Modification of high-lignin kraft pulps with laccase. Part 2. Xylanase-enhanced strength benefits

The effects of xylanase pretreatment of high lignin content softwood (SW) kraft pulp on subsequent pulp treatment with laccase in combination with gallic acid were investigated. Although xylanase pretreatment was ineffective in enhancing the laccase-facilitated biografting of gallic acid to kraft fibers, it was beneficial for subsequent treatment with laccase exclusively. Treating pulp fibers with xylanase followed by laccase provided a collective 25% and 46% increase in dry and wet tensile strength properties, respectively.     

Improvement of high-yield pulp properties by using a small amount of bleached wheat straw pulp

In this study, the potential of using bleached wheat straw pulp (BWSP) was explored to improve the tensile strength of the high-yield pulp (HYP) while preserving its high bulk property. The results showed that with the addition of 5-10% refined BWSP, the HYP tensile strength can be increased by about 10-20% without sacrificing the bulk. Similar results were obtained by adding refined BWSP into a mixed furnish of bleached kraft pulps (BKPs) and HYP. The explanation was that micro fines from refined BWSP can act as binders to improve the HYP interfiber bonding, as a result, the HYP tensile strength can be improved by using a small amount of BWSP, while the HYP bulk is not significantly affected.     

Wet strength improvement of unbleached kraft pulp through laccase catalyzed oxidation

Previous investigations have shown that laccase catalyzed oxidation of lignin containing wood fibers can enhance the strength of medium density fiberboards. In the present work it was investigated if laccase treatment had any impact on the tensile strength of a high yield unbleached kraft pulp. Treatment with laccase alone had only a very little effect on the wet strength of the pulp, whereas addition of lignin rich extractives increased the wet strength after the enzyme treatment significantly. A mediated oxidation gave a similar improvement of the wet tensile strength although no lignin was added to the fiber suspension. Furthermore, it was found that a heat treatment combined with a mediated oxidation gave a higher improvement in wet tensile strength than could be accounted for by the individual treatments. No change in dry tensile strength from the laccase treatment was observed. It is suggested that the observed improvement in wet tensile strength is related to polymerization of lignin on fibers in the hand sheet and/or coupling of phenoxy radicals on lignin associated to adjacent fibers. For the different mediators studied, a correlation was found between oxygen consumption upon mediated oxidation and generation of wet strength in the pulp.     

Potential of xylanase from thermophilic Bacillus sp. XTR-10 in biobleaching of wood kraft pulp

An extracellular xylanase produced under optimal conditions by a thermophilic strain of Bacillus sp. XTR-10 was evaluated for its potential application in biobleaching of wood kraft pulp. Spectrophotometric analysis showed considerable release of lignin derived compounds and chromophoric material by the xylanase treated pulp samples. Xylanase was found to be effective in the liberation of reducing sugars in the pulp filtrates with increment in enzyme dose and reaction time. Eight hours pretreatment with 40 IU of xylanase/g of dry pulp resulted in 16.2% reduction of kappa number with 25.94% ISO increase in brightness as compared to the control. The same treatment slightly lowered the tensile strength and burst index, however. Enzyme pretreatment of the pulp saved 15% active chlorine charges in single step and 18.7% in multiple steps chemical bleaching with attainment of brightness at the level of the control. These results indicate the potential of enzymatic pretreatment of pulp for reduction in environmental discharge of hazardous waste from the pulp and paper industry.     

A comparison of kraft, PS, kraft-AQ and kraft-NaBH4 pulps of Brutia pine

The aim of this work was to study the effect of adding PS, AQ and NaBH(4) into kraft pulping with special attention given to NaBH(4). Kraft, kraft-AQ, PS, and kraft-NaBH(4) pulps were produced under the same cooking conditions and the pulps produced were compared in terms of pulp and paper properties. Kraft method was modified by adding 0.1% AQ, 4% PS and 2% and 4% NaBH(4) and the resultant pulps displayed an increase in pulp yield and reduction in both kappa number and screening rejects. On the other hand, there observed an increase in both pulp yield and kappa number when the kraft was modified to PS method. The benefits of NaBH(4) addition into kraft pulping was a significant reduction in kappa number and screening rejects and a significant increase in pulp yield. The most notable outcome of NaBH(4) was 66.6% increase in pulp brightness when 4% NaBH(4) was added into kraft pulping. Of unrefined pulps, unrefined kraft pulp displayed the highest strength of pulp, which is described as tear index at a constant tensile index. Of refined pulps, kraft-AQ showed the highest pulp strength when refined to 6000 and 12,000 revs in PFI mill.     

