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.     

BEHAVIOR OF EUCALYPTUS GLOBULUS LIGNIN DURING KRAFT PULPING. II. ANALYSIS BY NMR,ESI/MS,AND GPC

ABSTRACT

Residual and dissolved lignin from different phases of kraft delignification of Eucalyptus globulus wood were isolated and characterized by 1D and 2D ¹H NMR, ¹³C NMR, Electrospray Ionization Mass Spectrometry (ESI/MS), and gel permeation chromatography (GPC). During the temperature rise period, below 70°C, about 20% of the lignin was dissolved without significant structural changes. Above 70°C, the lignin suffered significant degradation/fragmentation in the cell wall prior to dissolution. The lignin ether-linked syringyl units were the most susceptible to alkaline degradation. Through the course of pulping, the residual lignin (RL) revealed a gradual increase of aliphatic moieties of unknown structure, as well as a decrease of native structures such as phenylcoumaran and pino-/syringaresinol lignin units. A significant decrease of the β-O-4 structures content in RL was detected only at the final cooking temperature. The lignin dissolved in the black liquor (BL) consisted of highly branched oligomers with rather low molecular weight (average mass 800–1000 u). A part of BL (about 30%) was chemically linked to carbohydrates and possessed a large molecular weight distribution (500–4000 u). BL showed a progressive decrease in β-O-4 and pino-/syringaresinol structures and formation of enol ether and stilbene structures. The GPC analyses showed a continuous decrease of the molecular weight of both the residual and dissolved lignins during the pulping process, particularly in the residual stage.     

Molecular Mass Distribution of Lignin from the Alkaline Pulping of Hardwood,Softwood, and Wheat Straw

Abstract

The behavior of lignin during kraft (hardwood, softwood, and wheat straw) and soda-AQ (wheat straw) pulping was studied, mainly in terms of delignification degree and molecular mass distribution (MMD). In the initial delignification phase (at 140°C for 15–60 min), a prominent part of the dissolved softwood kraft lignin (18–25 g/L, MM mostly > 3,000 Da) was found in the liquid phase of chip cavities, rather than in the external bulk black liquor (5–7 g/L, MM mostly < 3,000 Da). The maximum weight average MM values ( _w) of the soluble lignin under conventional cooking conditions were detected for the kraft softwood (4,100 Da), and kraft birch (3,400 Da) when the degree of delignification was 65–75%, corresponding to a residual lignin content of 5–10%. The maximum _w of the dissolved wheat straw kraft (5,050 Da) and soda-AQ (5,900 Da) lignins was clearly higher than that of wood-based kraft lignins (2,950–4, 100 Da).     

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.     

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.     

Contents of α-O-4 and β-O-4 Bonds in Native Lignin and Isolated Lignin Preparations

An analytical calculation method for the estimation of the contents of alkyl aryl ether bonds (α-O-4 and β-O-4) in lignin was developed. In the framework of the method, Alkyl–O–Aryl type bonds are described as coupled phenolic hydroxyls (OH_phen). The method is based on the balance equation including the free and coupled OH_phen contents in dissolved and residual lignins, on the one hand, and their respective contents in native lignin, on the other. The free OH_phen content is calculated on the basis of the OH_phen contents of dissolved and residual lignin, determined by the aminolysis method in the course of kraft cooking of softwood. The calculation results for soluble lignin preparations are in good agreement with the 13C NMR (nuclear magnetic resonance) spectral data for the solutions. The content of Alkyl–O–Aryl bonds in native softwood (pine, spruce) lignin was estimated at 79/100 PPU (phenylpropane unit). In isolated lignin preparations, the contents of these bonds decrease in the sequence: Freudenberg lignin (71/100 PPU)> Bjorkman lignin (61/100 PPU)> Pepper lignin (44/100 PPU). Dissolved alkaline lignin still contains small amounts of Alkyl–O–Aryl bonds (36/100 PPU in soda lignin and an average of 23/100 PPU in soda-AQ lignin, kraft lignin, and kraft-AQ lignin). Residual lignin which represents the fraction of native lignin with inter-unit bonds resistant to kraft pulping contains 66/100 PPU of such bonds. A relatively high content of Alkyl–O–Aryl bonds (61/100 PPU) is preserved in technical hydrolysis lignins.     

