Cellulase-assisted refining of chemical pulps: Impact of enzymatic charge and refining intensity on energy consumption and pulp quality

Paper production requires fibres to be refined, meaning mechanically treated to present sufficient bonding potential. As it is a highly energy consuming stage, various charges of cellulase as a pre-treatment were investigated to reduce the energy consumption and improve paper properties. The enzyme was added during pulp slushing and conditions of treatment were chosen to be compatible with an industrial application. Results obtained after low consistency disc refining of a softwood bleached kraft pulp were compared at a given drainage index. Enzymatically-treated samples showed a better development of fibrillation leading to a stronger paper. Moreover, fibre swelling was significantly improved. The impact of cellulase charge added to the pulp was identified. However, for all cellulase charges tested, fibre intrinsic resistance was lowered. Consequently fibres became shorter and tear index dropped. A solution was found by applying a milder treatment consisting in reducing refining intensity. This was a way to limit the intense fibre cutting at high refining levels. Moreover, by treating pulp with cellulase, it became possible to reduce refining intensity by 33%, keeping breaking length similar to control.     

Ethanol-acetone pulping of wheat straw. Influence of the cooking and the beating of the pulps on the properties of the resulting paper sheets

The influence of independent variables in the pulping of wheat straw by use of an ethanol-acetone-water mixture [processing temperature and time, ethanol/(ethanol + acetone) value and (ethanol + acetone)/(ethanol + acetone + water) value] and of the number of PFI beating revolutions to which the pulp was subjected, on the properties of the resulting pulp (yield and Shopper-Riegler index) and of the paper sheets obtained from it (breaking length, stretch, burst index and tear index) was examined. By using a central composite factor design and the BMDP software suite, equations that relate each dependent variable to the different independent variables were obtained that reproduced the experimental results for the dependent variables with errors less than 30% at temperatures, times, ethanol/(ethanol + acetone) value, (ethanol + acetone)/(ethanol + acetone + water) value and numbers of PFI beating revolutions in the ranges 140-180 degrees C, 60-120 min, 25-75%, 35-75% and 0-1750, respectively. Using values of the independent variables over the variation ranges considered provided the following optimum values of the dependent variables: 78.17% (yield), 15.21 degrees SR (Shopper-Riegler index), 5265 m (breaking length), 1.94% (stretch), 2.53 kN/g (burst index) and 4.26 mN m2/g (tear index). Obtaining reasonably good paper sheets (with properties that differed by less than 15% from their optimum values except for the burst index, which was 28% lower) entailed using a temperature of 180 degrees C, an ethanol/(ethanol + acetone) value of 50%, an (ethanol + acetone)/(ethanol + acetone + water) value of 75%, a processing time of 60 min and a number of PFI beating revolutions of 1750. The yield was 32% lower under these conditions, however. A comparison of the results provided by ethanol, acetone and ethanol-acetone pulping revealed that the second and third process-which provided an increased yield were the best choices. On the other hand, if the pulp is to be refined, ethanol pulping is the process of choice.     

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.     

A comparative study of the effect of refining on physical and electrokinetic properties of various cellulosic fibres

The aim of this work was to study the influence of refining on various pulp properties such as freeness, specific surface area, specific volume, surface charge, total charge and elastic modulus. The results indicated that specific surface area of the pulps increased with increased refining, and at the same freeness level the pine pulp exhibited higher surface charge, surface area, and specific volume than the eucalyptus pulps. Also, the eucalypt pulps were much easier to beat than the pine pulps. The total fibre charge, as determined by conductometric titrations, was not affected by refining. However, the surface charge, as determined by titrations with poly-DADMAC, increased with refining. Increasing the specific surface area by refining resulted in a higher fibre surface charge and better fibre-fibre bonding. The change of the fibre surface charge during refining could be monitored using the FTIR characteristic bands within 1700-1300cm(-1).     

