改性微粒硅溶胶的研制及应用机理研究
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摘要
首次在我国研究开发了适合于造纸使用的铝改性微粒硅溶胶与硼改性微粒硅溶胶，其助留助滤效果优于进口硅溶胶NP882，其中硼改性微粒硅溶胶的助留助滤效果优于铝改性微粒硅溶胶。改性前硅溶胶的最佳制备条件为：用碱量8％，熟化温度T_(12)，熟化时间90min。铝盐改性的最佳条件为：改性程度A_3，改性温度为T_(24)，反应时间为1小时左右。硼改性最佳B／Si摩尔比在0.08—0.1之间。
选用超滤浓缩硼改性硅溶胶，其最佳条件为：室温下、截留分子量为1万的膜、操作压力为3.5kPa，硼改性硅溶胶浓度可浓缩到15％-16％左右。用阴离子及非离子的表面活性剂提高高浓度硅溶胶的稳定性，其中0.01％用量的DBS分散效果最佳，对硅溶胶的性能几乎没有影响，有利于实现产品商品化。
系统研究了阳离子聚合物／改性硅溶胶微粒体系的特征应用工艺及其电化学性能，发现阳离子淀粉／改性硅溶胶微粒助留体系的抗剪切能力比阳离子淀粉一元助留体系的强，其中阳离子淀粉／硼改性硅溶胶微粒体系抗剪切能力比阳离子淀粉／铝改性硅溶胶微粒体系的强。改性硅溶胶微粒体系适用于废纸浆和草浆等细小组分含量高的浆料，对木浆和废纸浆的助留助滤效果的影响中，阳离子淀粉+CPAM／改性硅溶胶助留助滤体系助留助滤效果比阳离子淀粉／改性硅溶胶助留助滤体系和CPAM／改性硅溶胶助留助滤体系好；对草浆助留助滤效果的影响中，阳离子淀粉／改性硅溶胶微粒体系有良好的助留助滤效果。其中硼改性微粒硅溶胶的助留助滤效果优于铝改性微粒硅溶胶。
阳离子淀粉／改性硅溶胶微粒助留助滤体系在pH值4—8时较为适用，在松香施胶体系中硫酸铝用量≤3％(较低)时也可适用；其体系抗电解质干扰能力强，白水中电解质含量低于100mM时，其体系可以采用封闭循环用水，减少水资源污染和浪费。
用IR谱、~(29)Si-NMR、~(11)B-NMR和~(27)Al-NMR谱以及透射电镜对铝改性硅溶胶与硼改性硅溶胶进行了结构形态与特征的分析研究，首次提出了铝改性粒硅溶胶与硼改性硅溶胶微粒硅溶胶的结构和形态特征。
通过几种絮聚模型-DDJ动态滤水仪法、结合激光粒度仪研究絮团大小的变化以及纸张匀度的比较，探讨了阳离子聚合物／改性硅溶胶微粒体系的絮聚过程与机理，为絮聚机理研究提供了一种新的思路和较简便的方法。阳离子聚合物／改性硅溶胶微粒体系的絮聚机理是，先加入阳离子聚合物，纤维与细小组分絮聚成大的絮聚体，受到高剪切力作用，初始絮聚体被打散成小碎块，为带负电荷的改性硅溶胶微粒暴露出更多的链圈和链尾。改性硅溶胶微粒就在这些吸附于不同纸料粒子上的链圈和链尾之间，靠静电中和以及与聚合物中非带电段的配合吸附作用，改性硅溶胶微粒粒径小只能使近距离的细小碎块桥联作用而发生重新絮聚，形成较初始絮聚体更小、更均一、致密的絮团网络。结果可以大幅度提高了细小纤维和填料的留着率，改善了纸料的滤水性，同时，又可获得良好的纸页匀度。
The preparation and their application in papermaking of aluminium modified silica sol (AMS) and boron modified silica sol (BMS) were first investigated in China. The retention and drainage efficiency of AMS and BMS were superior to that of imported silica sol NP882 and the retention and drainage efficiency of BMS was superior to that of AMS. The optimal conditions before modification were 8% alkali dosage, heat temperature T12 and heat time 90 minutes. And the optimal conditions of aluminium modification were modification degree A3, temperature T24 and reaction time about an hour. Or that of B/Si was 0.08-0.1.Ultrafiltration instrument was selected to condense BMS and its optimal conditions were 3.5kPa pressure with 10 million molecular weight membrane at room temperature. In order to improve the stability of high concentration silica sol, anion or no ion surface actives could be useful. 0.01% DBS was found to be the best dispersant and had almost no effect on silica sol which was in favor of its commerciality.Characteristic application process and electrochemistry performance of cationic polymers/modified silica sol (MS) were systemically studied, It was found that CS/MS microparticle retention and drainage aid system had better retention and drainage efficiency in the high shear condition than CS single retention aid system, meantime CS/BMS system was better than CS/AMS system. MS microparticle retention and drainage aid systems were applicable to pulp with high fines such as waste pulp and wheat straw pulp. Seen from the effects of MS microparticle retention and drainage aid systems on wood pulp and waste pulp, CS and CPAM/MS system had better retention and drainage efficiency than CS/MS system and CPAM/MS system. But CS/MS system had best retention and drainage efficiency in wheat straw pulp. In all pulp BMS had better retention and drainage effiency than AMS. CS/MS microparticle retention and drainage aid system was preferably applicable in pH value 4-8 and resin sizing systems with less than 3% aluminium sulfate. This system had good resist capability to electrolyte interfere so that cycle water with less than 100mM electrolyte could be used resulting in less water resource polluted and wasted.Flocculation mechanism of microparticle retention and drainage aid system was investigated with DDJ, Laser size instrument and paper formation which was a new ideal and simple method. The research results showed that in the addition of cationic polymer fibers and fines flocculated and broken up with high shear then more chain loops and tails were exposed and bridged by negative MS. Due to MS was microparticle and had high specific surface area and high negative charge density it made close fragments flocculated into smaller and more uniform and compact floc net so that it improved retention and drainage with excellent formation.
