Sulfuric acid bleaching of kraft pulp II: Behavior of lignin and carbohydrate during sulfuric acid bleaching

The purpose of this study was to investigate the behavior of lignin and carbohydrates in kraft pulps during sulfuric acid bleaching. Beech kraft pulp and red pine kraft pulp were bleached with dilute sulfuric acid at pH 1.3 with addition of sodium nitrate and sodium nitrite at 100°C for 1 h. The pulps were then extracted with aqueous sodium hydroxide solution at 70°C for 1 h. Lignin and carbohydrates in the acid effluents and the alkali effluents were analyzed. The carbohydrate compositions of unbleached and bleached kraft pulps were also determined. The residual lignin in kraft pulp was degraded to a molecular size similar to that of milled wood lignin during sulfuric acid bleaching without additives, and it was further degraded to a much smaller molecular size during sulfuric acid bleaching with additives. It was found that the amount of carbohydrate dissolved in the bleach effluents were only about 1 of the dry weight of the kraft pulp under these bleaching conditions. The carbohydrates dissolved during bleaching were mostly of hemicellulose origin.Part of this report was presented at the 8th International Symposium on Wood and Pulping Chemistry, Helsinki, July 1995     

Sulfuric acid bleaching of kraft pulp III: reactivity of kraft pulping-resistant structures under acidic conditions

To investigate the bleaching mechanism, a lignincarbohydrate complex (LCC) model compound, a vinyl ether-type lignin model dimer, and a hexeneuronic acid model compound were treated with dilute sulfuric acid of different pHs. Beech kraft pulp and red pine kraft pulp were also treated with dilute sulfuric acid and then extracted with aqueous alkali. The amount of hexeneuronic acid degradation products in acid effluents and lignin dissolved in alkali effluents were determined. It was found that the benzyl ether-type LCC bond and the vinyl ether bond in lignin were effectively cleaved under the pH where sulfuric acid bleaching of kraft pulp was effective. Hexeneuronic acid group was also effectively degraded during sulfuric acid bleaching. In beech kraft pulp bleaching, both lignin removal and hexeneuronic acid removal contributed to the kappa number reduction. In red pine bleaching, the contribution of hexeneuronic acid removal was negligible, and most of the kappa number reduction was achieved by the lignin removal.Part of this report was presented at the 9th International Symposium on Wood and Pulping Chemistry, Montreal, July 1997     

Distribution of chemical components in the walls of kraft and bisulphite pulp fibres

Summary Fines removed from the surfaces of Pinus radiata fibres by beating were identified and characterised in terms of microfibril orientations in the surfaces of beaten fibres. Fines fractions subjected to chemical analyses were selected so that chemical component data could be related to specific layers or lamellae in fibre walls.Carbohydrate distributions within the walls of kraft fibres differed from those in bisulphite fibres. In the kraft fibres, glucomannan increased and other hemicelluloses decreased from the primary wall to the outer lamellae of the S₂ layer of the secondary wall. In the bisulphite fibres, hemicelluloses were uniformly distributed throughout the outer wall layers, i. e., the primary wall and the S₁ and outer lamellae of the S₂ layers of the secondary wall. More galactan but less arabinan, xylan, and glucomannan were found in the outer layers than in the inner layers of the bisulphite fibres. Carbohydrate distributions were determined for a range of bisulphite pulp yields (53 to 80 percent).The outer layers of the bisulphite fibres contained more Klason lignin than the inner layers. Acid-soluble lignin contents were similar in the inner and outer layers.Helpful discussions with Dr. V. D. Harwood are gratefully acknowledged.     

Sulfuric acid bleaching of kraft pulp 1: Bleaching of hardwood and softwood kraft pulps

To develop a new nonchlorine bleaching technology, hardwood and softwood kraft pulps, before and after oxygen-alkali predelignification, were treated with dilute sulfuric acid solutions (pH 1.0-1.8) at 100°C for 1 h and then extracted with aqueous sodium hydroxide at 70°C for l h. Hardwood kraft pulp was successfully bleached. The delignification selectivity was similar to that seen with oxygen-alkali bleaching; and it was greatly enhanced by the addition of sodium nitrate and sodium nitrite. The sulfuric acid bleaching can replace the presently adopted oxygen and chlorine stages if the additives are allowed. This bleaching process was also effective for oxygen-bleached hardwood kraft pulp, but it was less effective for softwood kraft pulp and oxygen-bleached softwood kraft pulp. The effectiveness of the addition of sodium nitrate and sodium nitrite was more apparent for softwood kraft pulp than for hardwood kraft pulp.Part of this report was presented at the 7th International Symposium on Wood and Pulping Chemistry, Beijing, July 1993     

