农业副产物棉秆清洁制浆漂白技术及其机理的研究
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摘要
棉秆是我国北方地区资源丰富的农业副产物。本论文综述了我国制浆造纸工业发展状况,针对我国目前非木材原料的使用情况,提出对棉秆纤维原料进行合理利用的思路。论文以农业副产物棉秆为主要研究对象,根据棉秆实际应用中存在的问题和制浆技术发展趋势,进行了棉秆清洁制浆漂白技术及其机理的系统研究。针对棉秆化学浆尘埃较多的情况,探讨了影响尘埃度的因素,分析了不同漂剂对浆料尘埃的去除能力;进行了棉秆烧碱-AQ法蒸煮的改进及其纸浆ECF漂白的研究;探讨了生物酶脱棉秆皮果胶的效果;研究了全棉秆磺化化学机械法制浆及其后续漂白,提出了解决棉秆SCMP漂白难的有效途径。为改善棉秆机械浆的性能,详细探讨了白腐菌预处理的生物机械法制浆,并利用现代分析测试手段探讨了白腐菌预处理的生物机械法制浆的作用机制及相关机理。为棉秆资源的清洁高效利用提供技术依据和理论依据。
全棉秆漂白浆的尘埃主要来源于棉秆皮的黑色尘埃。在相近白度情况下,过氧化氢去除尘埃的能力优于次氯酸盐和二氧化氯,氯比氧有较好的除尘埃效果。对原料进行浸渍—挤压预处理可改善化学浆的漂白性能和去尘埃效果。不同蒸煮方法中以KP-AQ法和KP法制浆的除尘埃效果较好。
采用预处理和添加助剂的改进烧碱-AQ法蒸煮棉秆,可大幅度降低纸浆的卡伯值,显著提高纸浆的得率和白度,而粘度变化甚小。采用ODQP漂序漂白棉秆烧碱-AQ法浆,在ClO_2用量和H_2O_2用量均为1.5%并优化其它条件的情况下,常规烧碱-AQ浆白度可达80%ISO,而改进烧碱-AQ法浆可达88%ISO的高白度,而且尘埃度较低。实现了棉秆浆的高白度清洁漂白。
棉秆SCMP制浆研究表明,亚硫酸钠用量对成浆强度性能和松厚度影响较大。氢氧化钠用量对得率、强度、白度和松厚度影响较大。增加氢氧化钠用量,纸浆得率、白度和松厚度降低,强度提高。木聚糖酶预处理可提高棉秆机械浆白度和强度,且处理的位置越在制浆流程后阶段,效果越好,对性能的影响越大。SCMP制浆前的木聚糖酶预处理表现出相同的规律。
棉秆SCMP浆单段过氧化氢漂白较优工艺为H_2O_2 3%,NaOH/H_2O_2比为1.25,Na_2SiO_34%,MGSO_40.05%,EDTA0.3%,60℃,150 min,浆浓15%。SCMP浆P_1QP_2漂序中,P_1和P_2 H_2O_2用量比为35:65时白度最高,H_2O_2总用量为6%时,白度可超过60%ISO。氯预处理能提高SCMP漂后浆白度,改善纸浆强度。高锰酸钾预处理不能改善SCMP浆的过氧化氢漂白。PPa漂序不适合棉秆SCMP浆的漂白,而PaP:票序可显著改善H_2O_2漂白效果。三段漂白中,以PaPPa漂序和PaPP漂序较优。在H_2O_2总用量为5%时,白度超过60%ISO;H_2O_2总用量为7%时,白度达到66.8%ISO。木聚糖酶处理可以改善棉秆SCMP浆的过氧化氢漂白,其较优的处理条件为木聚糖酶用量40IU/g浆,pH值8,温度60℃,时间90min,浆浓8%。在此条件下,H_2O_2漂白浆的白度提高3.5%ISO。Lg-9粗酶液处理的PLP和LPP漂序均能改善漂后浆强度,但PLP白度较低,LPP为较好漂序,白度和强度均较好。BYBF粗酶液对纸浆漂白性能的影响与Lg-9相似。Sdu—4粗酶液与木聚糖酶组合的酶处理均能提高漂后浆白度,其顺序为LXP＞XLP＞(LX)P＞XP＞LP,木聚糖酶和漆酶组合进行处理的XLP和LXP漂序对纸浆强度改善较好。
棉秆皮脱果胶研究表明,木聚糖酶和果胶酶均能去除棉秆皮中的果胶,果胶酶脱果胶能力优于木聚糖酶,且纸浆得率较高,卡伯值较低,成浆滤水性较好。酶预处理后所得纸浆具有较高的漂白得率、白度和较低的尘埃度。棉秆皮酶处理对其后机械法纸浆的滤水性、强度和漂白性能均有一定的改善,以果胶酶和木聚糖酶共同处理所得浆料的打浆度最低,漂白的白度最高,但使纸浆得率有所降低。
Trametes versicolor和Lg-9有强的产漆酶能力,P.chrysosporiun25有强的产锰过氧化物酶能力。三个菌种对棉秆BMP制浆的影响规律相同,预处理时间延长,成浆得率、白度降低,不透明度和强度提高,松厚度下降。适宜的白腐菌处理能使成浆纤维长度增加,细小纤维含量降低,改善磨浆性能以及纸浆的可漂性,有效提高漂后纸浆白度。三个菌种中以Lg—9为最优菌种,成浆强度最高。
