Ulf Germgård

Cellulose dissolution in an alkali based solvent: influence of additives and pretreatments

The distinction between thermodynamic and kinetics in cellulose dissolution is seldom considered in the literature. Therefore, herein an attempt to discuss this topic and illustrate our hypotheses on the basis of simple experiments was made. It is well-known that cellulose can be dissolved in a aqueous sodium hydroxide (NaOH/H2O) solvent at low temperature but it is here shown that such an alkaline solvent can be considerably improved regarding solubility, stability and rheological properties as a whole if different additives (salts and amphiphilic molecules) are used in the dissolution stage. This work probes new aqueous routes to dissolve cellulose, thereby improving the potential to commercially dissolve cellulose in an inexpensive and environmentally friendly manner.

Characterisation of the undissolved residuals in CMC-solutions

The undissolved fibre and gel residuals that had not completely reacted to form fully dissolved carboxymethyl cellulose (CMC) ID the production of CMC were studied to clarify the reactivity of wood components ID the pulp. The undissolved residuals, the pulp and the CMC were therefore analysed on the fibre level, the cell-wall level and the chemical composition level. The results may be interpreted as indicating that the presence of undissolved residuals ID the CMC was not due to any chemical difference. The undissolved residuals were shown to consist mainly of swollen cell wall parts and some whole wood cells, mainly thick-walled compression wood and summerwood cells. They react more slowly ID the mercerisation and etherification, probably because of a greater diffusion resistance due to their larger dimensions or to a more dense structure. These cells are assumed to be less accessible for chemical penetration, but they may also contain supramolecular structures that slow down the CMC reaction.

Enzyme pretreatment of dissolving pulp as a way to improve the following dissolution in NaOH/ZnO

Abstract The dissolution of a softwood dissolving pulp in a NaOH/ZnO system was improved by means of a three-stage pretreatment with an initial xylanase treatment, followed by an alkaline extraction, and finally an endoglucanase stage. The solubility of the pulp increased from 29% to 81%, although the crystallinity and the specific surface area of the pulp did not change during the enzymatic treatment.

Effect of Various Pulp Properties on The Solubility of Cellulose in Sodium Hydroxide Solutions

Abstract The dissolution of pulps with varying characteristic properties, for example cellulose chain length or content of hemicellulose, has been investigated in two alkaline solvent systems [sodium hydroxide (NaOH)/urea/thiourea (8:8:6.5 by wt.) and NaOH/zince oxide (ZnO) (9:0.5 by wt.)]. One standard paper pulp, two dissolving pulps and three pretreated pulps were selected for this study. The dissolution parameters in focus were the fiber dimensions, average degree of polymerization (DP), polydispersity, water retention value and content of hemicelluloses. The solubility was not influenced by the fiber dimensions. The only significant properties, according to variable importance plot, were DP and composition of the hemicelluloses. It was also established that mass transfer effects during the dissolution stage plays an important role in the dissolution of cellulose derived from pulp fibers.

Validating continuous kraft digester kinetic models with online NIR measurements

Representative families of models for the chemical kinetics of kraft pulping taken from the literature spanning the last three decades are compared using data obtained from a series of autoclave cooks and an instrumented laboratory circulation digester. The differences within families is slight, and they reasonably explain the data with fitted parameters, and more crucially, even when using original parameters. However the Purdue model arguably fits the measured data better for the more modern cooking schemes, and has the advantage that it describes the kinetics of hemicelluloses such as arabinoxylan which are needed for for pulp property predictions.

The influence of extended mercerization on some properties of carboxymethyl cellulose (CMC)

Abstract Carboxymethyl cellulose (CMC) is produced commercially in a two stage process consisting of a mercerization stage in which the pulp is treated with alkali in a water alcohol solution and a second etherification stage whereby monochloro-acetic acid is added to the pulp slurry. In this study, the influence of the conditions of an extended mercerization stage was evaluated on the etherification stage concerning the degree of substitution (DS) and the filterability of the resulting CMC. The parameters studied were: (1) the ratio of cellulose I and cellulose II in the original pulp, (2) the concentration of alkali, (3) the temperature and (4) the retention time in the mercerization stage. The DS results indicate that the NaOH concentration in the mercerization stage is the most important among the parameters studied. When the NaOH concentration in the mercerization stage was high (27.5%), cellulose II showed a lower reactivity than cellulose I with respect to the DS obtained in the resulting CMC. The results from the filtration ability of CMC water solutions are interpreted that the amount of cellulose II in the original pulp and the temperature has a negative influence, while the NaOH concentration in the mercerization stage has a positive influence on the filtration ability. Retention time between 1 h–48 h in the mercerization stage had no effect on the DS or the filtration value. The filtration ability was assumed to be highly influenced by the presence of poorly reacted cellulose segments. The CMC samples with the lowest filtration ability at a given DS can be assumed to have the highest degree of unevenly substituted segments.

Model based kraft cooking optimisation

A recently proposed model for kraft delignification kinetics is used to generate optimum operating conditions for the production of kraft pulp. In contrast to previous models, the optimal profiles for temperature, [OH] and [HS] support the current operating practice in mill digesters. The optimisation results suggest coupling as high a [HS] as possible with a low [OH] but not below 0.2 M, at a low temperature for as long a cooking time as practical. It is also shown that the optimal [OH] conditions depends on whether the [HS] or the sulfidity is kept constant. These optimisation findings are summarised in a set of updated recommended procedures for industrial digester operation in order to maximise yield and selectivity.