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.     

PEG-BASED AQUEOUS BIPHASIC SYSTEMS AS IMPROVEMENT FOR KRAFT HARDWOOD PULPING PROCESS

Aqueous biphasic systems (ABS) represent wholly aqueous systems that are safe, nontoxic, nonflammable, and relatively environmentally benign as extraction media. We have studied detailed phase diagrams and partitioning data currently used in wholly aqueous solvent extraction or reactive extraction processes that may be applicable to the delignification of cellulosic materials at elevated temperature. The study results indicate that increasing the concentration of salt improves the degree of phase divergence. The partitioning results of different lignin species in PEG/salt ABS show that lignin prefers the polymer-rich phase of ABS. Four complete time-at-temperature (130-160°C) batch-cooking experiments were made using a Kraft pulping solution with and without PEG. The results for wood chips composed of a mixture of southern hardwood indicate that the use of PEG results in a pulp with lower Kappa number, lower lignin content, higher residual pulp yield, and reduced alkali consumption.     

醇溶剂提取松木木质素及其结构表征

为进一步理解有机溶剂对木质素的提取率以及结构的影响，系统地研究了6种有机醇溶剂（甲醇、乙醇、正丙醇、乙二醇、1,3-丙二醇和1,4-丁二醇）在提取过程中溶剂极性等特性对木质素收率的影响；同时采用SEM（扫描电镜）、GPC（凝胶渗透色谱仪）、NMR等方法进一步探讨了不同醇溶剂对木质素形貌、分子量与官能团等的影响。结果表明，在所研究的6种有机醇溶剂中，极性、碳链长度与羟基数目对木质素收率、形貌、分子量、官能团等具有显著的影响；羟基数相同时，碳链越长、极性越弱，木质素的收率越高，重均分子量相对越大；一元醇溶剂体系提取的木质素中C、H元素的含量随着碳链长度的增长而降低，而二元醇体系中提取的木质素中C、H元素的含量呈相反的变化趋势；同等碳数的有机醇溶剂随羟基数增多，木质素的收率降低，重均分子量也相应减小。     

Investigation of liquefied wood residues based on cellulose,hemicellulose, and lignin

Chinese eucalyptus was subjected to a liquefaction process using glycerol/ethylene glycol (EG) as liquefaction solvent. The effects of various liquefaction conditions, including reaction time, liquefaction temperature, acid concentration, and liquor ratio on the chemical composition of liquefied wood residues were studied. The results showed that the whole liquefaction process took place in two stages, the liquefaction yield of wood depended on the reaction temperature, acid concentration and liquor ratio. With increased acid concentration the liquefaction yield, acid‐insoluble lignin, and hemicellulose content of the residues were increased, and the relative content of cellulose was decreased. Fourier transform infrared (FT‐IR) analyses of the residues showed that hemicellulose and lignin were almost decomposed at the initial stages of reaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of chelating fabrics by radiation‐induced grafting of itaconic acid and acrylonitrile onto polypropylene nonwoven fabrics and subsequent amination of graft copolymer

A mixture of acrylonitrile (AN) and itaconic acid (IA) was cografted onto polypropylene (PP) nonwoven fabrics by preirradiation method. The effects of graft polymerization conditions such as temperature, reaction time, Mohr's salt concentration, solvent mixture ratio, and comonomer composition on the total grafting yield were investigated. The addition of AN as a comonomer increased the amount of IA that reacted with PP fabrics. An increase in the temperature from 40 to 60°C increased the grafting rate, but the final grafting yield decreased at high temperature. The addition of 0.01 wt % Mohr's salt to the reaction medium leaded to a sharp increase of grafting yield. The accelerative effect of solvent medium on the grating yield was higher in dimethylformamide (DMF) and methanol mixtures, when compared with DMF or methanol. Chelating fabrics was synthesized by subsequent amination of grafted fabric with ethylene diamine (EDA) and phenylhydrazine (PH). The conversion yield reached maximum value at about 90% for 80% PP‐g‐AN‐IA fabrics at 90°C. At same amination conditions, the conversion yield is higher when PP‐g‐AN‐IA fabrics react with EDA compared with PH. FT‐IR data indicate that amine groups were introduced onto PP‐g‐AN‐IA fabric through amide linkage between grafted AN or IA and EDA or PH. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