Lg-9菌处理能够使原料中木素含量明显下降,但在木素被降解的同时,部分碳水化合物也有一定程度的降解,其中以聚戊糖的降解较多,其他少量组分也均有不同程度的去除。与未经白腐菌处理的棉秆RMP浆相比,白腐菌处理所得浆料的纤维平均长度增加,而宽度基本不变。筛分分析表明,Lg—9菌处理能够使最后成浆中中、长纤维组分含量增加,细小纤维组分含量减少。
扫描电镜观察发现,白腐菌Lg—9预处理棉秆原料,菌丝体在棉秆表面漫——长,经菌处理后原料表面出现不同程度的凹坑和孔洞及不同深度的沟槽,表面变得粗糙不平,部分纤维细胞壁上出现小孔和洞隙。经菌处理后纤维变得柔软,磨浆过程中遭受的切断等损伤较少,纤维的柔软性增加,这是菌处理能够使浆料物理强度提高的原因之一。
紫外和红外光谱分析表明,Lg-9白腐菌处理及后续磨浆过程中,木素基本结构单元均有不同程度的脱除,菌处理过程中以紫丁香型木素结构单元脱除相对较多,而磨浆过程中以愈创木基木素结构单元脱除相对较多。菌处理和后续磨浆过程中木素结构中的羰基增多,木素间连接发生断裂出现更多的木素侧链和游离酚羟基。~1H-NMR和~(13)C-NMR分析表明,白腐菌处理和后续磨浆处理,并不能使木素结构中芳环结构发生开环,但能使苯环侧链发生断裂。还可使部分β-5/β-1结构单元发生降解,使部分含有羧基的大分子木素降解,但是羧基结构没有变化。
Cotton stalk is an abundant agricultural residue in north China.In this thesis,the development and the current status of pulp and paper industry in China was reviewed,and a proposal was put forward for using cotton stalk reasonably according to the situation of using non-wood fiber in China.The clean pulping and bleaching technology and its mechanism of cotton stalk were investigated in this thesis according to the existed problems in the use of this material and the development tendency of pulping technology.For solving the problem of high dirt content in cotton stalk chemical pulp,the parameters which affect the the dirt content were analyzed.The modified soda-AQ cooking and the pulp ECF bleaching were conducted. The removal of pection from cotton stalk bark was taken into the research with biological methods.The SCMP of cotton stalk and the pulp bleachability were researched systematically and some improved bleaching sequences were put forward.For improving the properties of cotton stalk refiner mechanical pulp,the white-rot fungi pretreatment technology was taken into the BMP process.Bio-mechanical pulping of cotton stalk and its mechanism were investigated in detail.Changes of fiber characteristics and lignin structure were analyzed by using advanced analysis methods,which could provide technical and theoretical support for the clean,efficient utilization of cotton stalk resource.
