Chemical aspects of kraft pulping

Summary Kraft pulping is interpreted in chemical terms on the basis of results from extensive qualitative and quantitative model experiments. In essence, the behavior of lignin is explained as a competition between degradation reactions, mainly involving aryl ether cleavage with participation of neighboring groups, and condensation reactions, comprising conjugate addition of carbanions to quinone methide intermediates. The initial phase of technical delignification is tentatively ascribed to the cleavage of - and -aryl ether bonds in phenolic lignin units, whereas the cleavage of -aryl ether bonds in non-phenolic lignin units is considered to be the rate-determining reaction of the bulk phase. The residual phase may possibly be attributed to the rupture of C-C linkages and to aryl ether cleavage without neighboring group participation. Experimental support for these correlations is provided. The interplay of the various lignin reactions, illustrated in a summarizing scheme, explains some known observations in kraft pulping.Attention is drawn to analogies between reactions involved in the degradation of carbohydrates and those reponsible for the degradation of lignin. From the chemical standpoint, therefore, the selectivity of delignification is due to differences in the reactivity of the wood polymers, rather than to differences in the mechanisms of the degradation reactions. This fact explains the limitations of selective delignification.Parts of this work have been reported at the Fifth Planary Meeting of the International Academy of Wood Science on Copenhagen, Denmark, June 19, 1976, and at the ACS meetings in Appleton, Wisc., May 17–19, 1978, and Honolulu, Hawaii, April 1–6, 1979     

Characteristics of lignin obtained from steam-exploded softwood with soda/anthraquinone pulping

Lignins were obtained from a mixture of softwood sawdust using a hydrolytic pretreatment and a subsequent soda-anthraquinone delignification/pulping stage. Their potential uses and the effect of the pretreatment conditions on the yield (% of recovered lignin from black liquors) and chemical composition of isolated lignins were evaluated. The severity factor used combined the temperature and time of the hydrolytic process in a single ordinate (R_o). The severity range was modified from log R_o = 2.6 to log R_o = 4.6 and the pulping conditions were constant throughout the experiments. The effect of the cooking time on the chemical composition of precipitated lignins was also studied between 135–170 min for original (non-pretreated) material. Yield, elemental analysis, molecular weight distribution, Fourier transform infrared spectra (FTIR), structure, and the methoxyl and aliphatic/aromatic alcohol content of the various lignins, were compared.     

Topochemistry of delignification in Douglas-fir wood with soda,soda-anthraquinone and karft pulping as determined by SEM-EDXA

Summary Delignification studies on 0.5 m sections of Douglas-fir earlywood tracheids pulped by soda, soda-anthraquinone (soda/AQ) and kraft pulping processes were performed by determining bromine concentrations in various morphological regions with SEM-EDXA technique. Soda/AQ pulping was much more selective in removing lignin from the middle lamella regions than either soda or kraft pulping. However, up to 50% delignification, more lignin was removed from the secondary wall by soda or kraft, compared to soda/AQ pulping. The kinetics of lignin removal in the various morphological regions were established. Addition of AQ and sodium sulfide resulted in an earlier transition from a slow initial to a rapid bulk delignification, particularly in the middle lamella, and in an enhanced bulk delignification in the secondary wall. Anthraquinone was also found to promote residual delignification in the secondary wall, where sodium sulfide was not effective. The opposite was observed for the bulk delignification in the middle lamella, where only sodium sulfide addition improved the rate significantly. The great differences observed in the bulk delignification rates between middle lamella and secondary wall in soda pulping as well as their response to additives suggest structural differences between middle lamella and secondary wall lignins.Paper No. 6712 in the Journal Series of the North Carolina Agricultural Research Service, Raleigh, North Carolina. The paper, an excerpt from the Ph. D. dissertation of Shiro Saka, was selected for the second place Wood Award for 1980 cosponsored by Forest Products Research Society and the Kirby Forest Industries, Inc., Houston, Texas, and presented at the American Chemical Society Annual Meeting, Las Vegas, Nevada, August, 1980     

Lignin-carbohydrate bonds in a residual soda spruce pulp lignin

Summary The behaviour of lignin-polysaccharide complex of spruce wood in soda pulping was studied by the characterization of lignin-saccharide fractions isolated from a series of soda pulps. The dioxane pulp lignins contain 8–14% of carbohydrates in which glucose was the predominant component. Its content increased with increasing degree of delignification indicating the formation of secondary lignin-carbohydrate linkage. Both glycosidic and ether type of bond between residual lignin and cellulose in pulp was proved by methylation analysis of the pulp dioxane lignin.The work was supported by the Slovak Academy of Sciences grant number 2/999389/92.     

