Characterization of the Residual Kraft Pulp Lignin In Situ by Sulfite Treatments

Abstract

The O₂ delignification of kraft pulps from Norway spruce was shown having a significant impact on the reactivity of the residual pulp lignin as revealed from their responses to sulfite treatments at pH 7.5. A substantial higher ratio of lignin sulfonation to the phenolic hydroxyl group content of residual pulp lignin was observed for the O₂ -delignified kraft pulps (～ 0.8) as compared to a value of ～ 0.3 for the unbleached samples and ～ 1 for the spruce wood lignin. Under the prevailing sulfite treatment conditions, the sulfonation would be largely attributed to the phenolic lignin component and the etherified structures containing an α -carbonyl or -unsaturated group. The contribution from the latter units, evaluated by a borohydride pretreatment of pulps prior to the sulfite treatment, can only account for approximately 15% of the sulfonation observed for the O₂ -delignified sample. Thus, the nature of phenolic structures in the O₂ -delignified pulps was more similar to that of the wood lignin than that of the kraft pulps.     

The xanthate method of grafting. III. Effect of lignin content on the graftability of wood pulp

Several commercial wood pulps of different chemical origin and with various lignin content were copolymerized with acrylonitrile using the xanthate grafting process. A number of experiments were carried out to evaluate the effects exerted by the residual lignin and by other wood components on the grafting reaction. The results obtained show that graft copolymers can be prepared in good yields with pulps containing as much as 23% lignin. With the aim to investigate the effect of lignin in more detail, two series of pulps were prepared by delignification of a crude sulfite pulp and a crude Kraft pulp to different levels of lignin content. Sodium chlorite was used as a bleaching agent. Copolymerization results obtained with these pulps indicate some fundamental differences in behavior between sulfite and Kraft pulps. In both cases, the copolymerization is afflicted by a short inhibition period whose duration, however, does not depend on the lignin content in the pulp.     

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.     

Soda—Oxygen bleaching of kraft bagasse pulp

Soda—oxygen bleaching of commercially available kraft bagasse pulp has been investigated. Alkali charge, temperature and oxygen pressure are important factors in controlling brightness and physical properties of the pulps produced. Pulp yields, lignin and degree of polymerisation of the bleached pulps decreased with increasing alkali charge from 2 to 6%. Strength properties as well as brightness increased by increasing alkali charge at 368 K, whereas optimum strength properties are obtained with 4% alkali at 383 K. In the range of oxygen pressure used, 5–8 kg cm^?2, DP as well as strength properties of the bleached pulps increased with increasing oxygen pressure. Brightness up to 61% was reached by soda-oxygen alone. To obtain higher brightness an afterbleaching step is necessary. The soda—oxygen—hypochlorite and soda—oxygen—chlorite pulps prepared have strength properties comparable with those of conventionally bleached pulps.     

Characterization of Residual Lignins Isolated from Unbleached and Semibleached Softwood Kraft Pulps

Abstract

Residual lignins in an unbleached and a semibleached softwood (Pinus taeda L.) kraft pulp were isolated by enzymatic hydrolysis of polysaccharides in the pulps. After purification, the residual lignins were characterized. A dissolved lignin was also isolated from the alkaline extraction spent liquor by acidification and characterized.

Results of the characterization indicate that extensive degradation of residual lignin in kraft pulp occurred during the first two stages of bleaching. The results also strongly support the previous finding that stable covalent linkages between residual lignins and carbohydrates in pulp any be the most probable cause for the residual lignins to resist delignification during kraft pulping and prebleaching.     

Optimized Catalytic Bleaching Sequences for Eucalyptus Kraft Pulp

Contemporary multi-stage bleaching processes partially remove residual lignin and hexenuronic acid from cellulosic pulps. The reactions in the steps could be faster and consume smaller amounts of chemicals. Catalytic bleaching (H_cat), utilizing hypochlorite (H), triethylenediamine (DABCO) and its derivative N-carboxymethyl triethylenediamine (CM-DABCO), is a new discovery that has the potential to improve the chemical and energetic efficiency of bleaching processes in chemical pulp mills, e.g. through reducing the reaction time of the bleaching processes. The objective of this study was to clarify if new kraft pulp bleaching sequences with initial stage of chlorine dioxide (ClO₂; D) and an intermediate stage of H_cat could provide fully bleached pulps. The bleaching sequences of the studied eucalyptus pulps include D₀E_(OP)H_cat(Q)P and H_catZ/DP, which attained a final brightness of 88 and 89% ISO, respectively. H_catZ/DP showed to be the best sequence for the catalytic bleaching of eucalyptus kraft pulps. This study may open new doors to future bleaching of cellulose pulps with fewer towers and decreased use of chemicals.     