The dirts of bleached whole cotton stalk chemical pulp came mainly from the black dust. The dirt removal ability of hydrogen peroxide bleaching was better than that of hypochlorite bleaching and chlorine dioxide bleaching.The dirt removal effectiveness of chlorine was better than that of oxygen.The impregnation-extrusion pretreatment could improve the bleachability and dirt removal of cotton stalk chemical pulp.The KP-AQ and KP pulping methods contributed to the good reduction of dirts.
Modified Soda-AQ cooking of cotton stalk with pretreatment and addition of auxiliary chemicals during cooking resulted in a much lower Kappa number,much higher pulp yield and brightness and preserved pulp viscosity compared to conventional Soda-AQ pulp.ODQP sequence was used for the bleaching of cotton stalk pulp.At the dosage of 1.5%of both ClO_2 in D stage and H_2O_2 in P stage and the optimal other conditions,the brightness of bleached conventional Soda-AQ pulp reached 80%ISO,the brightness of bleached modified Soda-AQ pulp was higher than 88%ISO and the dirt content in pulp was very low,which indicated the realization of high brightness,clean bleaching of cotton stalk chemical pulp.
The research of pectin removal from cotton stalk bark showed that both xylanase pretreatment and pectinase pretreatment could reduce the pectin content in cotton stalk bark. The effectiveness of pectinase pretreatment was better than that of xylanase.The pectinase pretreatment could improve pulp drainage ability and the pulp yield with lower Kappa number. For mechanical pulping of cotton stalk bark,the enzyme pretreatment could give the pulp better bleachability and lower beating degree but reduce the pulp yield.The pretreatment with pectinase and xylanase could give the bleached pulp highest brightness.
The investigation of SCMP pulping of cotton stalk showed that the dosage of sodium sulfite and sodium hydroxide had strong effect on the pulp strength properties and bulk.With increasing of sodium hydroxide dosage,the pulp yield,brightness and bulk decreased,while the strength properties increased.The enhancement of pretreatment temperature could strengthen the treatment degree and improve the pulp strength properties,while the brightness, bulk and pulp yield reduced.The xylanase pretreatment could improve the brightness and strength of cotton stalk BMP pulp.The xylanase pretreatment to SCMP pulp could give the same effectiveness as that to BMP pulp.
The optimum single stage H_2O_2 bleaching conditions to SCMP of cotton stalk were as follows:H_2O_2,3%;NaOH/H_2O_2.1.25;Na_2SiO_3,4%;MgSO_4,0.05%;EDTA,0.3%;60℃;150 min;pulp consistency,15%.In P_1QP_2 bleaching sequence,the bleached pulp could get the highest brightness when the H_2O_2 dosage ratio in P_1 and P_2 stage was 35:65.The chlorine pretreatment could increase the brightness of bleached pulp and improve the pulp strength. The potassium permanganate pretreatment couldn't improve the bleachability of SCMP. PaPPa and PaPP bleaching sequences could give the pulp good brightness.At a total H_2O_2 dosage of 5%,the brightness could reach 60%ISO.As total H_2O_2 dosage increased to 7%,the brightness would be higher than 66%ISO.The pretreatment of xylanase to SCMP could improve the hydrogen peroxide bleachability and the optimum pretreatment conditions were as follows:dosage of xylanase,40IU/g pulp;pH value,8;60℃;90min;pulp consistency, 8%.Both PLP and LPP bleaching sequences where L used the unpurified enzyme liquor from Lg-9 fungus and BYBF fungus respectively could improve the pulp strength.The PLP bleached pulp had lower brightness,while LPP bleached pulp had higher brightness.As crude nzyme liquor from Sdu-4 fungus and xylanase were used in the same or separate stage,the pulp bleachability could be improved.The order of pulp brightness was LXP＞XLP＞(LX)P＞XP＞LP.