Behavioural analysis of a nonionic detergent in the kraft pulp washing process using cryo-time-of-flight secondary ion mass spectrometry and cryo-scanning electron microscopy

In order to understand the kraft pulp decolouring mechanism on using a nonionic detergent, the pulp washing process and the resulting pulp handsheets were investigated by examining the brightness, kappa number, thioacidolysis product yield, and dewatering efficiency in the pressing sheet making process. The pulp decolouring could be attributed to a decrease in the lignin content and an improvement in the dewatering efficiency. Furthermore, the detergent distribution in the aqueous pulp suspension obtained during the pulp washing process was visualised using cryo-time-of-flight secondary ion mass spectrometry/scanning electron microscopy (cryo-TOF-SIMS/SEM). The detergent was clearly observed at the transverse surface of the pulp fibre cell wall and was also detected in the lumen of the fibres, suggesting the permeation of the detergent into the pulp fibre cell wall. Based on these results, the pulp decolouring mechanism can be proposed as follows: the detergent permeates into the pulp fibre cell wall and promotes the solution-exchange between the inside and the outside parts of the fibre cell wall, finally washing away the chromophoric substances such as lignin and its degradation products owing to the enhanced dewatering efficiency.     

Distribution of methyl-esterified galacturonan in chemical and mechanical pulp fibers

The effects of chemithermomechanical pulping (CTMP), high-temperature (HT)-CTMP pulping, and kraft pulping on the distribution of the pectin polymer, methyl-esterified polygalacturonan have been qualitatively evaluated using immunocytochemistry. Pectin was immunolocalized using an antibody (JIM7) specific for partly methyl-esterified polygalacturonan. A fluorescent antibody was linked to JIM7 and analyzed by epifluorescence microscopy. Pectin was found in both chemithermomechanical pulps in similar uneven patterns: Some fibers showed no labeling, whereas others showed extensive labeling in patches restricted to the fiber surfaces. Pectin labeling of bleached and unbleached kraft pulps did not show any presence of pectin. Labeling was correlated to the presence of compound middle lamella tissue left on the CTMP-treated surfaces. Pectin on pulp-fiber surfaces may affect the interfiber bonds and thereby the pulp properties.     

Evaluation of pulp and paper making characteristics of certain fast growing plants

Summary Four species of fast growing annual plant viz.Hibiscus sabdariffa, Crotalaria juncea, Tephrosia candida andHibiscus cannabinus and a variety of reed, Neyraudia reynaudiana were evaluated in the laboratory for their pulp and paper making properties. Data on proximate chemical analysis of raw materials, unbleached and bleached pulp properties, morphological properties of fibres and physical strength properties of paper sheets were evaluated. The unbleached pulp yields were 44.90–53.20% with all the five plant materials, while bleached pulp yields varied from 39.80–50.60%. The average fibre lengths and diameters of the unbleached pulp obtained from the five plant species were within the range of 0.75 mm–2.15 mm and 20–22 pun respectively. Paper hand sheets, made with bleached pulps (45° SR) obtained from the five plant species, gave burst indices 2.75–3.92 kPa m²/g, tear indices 3.73–9.61 m N m²/g and tensile indices 37.27–47.81 N mg^–1, indicating adequate strength properties for writing and printing type of paper.The authors thank Director, Regional Research Laboratory (CSIR), Jorhat, India, for his kind permission to publish this paper. The authors also wish to thank B. N. Tosh, JPF for his assistance.     

Sorption of kraft lignin from spent liquors on pulp fibres

In this investigation, the sorption of kraft lignin (KL) from spent liquors, membrane filtrated and model KL liquors on fully bleached softwood kraft pulp fibres, was studied. The time, temperature and alkalinity during the sorption experiments were chosen to reflect the conditions of black liquor impregnation of chips before the cooking operation. The amount of sorbed KL was estimated by brightness and kappa number measurements. A linear correlation between the k value and the kappa number was found. Among the parameters investigated, the concentration of metal non-process elements was found the most crucial for the sorption of KL on pulp fibres under black liquor impregnation. The influences of KL concentration, metal ion profile and KL molecular weight distribution on the KL sorption behaviour under black liquor impregnation are discussed.     

