非木材纸浆对环境友好的漂白新技术及其机理的研究
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摘要
近年来，尽管通过增加木浆比例和提高废纸资源的利用率来调整制浆造纸原材料结构，但非木材原料仍将是我国重要的纤维资源。麦草、蔗渣和竹子是我国主要的三种非木材纤维原料。本论文以麦草浆、蔗渣浆和竹子浆为研究对象，进行了对环境友好的ECF和TCF漂白及其机理的研究，为在我国实现无／少污染漂白提供技术和理论依据。
在对非木材纸浆OQP漂白的研究结果表明，较强的氧脱木素条件，即浆浓10％，NaOH用量2.5％，MgSO_4用量0.5％，氧压0.7MPa，温度105℃，时间75min，脱木素的效果比较好，且粘度下降不多。螯合处理的最佳pH值为3。H_2O_2漂白的最佳工艺条件为：浆浓10％，H_2O_23.5％，NaOH 1.5％(麦草浆)，1.6％(蔗渣浆)，MgSO_40.05％，90℃，时间4h。若在H_2O_2漂白时用氧加压，即采用压力过氧化氢漂白，有利漂终白度的提高，且粘度下降不大。
进行了低二氧化氯用量的DQP漂白的研究。采用低二氧化氯用量(麦草浆和竹子浆为1.5％，蔗渣浆为1.0％，均以有效氯计)和低过氧化氢用量(三种浆均为1.5％)的DQP漂白，可将麦草浆、蔗渣浆和竹子浆漂至83％ISO以上的白度，且DQP漂白浆有较高的粘度和强度，并有很好的白度稳定性。D段终点pH值的优化结果为：竹子浆、蔗渣浆、麦草浆均为4左右。三种非木材浆料(麦草浆、蔗渣浆、竹子浆)DQP漂序中螯合处理采用EDTA的适宜用量为0.1％～0.2％。H_2O_2漂段MgSO_4的合适用量(以Mg~(2+)计)为：蔗渣浆0.02％，竹子浆0.04％，而麦草浆由于镁的含量较高，可不加Mg~(2+)。
在达到相同的白度水平下，OQP和DQP漂白浆比对应的CEH漂白浆白度稳定性好，粘度也高得多。要达到相同的强度，OQP和DQP漂白浆所需的打浆转数或打浆能耗比CEH漂白浆少；在相同的打浆度下，OQP和DQP漂白浆的强度比CEH漂白浆好。QP和DQP漂白废水的污染负荷(CODcr、BOD_5和SS)比CEH漂白废水低得多。
本文在研究过渡金属离子对过氧化氢漂白的影响中发现，随着Cu~(2+)和Mn~(2+)含量的增加，残余H_2O_2迅速减少，过氧化氢漂白浆的白度逐渐降低，而卡伯值逐渐提高。随着Cu~(2+)含量的增加粘度逐渐降低，而一定量Mn~(2+)的存在有利于漂白浆粘度的提高。从纸页的物理强度看，随着漂白时Cu~(2+)加入量的增加，纸页的抗张、撕裂和耐破强度均降低。随着Mn~(2+)加入量的增大，裂断长逐渐降低，耐破指数略有提高，撕裂指数逐渐增加，撕裂指数的升高与粘度(聚合度)的提高有关。
Although the structure of raw materials has being adjusted through increasing the proportion of wood pulp and by effectively utilizing the waste paper source, non-wood species will still remain an important fiber resource. Wheat straw, bamboo and bagasse are the main non-wood species for papermaking in China. In this paper, ECF and TCF bleaching technologies and the mechanisms of bamboo, wheat straw and bagasse pulps were studied, which will provide theoretical understanding and technique support for realizing non or less pollution bleaching in our country.
Through studying OQP bleaching of non-wood pulps, it was found that stronger oxygen delignification conditions, namely pulp consistency 10%, NaOH charge 2.5 %, MgSO_4 0.5%, O_2 pressure 0.7Mpa, 105°C and 75min, resulted in better effect of delignification, and small loss of the viscosity of pulps. The optimal pH value of chelation was 3. The optimal process conditions of H_2O_2 bleaching were: pulp consistency 10%, H_2O_2 charge 3.5%, NaOH charge1.5% (wheat straw), 1.6% (bagasse), MgSO_4 0.05%, 90°C and 4h. It was beneficial for the improvement of final brightness if pressurized H_2O_2 bleaching was applied, but the viscosity decreased slightly.
Low chlorine dioxide charge DQP bleaching was carried out. The results indicated that the wheat straw, bamboo and bagasse pulps can be bleached to the brightness of above 83 % ISO by DQP sequence under low chlorine dioxide charge (wheat straw and bamboo1.5%, bagasse 1.0%, calculated as active chlorine) and low H_2O_2 charge (1.5% for the three pulps), and the DQP bleached pulps had higher viscosity and strength and better brightness stability. The optimal pH value in D stage was 4. The suitable EDTA charge in Q stage of DQP sequence for the three pulps was 0.1%-0.2%. The charge of MgSO_4(calculated as Mg~(2+)) was: 0.02% (bagasse), or 0.04% (bamboo), while wheat straw pulp did not need to add Mg~(2+) due to the high Mg~(2+) content in pulp.