Nitrogen containing additives in soda pulping of bagasse pith

Unbleached soda pulp was prepared from Egyptian bagasse pith by varying the alkali concentration and the time of heating at the boiling point of the liquor under atmospheric pressure. A linear relationship was observed between the dissolved pith and the dissolved lignin. Pulping with alkali concentration higher than 10% but not exceeding 16% was more effective, since more delignification took place with lower dissolved pith percentage. p- And m-nitrobenzoic acids and also hydroxylamine hydrochloride had a slight or no effect on the yield of the pulps. The alkali solubility percentage of the pulps prepared in the presence of any of the additives was lower than the control pulp. The delignification was enhanced more on the addition of hydroxylamine hydrochloride than p-nitrobenzoic acid, while m-nitrobenzoic acid seemed to have no effect. The yield of the pulps thus prepared, as determined by weighing, showed lower values than those determined by a chemical method. The soda delignification rate was shown to be proportional to the amount of unremoved lignin and the concentration of alkali in the liquor. The delignification reaction was found to follow approximately first-order kinetics.     

Quantification of Lignin and Hexenuronic Acid in Bleached Hardwood Kraft Pulps: A New Calibration Method for UVRR Spectroscopy and Evaluation of the Conventional Methods

Abstract

Lignin content determination is an important task when pulp bleaching is studied. However, none of the conventional methods were developed for bleached pulps and therefore they are accurate mainly for unbleached pulps. This article describes a new, rapid method to determine lignin and hexenuronic acid contents of bleached hardwood kraft pulps based on UV resonance Raman (UVRR) spectroscopy. The lignin contents of pulp samples were determined from the aromatic band heights of the UVRR spectra. Therefore the measurements gave the content of aromatic lignin in pulp, and did not include extensively oxidized lignin structures. The method was applicable for hardwood kraft pulps with lignin content less than 1%. The measured lignin content correlated linearly with the kappa number. The lignin content (% on pulp) equaled 0.15κ+0.16. The constant 0.16 was presumably caused by the incomplete oxidation of the lignin in the kappa number determination. Klason lignin or total lignin determinations were not accurate for these kinds of pulps. Hexenuronic acid content was simultaneously determined from the UVRR band height of unsaturated C?O and C?C structures. The linear correlation of this band with hexenuronic acid indicated that the content of other unsaturated structures was constant in all the pulps, was proportional to the hexenuronic acid content of the pulps, or was insignificantly low. When compared to conventional methods, the UVRR spectroscopic method is fast, requires little sample and pretreatment, and the procedure has good repeatability. In addition, the accuracy of this technique increases with decreasing lignin content (<1%) making it a very attractive method for bleaching studies.     

Infrared Absorption Spectra of Cellulose Pulps of Palm Tree

Palm leaves are used for the production of different cellulose pulps; their properties are investigated, the resulting pulps were bleached by a multistage process, the effects of the addition of solvent during the pulping process on the chemical structure of the pulps are discussed. The strength properties of the paper which is produced from unbleached and bleached pulps increased with increasing cellulose percentage and decreasing lignin content in the pulp. Infrared absorption spectra were recorded for different unbleached and bleached pulp in the frequency range 200–4000 cm^-1 by using the alkali halide disk technique; the factors which affect the experimental technique were calibrated through these studies. The structural units within pulping yield (holocellulose, hemicellulose, cellulose, lignin, and ash) were interpreted within the pulp network structure by the infrared absorption spectra, where different samples of unbleached, bleached soda, and kraft pulps were also elucidated by IR spectra, after preheating at different temperatures and with using different ratios of organic solvents. The addition of organic solvents decreased or increased the crystallinity indices, depending on the type of solvent and the pulping temperature. It was also found that, at the same pulping temperature (155°C) and with the same percent of organic solvents in the pulping liquor, the asymmetry indices also the mean hydrogen bonding strength (A _OH/A_CH) of the unbleached soda pulps (organosolv or nonorganosolv pulping) were less than that of unbleached kraft pulps, except for the pulps obtained by pulping with dioxan at 155°C. The mean hydrogen bond strength of the bleached pulps decreased or increased, depending on the type solvent used and the pulping temperature.     