Thermogravimetric analysis of pulps

Summary A differential and an integral method of kinetic analysis of the data from isothermal pyrolysis of two pulps have shown that a cotton linters pulp has a lower activation energy throughout the entire reaction than has a bleached pine kraft pulp. In all cases, the activation energy decreases with increasing conversion. The mean values obtained were 30 and 36 kcal/mole by the differential and integral methods, respectively, for pyrolysis of the cotton linters pulp and 42 and 45 kcal/mole, respectively, for pyrolysis of the bleached pine kraft pulp. Neither method of analysis used in this work requires prior determination or empirical statement of the reaction order n. This is essential to a proper analysis since it has been shown that the reaction order cannot be regarded as a constant if the complete pyrolysis reaction is studied.Contribution No. 100 from the Empire State Paper Research Institute, State University of New York College of Environmental Science and Forestry, Syracuse, New York 13210.     

NEW PULPING METHOD FOR LINERBOARD

Traditionallykraftwasusedaslinerforlinerboard.Thekrafpulpingyieldwaslow,andairpollutionhigh.SomeresearcheshaveshownthattheyieldofAS-AQpulpwasmuchhigherthanthatofkraft,andthestrengthwasequaltothatofkraft,exceptforasome-whatlowertearstrength.Thewashingprofi-clencyofAS-AQpulpwashigherandairpol-lutionwasmuchlowerthanthoseofkraft.SoAS-AQpulpwasthoughtasapromisingre-placementofkraftforlinerboard.lntheresearchPinuskoraiensiSandLarljgmehniwereusedasrawmaterials,withtheL,(3')experimentaldesignan…     

On the selectivity of ozone delignification of softwood kraft pulps

Summary Ozonation of kraft pulp and oxygen-delignified kraft pulp in acetic acid/water mixtures has been studied at different pulp consistencies with and without an inhibitor to obtain information about the limitations of the selectivity of the ozone treatment. The experiments have been performed according to a full factorial design and data have been analysed by stepwise regression analysis. The results show that a better delignification selectivity can be achieved when ozone is applied in acetic acid media instead of conventional aqueous media. By combining conventional oxygen delignification and ozonation in acetic acid, pulps with equal strength properties and better optical properties compared to those of conventional O(DC)E prebleached pulps can be obtained. This study has also revealed that the reagent is utilized far more efficiently in ozonation at high pulp consistency (35%) than in ozonation at low consistency (1%), and that a similar selectivity can be achieved in both types of ozonation by choosing appropriate conditions. The greater selectivity of ozonation in acetic acid than in water is interpreted in terms of different stabilities of the oxidant in these reaction media. The relation between the formation of hydroxyl radicals and the extent and selectivity of delignification during ozonation has been investigated. The final bleaching of pulps prebleached with ozone in acetic acid medium has been studied. Two final bleaching sequences are presented, by which pulps with ISO brightness levels of 79% and 90% can be produced.The authors are indebted to the Swedish National Board for Technical Development (Styrelsen för Teknisk Utveckling) for financial support for this work and to STORA Technology for pulp tests and analyses     

Effect of cold storage treatments and transplanting stress on gas exchange, chlorophyll fluorescence and survival under water limiting conditions of Pinus radiata stock-types

The capacity of radiata pine seedlings to overcome planting shock in wet and dry conditions and their dependence on previous history was analysed by studying post-planting resumption of gas exchange and photochemical reactions, and survival 2 months later. Even under well-irrigated soil conditions, seedlings showed the effects of stress: gas exchange was reduced, but a clear difference between soil-plugged (PR) seedlings and bare-root (BR) seedlings was observed. Drought enhanced the severity of photosynthesis deprivation. Photochemical reactions, analysed by chlorophyll a fluorescence parameters, were not affected by planting shock in conditions of available soil water, but altered dramatically when drought stress was raised, suggesting structural damage of photosynthetic machinery. Despite the dramatic sensitivity of radiata pine to water availability, rewatering produced remarkable recovery, indicating good photosynthetic components repair capacity, which depended, however, on stock quality at the moment of planting. The ability of radiata pine to cope with drought in terms of post-planting performance depended on both storage conditions and water availability at the planting site. These findings provide information for tree physiologists and foresters as to how the management of radiata pine seedlings before planting can affect post-planting performance potential under wet or dry environmental conditions.     