Laccase-initiated cross-linking of lignocellulose fibres using a ultra-filtered lignin isolated from kraft black liquor

In this work, the effect of Trametes pubescens laccase (TpL) used in combination with a low-molecular-weight ultra-filtered lignin (UFL) to improve mechanical properties of kraft liner pulp and chemi-thermo-mechanical pulp was studied. UFL was isolated by ultra-filtration from the kraft cooking black liquor obtained from softwood pulping. This by-product from the pulp industry contains an oligomeric lignin with almost twice the amount of free phenolic moieties than residual kraft pulp lignin. The reactivity of TpL on UFL and kraft pulp was studied by nuclear magnetic resonance spectroscopy and size exclusion chromatography. Laccase was shown to polymerise UFL and residual kraft pulp lignin in the fibres, seen by the increase in their average molecular weight and in the case of UFL as a decrease in the amount of phenolic hydroxyls. The laccase initiated cross-linking of lignin, mediated by UFL, which gives rise to more than a twofold increase in wet strength of kraft liner pulp handsheets without loosing other critical mechanical properties. Hence, this could be an interesting path to decrease mechano-sorptive creep that has been reported to lessen in extent as wet strength is given to papers. The laccase/2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) mediator system showed a greater increase in wet tensile strength of the resulting pulp sheets than the laccase/UFL system. However, other mechanical properties such as dry tensile strength, compression strength and Scott Bond internal strength were negatively affected by the laccase/ABTS system.     

Thermo-mechanical processing of sugar beet pulp. III. Study of extruded films improvement with various plasticizers and cross-linkers

Thermoplastic sugar beet pulp (thermo-mechanical processing was discussed in previous studies) was formed into film strips by extrusion. Film tensile properties are discussed according to the molecular structure of external plasticizer. Sorbitol, fructose and adipic acid have a marked antiplasticizing effect, while urea and xylitol gave higher ultimate tensile stress than glycerol for a comparable strain at break. Xylitol can be considered as the best plasticizer with UTS and EL of, respectively, 4.9 MPa and 11.3% and water absorption (85% RH, 25 °C) was less than 25%. Glycidyl methacrylate was directly used in the extrusion process as cross-linker. In high humidity atmosphere (97% RH, 25 °C), film water absorption was then kept under 40% while tensile strength and strain were improved of 50% and with a 30 min UV post-treatment the mass gain in absorption was even less than 30% after 5 days.     

Production of multi-fiber modifying enzyme from Mamillisphaeria sp. for refining of recycled paper pulp

Enzymatic modification of pulp is receiving increasing interest for energy reduction at the refining step of the paper-making process. In this study, the production of a multi-fiber modifying enzyme from Mamillisphaeria sp. BCC8893 was optimized in submerged fermentation using a response-surface methodology. Maximal production was obtained in a complex medium comprising wheat bran, soybean, and rice bran supplemented with yeast extract at pH 6.0 and a harvest time of 7 d, resulting in 9.2 IU/mL of carboxymethyl cellulase (CMCase), 14.9 IU/mL of filter paper activity (FPase), and 242.7 IU/mL of xylanase. Treatment of old corrugated container pulp at 0.2-0.3 IU of CMCase/g of pulp led to reductions in refining energy of 8.5-14.8%. The major physical properties were retained, including tensile and compression strength. Proteomic analysis showed that the enzyme was a complex composite of endo-glucanases, cellobiohydrolases, beta-1,4-xylanases, and beta-glucanases belonging to various glycosyl hydrolase families, suggestive of cooperative enzyme action in fiber modification, providing the basis for refining efficiency.     

