Delignification of wood pulp by hot alkali treatment following NO2/O2 pretreatment

Summary An effective delignification of kraft pulp without serious depolymerization of the cellulose was achieved by alkali treatment above 100°C, following pretreatment with NO₂/O₂ at approximately 50°C. Compared at the same degree of delignification the depolymerization of the carbohydrates and the yield were less than after oxygen bleaching of the pretreated pulp.     

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.     

Effect of xylanase on ozone bleaching kinetics and properties of Eucalyptus kraft pulp

Environmental pressure has led the pulp and paper industry to develop new technologies in order to reduce or suppress the presence of various pollutants in effluents from bleaching plants. One of the choices for this purpose is enzyme‐based biotechnology. This study deals with the effect of using a xylanase‐based enzymatic pretreatment, in a TCF (Totally Chlorine Free) sequence, on the properties of the resulting paper pulps. The hexenuronic acid content in the pulp and the physical properties of the paper were also studied. The performance of the xylanase was analysed through kinetic studies on ozone bleaching. The enzymatic pretreatment results in easier bleaching and delignification of the pulp, causing a bleach‐boosting effect. The decreased consumption of reagent is related to a decreased content of hexenuronic groups. The physical properties of the treated pulp are similar to those of untreated pulps. Cellulose degradation, delignification and chromophores' removal show first‐order kinetics. Enzyme pretreatment leads to differences between the kinetic constants of cellulose degradation and chromophores' removal, due to an increased accessibility to bleaching agents. The xylanase treatment leads to a lower floor kappa number (IK_∞) during the ozone stage. Copyright © 2003 Society of Chemical Industry     

Delignification and Bleaching Response of Earlywood and Latewood

Abstract

The delignification response in cooking and the impact of bleaching on earlywood and latewood were studied. Spruce earlywood and latewood chips were pulped by the kraft process and subsequently treated with one bleaching chemical at a time. In cooking, latewood required a higher alkali charge to reach the same kappa number. No difference in the light absorption coefficient between the different fiber types was observed. After oxygen delignification the earlywood fibers had a higher light absorption coefficient at the same kappa number. The difference in light absorbing material was maintained when bleaching was performed with chlorine dioxide, ozone, and peracetic acid. Hydrogen peroxide decreased the light absorbing structures in the earlywood to the same level as for latewood. The earlywood pulp had a higher brightness at a given kappa number than the latewood. The higher brightness remained through all bleaching operations and was primarily due to a higher light scattering ability.     

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.     

Acid Extraction of the Alkaline Wood Pulps (Kraft or SODA/AQ) Before or During Bleaching Reason and Opportunity

The decreases in kappa number of an unbleached alkaline hardwood pulp of carpinus betulus when performing dilute H₂SO₄ hydrolysis at about 100°C, either after or before oxygen bleaching are the same. The main parameters of this acid hydrolysis are specified by studying the acidification of unbleached alkaline pulp suspensions at room temperature, and the extraction kinetics at temperatures in the range of 88°–110°C by following UV absorbance of the hydrolysis liquors.

Among the dissolved products in the liquors 2-furancarboxylic acid has been identified. This acid results probably from the degradation in the acid medium of compounds present in the unbleached alkaline pulp, which are not oxidized by oxygen in the alkaline medium.     

漆酶和木聚糖酶预处理对麦草浆漂白性能的影响

生物漂白主要目的在于通过对纸浆预处理,减少后续漂白时漂剂用量,降低漂白废水对环境污染,同时改善纸浆性能。通过漆酶/木聚糖酶体系(LXS)和重组木聚糖酶(X)对麦草浆预处理,比较它们对浆料脱木素能力和漂白性能的影响。结果表明:麦草浆经过两种酶预处理后,都能降低浆料卡伯值,而漆酶处理后降低的幅度更大,与原浆和木聚糖酶处理浆相比分别降低32.64%和6.47%,但是在木聚糖酶处理液中能检测到更多的还原糖;两种酶处理浆在后续漂白中漂白至与对照浆相近白度时均能节省50%漂剂用量,且能改善浆料物理强度;比较两种酶对浆料漂白性能的影响,则是在相同漂剂用量时木聚糖酶漂白浆的白度稍高,而浆料得率和强度稍低;两种酶处理浆料的纤维素结晶度测定表明酶处理前后浆料的纤维素的结晶结构没有明显的变化,而且纤维素的结晶度都有不同程度的提高。通过扫描电镜观察以及X射线光电子能谱(XPS)分析,从理论上说明两者脱木素的差异。     

Dissolution of Lignin from Kraft Pulp after Treatment with Nitrogen Oxides

Laboratory experiments show that pretreatment with NO₂ including heating and ripening at 5% consistency and 90°C for 3 hours in the presence of NO₃- and H⁺ led to a dissolution of approximately 50–60% of the lignin in unbleached kraft pulp. Only 5–15% were dissolved when the treatment was terminated after heating to 90°C. An extensive fragmentation of the lignin during the ripening explains the extensive delignification in acid medium.

