Effects of hemicellulose extraction on the kraft pulp mill operation and energy use: Review and case study with lignin removal

The implementation of wood extraction prior to pulping (pre-hydrolysis), with subsequent recovery of hemicellulose, is expected to affect the operation of a conventional kraft pulp mill. The magnitude of impacts will depend especially on the extraction conditions. In this specific work, the consequences of integrating the auto-hydrolysis process are studied using a detailed mill balance. A softwood pulp mill in Finland was used as a reference. With 14.1% of wood extracted, the wood demand increased by 15.5% and the steam generation in the recovery boiler by 13.5%. The removal of approximately 17% of lignin from black liquor would put the flue gas side of the boiler back to the original required capacity. In turn, this would enable the simultaneous recovery of lignin and hemicellulose. To make this process economically feasible, the extra revenue from the sales of lignin and hemicellulose products would need to compensate for the additional operating costs in the pulp mill.     

AFM和XPS分析竹沥液对竹子半纤维素返黄的影响

研究了粉单竹的竹沥液对半纤维素返黄的影响，用AFM和XPS分析半纤维素表面微观形貌和表面化学成分的变化情况，为研究高得率竹浆的返黄提供依据。实验结果表明，添加竹沥液至从粉单竹中分离出来的半纤维素，其颜色加深，由白色变为浅褐色，SEM和AFM分析发现半纤维素表面吸附着竹沥液物质，而紫外光老化处理后，XPS图谱发现光氧化引起半纤维素表面的竹沥液物质结构发生变化。研究认为竹沥液中的物质沉积在半纤维素表面上会降低竹浆白度，光老化后增加竹浆返黄程度。     

高半纤维素浆粕制备Lyocell纤维的研究

采用半纤维素质量分数21%的高半纤维素浆粕在N-甲基吗琳-N-氧化物(NMMO)水溶液中制备Lyocell纤维,并与半纤维素质量分数为10%的高α-纤维素浆粕的可纺性进行了对比。结果表明:高半纤维素浆粕在溶剂NMMO·H_2O中更易溶解,其过滤性能和可纺性能好,可在较高浆粕浓度下纺丝,制备成Lyo- cell纤维的产率高,且能提高Lyocell纤维的力学性能。高半纤维素浆液的稳定性能略低,在溶剂回收中需要消耗较多的双氧水进行氧化回收溶剂NMMO。     

Comparison of the structures and properties of Lyocell fibers from high hemicellulose pulp and high α‐cellulose pulp

Lyocell fibers were produced from a cheap pulp with a high hemicellulose content and from a conventional pulp with a high α‐cellulose content. The mechanical properties, supermolecular structure, fibrillation resistance, and dyeing properties as well as the fibril aggregation size of the high hemicellulose Lyocell fiber and high α‐cellulose Lyocell fiber were compared. The results showed that the high hemicellulose spinning solution could be processed at a higher concentration, which improved the mechanical properties and the efficiency of the fiber process. Compared with the high α‐cellulose Lyocell fiber, the high hemicellulose Lyocell fiber had better fibrillation resistance and dyeing properties. Therefore, it is feasible that this cheap pulp with a high hemicellulose content can be used as a raw material for producing Lyocell fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A new approach for the production of cellulose acetate: Acetylation of mechanical pulp with subsequent isolation of cellulose acetate by differential solubility

A heretofore uninvestigated approach to the production of cellulose acetate, the acetylation of whole wood pulp with subsequent isolation of the cellulose derivative by differential solubility, is described. The mechanical pulp used was produced by refining aspen wood chips with a disc refiner. Two conventional acetylation techniques, the fibrous and solution process, were employed to acetylato all components of the pulp. The cellulose acetate was isolated from the acetylated lignin and hemicellulose by dissolving in dichloromethane/methanol (9:1, v/v). The advantage of this new approach is that the high cost involved in using an extensively purified dissolving pulp are avoided. Both acetylation techniques yielded a product that was about 84% cellulose acetate. The remaining acetylated components were lignin and hemicellulose. The yield of cellulose acetate, based on the cellulose content of the original pulp and the product, was 75–80%.     

Removing Hemicellulose from Pulps by Specific Enzymic Hydrolysis

The hemicellulose content (solubility in 18% NaOH) of a delignified mechanical aspen pulp was lowered from 23.4% to 18.2% by one-hour hydrolysis with xylanase isolated from the fungus Schizophpllum commune by fractional precipitation. After 24 h hydrolysis, the hemicellulose content was reduced further to 12.9%. The predominant hydrolysis products, xylose and xylobiose, confirmed the specificity of hydrolysis. A crude mixture of cellulolytic and hemicellulolytic enzymes from the same microorganism gave glucose as the major hydrolysis product, and a pulp with higher relative hemicellulose content. Xylan-specific hydrolysis of a low-yield sulfite pulp gave only a small decrease in pentosan content.     