Trametes versicolor and Lg-9 had strong capability of producing laccase.P. chrysosporiun 25 had strong capability of producing manganese peroxidase.For these three fungi the increasing of pretreatment time could decrease the pulp yield,brightness and bulk, improve the opacity properties and strength properties.The optimal white-rot fungi pretreatment could increase the mean fiber length,reduce the fines content,improve the refining performance and pulp bleachability,enhance the bleached pulp brightness.The Lg-9 fungus was the best one in these three fungi,as the strength of the resulted pulp was highest.
The lignin content in cotton stalk reduced obviously during pretreatment with Lg-9, while,with the lignin degradation,parts of carbohydrates were degraded in a certain extent. The pentosan got more degradation than cellulose.The other components got some removal in different extent.
The pretreatment of Lg-9 could make the mean fiber length of cotton stalk biomechanical pulp increase and fines content decrease.Compared with cotton stalk RMP pulp,the Lg-9 pretreated BMP fiber had longer average fiber length and lower f(?)nes content. The classification analysis illustrated that the pretreatment of Lg-9 could make the resultant pulp have more content of long fiber fraction and middle fiber fraction as well as lower ccntent of fines fraction.
The SEM observation showed that the mycelium of Lg-9 growed on the surface of the cotton stalk.The surface of Lg-9 treated cotton stalk had many pits,cavacities and grooves with different depth.The surface became abrasive.Some holes and cavacities existed in the fiber cell wall.The fiber pretreated by Lg-9 became soft and existed in the pulp with belt form. The enhancement of fiber softness and less damage of the fiber during refining were the reasons that Lg-9 pretreatment could improve the pulp strength properties.
The UV and IR analyses illustrated that parts of lignin units were removed during the Lg-9 treatment and subsequent refining.The removal of syringyl units during Lg-9 treatment was more than that of guaiacyl lignin units,while,during refining more guaiacyl lignin units were removed than syringyl lignin units.The carbonyl content in lignin increased during the Lg-9 treatment and the following refining.Some links between lignin units were broken up. The contents of lignin side chain and phenolic hydroxyl group increased.The~1H-NMR and ~(13)C-NMR analyses showed that the aromatic ring couldn't be broken up,parts ofβ-5/β-1 structue units were broken up.In addition,part of lignin molecules with carboxyl group was degraded without the structure change of the carboxyl group.
全棉秆漂白浆的尘埃主要来源于棉秆皮的黑色尘埃。在相近白度情况下,过氧化氢去除尘埃的能力优于次氯酸盐和二氧化氯,氯比氧有较好的除尘埃效果。对原料进行浸渍—挤压预处理可改善化学浆的漂白性能和去尘埃效果。不同蒸煮方法中以KP-AQ法和KP法制浆的除尘埃效果较好。