选用超滤浓缩硼改性硅溶胶，其最佳条件为：室温下、截留分子量为1万的膜、操作压力为3.5kPa，硼改性硅溶胶浓度可浓缩到15％-16％左右。用阴离子及非离子的表面活性剂提高高浓度硅溶胶的稳定性，其中0.01％用量的DBS分散效果最佳，对硅溶胶的性能几乎没有影响，有利于实现产品商品化。
系统研究了阳离子聚合物／改性硅溶胶微粒体系的特征应用工艺及其电化学性能，发现阳离子淀粉／改性硅溶胶微粒助留体系的抗剪切能力比阳离子淀粉一元助留体系的强，其中阳离子淀粉／硼改性硅溶胶微粒体系抗剪切能力比阳离子淀粉／铝改性硅溶胶微粒体系的强。改性硅溶胶微粒体系适用于废纸浆和草浆等细小组分含量高的浆料，对木浆和废纸浆的助留助滤效果的影响中，阳离子淀粉+CPAM／改性硅溶胶助留助滤体系助留助滤效果比阳离子淀粉／改性硅溶胶助留助滤体系和CPAM／改性硅溶胶助留助滤体系好；对草浆助留助滤效果的影响中，阳离子淀粉／改性硅溶胶微粒体系有良好的助留助滤效果。其中硼改性微粒硅溶胶的助留助滤效果优于铝改性微粒硅溶胶。
阳离子淀粉／改性硅溶胶微粒助留助滤体系在pH值4—8时较为适用，在松香施胶体系中硫酸铝用量≤3％(较低)时也可适用；其体系抗电解质干扰能力强，白水中电解质含量低于100mM时，其体系可以采用封闭循环用水，减少水资源污染和浪费。
用IR谱、~(29)Si-NMR、~(11)B-NMR和~(27)Al-NMR谱以及透射电镜对铝改性硅溶胶与硼改性硅溶胶进行了结构形态与特征的分析研究，首次提出了铝改性粒硅溶胶与硼改性硅溶胶微粒硅溶胶的结构和形态特征。
通过几种絮聚模型-DDJ动态滤水仪法、结合激光粒度仪研究絮团大小的变化以及纸张匀度的比较，探讨了阳离子聚合物／改性硅溶胶微粒体系的絮聚过程与机理，为絮聚机理研究提供了一种新的思路和较简便的方法。阳离子聚合物／改性硅溶胶微粒体系的絮聚机理是，先加入阳离子聚合物，纤维与细小组分絮聚成大的絮聚体，受到高剪切力作用，初始絮聚体被打散成小碎块，为带负电荷的改性硅溶胶微粒暴露出更多的链圈和链尾。改性硅溶胶微粒就在这些吸附于不同纸料粒子上的链圈和链尾之间，靠静电中和以及与聚合物中非带电段的配合吸附作用，改性硅溶胶微粒粒径小只能使近距离的细小碎块桥联作用而发生重新絮聚，形成较初始絮聚体更小、更均一、致密的絮团网络。结果可以大幅度提高了细小纤维和填料的留着率，改善了纸料的滤水性，同时，又可获得良好的纸页匀度。
The preparation and their application in papermaking of aluminium modified silica sol (AMS) and boron modified silica sol (BMS) were first investigated in China. The retention and drainage efficiency of AMS and BMS were superior to that of imported silica sol NP882 and the retention and drainage efficiency of BMS was superior to that of AMS. The optimal conditions before modification were 8% alkali dosage, heat temperature T12 and heat time 90 minutes. And the optimal conditions of aluminium modification were modification degree A3, temperature T24 and reaction time about an hour. Or that of B/Si was 0.08-0.1.Ultrafiltration instrument was selected to condense BMS and its optimal conditions were 3.5kPa pressure with 10 million molecular weight membrane at room temperature. In order to improve the stability of high concentration silica sol, anion or no ion surface actives could be useful. 0.01% DBS was found to be the best dispersant and had almost no effect on silica sol which was in favor of its commerciality.Characteristic application process and electrochemistry performance of cationic polymers/modified silica sol (MS) were systemically studied, It was found that CS/MS microparticle retention and drainage aid system had better retention and drainage efficiency in the high shear condition than CS single retention aid system, meantime CS/BMS system was better than CS/AMS system. MS microparticle retention and drainage aid systems were applicable to pulp with high fines such as waste pulp and wheat straw pulp. Seen from the effects of MS microparticle retention and drainage aid systems on wood pulp and waste pulp, CS and CPAM/MS system had better retention and drainage efficiency than CS/MS system and CPAM/MS system. But CS/MS system had best retention and drainage efficiency in wheat straw pulp. In all pulp BMS had better retention and drainage effiency than AMS. CS/MS microparticle retention and drainage aid system was preferably applicable in pH value 4-8 and resin sizing systems with less than 3% aluminium sulfate. This system had good resist capability to electrolyte interfere so that cycle water with less than 100mM electrolyte could be used resulting in less water resource polluted and wasted.Flocculation mechanism of microparticle retention and drainage aid system was investigated with DDJ, Laser size instrument and paper formation which was a new ideal and simple method. The research results showed that in the addition of cationic polymer fibers and fines flocculated and broken up with high shear then more chain loops and tails were exposed and bridged by negative MS. Due to MS was microparticle and had high specific surface area and high negative charge density it made close fragments flocculated into smaller and more uniform and compact floc net so that it improved retention and drainage with excellent formation.
引文
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