Electrical Properties of Precipitated Lignins from Different Black Liquors

Abstract

Some corelations over the structure and dielectric properties of precipitated lignins from different waste black liquors of various modified soda and kraft pulping of bagasse have been discussed. The dielectric and the electrical properties at the same temperatures and frequencies ranges for the tested samples showed some differences which seems to be attributed to the difference in the structure and intermolecular interaction between lignin molecules. These differences are discussed on the basis of the molecular structure obtained from the infrared spectra. The conduction mechanism in the case of kraft and kraft sulfite lignins is due to electron transfer from the valence band to the conduction band by thermal activation.     

Reactions of Conventional Kraft and Superbatch Pulp Residual Lignins with Peroxyformic Acid

Abstract

The residual lignins KRL and SRL, isolated from a conventional kraft pulp and a SuperBatch pulp respectively, were reacted with peroxyformic acid (PFA). The reagent consumptions were determined and the products fractionated according to their solubility. Both lignins consumed a roughly equal amount of PFA, which was nearly 50% higher than that consumed by kraft lignin. The undissolved fractions of PFA-treated residual lignins (yield >80%) contained less aromatic units, phenolic hydroxyl and methoxyl groups, and considerably more carboxyl groups (including those of formate esters) than the untreated lignins. The extent of these modifications was approximately equal for KRL and SRL, which together with the similar PFA consumptions and product yields of KRL and SRL indicates that the two residual lignins showed no essential difference in reactivity toward PFA. The effect of fiber wall morphology on delignification efficiency during PFA delignification is suggested to be small because of the cleavage of lignin-carbohydrate linkages occurring under acid conditions. The part of KRL remaining insoluble after PFA-treatment had a 40% higher molar mass than KRL while in the case of SRL there was hardly any such difference in molar mass. The lignins solubilized during the PFA treatments represented the most highly degraded part of the lignins, having very low molar masses and being richer in carboxyl groups and lower in aromatic units, phenolic hydroxyl, and methoxyl groups than the undissolved lignins.     

Impact of effective alkali and sulfide profiling on Eucalyptus globulus kraft pulping. Selectivity of the impregnation phase and its effect on final pulping results

BACKGROUND: Eucalyptus globulus is an important wood source for paper production and, in the last few years, great efforts have been made to assess its chemical specificities and improve the kraft pulping efficiency. Despite the existence of several works concerning mostly the kinetics of E. globulus kraft pulping there is a lack of systematic studies on the initial phase of pulping as well as on the impact of effective alkali (EA) charge profiling on the kraft pulping performance of this species. The aim of the present work is to assess the effect of initial effective alkali and sulfide charges on the lignin and carbohydrates removal on the impregnation phase and to investigate the effect of EA splitting charge on the whole E. globulus pulping process efficiency. RESULTS: When the EA charge at impregnation phase increases, the amount of dissolved wood increases until it reaches a constant value of about 20%. Maximum polysaccharide removal at impregnation phase was about 10% of total wood weight. Glucose removal during impregnation was attributed to the degradation and/or dissolution of E. globulus glucans. For EA charges at impregnation phase higher than ～15%, xylan retention on wood was roughly constant. Despite the differences found at impregnation phase on the amount of dissolved wood and lignin removal, it was demonstrated that these differences are almost completely attenuated until the end of the kraft pulping process. CONCLUSION: In the case of E. globulus, for a constant effective alkali charge, alkali profiling does not affect the whole kraft pulping performance. Copyright © 2007 Society of Chemical Industry     

Modified Kraft Pulping of Bagasse: Infrared Spectroscopy of Lignin

Abstract

The infrared spectroscopy of precipitated lignin from waste black liquors of bagasse pulping with kraft sulfite pulping process was investigated. Also the effect of anthraquinon and methanol addition in the soda, kraft and kraft-sulfite pulping liquor on the infrared specra of the precipitated lignin was studied. The presence of methanol in the pulping liquor causes an increase in the degradation as well as increase in the carboxylic group in the precipitated lignin. Also, the phenolic hydroxyl group in case of kraft lignin is higher than soda lignin. Presence of sulfite in the kraft-sulfite pulping liquor produces lignin hydroxyl groups.     

