麦草碱性亚硫酸盐制浆生物炼制的研究(I) ——深度脱木质素及木质素磺化特性

提出了非木材木质纤维生物质碱性亚硫酸盐制浆(ASP)生物炼制的理念,研究了总用碱量、亚硫酸化度、温度和时间对麦草碱性亚硫酸盐法蒸煮深度脱木质素特性和木质素磺化的影响。结果表明:麦草ASP法具有高的深度脱木质素选择性;深度脱木质素延伸与木质素磺化度提高具有一致性;总用碱量、亚硫酸化度、最高温度和保温时间对深度脱木质素选择性和木质素磺化度都有重要的影响;在总碱用量18.0%,亚硫酸化度85.0%,液比值3.5,最高温度168℃,保温150 min的条件下,可制得卡伯值8.8,得率56.8%,黏度为33.3 mPa.s的优良纸浆,此时黑液中磺化木质素磺酸基含量达2.16 mmol/g(以固形物计)。从深度脱木质素选择性、木质素磺化和纸浆基本特性考虑,麦草ASP法具有制浆生物炼制的前景。     

硫酸盐竹浆氧脱木质素和全无氯漂白的研究

通过比较不同条件下氧脱木质素后浆料的卡伯值、黏度、得率、白度和脱木质素选择性等指标,研究了硫酸盐竹浆卡伯值25.6氧脱木质素工艺参数,发现用碱量和温度是决定氧脱木质素效果的主要因素.最佳工艺条件为:用碱量3.5%,温度85℃,氧气压力0.6MPa,保温时间80min.两段氧脱木质素(中间不洗涤)可以提高木质素脱除率和选择性.研究还发现,在氧碱脱木质素过程中加入醌类混合物助剂(表示为Oq),可使浆料的黏度和氧脱木质素的选择性大大提高.采用OQ(PO)、(O1O2)Q(PO)、OQ(PO)1(PO)2和OqQ(PO) 4种短漂序都可使竹浆白度达到80%(ISO) 以上,且具有很好的白度稳定性.OQ(PO)、(O1O2)Q(PO)和OQ(PO)1(PO)2 3种漂序漂后浆纸页强度性能相近,OqQ(PO)漂后浆的抗张指数、撕裂指数和耐破指数明显高于其它3种漂序.     

相思木EMCC硫酸盐浆氧脱木质素前后酶处理的影响研究

研究了酶处理对相思木EMCC(延伸改良连续蒸煮)硫酸盐浆(KP浆)氧脱木质素效果的影响。结果表明,由白腐菌直接合成的漆酶/木聚糖酶体系(LXS)预处理相思木EMCC硫酸盐浆的的适宜酶用量为7 IU/g;LXS预处理后浆料氧脱木质素的适宜反应时间、最高反应温度及用碱量分别为60 min、100℃和2.5%;利用LXS进行氧脱木质素后处理的适宜反应时间及酶用量分别为2 h和5 IU/g。SEM观察到经过酶处理后纤维表面及横切面出现大量的裂隙及孔隙,其中以酶后处理最为明显,为后续漂白中化学药品的渗透和漂白降解产物的溶出创造条件。     

麦草低温氧碱蒸煮黑液降黏技术

麦草经碱法蒸煮后,所得浆料不经洗涤,直接通入氧气进行处理。以黑液黏度,浆料卡伯值为考核指标,设置4因素3水平正交试验,对试验结果作极差分析发现,在用碱量0～2%、氧压0.2～0.6 MPa、温度70～100℃和时间30～90 min内得到较适宜的工艺条件为:用碱量1%,氧压0.6 MPa,温度85℃,时间60 min。氧碱蒸煮结果为:黑液黏度3.4 mPa.s,浆料卡伯值17.9。与第一段碱法蒸煮相比,黑液黏度降低33.3%,浆料卡伯值降低11.8%。     

马尾松硫酸盐浆两段氧脱木质素最佳工艺条件的研究

研究了马尾松硫酸浆两段氧脱木质素的最佳工艺条件。结果表明，第一段氧脱木质素的条件为：氧压0．6MPa，温度100℃，时间80min,NaOH 量5％，MgSO4用量0．5％，浆浓10％；第二段氧脱木质素的条件为：氧压0．4MPa，温度90℃，时间60min，NaOH用量3％，MgSO4用量0．5％，浆浓10％。在此条件下，OIOⅡ木质素脱除率达到72．5％，粘度775．2cm^3/g,得率90．5％。经过氧脱木质素后浆的裂断长5．8km，耐破指数5．3kPa.m^2/g，撕裂指数12．7mN.m^2/g。     

