Optimization of beech wood pulping in catalyzed acetic acid media

Fagus sylvatica wood samples were treated in HCl‐catalyzed, acetic acid solutions. The effects of selected operational variables (catalyst concentration, reaction time and liquor to wood ratio) on pulp yield, composition of pulps and composition of pulping liquors were assessed using incomplete, second‐order, centred, factorial designs. Pulp composition was measured by the contents in cellulose, xylan and lignin. The concentrations of glucose, xylose and furfural in pulping liquors were also considered as experimental variables. Under selected conditions, pulps with 5.8% to 7.5% Klason lignin (kappa numbers in the range 25 to 33), 77.2% to 85.3% cellulose and 3.3% to 6.1% xylan were obtained at 45.8% to 50.0% pulp yield. The selected pulps showed good SCAN viscosity (723 to 814 mL/g) and alkaline resistances which were affected by the acetyl group content of samples (6.6 to 7.6 weight percent).     

Ethanol‐based pulping from Cynara cardunculus L

A non‐conventional pulping process based on the delignification of cardoon (Cynara cardunculus L) in ethanol–water mixtures has been studied to evaluate its pulping potential and to establish the optimum pulping conditions for this lignocellulosic material. The variables analyzed were the concentration of ethanol in the cooking liquor, the pulping time and temperature. Variable optimization was performed by a central composite design. High viscosity, low kappa number and acceptable screened yield were used as pulp quality criteria to optimize cooking conditions. Pulps having low kappa numbers and viscosities greater than 900 cm³/g^?1 were obtained. The total pulp yield was low compared with wood pulping due to the high contents of extractives and ash in cardoon. The amount of rejects in the pulp is of importance, especially for pulps with a high kappa number. The most suitable pulping conditions were 188 °C, 135 min and 50% (w/w) ethanol concentration. In these conditions the kappa number of the pulp was around 26, the pulp viscosity greater than 1100 cm³ g^?1 and a screened pulp yield of about 31% was obtained. Copyright © 2005 Society of Chemical Industry     

Evaluation of Prosopis juliflora as a potential feedstock for the production of sodium lignosulfonate from the spent liquor of a laboratory digester

Abstract

Chopped stems of Prosopis juliflora, an invasive xerophyte, were digested in a laboratory digester following alkaline sulfite pulping process to generate spent liquor whereby lignin underwent sulfonation to produce sodium lignosulfonate (SLS). SLS was concentrated from the spent liquor by ultrafiltration. Raw wood was featured by high lignin (23.5%), low extractives (1.0%), low wax (0.41), and low ash (2.25%) content thus making it an ideal feedstock to produce lignosulfonates with appreciable physico-chemical property and relatively high mechanical strength. Attempts were made to provide basic information on SLS structure and structural changes that might occur during pulping of P. juliflora under the present experimental conditions. Spectral and X-ray diffraction studies on as-produced SLS revealed substantial depolymerization and structural modification of lignin during sulfite pulping. The derived SLS had higher crystallinity index than the feedstock wood. Effect of average size of raw wood chip and dose of sodium sulfite in the overall yield of pulp and SLS along with the kappa number of the pulp were also analyzed. Findings from this study would serve to cultivate a better understanding of the potential of P. juliflora as a feedstock, so far unexplored, to produce SLS???a value-added product with numerous commercial applications. The use of this particular plant species in paper and pulp industry could also be considered as an effective means of integrated agro management in rural areas.     

A contribution to the modeling of kraft pulping

This paper presents a mathematical model for pulping that considers the effect of alkali diffusion and chemical reaction. An approximation for 3-dimensional diffusion in wood chips is tested against pulping data. A method for predicting pulp viscosity is also presented. The model simulates the effect of key pulping variables on pulp kappa number, viscosity, yield, residual alkalinity and pulping uniformity. Experimental data from a number of sources are successfully predicted by the model.     

QUATAM PROCESS—NEW SULFUR-FREE DELIGNIFICATION

ABSTRACT

An essentially new alkaline chemical pulping process—the Quatam process—has been introduced using an organic base for producing cellulose fibers from wood and annual plants. Solutions of quaternary ammonium compounds, preferably tetramethylammonium hydroxide (TMAH), serve as pulping liquors. The process produces high quality pulp with low kappa number, high brightness and good viscosity—without using sulfur-containing compounds. The process is suitable for both hardwood and softwood. The pulping selectivity of TMAH is demonstrated. Bleachability and mechanical properties of the resulting pulp are compared to those of conventional Kraft pulp.     

