the introduction of 100% fatty acids of tall oil from the furfural-acetone monomer content, increases by 37%, with the introduction of 150% fatty acids of tall oil, the strength increases slightly - by 1.5%, but the density increases significantly and water absorption decreases with respect to the standard sample. Additives of crude tall oil (up to 150% of furfural-acetone monomer) lead to an increase in density, a decrease in water absorption - by 84%, but reduce the compressive strength of samples by 12%. The improvement in the physicochemical properties of the composite material was explained by the alleged chemical interaction of tall oil fatty acids with mono- and difurfurilideneneacetone (furfural-acetone monomer), which takes place with the formation of new polymers. This is confirmed by DTA data, chromatograms of the furfural-acetone monomer - fatty acids of tall oil (TLC) mixture, and IR spectra. The use of fatty acids of tall oil or crude tall oil, non-expensive, non-toxic products of natural origin in the composite material, can reduce the consumption rates of furfural-acetone monomer and improve the quality of the polymer.

About 1949, with the advent of effective fractional distillation, the tall oil industry came of age, and tall oil fatty acids (TOFA), generally any product containing 90% or more fatty acids and 10% or less of rosin, have grown in annual volume ever since, until they amount to 398.8 million pounds annual production in the U.S. in 1978. Crude tall oil is a byproduct of the Kraft process for producing wood pulp from pine wood. Crude tall oil is about 50% fatty acids and 40% rosin acids, the remainder unsaps and residues; actually, a national average recovery of about 1–2% of tall oil is obtained from wood. On a pulp basis, each ton of pulp affords 140–220 pounds black liquor soaps, which yields 70–110 pounds crude tall oil, yielding 30–50 pounds of TOFA. Separative and upgrading technology involves: (a) recovery of the tall oil; (b) acid refining; (c) fractionation of tall oil; and occasionally (d) conversion to derivatives. TOFA of good quality and color of Gardner 2 corresponds to above 97% fatty acids with the composition of 1.6% palmitic & stearic acid, 49.3% oleic acid, 45.1% linoleic acid, 1.1% miscellaneous acids, 1.2% rosin acids, and 1.7% unsaponifiables.

Crude tall oil and two of its derivatives were assessed for antifeedant and growth inhibitory effects, via incorporation into an artificial diet, in the variegated cutworm (Peridroma saucia Hübner). The substances tested are both toxic to neonate P. saucia and inhibitory to larval growth. The dietary LC50 (lethal concentration for 50% mortality) values are 4.3, 4.7, and 5.3% fresh weight for depitched tall oil (DTO), crude tall oil (CTO), and tall oil pitch (TOP), respectively. These materials significantly reduced growth, feeding, and dietary utilization by first-, second-, third-, and fourth-instar larvae in chronic larval growth bioassays, choice and no-choice feeding tests, and nutritional experiments. The EC50s (effective concentration to inhibit growth by 50% relative to controls) of DTO, CTO, and TOP were 1.4, 2.0, and ≥2.4%, respectively, when first-instar larvae fed on treated diets for 10 days. DTO significantly reduced both growth and consumption rates with corresponding reduction in the efficiency of conversion of food (i.e. nutritional efficiency), suggesting that both antifeedant and toxic effects are involved in larval growth inhibition. DTO and CTO are consistently more biologically active than TOP. Our results suggest that an environmentally sound, low cost natural pest control agent may be developed based on tall oil.

Esterification of crude tall oil catalyzed by Beta zeolite

A new process for biodiesel production from tall oil via catalytic distillation

Tall oils are a second-generation feedstock with perspective use in polyurethane materials. This study compared crude tall oil and tall oil fatty acid bio-polyols to determine whether crude tall oil could be used for polyurethane foam production making the production more cost-effective. Polyols were synthesized in a two-step process. At first, double bond epoxidation followed by oxirane ring-opening, and transesterification with multifunctional alcohols. The epoxidation process was studied with acid value and relative conversion to oxirane analysis. The obtained polyols were analyzed for acid value, hydroxyl value, viscosity, and with Fourier transform infrared spectroscopy analysis. The results showed suitable hydroxyl values for almost all polyols, including crude tall oil polyols, but the high viscosity limits the use of most of the polyols.

The resin acid composition of Finnish tall oil rosin was investigated by gas chromatography and mass spectrometry employing open tubular capillary columns. On a column coated with 1,4‐butanediol succinate, 16 resin acids found in tall oil rosin samples were well resolved, and mass spectra could be recorded. All resin acids were confirmed to be of the pimaric and abietic types by gas chromatographymass spectrometry. Eight of the acids were not detected in the corresponding crude tall oils and evidently had been formed during the technical distillation process. The presence of 8,15‐pimaradien‐18‐oic and 8,15‐isopimaradien‐18‐oic acids in the rosin, but not in the crude tall oil, indicates that the pimaric type acids also undergo extensive isomerization during tall oil distillation. Additionally, three dihydroabietic acids and two acids with identical mass spectra, tentatively stereoisomers of 7,9(11)‐abietadien‐18‐oic acid, were formed during the distillation process.