Thioacidolytic analysis of residual lignins isolated from the chemical pulps of spruce (Picea abies) and beech (Fagus sylvatica) wood

Eight different residual lignins isolated from unbleached chemical pulps [sulfite, kraft, alkaline sulfite-anthraquinone-methanol (ASAM), soda/AQ/MeOH] of spruce and beech were characterized using gel permeation chromatography (GPC), thioacidolysis, and desulfurization to determine average molecular weight, amounts of uncondensed β-O-4 linkages, and dimeric linkage patterns, respectively. The total amounts of G-CHSEt-CHSEt-CH₂SEt and S-CHSEt-CHSEt-CH₂SEt were markedly reduced in residual lignins to 40% to 80% of the values for the corresponding milled wood lignins (MWLs). The number of dimeric units determined by thioacidolysis and desulfurization of the residual lignins was decreased by onehalf to one-fifth compared to the MWLs. Among the diverse types of dimeric units, reduction of β-1 and β-5 units was significant in most of the residual lignins, with the exception of beech ASAM residual lignin. Compared to beech MWL, 40% more C6–C3 main monomers were detected, whereas the relative composition of the dimeric units in the beech residual lignin was very similar to that in the beech MWL. The average molecular weights of residual lignins were less than those of the MWLs. However, the average molecular weights of the spruce kraft and soda residual lignins were determined to be higher than those of the corresponding MWLs.     

Phenomenological kinetics of wood delignification: application of a time-dependent rate constant and a generalized severity parameter to pulping and correlation of pulp properties

Summary Kraft delignification kinetics has been modelled on the basis of a first order decay process with a time-dependent rate constant. A generalized severity parameter derived from this kinetic model, R_oh, has been applied to describe the lignin solubilization during alkaline (soda and Kraft) and bisulphite pulping of different wood species. The model has been succesfuly applied to data sets available from the literature. Our approach has combined the main process variables (temperature, time and chemical load) into a single parameter, R_oh, which is then used as a reaction ordinate to map the changes in chemical composition and physical properties. An extension of the initial formulation of the R_oh parameter has been made to cover the situations where the catalytic system is composed by two active chemical species, as in the Kraft process.Symbols C Lignin concentration - C₀ Lignin concentration at t = 0. - _a Average activation energy (kJ/mol) - f_i Conversion of the reacting substrate (lignin) - F[ ] A function of the conversion - g(E) Distribution of activation energies function - k(t) Time-dependent rate constant - K Severity model constant - R_oh The generalized severity parameter, or reaction ordinate - S _i ⁰ Initial concentration of the reactive substrate (lignin) - t Reaction time (min) - T(t) Reaction temperature (°C),which may vary as a function of time in non isothermal conditions - T_ref Reference temperature (°C), normally choosen in the middle of the experimental conditions used - X(t) Chemical load (g chemical/g o.d. wood), for the first active specie - X_ref Reference chemical load (g chemical/g o.d. wood). - Y(t) Chemical load (g chemical/g o.d. wood), for the second active specie - Y_ref Reference chemical load (g chemical/g o.d. wood) Greek Letters Constant in k(t) (min^-) - Parameter defining the shape of the Kohlrausch function which describes the distribution of activation energies - () Euler's gamma function - Parameter expressing the strength of the first active chemical in the specific reaction considered - Parameter expressing the strength of the second active chemical in the specific reaction considered - ₀ Effective lifetime (min). - /- Average lifetime (min). - Parameter expressing the importance of temperature in the specific reaction considered. For instance a value of 14.75 will indicate that the rate of reaction has doubled ten degrees above the reference temperature, all the other variables remaining constant. Authors are indebted to CICYT (Science and Technology Inter Ministerial Commission, Spanish Government) and Generalitat de Catalunya (Catalan Regional Government) for financial support, project number QFN92-4317 and grant number AIRE 92/I-22. Contributions of the National Science and Engineering Research Council of Canada (NSERC) and Fonds des Chercheurs et Actions de Recherche (FCAR) are gratefully acknowledged.     