乙酰溴法对小兴安岭碱法杨木黑液提取物成分的研究

衍生化后的还原裂解(DFRC)法作为木质素结构解析的新方法,可以对碱法杨木黑液提取物中大分子结构的β-O-4醚键和α芳基醚键实施选择性的高效断裂.实验采用DFRC法对碱法萃取的杨木木质素进行降解,通过GC及GC-MS,分析研究了小兴安岭碱法杨木黑液提取物的成分和结构.结果表明:碱法杨木黑液提取物中主要包括4类化合物:B...     

植物纤维原料及纸浆中的木素―碳水化合物复合体

造纸工业中所用的木质纤维原料主要是由纤维素、半纤维素和木素组成的。纤维聚合物之间存在相互作用。研究证明,在木材和纸浆中,部分木素和碳水化合物发生化学键联接形成木素―碳水化合物复合体结构。文章着重介绍了复合物中三种重要化学键的键型;结合前人的研究成果,综述了云杉木、杨木、麦草以及各种针叶木浆和阔叶木浆中的木素―碳水化合物复合体(LCC);此外,对LCC的形成机理和蒸煮过程中形成新LCC的可能性加以阐述。     

Methanol-based pulping of eucalyptus globulus

The autocatalyzed pulping of Eucalyptus globulus wood with methanol-water mixtures was studied. A surface response design was employed to develop mathematical models describing the pulp properties as a function of cooking time, cooking temperature and methanol concentration. The ranges studied for these variables were 40–120 min, 170-200°C and 30-70% (w/w), respectively. The pulp properties modeled were kappa number, total yield, screenings content, screened yield and viscosity. Under the optimum cooking conditions pulps with low kappa number and acceptable viscosity can be obtained with a high yield.     

Kraft pulping of Eucalyptus nitens wood chips biotreated by Ceriporiopsis subvermispora

Eucalyptus nitens and E. globulus are wood species used in kraft pulping in Chile and Australia. Although E. nitens adapts very well to cold regions it requires more severe cooking conditions to produce bleachable kraft pulps. An attempt was made to find out whether a pre‐treatment with Ceriporiopsis subvermispora would improve its performance during kraft pulping and the pulp properties. The biotreatment of the chips carried out for a period of 15 days resulted in 13.3% lignin loss and a limited glucan degradation (2%). The pulping of biotreated samples required lower active alkali charge to reach the target kappa number compared to the control untreated sample and exhibited better pulping selectivity. The pulp yield increased by 3% and 1.5% for the pulps of 22 and 16 kappa numbers, respectively. The biotreated pulp's strength properties were improved and were similar to those of E. globulus reference pulp. Copyright © 2006 Society of Chemical Industry     

Extraktion von Zellstoff aus Nicht-Holzpflanzen und Vergleich mit Holzpflanzen

One trend in the pulp and paper industry is the use of nonwood plants, such as annual plants and grasses. They are intended to substitute trees as a raw material source for pulp. Since the composition and fiber properties differ, they need to be evaluated. In this feasibility study, pulp was extracted from hops, hemp, and miscanthus, yields and fiber properties were investigated and compared with available data for pulp from pine and spruce (Northern Bleached Softwood Kraft). Very high yields of up to 86.6 wt % were found for natural pulping and a low kappa number of 3.5 for miscanthus. Accordingly, almost all the lignin was removed. This confirms the high chemical efficiency of the pulps and underlines the great potential of annual plants and grasses.     

Mechanistic Differences Between Kraft and Soda/AQ Pulping. Part 1: Results from Wood Chips and Pulps

Abstract

Soda pulping catalyzed by anthraquinone (AQ) or 2-methylanthraquinone (MAQ) can produce hardwood chemical pulps similar to kraft pulps in all respect but for bleachability. Results accumulated in our laboratory suggest that the residual lignin in pulps from anthraquinone catalyzed processes is less reactive toward bleaching chemicals than that in kraft pulps. Analyses of pulps by periodate and permanganate oxidations suggest that the residual lignin from the non-sulfur processes contained more condensed structures than kraft residual lignin. The low reactivity of these structures is believed to be responsible for the lower brightness of bleached soda-AQ (SAQ) pulps. Pulping and bleaching trials with hardwood chips demonstrated that shortening of the cooking time and/or increasing the alkalinity is one strategy for improving bleachability of SAQ pulps. When sugar maple (Acer saccharum) chips were SAQ cooked for 1.0 and 2.0 h at 165°C, the higher kappa number pulp produced after 1.0 h of cooking bleached to a significantly higher brightness with a small increase in the chlorine dioxide application.     