Neural fuzzy model applied to ethylene-glycol pulping of non-wood raw materials

We studied the influence of the operational variables (viz. ethylene-glycol concentrations of 50-70%, temperatures of 155-185 degrees C, times of 30-90 min and numbers of PFI beating revolutions of 500-1500) on pulp yield and various paper properties (breaking length, stretch, burst index, tear index and brightness) obtained in the ethylene-glycol pulping of vine shoots, cotton stalks, leucaena (Leucaena leucocephala) and tagasaste (Chamaecytisus proliferus). The fuzzy neural network models used reproduced the experimental results with errors less than 15% and smaller than those provided by second-order polynomial models in all cases. An ethylene-glycol concentration of 65% at 180 degrees C for 75 min and 1500 PFI beating revolutions were found to provide substantial savings in energy, chemicals and facility investments as a result of operating under milder conditions than the strongest ones studied in this work. Tagasaste was found to be the most suitable raw material among those tested as it provided the paper sheets with the highest breaking length (4644 m), stretch (2.87%), burst index (2.46 kN/g), tear index (0.33 m Nm(2)/g) and brightness (40.92%); its pulp yield was also high (62.88%), which reflects efficient use of this raw material.     

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.     

A comparative study of the effect of refining on charge of various pulps

This work studied the influence of refining on various pulp properties such as freeness, specific surface area, specific volume, water retention value, surface charge, total charge and tensile index of five different pulps. At a freeness level the wheat straw pulp exhibited higher surface charge and total charge compared to other pulps. The specific surface area, specific volume and water retention value of the pulps increased with increased refining. The total fibre charge as determined by conductometric titrations was not affected by refining. However, the surface charge as determined by titrations with poly-DADMAC increased with refining. The increases in specific surface area of pulps by refining resulted in a higher fibre surface charge and also better fibre-fibre bonding. The linear regression models developed using experimental data were found to be accurate. The comparison of model predicted data and the experimental data showed an excellent agreement between them.     

Biological bleaching of hardwood kraft pulp using Trametes (Coriolus) versicolor immobilized in polyurethane foam

Summary Incubation of hardwood kraft pulp (HWKP) in agitated aerated cultures of the white-rot fungus Trametes versicolor increases pulp brightness and decreases its residual lignin content. A consequence of this biobleaching with whole cultures is that the resulting pulp also contains fungal biomass (up to ca. 10% (w/w)). In this report culture conditions for the immobilization of T. versicolor on polyurethane foam and bleaching of HWKP with the immobilized fungus are described. The major advantage of using immobilized fungus to bleach HWKP is that the fungal biomass can be separated from the pulp after treatment, resulting in a biologically bleached pulp free of fungal mycelium. From an analysis of pulp samples bleached with free and foam-immobilized mycelium, we conclude that fungal biomass in pulp treated with free mycelium accounts for up to 25% of the reduction in pulp viscosity (indication of cellulose chain length) whereas the zero span breaking length (indication of fibre strength) is not significantly affected by the presence of the fungus. Immobilization of the fungus on polyurethane foam also allows the repeated use of the same fungal biomass to bleach successive batches of pulp, either immediately or after storage at 4°C. Offprint requests to: I. D. ReidIssued as NRCC no. 30975     

Bleaching of wheat straw-rich soda pulp with xylanase from a thermoalkalophilic Streptomyces cyaneus SN32

An alkalistable endoxylanase from Streptomyces cyaneus SN32 was applied in bleaching of wheat straw enriched soda pulp. The xylanase dose of 10 IUg(-1) moisture free pulp exhibited maximum bleach boosting of soda pulp (pH 9.5-10.0) optimally at 65 degrees C after 2 h of reaction time. Pre-treatment of pulp with xylanase and its subsequent treatment with 6% hypochlorite reduced the kappa number by 8.7%, enhanced the brightness index by 3.56% and improved other paper properties such as tear index and burst index. The enzymatically-prebleached pulp when treated with 10% reduced level of hypochlorite (5.4%) gave comparable brightness of resultant hand sheets to the fully bleached pulp (6% hypochlorite).     