Under the similar brightness level, compared with CEH bleached pulps, OQP and DQP bleached pulps had better brightness stability, much higher pulp viscosity, better strength properties and lower pollution loads. The OQP and DQP bleached pulps needed less PFI revolution or less beating energy to reach the same strength properties as the CEH bleached pulps. The OQP and DQP bleached pulps had better strength at the same beating degree. The total pollution loads (CODcr, BOD_5 and SS) of QP and DQP effluent were much lower than those of CEH effluent.
在对非木材纸浆OQP漂白的研究结果表明，较强的氧脱木素条件，即浆浓10％，NaOH用量2.5％，MgSO_4用量0.5％，氧压0.7MPa，温度105℃，时间75min，脱木素的效果比较好，且粘度下降不多。螯合处理的最佳pH值为3。H_2O_2漂白的最佳工艺条件为：浆浓10％，H_2O_23.5％，NaOH 1.5％(麦草浆)，1.6％(蔗渣浆)，MgSO_40.05％，90℃，时间4h。若在H_2O_2漂白时用氧加压，即采用压力过氧化氢漂白，有利漂终白度的提高，且粘度下降不大。
进行了低二氧化氯用量的DQP漂白的研究。采用低二氧化氯用量(麦草浆和竹子浆为1.5％，蔗渣浆为1.0％，均以有效氯计)和低过氧化氢用量(三种浆均为1.5％)的DQP漂白，可将麦草浆、蔗渣浆和竹子浆漂至83％ISO以上的白度，且DQP漂白浆有较高的粘度和强度，并有很好的白度稳定性。D段终点pH值的优化结果为：竹子浆、蔗渣浆、麦草浆均为4左右。三种非木材浆料(麦草浆、蔗渣浆、竹子浆)DQP漂序中螯合处理采用EDTA的适宜用量为0.1％～0.2％。H_2O_2漂段MgSO_4的合适用量(以Mg~(2+)计)为：蔗渣浆0.02％，竹子浆0.04％，而麦草浆由于镁的含量较高，可不加Mg~(2+)。
在达到相同的白度水平下，OQP和DQP漂白浆比对应的CEH漂白浆白度稳定性好，粘度也高得多。要达到相同的强度，OQP和DQP漂白浆所需的打浆转数或打浆能耗比CEH漂白浆少；在相同的打浆度下，OQP和DQP漂白浆的强度比CEH漂白浆好。QP和DQP漂白废水的污染负荷(CODcr、BOD_5和SS)比CEH漂白废水低得多。
本文在研究过渡金属离子对过氧化氢漂白的影响中发现，随着Cu~(2+)和Mn~(2+)含量的增加，残余H_2O_2迅速减少，过氧化氢漂白浆的白度逐渐降低，而卡伯值逐渐提高。随着Cu~(2+)含量的增加粘度逐渐降低，而一定量Mn~(2+)的存在有利于漂白浆粘度的提高。从纸页的物理强度看，随着漂白时Cu~(2+)加入量的增加，纸页的抗张、撕裂和耐破强度均降低。随着Mn~(2+)加入量的增大，裂断长逐渐降低，耐破指数略有提高，撕裂指数逐渐增加，撕裂指数的升高与粘度(聚合度)的提高有关。
Although the structure of raw materials has being adjusted through increasing the proportion of wood pulp and by effectively utilizing the waste paper source, non-wood species will still remain an important fiber resource. Wheat straw, bamboo and bagasse are the main non-wood species for papermaking in China. In this paper, ECF and TCF bleaching technologies and the mechanisms of bamboo, wheat straw and bagasse pulps were studied, which will provide theoretical understanding and technique support for realizing non or less pollution bleaching in our country.
Through studying OQP bleaching of non-wood pulps, it was found that stronger oxygen delignification conditions, namely pulp consistency 10%, NaOH charge 2.5 %, MgSO_4 0.5%, O_2 pressure 0.7Mpa, 105°C and 75min, resulted in better effect of delignification, and small loss of the viscosity of pulps. The optimal pH value of chelation was 3. The optimal process conditions of H_2O_2 bleaching were: pulp consistency 10%, H_2O_2 charge 3.5%, NaOH charge1.5% (wheat straw), 1.6% (bagasse), MgSO_4 0.05%, 90°C and 4h. It was beneficial for the improvement of final brightness if pressurized H_2O_2 bleaching was applied, but the viscosity decreased slightly.
Low chlorine dioxide charge DQP bleaching was carried out. The results indicated that the wheat straw, bamboo and bagasse pulps can be bleached to the brightness of above 83 % ISO by DQP sequence under low chlorine dioxide charge (wheat straw and bamboo1.5%, bagasse 1.0%, calculated as active chlorine) and low H_2O_2 charge (1.5% for the three pulps), and the DQP bleached pulps had higher viscosity and strength and better brightness stability. The optimal pH value in D stage was 4. The suitable EDTA charge in Q stage of DQP sequence for the three pulps was 0.1%-0.2%. The charge of MgSO_4(calculated as Mg~(2+)) was: 0.02% (bagasse), or 0.04% (bamboo), while wheat straw pulp did not need to add Mg~(2+) due to the high Mg~(2+) content in pulp.
Under the similar brightness level, compared with CEH bleached pulps, OQP and DQP bleached pulps had better brightness stability, much higher pulp viscosity, better strength properties and lower pollution loads. The OQP and DQP bleached pulps needed less PFI revolution or less beating energy to reach the same strength properties as the CEH bleached pulps. The OQP and DQP bleached pulps had better strength at the same beating degree. The total pollution loads (CODcr, BOD_5 and SS) of QP and DQP effluent were much lower than those of CEH effluent.
引文
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