Feasibility of utilizing Rhizoclonium in pulping and papermaking

Material of Rhizoclonium from brackish water in Taiwan was investigated for its possible use in pulping and papermaking. After beating, this filamentous alga produced a pulp with a length to width ratio of about 10, much less than that of a typical wood pulp. Handsheets made from this pulp had a moderate breaking length of 4.02 km. Cooking pre-beaten pulp with a low chemical charge (5–25%NaOH) at a low cooking temperature (100 ^°C), and for a short time (30–120 min) gave high algal pulp yields (70–80%). This cooking process was sulfur-free, but the water requirement was high. After cooking and further caustic soda and bleaching treatments, wide-angle X-ray diffraction and FTIR spectroscopy showed that the crystallinity of the algal pulp increased substantially, but type I cellulose conformation was retained. The best pulp mechanical strengths (breaking length 5.23 km,zero-span tensile strength 79.2 Nm g^-1, bursting index of 2.2 kpa m² g^-1) were obtained after cooking for 1 h with 20% NaOH. Because of the morphological characteristics of the algal strands, the pulp generally lacked bursting, tearing and folding strengths, but proper blending with softwood pulp increased the tensile breaking length to8.40 km, the tearing index to 14.5 mNm² g^-1, the bursting index to 6.42 kpam² g^-1 and the folding endurance to 4299 double folds, i.e. levels comparable to a typical kraft pulp. The algal pulp thus showed clear potential as a supplement for traditional medium strength wood pulps. This revised version was published online in August 2006 with corrections to the Cover Date.     

Effect of beating on recycled properties of unbleached eucalyptus cellulose fiber

The effects of beating on recycled properties of eucalyptus cellulose fiber were studied by analyzing the changes of morphological parameters (fiber length and the fines content), physical properties (tensile strength, breaking length and the stretch), WRV, crystal structure of cellulose and pore structure of cellulose fiber. The results showed that beating caused the fine content increase. Tensile strength, breaking length and the stretch increased with the increasing beating time. WRV of the first cycle beaten eucalyptus pulp was increased by 32.1%, compared to the first cycle unbeaten pulp. WRV increased with the increase in beating degree. However, crystallinity of cellulose increased, and then decreased with an increase in beating degree. FTIR spectra showed that there were no drastic changes in the functional groups of the eucalyptus pulp cellulose during beating. Fiber pore size was gradually diverted into macropore with the increase in beating degree, resulting in the mean pore volume increased.     

Treatment of recycled kraft pulps with Trichoderma reesei hemicellulases and cellulases

Effects of recycling ECF-bleached softwood kraft pulp on pulp properties were evaluated in the laboratory. The tensile strength, fiber flexibility and WRV lost during drying of the pulp were recovered by refining between the cycles which, however, resulted in deteriorated drainage properties. The recycled pulps were treated with purified Trichoderma reesei cellulases and hemicellulases and the changes in fiber properties due to enzymatic treatments were characterized. The endoglucanases (EG I and EG II) significantly improved pulp drainage already at low dosage levels, and EG II was found to be more effective at a given level of carbohydrate solubilization. Combining hemicellulases with the endoglucanase treatments increased the positive effects of the endoglucanases on pulp drainage. However, as a result of the endoglucanase treatments a slight loss in strength was observed. Combining mannanase with endoglucanase treatments appeared to increase this negative effect, whereas the impact of xylanase was not significant. Although the drainage properties of the pulps could be improved by selected enzymes, the water retention capacity of the dried hornified fibers could not be recovered by any of the enzymes tested.     

Enhanced production of a thermostable xylanase from Streptomyces sp. QG-11-3 and its application in biobleaching of eucalyptus kraft pulp

A thermostable and cellulase-free xylanase has been produced from Streptomyces sp. QG-11-3 in solid substrate fermentation using wheat bran and eucalyptus kraft pulp as the prime solid substrates. The maximum xylanase yield obtained using these two substrates were 2360 U/g and 1200 U/g dry solid substrate at substrate:moisture ratios of 1:3 and 1:2.5, respectively. In immobilized cell system using polyurethane foam (PUF) and three nonwoven fabrics, namely, polyester, silk, and cotton, the xylanase yields were enhanced by 2.5-fold (203 U/ml), 1.91-fold (155 U/ml), 1.54-fold (125 U/ml), and 1.47-fold (119 U/ml), respectively, compared to the xylanase yield in liquid-batch fermentation (81 U/ml). In the biobleaching experiments, the xylanase dose of 3.5 U/g moisture free pulp exhibited the optimum bleach boosting of eucalyptus kraft pulp at pH 8.5 and 50 degrees C after 2 h of treatment. When xylanase treated pulp was subsequently treated with 4.5% chlorine, it resulted in reduction of kappa number by 25%, enhanced the brightness (%ISO) by 20% and improved the pulp properties such as tensile strength and burst factor by up to 63% and 8%, respectively.     