Soda-anthraquinone pulping of palm oil empty fruit bunches and beating of the resulting pulp

The influence of soda-anthraquinone pulping variables (temperature, time and soda concentration) and beating (number of PFI beating revolution) of palm oil empty fruit bunches (EFB) on the resulting paper sheets was studied, with a view to identifying the optimum operating conditions. Equations were derived that reproduced the properties of the paper sheets with errors less than 10-12% in 90-95% of cases. An optimum compromise was found as regards operating conditions (15% soda, 170 degrees C, 70 min and 2400 number of PFI beating revolutions) that provided paper properties departing by less than 12% from their optimum values (59.63 Nm/g tensile index, 4.48% stretch, 4.17 kN/g burst index and 7.20 m Nm(2)/g tear index), and a beating grade of 47.5 degrees SR, acceptable to obtain paper sheets. Because these conditions involve a lower soda, temperature, time and beating than those required to maximize the studied paper properties, they can save chemical reagents, energy and immobilized capital for industrial facilities. On the other hand, the stretch properties of these pulp beaten are higher than those of others non-wood pulps, as wheat straw and olive wood.     

Ethyleneglycol pulp from tagasaste

In this work, we examined the influence of operational variables [viz. Ethyleneglycol concentration (50-70%), temperature (155-185 degrees C), time (30-90 min) and number of PFI beating revolutions (500-1500)] in the ethyleneglycol pulping of tagasaste (Chamaecytisus proliferus) on pulp yield and the breaking length, stretch, burst index, tear index and brightness of paper sheets formed from it. Application of a fuzzy neural network model in combination with an experimental factorial design allowed the results for the dependent variables to be predicted as a function of the operating conditions used with errors less than 15% in all cases. The operating conditions of choice provided pulp with a high yield (56.85%) and a low brightness (22.51%) which may thus be useful to obtain non-white paper.     

Endoglucanase enzymatic modification of kraft pulp during recycling

Objective

To investigate the cellulose modification process on kraft pulp during recycling by mono-endoglucanase.

Results

Pichia pastoris expressing endoglucanase, EG1, was grown in a 10 l fermenter yielding a high carboxymethyl cellulase (CMCase) activity of 340 U mg^?1. EG1-mediated modification of kraft pulp resulted in a paper sheet with the tensile index and burst index increased by 10 and 6.5 %, respectively. The kink index (indicating abrupt bends in fibres) of the enzyme-treated group decreased sharply by 45 % after the first recycling, compared with a reduction of only 1 % in the control group. Furthermore, EG1 treatment decreased the growth of crystallinity from 73.5 to 73.2 % and crystal size from 7.45 to 7.21 nm, which alleviated paper aging.

Conclusion

Endoglucanase EG1 modifies the interfacial properties of fibers, which affects fibre morphology during the recycling process and improves the technical properties of the resulting pulp and paper.

     

A comparative study of the effect of refining on organosolv pulp from olive trimmings and kraft pulp from eucalyptus wood

This paper examines the influence of the degree of refining of different pulps, produced from olive trimmings and eucalyptus wood, on various physical properties. Corresponding pulps were obtained by means of different cooking processes. Pulp from olive trimmings was obtained by means of an organosolv process and pulp from eucalyptus was obtained by means of a kraft process. Pulp from olive trimmings exhibited a lower specific surface area, water retention volume, breaking length, stretch and burst index, but a higher porosity, than eucalyptus pulp. On the other hand, the same degree of refining was achieved with less energy for olive pulp than for eucalyptus pulp. Mixed pulp from olive trimmings and eucalyptus provided paper sheets with acceptable physical properties but with reduced refining energy costs relative to eucalyptus pulp alone.     

