New Insights into Lignin Modification during Chlorine Dioxide Bleaching Sequences (III): The Impact of Modifications in the (EO) versus E Stage on the D1 Stage

Abstract

Chlorine dioxide delignification (D₀) modifies kraft residual lignin by oxidizing phenolic groups to both quinone and muconic acid structures. Alkaline extraction (E), in addition to removing solubilized lignin, converts quinone moieties to polyphenols. These polyphenols are easily oxidized by oxygen in an (EO) stage or by ClO₂ in a D₁ stage to hydroxyquinones (～1.8 mmol/g lignin). Pulps treated by D₀E consume considerably more ClO₂ in the D₁ than D₀(EO), and have lower bleachability, as was quantified by a simple bleaching model. Both D₀E and D₀(EO) pulps approach a common brightness ceiling (～83 ISO) when excess ClO₂ is applied. Examination of the post‐D₁ b* values indicates that D₀E and D₀(EO) also have similar asymptotic b* values (～6), indicating that both pulps have similar residual chromophores. Hydroxyquinone structures appear to be eliminated in the D₁ stage for D₀(EO) pulps, and at high ClO₂ levels for D₀E pulps.     

The Influence of the Bleaching Medium on Caustic Extraction Efficiency (II): Oxidized Lignin Solubility

Abstract

Caustic extractions performed with >50% ethanol solutions severely hindered lignin removal from chlorine dioxide (D₀) treated pulps. In this study, we show that the alkali solubility of an isolated D₀ lignin decreased as the concentration of ethanol in the medium was increased from 50 to 75%. In addition, the amount of dissolved lignin in the alkaline extraction effluents approached its solubility limit when the medium contained more than 50% ethanol. These results indicate that alkaline extractions of D₀-stage pulps with ethanol-rich media were limited by the lower solubility of ionized lignin fragments in these solutions as compared to water. An empirical solubility parameter analysis predicted that non-ionized D₀ lignins should be more soluble in ethanol than in water. Indeed, delignification with an acid extraction stage was improved when the water was replaced with ethanol.     

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.     

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.     

Comparative Studies of Chlorine Dioxide Reactions with Muconic Acid Derivatives and Lignin Model Compounds

Abstract

The reaction of chlorine dioxide with different types of lignin model compounds was investigated in order to compare the kinetics and to evaluate the amount of oxidant consumed by the different substrates. Complete reaction of lignin model compounds was observed at ClO₂‐to‐substrate molar ratios of 0.9–1.2, which corresponds to an electron transfer varying between 5–6 equivalents per mole of substrate. Muconic acid derivatives also fully reacted, at a ClO₂‐to‐substrate molar ratio of 1.2, with the oxidant consumption being about 4 equivalents per mole of substrate. The reaction of mixtures of phenolic, non‐phenolic, and muconic acid type substrates showed that the reaction rates of non‐phenolic and muconic acid type substrates were rather similar. This study suggests that further reaction between ClO₂ and the primary lignin oxidation products, such as muconic acid type structures could be the cause of overconsumption of oxidant in a D stage.     

Effect of Eucalypt Pulp Pretreatment with Hot Acid Hydrolysis on (aZe)DP and (aZe)(EP)P Bleaching Performance

The effect of pulp pretreatment with hot acid hydrolysis on high consistency ozone bleaching was evaluated. An experimental plan was set up involving the full optimization of the A-stage and its application in Elemental Chlorine Free–ECF–[A/(aZe)DP and A(aZe)DP] and Total Chlorine Free–TCF–[A/(aZe)(EP)P and A(aZe)(EP)P] sequences for eucalypt kraft pulp bleaching. The A-stage removed a significant amount of lignin and HexA from the pulp, and the subsequent Z-stage remained efficient after completion of the A-stage. The chemical savings caused by the A-stage were significant (～7 kg ClO₂/adt). The optimum conditions for the A-stage were pH 3.0, 90°C for 120 min, and 10% consistency. The strength properties of pulps bleached with the (aZe)DP (reference) and A/(aZe)DP ECF sequences were similar, but the TCF sequence A/(aZe)(EP)P delivered slightly lower strength properties than the ECF sequences. Fiber peeling studies indicated that the HexA present in the kraft pulp is not concentrated on the fiber surface, as previously thought.     

