The purpose of this
study was to investigate the use of organosolv
lignin as a sizing agent for thermoformed pulp products as a sustainable
material with improved water resistance. For this purpose, an in-house-produced
organosolv lignin from softwood (Norway Spruce) was mixed with bleached
and unbleached chemi-thermomechanical pulp fibers. In addition, the
isolated organosolv lignin was characterized by ATR–FTIR spectroscopy,
size-exclusion chromatography, and thermogravimetric analysis. The
analysis showed that organosolv lignin was of a high purity and practically
ash-free, exhibiting low molecular weight, a glass transition temperature
below the thermoforming temperature, and a high content of phenolic
OH groups. The mechanical properties and water resistance of the organosolv
lignin-sized thermoformed pulp materials were measured. A small decrease
in strength and an increase in stiffness and density were observed
for the lignin-sized thermoformed materials compared to the reference,
that is, unsized materials. The addition of organosolv lignin decreased
the wettability and swelling of the thermoformed product. These results
are due to the distribution of organosolv lignin on the surface, filling
in the pores and cavities, and providing a tighter fit within the
thermoformed materials. In conclusion, the results from our study
encourage the use of organosolv lignin as a sizing additive to thermoformed
products, which can improve the water resistance to use it in sustainable
packaging applications.
The H-factor, a parameter used extensively to analyze and predict the outcome of kraft pulping, is applied to organosolv pretreatment. The total solid yield after organosolv pretreatment fits well with the H-factor. The concept has been extended to apply to the individual biomass polymers using unique values for the activation energy for the depolymerization of the individual biomass polymers, giving the O-factor concept analogous to the P factor used for analyzing prehydrolysis kinetics. The results showed a linear relationship between ln(L0/L) and O-factor at an activation energy of 96 kJ/mol. The best linear fit for mannan and xylan degradation was obtained at O-factor activation energies of 104 kJ/mol and 142 kJ/mol, respectively, and the formation of furfural and 5-HMF gave a good linear fit using an O-factor activation energy of 150 kJ/mol. The O-factor is thus a useful concept for analyzing organosolv pretreatment when the temperature during pretreatment is not constant.
Removal of extractives from the pulp furnish is of great importance for the improvement of paper machine efficiency and also for reducing the energy consumption during the thermomechanical pulp refining process. Extractives can exist in many different forms in the process water; as colloidal particles, dissolved or attached to fines and fibres. It is therefore important to know in which form they exist in order to fully understand their behaviour. In this paper, we report on an evaluation of the removal of extractives released from chips of different raw materials pre-treated in an Impressafiner, in pilot and in mill scale. In pilot trial the raw materials used were loblolly pine and white spruce and in the mil scale trial the raw material used was norway spruce. The colloidal stability of extractives present in the pressate water from the Impressafiner and their flocculation behaviour by cationic polymers (CPAM and Poly-DADMAC) under different conditions was also investigated. Calculations of mass balances around an Impressafiner showed that it was possible to remove up to 40% of extractives before the refining process. The reduction in total extractives content was mainly due to released resin acids while fatty acids, triglycerides, steryl esters and sterols to a large extent remained in the wood chips after pre-treatment. The removal of extractives from pine was four times higher than from spruce chips. The results can be explained in terms of the extractive composition in the raw material and the morphological differences in the wood structure.
The redeposition of lignin to the fiber surface after organosolv pretreatment was studied using two different reactor types. Results from the conventional autoclave reactor suggest that redeposition occurs during the cooling down stage. Redeposited particles appeared to be spherical in shape. The size and population density of the particles depends on the concentration of organosolv lignin in the cooking liquor, which is consistent with the hypothesis that reprecipitation of lignin occurs when the system is cooled down. The use of a displacement reactor showed that displacing the spent cooking liquor with fresh cooking liquor helps in reducing the redeposition and the inclusion of a washing stage with fresh cooking liquor reduced the reprecipitation of lignin, particularly on the outer fiber surfaces. Redeposition of lignin was still observed on regions that were less accessible to washing liquid, such as fiber lumens, suggesting that complete prevention of redeposition was not achieved.
In this article, we explored solvents with lower harmfulness than established systems for UV spectrophotometry of lignin. By measuring the absorptivity in DMSO solvent at 280 nm, the purity of the lignin samples was addressed and compared with Klason and acid-soluble lignin. The general trend was an increasing absorptivity with increasing lignin purity; however, considerable scattering was observed around the sample mean. The Hansen solubility parameter (HSP) of four technical lignins was furthermore determined. The model was in line with the UV measurements, as solvents closer in HSP correlated with a higher absorptivity. Ethylene glycol was identified as a good solvent for lignin with low UV-cutoff. In addition, mixtures of propylene carbonate, water, and ethanol showed good suitability and a low cutoff of 215 nm. While DMSO itself was poorly suited for recording alkali spectra, blending DMSO with water showed great potential. Comparing three methods for determining phenolic hydroxyl units by UV spectrophotometry showed some discrepancies between different procedures and solvents. It appeared that the calibrations established with lignin model compounds may not be fully representative of the lignin macromolecule. More importantly, the ionization difference spectra were highly affected by the solvent of choice, even when using what are considered "good" solvents. At last, a statistical comparison was made to identify the most suitable solvent and method, and the solvent systems were critically discussed. We thus conclude that several solvents were identified, which are less harmful than established systems, and that the solubility of lignin in these is a crucial point to address when conducting UV spectrophotometry.
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