Optimization of hydrogen peroxide in totally chlorine free bleaching of cellulose pulp from olive tree residues

The influence of the operating conditions used in the bleaching of olive wood trimmings pulp (viz. hydrogen peroxide concentration and time) on the yield, kappa index and viscosity of the resulting pulp and on strength-related properties of paper sheets was studied to determine the optimal bleaching conditions of this pulp. Hydrogen peroxide bleached pulps at different sequences (oxygen, ozone, chlorine dioxide and alkaline extractions) were compared. Hydrogen peroxide bleaching proved to be suitable for this pulp. Considerable improvements in viscosity were obtained with respect to other bleaching sequences such as oxygen, ozone and chlorine dioxide. Hydrogen peroxide bleaching decreased the kappa index 51.3% less than ozone bleaching, 25.0% less than chlorine dioxide (D) and 6.3% less combined chlorine dioxide-alkaline extraction (DE). To obtain kappa indices 50.9% and 37.9% lower than the index achieved by hydrogen peroxide, oxygen (LaO(p)) and ozone (LaO(LaZ)R) sequences respectively were needed. Lower-medium levels of hydrogen peroxide concentrations (1-3%) and high reaction times (210 min) proved to be suitable for bleaching of pulp olive trimming residues. This approach could be used on this residue to produce adequately bleached pulp.     

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.     

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).     

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.     

TCF bleaching of wheat straw pulp using ozone and xylanase. Part A: paper quality assessment

The XOAZRP TCF sequence was applied to bleach wheat straw pulp. Following each bleaching stage, the properties of the pulp (viz. kappa number, standard viscosity, borohydride viscosity and brightness) and of the resulting effluents were determined. The performance of the reagents was analyzed through the studies of xylanase treatment and crystallinity and scanning electron microscopy of the pulps. Finally, the pulp was refined at 1000 revolutions in a PFI mill and the mechanical properties of the resulting paper were determined and compared with those of paper from a eucalyptus pulp. Despite its shortcomings, wheat straw pulp can be effectively bleached with the proposed TCF sequence.     

Extracting hemicelluloses prior to aspen chemi-thermomechanical pulping: Effects of pre-extraction on pulp properties

Pre-extraction of hemicelluloses prior to pulping and conversion of the extracted hemicelluloses to other by-products will provide additional revenues to traditional pulp and paper industry. The effects of hemicelluloses pre-extraction with sulfuric acid on aspen (Populus tremuloides) chemi-thermomechanical pulp (CTMP) properties were investigated in this study. The sulfuric acid pre-extraction resulted in a release of 11% of hemicelluloses (determined as xylan) and acetic acid, especially at the second press-impregnation stage. Compared with CTMP without acid pre-extraction, the acid pre-extraction significantly reduced refining energy to a given freeness, and the pulps produced from acid pre-extracted chips have lower shives, higher strength properties except zero-span breaking length, lower bulk, but lower brightness at a similar specific refining energy. This study provides useful information for integration of biorefinery in mechanical pulp mills in the future.     

Rice straw pulp obtained by using various methods

Rice straw was used as an alternative raw material to obtain cellulosics pulps. Pulping was done by using classics reagents as soda (with anthraquinone and parabenzoquinone as aditives), potassium hydroxide and Kraft process. The holocellulose, alpha-cellulose and lignin contents of rice straw (viz. 60.7, 41.2 and 21.9 wt%, respectively) are similar to those of some woody raw materials such as pine and eucalyptus, and various non-wood materials including olive tree prunings, wheat straw and sunflower stalks. Pulping tests were conducted by using soda, soda and anthraquinone at 1 wt%, soda and parabenzoquinone at 1 wt%, potassium hydroxide and sodium sulphate (Kraft process) under two different sets of operating conditions, namely: (a) a 10 wt% reagent concentration, 170 degrees C and 60 min; and (b) 15 wt% reagent, 180 degrees C and 90 min. The solid/liquid ratio was 6 in both cases. Paper sheets made from pulp extracted by cooking with soda (15 wt%) and AQ (1 wt%) at 180 degrees C and 90 min pulp exhibit the best drainage index, breaking length, stretch and burst index (viz. 23 degrees SR, 3494 m, 3.34% and 2.51 kN/g, respectively).     

