Pulp Delignification Research Articles

Effect of treating birch kraft pulp with peracetic acid before O2-delignification on the properties of pulp and consumption of ClO2 in D0ED1 bleaching

The influence of pre-treating Kappa number of 18.0 industrial birch kraft pulp with peracetic acid (Paa) before oxygen delignification (OD) was studied relative to the pulps’ level of delignification, yield, brightness, intrinsic viscosity (IV), FS-number, tear index (TI), and the consumption of chlorine dioxide (ClO2) in its subsequent Elemental Chlorine Free (ECF) bleaching. The study showed that such pretreatment is a way to extend the delignification of such pulp quite selectively in OD based on values of IV, FS-number, and TI, and to reduce significantly the consumption of ClO2 required to bleach this pulp to a brightness of 87%. This reduction depended on the amount of Paa used for pulp pretreatment. For example, when 0.33% and 0.66% as active oxygen (A.O.) of Paa were used, ClO2 consumption to bleach the pulp to 87% was lowered by 15.4% and 42.3%, respectively. As high as a 61.5% reduction in ClO2 consumption in its bleaching could be obtained using 0.66% as A.O. on pulp and change of time of OD. This result allows for a significant decrease in the chlorine passing to the filtrates from washing the pulp after the D0 and E stages to the pulp mill wastewater treatment plant.

New insights into kinetics and mechanisms of acid sulphite delignification of Eucalyptus globulus wood

The kinetics of Eucalyptus globulus wood delignification in Mg-base acid sulphite pulping of dissolving pulp was studied using a pilot-scale batch digester simulating the industrial process. The behavior of lignin during impregnation, heating-up and bulk delignification at the final temperature was evaluated by the analysis of acid-insoluble lignin in wood and wood residue after pulping. The dynamics of lignin dissolution was followed by its structural analysis in solid residues and in solution by wet chemistry and 1D and 2D nuclear magnetic resonance (NMR) spectroscopy. About 30 % and 20 % of the lignin were removed in the impregnation and heating-up pulping steps, respectively. About 45 % of the lignin was removed at the final pulping temperature in bulk and 3 % in the residual delignification stages. The kinetics of bulk delignification followed a pseudo-first-order kinetics with an effective activation energy of 138.4 kJ/mol in the temperature range of 140–148 °C. Bulk delignification follows an undefined overall order in the hydrogen and bisulfite ions and depended on the partial pressure of SO2 at ca. 0.60 order within the range of combined SO2 in pulping acid of 1.14–1.66 % and total SO2 loads of 6.2–7.0 %. Minimum degree of lignin sulphonation to be dissolved in the pulping liquor was suggested to be about 0.35 sulphonic groups per one phenyl propane unit. Lignin removal during pulping showed dependence on its location in different morphological parts of the fibers and related structural characteristics, which were discussed accordingly. A role of the polysaccharide complex in the accessibility of lignin was highlighted. A noticeable cleavage of β-O-4 linkages occurred in lignin already dissolved in pulping liquor at the end of cooking.

Properties of Sustainable Packaging Paper Fabricated from Banana Fibers Using Banana Peel Lye As a Pulping Delignification Reagent

ABSTRACT This study aimed to establish a sustainable fabrication method for packaging paper using a Potassium-based delignification alkali; banana peel lye (BPL) to pulp banana stem fibers. This was an experimental study where Caustic soda was used as a positive control. The packaging paper was constructed using a handmade craft method described by TAPPI 2002. The packaging properties were tested according to the KEBS EAS 859:2017 standard for packaging, which outlines the minimum/maximum requirement for three properties; bursting strength, tearing resistance, and water absorbency. The results indicate that the pulping process using BPL yielded more fiber than the NaOH pulping process at 68% and 56%, respectively. The test results for the packaging paper revealed that BPL and NaOH packaging paper surpassed the minimum KEBS requirement for bursting strength and tearing resistance however it had a high water absorbency rate. The property tests statistical analysis showed that for all three tests, there was no significant difference between the packaging papers made with BPL and those made from NaOH indicating that BPL is a suitable replacement for NaOH. Further research is recommended to improve water absorption properties as well as to experiment with surface enhancement treatments such as dyeing.