Effect of Kraft Cooking Conditions on the Chemical Composition of the Surface and Bulk of Spruce Fibers

By varying cooking temperature, alkali charge, ionic strength, and cooking time in Kraft pulping of spruce chips, pulps ranging between kappa numbers 20–80 were obtained. The unbleached Kraft pulp fibers were subjected to mechanical peeling in order to separate the surface material from the bulk of the fibers and the carbohydrate composition and lignin content of the two fractions were analyzed. As expected, the lignin and xylan contents were higher on the fiber surface than in the fiber wall. The percentage of xylan on the fiber surface was fairly constant, independent of different pulping conditions or degree of delignification. The lignin proportion on the fiber surface gradually decreased with decreasing kappa number. At a given kappa number, pulping at a higher temperature resulted in less lignin on the fiber surface, probably because of the higher solubility of lignin at higher temperature. Cooking at lower alkali charge also resulted in lower lignin content on the fiber surface at a given kappa number. In this case, there was more time available for degradation of the surface lignin since the lower alkali charge resulted in longer cooking time needed to reach a certain kappa number.     

The use of Isocyanate as a Bonding Agent to Improve the Mechanical Properties of Polyethylene-Wood Fiber Composites

Abstract

Chemithermomechanical pulp (CTMP) of aspen was used as a filler in high density (HDPE) and linear low density (LLDPE) polyethylenes. To improve the bonding between the fiber and polymer, different chemical treatments of the fiber a) treatment with different isocyanates b) coating with maleic anhydride was carried out. Composites with isocyanate treated wood fibers produced higher tensile strength compared to untreated fiber composites. But when compared to diisocyanate, the polyisocyanate treated fibers produced higher gain in strength. HDPE or LLDPE filled with maleic anhydride coated CTMP aspen fibers showed a slight decrease in strength with the increase in filler concentration. Tensile modulus generally increased with filler loading and was not much affected by fiber treatment.     

马尾松化学热磨机械浆酶法改性研究

利用漆树漆酶/介体体系对马尾松化学热磨机械浆进行生物酶处理及后续H2O2漂白,探索漆酶生物改性最佳工艺条件。结果表明,在漆酶用量为2.0 U/g,2,2’-连氮-二(3-乙基噻唑-6-磺酸)(ABTS)用量0.5%,酶处理温度50℃,酶处理时间60 min时,与对照浆相比,纸浆白度可提高3.0%ISO,抗张指数、撕裂指数分别提高22.5%、7.9%。纤维长度、粗度分析及扫描电镜谱图显示,漆酶处理只发生在纤维表面,有利于表面木素的降解溶出,从而提高了纸浆的白度和可漂性。     

废新闻纸纤维素酶、半纤维素酶与漆酶/介体协同脱墨作用

利用纤维素酶、半纤维素酶与漆酶/介体协同对废新闻纸脱墨,对脱墨浆性能的检测结果表明,与单独使用纤维素酶、半纤维素酶和漆酶的脱墨浆相比,协同脱墨浆的残余油墨浓度降低,强度性能提高,经H₂O₂漂白后的白度提高,说明纤维素酶、半纤维素酶与漆酶具有协同脱墨作用,脱墨后纸浆纤维性能有所改善。测定纤维平均长度、粗度、比容和比表面积,并利用环境扫描电境（ESEM）对脱墨过程中脱墨浆纤维的表面性能变化进行了分析,发现与对照浆相比,协同脱墨浆纤维的平均长度和粗度有所降低,而比容和比表面积均提高;纤维素酶、半纤维素酶与漆酶/介体处理后,纤维表面出现细小纤维。     

Graft Pulping in Organosolv Systems

It has been previously demonstrated that free radicals are produced in the delignification of wood. These free radicals can be utilized to initiate grafting of vinyl polymers to the wood pulp. This simultaneous delignification and graft copolymerization has been referred to as graft pulping. The grafting of a variety of vinyl monomers to aspen wood pulp in alcohol-based solvent pulping has been evaluated in this study. Variables evaluated included cooking conditions, catalysts and two-stage pulping. The analysis of the reaction is complicated due to effects of the vinyl monomers on the delignification process and losses of wood during the extraction sequences. Although only low levels of polymer loading were obtained when single monomers were added to the pulping solvent, much better results were obtained using a binary monomer system of acrylonitrile(AN) and styrene(ST). At a monomer addition level of 10% (1.75% AN, 8.25% ST) to the aqueous ethanol solvent, a 14.6% polymer loading was achieved with the majority of the graft as polystyrene (88%) . The use of a two-stage pulping sequence improved the polymer loading of polyacrylonitrile but not polystyrene. Lignin was the primary site of grafting.     

