Sulfur-free dissolving pulps and their application for viscose and lyocell

In this study, the concept of multifunctional alkaline pulping has been approved to produce high-purity and high-yield dissolving pulps. The selective removal of hemicelluloses was achieved by either water autohydrolysis (PH) or alkaline extraction (E) both applied as pre-treatments prior to cooking. Alternatively, hemicelluloses were isolated after oxygen delignification in a process step denoted as cold caustic extraction (CCE). Eucalyptus globulus wood chips were used as the raw material for kraft and soda-AQ pulping. In all process modifications sulfur was successfully replaced by anthraquinone. By these modifications purified dissolving pulps were subjected to TCF bleaching and comprehensive viscose and lyocell application tests. All pulps met the specifications for dissolving pulps. Further more, CCE-pulps showed a significantly higher yield after final bleaching. Morphological changes such as ultrastructure of the preserved outer cell wall layers, specific surface area and lateral fibril aggregate dimension correlated with the reduced reactivity towards regular viscose processing. The residual xylan after alkali purification depicted a lower content of functional groups and a higher molecular weight and was obviously entrapped in the cellulose fibril aggregates which render the hemicelluloses more resistant to steeping in the standard viscose process. Simultaneously, the supramolecular structure of the cellulose is partly converted from cellulose I to cellulose II by the alkaline purification step which did not influence the pulps reactivity significantly. Nevertheless, these differences in pulp parameters did not affect the lyocell process due to the outstanding solubility of the pulps in NMMO. Laboratory spinning revealed good fiber strength for both, regular viscose and lyocell fibers. The high molecular weight xylan of the CCE-treated pulps even took part in fiber forming.     

Reactivity of dissolving pulps modified by TEMPO-mediated oxidation

The reactivity of dissolving pulps towards derivatization or dissolution is a crucial quality parameter and is mainly determined by the accessibility of the hydroxyl groups. When dissolving pulps are produced from paper-grade pulps by cold caustic extraction (CCE), their reactivity is often inferior as compared to commercial prehydrolysis kraft dissolving pulps. It was hypothesized that pulp reactivity can be enhanced by the introduction of small amounts of substituents to facilitate interchain accessibility. In this study, CCE-treated Eucalyptus globulus kraft paper pulp was subjected to TEMPO-mediated oxidation to initiate partial oxidation of the C₆-hydroxyl groups to carboxyl groups. The effect of this pulp modification on the reactivity towards xanthation and the subsequent dissolution in diluted aqueous alkali solution (viscose process) as well as the dissolution in complexing and non-complexing solvents, respectively, was thoroughly examined. The results revealed that the oxidized pulps rich in C₆-carboxylate groups impeded the xanthation reaction obviously because of the reduced availability of hydroxyl groups. When N-methylmorpholine-N-oxide monohydrate was used as a direct solvent, a very high content of C₆-carboxylate groups was found to reduce the solubility of the pulp fibers as less hydrogen bonds can be formed with NMMO·H₂O. In the case of dissolution in the complexing solvent cupriethylenediamine, the dissolution mechanism of cellulose was not deteriorated by the high content of C₆-carboxylate groups. Instead, the oxidation procedure increased the hydrophilic character and the swelling capacity of the outer cell wall layers allowed homogeneous dissolution.     

SO2–ethanol–water (SEW) fractionation process: production of dissolving pulp from spruce

SO₂–ethanol–water (SEW) fractionation process is a highly attractive platform for future lignocellulosic Biorefineries. Its governing advantages include high flexibility in the selection of the raw material, simple and efficient recovery of fractionation chemicals, absence of carbohydrate degradation (both cellulose and hemicelluloses), and high reaction rates. The process is suitable for production of various carbohydrate- and lignin-based products including papermaking pulp, glucose, bioalcohols and lignosulfonates. The present paper addresses the possibility of producing dissolving pulp from spruce using SEW fractionation followed by ECF bleaching with and without hot caustic extraction. Comprehensive characterisation of chemical and macromolecular properties of the SEW dissolving pulps was complemented by determining the quality of viscose. The comparison with conventional viscose-grade acid sulfite pulps revealed close proximity in all properties. Therefore, considering the advantages of SEW process, it is suggested as a possible replacement for acid sulfite process in dissolving pulp manufacturing.     