Sequential catalytic lignin valorization and bioethanol production: an integrated biorefinery strategy

BackgroundThe effective valorization of lignin and carbohydrates in lignocellulose matrix under the concept of biorefinery is a primary strategy to produce sustainable chemicals and fuels. Based on the reductive catalytic fractionation (RCF), lignin in lignocelluloses can be depolymerized into viscous oils, while the highly delignified pulps with high polysaccharides retention can be transformed into various chemicals.ResultsA biorefinery paradigm for sequentially valorization of the main components in poplar sawdust was constructed. In this process, the well-defined low-molecular-weight phenols and bioethanol were co-generated by tandem chemo-catalysis in the RCF stage and bio-catalysis in fermentation stage. In the RCF stage, hydrogen transfer reactions were conducted in one-pot process using Raney Ni as catalyst, while the isopropanol (2-PrOH) in the initial liquor was served as a hydrogen donor and the solvent for lignin dissolution. Results indicated the proportion of the 2-PrOH in the initial liquor of RCF influenced the chemical constitution and yield of the lignin oil, which also affected the characteristics of the pulps and the following bioethanol production. A 67.48 ± 0.44% delignification with 20.65 ± 0.31% of monolignols yield were realized when the 2-PrOH:H2O ratio in initial liquor was 7:3 (6.67 wt% of the catalyst loading, 200 °C for 3 h). The RCF pulp had higher carbohydrates retention (57.96 ± 2.78 wt%), which was converted to 21.61 ± 0.62 g/L of bioethanol with a yield of 0.429 ± 0.010 g/g in fermentation using an engineered S. cerevisiae strain. Based on the mass balance analysis, 104.4 g of ethanol and 206.5 g of lignin oil can be produced from 1000 g of the raw poplar sawdust.ConclusionsThe main chemical components in poplar sawdust can be effectively transformed into lignin oil and bioethanol. The attractive results from the biorefinery process exhibit great promise for the production of valuable biofuels and chemicals from abundant lignocellulosic materials.

A new look at the kinetics of oxygen delignification of softwood kraft pulp

Abstract Using a Berty-type CSTR reactor, Ji (2007. Kinetics and mechanism of oxygen delignification, Ph.D. thesis. The University of Maine) obtained oxygen delignification kinetics first order in lignin when neglecting the higher initial delignification phase. In the present study the same Berty/CSTR reactor with an improved temperature control was used to determine the oxygen delignification kinetics of Southern Pine kraft pulp, with the kinetics now corrected for lignin removed by oxygen-free alkaline leaching. This removes the initial high delignification rate peak so that the kinetics over the entire lignin range can be modelled as first order in “reactive” lignin, which is lignin corrected for a small amount of unreactive lignin. It suggests that softwood pulp oxygen delignification consists of two contributions; phenolic delignification and alkaline leaching. The initial alkaline leaching phase is mathematically described by semi-infinite alkaline diffusion of dissolved lignin trapped in the cell wall after pulp washing. For phenolic delignification, the reaction orders in alkali concentration and oxygen of the power law delignification equation are 0.3 and 0.44 respectively, while the activation energy is 63 kJ/mol. Taking into account the unreactive HexA, the small amount of unreactive lignin, and the lignin removed by alkaline leaching, the kappa number is well predicted by the new delignification kinetics.

Morphological Differences between Virgin and Secondary Fibers

The properties of the fibers determine the quality of the pulp and, thus, the quality of the paper made from it. Recognition of properties, which fiber and paper pulp should be characterized by, in order to achieve required paper properties, is, therefore, a subject of research and interest of many papermaking research experts and scientists. Fibers are subject to deformation and possible weakening under the influence of chemical and mechanical factors, and therefore the quality of the fibers decreases each time they are used in production when it comes to recycled pulps. Then again, the key factor determining the quality of the primary fiber is the degree of pulp delignification. In the article, an attempt was made to define the impact of delignification of virgin pulp on morphological properties of fibers, and compare them with the properties of recycled paper pulp, in order to find correlations. The current economic and raw material situations in the wood market force one to seek new solutions to limit the use of virgin fibers, which is extremely important for the economy of the paper mill, environmental protection and raw material management.