Combination treatment of kenaf bast fiber for high viscosity pulp

The viscosity of kenaf bast fiber has been found to be highly sensitive and variable with different pulping methods; therefore, it is important to choose proper chemicals and conditions for pulping and bleaching of kenaf bast fiber. From several pulping experiments, a nonconventional pulping method with a combination of ammonium oxalate pretreatment followed by soda pulping at normal pressure and then acidic chlorite delignification was developed to obtain high-viscosity pulp (162 centipoise). The optimum level of alkali dosage of soda pulping for high-viscosity pulp was found to be 15% (on pulp as NaOH). Pulps showed linear relations between viscosity and xylose or glucose contents, but the combination pulping method gave extremely high pulp viscosity, beyond the relations. The highest viscosity pulp from kenaf bast fiber demonstrated a tear index about twofold and a folding endurance 6.2-fold higher than those of Manila hemp pulp with comparable tensile and burst indexes. The high-viscosity pulp could be used in the production of high-quality currency paper or longevity paper for special uses.Part of this paper was presented at the 43rd Lignin Symposium, Fuchu, Tokyo, October 26–27, 1998     

Phenyl nucleus-exchange method for the degradation of lignin

Summary The phenyl nucleus-exchange method (NE-method) is a procedure for the degradation of lignin which allows the C–C linkages between the side chains and the phenyl nuclei to be cleaved selectively, and the phenyl nuclei to be liberated finally as polyhydric phenols. The important characteristic of this method is to take advantage of the dealkylation in diphenylmethane type structures in the presence of boron trifluoride and excess phenol, for the degradation of lignin. The lignin building units which give phenol monomers (guaiacol and/or catechol in softwood lignin) almost quantitatively by this method are noncondensed types and diphenylmethane types, and each of these units has any of the benzyl alcohol, the benzyl ether, the conjugated double bond, the -carbonyl group and the C-aryl bond, in the side chain. The yields of phenyl nuclei are about 25–30% in softwood protolignins and about 8–13% in technical lignins. In this paper, the reaction theory and the degradation mechanism of lignins in the NE-method are outlined.     

Examination of polychlorinated dibenzo-<Emphasis Type="Italic">p</Emphasis>-dioxins and polychlorinated dibenzofurans in process water of kraft pulp bleaching mill using chlorine dioxide from the aspect of environmental water quality

Process water of a pulp mill with extended kraft cooking, two-stage oxygen delignification, and chlorine dioxide bleaching was examined from the aspect of a new standard for environmental water quality in Japan. According to the new standard, the concentration of dioxins – polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, coplanar polychlorinated biphenyls – in environmental water is restricted to less than 1pg TEQ/l. We clarified that the concentrations of the dioxins in sewers in the chlorine dioxide stage and the alkali stage were less than 1pg TEQ/l and that the 2,3,7,8-tetrachlorodibenzofuran concentrations were 0.5pg/l or less. In addition, a main source of 1,3,6,8- and 1,3,7,9-tetrachlorodibenzo-p-dioxins in the process water seemed to be an agrochemical in water supplied from a river.     

Influence of pulping variables on the properties of Elaeis guineensis soda pulp as evaluated by response surface methodology

Response surface methodology with central composite design was used to investigate the influence of pulping conditions, viz. cooking temperature, time-at-temperature and alkali charge for alkaline pulping of oil palm empty fruit bunch fibres, on the properties of the pulp and paper obtained (screened yield, Kappa number, tensile and tear indices). Quadratic models consisting of the three independent variables were found to accurately describe the pulping of this material with correlation between the actual and predicted values of the response variables having a relatively good degree of R². The delignification of oil palm empty fruit bunch fibre can be achieved with ease using sodium hydroxide as the sole cooking agent to about 30–45% yield with the process greatly enhanced by an increase in temperature. Although, a relatively low temperature (about 160°C) within the limits of pulping time (60–120 min) and of alkali charge between 20 and 30% is generally sufficient.     