TCF BLEACHED PULPS FROM MISCANTHUS SINENSIS BY THE IMPREGNATION RAPID STEAM PULPING (IRSP) PROCESS

ABSTRACT

The production of bleached cellulose pulps from elephant grass (Miscanthus sinensis) via a two-stage soda pulping process and a TCF bleaching sequence is evaluated in this work. The impregnation rapid steam pulping process (IRSP) involves impregnating of the lignocellulosic material with the pulping liquor, withdrawing the excess liquor and rapidly steaming the impregnated material at 180–200°C for a short time. In this paper the process variables and their effect on the kappa number, yield and viscosity of the unbleached pulps are discussed. Bleaching by an ozone-based TCF sequence was tested, and the papermaking properties of the bleached pulp were determined. A kappa number of 19 was obtained by impregnating at an alkali charge of 30 + 0.1% anthraquinone carboxylic acid (AQCA) and pulping at 180°C for only 15 min. Kappa was reduced to 16 by extending pulping time to 26 min. The alkali consumption during impregnation and pulping was 10.2 g NaOH/100 g of dry Miscanthus. Screened pulp yield, viscosity and brightness for this pulp were 54.6%, 913 mL/g and 37.3%, respectively. After bleaching, the pulp had an ISO brightness of 87.4% and a viscosity of 700 mL/g. Refining in a PFI mill provided optimal strength properties of the bleached pulp at 4500 revolutions (71°SR): breaking length 7.2 km, tensile index 72 N m/g, and burst index 4.3 kN/g. Tear index was 7.9 mN m²/g at this degree of refining.     

Behavior of Eucalyptus Wood Xylans across Kraft Cooking

Abstract

The 4-O-methylglucuronoxylans isolated from wood, pulp, and black liquor from six eucalyptus wood species were characterized. The ¹H nuclear magnetic resonance (NMR) studies revealed that all eucalyptus wood xylans contain O-2-substituted 4-O-methylglucuronic acid (MeGlcA) groups with hexose residues (9–26%). Their molecular weight (Mw) and polydispersity varied in the range of 26,083–28,405 g.mol^?1 and 1.13–1.17, respectively. The xylan retention during pulping increased with increasing degree of MeGlcA substitution in the xylose ring. An average of 54% xylans was retained in the pulp and the remaining 46% were degraded and/or dissolved in the black liquor (39% degraded and 7% dissolved). The average Mw of the xylans retained in the pulp and dissolved in the black liquor is influenced by pulp kappa number and averaged 20,134 and 14,778 g.mol^?1, respectively, at kappa 17. The average substitution degree of uronic acids, including MeGlcA and hexenuronic acids (HexA) in the xylans isolated from pulps (kappa 17) and black liquors were 1.05 and 1.13/10 xyloses, respectively. Of the total uronic acids present in the six original woods, an average of 36% w/w was retained in the pulps.     

Effect of Alkaline Hemicellulose Extraction on Kraft Pulp Fibers from Eucalyptus Grandis

Abstract

The alkaline extraction of hemicelluloses from hardwoods prior to pulping, for further conversion to value-added products, seems to be a promising pathway for paper mills to increase profit and improve sustainability. However, the amount of hemicellulose extracted will be limited by the requirement to maintain pulp quality and pulp yield in comparison to existing pulping processes. The effects of NaOH concentration, temperature, and time on hemicellulose extraction of Eucalyptus grandis were studied using a statistical experimental design. Extracted wood chips were subjected to kraft pulping to evaluate the effect of the extraction on cooking chemicals, pulp quality, and handsheet paper strengths. The selective xylan recovery (12.4% dry mass) from E. grandis combined with low-cooking, active alkali charge, and less cooking time advantaged the xylan extraction and subsequent modified kraft pulping process under the studied conditions. Pulp viscosity, breaking strength, and tensile index of handsheets were slightly improved.     

Soda Pulping of Hardwoods Catalyzed by Anthraquinone and Methyl Substituted Anthraquinones

Abstract

Black liquor gasification (BLG) as well as the recovery of lignin and other organic compounds from pulping black liquor would be aided if an efficient sulfur‐free pulping process could be developed. This has provided new impetus for research on soda pulping with redox catalysts instead of sodium sulfide that is presently used in the kraft process. Soda/anthraquinone (AQ) pulping afforded white birch (Betula papyrifera) and sugar maple (Acer saccharum) pulps with equal if not superior strength to kraft pulps. However, the delignification rate was significantly lower for soda/AQ pulping. When AQ was replaced by 2‐methylanthraquinone (2‐MAQ) a delignification rate only slightly lower than that of kraft pulping was obtained at the same effective alkali (EA). At a kappa number of ～20, a soda/2‐MAQ pulp was produced from sugar maple at a higher yield (1.2% on chips) than for a kraft pulp. 2‐MAQ was synthesized, as a powder, at 75% yield using an AlCl₃–mediated Friedel‐Crafts reaction that is one of the methods used for commercial production of AQ.