麦草浆二氧化氯与氧气脱木素效率及相应漂白流程的对比

对麦草浆二氧化氯与氧气脱木素效率及相应的漂白流程进行了对比研究。结果表明,ClO2脱木素(D0)对木素的修饰和改性效果好于氧脱木素(O),在脱木素率低于及接近氧脱木素率的条件下,D0浆的可漂性均大于O浆。在D0段和O段脱木素率相同的条件下,采用D0A/QP、D0EP漂白流程漂后纸浆白度分别比OA/QP漂白流程高11.2和10.3个百分点。D0段废液和相应D0A/QP漂白流程三段混合废水的CODCr负荷均比O段和OA/QP漂白流程混合废水的CODCr负荷轻。D0段和O段废液的紫外光谱都呈现出木素苯环的特征吸收。纸浆的FT-IR谱图分析表明,D0浆和O浆中的羟基和羰基数量增多,随着漂白的进行,羰基等主要发色基团逐渐消除,纸浆白度得到提高。纸浆纤维形态的SEM分析显示,D0段和相应的D0A/QP漂白流程对纤维表面的破坏和损伤较O段和相应的OA/QP漂白流程轻。     

Bio‐Chemimechanical Pulps from Eucalyptus grandis: Strength Properties,Bleaching, and Brightness Stability

Abstract

Eucalyptus grandis wood chips were treated with the white‐rot fungus Ceriporiopsis subvermispora in a 100‐L bioreactor for 15 days. The treatment was characteristic of a selective biodelignification (7.6±0.2% and 0.3±0.2% of lignin and glucan losses, respectively) with concomitant extractive removal (17.7±0.2%). Biotreated samples and non‐inoculated controls were pre‐cooked in alkaline sulfite and post‐refined in a Jokro mill. The biotreated pulps fibrillated more rapidly and contained lower amounts of rejects than the control. To achieve a freeness of 400 mL, the control pulp required 125 min of beating, whereas the biopulp required only 95 min, a reduction of 24%. Unbleached biopulps had better strength properties than control pulps because higher tensile indexes were obtained for the entire range of tear indexes. Bleaching with 8% hydrogen peroxide increased the brightness of these pulps by 17 points. At low peroxide loads, the brightness increase for biopulps was lower than for the control pulps. Still, the bleachability of sboth pulps was similar for peroxide loads higher than 2%. After a two‐stage H₂O₂‐bleaching sequence, final brightnesses for the control and biopulps were 59.7±0.8% and 60.5±0.4%, respectively. Brightness stability of the bleached control and bio‐CMP pulps to photo and thermal aging were very similar.     

SO2-Ethanol-Water (SEW) Pulping: I. Lignin Determination in Pulps and Liquors

Abstract

Quantitative determination of lignin in SO₂-ethanol-water (SEW) pulps and spent liquors is described. The methods developed for conventional sulfite pulping are successfully applied to the SEW process. Linear correlations between Klason/total lignin content and kappa number are found over a wide pulp yield range for spruce, beech, and wheat straw. Lignin content of the spruce spent SEW liquors is determined using either hydrogen peroxide to remove SO₂ and dilution by 3% sulfuric acid or simply by dilution with 0.1M sodium hydroxide. The recommended wavelength is 280 nm. The experimentally found values for the extinction coefficient of dissolved lignin in 3% sulfuric acid and in 0.1M NaOH are 19 and 23 L/(g·cm), respectively. The interference of furanic compounds is eliminated by reduction with sodium borohydride.     