Thermo-mechano-chemical pretreatment of wood in a process development unit

Summary Continuous thermo-mechano-chemical pretreatment of wood (particle size: 0.25–0.50 mm) was conducted by steam injection for rapid heating-up of slurry (170–215°C), flow through homogenization valves (mechanical effects), and autohydrolysis in a plug flow reactor (90–95 s) (thermochemical reactions). The process was carried out in aqueous phase without addition of any chemicals. Residues resulting from the pretreatment were characterized by thermal and elemental analyses. The extent and selectivity (hemicellulose removal and delignification) of the wood solubilization were analyzed as a function of pretreatment temperature and the thermal severity factor, the goal being the optimization of hemicellulose dissolution. Experimental results were compared with those previously obtained in a batch cascade reactor system.Thanks are due to the Natural Science and Engineering Research Council (NSERC) of Canada and the Fonds pour la formation de chercheurs et l'aide à la recherche (FCAR) of Quebec for financial support. The author wishes to express his gratitude to the Université de Sherbrooke, Canada, where experimental trials were carried out     

Evaluation of chloroform formed in process of kraft pulp bleaching mill using chlorine dioxide

Chloroform formation, balance, and discharge were estimated in a kraft pulp mill that used an elemental chlorine-free (ECF) bleaching line with chlorine dioxide as well as an effluent treatment process. This was achieved by collecting and analyzing discharge water and air samples that contained measurable levels of chloroform. Chloroform formation in ECF bleaching of hardwood oxygen-delignified kraft pulp (LOKP) was estimated to be 2.07–5.34g/pulp air-dried ton (adt), and approximately 30% of the chloroform produced was discharged to bleaching effluents. Chloroform in the effluents was not decomposed by activated sludge, and more than 97% was emitted to the air by volatilization. It is suggested that chloroform formation in Japanese LOKP bleaching mills can be decreased to 16–42t/year with a production of 8 million adt pulp by introducing ECF bleaching into all mills. This is a considerable fall from the chloroform discharge from ECF and chlorine bleaching mills in Japan that was estimated to be approximately 1000t for the 1999 fiscal year.     

桉树制浆综述

本文介绍了(1)用桉木生产漂白化学浆,包括硫酸盐法和碱一蒽醌法制浆;(2)用按木生产漂白半化学浆,主要是中性亚硫酸盐半化学高得率浆;(3)用桉木生产漂白化学机械浆,包括冷碱法和亚硫酸盐法制浆;(4)用桉木生产漂白化学热磨机械浆。     

Characterization of lignin-derived products from various lignocellulosics as treated by semi-flow hot-compressed water

To elucidate the decomposition behaviors of lignin from different taxonomic groups, five different lignocellulosics were treated with hot-compressed water (230 °C/10 MPa/15 min) to fractionate lignins into water-soluble portions, precipitates, and insoluble residues. The lignin-derived products in each fraction were characterized and compared. The delignification of monocotyledons [nipa palm (Nypa fruticans) frond, rice (Oryza sativa) straw, and corn (Zea mays) cob] was more extensive than that achieved for Japanese cedar (Cryptomeria japonica, gymnosperm) and Japanese beech (Fagus crenata, dicotyledon angiosperm). The water-soluble portions contained lignin monomers like coniferyl alcohol and phenolic acids, while the precipitates contained higher molecular weight lignin with high content of ether-type linkages. Lignin in the insoluble residues was rich in condensed-type structures. In all five lignocellulosics, ether-type linkages were preferentially cleaved, while condensed-type lignin showed resistance to hot-compressed water. In the monocotyledons, lignin–carbohydrate complexes were cleaved and gave lignins that had higher molecular weights than those eluted from the woods. These differences would facilitate the delignification in monocotyledons. Such information provides useful information for efficient utilization of various lignocellulosics.     

Lignin characterization of triploid clones of Populus tomentosa Carr.

In order to understand the structural characteristics of lignin in triploid clones of Populus tomentosa and its changes in the processes of pulping and bleaching, milled wood lignin (MWL), lignin carbohydrate complex (LCC) and the residual lignin from kraft pulp (KP) and sulfite pulp (SP) were isolated and analyzed by Fourier transform infrared (FTIR) spectrum and ¹³C nuclear magnetic resonance (NMR). The most diagnostic peaks were assigned and the differences were discussed. The spectral patterns reveal that triploid P. tomentosa shows the specific features of hardwood from temperate areas, but in the spectrum of FTIR, the strength ratio of A 1270 cm⁻¹ to A1226 cm⁻¹ is 0.88, higher than the average of hardwood from temperate areas, which will make the lignin delignification more difficult during pulping and bleaching. The LCC from triploid P. tomentosa is mainly composed of xyloglucan and glucuronic acid, and other glucides have much lower ratio. In LCC FTIR, there are three peaks at 1 427, 1 329 and 1 046 cm⁻¹, indicating that both semi-cellulose and cellulose could exist in LCC, and that there might be relationships between cellulose and lignin. Compared with the residual lignin from KP and SP, the condensed structure in KP is more than that in SP.     