Acetic acid pulping of wheat straw under atmospheric pressure

Atmospheric acetic acid pulping of wheat straw was carried out. Pulping conditions and their effects on pulp properties were investigated in detail, and a comparison between acetic acid (AcOH) pulp and soda-anthraquinone (AQ) pulps of wheat straw was made of the chemical composition, strength, and fiber morphology of the pulps. Wheat straw was successfully pulped and fractionated into pulp (cellulose), acetic acid lignin, and sugars (monosaccharides from hemicellulose), making it easy to utilize them. It was found that among the pulping conditions the dosage of H₂SO₄ as catalyst was the most notable, and the extent and rate of delignification could be controlled by varying the amount of the catalyst. The results also showed that acetic acid pulp was quite different from soda-AQ pulp. About 70% of the ash or 90% of the silica in wheat straw were kept in AcOH pulp. The ash might function as filler and be beneficial to the printability of paper. It was known that many epidermal cells existed in AcOH pulp in bundles or in single cells. These ash-rich nonfiber cells seemed to hinder the bonding between fibers. AcOH pulp had lower strength than soda-AQ pulp, which might result mainly from the chemical damage of fibers caused by acid, not from the depolymerization of cellulose.Part of this paper was presented at the 65th Pulp and Paper Research Conference of Japan TAPPI, Tokyo, June 1998     

The influence of heartwood on the pulping properties of Acacia melanoxylon wood

The pulping wood quality of Acacia melanoxylon was evaluated in relation to the presence of heartwood. The sapwood and heartwood from 20 trees from four sites in Portugal were evaluated separately at 5% stem height level in terms of chemical composition and kraft pulping aptitude. Heartwood had more extractives than sapwood ranging from 7.4% to 9.5% and from 4.0% to 4.2%, respectively, and with a heartwood-to-sapwood ratio for extractives ranging from 1.9 to 2.3. The major component of heartwood extractives was made up of ethanol-soluble compounds (70% of total extractives). Lignin content was similar in sapwood and heartwood (21.5% and 20.7%, respectively) as well as the sugar composition. Site did not influence the chemical composition. Pulping heartwood differed from sapwood in chemical and optical terms: lower values of pulp yield (53% vs 56% respectively), higher kappa number (11 vs. 7), and lower brightness (28% vs 49%). Acacia melanoxylon wood showed an overall good pulping aptitude, but the presence of heartwood should be taken into account because it decreases the raw-material quality for pulping. Heartwood content should therefore be considered as a quality variable when using A. melanoxylon wood in pulp industries     

Steam explosion pretreatment used to remove hemicellulose to enhance the production of a eucalyptus organosolv dissolving pulp

The steam explosion (SE) pretreatment associated with the organosolv process was investigated to produce dissolving pulp from eucalyptus. Prehydrolysis Kraft (PHK) pulping was also done to produce viscose and acetate grade pulps as reference. The organosolv pulps were delignified in two steps with sodium chlorite. Viscose and acetate grade PHK pulps were bleached by OD₀(EH)D₁P and OD₀(EP)D₁PCCE sequences, respectively. Dilute acid-catalyzed (with acid addition) SE pretreatment dissolved more xylan than auto-catalyzed (no acid addition) SE pretreatment. Steam-exploded unbleached organosolv pulps showed lower residual lignin content and screened yield than unbleached organosolv pulps without SE pretreatment. Steam explosion pretreatment helped to decrease lignin content and damaged fiber length of unbleached organosolv pulps. The 1.0% H₂SO₄ organosolv pulp (organosolv dissolving pulp at bioconversion conditions) showed the highest reactivity. Even showing low viscosity for some applications, in general, the organosolv dissolving pulps produced in this study can be used for making lyocell fibers.     

白腐菌预处理对杨木硫酸盐法制浆性能的影响

以杨木和白腐菌为研究对象,测定白腐菌预处理前后杨木化学组成与纤维形态的变化,找出合适菌株和最佳的预处理时间,进行硫酸盐法制浆前的预处理,比较制浆后浆料的卡伯值、得率、黏度和纸张的物理性能.结果表明:对木质素降解程度由大到小为香菇菌、云芝菌、杂色木云芝菌、脉射菌、佛罗里达侧耳和糙皮侧耳,香菇菌对综纤维素的降解程度最大,杂色木云芝菌的降解最小;预处理后,杨木纤维平均长度略有降低,纤维的长宽比得到了提高,壁腔比下降;与参照样相比,经脉射菌、杂色木云芝菌和佛罗里达侧耳预处理后制得的浆料,卡伯值降低、得率增加、黏度增加、脱木素选择性提高,纸张的撕裂指数和抗张指数均增加;经过香菇菌预处理后得到的浆料,虽然卡伯值降低、脱木素选择性增加,但是黏度和得率却在下降,纸张的撕裂指数和抗张指数减小.经过这4种白腐菌预处理后,纸张的耐折度和白度均大于对照.     