采用预处理和添加助剂的改进烧碱-AQ法蒸煮棉秆,可大幅度降低纸浆的卡伯值,显著提高纸浆的得率和白度,而粘度变化甚小。采用ODQP漂序漂白棉秆烧碱-AQ法浆,在ClO_2用量和H_2O_2用量均为1.5%并优化其它条件的情况下,常规烧碱-AQ浆白度可达80%ISO,而改进烧碱-AQ法浆可达88%ISO的高白度,而且尘埃度较低。实现了棉秆浆的高白度清洁漂白。
棉秆SCMP制浆研究表明,亚硫酸钠用量对成浆强度性能和松厚度影响较大。氢氧化钠用量对得率、强度、白度和松厚度影响较大。增加氢氧化钠用量,纸浆得率、白度和松厚度降低,强度提高。木聚糖酶预处理可提高棉秆机械浆白度和强度,且处理的位置越在制浆流程后阶段,效果越好,对性能的影响越大。SCMP制浆前的木聚糖酶预处理表现出相同的规律。
棉秆SCMP浆单段过氧化氢漂白较优工艺为H_2O_2 3%,NaOH/H_2O_2比为1.25,Na_2SiO_34%,MGSO_40.05%,EDTA0.3%,60℃,150 min,浆浓15%。SCMP浆P_1QP_2漂序中,P_1和P_2 H_2O_2用量比为35:65时白度最高,H_2O_2总用量为6%时,白度可超过60%ISO。氯预处理能提高SCMP漂后浆白度,改善纸浆强度。高锰酸钾预处理不能改善SCMP浆的过氧化氢漂白。PPa漂序不适合棉秆SCMP浆的漂白,而PaP:票序可显著改善H_2O_2漂白效果。三段漂白中,以PaPPa漂序和PaPP漂序较优。在H_2O_2总用量为5%时,白度超过60%ISO;H_2O_2总用量为7%时,白度达到66.8%ISO。木聚糖酶处理可以改善棉秆SCMP浆的过氧化氢漂白,其较优的处理条件为木聚糖酶用量40IU/g浆,pH值8,温度60℃,时间90min,浆浓8%。在此条件下,H_2O_2漂白浆的白度提高3.5%ISO。Lg-9粗酶液处理的PLP和LPP漂序均能改善漂后浆强度,但PLP白度较低,LPP为较好漂序,白度和强度均较好。BYBF粗酶液对纸浆漂白性能的影响与Lg-9相似。Sdu—4粗酶液与木聚糖酶组合的酶处理均能提高漂后浆白度,其顺序为LXP＞XLP＞(LX)P＞XP＞LP,木聚糖酶和漆酶组合进行处理的XLP和LXP漂序对纸浆强度改善较好。
棉秆皮脱果胶研究表明,木聚糖酶和果胶酶均能去除棉秆皮中的果胶,果胶酶脱果胶能力优于木聚糖酶,且纸浆得率较高,卡伯值较低,成浆滤水性较好。酶预处理后所得纸浆具有较高的漂白得率、白度和较低的尘埃度。棉秆皮酶处理对其后机械法纸浆的滤水性、强度和漂白性能均有一定的改善,以果胶酶和木聚糖酶共同处理所得浆料的打浆度最低,漂白的白度最高,但使纸浆得率有所降低。
Trametes versicolor和Lg-9有强的产漆酶能力,P.chrysosporiun25有强的产锰过氧化物酶能力。三个菌种对棉秆BMP制浆的影响规律相同,预处理时间延长,成浆得率、白度降低,不透明度和强度提高,松厚度下降。适宜的白腐菌处理能使成浆纤维长度增加,细小纤维含量降低,改善磨浆性能以及纸浆的可漂性,有效提高漂后纸浆白度。三个菌种中以Lg—9为最优菌种,成浆强度最高。
Lg-9菌处理能够使原料中木素含量明显下降,但在木素被降解的同时,部分碳水化合物也有一定程度的降解,其中以聚戊糖的降解较多,其他少量组分也均有不同程度的去除。与未经白腐菌处理的棉秆RMP浆相比,白腐菌处理所得浆料的纤维平均长度增加,而宽度基本不变。筛分分析表明,Lg—9菌处理能够使最后成浆中中、长纤维组分含量增加,细小纤维组分含量减少。
扫描电镜观察发现,白腐菌Lg—9预处理棉秆原料,菌丝体在棉秆表面漫——长,经菌处理后原料表面出现不同程度的凹坑和孔洞及不同深度的沟槽,表面变得粗糙不平,部分纤维细胞壁上出现小孔和洞隙。经菌处理后纤维变得柔软,磨浆过程中遭受的切断等损伤较少,纤维的柔软性增加,这是菌处理能够使浆料物理强度提高的原因之一。
紫外和红外光谱分析表明,Lg-9白腐菌处理及后续磨浆过程中,木素基本结构单元均有不同程度的脱除,菌处理过程中以紫丁香型木素结构单元脱除相对较多,而磨浆过程中以愈创木基木素结构单元脱除相对较多。菌处理和后续磨浆过程中木素结构中的羰基增多,木素间连接发生断裂出现更多的木素侧链和游离酚羟基。~1H-NMR和~(13)C-NMR分析表明,白腐菌处理和后续磨浆处理,并不能使木素结构中芳环结构发生开环,但能使苯环侧链发生断裂。还可使部分β-5/β-1结构单元发生降解,使部分含有羧基的大分子木素降解,但是羧基结构没有变化。
Cotton stalk is an abundant agricultural residue in north China.In this thesis,the development and the current status of pulp and paper industry in China was reviewed,and a proposal was put forward for using cotton stalk reasonably according to the situation of using non-wood fiber in China.The clean pulping and bleaching technology and its mechanism of cotton stalk were investigated in this thesis according to the existed problems in the use of this material and the development tendency of pulping technology.For solving the problem of high dirt content in cotton stalk chemical pulp,the parameters which affect the the dirt content were analyzed.The modified soda-AQ cooking and the pulp ECF bleaching were conducted. The removal of pection from cotton stalk bark was taken into the research with biological methods.The SCMP of cotton stalk and the pulp bleachability were researched systematically and some improved bleaching sequences were put forward.For improving the properties of cotton stalk refiner mechanical pulp,the white-rot fungi pretreatment technology was taken into the BMP process.Bio-mechanical pulping of cotton stalk and its mechanism were investigated in detail.Changes of fiber characteristics and lignin structure were analyzed by using advanced analysis methods,which could provide technical and theoretical support for the clean,efficient utilization of cotton stalk resource.