Physicochemical characterization of lignin recovered from microwave‐assisted delignified lignocellulosic biomass for use in biobased materials

Lignocellulosic biomass (Moso Bamboo, Chinese tallow tree wood, switchgrass, and pine wood) was subjected to a novel delignification process using microwave energy in a binary glycerol/methanol solvent. The physicochemical properties of the recovered lignin were analyzed prior to its application in the fabrication of polylactic acid (PLA)–lignin composites. The results showed that the samples had a high Klason lignin content (>75%) and retained their natural structure. Thermogravimetric analysis revealed that the recovered lignin exhibited a different thermal decomposition pattern from that of commercial lignins. All the recovered lignins had good solubility in common organic solvents (acetone, 1,4‐dioxane, THF, DMSO, and ethanol/water) and 1 mol/L NaOH solution. The addition of lignin into the PLA matrix resulted in the improvement in tensile properties of PLA–lignin composites. PLA films with low lignin content had good UV light‐resistant properties, indicating that the recovered lignin has potential in packaging of light‐sensitive products. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42635.     

木质素结构及热解特性

为研究结构类型和提取方法对木质素热解特性的影响,本研究采用Klason方法预处理得到的棉杆、核桃壳Klason木质素和贝克曼方法预处理得到的核桃壳磨木木质素（MWL）,并结合傅里叶红外光谱仪（FT-IR）和快速热解仪-气相色谱/质谱联用（Py-GC/MS）对其化学结构和热解特性进行分析。FT-IR表明碱木质素为G型木质素,棉杆木质素属于GS类型木质素,而核桃壳木质素具有 HGS木质素的特征;Py-GC/MS分析发现原料的变化以及提取方法对木质素热解产物的组成有明显的影响,在棉杆Klason木质素中邻苯二酚类产物含量为28.18%,而在核桃壳Klason和磨木木质素的含量分别为18.12%和35.11%。同时研究表明经两种方法处理的木质素结构有明显的不同,其中Klason木质素结构中苯丙酸侧链上的α-和β-醚键明显断裂,而贝克曼处理主要体现在苯基芳基醚键的断裂。     

THE INFLUENCE OF THE BLEACHING MEDIUM ON CHLORINE DIOXIDE DELIGNIFICATION

Chlorine dioxide delignification (D₀) stages performed in 90% ethanol resulted in post-D₀ kappa numbers that were 2 to 2.5 units lower than those performed in water. In spite of the reduction in kappa number, various gravimetric and UV spectroscopic techniques for measuring residual lignin indicated that the ethanol medium did not significantly enhance D₀ stage lignin removal. Differences in post-D₀ kappa numbers between the ethanol-based and aqueous systems were ascribed to how the bleaching medium affects ClO₂ oxidation of residual lignin. Ethanol-based D₀ stages resulted in an oxidized lignin that contains fewer muconic acid structures and more quinone structures than the aqueous-based systems. Indirect evidence from sodium hydrosulfite reduction implied that quinone moieties consume less KMnO₄ than aromatic structures in lignin during the kappa number test.     

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.     

Use of a Novel Extremophilic Xylanase for an Environmentally Friendly Industrial Bleaching of Kraft Pulps

Xylanases can boost pulp bleachability in Elemental Chlorine Free (ECF) processes, but their industrial implementation for producing bleached kraft pulps is not straightforward. It requires enzymes to be active and stable at the extreme conditions of alkalinity and high temperature typical of this industrial process; most commercial enzymes are unable to withstand these conditions. In this work, a novel highly thermo and alkaline-tolerant xylanase from Pseudothermotoga thermarum was overproduced in E. coli and tested as a bleaching booster of hardwood kraft pulps to save chlorine dioxide (ClO₂) during ECF bleaching. The extremozyme-stage (EXZ) was carried out at 90 °C and pH 10.5 and optimised at lab scale on an industrial oxygen-delignified eucalyptus pulp, enabling us to save 15% ClO₂ to reach the mill brightness, and with no detrimental effect on paper properties. Then, the EXZ-assisted bleaching sequence was validated at pilot scale under industrial conditions, achieving 25% ClO₂ savings and reducing the generation of organochlorinated compounds (AOX) by 18%, while maintaining pulp quality and papermaking properties. Technology reproducibility was confirmed with another industrial kraft pulp from a mix of hardwoods. The new enzymatic technology constitutes a realistic step towards environmentally friendly production of kraft pulps through industrial integration of biotechnology.     