Bioethanol production from bio‐ organosolv pulps of Pinus radiata and Acacia dealbata

Wood chips from Pinus radiata and Acacia dealbata were pretreated with the white‐rot fungi Ceriporiopsis subvermispora and Ganoderma australe, respectively, for 30 days at 27 °C and 55% relative humidity, followed by an organosolv delignification with 60% ethanol solution at 200 °C for 1 h to produce pulps with high cellulose and low lignin content. Biotreatment for 30 days was chosen based on low weight and cellulose losses (lower than 4%) and lignin degradation higher than 9%. After organosolv delignification, pulp yield for P. radiata and A. dealbata pulps was 45–49% and 31–51%, respectively. P. radiata bio‐pulps showed higher glucan (93%) and lower lignin content (6%) than control pulps (82% glucan and 13% lignin). A. dealbata bio‐pulps also showed higher glucan (95%) and lower lignin content (2%) than control pulps (92% glucan and 4% lignin). Pulp suspensions at 2% consistency were submitted either to separate enzymatic hydrolysis and fermentation (SHF) or simultaneous enzymatic saccharification and fermentation (SSF) for bioethanol production. The yeast Saccharomyces cerevisiae was used for fermentation. Glucan‐to‐glucose conversion in the enzymatic hydrolysis of control and bio‐pulps of P. radiata was 55% and 100%, respectively, and it was 100% for all pulp samples case of A. dealbata. The highest ethanol yield (calculated as percentage of theoretical yield) during SHF of P. radiata control and bio‐pulps was 38% and 55%, respectively, and for A. dealbata control and bio‐pulps 62% and 69%, respectively. The SSF of P. radiata control and bio‐pulps yielded 10% and 65% of ethanol, respectively, and 77% and 82% for A. dealbata control and bio‐pulps, respectively. In wood basis, the maximum conversion obtained (g ethanol per kg wood) in SHF was 37% and 51% (for P. radiata and A. dealbata pulps, respectively) and 44% and 65% in SSF (for P. radiata and A. dealbata pulps, respectively) regarding the theoretical yield. The low wood‐to‐ethanol conversion was associated with low pulp yield (A. dealbata pulps), high residual lignin amount (P. radiata pulps) and the low pulp consistency (2%) used for SHF and SSF. Copyright © 2007 Society of Chemical Industry     

Methylmethacrylate Grafting onto Cotton Stalk Pulp

Grafting of cotton stalk pulp with methylmethacrylate monomer using a ceric salt redox system is carried out. The effect of different variables—for example, monomer dose, reaction time, reaction temperature, acid concentration, initiator concentration, and liquor ratio—are studied. The effect of the presence of different amounts of residual lignin in cotton stalks pulp on the grafting process is demonstrated. Residual lignin percentage in the pulp plays an important role in determining the grafting rate. A sharp decrease in the grafting rate is observed by increasing the residual lignin percent in pulp from 1.64% to 4.96%. As the residual lignin percentage in the pulp is increased to 12% in pulp, the grafting reaction is nearly stopped. Optimization of the grafting conditions is clarified.     

Changes of Molecular Characteristics of Residual Pulp Lignin in Two-Step Soda-Oxygen Pulping

In order to explain the behavior of soda pulp in the following next oxygen stage, the molecular characteristics of the residual lignins isolated from spruce and pine wood pulps cooked to yieldB between 71.8 and 49.8% in the soda pretreatment step were examined. The revealed differences in the cross-linking density and degree of condensation correlated with the effectiveness of lignin removal from soda pulps in the oxygen stage.     