Oxidative cleavage of lignin aromatics during chlorine bleaching of kraft pulp

Methanol liberation and methoxyl loss during chlorine bleaching of softwood kraft pulp were quantitatively investigated to estimate the degree of structural modification of lignin aromatics. An increase in the chlorine multiple led to enhanced methoxyl loss from lignin. Our result, using pH-adjusted chlorine water (pH 5.7), by which chlorination under oxidation-favorable conditions was achieved, strongly supported the importance of the oxidation reaction by chlorine during delignification and lignin degradation. It was also suggested that methanol can be produced not only via catalytic hydrolysis by chlorine but via oxidative cleavage of the ether bond as well. The infrared spectrum of chlorolignins suggested that chlorine oxidation can open aromatic rings to muconic acid derivatives without cleaving ether bonding of the methoxyl group. No straight relation between the methoxyl content and the kappa number of chlorinated pulps was shown. The methoxyl content of bleached kraft pulps subjected to successive chlorination and alkali extraction showed a good relation with the kappa number. This means that almost all the portions of the oxidatively modified lignin structure were successfully removed during these treatments, and the aromatic structures of residual lignin in chlorinated and alkali-extracted pulps were thought to remain intact.Part of this paper was presented at the 46th Annual Meeting of the Japan Wood Research Society, Kumamoto, April 1996; the 10th International Symposium on Wood and Pulping Chemistry, Yokohama, June 1999; and the 67th Pulp and Paper Research Conference, Tokyo, June 2000     

European hardwoods versus Eucalyptus globulus as a raw material for pulping

The importance of eucalypt as a raw material for pulping is steadily growing. Eucalyptus globulus was compared with European hardwood species using two alkaline pulping processes, kraft and alkaline sulfite, anthraquinone pulping (ASA), which is a recently developed modified alkaline sulfite process. All cooks were performed to similar kappa numbers. Poplar cooks resulted in the highest yields followed by eucalypt and birch which were on the same level. Yield of beech pulps was definitely lower. ASA pulps show a moderate higher yield due to the less alkaline pH-profile of the cooking liquor. This yield advantage was maintained and even enhanced after TCF-bleaching. The bleaching response of all pulps was excellent. The birch pulps had the highest tensile strength followed by the poplar and beech pulps. Surprisingly eucalypt pulps had the lowest tensile strength. But this was compensated by the very good tear index of eucalypt pulps. The runnability factor, as an index for the overall strength potential, was on the same level for all pulps. Due to the higher hemicellulose content of the ASA pulps their tensile strengths were higher, but tear strengths lower compared to the kraft pulps. The different morphology of the hardwoods investigated resulted in different volumes and light scattering coefficients of the corresponding pulps. Dedicated to Prof. Dr. Dr. h. c. mult.Walter Liese on the occasion of his 80th birthday.     

Studies on the effect of prehydrolysis and amine in cooking liquor on producing dissolving pulp from jute (Corchorus capsularis)

Dissolving pulps are the raw materials for the production of many different end-products. Jute is a very good source of cellulose. In this investigation, jute fiber was subjected to pulping in soda process in order to produce dissolving pulp under different prehydrolysis conditions and compared with prehydrolysed kraft pulp from jute. An increase of the prehydrolysis temperature or H₂SO₄ in prehydrolysis liquor increased the α-cellulose content and decreased the viscosity of pulp. The effect of ethylenediamine in soda liquor was also investigated when producing dissolving pulp. Jute fiber produced pulp having 90–97% α-cellulose. Ethylenediamine in soda liquor produced pulp of higher yield, viscosity and higher α-cellulose content than that of prehydrolysis soda or kraft pulp. The α-cellulose content and viscosity were increased with the increase of amine in soda liquor. The kappa number of dissolving pulp from jute was very low (9–5), which indicated that less bleaching chemicals are required for bleaching. The bleachability of soda-ethylenediamine pulp was lower than prehydrolysed soda and kraft pulp in ECF bleaching sequences. The bleachability of soda-ethylenediamine pulp was improved at the sacrifice of pulp yield when prehydrolysis was done prior to pulping. The alkali solubility S ₁₀ and S ₁₈ were 4–9 and 2–4%, respectively.     

Influence on pulping yield and pulp properties of wood density of Acacia melanoxylon

Wood density and pulp yield are key parameters in the evaluation of tree productivity and quality for pulping and their relationships are of high practical importance. The influence of wood density on pulp yield and other pulp quality parameters was investigated using Acacia melanoxylon and its natural variability as a case study. Twenty trees were harvested (five trees in each of four sites in Portugal), and wood discs taken at different height levels, from the base to the top of the tree, providing 100 wood samples, covering the natural variability of wood density ranging from 449?kg?m^?3 to 649?kg?m^?3. Under the same experimental conditions of kraft pulping, screened pulp yield ranged 47.0?C58.2?%, Kappa number 10.9?C18.4, ISO brightness 14.9?C45.6, fibre length 0.660?C0.940?mm and fibre width 16.2?C22.9???m. The pulp yield and Kappa number were not correlated with wood density. Higher pulp yields were associated with lower Kappa numbers and alkali consumption, suggesting the important role of chemical composition of wood on kraft cooking. The results confirm the high pulping potential of Acacia melanoxylon trees grown in Portugal and suggest the possibility of tree selection using both wood density and pulp yield.     