Characterization of a New Laccase from Vibrio sp. with pH-stability, Salt-tolerance, and Decolorization Ability.

Laccases have been widely used for fruit juice clarification, food modification, and paper pulp delignification. In addition, laccases exhibit remarkable performance in the degradation of toxic substances, including pesticides, organic synthetic dyes, antibiotics, and organic pollutants. Thus, the screening and development of robust laccases has attracted significant attention. In this study, Vibrio sp. LA is a strain capable of producing cold-adapted laccases. The laccase coding gene L01 was cloned from this strain and expressed in Yarrowia lipolytica, a host with good secretion ability. The secreted L01 (approximate MW of 56,000 Da) had the activity and specific activity of 18.6 U/mL and 98.6 U/mg toward ABTS, respectively. The highest activity occurred at 35 °C. At 20 °C, L01 activity was over 70% of the maximum activity in pH conditions ranging from 4.5-10.0. Several synthetic dyes were efficiently degraded by L01. Owing to its robustness, salt tolerance, and pH stability, L01 is a promising catalytic tool for potential industrial applications.

The effect of treating pine regular kraft pulp with peracetic acid before O2-delignification on the consumption of ClO2 in D0ED1 bleaching

Effects of pre-treating pine kraft pulp kappa number 31.5 with peracetic acid (Paa) (0.33% and 0.66% as active oxygen based on oven-dried pulp) before O2-delignification were studied relative to the consumption of chlorine dioxide in a subsequent Elemental Chlorine Free (ECF) bleaching process. The study showed that such pre-treatment is an effective way to extend the delignification of the pine pulp and to reduce the consumption of chlorine dioxide required to bleach the pulp to a brightness of 87%. The reduction in chlorine dioxide required to bleach the pine pulp depended on the amount of Paa used for pre-treatment. Furthermore, the research showed that decreasing the kappa number of the pine pulp to approximately 7.5 units (with Paa pre-treatment and lengthening of O2-delignification process) caused an over-proportional reduction (by approximately 62.5%) in chlorine dioxide consumption to bleach the pulp to 87% brightness.

Recent advances in use of 4- coumarate coenzyme a ligase (4CL) as target gene for improving delignification of paper pulp in Leucaena leucocephala in Indian perspective: A review & case study

Lignin provides support to plants by filling the gaps in cellulose, hemicellulose and pectin components but it is an undesired ingredient of pulp as it imparts black to brown colour to the pulp during paper making process. To remove lignin a lot of chemicals and bleaching agents are used which contribute to major fraction of environmental pollution as well as cost determination of paper making process. In India majorly Leucaena leucocephala is employed for obtaining pulp raw material owing to its properties suited for paper production such as vessel percentage, felting power, runkel ratio, tensile strength etc which is better than other commonly employed sources for paper pulp as raw material. In this review paper we focused on recent advances in the use of 4CL enzyme as target gene towards achieving model designer Leucaena leucocephala trees which can be a possible solution to this problem significantly minimizing the environmental pollution and cost of production. It is known from previous studies that better S/G lignin monomer ratio favours easy extractability of lignin from pulp. Different isoforms with different substrate specificities are known in different plants and knowledge of this differential substrate specificity in conjunction with regulation of expression of these isoforms can help in attaining desired S/G lignin monomer ratio. Thus, these model designer plants would be capable of naturally producing easily amenable lignin towards delignification by altering the S/G lignin ratio and can significantly cut the environmental pollution and cost determining factors for paper production.