Preparation,characterization, and properties of unbleached,bleached, and grafted pulps from JRC‐321 variety jute fiber

Graft copolymerization onto jute pulps opened the door to new concepts in pulp and paper research. Jute pulp from the JRC‐321 variety white jute fiber was prepared by the alkaline sulfite pulping process. The pulp obtained was bleached by the chlorination, extraction, and hypochlorite sequence technique to remove excess lignin for making bright and good quality paper. Special attention was focused on the graft copolymerization of acrylamide monomer onto the unbleached and bleached pulps by the use of a complex initiating system: Cu(II)/glycine/KHSO₅ in aqueous solution. It was found that percentage grafting was high in the case of bleached pulp. The grafted pulps so obtained were characterized by FTIR and their thermal behavior was characterized by TGA. Their mechanical properties such as tensile strength, percentage elongation, and tenacity were measured and compared. The physical properties such as rot‐resistance and water‐retention capacity of the grafted and the ungrafted pulps were determined. The effect of the percentage grafting variation on the above mentioned properties was examined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1963–1969, 2002     

裂解-气质联用分析氧漂过程中木素结构的变化

从针叶木硫酸盐原浆、氧漂浆以及氧漂后的废液中分离出残余木素,在四甲基氢氧化铵（TMAH）存在下,采用裂解气相色谱-质谱联用(Py-GC-MS)的方法研究了氧漂过程中木素分子结构的变化.对裂解产物的分析表明,木素裂解时产生多种甲基化的芳香化合物,以愈创木基型化合物为主;氧漂能够氧化和降解木素分子,产生更多的羧基化合物,氧化程度高的木素分子容易从纸浆中溶出,氧漂优先脱除沉积在纤维表面上的短侧链木素.     

The xanthate method of grafting. IV. Grafting of acrylonitrile onto high-yield pulp

A series of pulps with different lignin content was prepared from a softwood sodium bisulfite high-yield pulp. Sodium chlorite at pH 4 served as the delignification agent. The resulting pulps were subjected to grafting with acrylonitrile using the cellulose xanthate–hydrogen peroxide redox system to initiate the copolymerization reaction. The resulting products were isolated and analyzed for homopolymer content by dimethylformamide extraction. The results indicate that the presence of larger amounts of lignin in pulp may have a favorable effect on grafting. The plots of total conversion as well as of polymer loading show a minimum centered around approximately 15% of lignin. This minimum is observed invariably at five different reaction times and it coincides with the maximum concentration of reductive groups in the pulps as well as with the maximum cation exchange capacity. The parameter of grafting efficiency has a tendency to increase with rising lignin content, reflecting the lower relative yields of homopolymer obtained with high-lignin pulps. This observation is discussed in relation to possible chain transfer reactions by lignin.     

ON THE FORMATION OF POLY (P-PHENYLENE TEREPHTHALAMIDE) PULPS FROM STIRRED SOLUTIONS

PPTA (poly (p-phenylene terephthalamide)) may precipitate directly from stirred solution by the use of glycerol or glycerol/water coagulant in fibrous pulp form—short fibers with attached fine fibrils that are called PPTA pulp. Scanning electron micrographs show that the precipitated PPTA pulps have a ribbon-like structure similar to Twaron pulps. The wide-angle X-ray diffraction patters of the resultant pulps exhibit three diffraction peaks at 2θ–20.5, 23.5, and 28.5 corresponding to the {110}, {200}, and {004} crystal faces of PPTA fibers, and the peaks are not as sharp as those of fibers. The process yields PPTA pulps with properties such as specific surface areas and mean length depending on the stirring speed, and the ratio of the viscosity of the PPTA/H₂SO₄ solution to that of the coagulant. The inherent viscosity of the pulps determined by that of the PPTA bulk, which can be easily polycondensated to the desired specification.     