Reactivity of dissolving pulp: characterisation using chemical properties, NMR spectroscopy and multivariate data analysis

The reactivity of dissolving pulp was experimentally determined in termsof residual cellulose in viscose. The correlations between 11 chemicalproperties of pulp and filter values and residual cellulose contents of viscosewere then investigated by multivariate data analysis. Both the viscose filtervalue and the residual cellulose were well modelled from the 11 propertiesby partial least squares regression. The results show that pulps with highacetone extractable fractions, high magnesium contents, low alkali resistanceand low viscosity, gave low viscose filter values and low residual cellulosecontents. Pulps with low residual cellulose contents also had low carboxylgroupcontents and low polydispersity. The results are interpreted as that in pulpwith high reactivity, the hemicellulose content is low and that the cellulosechains are shorter and more soluble in alkali. An explanation of the positiveeffect from the high extractive content is that the extractives facilitate thediffusion of carbon disulfide. A principal component analysis of CP/MAS¹³C-NMR spectral data of six pulp samples showed that differences inreactivity between the pulps could be explained by variations in the hydrogenbonds in the cellulose and/or changes in the glucosidic bonds. In a separatestudy electron beam processing enhanced the reactivity, i.e. lowered theresidual cellulose content, of the investigated pulps. The magnitude of theelectron dose, within the tested range (5.4–23.7 kGy), didnotseem to be important, but the reactivity within pulp sheets tended to be ratherinhomogeneous.     

13C CPMAS NMR investigations of cellulose polymorphs in different pulps

In order to obtain information about the crystallinity and polymorphs of cellulose, and the occurrence of hemicelluloses in pulp fibers, wood cellulose, bacterial cellulose, cotton linters, viscose, and celluloses in different pulps were investigated by solid state ¹³C CPMAS NMR spectroscopy. A mixed softwood kraft pulp and a dissolving-grade pulp were treated under strongly alkaline and acidic conditions and the effect on cellulose crystallinity was studied. The presence of different crystalline polymorphs of cellulose and the amounts of hemicelluloses are considered.     

Properties and treatments of pulps from recycled paper. Part II. Surface properties and crystallinity of fibers and fines

Surface properties of bleached kraft pulps were evaluated before and after recycling, and after a series of chemical treatments designed to improve and/or modify the pulp characteristics. The surface free energy characteristics of the pulps were determined using the Wilhelmy technique, and ESCA and ATR-FTIR methods were used to evaluate the chemical composition of the surfaces of the pulp fibers. In general rather small changes were noted at the fiber surfaces with recycling and chemical treatment. Recycling tended to increase the acid component and decrease the base component of the surface free energy of the pulps. This could result from exposure of carboxyl groups from hemicelluloses and/or from oxidized layers from the bleaching process. ESCA analyses also indicated increased carboxyl concentration at the surfaces of the recycled fibers. Although treatment with aqueous bases and organic solvents tended to increase the hydroxyl content on the surface of recycled pulps, the chemical treatments were not beneficial to pulp quality. AFM and SEM of fiber and fine surfaces of kraft pulps revealed that the fines fraction was altered to a much greater extent with recycling. Although recycled fibers appeared to have improved wettability, these small changes in the surface characteristics do not appear to play the dominant role in the characteristics of recycled pulps. Recycling did not change the crystallinity of whole pulps, but it increased the crystallinity of the fines fraction. The increase in the crystallinity of the fines fraction and the reduction in the water retention value (WRV) and the bulk carboxyl content (xylan) of the recycled pulps, as noted in Part I of this paper, appear to play the predominant role in determining the characteristics of recycled pulps. It appears that the loss of the hemicelluloses in the bulk of the fiber with recycling is much more important for internal fibrillation than the apparent small increase of hemicelluloses at the surface of recycled fibers.     

Novel concepts of dissolving pulp production

Herein, we report about existing and novel dissolving pulp processes providing the basis for an advanced biorefinery. The SO₂–ethanol–water (SEW) process has the potential to replace the acid sulphite process for the production of rayon-grade pulps owing to a higher flexibility in the selection of the raw material source, substantially lower cooking times, and the near absence of sugar degradation products. Special attention is paid to developments that target toward the selective and quantitative fractionation of paper-grade pulps into hemicelluloses and cellulose of highest purity. This target has been accomplished by the IONCELL process where the entire hemicellulose fraction is selectively dissolved in an ionic liquid in which the H-bond basicity and acidity are adequately adjusted by the addition of a co-solvent. At the same time, pure hemicellulose can be recovered by further addition of the co-solvent, which then acts as a non-solvent. The residual pure cellulose fraction may then enter a Lyocell process for the production of regenerated cellulose products.     