DEVELOPMENT TECHNOLOGY OF SULFITE PULP TCF BLEACHING FOR CHEMICAL PROCESSING

An environmentally friendly chlorine-free technology for producing wood sulfite soluble pulp using only one oxidizing bleaching agent – hydrogen peroxide has been developed: unconventional catalyzed peroxide delignification and hydrogen peroxide bleaching. The conditions of cooking, delignification, extraction and bleaching of spruce sulfite pulp obtained as a result of studies, as well as successful combinations of conditions of all stages made it possible to obtain two types of soluble pulp by one technology: soluble pulp for nitration (for gunpowder) was obtained under a short scheme including a delignification step and hot alkaline extraction; by continuing this scheme with hydrogen peroxide bleaching in two steps, viscose pulp was obtained. The use of this technology will make it possible to implement a double import substitution – in raw materials (wood instead of cotton) and in finished products (pulp for chemical processing - for nitration and viscose pulp, which are currently imported).

Inhibitions of microbial fermentation by residual reductive lignin oil: Concerns on the bioconversion of reductive catalytic fractionated carbohydrate pulp

Reductive catalytic fractionation (RCF) is an emerging biomass valorization strategy with high atom economy, which primarily outputting extensively depolymerized reductive lignin oil and highly delignified pulp. In downstream processes, the polysaccharide rich pulp can be potentially transferred into various value-added biochemicals through fermentation. In this study, the negative influences of the residual lignin oil that remaining on the surface of the RCF pulp towards different industrial microbes (total 9 species, categorized into eukaryotes, Gram-negative, and Gram-positive strains) was investigated. Results indicated the reduced lignin fractions were the key inhibitors in the RCF lignin oil, whilst the polarities, molecular weight, and the substitution groups of lignin possessed significant impacts on the growth of strains. Meanwhile, the resistance to RCF lignin oil by different category of industrial strains was analyzed. Generally, eukaryotes exhibited better resistance than the Gram-negative and Gram-positive strains. Took bioethanol and acetone-butanol-ethanol fermentation as examples, the negative influence of the lignin oil on biochemicals production using the RCF pulp as substrate was explored. Batch fermentation results revealed that the RCF lignin oil limited both the sugars (glucose and xylose) metabolism and the pathways toward bio-alcohols production of the microorganism. Therefore, it is vital to take continuous technical improvement in order to minimize the negative influences of the residual lignin oil on downstream biotransformation of the RCF pulps.

The effects of high alkali impregnation and oxygen delignification of softwood kraft pulps on the yield and mechanical properties

Abstract This study investigated whether the yield improvement after high alkali impregnation (HAI) is maintained after oxygen delignification and whether the potential of oxygen delignification to increase the mechanical properties is affected by high alkali impregnation. The yield improvement achieved by high alkali impregnation (1 %) was preserved after oxygen delignification, particularly of glucomannan. The total fiber charge and swelling increased after oxygen delignification regardless of the type of impregnation in the cooking step. The tensile index improvement obtained by oxygen delignification was retained if this was preceded by high alkali impregnation. The stiffness index was higher and elongation slightly lower after HAI impregnation than after a standard (REF) impregnation. Fibers obtained through high alkali impregnation seem to be slightly less deformed and slightly wider than fibers obtained after a standard impregnation.

Biotechnological Applications of Manganese Peroxidases for Sustainable Management

Microbial manganese peroxidases (MnPs) are ligninolytic enzymes primarily responsible for degrading lignin, but they are also capable of degrading dyes, organic pollutants, and emerging contaminants in wastewater. They have been isolated and characterized from many white-rot fungi and few bacteria. For microbial MnPs, the optimum pH range is between 3.5 and 9.0; the optimum temperature range is between 25°C and 70°C. Their molecular weights range between 25 kDa and 68 kDa. By oxidizing Mn2+ to Mn3+, they can oxidize a wide range of phenolic and non-phenolic substrates. MnPs can be used in a wide range of industrial applications, including delignification of pulp, wastewater treatment, biofuel production, dye removal, biopulping, biobleaching, and juice extract clarification. The purpose of this review is to summarize biotechnological applications of manganese peroxidases.