杨木预水解液中化学组分质量浓度的P因子调控

为研究P因子对木质纤维原料预水解液中化学组分质量浓度的调控机制,分析了不同预水解温度（170~210℃）和预水解时间（30~120 min）条件下,杨木预水解液中固形物、木质素、木糖和葡萄糖质量浓度的变化规律。结果表明：升高预水解温度和延长预水解时间,固形物、木质素和葡萄糖质量浓度均逐渐增大。而木糖质量浓度随温度的升高而降低;190℃时,木糖质量浓度随预水解时间延长迅速减小。P因子对杨木预水解液中化学组分的质量浓度具有调控作用。固形物、木质素和葡萄糖质量浓度随P因子增加呈指数增大。而木糖质量浓度随P因子增加呈指数减小,P因子小于3 300时,木糖质量浓度随P因子增加迅速减小。     

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.     

一种紫外光快速固化的星形化合物的合成与表征

采用发散法 ,以乙二胺 (EDA)、三羟甲基丙烷三丙烯酸酯 (TMPTA)为原料 ,直接进行Michael加成反应 ,合成了外围带 8个碳碳双键的星形化合物 ,用IR、1HNMR和元素分析测定了它的结构。并讨论了反应温度、反应时间、投料量比以及溶剂的含量对反应的影响。结果表明 :投料比为n(TMPTA)∶n(EDA) =5∶1,甲醇为溶剂占体系总质量的 2 7 84 %。适宜的反应温度为 30℃ ,反应时间为 6h ,其产率为 6 5 11% ,星形化合物的质量分数为 97 5 7%。此产物在光引发剂和活性稀释剂存在时 ,紫外光辐照下比市售齐聚物 6 0 1、6 0 2组成的相似体系固化速度快 4～ 87倍     

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.     

Investigation and Characterization of Lignin Precipitation in the LignoBoost Process

Lignin of high purity can be separated from black liquor using the LignoBoost process, of which the overall efficiency is largely dependent on the precipitation yield of lignin, which depends on the properties of black liquor and process conditions. In this paper, the influences of process conditions on the precipitation yield of lignin from mixed hardwood/softwood black liquor were investigated. The Klason and standard UV method were used to determine lignin concentration. The chemical and structural properties of lignin were also analyzed. The results showed that the precipitation yield of lignin increased along with a decrease in pH and temperature, or with an increase in the ion strength of black liquor, and the yield was lower when mixed softwood/hardwood black liquor was used. It also showed that at a higher precipitation yield the precipitated lignin had a lower average molecular weight but had higher methoxyl and phenolic hydroxyl content.     

Effect of Kraft Cooking Conditions on the Chemical Composition of the Surface and Bulk of Spruce Fibers

By varying cooking temperature, alkali charge, ionic strength, and cooking time in Kraft pulping of spruce chips, pulps ranging between kappa numbers 20–80 were obtained. The unbleached Kraft pulp fibers were subjected to mechanical peeling in order to separate the surface material from the bulk of the fibers and the carbohydrate composition and lignin content of the two fractions were analyzed. As expected, the lignin and xylan contents were higher on the fiber surface than in the fiber wall. The percentage of xylan on the fiber surface was fairly constant, independent of different pulping conditions or degree of delignification. The lignin proportion on the fiber surface gradually decreased with decreasing kappa number. At a given kappa number, pulping at a higher temperature resulted in less lignin on the fiber surface, probably because of the higher solubility of lignin at higher temperature. Cooking at lower alkali charge also resulted in lower lignin content on the fiber surface at a given kappa number. In this case, there was more time available for degradation of the surface lignin since the lower alkali charge resulted in longer cooking time needed to reach a certain kappa number.     

