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.

Nickel (oxy)hydroxides (NiOxHy) are promising cost-effective materials that exhibit a fair catalytic activity for the ethanol oxidation reaction (EOR) and could be used for sustainable energy conversion. Doping the NiOxHy structure with other metals could lead to enhanced catalytic properties but more research needs to be done to understand the role of the doping metal on the EOR. We prepared NiOxHy films doped with Fe or Co with different metallic ratios by electrodeposition and evaluated the EOR. We found a positive and negative effect on the catalytic activity after the incorporation of Co and Fe, respectively. Our results suggest that Ni atoms are the active sites for the EOR since Tafel slopes were similar on the binary and pristine nickel (oxy)hydroxides and that the formal potential of the Ni(II)/Ni(III) redox couple is a good descriptor for the EOR activity. This work also highlights the importance of controlled metal doping on catalysts and may help in the design and development of improved materials for the EOR.

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.

The characteristics of two novel types of technical lignin, namely Ecohelix (EH) and CleanFlow black lignin (CFBL), isolated from two different pulping process side streams, were analyzed. EH and CFBL were analyzed in terms of general composition, chemical functionalities, molar mass distribution, and thermal stability. For comparison, two relevant types of commercially available lignosulfonate and kraft lignin were used. The results showed that EH contains a large amount of sulfonated lignin, together with carbohydrates and ash. As such, it can be considered a lignin-carbohydrate hybrid molecule. CFBL was found to contain 91.5% Klason lignin and the lowest amount of carbohydrates (0.3%). EH showed the highest content of aliphatic OH groups (5.44 mmol/g) and CFBL a high content of phenols (4.73 mmol/g). EH had a molecular weight of 31.4 kDa and a sufficient thermal stability. CFBL had the lowest molecular weight (M-w = 2.0 kDa) and thermal stability of all kraft lignins analyzed in this study. These properties highlighted that EH is a suitable building block for material development and that CFBL is a promising material for the production of biofuel and biochemicals.

To investigate the dispersibility of dried cellulose nanofibers (CNFs), various additions (glycerol, octanol, glycol, and sodium perchlorate) were added to CNFs prior to drying. Glycerol was the only species to show any significant effect on re-dispersibility. The sedimentation was slower, and the transmittance of the solution was comparable to that of its undried counterpart. Increasing the amount of glycerol showed a clear trend with regard to dispersibility. The mechanical properties of films were maintained for samples that were dried and redispersed in the presence of glycerol.

A series of optically transparent composites were made by using tunicate cellulose membranes, in which the naturally organized cellulose microfibrillar network structure of tunicate tunics was preserved and used as the template and a solution of glycerol and citric acid at different molar ratios was used as the matrix. Polymerization through ester bond formation occurred at elevated temperatures without any catalyst, and water was released as the only byproduct. The obtained composites had a uniform and dense structure. Thus, the produced glycerol citrate polyester improved the transparency of the tunicate cellulose membrane while the cellulose membrane provided rigidity and strength to the prepared composite. The interaction between cellulose and polyester afforded the composites high thermal stability. Additionally, the composites were optically transparent and their shape, strength, and flexibility were adjustable by varying the formulation and reaction conditions. These composites of cellulose, glycerol, and citric acid are renewable and biocompatible and have many potential applications as structural materials in packaging, flexible displays, and solar cells.