Isolation of hemicelluloses by ultrafiltration of thermomechanical pulp mill process water—Influence of operating conditions

Hemicelluloses could be used to replace fossil-based materials in several high-value-added products. Today, vast amounts of hemicelluloses are discharged from pulp mills all over the world as waste, but these could be isolated by membrane filtration, and utilized in various applications. In this study, the hemicellulose galactoglucomannan was isolated from process water from a thermomechanical pulp mill using ultrafiltration. The retention of hemicelluloses and lignin, and the flux and fouling of three ultrafiltration membranes (ETNA01, ETNA10 and UFX5) were studied at various operating conditions. One of the membranes (UFX5) was found to have a high hemicellulose retention (above 90%) independent of flux and pressure. With the ETNA01 membrane it was impossible to combine a high flux with high hemicellulose retention, while with the ETNA10 membrane the hemicellulose retention could be increased above 90% by running at transmembrane pressures above the critical flux. The UFX5 membrane could be used at the temperature of the process water in the pulp mill (75–85 °C), while the ETNA10 membrane could only withstand temperatures below 60 °C, increasing the cost due to the need to cool the process water. However, the susceptibility of UFX5 to fouling was much greater than for ETNA10, which would increase the cleaning cost of the UFX5 membrane.     

On-Site Recovery of Hemicelluloses from Thermomechanical Pulp Mill Process Water by Microfiltration and Ultrafiltration

During mechanical defibration of wood, a minor fraction of the wood mass is dissolved in the process water. These dissolved substances represent an extra energy demand when they are treated in the mill’s wastewater treatment plant. Galactoglucomannan, the main hemicellulose in spruce, can be recovered from thermomechanical pulp mill process water by a process based on microfiltration (MF) and ultrafiltration (UF). The purpose of this work was to study the scale-up of the process from laboratory scale to continuous industrial scale. MF was first studied in the laboratory, and then combined with UF in a continuous pilot process on-site at a pulp mill. The data obtained were used to estimate the cost of the membrane processes for galactoglucomannan recovery which was found to be about €1160 per ton hemicelluloses.     

高半纤维素浆粕纺制Lyocell纤维的结构与性能

采用成本低、半纤维素含量高的浆粕纺制Lyocell纤维,重点对制得的高半纤维素Lyocell纤维的结晶、取向、力学性能、原纤化和染色性等进行了研究。研究表明:这种用高半纤维素浆粕纺制的Lyocell纤维与用高α-纤维素浆粕纺制的Lyocell纤维相比,它的模量、结晶度、取向度、抗原纤化能力和染色性等都好于后者。     

Aluminiumchlorid‐katalysierter Organosolv‐Aufschluss von Buchenholz

The Organosolv pulping is a process to separate lignocellulosic biomass into its components cellulose, hemicellulose and lignin. Usually this process is catalyzed by Brønsted acids. In this work the Brønsted acid is replaced by the Lewis acid aluminum chloride. Much less aluminum chloride is needed to achieve similar pulp properties like high cellulose recovery, high hemicellulose and lignin removal. Also aluminum chloride catalyzes the degradation of xylose to the important basic chemicals furfural and lactic acid.     

Development of antifouling ultrafiltration PES membranes for concentration of hemicellulose

A new approach for one-stage facile membrane modification during non-solvent induced phase separation (NIPS)-process is proposed. The novelty of this study is that cheap and commercially available anionic high molecular polyacrylamide-based flocculant (AHMPF) is applied for the first time as an additive to coagulation bath (CB). The series of polyethersulfone membranes were prepared using 0.05–0.3 wt% AHMPF aqueous solution as CB at different temperatures (25–50°C) via NIPS. The effect of AHMPF concentration on the structure, composition and hydrophilicity of membranes was investigated. The separation and antifouling performance were evaluated during filtration of bovine serum albumin (BSA) solution and thermomechanical pulp mills process water (ThMP) in order to concentrate hemicellulose. The successful immobilization of AHMPF into the structure of membranes selective layer (not bottom layer) was confirmed by FTIR spectroscopy. It was established that despite the similar rejection of hemicellulose (88.8–93%) and lignin (20–21.4), modified membranes demonstrate 3–8 times higher flux and 2 times higher FRR (43.8% for reference membrane and 86.5% for modified one) in ThMP ultrafiltration. The developed membrane was found to be highly efficient in hemicellulose concentration and purification in pulp industry.     