The dirts of bleached whole cotton stalk chemical pulp came mainly from the black dust. The dirt removal ability of hydrogen peroxide bleaching was better than that of hypochlorite bleaching and chlorine dioxide bleaching.The dirt removal effectiveness of chlorine was better than that of oxygen.The impregnation-extrusion pretreatment could improve the bleachability and dirt removal of cotton stalk chemical pulp.The KP-AQ and KP pulping methods contributed to the good reduction of dirts.
Modified Soda-AQ cooking of cotton stalk with pretreatment and addition of auxiliary chemicals during cooking resulted in a much lower Kappa number,much higher pulp yield and brightness and preserved pulp viscosity compared to conventional Soda-AQ pulp.ODQP sequence was used for the bleaching of cotton stalk pulp.At the dosage of 1.5%of both ClO_2 in D stage and H_2O_2 in P stage and the optimal other conditions,the brightness of bleached conventional Soda-AQ pulp reached 80%ISO,the brightness of bleached modified Soda-AQ pulp was higher than 88%ISO and the dirt content in pulp was very low,which indicated the realization of high brightness,clean bleaching of cotton stalk chemical pulp.
The research of pectin removal from cotton stalk bark showed that both xylanase pretreatment and pectinase pretreatment could reduce the pectin content in cotton stalk bark. The effectiveness of pectinase pretreatment was better than that of xylanase.The pectinase pretreatment could improve pulp drainage ability and the pulp yield with lower Kappa number. For mechanical pulping of cotton stalk bark,the enzyme pretreatment could give the pulp better bleachability and lower beating degree but reduce the pulp yield.The pretreatment with pectinase and xylanase could give the bleached pulp highest brightness.
The investigation of SCMP pulping of cotton stalk showed that the dosage of sodium sulfite and sodium hydroxide had strong effect on the pulp strength properties and bulk.With increasing of sodium hydroxide dosage,the pulp yield,brightness and bulk decreased,while the strength properties increased.The enhancement of pretreatment temperature could strengthen the treatment degree and improve the pulp strength properties,while the brightness, bulk and pulp yield reduced.The xylanase pretreatment could improve the brightness and strength of cotton stalk BMP pulp.The xylanase pretreatment to SCMP pulp could give the same effectiveness as that to BMP pulp.