Fiber fractionation to understand the effect of mechanical refining on fiber structure and resulting enzymatic digestibility of biomass

Mechanical refining results in fiber deconstruction and modifications that enhance enzyme accessibility to carbohydrates. Further understanding of the morphological changes occurring to biomass during mechanical refining and the impacts of these changes on enzymatic digestibility is necessary to maximize yields and reduce energy consumption. Although the degree of fiber length reduction relative to fibrillation/delamination can be impacted by manipulating refining variables, mechanical refining of any type (PFI, disk, and valley beater) typically results in both phenomena. Separating the two is not straightforward. In this study, fiber fractionation based on particle size performed after mechanical refining of high-lignin pulp was utilized to successfully elucidate the relative impact of fibrillation/delamination and fiber cutting phenomena during mechanical refining. Compositional analysis showed that fines contain significantly more lignin than larger size fractions. Enzymatic hydrolysis results indicated that within fractions of uniform fiber length, fibrillation/delamination due to mechanical refining increased enzymatic conversion by 20–30 percentage points. Changes in fiber length had little effect on digestibility for fibers longer than ~0.5 mm. However, the digestibility of the fines fractions was high for all levels of refining even with the high-lignin content.     

Modification of paper properties by the pretreatment of wastepaper pulp with Graphiumputredinis, Trichodermaharzianum and fusant xylanases

Graphiumputredinis, Trichodermaharzianum and fusant were used in the present study to produce extracellular xylanases, an important industrial enzyme used in pulp and paper industry produced in a minimal medium supplemented with oat spelt xylan (1%, w/v) pH 7.0 at 27+/-2 degrees C. The enzyme was purified to homogeneity by DEAE-Cellulose and Superdex 75 FPLC column, respectively. The enzyme was found to be a monomer as determined by SDS gel electrophoresis. The optimum pH and temperature for purified G. putredinis, T. harzianum and fusant xylanases were 5.0-6.0 and 50-70 degrees C, respectively. Pretreatment of paper pulp with G. putredinis, T. harzianum and fusant xylanases decreased pulp kappa number. Xylanases particularly that of fusant at 5 IU/g pulp concentration and 1.5% pulp consistency at 60 degrees C for 18 h followed by EDED process yielded good quality paper from waste paper pulp. A significant increase in pulp brightness and improvement in various pulp properties, viz. burst capacity, thickness and bulkness of the treated pulp were observed in comparison to the conventional chemical bleaching. Easy purification and high stability of these enzymes makes it amicable for industrial applications.     

Comparative study of paper sheets from olive tree wood pulp obtained by soda,sulphite or kraft pulping

Paper sheets from olive tree wood pulp obtained by soda, sulphite or kraft pulping were studied to examine the influence of pulp beating on properties of the paper sheets.Paper sheets from kraft and sulphite pulps exhibited the highest resistance, and sulphite pulp the highest brightness. Soda pulp required more intensive beating than did kraft or sulphite pulps; in fact, the PFI beater had be operated at a 40–50% higher number of beating revolutions to obtain soda pulp with 70–80° SR.The breaking length, stretch, burst index and tear index of paper sheets obtained from kraft pulp, beaten to a Shopper–Riegler index of 70–80° SR were 20–30%, 30–50%, 50–60% and 15–35% higher, respectively, than those of sheets obtained from soda pulp.     

Composition of citrus pulp

Eight groups of citrus varieties grown in Spain were included in this study. Citrus pulp composition was (dry matter basis) 60–65% peel, 30–35% segment pulp and 0–10% seeds. Citrus seeds had a high percentage of protein, ether extract and crude fibre. Segment pulp contained slightly less fibre than citrus pulp. The proximate composition of citrus pulp was similar to that of the peel fraction and did not differ from previous results. Significant differences in fibre and acid detergent lignin of the dried citrus pulp samples were found between varieties.The drying process was studied. Temperatures over 130°C and the addition of calcium hydroxide affected some fractions of the pulp, mainly by increasing ash and fibre contents.     

Biokraft pulping of European black pine with Ceriporiopsis subvermispora

European black pine (Pinus nigra Arn.) chips were treated with the white-rot fungus Ceriporiopsis subvermispora for periods ranging from 20 to 100 days. The effects of pretreatment on the chemical composition of wood and kraft pulping were investigated. The results showed that fungal pretreatment reduced the lignin and extractive content of wood chips. Also, weight losses occurred. Kappa number, viscosity, and reject ratio of biokraft pulps decreased. Biokraft pulps gave better response to beating, which led to significant energy saving during refining. The tear index, burst index, and tensile index of biokraft pulps were found to be lower than those of kraft pulps. However, the tensile index and burst index of 20-day biotreated and unbeaten pulp was higher than those of kraft pulp. Also, the tear index of 20-day biotreated and beaten pulp was higher than that of kraft pulp. The brightness of biokraft pulps decreased irregularly with increasing incubation time.     