Studies on the effect of prehydrolysis and amine in cooking liquor on producing dissolving pulp from jute (Corchorus capsularis)

Dissolving pulps are the raw materials for the production of many different end-products. Jute is a very good source of cellulose. In this investigation, jute fiber was subjected to pulping in soda process in order to produce dissolving pulp under different prehydrolysis conditions and compared with prehydrolysed kraft pulp from jute. An increase of the prehydrolysis temperature or H₂SO₄ in prehydrolysis liquor increased the α-cellulose content and decreased the viscosity of pulp. The effect of ethylenediamine in soda liquor was also investigated when producing dissolving pulp. Jute fiber produced pulp having 90–97% α-cellulose. Ethylenediamine in soda liquor produced pulp of higher yield, viscosity and higher α-cellulose content than that of prehydrolysis soda or kraft pulp. The α-cellulose content and viscosity were increased with the increase of amine in soda liquor. The kappa number of dissolving pulp from jute was very low (9–5), which indicated that less bleaching chemicals are required for bleaching. The bleachability of soda-ethylenediamine pulp was lower than prehydrolysed soda and kraft pulp in ECF bleaching sequences. The bleachability of soda-ethylenediamine pulp was improved at the sacrifice of pulp yield when prehydrolysis was done prior to pulping. The alkali solubility S ₁₀ and S ₁₈ were 4–9 and 2–4%, respectively.     

A mathematical model of kraft pulping related to the alkali concentration in the cooking liquor

Summary A new mathematical model for checking and controlling the kraft pulping process has been derived. The model is based on the modified relationship between the lignin content and the alkali concentration of a cooking liquor expressed as the ratio of lignin/active alkali vs. concentration of the active alkali in a cooking liquor. The derived model characterizes the variation of the lignin content of the partially delignified wood or pulp with the concentration of the residual alkali in a cooking liquor during an entire pulping cycle, i.e. during the initial, transition, bulk and residual phases of the kraft delignification. The relationship between the lignin content of the partially delignified wood ships or pulp and the concentration of the residual alkali in a cooking liquor is expressed by the logarithmic straight line equation or its power form. The slope and intercept constants of the derived equation for the individual phase of delignification have different values. Received 5 June 1996     

OH法制浆工艺研究

研究了在氨水中添加少量钾碱作为蒸煮剂的稻草制浆新工艺，系统讨论了蒸煮液的用量和配比，液固化，蒸煮最高温度和保温时间对蒸煮效果的影响，继而确定了适宜工艺条件，结果表明，该蒸煮体系对稻草木质素的脱除率达到85．12％，纸浆得率38．12％，通过红外光谱（IR）测定了稻草蒸煮过程中木质素的结构变化，蒸煮黑液中因富含氮、磷、钾和有机质，可作为有机肥料资源用于农业生产，该工艺有望实现禾草类原料制浆工艺的清洁生产。     

氧漂过程中脱木质素与木质素氧化之间定量关系的研究

对氧碱漂白过程中木质素氧化进行定量分析,分析方法是基于氧化前后高锰酸钾消耗量的变化。该方法对溶出残余木质素的氧化结果分析发现其呈明显3个阶段：第一段木质素氧化的当量电荷数约4～5／木质素单元;木质素总氧化电荷数大约为9／木质素单元。这些数据以及甲氧基的脱除（75％）均表明：木质素的氧化不仅发生在酚型木质素单元,同时也发生在非酚型结构单元上。只有第一阶段氧化反应是木质素与氧气直接反应,而在第二、三阶段主要是协同氧化作用,氧化反应过程中产生的活性氧基团扮演了一定角色。通过对低浓度针叶材硫酸盐浆的氧漂研究发现：当卡伯值下降一半（25．4至13．4）时平均每个木质素单元氧化3当量电子,氧漂后的纸浆中仍然有大量未被氧化的残余木质素。定量地证明了在氧漂过程中木质素氧化是脱木质素反应的实质。     

Sulfuric acid bleaching of kraft pulp 1: Bleaching of hardwood and softwood kraft pulps