Spectral analysis and kinetic studies of enzymatic delignification of kraft wood pulp by xylanase

The traditional bleaching methods used chlorine as bleaching agent which produced large amount of chlorinated organic compounds including dioxins which are persistent environmental pollutants. The alternate methods using peroxides and enzymes were developed to achieve total chlorine free bleaching. The xylanase enzyme was used as bleaching agent in this study. The delignification study was performed to evaluate the optimum conditions required for obtaining minimum kappa number of the pulp to remove maximum lignin from the wood fibres. The interactions of various factors such as pulp consistency, enzyme dosage and temperature were studied. The best conditions for enzymatic bleaching obtained were 10% consistency, 50 IU of enzyme dosage and 52oC in the range studied. The predicative mathematical models were developed for enzymatic bleaching. The activation energy for xylanase delignification of paper pulp was 13.989kJ/mol. The significant functional groups in bleached pulp samples were analysed using Fourier transform infrared spectroscopy and the surface morphology of pulp fibres was studied using Scanning electron microscopy images.

Delignification of unbleached pulp by ternary deep eutectic solvents

Abstract The processing of lignocellulosic materials is very limited because of their low solubility in water and some organic solvents. Fifteen ternary deep eutectic solvents (DESs) were prepared and tested as solvents suitable for delignification of unbleached pulp. The selected ternary DESs are composed of quaternary ammonium salts and amino acids as hydrogen-bond acceptors, and organic acids and polyvalent alcohols as hydrogen bond donors, with molar ratios varying for the individual components. The delignification efficiency is significantly influenced by the degree of penetration of the solvent into the pulp fibre structure. Therefore, the density and viscosity analysis of individual solvents was performed. Unbleached beech pulp with initial kappa number 13.9 was treated with the prepared DESs. The kappa number indicates the residual lignin content or the bleachability of pulp. The efficiency of the solvents ranged from 1.4% to 28.1%. The most suitable for the pretreatment of fibres, based on lignin removal efficiency, were found to be three DESs, in the following order: malonic acid/choline chloride/1,3-propanediol (1:1:3) > choline chloride/acetamide/lactic acid (1:2:3) > choline chloride/urea/lactic acid (1:2:3).

Displacement washing of softwood pulp cooked to various levels of residual lignin content

This study investigates the influence of the degree of delignification of kraft spruce pulp cooked at seven different kappa numbers, ranging from 18.1 to 50.1, on the efficiency of displacement washing under laboratory conditions. Although the pulp bed is a polydispersive and heterogeneous system, the correlation dependence of the wash yield and bed efficiency on the Péclet number and the kappa number of the pulp showed that washing efficiency increased not only with an increasing Péclet number, but also with an increasing kappa number. The linear dependence between the mean residence time of the solute lignin in the bed and the space time, which reflects the residence time of the wash liquid in the pulp bed, was found for all levels of the kappa number. Washing also reduced the kappa number and the residual lignin content in the pulp fibers.

Expression of an alkaline feruloyl esterases from thermophilic Chaetomium thermophilum and its boosting effect on delignification of pulp

Exploration of feruloyl esterase (FAE) with the resistance to heat and alkali conditions in biobleaching process to improve the separation efficiency of lignocellulose is the key to achieving green papermaking. Herein, we expressed FAEB of C. thermophilum and obtained a thermostable alkaline FAE that can effectively promote the removal of lignin from pulp. The faeB gene was successfully obtained through genomic Blast strategy and high-efficiency expressed under the control of strong alcohol oxidase promoter in Pichia pastoris. The recombinant CtFAEB has an optimal temperature of 65 °C and pH of 7.0. After treated at 65 °C for 1 h, CtFAEB can still retain 63.21 % of its maximum activity, showing a good thermal stability. In addition, the recombinant CtFAEB has broad pH stability and can retain about 56 % of the maximum activity even at pH 11.0. Compared with the effect of mesophilic FAE, pretreatment with thermostable CtFAEB can promote the delignification by laccase and alkaline hydrogen peroxide from the pulp at 70 °C and pH 9.0. Alignment of the protein sequences of CtFAEB and mesophilic FAE suggested that the percentage of amino acids that easily form alpha helix in CtFAEB increases, which enhances its structural rigidity and thereby improves its thermal stability and alkali tolerance. Our study provides an effective method to obtain thermostable and alkaline FAEs, which will promote its application in biobleaching and other biorefining industries.