Reactivity of Dissolving Pulp for Processing Viscose

Summary : Pulp reactivity is a kinetic term and is always connected with a certain derivatization process. The quality and hence the market value of the pulp is determined by such characteristics as α- cellulose content, solubility, brightness, ash content, as well as the amount of soluble material in dichloromethane. However, solubility data, especially S₁₈ and S₁₀ values do not characterise dissolving pulp reactivity. These are indicative of pulp solubility and provide some information regarding losses of material during pulp processing. One way by which the pulp reactivity for viscose making can be characterised is the investigation of the mercerisation step. Following the mercerisation kinetics by help of the molecular weight distribution of cellulose II the behaviour especially of the high molecular weight cellulose gives information regarding the accessibility and therefore, about the reactivity of the pulp aside from losses in low molecular weight cellulose. This behaviour will be shown on different pulps and the physicochemical background will be discussed in relation to results obtained from wide angle X-ray scattering and Raman investigations. The influence of the behaviour of the pulp during mercerising on the viscose process, and the molecular weight distribution of the viscose including the distribution of the xanthogenate groups along the chain was investigated and will also be discussed.     

Hemicellulose Composition in the Outer Cell Wall Layers of Paper Grade and Dissolving Pulp

The hemicellulose content of pulp is dependent on different factors, such as the wood species, the conditions with cooking and bleaching harmonised with the application. In addition to the hemicellulose content, a special interest for the valuation of pulp and the decision of arrangements of the production process is the hemicellulose distribution across the cell wall layers and the influence of several process stages on the hemicellulose distribution across the cell wall layers. The investigations were carried out on dissolving pulp and paper grade pulp. For paper grade pulp, the influence of separate bleaching steps and several bleaching sequences on the distribution of hemicellulose across the cell wall were investigated. Regarding the selected dissolving pulps which were produced according to an acid bisulphite process and a pre-hydrolysis sulphate process the influence of the cooking process on the hemicellulose distribution across the cell wall layers was of a special interest.     

Bleachability and characterization by fourier transform infrared principal component analysis of acetosolv pulps obtained from sugarcane bagasse

Sugarcane bagasse Acetosolv pulps were bleached by xylanase and the pulps classified by using Fourier transform infrared (FTIR) spectroscopy and principal component analysis (PCA). Pulp was treated with xylanase for 4–8 h with stirring at 30°C. Some samples were further extracted with NaOH for 1 h at 65°C. FTIR spectra were recorded directly from the dried pulp samples by using the diffuse reflectance technique. Reduction in kappa number of 69% was obtained after sequence xylanase (4 h)-alkaline extraction. During bleaching the viscosity decreased only 12%. FTIR-PCA showed that the first three principal components (PCs) explained more than 90% of the total variance of the pulp spectra. PC2×PC1 plot showed that the points related to pulps from sequence xylanase (4 h)-alkaline extraction are different from the other. This group isenlarged by plotting PC3×PC1 or PC3×PC2 containing all pulps submitted to alkaline extraction. PC2 and PC3 are the principal factor for differentiation of the pulps. These PCs suffer influence of the ester bands (1740 and 1244 cm⁻¹). On the other hand, the pulps bleached only with xylanase could not be differentiated from the nonbleached pulps.     

Hemicellulose in Dissolving Pulp and its Behaviour during its Processing to Viscose

The amount of “hemicellulose” in pulps varies according to wood species, and the pulping processes including their bleaching agents. Making viscose cellulosic and non-cellulosic material is removed during mercerisation which is the first processing step. Low molecular weight material is also formed during the reduction of the degree of polymerisation in order to fit the alkali cellulose for xanthation and dissolving, respectively. In this work commercially available dissolving pulps with respect to their behaviour during the preparation of viscose fibres shall be discussed. For these investigations a Eucalyptus sulphite and a Eucalyptus pre- hydrolysed sulphate pulps were selected.     