Development of high-retention water absorbent from cellulosic materials: water absorbent from bleached kraft pulp

This paper describes the synthesis of highretention water absorbents from kraft pulp and examination of their properties. A bleached kraft pulp from mixed hardwoods (LBKP) was carboxymethylated, then crosslinked with polyethylene glycol diglycidyl ethers (PEGDGE) with different degrees of polymerization under different conditions. A crosslinking agent with longer chain length might be advantageous for preparing a water absorbent with high water retention, and water retention could be improved at lower molar ratio of the crosslinking agent to the glucose unit. Isolation of carboxymethylated LBKP before crosslinking was advantageous for higher water absorbence. A water absorbent with a water retention value of as high as 500 times its weight was obtained.Part of this paper was presented at the annual meeting of the Society of Fibre Science and Technology, Tokyo, June 22–24, 1998     

北美地区杨树木材利用现状与前景

过去20多年, 北美地区的杨树已经从杂草树种转变为产生巨大经济效益的用材林树种, 杨树木材因其具有较高纤维素含量和较低的木质素含量, 适合用作纸浆和纸制品的原料。杨木制浆方法有机械法、化学法、半化学法和化学机械法, 杨木浆可以作为高级纸、纸板、新闻纸和包装纸。杨木牛皮纸浆与针叶材牛皮纸浆混合, 具有良好的成纸性能, 透明度高, 适合制作高级用纸。杨木也是传统的锯材、单板和胶合板工业的原材料, 用来生产锯材、单板、胶合板、木质复合板、包装箱、集装箱、火柴杆和筷子等。最近10年杨木定向刨花板和结构复合板产量显著增加, 利用前景广阔。从资源生产的角度来看, 在改良木材化学组成、纤维质量和自然耐久性等方面进行木材性质改良的转基因杨树研究取得了长足进展。从资源利用角度来看, 高价值的工程复合板和高得率的纸浆和纸产品将会在未来发展中快速增长。     

Evaluation of paper permanence

Summary The thermal stability of papermaking pulps under conditions of accelerated aging and at pyrolytic temperatures was examined. Degradation was found to be extremely complex and influenced by both the technical processes of papermaking and by the experimental methods used. At moderate temperatures, as used for accelerated aging, the folding endurance test was found to be a sensitive measure of degradation. Methods of reducing the variability of the test were considered, and a new technique capable of handling widely different results was developed and evaluated.Several papermaking pulps were artificially aged and the resultant loss of strength attributed to the interaction between a gradual fiber strength reduction and a rapid increase in interfiber bonding. Excessive initial inter-fiber bonding decreased handsheet stability. Softwood sulfite and kraft pulps were more stable than a birch kraft pulp, but the behavior of sulfite pulps varied greatly. The presence of lignin or a high hemicellulose content was not of itself sufficient to cause rapid aging.The pyrolytic behavior of pulps was investigated using thermogravimetric analysis. Papermaking pulps had mean pyrolytic activation energies between 30–45 kcal/mole. The activation energy decreased as the reaction proceeded. Correlation of these activation energies with the rate of loss of physical properties during accelerated aging was not good. The results indicated that the rate determining reactions for pyrolysis and for low temperature degradation are different but that the pyrolytic behavior is partially determined by the supramolecular structure. Empirical stability indices, based on both the integral and differential thermograms, were calculated, and these correlated well with the relative rates of loss of physical properties.A large part of this paper is based on the thesis of R. D. Carwell. Contributions were also made by L. Lyon and M. C. Varshney. This work was partially funded by the National Bureau of Standards     

Characterisation of pulp demethylation during chlorine dioxide bleaching

Summary The methoxyl loss from softwood kraft pulp during chlorine dioxide treatment can be accounted for by methanol and the methoxyl content of dissolved organic material in the bleach filtrate. This was established by a methoxyl group mass balance made at different bleaching times. It was found that ClO₂ rather than the in-situ generated hypochlorous acid is mainly responsible for the methanol formation. It was shown that fully methylated pulp is hardly demethylated by ClO₂ under industrial ClO₂ bleaching conditions when hypochlorous acid is effectively captured. Furthermore, the rates of formation of methanol and methoxyl group containing dissolved organic material are proportional to each other. The experimental evidence suggest that demethylation and delignification are closely related during ClO₂ treatment of softwood kraft pulp.