THE EFFECT OF LIGNIN CONTENT OF WOOD FIBERS ON PULP SCREENING/SEPARATION

An experimental investigation of the effect of lignin content of wood fibers on pulp screening is conducted. A non-uniform lignin distribution may exist in wood pulp due to variations in wood chip characteristics, and/or cooking conditions in a digester. Pulp screening was conducted in a modified Williams Freeness tester at different fiber lignin contents and pulp consistencies. The study indicated a large drop in pulp accepts fraction, thus a substantial fiber loss, with an increase in lignin content. The fiber loss was more significant at higher consistencies of pulp. This study suggests that the fiber lignin content should be considered an important process variable affecting the efficiency of pulp screening processes.     

1,4-丁二醇提取玉米芯木质素的研究

以1,4-丁二醇为溶剂提取玉米芯中的木质素,考察了反应温度、原料／溶剂固液比（g/mL）、1,4-丁二醇的质量分数、反应时间等因素对木质素收率的影响。最佳萃取条件为：反应温度200℃,固液比（g／mL）1：10,1,4-丁二醇的质量分数90％,反应时间1h,以少量硫酸作为催化剂,木质素收率37．03％。红外光谱分析结果表明,1,4．T-醇提取的玉米芯木质素较好地保存了木质素原有结构。     

木质素-EVA扭矩流变性能试验研究

研究了影响木质素与乙烯醋酸乙烯酯共聚物（EVA）共混物在扭矩流变仪中的共混最大扭矩、平衡扭矩以及达到平衡扭矩时间的各个因素。结果表明，木质素、增容剂、增塑剂、转速、温度对扭矩值有明显影响；木质素／EVA共混体系达到平衡扭矩时的平均时间随木质素的含量增加，扭矩值减小到最小后又逐渐增加。木质素／EVA共混物热溶胶的粘度表现出非牛顿流体的假塑性流体，热溶胶粘度随温度的上升而减小，木质素／EVA共混体系具有可加工性。     

温度对二氧化碳酸析提取黑液中木质素的影响

以碱法制浆的松木黑液为原料,用二氧化碳酸化黑液提取其中的木质素,考察了反应温度(40~80℃)对酸析木质素产率及其无机盐和糖分等含量的影响,采用凝胶渗透色谱(GPC)、离子色谱仪(IC)、元素分析仪和热重分析仪(TG)对木质素产物进行结构表征。结果表明,温度升高不利于木质素析出,产率下降;但较高温度下制备的木质素中无机盐、糖分及硫含量低,纯度高;同时温度越高,木质素相对分子质量越大,甲氧基含量增大,但酚羟基含量减小。TG和DTG曲线显示,反应温度升高木质素最大失重速率增加,残余量减少。     

EFFECT OF PRETREATMENT CONDITIONS ON STRUCTURAL CHARACTERISTICS OF WHEAT STRAW

Structural characteristics of lignocellulosic biomass such as surface area, pore volume, crystallinity, hemicellulose, and lignin content significantly affect the yield of fermentable sugars for bioethanol production. In the present work, the effect of dilute acid pretreatment was studied on structural characteristics of wheat straw, using different combinations of process variables (temperature, time, and acid concentration). Pretreated wheat straw (PWS) exhibited higher available surface area and pore volume along with low hemicellulose and lignin content. Crystallinity index (CrI) of biomass at different pretreatment conditions showed an increased trend followed by sharp decrease at high temperature (190°C) conditions. Maximum increase in surface area (7.1 m²/g compared to 4.0 m²/g for untreated wheat straw) was obtained at pretreatment conditions of 180°C temperature, 0.5% (v/v) acid, and 7 min time. SEM imaging of biomass revealed that pore breaking, compression of pores, and partial pore blocking in the case of high temperature (190°C) pretreatment conditions may be the reason behind decreased surface area of biomass. FT-IR analysis showed almost complete hemicellulose removal and acid-soluble lignin removal after dilute acid pretreatment but insufficient removal of acid insoluble lignin.

