非离子助留助滤体的凝胶絮凝机理的研究
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摘要
本论文在大量实验事实的基础上提出了凝胶助留助滤机理,建立了机理模型。用聚氧化乙烯(PEO)-酚醛树脂助留助滤体系验证凝胶助留助滤机理,沿着凝胶助留助滤机理这一思路成功开发了PEO-硅溶胶新型双元助留助滤体系。最后对凝胶助留助滤机理进行了总结和推广,使其具有更广泛的应用范围,并为未来的研究提供了参考方向：
1.实验证明能够形成凝胶的物质在相应条件下都对浆料有一定的絮聚作用。只是由于受到各种因素的影响絮聚效果各有不同,如PEO-酚醛树脂凝胶体系、PEO-硅溶胶凝胶体系、PEO-膨润土凝胶体系具有良好的絮聚效果,能够或已经开发成为有效的助留助滤体系；聚丙烯酸钠(PAAS)-PEO体系和甲基纤维素(MC)尽管对浆料也有明显的絮聚效果,但由于PAAS对金属离子敏感、MC在其凝胶温度(63℃左右)以上才产生絮聚效果,因此这两种体系实际应用时可能存在较大困难；而PAAS-聚乙二醇(PEG)凝胶体系的絮聚效果则较差。
2.PEO-酚醛树脂体系的助留助滤效果与PEO-酚醛树脂凝胶的自身性质存在千丝万缕的联系：当PEO用量一定时,酚醛树脂用量在约为该量的5倍时获得做大的凝胶量,而当酚醛树脂用量为PEO用量的5倍时,浆料可获得最大的细小组分留着率;在酸性条件下,PEO-酚醛树脂凝胶的强度较差,而此时PEO-酚醛树脂助留助滤体系的抗剪切性能也比中碱性条件下差。
3.根据凝胶助留助滤机理这一思路发现PEO-硅溶胶体系对浆料具有明显的絮聚效果,进一步的研究表明该体系在较低的用量下具有良好的助留助滤效果,能够成为一种新型双元助留助滤体系。当PEO用量为0.01%、硅溶胶用量为0.1%时,浆料打浆度可由54°SR下降至31°SR左右,细小组分留着率和填料可达到90%左右。除此之外,该助留助滤体系对纸张匀度、强度和白度影响较小,可用于文化用纸的抄造。
4.已知外部环境变化是引起凝胶收缩脱水的根本原因,也是凝胶助留助滤机理的根本原因。但研究发现在外部环境既定的情况下凝胶助留助滤机理则与助留助滤体系产生的凝胶量(凝胶量与凝胶各组分浓度、配比及分子量等有关)、凝胶的收缩脱水时间、凝胶的强度和弹性等因素有直接关系。从这一角度考虑造纸湿部较适用于温度和pH敏感型凝胶,即会响应温度或pH值变化而收缩脱水的凝胶体系,如羟丙基纤维素(HPC)的凝胶温度为40～45℃,可能产生与甲基纤维素相似的絮聚效果；聚乙烯基吡咯烷酮(PVP)在中性或酸性条件下可与多种物质作用形成络合物。这些凝胶体系构成了凝胶助留助滤机理新的研究方向。
5.凝胶助留助滤机理认为阳离子助留助滤剂及微粒助留助滤体系是通过静电耦合作用或螯合作用与纤维和填料共同形成了一种特殊的三维网状结构而实现助留助滤目的的,拓宽了凝胶助留助滤机理的应用范围。
In this thesis, gel retention and drainage mechanism was put forward on the basis of many experiments, and a mechanism model was established too. Polyethylene oxide(PEO)-phenolic resin(PR) retention system was used to inspect and verify gel retention and drainage mechanism. A new dual PEO-silica sol two-component retention and drainage aids system was successfully developed along the idea of gel retention mechanism. In the end of the thesis, gel retention and drainage mechanism was summarized and popularized, it will gain a broader range of applications and provide a reference direction for future researches.
1. Experiments showed that the materials which could gelate all had a flocculation effect on pulp under the same conditions. But their flocculation effects were different due to various influence factors. For example PEO-PR gel system, PEO-silica gel system and PEO-bentonite gel system had good flocculation effect. And they can/have become effective retention systems. Polyacrylate sodium(PAAS)-PEO system and methylcellulose(MC) both had perfect flocculation effect on pulp too, but PAAS was very sensitive to metallic ion and MC didn't gain a good flocculation before the pulp temperature reached the gelatum temperature of MC(which is about 63℃) or above, so PAAS-PEO system and MC used for retention system was more difficult than PEO-PR system. And flocculation effect of PAAS-PEG gel system was poor.