Fractionated dissolution of the remaining lignin by alkaline extraction gave fractions with small variation in N-contents (2.9–3.4%) and hydrophilicity. The last fraction exhibited the highest sorption of water vapor. The delignification was related to the decrease in molecular size during the pretreatment and during the subsequent alkaline treatments.     

Inorganic Reactions in Chlorine Dioxide Bleaching of Softwood Kraft Pulp

Abstract

A softwood kraft pulp (27 kappa) was bleached with chlorine dioxide to various end pH values. The formation of chlorite, chlorate, and chloride was measured to quantify the amount of chlorine dioxide wasted as a function of pH during a D_o (pre‐bleaching) stage. Chlorate formation increased with a decrease in final pH. Conversely, residual chlorite increased with an increase in the final pH. After 120 min of bleaching the total residual chlorite and chlorate showed that no substantial increase in residual oxidant occurs when bleaching to an end pH below 3.4. As a result, the brightness and permanganate numbers for low pH chlorine dioxide bleached pulps did not differ when bleaching to an end pH between 3.4 and 1.8. However, decreasing the pH below 3.4 did result in increased organic chloride formation. The results are contrary to previous studies where the maximum bleaching efficiency for a D₁ stage was reported to occur when the end pH was between 3 and 4.     

Simulating the impact of kraft pulping and bleaching parameters on Eucalyptus camaldulensis pulp properties using MATLAB

In this work, Eucalyptus camaldulensis was evaluated as the raw material for chemical pulp under different pulping and bleaching conditions. The pulping was carried out at different H‐factors, and at different effective alkalis. The resulting pulps were then oxygen delignified and bleached using various dosages of bleaching chemicals in a D₀EpD₁ sequence. The effect of independent variables (pulping or bleaching variables) on dependent variables (pulp properties) was analysed based on the multivariable least square method via MATLAB software. An agreement was found between the results predicted from the models and the experimental data. To obtain a kappa number of 15, the optimum pulping conditions were a temperature of 155°C, a time of 225 min, and an EA of 23%. Also, the hexenuronic acid (HexA) content of cooked pulp was significantly decreased in the chlorine dioxide bleaching stages, and was only marginally related to the final HexA content of bleached pulps.     

TCF BLEACHED PULPS FROM MISCANTHUS SINENSIS BY THE IMPREGNATION RAPID STEAM PULPING (IRSP) PROCESS

ABSTRACT

The production of bleached cellulose pulps from elephant grass (Miscanthus sinensis) via a two-stage soda pulping process and a TCF bleaching sequence is evaluated in this work. The impregnation rapid steam pulping process (IRSP) involves impregnating of the lignocellulosic material with the pulping liquor, withdrawing the excess liquor and rapidly steaming the impregnated material at 180–200°C for a short time. In this paper the process variables and their effect on the kappa number, yield and viscosity of the unbleached pulps are discussed. Bleaching by an ozone-based TCF sequence was tested, and the papermaking properties of the bleached pulp were determined. A kappa number of 19 was obtained by impregnating at an alkali charge of 30 + 0.1% anthraquinone carboxylic acid (AQCA) and pulping at 180°C for only 15 min. Kappa was reduced to 16 by extending pulping time to 26 min. The alkali consumption during impregnation and pulping was 10.2 g NaOH/100 g of dry Miscanthus. Screened pulp yield, viscosity and brightness for this pulp were 54.6%, 913 mL/g and 37.3%, respectively. After bleaching, the pulp had an ISO brightness of 87.4% and a viscosity of 700 mL/g. Refining in a PFI mill provided optimal strength properties of the bleached pulp at 4500 revolutions (71°SR): breaking length 7.2 km, tensile index 72 N m/g, and burst index 4.3 kN/g. Tear index was 7.9 mN m²/g at this degree of refining.     

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 Impact of Xylanase and Hot Acid Pretreatment on HexAs in Eucalyptus Kraft Pulp Bleaching

The influence of the presence of hexenuronic acid (HexA) in eucalyptus kraft pulp on the efficiency of D₀EpD₁ was investigated by separately using both commercial cellulase-free xylanase and hot acid pretreatments. In comparison to the xylanase pretreatment, the hot acid pretreatment was more than four-fold effective in removing the HexAs (61%) and concomitantly reduced the kappa number, but resulted in lower viscosity. After subsequent D₀EpD₁ bleaching, the final brightness and its stability were improved remarkably, especially under xylanase pretreatment. At the same brightness of 85% ISO, the xylanase pretreatment reduced the consumption of active chlorine (35.6%) more than the acid pretreatment did (27.5%). The total relative active chlorine savings for the xylanase pretreatment over the acid pretreatment was therefore nearly 23%. The HexA component can be removed considerably in both D₀ and D₁ stages during the D₀EpD₁ bleaching sequence, while only slightly in the Ep stage. The use of xylanase and acid pretreatment both resulted in insignificant physical strength losses for the bleached pulps.     