Characterization of hemicelluloses in process streams in thermomechanical and chemi-thermomechanical pulp mills

Increased interest in hemicelluloses as a renewable source of biopolymers has resulted in an interest in hemicelluloses in process streams in pulp mills. The aim of this study was to compare potential positions for the withdrawal of hemicelluloses from mechanical pulp mills. Samples were withdrawn at a total of fourteen positions from two thermomechanical and two chemi-thermomechanical pulp mills. The molecular mass distributions of hemicelluloses and lignin were determined by size-exclusion chromatography. Hemicelluloses showed peaks in the molecular mass interval of 0.2–2 kDa and 4–60 kDa, whereas lignin showed peaks in the range of 0.5–4 kDa, but no peak in the high-molecular-mass region. Glucomannan accounts for approximately two-thirds of the hemicellulose content of softwood, and mannan and glucan were thus the dominating saccharides in all samples. Mannan was preferentially found in fractions with a molecular mass ranging from 4 to 22 kDa.     

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.     

Selecting the Pre-Hydrolysis Conditions for Eucalyptus Wood in A Fractional Exploitation Biorefining Scheme

The operating conditions for the autohydrolysis of eucalyptus wood were optimized with a view to maximizing hemicellulose extraction while preserving the integrity of glucan. The influence of the operating conditions used in the soda–anthraquinone pulping of the solid phase resulting from the autohydrolysis process was examined. Autohydrolysis of the raw material at a liquid/solid ratio of 8 kg water/kg material at 180°C for 30 min was found to provide a commercially useful liquid phase containing most of the starting hemicellulose. The autohydrolysis treatment allowed the subsequent production of soda–anthraquinone cellulose pulp and paper with properties as good as or even better than those obtained without the pretreatment.     

Sequential acid and enzymic hydrolysis of sugar beet pulp

Fermentable sugars from beet pulp were obtained in a two-stage hydrolytic process. The first stage involved mild acid treatment to hydrolyze the hemicellulose, producing a pentose-rich syrup and a cellulose-rich fraction. The second stage was the enzymic saccharification of the cellulose fraction with fungal cellulases to produce a glucose-rich syrup. The acid hydrolysis stage was evaluated to optimize the type of acid, acid concentration, temperature and reaction time. Solubilization was markedly temperature-dependent, whereas the specificity of hemicellulose degradation depended on the type of acid utilized. The effects of different reaction times, enzyme-to-substrate ratios and particle sizes on the enzymic stage were studied. Both saccharification rate and the extent of final conversion to glucose were markedly affected by the enzyme-to-substrate ratio. Sugars recovered from the enzymic degradation of cellulose were partially fermented by Saccharomyces cerevisiae ATCC 4126.     

Assessment of potential approaches to improve Eucalyptus globulus kraft pulping yield

The main goal of this work is to study the potential approaches to improve polysaccharides retention during Eucalyptus globulus kraft pulping. The addition of anthraquinone to kraft pulping leads to the highest pulp yield while the addition of urea promotes lower depolymerization of polysaccharides (higher pulp viscosity), but does not have a significant effect on yield. The early interruption of kraft cooking followed by oxygen delignification is a reliable approach to increase pulp yield, particularly when pulping is interrupted at the end of the faster and more selective kinetic regime (bulk phase). Yield loss during oxygen delignification is considerably lower than that incurred in the last phase of kraft pulping. Pulping with OH^?/HS^? charge profiling, carried out with liquor injection in three different phases leads to a yield increase. However, this increase results from a lower total alkali charge applied when profiling pulping is compared to standard pulping conditions, rather than to alkali profiling. Standard kraft pulping with different active alkali (AA) charges demonstrated that this operational variable is determinant for pulp yield and viscosity. Pulping experiences with lower AA (14%) resulted in a higher and almost constant pulp viscosity and in a higher pulp yield, assigned to improved retention of both cellulose and xylan. During the last stage of pulping, cellulose content decreases, this being mainly responsible for the decrease of pulp yield, while xylan content is almost constant, a feature attributed to the peculiar structure of this E. globulus's hemicellulose. Copyright © 2007 Society of Chemical Industry     

Alkali–methanol–anthraquinone pulping of Miscanthus x giganteus for thermoplastic composite reinforcement