Effect of Totally Chlorine Free and Elemental Chlorine Free Sequences on Whole Stem Kenaf (Hibiscus cannabinus) Pulp Characteristics

Totally chlorine free (TCF) and elemental chlorine free (ECF) single and multistage sequences were used to bleach whole stem kenaf pulp. The results indicated that in contrast to unbleached kraft wood pulps, kraft kenaf pulps can be easily bleached to a brightness of 91.4% using a four-stage TCF [Q₁(PO)Q₂P] bleaching sequence. The ECF bleaching pulps had slightly higher selectivity and yield than those of the TCF bleached pulps. The strength properties of the TCF [Q₁(PO)Q₂P] and ECF (D₁ED₂EP) bleached pulps were comparable, with the exception of tear index and tensile index, which were slightly higher and lower for TCF pulps, respectively.     

Fractional Separation and Structural Characterization of Chlorophyll and Lignin from Perennial Ryegrass (L. perenne) and Cocksfoot Grass (D. glomerata)

Abstract

One chlorophyll rich fraction and two lignin preparations were separated from perennial grass and cocksfoot grass by sequential three‐stage treatments with 80% ethanol containing 0.2% NaOH, 2.5% H₂O₂?0.2% EDTA containing 1.5% NaOH, and 2.5% H₂O₂?0.2% TAED containing 1.0% NaOH at 75°C for 3 h, respectively, which released 4.6 and 3.6% chlorophyll rich fraction, 2.3 and 5.8%, and 0.9 and 1.0% lignin preparations, except for releasing 8.0 and 10.4%, 79.1 and 77.0%, and 12.9 and 12.5% of the original hemicelluloses, respectively. The lignin fractions obtained from the two different grasses had very similar molecular weights and structural composition. The NMR spectra of the lignin preparations revealed the presence of p‐hydroxyphenyl, guaiacyl, and syringyl structures, and the lignin in chlorophyll rich fraction contained more guaiacyl and syringyl units than p‐hydroxyphenyl unit, whereas the reverse trend was found in the two lignin preparations. The lignin preparations are distinguished with straw and wood lignins by relatively higher contents of p‐hydroxyphenyl unit and lower amounts of condensed units (β‐5 and 5‐5′) and resinol units (β‐β). This difference in distribution of structural units indicated some structural heterogeneity between grass and straw/or wood lignin.     

Strategies to reduce the brightness reversion of industrial ECF bleached Eucalyptus globulus kraft pulp

BACKGROUND: Brightness stability is a key property of bleached chemical pulps and is primarily determined by wood species and bleaching process conditions. Eucalyptus globulus is becoming a very important raw material for hardwood pulp production. In spite of this importance, there is a relative lack of systematic studies in the literature dealing with the subject. This research aims to study the effect of some of the foremost bleaching parameters of a DEDD bleaching sequence as well as the effect of a final P stage (DEDP instead of DEDD) in the brightness stability of bleached E. globulus kraft pulps. RESULTS: The increase of the D₀ stage temperature from 55 °C to 90 °C caused an increase in brightness stability. Increasing the ClO₂ charges from 2.8% to 3.2% also improved significantly the brightness stability. A high H₂SO₄ charge in the D₀ stage (10 kg tonne^?1 pulp) diminished the brightness stability. The combination of H₂O₂ addition to the E stage and ClO₂ reduction in the two final D stages does not affect brightness reversion. Raising the D₂ stage temperature from 65 °C to 82 °C decreased the brightness reversion, while an increase was obtained when the temperature rose above 82 °C. Substitution of the last ClO₂ stage in the DEDD sequence by a H₂O₂ stage (DEDP) significantly reduced the brightness reversion. CONCLUSION: For an existing pulp mill in which the implementation of new technologies to improve brightness reversion is considered, the results obtained showed that brightness stability can be improved without any significant capital investment. Copyright © 2007 Society of Chemical Industry     