Delignification of Low-Energy Mechanical Pulp (Asplund Fibers) in a Deep Eutectic Solvent System of Choline Chloride and Lactic Acid.

Deep eutectic solvents (DESs) are considered as a green and environmentally benign solvent class for various applications, including delignification of biomass. One of the major challenges in the delignification of biomass by DES is attributed to the limitations in mass transfer. By subjecting wood chips to a low-energy mechanical refining, i.e., the Asplund process, the accessible surface area increases greatly, which in turn improves the mass transfer and increases the reaction rate. In this research, the DES delignification of Asplund fibers made of Norway spruce was studied as a strategy to produce papermaking fibers under mild conditions. A DES consisting of lactic acid and choline chloride was used due to its proven performance in delignification. Various operational conditions, such as temperature, time, DES-to-wood ratio, and the type of stirring were studied. A novel parameter, Q, allowed to evaluate the impact of the operational conditions on the quality of the pulp in terms of delignification degree and fiber length. The results showed that cooking temperature had the most significant effect on the pulp quality. Additionally, it was observed that cooking times between 30 and 45 min result in a pulp yield of about 50%, while fibers have a lignin content of about 14% and a fiber length of 0.6 mm. These results demonstrate that it is possible to obtain fibers of relatively good quality from DES delignification using Asplund fibers as the starting material.

The Dual Effect of Ionic Liquid Pretreatment on the Eucalyptus Kraft Pulp during Oxygen Delignification Process.

Oxygen delignification presents high efficiency but causes damage to cellulose, therefore leading to an undesired loss in pulp strength. The effect of ionic liquid pretreatment of [BMIM][HSO4] and [TEA][HSO4] on oxygen delignification of the eucalyptus kraft pulp was investigated at 10% IL loading and 10% pulp consistency, after which composition analysis, pulp and fiber characterizations, and the mechanism of lignin degradation were carried out. A possible dual effect of enhancing delignification and protecting fibers from oxidation damage occurred simultaneously. The proposed [TEA][HSO4] pretreatment facilitated lignin removal in oxygen delignification and provided fibers with improved DP, fiber length and width, and curl index, resulting in the enhanced physical strength of pulp. Particularly, its folding endurance improved by 110%. An unusual brightness reduction was identified, followed by detailed characterization on the pulps and extracted lignin with FTIR, UV, XPS, and HSQC. It was proposed that [TEA][HSO4] catalyzed the cleavage of β-O-4 bonds in lignin during the oxygen delignification, with the formation of Hibbert’s ketones and quinonoid compounds. The decomposed lignin dissolved and migrated to the fiber surface, where they facilitated the access of the oxidation agent and protected the fiber framework from oxidation damage. Therefore, it was concluded that ionic liquid pretreatment has a dual effect on oxygen delignification.

Differences and similarities between kraft and oxygen delignification of softwood fibers: effects on mechanical properties

Charged groups in pulp have been shown to enhance the tensile strength of the paper produced from the pulp. Oxygen delignification introduces charged groups and it is of interest to determine how the delignification should be distributed between the cooking and the oxygen stage with respect to mechanical properties. A number of unbleached kraft cooked and oxygen delignified pulps within a wide kappa number range were produced and refined, and the effects of the refining on the morphology and mechanical properties were studied. The WRV correlated with the fiber charge and at a given fiber charge, kraft cooked and oxygen delignified pulps had the same WRV development in refining, although they had significantly different kappa numbers. The tensile strength development during refining depends on the fiber rigidity which is affected by the lignin content, the fiber charge and the chemical and mechanical processes used. Refining increased the curl of the kraft cooked pulps and decreased the curl of oxygen delignified pulps, irrespective of kappa number. A greater increase in tensile strength was seen for the pulps with a higher fiber charge and WRV, probably because of the greater degree of fibrillation achieved in the beating process. Despite the greater fiber deformation in the oxygen delignified pulps, the strength can be increased by a larger amount of charged groups and a greater swelling of the fibers.Graphic abstract