The effect of hemicelluloses on wood pulp nanofibrillation and nanofiber network characteristics

Hemicelluloses as matrix substances showed an important role in nanofibrillation of wood pulp. Never-dried and once-dried pulps with different amounts of hemicelluloses were fibrillated using a grinding treatment. The degree of fibrillation was evaluated by scanning electron microscopy observation of the fibrillated pulps and light transmittance measurements of the fibrillated pulp/acrylic resin composites. With a one-pass grinding treatment, the once-dried pulp with higher hemicellulose content was fibrillated into 10-20 nm wide fibers as easily as the never-dried pulps, while the once-dried pulp with lower hemicellulose content was not fibrillated into uniform nanosized fibers. This result indicates that hemicelluloses act as inhibitors of the coalescence of microfibrils during drying and facilitate the nanofibrillation of once-dried pulp. Furthermore, hemicelluloses provide adhesion between nanofibers, contributing to reduction of thermal expansion and enhancement of mechanical properties in the composites.     

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.     

Use of laccase in pulp and paper industry

Laccase, through its versatile mode of action, has the potential to revolutionize the pulping and paper making industry. It not only plays a role in the delignification and brightening of the pulp but has also been described for the removal of the lipophilic extractives responsible for pitch deposition from both wood and nonwood paper pulps. Laccases are capable of improving physical, chemical, as well as mechanical properties of pulp either by forming reactive radicals with lignin or by functionalizing lignocellulosic fibers. Laccases can also target the colored and toxic compounds released as effluents from various industries and render them nontoxic through its polymerization and depolymerization reactions. This article reviews the use of both fungal and bacterial laccases in improving pulp properties and bioremediation of pulp and paper mill effluents.     

Semichemical pulping of Miscanthus giganteus. Effect of pulping conditions on some pulp and paper properties

Miscanthus is an interesting raw material for pulp production, it is a high yield low maintenance plant with a high cellulose and hemicellulose content. Its semichemical pulp can be beneficial in paper for cardboard production process, which nowadays is usually made from secondary fibers, by increasing the mechanical properties of the paper produced. In this study, the influence of the percentage of NaOH used related to the dry Miscanthus weight, digestion time and refining time on some pulp and paper properties have been studied and compared with pulp obtained from commercial fluting paper (CF). Fiber size distribution of the Miscanthus pulp was found to contain a higher fines (less than 0.2 mm) percentage than the CF pulp. Hand-sheets made from Miscanthus pulp showed better mechanical properties than the ones made with the CF pulp. CMT, RCT and CCT indexes were higher when using 100% Miscanthus pulp or mixtures of Miscanthus and CF pulp. The only property which worsened was Gurley porosity. Of the three operational variables changed, refining time exerts the most significant influence on the pulp and paper properties measured.     

Alkaline pulping of some eucalypts from Sudan

Four eucalypts (Eucalyptus camaldulensis, Eucalyptus microtheca, Eucalyptus tereticornis and Eucalyptus citriodora) grown in Sudan were examined for their suitability for pulping and papermaking with different alkaline methods. Their physical, morphological and chemical characteristics are reported. The pulping trials with E. citriodora and E. tereticornis were carried out using the kraft-AQ, soda-AQ, modified AS/AQ (ASA), ASAM and kraft methods. For the other two species, only the ASAM and the kraft process were applied. ASAM pulping gave the best results in terms of yield, degree of delignification, mechanical and optical pulp properties. The best pulps, obtained in kraft and ASAM cooking of E. citriodora, were bleached to 88% ISO brightness in a totally chlorine free bleaching sequence (OQ1O/PQ2P). The bleached pulps, especially the ASAM pulp, showed good papermaking properties and would be suitable for manufacture of writing and printing grades of paper.     

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.     

Kraft pulp biobleaching and mediated oxidation of a nonphenolic substrate by laccase from Streptomyces cyaneus CECT 3335

A new laccase (EC 1.10.3.2) produced by Streptomyces cyaneus CECT 3335 in liquid media containing soya flour (20 g per liter) was purified to homogeneity. The physicochemical, catalytic, and spectral characteristics of this enzyme, as well as its suitability for biobleaching of eucalyptus kraft pulps, were assessed. The purified laccase had a molecular mass of 75 kDa and an isoelectric point of 5.6, and its optimal pH and temperature were 4.5 and 70 degrees C, respectively. The activity was strongly enhanced in the presence of Cu(2+), Mn(2+), and Mg(2+) and was completely inhibited by EDTA and sodium azide. The purified laccase exhibited high levels of activity against 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) and 2,6-dimethoxyphenol and no activity against tyrosine. The UV-visible spectrum of the purified laccase was the typical spectrum of the blue laccases, with an absorption peak at 600 nm and a shoulder around 330 to 340 nm. The ability of the purified laccase to oxidize a nonphenolic compound, such as veratryl alcohol, in the presence of ABTS opens up new possibilities for the use of bacterial laccases in the pulp and paper industry. We demonstrated that application of the laccase from S. cyaneus in the presence of ABTS to biobleaching of eucalyptus kraft pulps resulted in a significant decrease in the kappa number (2.3 U) and an important increase in the brightness (2.2%, as determined by the International Standard Organization test) of pulps, showing the suitability of laccases produced by streptomycetes for industrial purposes.     