To develop a new nonchlorine bleaching technology, hardwood and softwood kraft pulps, before and after oxygen-alkali predelignification, were treated with dilute sulfuric acid solutions (pH 1.0-1.8) at 100°C for 1 h and then extracted with aqueous sodium hydroxide at 70°C for l h. Hardwood kraft pulp was successfully bleached. The delignification selectivity was similar to that seen with oxygen-alkali bleaching; and it was greatly enhanced by the addition of sodium nitrate and sodium nitrite. The sulfuric acid bleaching can replace the presently adopted oxygen and chlorine stages if the additives are allowed. This bleaching process was also effective for oxygen-bleached hardwood kraft pulp, but it was less effective for softwood kraft pulp and oxygen-bleached softwood kraft pulp. The effectiveness of the addition of sodium nitrate and sodium nitrite was more apparent for softwood kraft pulp than for hardwood kraft pulp.Part of this report was presented at the 7th International Symposium on Wood and Pulping Chemistry, Beijing, July 1993     

杨木制浆技术的新进展

本文介绍了用杨木生产漂白化学浆,包括硫酸盐法,硫酸盐-蒽醌法,烧碱-蒽醌法和碱性亚硫酸钠-蒽醌法制浆;用杨木生产漂白化学热磨机械浆;用杨木生产碱性过氧化氢机械浆;特别是杨木碱性过氧化氢机械浆是90年代发展研制成功的高得率、高白度和强度性好的新化学机械浆种,它适用于配抄低定量胶印新闻纸、低定量涂布纸等。     

Polyelectrolyte swelling behavior of chlorite delignified spruce wood fibers

Summary A coarse thermomechanical Asplund pulp was prepared from Norway spruce (Picea abies). The pulp was delignified to different degrees using acidified sodium chlorite. The swelling behavior (measured as water retention value=WRV) of the resulting pulps was studied under various chemical conditions (pH and conc. of NaCl). It is shown that chlorite-delignified pulps have an appreciable polyelectrolytic character. Whereas the WRV of an Asplund pulp does not respond to changes in the chemical environment, the delignified pulp has a WRV of 155 at pH 3 and 250 at pH 9. Compared under the same chemical conditions, the WRV increases with increasing degree of delignification (<70%) and is approximately constant at high degrees of delignification (>70%).The authors are indebted to Mr. Claes Beer at Sund-Defibrator, who assisted with the preparation of the Asplund pulp     

桉树制浆综述

本文介绍了(1)用桉木生产漂白化学浆,包括硫酸盐法和碱一蒽醌法制浆;(2)用按木生产漂白半化学浆,主要是中性亚硫酸盐半化学高得率浆;(3)用桉木生产漂白化学机械浆,包括冷碱法和亚硫酸盐法制浆;(4)用桉木生产漂白化学热磨机械浆。     

Combination treatment of kenaf bast fiber for high viscosity pulp

The viscosity of kenaf bast fiber has been found to be highly sensitive and variable with different pulping methods; therefore, it is important to choose proper chemicals and conditions for pulping and bleaching of kenaf bast fiber. From several pulping experiments, a nonconventional pulping method with a combination of ammonium oxalate pretreatment followed by soda pulping at normal pressure and then acidic chlorite delignification was developed to obtain high-viscosity pulp (162 centipoise). The optimum level of alkali dosage of soda pulping for high-viscosity pulp was found to be 15% (on pulp as NaOH). Pulps showed linear relations between viscosity and xylose or glucose contents, but the combination pulping method gave extremely high pulp viscosity, beyond the relations. The highest viscosity pulp from kenaf bast fiber demonstrated a tear index about twofold and a folding endurance 6.2-fold higher than those of Manila hemp pulp with comparable tensile and burst indexes. The high-viscosity pulp could be used in the production of high-quality currency paper or longevity paper for special uses.Part of this paper was presented at the 43rd Lignin Symposium, Fuchu, Tokyo, October 26–27, 1998     

On the selectivity of ozone delignification of softwood kraft pulps

Summary Ozonation of kraft pulp and oxygen-delignified kraft pulp in acetic acid/water mixtures has been studied at different pulp consistencies with and without an inhibitor to obtain information about the limitations of the selectivity of the ozone treatment. The experiments have been performed according to a full factorial design and data have been analysed by stepwise regression analysis. The results show that a better delignification selectivity can be achieved when ozone is applied in acetic acid media instead of conventional aqueous media. By combining conventional oxygen delignification and ozonation in acetic acid, pulps with equal strength properties and better optical properties compared to those of conventional O(DC)E prebleached pulps can be obtained. This study has also revealed that the reagent is utilized far more efficiently in ozonation at high pulp consistency (35%) than in ozonation at low consistency (1%), and that a similar selectivity can be achieved in both types of ozonation by choosing appropriate conditions. The greater selectivity of ozonation in acetic acid than in water is interpreted in terms of different stabilities of the oxidant in these reaction media. The relation between the formation of hydroxyl radicals and the extent and selectivity of delignification during ozonation has been investigated. The final bleaching of pulps prebleached with ozone in acetic acid medium has been studied. Two final bleaching sequences are presented, by which pulps with ISO brightness levels of 79% and 90% can be produced.The authors are indebted to the Swedish National Board for Technical Development (Styrelsen för Teknisk Utveckling) for financial support for this work and to STORA Technology for pulp tests and analyses     