Oxygen Delignification Chemistry and Its Impact on Pulp Fibers

Abstract

Two southern pine kraft pulps with kappa numbers of 30.0 (SW1-0) and 48.0 (SW2-0) were oxygen delignified by 30–60% by varying the reaction temperature (78–110°C) and charge of sodium hydroxide (1.6–4.4%). O-bleachability was found to be correlated to the incoming kappa number and charge of sodium hydroxide employed. In general, a lower charge of caustic and a higher brownstock kappa number improved pulp bleachability. The residual lignin in the brownstocks and O-delignified kraft pulp samples was isolated and characterized by ¹³C and ³¹P NMR. ¹³C NMR analysis of the residual lignin samples indicated that the post-oxygen delignified pulps were enriched with α-carbonyl groups and carboxylic acid groups. The content of β-O-aryl structures was increased by 23–36% depending on the extent of oxygen delignification. The post-oxygen delignified pulps were also shown to have increased substituted aryl carbons. ³¹P NMR indicated that the relative content of condensed phenolic units increased by 9–20% after the oxygen delignification, depending on the severity of the O-stage. This observation was probably due to the accumulation or formation of 5,5-biphenyl structures in the process. The physical strength properties of brownstock and post-oxygen delignified pulps were assessed in terms of zero-span strength, tensile strength, tear strength, and burst strength. Oxygen delignification led to a slight increase in the curls and kinks of the pulp fibers. The O-stage was shown to cause a 4.8–15.6% decrease in zero-span strength. In contrast, oxygen delignification increased tensile strength. This result could be explained as the improvement of fiber bonding after the oxygen bleaching.     

Evaluation of the contribution of lignin stilbene phenol units in the photoyellowing of peroxide-bleached lignin-rich pulps

In order to assess and quantify the contribution of stilbene phenols in photoreversion of bleached high-yield pulps, a method to reduce the stilbene double bond and quantify the formed diphenylethane was developed on 4-benzyloxy-3,3′-dimethoxy-4′-hydroxystilbene, as lignin monomer model, and also on a more sophisticated lignin polymer model constituted by a polystyrene framework containing 4,4′-dihydroxy-3,3′-dimethoxystilbene elements as pendent groups. The method used RhCl(PPh₃)₃ as soluble catalyst to get an efficient hydrogenation and AlCl₃ in benzene to liberate the diphenylethane from the polymer framework. For the first time a semiquantitative evaluation of the content of the stilbene phenols formed from β-1 units was given for high-yield pulps. The value of 2 p-stilbene phenols for 1000 C₉ lignin units found indicates that they are present in very small quantities after the peroxide bleaching. UV irradiation of the polystyrene model adsorbed on solid cellulose matrix had revealed an efficient stabilization after the hydrogenation treatment. This was not the case for the peroxide bleached pulp showing that the p-stilbene phenols formed from β-1 units are not the main contributors of the rapid yellowing of bleached lignin-rich pulps. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2517–2531, 1998     

Chemical Structure of Residual Lignin from Kraft Pulp

Structural characteristics of wood lignin and residual lignin in conventional and modified kraft pulps were examined employing elemental and methoxyl analysis and ¹³C, ¹H, and ³¹P-NMR. The structural analysis revealed that kraft residual lignin differs significantly from wood lignin while differences between residual lignins in conventional and EMCC® pulps have similar structural characteristics at kappa numbers corresponding to the point where the selectivity of the cook becomes poor. NMR analysis suggested that residual lignin, compared to the wood lignin, is much less reactive towards pulping chemicals due to the low content of aryl ether linkages and the prevalence of condensed type structures.     

Dissolution of Ethylenediamine Pretreated Pulp with High Lignin Content in LiCl/DMSO without Milling

Abstract

Various hardwood and softwood chemical pulps, including those with relatively high lignin content (up to ca. 10.5%), were completely dissolved without milling in lithium chloride/dimethyl sulfoxide (LiCl/DMSO) after a pretreatment with ethylenediamine (EDA). Because milling of the sample is not required, degradation of the cell wall components caused by milling does not take place. After the EDA pretreatment, the crystallinity of the pulps remained as high as the original pulps, although the crystal structure changed. This is the first time that transparent solutions of underivatized pulps with high lignin content were obtained in a simple organic solvent system. Interestingly, even in the case of coarse wood meal (40–80 mesh) about 70% could be dissolved after repeating the dissolving procedure two times. The formation of a pulp–EDA or wood–EDA complex seems to be critical for the dissolution in LiCl/DMSO. The nuclear magnetic resonance (NMR) spectrum of the EDA treated pulp solution had good resolution even though the degree of polymerization (DP) of the cellulose in the pulp is very high.