Enhanced production of cellulase-free thermostable xylanase by Bacillus pumilus ASH and its potential application in paper industry

A very high level of cellulase-free, thermostable xylanase has been produced from newly isolated strain of Bacillus pumilus under submerged fermentation in a basal medium supplemented with wheat bran (2%, w/v) pH 8.0 and at 37 °C. After optimization of various production parameters, an increase of nearly 13-fold in xylanase production (5407 IU/ml) was achieved. The produced xylanase is stable in neutral to alkaline pH region at 70 °C. The suitability of this xylanase for use in the bioleaching of eucalyptus Kraft pulp was investigated. A xylanase dose of 5 IU/g of oven dried pulp of 10% consistency exhibited the optimum bleach boosting of the pulp at pH 7.0 and 60 °C after 180 min of treatment. An increase of 5% in brightness along with an increase of 21% and 28% in whiteness and fluorescence respectively, whereas 18% decrease in the yellowness of the biotreated pulp was observed. Enzyme treated pulp when subjected to chemical bleaching, resulted in 20% reduction in chlorine consumption and up to 10% reduction in consumption of chlorine dioxide. Also a reduction of about 16% in kappa number and 83% in permanganate number, along with a reduction in COD value and significant improvement in various pulp properties, viz. viscosity, tensile strength, breaking length, burst factor, burstness, tear factor and tearness were observed in comparison to the conventional chemical bleaching.     

An experimental approach to modeling the strength of canine teeth

The strength of canine teeth in several carnivores is found through direct fracture experiments. The average forces required to break the canines of adult animals are coyote 1170 N, red fox 533 N, bobcat 737 N and raccoon 512 N. Stresses created in teeth at the breaking load are predicted by finite-element analysis and beam theory. The ultimate tensile stress sustainable in these teeth is 338 MPa in adult animals. The large pulp cavity in the canines of young animals significantly weakens the bases of their teeth (by about 25%), but as the animal ages the pulp cavity decreases and has little effect on overall tooth strength. The tooth material of young of the year is significantly weaker than that from older animals (by about 35%). With the experimentally derived ultimate tensile stress, finite-element analysis can estimate the breaking load of canines for several carnivores. A significant allometric relationship exists between log of body weight and log of strength of tooth (slope=0.81).     

Laccase treatment of recycled blue dyed paper: physical properties and fiber charge

Recycled blue colored paper was treated with laccase under various combinations of physical and chemical parameters including enzyme concentration, temperature, oxygen, and reaction time. Laccase treatment of recycled dyed pulp increased acid group content, tear index, tensile index, and color removal in a dose-dependent manner. Lengthening the treatment time from 2 to 4 h was beneficial to acid group content (12% increase), dye removal, and tensile index but had a detrimental 8% decrease on the tear index. A higher reaction temperature (65 vs. 45 degrees C) had a beneficial effect on acid group content (+31%), and tensile index (+26%) and a slightly negative effect on tear index (-5%), but significantly reduced the ability of laccase to remove color. Comparison of reactions subjected to different levels of oxygen supplementation showed the greatest beneficial effect for laccase treatment with slow oxygen bubbling. The experimental results indicate that laccase treatment increases fiber carboxylic acid content and tensile strength, in addition to reducing the color of the enzyme treated paper.     