[Supplementary material is available for this article. Go to the publisher's online edition of Chemical Engineering Communications for the following free supplemental resource: figure showing XRD pattern of biomass with respect to different pretreatment conditions.]     

工业碱木素热化学转化制备酚类化学品

引言 工业碱木素是碱法制浆过程中产生的重要副产物之一,其排放污染问题越来越受到关注,目前工业处理方法只是将其浓缩燃烧以回收能源和残碱.木质素是一种化学结构复杂的天然高分子聚合物(主要由愈创木基丙烷、紫丁香基丙烷和对羟苯基丙烷通过醚键和碳碳共价键相联),其分子量从几千至几十万,数量上仅次于纤维素,利用潜力较大.     

Effect of graft copolymerization of 2-hydroxyethyl methacrylate on the properties of polyester fibers and fabric

Graft copolymerization of hydroxyethyl methacrylate (HEMA) onto poly(ethylene terephthalate) (PET) fibers using benzoyl peroxide (BP) as initiator was carried out in water and in water/organic solvent as a reaction medium. The effect of initiator concentration, reaction time, temperature, and reaction medium as well as addition of FeSO₄ to the polymerization medium was studied. Percent grafting was enhanced significantly by increasing BP concentration up to 0.016 mol/L and then decreased upon further increase in initiator concentration. Increasing the monomer (HEMA) concentration up to 0.48 mol/L improves significantly the graft yield. Raising the polymerization temperature up to 85°C causes a significant increase in grafting yield; further increase in temperature leads to decrease in graft yield. Incorporation of Fe⁺² ions in the polymerization system decrease the graft yield. The same situation is encountered when water/solvent mixture is used as reaction medium. Solvent employed were methanol, toluene, and benzene.     

芦苇烧碱-蒽醌浆生物漂白的研究

对芦苇烧碱-蒽醌浆进行漆酶/介体体系脱木素处理结合过氧化氢漂序进行漂白。结果表明,分别利用三种介体HBT、VIO和NHA辅助漆酶脱木素,导致浆的白度均有不同程度的降低,降低的幅度与介体种类和用量有关。在相同浓度时,浆白度的降低幅度随介体的氧化还原电势的增大而增大。根据过氧化氢漂白的结果,可以认为LMS-QP最佳处理条件为使用介体NHA,用量为0.5%,漂白时间为2 h。对用2%VIO为介体脱木素后的浆残余木素分析表明,经过漆酶/介体体系处理浆料,浆残余木素中的羰基含量相对提高。     

A Partial Magnesium Hydroxide Substitution for Sodium Hydroxide in Peroxide Bleaching of an Aspen CTMP

Abstract

A partial substitution of sodium hydroxide (NaOH) by magnesium hydroxide (Mg(OH)₂) as the alkali source was studied in peroxide bleaching of an aspen chemi-thermomechanical pulp (CTMP). The effects on pulp properties, including pulp strength, optical property and carboxylic groups content, and process characteristics, such as oxalate and anionic trash formation, were studied. The X–ray photoelectron spectroscopy (XPS) technique was used to determine the lignin and extractives concentrations on the fiber surface. With the increased Mg(OH)₂ substitution ratio, the peroxide bleaching process gave a higher pulp yield and peroxide bleaching efficiency, produced pulps with higher light scattering coefficient and bulk, while the total oxalate, anionic trash, and chemical oxygen demand load (COD) were less. The total carboxylic groups content and the surface charge of pulp fibers were decreased. The underlying mechanism responsible for the decreased strength properties, when the Mg(OH)₂ substitution ratio was increased, is discussed.