Investigation of the Chemistry of Oxygen Delignification of Low Kappa Softwood Kraft Pulp using an Organic/Inorganic Chemical Selectivity System

Abstract

Oxygen delignification (OD) of low kappa softwood kraft pulp was examined in two steps without inter‐stage washing as part of an overall program to evaluate the efficiency of a selectivity enhancement system consisting of phenol and magnesium sulfate. Black liquor carryover in the reaction system did not substantially affect delignification and the selectivity of these OD reactions. The residual lignins from both the original pulp and oxygen‐delignified pulp with and without the phenol/MgSO₄ selectivity enhancement system were prepared and characterized using NMR spectroscopy. The effluent lignins after oxygen delignification were also prepared and characterized. The lignin characterizations provided the basis for the rationalization of the selectivity observed. A significant finding of this study was that the phenol/MgSO₄ system in the oxygen delignification reaction appeared to hinder phenolic guaiacyl unit condensation. It also appeared to enrich the levels of p‐hydroxyphenyls in the residual lignin.     

The Lignin of the Diffuse Porous Angiosperm Tree Triplochyton scleroxylon K. Schum with Low Syringyl Content

“Milled wood lignin” was isolated from Triplochyton scleroxylon tree (wawa MWL) and subjected to elemental analysis before and after acid treatment, and to analytical pyrolysis. Both FT-IR and ¹H NMR spectra were recorded. For comparison, lignins from spruce and beech isolated by the MWL, dioxane/HCl (DIL), and Cuene (CUL) techniques were also characterized. The residual carbohydrate content of the lignins was estimated. Wawa MWL is a GS lignin with 88% G and 12% S content. The utility of analytical pyrolysis and FT-IR for lignin classification is discussed. FT-IR spectroscopy, calibrated with data of 50 MWLs (PLS approach), gives reliable results with a minimum of experimental work. The yields of S phenols obtained by pyrolysis has to be multiplied with a factor around 0.5 for correction if the S content of a lignin is low. The cross-linking indices and OH_phen/OH_aliph ratios of lignins increase in the order MWL < DIL < CUL. ¹H NMR spectroscopy is also helpful to recognize the S/G ratio of a lignin.     

硫化钠预处理制浆残余木质素的化学结构特性

用化学和波谱分析研究了硫化钠预处理硫酸盐制浆中残余木质素的化学结构特性。结果表明 ,硫化钠处理能促进硫与木片中木质素的结合 ,而甲氧基的含量有所下降。与对照硫酸盐制浆相比 ,预处理条件下木质素的缩合程度较低 ,经过蒸煮后残余木质素的缩合程度有较大的提高。     

2D Nmr Study of Residual Lignin in Beech Kraft Pulp Combined with Selective Cleavage with Pivaloyl Iodide

Structures of acetylated residual lignin obtained from unbleached beech kraft pulp were investigated by 2D NMR in combination with selective cleavage of non-phenolic α-alkyl ether bonds with pivaloyl iodide generated in situ from pivaloyl chloride / sodium iodide. β-O-4 and resinol structures still remained in this polymer lignin. Furthermore, carbohydrates were proved to be linked glycosidically to benzyl carbons of lignin. Possibly this inhibits complete delignification during kraft pulping.     

Formation and Reaction of Coniferyl Alcohol During Alkaline Pulping

The formation and subsequent disappearance of coniferyl alcohol during kraft and soda-AQ (anthraquinone) pulping of western hemlock wood meal have been studied under isothermal condition. At 140°C, the amount of coniferyl alcohol generated increases to a sharp maximum (0.4% of total lignin in kraft and 1.9% in soda-AQ pulping) and then declines rapidly to low values. It was found that the disappearance of coniferyl alcohol was mainly due to condensation with other components of dissolved lignin. Nearly identical activation energies, 125 kJ mole^?1 for kraft and 128 kJ mole^?1 for soda-AQ pulping, were derived from the initial rates of coniferyl alcohol formation, conforming closely with the value 121 kJ mole^?1 for the cleavage of phenolic β-ether model compounds in the kraft process.     