Immobilization of cellulases on the reversibly soluble polymer Eudragit S‐100 for cotton treatment

Cellulases can penetrate into the fiber, causing tensile strength loss of the cellulosic fibers or fabrics. To minimize the tensile strength loss, we have immobilized cellulases on Eudragit S‐100. The characteristics of covalent Eudragit cellulase were evaluated using gel filtration analysis and UV spectra. Gel filtration analysis revealed that the cellulases were covalently bound to the polymer. Covalent Eudragit cellulase was loaded with the enzyme of about 40% and had a relative activity about 80% at a Eudragit S‐100 concentration of 15 g/L. When cellulase is bound to the polymer, the solubility profile becomes similar to the one of Eudragit. In addition, the effects of the enzyme on the cotton yarns and fabric using cellulases have been investigated. Native and immobilized cellulases caused improvements in whiteness and wrinkle recovery angle of the fabric in comparison to the control samples. The bending stiffness results show that native and immobilized cellulase treated cotton fabric has an improved softness than the control samples. It was found that using the immobilized cellulase reduced the weight and tensile strength, because the hydrolytic attack is only limited to the surfaces of cotton fibers.     

Fiber modification of kraft pulp with laccase in presence of methyl syringate

An approach aiming at improving paper properties is to use laccase to copolymerize low-molecular weight phenols with the pulp before papermaking. The addition of methyl syringate (MS) gave a twice wet tensile index of unbleached kraft pulp with laccase treatment but had little effect on the dry tensile index and substantially decreased the brightness of pulp. The radical concentration in laccase-treated fibers increased up to 2.5 times of that in control sample after 60 min. The radical concentration in laccase/MS-treated fibers increased up to 20 times of that in control sample within 2 min, and a highest radical concentration (increased by near 65 times) was obtained after 40 min. A strong agglutination of large-area fibers in handsheet was observed after laccase/MS treatment. The surface lignin coverage of the laccase-treated fibers increased from 54.96% (control) to 59.36%, while that of the laccase/MS-treated fibers increased only up to 55.22%. It is suggested that the graft of MS on fiber and degradation of surface lignin occurred simultaneously. The addition of MS can enhance the activation of fibers and extend the enzymatic oxidation of lignin within the cell wall. An increased bonding area of fibers resulting from interaction of laccase, MS and fibers via radical-coupling reaction maybe account for the significantly improved wet strength of pulp.     

Cynara cardunculus L. alkaline pulps: alternatives fibres for paper and paperboard production

The pulping of Cynara cardunculus L. (cardoon) was performed under conditions for kraft, kraft-AQ and soda-AQ processes. The best results in terms of delignification degree, expressed as kappa number, pulp viscosity and screened yield, were obtained for the kraft-AQ process with 0.20% of anthraquinone (AQ). The papermaking potential of the selected pulp was studied attending to biometric fibre characterisation, refining aptitude, optical and strength properties. All properties were compared against a Eucalyptus globulus pulp at different refining degrees. The cardoon pulp was also evaluated concerning its potential to board manufacture, alone and in mixtures with pine pulp, giving rise to promising results for liner manufacture.     

Modification of eucalyptus CTMP fibres with white-rot fungus Trametes hirsute - Effects on fibre morphology and paper physical strengths

White-rot fungus Trameteshirsute (T.h. 19-6) was used for modifying the eucalyptus CTMP fibres. Results show that the T.h. 19-6 removed mainly lignin (by 7.42%) and extractive (by 11.52%) after a short period of 5days incubation. Due to the fungal degradation of the fibre wall materials, the middle lamella remainder on the fibre surface was significantly reduced and the fibre wall structure was loosened, which led to an increase in fibre internal bonding strength by 32% and an increase in handsheet tensile index and tear index by 49%, and 34%, respectively. A subsequent PFI refining process further amplified the fungal treatment effect, resulting in extensive fibre internal fibrillation. Compared with untreated pulp, fungus-treated pulp reached the same freeness levels with less PFI revolutions, indicating potential energy saving in the refining process.     

Enzymatic treatment of mechanical pulp fibers for improving papermaking properties

Three enzyme preparations (crude cellulase, laccase, and proteinase) were evaluated for their potential to improve the papermaking properties of mechanical pulp. After treating a long fibre-rich fraction of the pulp with enzyme, the fibres were recombined with untreated fines for handsheet making and testing. None of the enzymes altered the retention of fines or the consolidation of the furnish mix during handsheet formation. All three enzymes increased tensile stiffness index, which is a measure of the initial resistance of the handsheets to strain. Only the laccase preparation, an enzyme that modifies pulp lignin, consistently increased fibre bonding to enhance other strength properties of the handsheets.