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.     

Development of Phenolic Lignin During ClO2 Bleaching of Kraft Pulp

The development of the phenolic lignin content in kraft pulp during ClO₂ bleaching was quantitatively determined by the periodate oxidation method. The effect of hypochlorous acid, an intermediate formed during chlorine dioxide bleaching, was eliminated by addition of sulfamic acid, a scavenger of hypochlorous acid. It was found that the number of free phenolic lignin groups per 100 lignin monomer units decreased from about 29 for unbleached kraft lignin to about 6.5 after 1 minute of ClO₂ bleaching. It was also shown that the in-situ generated hypochlorous acid created phenolic hydroxyl groups during chlorine dioxide bleaching. Since it was found that delignification by chlorine dioxide itself was mostly restricted to free phenolic lignin, these findings were used to explain the effect on delignification of addition order of chlorine and chlorine dioxide during bleaching of kraft pulp.     

Treatment of wood pulp with nitrogen dioxide before oxygen bleaching

Summary Pretreatment of kraft pulp with nitrogen dioxide and oxygen before conventional oxygen bleaching with magnesium sulfate as protector leads to markedly decreased lignin contents after a given duration of the oxygen bleaching. An increased temperature during the pretreatment favours the delignification. The most striking effect of the pretreatment is that it leads to a suppressed rate of depolymerization of the cellulose during the oxygen bleaching.     

Formation of aldonic acid end groups during NO2/O2 treatment and alkali cooking of wood meal

Summary The increased carbohydrate yield after NaOH cooking of wood resulting from NO₂/O₂ pretreatment is related to the oxidation of reducing sugar end groups to aldonic acid groups during both the pretreatment and the subsequent alkali cook. This leads to a suppressed end-wise degradation during the alkali cook, reflected in a lowered formation of 3-deoxyaldonic and 2-C-methylglyceric acid end groups in competing reactions.     

Tetrahydrofurfuryl Alcohol (THFA) Pulping of Rice Straw

Abstract

A 80–95% solution of tetrahydrofurfuryl alcohol (THFA) added with 0.15–0.5% catalytic hydrochloric acid (HCl) was used to pulp rice straw. The pulping conditions applied for organosolv digestions of the straw at atmospheric pressure and 120°C cooking for 4 h. The characteristics of the digestion, chemical properties of the resulting pulp, and the handsheet physical properties were evaluated. As for the pulp yields, the method has high delignification specificity, at kappa number 20, the yield was ca. 60%, about 15–20% higher than the traditional alkaline pulping method. Furthermore, with increasing THFA concentrations, efficacies of delignification also increased. Increasing the catalyst dosage also caused an increase in delignification. Delignification rate of 120°C cooking are not so appreciable, but high yield were retained. If cooking temperatures were increased to 130 and 150°C, although even higher delignification rates were achievable, the yield decreased as well. During the cooking the dissolution of carbohydrate was low, at most 23%, consisting of mostly hemicelluloses, which was as high as 78% of the dissolved carbohydrates. The optimal conditions of the THFA/HCl cooking applied 95% THFA, 0.50% HCl, temperature of 120°C, and cooking time of 240 min. Residue lignin in the resulting pulp was low, and can be bleached to high brightness easily with a conventional bleaching sequence. If, however, energy and operation efficiency was a primary consideration, then a procedural heating scheme could be employed. The physical properties of the THFA pulp handsheets were inferior to those of the kraft pulp. The main reason was the damage to cellulose sustained during the acidic cooking condition.     

低温氧碱麦草浆的全无氯漂白

单段麦草氧碱浆压力H2O2(Ppt)漂白,在用碱量4%(NaOH计),Na2SiO3用量3%时的脱木素及漂白效果较好,与原浆相比,卡伯值从17.9下降至6.7,下降了62.6%,白度从36.2%ISO上升至73.6%ISO,增加了50.8%,表明Ppt漂白效果明显。压力H2O2漂白后浆料不经螯合直接进行H2O2补漂,与螯合处理后漂白对比,发现两者均可将麦草氧碱纸浆漂至白度80%ISO左右,而采用Ppt-Q-P漂白比Ppt-P漂白的纸浆白度高4.0%ISO左右,浆料黏度在929.6～1 025.0 mL/g之间。     

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.