The effects of xylanase type enzymes on the different layers of birch wood ORGANOSOLV pulp fibre walls

Some effects of the xylanase treatment on the separate birch ORGANOSOLV pulp fibre wall morphological layers were examined. These investigations were focused on the outer layers, i.e. the primary wall (P) and the outer layer of the secondary wall (S₁), as well as the central layers, i.e. the central layer of the secondary wall (S₂) and the tertiary wall (T). Step by step, the fractionation of the pulp components in the polar solvents N,N-dimethylformamide (DMFA), dimethylsulphoxide (DMSO) and DMSO/H₃PO₄ was used as a mild technique for the isolation of the lignin-carbohydrate complexes. The different residual amounts of lignin and hemicelluloses in the outer and central pulp fibre wall layers as well as the different lignin-hemicellulose ratios were determined. The size-exclusion chromatographical (SEC) analysis showed a higher initial lignin content in the region of the high molecular mass (MM) fibre wall fraction extracted with “DMSO/H₃PO₄” than the outer cell wall layers. In the central layers, the amounts of soluble lignin (calculated on the mass of total dissolved substance) were approximately the same for all the three solvents. The xylanase treatment brought the most considerable changes in the high MM part of the residual lignin (the lignin carbohydrate complex). This was true for both the P-S₁ and S₂-T layers. The careful brightness comparison of the outer and central fractions after the X-E-P-P bleaching sequence showed a surprisingly low bleachability of the outer layer fraction. The xylanase action depended on the composition of the lignin-carbohydrate complex (LCC) and the extent of the maintenance of the outer layers during the pulping process.     

Differential and synergistic effects of xylanase and laccase mediator system (LMS) in bleaching of soda and waste pulps

AIMS: Investigation of waste pulps and soda pulp bleaching with xylanase (X) and laccase mediator system (LMS) alone and in conjunction (one after the other) (XLMS). METHODS AND RESULTS: Soda and different grades of waste pulp fibres [used for making three-layered duplex sheets - top layer (TL), protective layer (PL) and bottom layer (BL)] when pretreated with either xylanase (40.0 IU g(-1)) or LMS (up to 200.0 U g(-1)) alone and in combination (one after the other) (XLMS) exhibited an increase in release of reducing sugars [up to 881.0% soda pulp; up to 736.6% (TL), up to 215.7% (PL) and up to 198.0% (BL) waste pulp], reduction in kappa number [up to 17.6% soda pulp; up to 14.0% (TL), up to 25.3% (PL) and up to 10.9% (BL), waste pulp], improvement in brightness [up to 20.4% soda pulp; up to 23.6% (TL), up to 8.6% (PL) and up to 5.0% (BL), waste pulp] when compared with the respective controls. The usage of XLMS along with 15% reduced level of hypochlorite at CEHHXLMS/EHHXLMS bleaching stage reduced kappa number [5.5% soda pulp; 11.4% (TL), 7.9% (PL), waste pulp] and improved brightness [1.0% soda pulp; 0.9% (TL), 1.4% (PL) waste pulp] when compared with the controls. Scanning electron microscopic studies revealed development of cracks, flakes, pores and peeling off the fibres in the enzyme-treated pulp samples. These modifications of the fibre surface during enzymatic bleaching in turn indicated the removal of lignin and derived compounds from the fibre cell wall. CONCLUSIONS: The work describes synergistic action of xylanase with LMS for bleaching of waste and nonwood pulps for eco-friendly production of paper and thus reveals a new unexploited arena for enzyme-based pulp bleaching. SIGNIFICANCE AND IMPACT OF THE STUDY: The drastic improvement in pulp properties obtained after xylanase and LMS treatment would improve the competitiveness of enzyme-based, environmentally benign processes over chemicals both economically and environmentally.