【作者】 张美云；

【导师】 谭国民；

【作者基本信息】 天津科技大学 ， 制浆造纸工程， 2004， 博士

【摘要】 自催化乙醇制浆是溶剂法制浆的一种，可彻底解决传统化学制浆的污染问题。本文选取麦草、荻、龙须草三种有代表性的非木材纤维原料，对其自催化乙醇制浆工艺及其机理分别进行了系统的研究。包括：制浆工艺参数优化、脱木素反应历程、脱木素动力学和反应机理，并对三种浆的漂白、打浆、抄纸性能做了初步评价，同时以龙须草乙醇浆为代表深入探讨了其TCF漂白工艺和机理。所得结果为推动乙醇制浆的技术进步提供了技术支撑和理论依据。 麦草自催化乙醇制浆的最佳工艺参数是：温度195℃，液比1：8，乙醇浓度50％～60％，保温70min，该条件下成浆Kappa价68.43，细浆得率57.30％，该浆易漂白，强度性质优于Soda-AQ浆，接近KP浆；蒸煮脱木素历程分为两个阶段，从蒸煮开始到保温20min为大量脱木素阶段，从保温20min到蒸煮结束为木素残余脱除阶段，两阶段木素脱除率分别为75.39％和11.27％。麦草乙醇法在大量脱木素后即已成浆，在纤维分离点处细浆得率为57.30％，Kappa价为68.43。试验还得出了浆中木素含量与Kappa价的线性关系。 对荻的研究表明：影响制浆的四个因素分别是保温温度(Tmax)、液比(r)、保温时间(t)和乙醇浓度(C)。经优化得出的最佳工艺条件为：保温温度195℃，液比1：10，乙醇浓度55％(V／V)，保温120min，该条件下成浆Kappa价50.8，细浆得率61.32％，浆中总木素含量5.43％；反应动力学研究表明，蒸煮脱木素历程分为两个阶段：从蒸煮开始到保温30min为大量脱木素阶段，这之后便进入残余脱木素阶段。脱木素反应为一级反应。大量脱木素阶段和残余脱木素阶段的活化能分别为77.13KJ／mol和156.7KJ／mol。用IR、~1HNMR对MWL和CL(从黑液中提取的木素)的分析结果表明，两者结构变化较小，反应过程中紫丁香基结构单元(S型)和对羟苯基结构单元(H型)木素易被脱除，并伴有木素α-O-4醚键的断裂。浆张性能对比说明，自催化乙醇法本色浆打浆适应性和可漂性均优于KP本色浆，用TCF漂可获得白度和质量都很好的漂白浆。 对龙须草的研究表明：对细浆得率和纸浆卡伯价的影响因素均为Tmax＞r＞C＞t。经单因素试验优化得出最佳工艺条件为：保温温度180℃，液比1：10，乙醇浓度55％(V／V)，保温120min，该条件下成浆Kappa价38.13，细浆得率53.18％，浆中总木素含量4.64％。龙须草乙醇浆的打浆适应性优于KP浆；制浆机理研究表明，蒸煮脱木素历程分为两个阶段：从蒸煮开始到 摘要旦鱼鱼鱼国旦旦旦鱼鱼鱼鱼鱼旦鱼鱼鱼鱼鱼鱼鱼旦鱼旦保温40niln为大量脱木素阶段，这之后便进人残余脱木素阶段。两阶段的木素脱除率分别为79.16%和88.90%。在纤维分离点处粗浆得率为56.6%，KapPa价为50.0，浆中总木素含量为7.10%。试验还得出了浆中木素含量与Kappa价的线性关系。碳水化合物的溶出与木素的脱除相似，也分为主要溶出阶段和少量溶出阶段，保温初期聚戊糖大量溶出，保温后期聚己糖的溶出速度加快。 本文对龙须草自催化乙醇浆的TCF漂白进行了研究，通过试验，优化出(oP)1(oP)ZzP漂白流程，并着重研究了这种流程的漂白机理。本文还对原浆及各段漂白程序所得浆样进行了扫描电镜(SEM)观察，得到浆料纤维形态变化的规律;本文还利用紫外光谱(UV)、红外光谱(琅)、核磁共振谱(‘HNMR)、凝胶渗透色谱(GPc)对龙须草原料及未漂浆中木素的结构进行了对比研究，深人探讨了龙须草自催化乙醇法制浆过程中木素的反应，以及成浆之后浆中木素对漂白的影响。工艺试验结果表明:龙须草自催化乙醇浆通过(op)1(Op)ZZP漂白，全漂浆白度为80.5%sBD，粘度740川叮g，返黄值0.25。对原料及未漂浆二氧六环木素的uv、IR、IHNMR测试表明:龙须草木素是GsH型木素，其中愈疮木基(G)单元含量最大，在自催化乙醇法蒸煮时溶出最快。另外还有一定量的对经苯基单元和紫丁香基单元，根据(‘HNMR)图，初步确定龙须草原料木素在自催化乙醇法蒸煮过程中产生的缩合很少，产生的LCC连接也很少。对原料及未漂浆二氧六环木素的GPC测试表明:龙须草原料木素的分子量在ro，000左右，未漂浆木素分子量不到8，000;两者相比，虽然蒸煮后木素分子量降低的不多，但从GPC谱图可知，成浆后木素分子量分布均一化，没有特别高的分子量的缩合产物，因而漂白时脱木素比较容易。更多还原

