Tall oil is a valuable byproduct in chemical pulping of wood, and its fractions have a large spectrum of applications as chemical precursors, detergents, and fuel. High recovery of tall oil is important for the economic and environmental profile of chemical pulp mills. The purpose of this study was to investigate critical parameters of tall oil separation from black liquor. To investigate this in a controlled way, we developed a model test system using a "synthetic" black liquor (active cooking chemicals OH- and HS- ions), a complete process for soap skimming, and determination of recovered tall oil based on solvent extraction and colorimetric analysis, with good reproducibility. We used the developed system to study the effect of the ratio of fatty acids to rosin acids on tall oil separation. When high amounts of rosin acids were present, tall oil recovery was low, while high content of fatty acids above 60% significantly promoted tall oil separation. Therefore, manipulating the content of fatty acids in black liquor before the soap skimming step can significantly affect the tall oil solubility, and hence its separation. The findings open up chemical ways to improve the tall oil yield. Application: Controlling the ratio of fatty acids to rosin acids in kraft pulping can significantly affect the tall oil separation and improve its yield and quality.

Efficient sorbents for the removal of cationic dye were prepared from sugarcane bagasse (stalk) and straw (leaves) by oxidative pre-treatment with hydrogen peroxide (H2O2) in acetic acid. The effects of variables, such as concentration of H2O2, temperature and time on the properties of the fiber sorbents obtained were studied according to a 2(3) full-factorial design. For comparison, an oxidative treatment of sugarcane biomass with glacial acetic acid was also used. The yields of the materials obtained and their chemical composition were characterized and compared. Fourier transform infrared spectroscopy, field-emission scanning electron microscopy and benzene vapor adsorption were used to investigate the structural properties and morphology of the initial materials and sorbents. The sorption of methylene blue dye was used to assess the efficiency of dye removal by the sorbents. The pre-treatment conditions significantly affected the sorbent yield, their chemical composition (contents of cellulose, lignin and ash) as well as their sorption properties. The cellulosic sorbent (C-sorbent) from sugarcane bagasse obtained by pre-treatment with H2O2 in acetic acid and the lignocellulosic sorbent (LC-sorbent) from sugarcane straw obtained by pre-treatment with glacial acetic acid, had the highest sorption capacity for the methylene blue dye. For both types of sorbents, the sorption capacity increased with chemical pretreatment as a result of an increase in pore volume.

This paper investigated the impact of the amounts of lignin and hemicelluloses on cellulose nanofibers (CNFs). Birch and spruce wood were used to prepare holocellulose and cellulose samples by classical methods. To better assess the effect of the chemical composition on the CNF performance and simplify the process for CNF preparation, no surface derivatization method was applied for CNF preparation. Increased amounts of hemicelluloses, especially mannans, improved the defibration process, the stability of the CNFs and the mechanical properties, whereas the residual lignin content had no significant effect on these factors. On the other hand, high lignin content turned spruce nanopapers yellowish and, together with hemicelluloses, reduced the strain-at-break values. Finally, when no surface derivatization was applied to holocellulose and cellulose samples before defibration, the controlled preservation of residual lignin and hemicelluloses on the CNFs indicate to be crucial for the process. This simplified method of CNF preparation presents great potential for forest-based industries as a way to use forestry waste (e.g., branches, stumps, and sawdust) to produce CNFs and, consequently, diversify the product range and reach new markets.