Characterization and comparison of Acetosolv and Milox lignin isolated from crofton weed stem

Crofton weed (Eupatorium adenophorum Spreng) is an invasive species in China, which has damaged native ecosystems and caused great economic losses. To use the weed instead of simple control and management of it, the weed stem of was delignified by Acetosolv and Milox processes to obtain lignin. The lignins (Acetosolv lignin, AL; and Milox lignin, ML) were characterized and compared through several analysis methods. It was found that both of AL and ML were syringyl‐guaiacyl type (GS) lignin, but that the chemical composition and structure of the two lignins were somewhat different. The obtained C₉ expanded formulas for AL and ML were C₉H_9.16O_3.50N_0.13(OCH₃)_0.97(Ph? OH)_0.34Ac_0.22 and C₉H_7.96O_3.13N_0.13(OCH₃)_1.23(Ph? OH)_0.51Ac_0.14, respectively. According to an elementary analysis, the two lignins had similar higher heat value of 20.0–21.0 MJ kg^?1, which were similar to that of raw coal. Gel permeation chromatography analysis indicated the two lignins had similar molecular weights. Notwithstanding that the Ultraviolet, Fourier transform infrared, and ¹H‐NMR spectra illustrated that the two lignins had similar chemical functional groups, the AL showed more acetyl groups signals. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Wood Fiber Quality and Kraft Pulping Efficiencies of Trembling Aspen (Populus tremuloides Michx) Clones

Abstract

The natural variation in wood and pulp fiber quality of 15 aspen (Populus tremuloides Michx) clones, represented by 47 trees, was assessed from 4 different sites in British Columbia, Canada. Kraft pulping trials revealed substantial variation in the pulping efficiencies, illustrated by differences of 6% in total pulp yield, ～30% differences in H‐factor required to attain a target kappa of 21, and differences of up to 2 ISO brightness units in bleachability of kappa 21 pulp. Clearly, enormous variation exists in the natural stands of aspen, and presents some exciting opportunities for selecting clonal aspen for targeted end‐product applications. A comprehensive characterization of wood chemical composition, wood density, and fiber properties indicated that pulp yield is directly related to syringyl lignin monomer composition, and not inherent wood density, regardless of geographic locations, whereas pulp bleachability and viscosity appear to be associated with the inherent cell wall thickness of the starting wood resources (fiber coarseness). These findings suggest that geographic location imparts influences on wood fiber coarseness traits, while substantial genetic variability exists on all sites.     

Extraction and characterization of lignins from maize stem and sugarcane bagasse

Lignins were isolated from maize stem and sugarcane bagasse by using mild dioxane or acidic dioxane solution. The result of nitrobenzene oxidation of the isolated lignins shows that there is a high proportion of p‐hydroxyphenyl alcohol in the lignins of maize stem and sugarcane bagasse. The lignins isolated from maize stem and sugarcane bagasse have relatively same value of the weight‐average (M _w = 3405–3868 g mol⁻¹) and number‐average (M _n = 1411–1612 g mol⁻¹) molecular weights, and polydispersity (M _w/M _n = 2.24–2.51). Acidic dioxane treatment did attack the β‐aryl ether structures in lignins, in particular for β‐aryl syringyl ethers, and broke the ester bonds between arabinose and ferulic acid that etherified to lignins, and it also cleaved lots of bonds in hemicellulosic polymer. The proportion of β‐O‐4 (threo) guaiacyl units is higher than that of β‐O‐4 (erthreo) guaiacyl units. The phenyl glycoside and benzyl ether linkages between lignin and hemicelluloses are also demonstrated in NMR analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011