Evaluation of new organosolv dissolving pulps. Part I: Preparation, analytical characterization and viscose processability

New acidic organosolv pulping processes, such as Acetosolv, Formacell and Milox, promise to have superior potential in terms of purification selectivity and specific investment costs. Consequently, a thorough investigation of these new acidic pulping processes in comparison to state-of-the-art acidic magnesium sulfite technology was conducted. The impact of pulping and bleaching parameters on the physical and chemical characteristics was studied to compare process efficiency and selectivity for each type of pulp made from Eucalypt wood. In addition to a detailed analysis of the chemical composition and physical properties on a molecular and supramolecular level, the TCF-bleached dissolving pulps were tested for their applicability in viscose fiber production. The influence of pulp properties as determined by standard and advanced analytical methods on process performance and selected fiber properties is emphasized.     

Dissolving-grade birch pulps produced under various prehydrolysis intensities: quality,structure and applications

Aqueous-phase prehydrolysis followed by alkaline pulping is a viable process to produce wood-based dissolving pulps. However, detailed characterisation of the achievable pulp quality, performance and cellulose structure is yet lacking. In this study, the production of hemicellulose-lean birch soda-anthraquinone pulps after prehydrolysis under various intensities was investigated. Increasing prehydrolysis intensity resulted in pulps of higher purity but lower cellulose yield and degree of polymerisation. Higher cellulose yield by using sodium borohydride during pulping was achieved at the expense of reducing pulp purity. Cellulose crystallinity was similar in all pulps indicating simultaneous degradation of both crystalline and amorphous cellulose regions. Reinforced prehydrolysis seemingly increased the cellulose crystal size and the interfibrillar distances. Moderate intensity prehydrolysis (170 °C) resulted in a pulp well suited for viscose application, whereas reinforced prehydrolysis favoured the production of acceptable cellulose triacetate dope. The performance of the pulps in viscose and acetate applications was strongly related to the chemical and structural properties.     

Effect of pulp composition on the characteristics of residuals in CMC made from such pulps

Four different spruce sulphite pulp samples were used for the preparation of carboxymethylcellulose (CMC). The characteristics of the unreacted fibre and particle residuals obtained in the CMC-preparation were used to establish a correlation between the hemicellulose in the pulp and the intrinsic viscosity, i.e.,␣cellulose chain length and the occurence of unreacted residuals. It was shown that the residual particles in the CMC consisted of fibres, fibre fractions and gel particles of different degrees of substitution. The results suggested that pulps with long cellulose chains, i.e., pulps with high intrinsic viscosities, resulted in particles that were more substituted and more swollen. These pulps also resulted in more substituted hemicelluloses in the CMC and more substituted residuals. It was also suggested that galactoglucomannan in the cellulose pulps is favourable for the swelling which results in more substituted hemicelluloses in the CMC and more swollen residuals. The amount of residuals was influenced mainly by the characteristics of the cellulose in the pulp. It is therefore believed that a combination of high viscosity and a suitable combination of hemicelluloses is the most favourable way of eliminating the occurrence of undissolved residuals in CMC.     

Effect of dose of xylanase on bleachability of sugarcane bagasse ethanol/water pulps

Pulps obtained from the ethanol/water cooking of sugarcane bagasse were bleached with the xylanase enzyme obtained from the fungus Thermomyces lanuginosus IOC-4145 and with the commercial enzyme Cartazyme HS from Sandoz. By changing the enzyme dose from 4.3 to 36 IU/g of pulp, kappa number and viscosity were maintained when the xylanase from T. lanuginosus was used. On the other hand, by using Cartazyme HS, kappa number decreased by 17%, reaching 35.5. This pulp was further extracted with NaOH without a decrease in viscosity (10 cP), and pulp with a kappa number of 13 was obtained. Xylanases had no significant effect on the ethanol/water pulps.     

Viscosity control and reactivity improvements of cellulose fibers by cellulase treatment

Cellulase treatment for decreasing viscosity of cellulose (dissolving pulp) is a promising approach to reduce the use of toxic chemicals, such as hypochlorite in the dissolving pulp manufacturing process. In this study, the use of an endoglucanase-rich cellulase to replace the hypochlorite for this purpose and its improvements of the Fock reactivity were investigated. The results showed that at a given viscosity level, the replacement of hypochlorite treatment with a cellulase treatment in the bleach plant under otherwise the same conditions led to a higher Fock reactivity (72.0 vs 46.7 %). These results were due to the enzymatic peeling/etching mechanism, which partially peeled the primary wall of the fibers, thus improving the accessibility of fibers. The improved accessibility of the enzymatic treated pulp was supported by the positive fiber morphological changes determined, based on the SEM, BET and WRV methods. The alkali solubility results further supported the conclusion.     