【Abstract】 Auto-catalyzed ethanol-water pulping is one kind of organosolv pulping; it can completely solve the pollution problem of conventional chemical pulping. In this paper, the technology and mechanism of auto-catalyzed ethanol-water pulping of three typical non-wood fiber which are wheat straw, silvergrass, Chinese alpine rush were investigated separately. Including: the optimizing the technologic parameter of pulping; the response couse of delignification; the kinetics and the response mechanism of delignification and also preliminarily evaluating beating, bleaching and papermaking properties of three kind of pulp. TCF bleaching technology and mechanism of Chinese alpine rush EW pulp was probed into as an example. The results obtained from EW process can provide the technical support and the academic foundation for promoting the technologic progress of EW pulping.1. The results of wheat straw EW pulping showed that a cooking temperature of 195 C, liquid ratio of 1:8, an ethanol concenreation of 50% ~ 60%, and a time at Tmax of 70 minutes appeared to be desirable. Under the conditions, the screened pulp yield, kappa No. was 57.30% and 68.43 respectively. Study of dellignification course suggested that it could be divided into two phases: The first phase from the cooking to the time at Tmax of 20 min. was the bulk phase of the dilignification. During the first phase the pulp delignified by 75.39%. The second one, the period from 20 min. to 70 min. at Tmax is the residual delilgnification phase, the pulp delignified by only 11.27%. The wheat straw changed into pulp at the initial stage of bulk delignification phase with ethanol-water. The screened pulp yield was 57.30% in the fiber liberation point and kappa No. was 68.43% correspond. The linear relationship between the lignin contents of pulp and kappa No. of the screened pulp was obtained in this experiment.2. To silvergrass, the factors which influence the pulping were cooking temperature (Tmax), liquid ratio (r), cooking time at Tmax (t) and EW concenreation (C). The optimum cooking conditions were : Tmax :195 C, t: 120min., r: 1:10 and C :55%(V/V). Under these conditions, the screened pulp yield, kappa No. and total lignin (% on o.d pulp ) was 61.32%, 50, 8 and 5.43,separately.The lingnification kinetics of silvergrass occurred in two phase: principal (from beginning to 30 min.) and residual (from 30 min to end), and the delignification followed a first order reaction. The calculated Arrhenius activation energy Ep (principal phases) and Er (residual phases) was 77.13 KJ/mol and 156.7KJ/mol, respectively.IR and 1HNMR analysis showed that the structure of MWL and CL (lignin separated from black liquor) was alike. But there were more syringy (S) and parahydroxy-pheny (H) in CL, cleavage of a -ether linkages( a -O-4) was more than that in MWL.The characteristic of auto-catalyzed EW brown pulp was their easy bleach ability and beating compared with brown Kraft pulp, EW pulp with good brightness and strength properties could be produced with TCP bleaching.3. To Chinese alpine rush, the factor influencing screened pulp yield and kappa No. from great to small was both Tmax > r > C > t. In the range of pulping conditions investigated, a cooking temperature of 1801, a liquid ratio of 1:10, an ethanol concentration of 55% and a time at Tmax of 120 minutes provided a good compromise. Under these conditions, an adequate rate of delignification (kappa No. 38.13) and a high-screened pulp yield 53.18% was achieved. Total lignin in the pulp was 4.64%. Pulp properties indicated that EW pulp was beaten easily. Study of pulping mechanism suggested that delignification course could be divided into two phases: principal (from beginning to 40 min.) and residual (from 40 min to end), The percent of delignification of the two phases was 79.16% and 88.90% respectively. The unscreened pulp yield, kappa No. and total lignin in the pulp was 56.6%, 50.0, 7.10% separately at the liberation point. The linear relationship be更多还原