木质素分级对其应用性能的影响

木质素是一种结构复杂的天然芳香类聚合物,功能基团丰富,具有良好的开发应用前景。工业碱木质素是当前木质素转化利用的主体,主要源于制浆黑液。由于原料来源、制浆工艺的影响,木质素多分散性高、结构与性能不一,致使相应的木质素基产品的均一性与稳定性较差。通过木质素分级可以获得具有不同分子量或特定化学结构特征的木质素级分,促使各级分的多分散性降低、均一性提高,进而针对特定性能的级分进行改性或者直接利用可进一步提高产品的稳定性。对现行木质素的主要分级方式进行了总结,重点探讨了工业碱木质素的分级方式对其后续利用的影响及存在问题。最后,针对木质素不同级分的特点对木质素未来分级的方向及应用前景提出了展望。     

同位素标记法用于植物纤维中LCC蒸煮过程中结构变化的研究

为了研究植物纤维原料中的木素-碳水化合物复合体(lignin-carbohydrate complexes,LCCs)在硫酸盐法蒸煮过程中的结构变化,向天然植物稻秆中投入带¹³C同位素标记的松柏醇葡萄糖苷,用Björkman的方法将木素-碳水化合物复合体从稻秆粉末中分离出来,结合红外光谱和高分辨率的液态¹³C NMR检测分析发现木素与糖类主要是通过苯甲醚键、酯键和缩醛键连接。其中,在LCC中木素的主要结构为β-O-4结构。将分离出来的带标记的LCC模拟硫酸盐法蒸煮,分离得到木素-碳水化合物复合体的硫酸盐木素。通过对天然稻秆LCC硫酸盐木素和稻秆LCC硫酸盐木素-[α-¹³C]的红外光谱和高分辨率¹³C NMR分析,证实了在稻秆LCC硫酸盐蒸煮后,产物中还存在少量以苯甲醚键和缩醛键连接的LC结构。另外,所得硫酸盐木素主要以β-O-4结构为主,含有少量的β-β、β-5和β-1结构。     

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.     

Structural Characterization of Pine Kraft Lignin: BioChoice Lignin vs Indulin AT

BioChoice lignin (BCL) is a newly commercialized pine kraft lignin from Plymouth Mill of Domtar, which is precipitated from black liquor of bleachable-grade pulp. Indulin AT is a pine kraft lignin commercialized by Meadwestvaco for the past 60 years, which is precipitated from black liquor of linerboard-grade pulp. Thus, the two technical lignins are produced under quite different conditions in terms of alkali charge and pulping time/temperature. While the chemical structure of Indulin AT is well documented, that of BCL is totally unknown. In this study, chemical structures of BCL and Indulin AT are characterized using modern analytical techniques and compared with those of pine milled wood lignin (MWL) in order to elucidate the structural changes that occur during kraft pulping and the structural differences, if any, between BCL and Indulin AT. Both BCL and Indulin AT are structurally very different from the native lignin (MWL) in wood, indicating drastic structural modification during the kraft pulping process. Surprisingly, BCL and Indulin AT are structurally very similar, in spite of the fact that they are produced under different process conditions. However, there are subtle structural differences between BCL and Indulin AT. BCL has higher phenolic hydroxyl, catechol, enol ether, and stilbene contents, but lower methoxyl and β-O-4 contents. These differences are explained by the different pulping conditions under which the two technical lignins are produced.     

Xylanase-Resistant Xylan In Unbleached Kraft Pulp

A water-soluble chromophoric xylanase-resitant xylan fraction (LF-D) was separated from a hardwood unbleached kraft pulp (UKP) after hydrolysis with a cellulase/ xylanase-membrane bioreactor. LF-D contained over 70% unremovable inorganic atoms including Si, Na, and S, together with a β-1,4- linked xylan. A nucleus exchange reaction and a nitrobenzene oxidation showed that LF-D contained a trace amount of a lignin component abundant in quinoid structures which had been partly demethylated during the course of kraft pulping. On the other hand, a higher molecular weight residual lignin fraction (HF-P), which was obtained from an impermeable part of the enzymatic digests, was found to have a diphenylmethane structure. LF-D was partially decolorized by Coriolus versicolor and bacterial microflora without action of extracellular lignin peroxidase, Mn-peroxidase, laccase or xylanase.