This work summarizes the impact of solvent fractionation on the chemical structure, antioxidant activity, heating values, and thermal and adsorption properties of industrial hardwood and softwood kraft lignins. The aim of the research was to develop a simple approach for obtaining lignin fractions with tailored properties for applications in certain materials. Four common industrial solvents, namely, ethyl acetate, ethanol, methanol and acetone, in various combinations, were found to be efficient for separating spruce and eucalyptus kraft lignins into fractions with low polydispersities. The ethanol fraction of spruce and the ethyl acetate fraction of eucalyptus afforded the highest yields. Gel-permeation chromatography analysis was used to evaluate the efficiency of the chosen solvent combination for lignin fractionation. The composition and structure of the lignin material was characterized by elemental analysis, analytical pyrolysis (Py-GC/MS/FID) and P-31 NMR spectro-scopy. The thermal properties of the lignin samples were studied using thermogravimetric analysis. Proximate analysis data (ash, volatile components, organic matter and fixed carbon) was obtained through the direct measurement of weight changes in each experimental curve, and the high heating values (in MJ/kg) were calculated according to equations suggested in the literature. The adsorption properties of fractionated kraft lignins were studied using methylene blue dye. The correlations observed between molecular weight, composition and functionality and the thermal, radical scavenging and adsorption properties of the lignin fractions provides useful information for selecting the appropriate solvent combinations for specific applications of lignin raw materials (including their use as antioxidants, biofuels or sorbents in water treatment processes).

The exact mechanism behind the disintegration of chemical pulp fiber into cellulose nanofibers is poorly understood. In this study, samples were subjected to various homogenization cycles, indicating that the mechanism is a stepwise process. In the earlier stages of the mechanical process, a large amount of macrofibrils were created as the larger structures disappeared. Upon mechanical treatment these macrofibrils disappeared despite the increasing yield of cellulose nanofibers. The proposed model expands the understanding of the disintegration pathway and may provide additional insight as to how wood cells are converted into microfibrils.

Tall oil is one of the most valuable by products in chemical pulpingof wood and is considered an important renewable alternative to petroleum.Its fractions have a large spectrum of applications including chemicalprecursors, detergents and energy. High recovery of tall oil is important forthe economic, sustainability, and environmental profile of industrial chemicalpulping. The purpose of this study was to develop ways to increase the yieldof tall oil based on its solubility in black liquors.To investigate this in a controlled way, a model system with a “synthetic”black liquor and a complete methodology for soap skimming anddetermination of recovered tall oil was developed based on solvent extractionand colorimetric analysis with good reproducibility. This model system allowsinvestigations of different parameters in small scale with high control overdifferent conditions.The developed system was used to study the effect of fatty acid addition andthe effect of lignin content on improving tall oil recovery. The presence ofrosin acids in the black liquor significantly reduced soap separation, whileincreasing the fatty acid content up to 60-70% greatly improved soaprecovery. Addition of lignin reduced tall oil recovery in the case of liquors withmore than 50% fatty acids, but slightly increased recovery in liquors withmore than 50% rosin acids. Furthermore, the presence of some ligninseemed to promote separation of the tall oil (reduced its solubility), while highamounts led to inhibition of its recovery.The experimental results clearly indicated that manipulating the content offatty acids and/or lignin before the soap skimming step significantly affect thetall oil solubility, opening up for chemical ways to improve its recovery.However, experiments in real industrial liquors and pulp mill conditions shouldbe considered to assess the actual tall oil yield improvement and processeconomics.

Lignin fractions having different molecular weights and varied chemical structures isolated from kraft lignins of both softwood and hardwood via a sequential solvent fractionation technique were incorporated into a tunicate cellulose nanofibers (CNF)-starch mixture to prepare 100% bio-based composite films. The aim was to investigate the impact of lignin structural diversity on film performance. It was confirmed that lignin's distribution in the films was dependent on the polarity of solvents used for fractionation (acetone > methanol > ethanol > ethyl acetate) and influenced the optical properties of the films. The -OH group content and molecular weight of lignin were positively related to film density. In general, the addition of lignin fractions led to decrease in thermal stability and increase in Young's modulus of the composite films. The modulus of the films was found to decrease as the molecular weight of lignin increased, and a higher amount of carboxyl and phenolic -OH groups in the lignin fraction resulted in films with higher stiffness. The thermal analysis showed higher char content formation for lignin-containing films in a nitrogen atmosphere with increased molecular weight. In an oxygen atmosphere, the phenol content, saturated side chains and short chain structures of lignin had impacts on the maximum decomposition temperature of the films, confirming the relationship between the chemical structure of lignin and thermo-oxidative stability of the corresponding film. This study addresses the importance of lignin diversities on composite film performance, which could be helpful for tailoring lignin's applications in bio-based materials based on their specific characteristics.