世界木材制浆技术新进展

文章论述了木材制浆技术的新进展，在硫酸盐法制浆技术的革新方面，推荐了间歇蒸煮的快速置换加热（ＲＤＨ）技术与连续蒸煮的改良连续蒸煮（ＭＣＣ）和深度脱木素改良连续蒸煮（ＥＭＣＣ）技术。还介绍了超高得率制浆方法，特别是碱性过氧化氢机械制浆（ＡＰＭＰ）法和爆破制浆（ＥＰ）法，用这两种方法生产的纸浆得率高、白度高、强度高、能耗较低。     

Prehydrolysis of beechwood

Summary The kinetics of the isothermal prehydrolysis of beechwood at 160°C and 170°C were investigated. It was shown that the hydrolysis of the hemicellulose portion was realised in two phases. The depth and rate of the first rapid prehydrolysis phase and the second slow phase depend on the temperature used. The lignin content in the prehydrolysed chips increased with the duration of the prehydrolysis due to the easily removable hemicellulose portion. The maximum amount of lignin extracted was gained after 45–60 minutes of isothermal prehydrolysis at 160°C with the yield decrease to 82–80 per cent and at 170°C with the yield decrease to 70–68 per cent. At the temperature of 160°C the amount of the lignin portion extracted was about 5 per cent and at 170°C at about 10 per cent of the whole lignin content in wood. The extraction of the whole hemicellulose portion present in wood was attained at 160°C after 5 hours prehydrolysis time, at 170°C after 80 minutes.By the prehydrolysis of hardwood to 30 per cent loss of the wood substance highly purified dissolving pulp was prepared by AQ catalysed sodium pulping. The pulp attained was characterised by a high alpha-cellulose content over 97 per cent and a low solubility in solutions of alkali. The sulphur-free delignification together with the low consumption of active chlorine (1.5–1.7 per cent) cause less environmental pollution.     

Relationship of water to adventitious rooting in stem cuttings of Populus species

Populus species, characterized by fast growth and easy vegetative propagation, are widely used in agroforestry practices. The substantial water requirement of poplars make them interesting subjects for water balance studies. No information exists on soil moisture requirements for initial root and shoot growth of Populus cuttings. This study on leafless hardwood cuttings of Populus x euramericana (Dode) Guinier cv. Robusta examined the dynamics of water use during propagation, as influenced by two initial soil water potentials (–0.006 and –0.06 MPa). Differences in the initial water potential of the cuttings was achieved by three pretreatments i.e., fresh, soaked and dried. Initial _shoot was –1.45, –0.10 and –2.10 MPa in fresh, soaked and dried cuttings, respectively. Soil moisture had a major effect on rooting. Water-stressed cuttings took a longer time to root and had fewer roots. Pre-soaking of cuttings stimulated rooting, particularly under the drier soil moisture conditions. Initially the water potential of cuttings decreased with time and with the formation of roots it stabilized in all the pretreatments. The reduction in water potential of cuttings after planting was related to an increase in resistance to water flow in the xylem.This revised version was published online in November 2005 with corrections to the Cover Date.     