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.     

Thermogravimetry study of xylanase- and laccase/mediator-treated eucalyptus pulp fibres

Thermogravimetric analyses (TGA) was applied to study the effects of enzymatic bleaching of eucalyptus pulp with xylanase and a laccase-mediator system. The thermal degradation profile of the pulps was sensitive to the enzymatic treatments. Xylanase treatment produced an ordered and clean microfibril, whereas laccase oxidized surface cellulose chains and increased the amorphous (paracrystalline) cellulose content. In this case, pulp viscosity decreased from 972 to 859 mL/g and apparent pulp crystallinity calculated from TGA data decreased almost 50%. Alkaline extraction was necessary to recover pulp crystallinity and to remove oxidized lignin in the laccase-treated samples. TGA data allowed differentiating and quantifying crystalline and amorphous cellulose. This thermogravimetric approach is a simple method in order to monitor superficial changes in cellulosic microfibrils.     

Preparation and characterisation of methylcellulose from annual cardoon and juvenile eucalyptus

We have studied the preparation of methylcellulose from annual cardoon and juvenile eucalyptus. The high cellulose and low lignin contents of these plants make them potential alternative resources for cellulose derivation. Their high quality pulps were obtained by the Impregnation Rapid Steam Pulping (IRSP) process and Total Chloride Free (TCF) bleaching sequences using hydrogen peroxide. The bleached pulp was methylated twice in an isopropanol slurry at 60 °C for 22 h after mercerisation in 40% NaOH solution. Yields of water-soluble and alkali-soluble methylcellulose were determined by solvent extraction. Substitution patterns of methylcellulose were determined by ¹³C Nuclear Magnetic Resonance (NMR) spectroscopy. The intrinsic viscosities and solution properties of methylcellulose were measured in either 4% NaOH solution or dimethyl sulphoxide (DMSO). This study shows that annual cardoon and juvenile eucalyptus can produce high-quality methylcellulose, which can be used as alternative resources for the production of methylcellulose.     

Alkaline pulping with additives of date palm rachis and leaves from Sudan

Soda-anthraquinone (soda-AQ), alkaline sulphite-anthraquinone (AS-AQ) and alkaline sulphite-anthraquinone-methanol (ASAM) pulping of date palm rachis and leaves from Sudan was carried under different conditions, and pulps with variable yields and mechanical properties were obtained. The date palm rachis gave best yields and mechanical properties with the AS-AQ or the ASAM process, while the leaves were best pulped with the soda method with low yield, but very good strength properties. Blending with 10% and 30% kenaf bark pulp was beneficial, especially for the AS-AQ pulps. Totally chlorine free (TCF) bleached rachis pulps were obtained of high brightness and strength properties suitable for use in writing and printing papers.     

New approach for upgrading pulp & paper quality: Mild potassium permanganate treatment of already bleached pulps

The present work introduces mild – room temperature – potassium permanganate treatment of cellulosic materials, namely already bleached pulps. Such treatment represents a new approach for upgrading pulp and paper quality, which is lacking in the literature. Potassium permanganate was investigated as a purifying and mild oxidizing agent for commercial already bleached softwood and bagasse pulps. It was found that treatment of the bleached beaten pulps, with 0.25–2% KMnO₄ (based on pulp weight), led to significant improvement in paper properties. The strength (breaking length) increased greatly and the brightness increased significantly due to treatment. The improvements were related to the degree of polymerization, and to the alphacellulose content of pulps.Moreover, potassium permanganate serves as a disinfectant and deodorizer. Thus treatment of bleached pulps with KMnO₄ is a promising remedy for the side effects which pulps suffer, during transportation and storage, before papermaking.     

Studying the effects of laccase-catalysed grafting of ferulic acid on sisal pulp fibers

Functionalization of sisal specialty pulp fibers by laccase-catalysed grafting of ferulic acid (FRC) was investigated. To this end, the extent of phenol coupling to fibers under different reaction conditions (laccase and FRC rates, and time) was evaluated in terms of pulp properties including kappa number (expressed as the combined contributions of lignin and hexenuronic acids), brightness, Klason lignin and surface anionic charge after Soxhlet extraction of acetone-treated pulp. The specific treatment resulting in the highest degree of grafting was then used in a comparative study of the effects of applying the laccase-FRC system to refined and unrefined pulp with a view to confirming whether the increased surface area obtained by effect of fibrillation would lead to enhanced grafting. Based on the results, refining the pulp prior to the enzyme treatment resulted in increased grafting which in turn led to handsheets with improved strength-related properties (particularly wet tensile strength) relative to control samples.