Dissolution and dispersion of spruce wood components into hot water

Summary The dissolution and dispersion of components from Norway spruce (Picea abies) wood were examined in laboratory experiments to determine the factors influencing variations in dissolved and colloidal substances in mechanical pulp suspensions. Finely ground, fresh spruce wood was suspended in water at 90 °C and was agitated intensively for up to 12 h, after which the concentrations of dissolved and dispersed lipophilic extractives, lignans, carbohydrates and lignins were determined. Sapwood and heartwood were studied separately. Effects of pH and added electrolytes on the dissolution and dispersion of wood components were also investigated.Higher amounts of lipophilic extractives, and especially of triglycerides, were dispersed from sapwood than from heartwood. The release of lipophilic extractives continued for up to 3 h, after which the concentrations in the suspensions leveled off. At this stage the composition of the dissolved and dispersed lipophilic extractives equaled that of the wood. The amount of lipophilic extractives in the suspensions increased with increased pH, in the range of 4.5–6.7, but was lower in the presence of electrolytes. The dissolution of carbohydrates continued even beyond 3 h of agitation. The high water temperature induced hydrolytic reactions, thereby releasing especially arabinose. The release of arabinose through the hydrolytic cleavage from polysaccharides was more extensive at pH 4.5 than at pH 5.5 and 6.7. More polysaccharides containing galacturonic acid units (pectins) were dissolved at a higher pH. Much more polysaccharides containing glucose, most probably starch, were present in the sapwood suspensions. The dissolution of lignins also continued throughout the 12 h experiment. The measured UV-absorption, after extraction of lignans, was roughly the same for sapwood and heartwood suspensions. Slightly less lignins were released in the presence of electrolytes. Lignans were released only from heartwood.     

Formation of a complex with aluminum by ozone-treated kraft lignins and their low molecular weight fragments

The formation of a complex with aluminum by low molecular weight compounds and saponified ozone-treated kraft lignins was evaluated based on the decrease in pH of their solutions on the addition of 0.1 M AlCl₃. Decreases in pH were observed with the solutions containing compounds having adjacent carboxyl groups (oxalic acid), carboxyl/alcoholic hydroxyl groups (glycolic acid), carboxyl/formyl groups (glyoxylic acid), and phenolic hydroxyl groups (protocatechuic acid) on the addition of 0.1 M AlCl₃. The malonic and phthalic acids, having two carboxyl groups, were also effective. These results show that the compounds were effective in forming complexes with aluminum. This finding corresponds to the fact that aluminum toxicity is reduced by formation of a complex with aluminum, except in phthalic acid. The chemical structures stated above in ozone-treated kraft lignins contribute, at least partly, to the complex with aluminum. The pH of solutions containing saponified ozone-treated kraft lignins and alkaline-treated kraft lignin decreased more than that without modified kraft lignins on the addition of 0.1 M AlCl₃, showing that they were effective in forming a complex with aluminum. The high molecular weight part of saponified ozone-treated kraft lignin was effective in forming a complex with aluminum and in reducing its toxicity.     

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.     

Effects of temperature on reproductive capacity and longevity of Trissolcus simoni, an egg parasitoid of Eurygaster integriceps

In order to understand the effects of temperature on Trissolcus simoni, some parameters of the life tables of adult parasitoids were investigated under laboratory conditions. The following parameters were measured (the values in parentheses were obtained at 20, 26, and 32 °C temperatures, respectively): net reproductive rate (R_o=37.785, 40.301, and 58.299), intrinsic rate of population increase (r_m=0.111, 0.221, and 0.325), generation time (T=32.77, 16.60, and 12.49 days), doubling time (DT=6.245, 3.136, and 2.133), and finite rate of increase (=1.117, 1.247, and 1.385). Fecundity increased with increasing temperature. The values for total number of eggs deposited per female were 50.1, 64.1, and 68.1, and average female longevity was 24.2, 13.8, and 11.1 days at 20, 26, and 32°C, respectively. Temperature had a significant effect on longevity and oviposition and post-oviposition periods. The results of the study are discussed and compared with life-table parameters of other scelionids.     

造纸废液喷雾干燥工艺参数影响因素探讨

通过对目前造纸工业中6种主要造纸废液的成分对喷雾干燥工艺参数造成影响的研究，得出了不同造纸废液的喷雾干燥有不同的工艺条件，分析了废液的浓度、温度和粘度之间的相应关系，最后针对喷雾干燥出口温度高、热效率较低的特点，提出了用干燥后的热尾气浓缩稀废液节能新工艺。     

人工林杉木与马尾松制浆性能的比较和评价

对人工林杉木与马尾松进行了制浆性能比较,测定了它们的纤维形态和化学组成,优选出最佳蒸煮工艺条件,测定了浆料的物理强度,最后用座标综合评定法来全面评价它们的制浆性能。结果认为,人工林杉木木材制浆性能略优于马尾松。研究结果为杉木在造纸上的应用提供了重要的依据。     

Studies on milled wood lignins from spruce part 1. Composition and molecular properties