The potential of pulp fiber–reinforced thermoplastics is currently not fully explored in composites. One of the main reasons is that pulp fibers are extracted for the use in papermaking and are thus not optimized for use as reinforcements in thermoplastics. Furthermore, currently used processing methods constitute several severe thermomechanical steps inducing premature degradation of the fibers. A systematic development of these composite materials requires the study of both these aspects. The goal of this work was to optimize fiber extraction against properties relevant to the reinforcement of thermoplastics. To this end, thick‐walled Miscanthus x giganteus pulp fibers were selected. The fibers were pulped by the alkaline–methanol–anthraquinone process. An unreplicated factorial design was applied to determine the effect of key operating variables on fiber thermal stability and mechanical properties. The thermomechanical properties of pulp fibers depend primarily on the morphology and chemical composition of the fiber resource in terms of the respective amounts of lignin, hemicellulose, and cellulose, all strongly influenced by the choice of pulping conditions. Optimal pulping parameters were identified, allowing production of fibers thermally stable up to 255°C with an aspect ratio of 40, a straightness of 95%, and tensile strength as high as 890 MPa. Specific stiffness and strength values with respect to density and material cost of 56 GPa m^?3 $^?1 and 820 MPa m^?3 $^?1 were highly competitive with glass fibers, with corresponding values of 15 GPa m^?3$^?1 and 270–490 MPa m^?3 $^?1, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2132–2143, 2004     

Bleached extruder chemi‐mechanical pulp fiber‐PLA composites: Comparison of mechanical,thermal, and rheological properties with those of wood flour‐PLA bio‐composites

An environmentally friendly bleached extruder chemi‐mechanical pulp fiber or wood flour was melt compounded with poly(lactic acid) (PLA) into a biocomposite and hot compression molded. The mechanical, thermal, and rheological properties were determined. The chemical composition, scanning electron microscopy, and Fourier transform infrared spectroscopy results showed that the hemicellulose in the pulp fiber raw material was almost completely removed after the pulp treatment. The mechanical tests indicated that the pulp fiber increased the tensile and flexural moduli and decreased the tensile, flexural, and impact strengths of the biocomposites. However, pulp fiber strongly reinforced the PLA matrix because the mechanical properties of pulp fiber‐PLA composites (especially the tensile and flexural strengths) were better than those of wood flour‐PLA composites. Differential scanning calorimetry analysis confirmed that both pulp fiber and wood flour accelerated the cold crystallization rate and increased the degree of crystallinity of PLA, and that this effect was greater with 40% pulp fiber. The addition of pulp fiber and wood flour modified the rheological behavior because the composite viscosity increased in the presence of fibers and decreased as the test frequency increased. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44241.     

Non-destructive Determination of Wood Constituents by Fourier Transform Raman Spectroscopy

The feasibility of using FT-Raman spectroscopy for rapid determination of various wood constituents non-destructively was examined using five Eucalyptus species, including samples of various ages and colors of samples, which are of importance as a plantation source. Wood constituents which relate to pulp properties (holocellulose, α -cellulose, hemicellulose, lignin, extractives, alkali-extractives, total-extractives, and extractives-free (EF) wood constituents for holocellulose, α -cellulose, hemicellulose and lignin) were measured. The application of 2nd derivatives transformation of Raman spectroscopic data revealed highly significant correlations between wet chemical and Raman predicted values for all traits except EF-hemicellulose, with standard error of prediction (SEP) < 0.8 points in the calibration (for known samples) and SEP < 3.4 points in the prediction (for unknown samples), respectively. Consequently, this non-destructive method has proved its validity for analyzing various Eucalyptus native wood meal samples, regardless of their age and color, to determine wood constituents and EF-wood constituents except hemicellulose. Use of this method will reduce the costs of tree improvement programs and the minimal sample size needed will allow trees to be non-destructively sampled.     

Production of enzymes from potato pulp using batch operation of a bioreactor

Trichoderma reesei strains MCG77 and Rut C30 were cultivated in batch operation in a stirred tank reactor on potato pulp (PP) consisting of starch, pectin, cellulose, and hemicellulose; potato pulp residue (PR) without starch and pectin; or enzymatic residue (ER), respectively, as substrate and potato protein liquor (PPL) as supplement. The enzyme mixtures produced by the fungi were characterized by four assays: with avicelase, CMCase, xylanase, and FP-activities. Trichoderma reesei Rut C30 yielded higher activities than Trichoderma reesei MCG77. The enzyme activities and productivities obtained with PR are comparable to those obtained by other groups using pure cellulose and a synthetic nutrient solution in batch culture. An optimal operation strategy was derived to obtain maximum enzyme activity and productivity. After converting PR with the enzymes produced and using the residue, ER, as substrate for enzyme production, 85% (w/w) of the pulp was utilized.