Some aspects on the kinetics of etherification in the preparation of CMC

Carboxymethylcellulose (CMC) was prepared from nine commercial dissolving pulps with different origins, viscosities and S₁₈-values. The rate of the etherification reaction and the final DS were studied with respect to the influence of pulp composition, pulp viscosity and S₁₈-value, and with respect to the sodium hydroxide and sodium monochloro-acetate charges. The possible influence on the final DS-value of the CMC of the washing procedure after the etherification was also investigated.     

Compression molded wood pulp biocomposites: a study of hemicellulose influence on cellulose supramolecular structure and material properties

In this study, the importance of hemicellulose content and structure in chemical pulps on the property relationships in compression molded wood pulp biocomposites is examined. Three different softwood pulps are compared; an acid sulfite dissolving grade pulp with high cellulose purity, an acid sulfite paper grade pulp and a paper grade kraft pulp, the latter two both containing higher amounts of hemicelluloses. Biocomposites based the acid sulfite pulps exhibit twice as high Young’s modulus as the composite based on paper grade kraft pulp, 11–12 and 6 GPa, respectively, and the explanation is most likely the difference in beating response of the pulps. Also the water retention value (WRV) is similarly low for the two molded sulfite pulps (0.5 g/g) as compared to the molded kraft pulp (0.9 g/g). The carbohydrate composition is determined by neutral sugar analysis and average molar masses by SEC. The cellulose supramolecular structure (cellulose fibril aggregation) is studied by solid state CP/MAS ¹³C-NMR and two forms of hemicellulose are assigned. During compression molding, cellulose fibril aggregation occurs to higher extent in the acid sulfite pulps as compared to the kraft pulp. In conclusion, the most important observation from this study is that the difference in hemicellulose content and structure seems to affect the aggregation behaviour and WRV of the investigated biocomposites.     

Purification of cellulosic pulp by hot water extraction

Hot water extraction (HWE) of pulp in a flow-through reactor was evaluated as a method to purify paper-grade pulps. About 50–80 % of the xylan and up to 50 % of the lignin in unbleached birch Kraft pulp was extracted by the HWE without losses in cellulose yield. The residual xylan content in the extracted pulps was predominantly too high for dissolving-grade applications, but some of the pulps with a xylan content of 5–7 % might still be suitable as rayon-grade pulps. Increasing extraction temperature lowered the xylan content at which cellulose yield started to decrease. Furthermore, at any given xylan content, increasing extraction temperature resulted in cellulosic pulp with higher degree of polymerization. The extracted xylan was recovered almost quantitatively as xylo-oligosaccharides. The results suggest that HWEs at elevated temperatures may be applied to purify cellulosic pulps, preferably containing a low xylan content, and to recover the extracted sugars.     

Molecular properties of hemicelluloses located in the surface and inner layers of hardwood and softwood pulps

The molecular properties of hemicelluloses located in the surface and inner layers of fibers present in hardwood and softwood pulps, together with the effects of different bleaching processes on these properties, have been investigated in this study. In order to separate the hemicelluloses located in these two layers, fibers were subjected to mechanical peeling and then separated by filtration into surface (filtrate) and inner layer materials. The materials thus obtained were characterized with respect to their polysaccharide compositions and uronic acid contents. The molar mass parameters of the hemicelluloses (extracted by alkali) were determined by employing size-exclusion chromatography in combination with off-line MALDI mass spectrometry. For all of the pulps examined, the relative content of xylan was found to be greater in the surface layer of the fiber than in the corresponding inner layer. The xylan polymers of the surface layer exhibited higher molar masses and lower frequencies of uronic acid side groups than did the xylans in the inner fiber layer. In connection with ozone treatment, hexenuronic acid residues in the surface layer xylan were removed to a greater extent than in the case of the inner layers, indicating a gradient for the reaction with ozone across the fiber wall. The xylan polymer remaining on the surface of the softwood pulps after completion of the chlorine dioxide bleaching process was predominantly uncharged.