Summary Isolation of six milled wood lignins (MWL) from spruce under different conditions resulted in variable yields between 2.2% and 11.8% related to wood lignin. The composition of crude and purified lignins was evaluated with regard to non-hydrolyzable residue, acid-soluble lignin and polysaccharide content, which varied from 0.9 to 2.5%, depending on isolation conditions. The polysaccharide moiety of the crude and purified lignins contained a high percentage of glucose, probably derived from cellulose. The molecular size distributions determined by gel chromatography on different gels showed a broad distribution for all isolated lignins. A probable maximum of 40,000 for the molecular weight of milled wood lignins was determined by ultracentrifugation. Some of the lignin fractions were examined in the electron microscope.The authors are indepted to Prof. E. Killmann and Mrs. M. Bäumle (Institute for Technical Chemistry, Technical University of Munich) for assistance with the ultracentrifuge measurements and Dr. M. Stoll for precious suggestions and discussions. Submitted by Deutsche Forschungsgemeinschaft (DFG).     

Comparative study of Kenaf varieties and growing conditions and their effect on kraft pulp quality

Kenaf (Hibiscus cannabinus L.) is an annual plant which produces a very high fiber yield per hectare and has demonstrated to be a suitable material for pulping. The crop conditions influence fiber production, but there is no information about their effect on pulp quality. The aim of this work was to study the effect of kenaf varieties and crop conditions (watering dose and harvesting time) on sulfate pulp quality. The study has been made on bast fiber sulfate pulps due to their high added value. The quality criteria were fiber dimensions, chemical composition and pulp quality. Kenaf variety or crop conditions have significant effect on fiber dimensions, holocellulose content, kappa number and breaking strength. To obtain high fiber yield and good delignified pulps it is recommended to grow the Salvador variety and to employ advance harvesting. Received: 20 January 1999     

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     

High-yield pulping of aspen wood: Relation between pulp properties and fibre characteristics by multiple linear regression

Summary High-yield pulps have been obtained by means of steam explosion pulping. This process was carried out as follows: 1) chips soak impregnation (60 °C, 24 h, L/C = 6) in solutions containing 8% Na₂SO₃ and a variable concentration of either Na₂CO₃ or NaHCO₃, ranging from 0 to 2%; 2) cooking at high temperature (190–200 °C) for short time (2-1 min); 3) rapid pressure release. This work shows that mechanical properties were substantially improved when adding a second chemical to the Na₂SO₃ impregnation solution. Moreover, refining energy requirement was significantly reduced. However, the higher chemical charge used made the optical properties drop. In this paper, mathematical models have been proposed in order to accurately predict specific refining energy and paper properties from sulfonate content and pulp yield. In addition, the relative importance of these two parameters has been studied.Thanks are due to the Natural Science and Engineering Council of Canada (NSERC) and Fonds pour la Formation de chercheurs et l'aide à la recherche of Quebec (FCAR) for their financial support.     

Composition and structure of organosolv lignins from four eucalypt species

Lignins were extracted from different species using organosolv process (ethanol/water). Obtained organosolv lignins were characterised by various methods to determine their composition, structure and functional groups with the purpose of evaluating their potential use for obtaining value-added compounds. The purity of organosolv lignins was determined. The total phenols content and the antioxidant power were analysed in order to know the reactivity of lignins. The ratio S/G was determined by nitrobenzene oxidation. In addition, molecular weight distribution, infrared spectroscopy and thermo gravimetrical analysis were carried out in order to determine the physical and chemical properties of organosolv lignins. Obtained organosolv lignins have very high purity and low sugar and inorganic contamination. All organosolv lignins samples have high polydispersity, and lignin from grey ironbark wood had the highest molecular weight average. Among the organosolv lignins, lemon-scented gum showed the highest average value of S/G ratio and the lowest average value of total phenols.     

A new modified pulping process alternative to sulphate method “Alkali-Sulfite-Antraquinone-Ethanol (ASAE)”

Summary In this study, ASAM method was modified by the use of ethanol instead of methanol. This new organosolv pulping method is referred to as ASAE. Brutia pine (Pinus brutia Ten.) was chosen as raw material in cooking because of its wide-spread usage in Turkish sulphate mills. 28 cooks were made by changing the cooking conditions systematically to achieve the most effective cooking parameters for yield and physical properties of ASAE pulps. Also, a control sulphate cook was made. After statistical evaluations of the data optimum pulping conditions were determined to be 20% Na₂SO₃ with 50% ethanol ratios and 150 min cooking time at maximal temperature. It was found that ASAE pulps had higher yield, viscosity, brigthness and strength properties than sulphate control pulps with the exception of breaking length. Furthermore bad-odour problems were absent during the blowing and washing process in the laboratory trials.     

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.