竹子深度脱木质素蒸煮与常规硫酸盐法蒸煮的比较

为了提高竹浆性能和减少环境污染,对福建丛生小径竹进行了实验室模拟延伸改良连续蒸煮(EMCC)和常规硫酸盐法蒸煮(CKC)的研究。结果表明,EMCC蒸煮通过分段加入蒸煮药液和在逆流段进行药液置换,比CKC具有更高的脱木质素选择性。在蒸煮相同卡伯值的竹浆时,EMCC浆比常规硫酸盐浆(CK浆)具有更高细浆得率、较低粗渣率、更高粘度和更好强度性能。在相同的打浆度下,EMCC浆抗张指数、耐破指数和撕裂指数都比常规硫酸盐浆高。     

Improved method for evaluation of cellulose degradation

 Use of a fundamental concept, henceforth referred to as the scission fraction of cellulose unit (SFCU), was suggested to clarify the cleavage reactivity of cellulose during oxygen delignification (OD). According to the SFCU theory, the cleavage activity of pulp cellulose remains relatively undisturbed provided the experimental conditions are maintained regardless of pulp origin. SCFU is a universal variable for evaluating how processes and additives affect the degree of pulp cellulose degradation. Specifically in this study, the effects of the protector additives MgSO₄ and phenol on the oxygen delignification (OD) process were investigated. Both phenol and MgSO₄ retard the cleavage rate of the cellulose chain, but the retarding effect of MgSO₄ is greater than that of phenol. Phenol alone cannot significantly improve the selectivity of the OD process, whereas MgSO₄ can decrease the cleavage rate of cellulose and increase the selectivity of OD. Moreover, synergistic selectivity enhancement for pulp using a combination of MgSO₄ and phenol was observed. The protective effect of various chemical protectors was additive, whereas the retarding effect on delignification was not. Received: December 21, 2001 / Accepted: July 22, 2002 Acknowledgments We acknowledge the member companies of the Institute of Paper Science and Technology whose interest drives most of our research efforts. Additionally, we gratefully acknowledge the Department of Energy (grant DE-FC07-02ID14261) whose support has made part of this work possible.     

TCF Bleaching of Populus tomentosa Kraft Pulps with H2O2 Pretreatment under Acid Condition

The process of peroxide bleaching of Populus tomentosa kraft pulp with H2O2 pretreatment under acid condition was studied. The variations of pulp characteristics such as brightness, Kappa number and viscosity during the peroxide bleaching process were discussed and the concept of the A/B value was presented for the first time. The results show that acid pretreatment with H2O2 is essential to improve pulp brightness and avoid viscosity loss. The conclusion is reached that the A/B value has great influence on pulp properties when the total amount of peroxide used in the bleaching process is 2%–5%. Pulp with a high viscosity and brightness can be obtained when A/B is about 0.15.     

Residual extractives in aspen kraft pulps and their impact on kappa number and Klason lignin determination

We investigated the impact of residual extractives on lignin determination by lignin content difference between unextracted and extracted pulps, residual extractives analysis, and lignin content contribution from model extractive compounds. There were two different kinds of extractives in aspen kraft pulp. The extractives impacting on kappa number determination were well removed in oxygen delignification; these were mainly unsaturated fatty acids. However, the extractives impacting on Klason lignin determination were largely resistant to oxygen delignification; these were mainly saturated fatty acids, sterols, and hydrocarbons. Oxidation of unsaturated fatty acids was the main reaction in oxygen delignification. These trends were confirmed by simulation of lignin content determination with three model extractive compounds (β-sitosterol, linoleic acid, and palmitic acid). The publication of this article was made possible by an Emachu Research Fund. The authors are grateful for the fund.     

DMD的活化预处理及其全无氯漂序的研究

研究了桉木硫酸盐浆对氧脱木质素段和过氧化氢漂段的活化作用以及ＤＭＤ用量对氧段和过氧化氢段浆性能的影响,使经ＭＯＱＭＰ多段漂白的纸浆最终白度达８０％以上,纸浆粘度满足要求,可以实现桉木硫酸盐浆的全无氯漂白。