The optimum single stage H_2O_2 bleaching conditions to SCMP of cotton stalk were as follows:H_2O_2,3%;NaOH/H_2O_2.1.25;Na_2SiO_3,4%;MgSO_4,0.05%;EDTA,0.3%;60℃;150 min;pulp consistency,15%.In P_1QP_2 bleaching sequence,the bleached pulp could get the highest brightness when the H_2O_2 dosage ratio in P_1 and P_2 stage was 35:65.The chlorine pretreatment could increase the brightness of bleached pulp and improve the pulp strength. The potassium permanganate pretreatment couldn't improve the bleachability of SCMP. PaPPa and PaPP bleaching sequences could give the pulp good brightness.At a total H_2O_2 dosage of 5%,the brightness could reach 60%ISO.As total H_2O_2 dosage increased to 7%,the brightness would be higher than 66%ISO.The pretreatment of xylanase to SCMP could improve the hydrogen peroxide bleachability and the optimum pretreatment conditions were as follows:dosage of xylanase,40IU/g pulp;pH value,8;60℃;90min;pulp consistency, 8%.Both PLP and LPP bleaching sequences where L used the unpurified enzyme liquor from Lg-9 fungus and BYBF fungus respectively could improve the pulp strength.The PLP bleached pulp had lower brightness,while LPP bleached pulp had higher brightness.As crude nzyme liquor from Sdu-4 fungus and xylanase were used in the same or separate stage,the pulp bleachability could be improved.The order of pulp brightness was LXP＞XLP＞(LX)P＞XP＞LP.
Trametes versicolor and Lg-9 had strong capability of producing laccase.P. chrysosporiun 25 had strong capability of producing manganese peroxidase.For these three fungi the increasing of pretreatment time could decrease the pulp yield,brightness and bulk, improve the opacity properties and strength properties.The optimal white-rot fungi pretreatment could increase the mean fiber length,reduce the fines content,improve the refining performance and pulp bleachability,enhance the bleached pulp brightness.The Lg-9 fungus was the best one in these three fungi,as the strength of the resulted pulp was highest.
The lignin content in cotton stalk reduced obviously during pretreatment with Lg-9, while,with the lignin degradation,parts of carbohydrates were degraded in a certain extent. The pentosan got more degradation than cellulose.The other components got some removal in different extent.
The pretreatment of Lg-9 could make the mean fiber length of cotton stalk biomechanical pulp increase and fines content decrease.Compared with cotton stalk RMP pulp,the Lg-9 pretreated BMP fiber had longer average fiber length and lower f(?)nes content. The classification analysis illustrated that the pretreatment of Lg-9 could make the resultant pulp have more content of long fiber fraction and middle fiber fraction as well as lower ccntent of fines fraction.
The SEM observation showed that the mycelium of Lg-9 growed on the surface of the cotton stalk.The surface of Lg-9 treated cotton stalk had many pits,cavacities and grooves with different depth.The surface became abrasive.Some holes and cavacities existed in the fiber cell wall.The fiber pretreated by Lg-9 became soft and existed in the pulp with belt form. The enhancement of fiber softness and less damage of the fiber during refining were the reasons that Lg-9 pretreatment could improve the pulp strength properties.
The UV and IR analyses illustrated that parts of lignin units were removed during the Lg-9 treatment and subsequent refining.The removal of syringyl units during Lg-9 treatment was more than that of guaiacyl lignin units,while,during refining more guaiacyl lignin units were removed than syringyl lignin units.The carbonyl content in lignin increased during the Lg-9 treatment and the following refining.Some links between lignin units were broken up. The contents of lignin side chain and phenolic hydroxyl group increased.The~1H-NMR and ~(13)C-NMR analyses showed that the aromatic ring couldn't be broken up,parts ofβ-5/β-1 structue units were broken up.In addition,part of lignin molecules with carboxyl group was degraded without the structure change of the carboxyl group.
引文
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