Recent progress in the chemistry and topochemistry of compression wood

Summary A review of the chemistry and topochemistry of compression wood with 200 references. Compression wood contains on the average 30% cellulose, 35–40% lignin, 10% galactan, 9% galactoglucomannan, 8% xylan, and 2% of a 1,3-glucan (laricinan). The cellulose is less crystalline, and the xylan has fewer arabinose side chains than in normal wood. The lignin is composed of guaiacylpropane and p-hydroxyphenylpropane units. It is more condensed, has a higher proportion of carbon-carbon bonds, and contains fewer arylglycerol--aryl ether structures than a normal conifer lignin. The ray cells and the primary wall of the tracheids have the same chemical composition in normal and compression woods. The galactan is largely located in the outer region of the secondary wall. Only 5–10% of the lignin in compression wood tracheids is extracellular. The middle lamella is less lignified than in normal wood, while the S₁ and inner S₂ layers have a lignin concentration of 30–40% which is twice as high as in normal wood. The lignin content of the S₂ (L) layer is equal to or higher than that of the intercellular region along the wall. The review is concluded with a brief reference to areas where present information is incomplete or lacking.A portion of an Academy Lecture of the International Academy of Wood Science, presented at the International Symposium on Wood and Pulping Chemistry (Ekmandagarna 1981), held in Stockholm, Sweden, June 9–12, 1981. Reprints of the unabridged review, published under the title Recent Progress in the Chemistry, Ultrastructure, and Formation of Compression Wood in the preprints of the symposium (SPCI Report 38, Vol. 1, p. 99–147) are available from the author. I wish to express my gratitude to my colleague Professor Robert A. Zabel for generous travel assistance     

Lignin Characterization of Triploid Clones of Populus tomentosa Carr.

In order to understand the structural characteristics of lignin in triploid clones ofPopulus tomentosa and its changes in the processes of pulping and bleaching, milled wood lignin （MWL）, lignin carbohydrate complex （LCC） and the residual lignin from kraft pulp （KP） and sulfite pulp （SP） were isolated and analyzed by Fourier transform infrared （FTIR） spectrum and ^13C nuclear magnetic resonance （NMR）. The most diagnostic peaks were assigned and the differences were discussed. The spectral patterns reveal that triploid P tomentosa shows the specific features of hardwood from temperate areas, but in the spectrum of FTIR, the strength ratio orAl270 cm^-1 to A1226 cm^-1 is 0.88, higher than the average of hardwood from temperate areas, which will make the lignin delignification more difficult during pulping and bleaching. The LCC from triploid P tomentosa is mainly composed of xyloglucan and glucuronic acid, and other glucides have much lower ratio. In LCC FTIR, there are three peaks at 1 427, 1 329 and 1 046 cm^-1, indicating that both semi-cellulose and cellulose could exist in LCC, and that there might be relationships between cellulose and lignin. Compared with the residual lignin from KP and SP, the condensed structure in KP is more than that in SP.     

Alkaline pulping with additives. A review

Summary The technology and chemistry of recent advances in alkaline pulping are reviewed from the standpoint of the authors' work over the past few years. Topics reviewed include soda-amine [particularly soda-ethylenediamine (EDA)], soda-anthraquinone (AQ), kraft-AQ, and soda-AQ/EDA pulping and their effects on pulp strength properties and bleachability. There is evidence to support the concept that the rates of all alkaline delignification reactions, including kraft, are controlled by a reductive step which transfers electrons to the degrading lignin.     

Industrial utilization of tobacco stalks II: preparation and characterization of tobacco pulp by steam explosion pulping

Our previous paper showed tobacco stalks to posses the characteristics of a raw material for pulp and paper application. It contains the major biomass constituents and cell components common to wood species. In this study, preparation and characterization of tobacco stalk pulp by steam explosion (SE) pulping at two chemical pretreatments were attempted. Chemical pretreatment prior to SE pulping improved the brightness, yield, and strength properties of the resulting tobacco SE pulps in the order: 6% Na₂SO₃ + 1% NaOH > 6% Na₂SO₃ > control (untreated). The 6% Na₂SO₃ + 1% NaOH-impregnated tobacco stalks produced SE pulps of good fiber length distribution and considerable properties that compare well with pulps from other raw materials obtained from previous studies, and the nonimpregnated ones showed strength properties superior to those of their poplar counterpart. Prior to bleaching, pretreating the tobacco stalk SE pulps with two stages, 2% NaOH at 90°C, improved the initial pulp brightness by about 5 points. Two-stage 6% H₂O₂ bleaching gave a comparable effect with hypochlorite bleaching for both tobacco and poplar, giving a 29–34 brightness point increase for tobacco SE pulp and 61 for the poplar samples. The differences in the bleaching responses for untreated tobacco and poplar SE pulps were attributed to the differences in their lignin structure, as shown in the total yield of their respective nitrobenzene oxidation products and FT-IR spectra. Tobacco SE pulps contain more of the guaiacyl-type lignin and poplar the syringyl-type lignin.This paper was presented in part during the 1998 CORESTA (Cooperation Centre for Scientific Research Relative to Tobacco) Congress, Brighton, UK, October 1998