2. Retention and drainage effect of PEO-PR resin system was related to the nature of PEO-phenolic resin gel itself: if the consistency of PEO was assured most gel amount was gained when the dosage of PR was about 5 times as much as the amount of PEO; and the biggest fines retention was obtained as phenolic resin was just 5 times the dosage of PEO. In acidic condition, strength of PEO-PR gel was poor, while in neutral and alkaline conditions the shear resistance of PEO-PR retention system was preferred to in acidic condition.
3. According to gel retention and drainage mechanism, PEO-silica system was found obvious flocculation effects on pulp; further research showed that this system had good retention and drainage effects at low dosage. When the dosage of PEO was 0.01% and silica was 0.1%, the beating degree reduced from 54°SR to 31°SR; fines retention and filler retention reached 90%. In addition, this retention system affected little on the paper evenness, strength and whiteness.
4. It is known that changes in the external environment are the root cause of dehydration and shrinkage of gel and the gel retention mechanism. However, under the given external environment, gel retention mechanism is directly related to gel amount the systems produce (amount of gel is related to concentration, molecular weight and mixture ratio of gel components and so on), the gel contraction and dehydration time, gel strength and elasticity and other factors. From this point of view, humid part of paper is suitable for thermo-responsive hydro gel and pH sensitive gel which respond to changes of temperature or pH and then dehydrate and shrink, such as Hydroxypropylcellulose(HPC) which gelatum temperature is 40-45℃is likely to produce a flocculation effect as MC, and polyvinyl pyrrolidone (PVP) forms complex compound with many chemical compound in neutral or acidic condition. These gels are the new research directions of retention and drainage mechanism.
5. During the gel retention and drainage retention mechanism, cationic retention systems and particulate retention systems work with fiber and filler to form a special three-dimensional network structure via electrostatic coupling or chelating, which achieve the filtering purposes and broaden application ranges of gel retention and drainage mechanism.
1.实验证明能够形成凝胶的物质在相应条件下都对浆料有一定的絮聚作用。只是由于受到各种因素的影响絮聚效果各有不同,如PEO-酚醛树脂凝胶体系、PEO-硅溶胶凝胶体系、PEO-膨润土凝胶体系具有良好的絮聚效果,能够或已经开发成为有效的助留助滤体系；聚丙烯酸钠(PAAS)-PEO体系和甲基纤维素(MC)尽管对浆料也有明显的絮聚效果,但由于PAAS对金属离子敏感、MC在其凝胶温度(63℃左右)以上才产生絮聚效果,因此这两种体系实际应用时可能存在较大困难；而PAAS-聚乙二醇(PEG)凝胶体系的絮聚效果则较差。
2.PEO-酚醛树脂体系的助留助滤效果与PEO-酚醛树脂凝胶的自身性质存在千丝万缕的联系：当PEO用量一定时,酚醛树脂用量在约为该量的5倍时获得做大的凝胶量,而当酚醛树脂用量为PEO用量的5倍时,浆料可获得最大的细小组分留着率;在酸性条件下,PEO-酚醛树脂凝胶的强度较差,而此时PEO-酚醛树脂助留助滤体系的抗剪切性能也比中碱性条件下差。
3.根据凝胶助留助滤机理这一思路发现PEO-硅溶胶体系对浆料具有明显的絮聚效果,进一步的研究表明该体系在较低的用量下具有良好的助留助滤效果,能够成为一种新型双元助留助滤体系。当PEO用量为0.01%、硅溶胶用量为0.1%时,浆料打浆度可由54°SR下降至31°SR左右,细小组分留着率和填料可达到90%左右。除此之外,该助留助滤体系对纸张匀度、强度和白度影响较小,可用于文化用纸的抄造。
4.已知外部环境变化是引起凝胶收缩脱水的根本原因,也是凝胶助留助滤机理的根本原因。但研究发现在外部环境既定的情况下凝胶助留助滤机理则与助留助滤体系产生的凝胶量(凝胶量与凝胶各组分浓度、配比及分子量等有关)、凝胶的收缩脱水时间、凝胶的强度和弹性等因素有直接关系。从这一角度考虑造纸湿部较适用于温度和pH敏感型凝胶,即会响应温度或pH值变化而收缩脱水的凝胶体系,如羟丙基纤维素(HPC)的凝胶温度为40～45℃,可能产生与甲基纤维素相似的絮聚效果；聚乙烯基吡咯烷酮(PVP)在中性或酸性条件下可与多种物质作用形成络合物。这些凝胶体系构成了凝胶助留助滤机理新的研究方向。
5.凝胶助留助滤机理认为阳离子助留助滤剂及微粒助留助滤体系是通过静电耦合作用或螯合作用与纤维和填料共同形成了一种特殊的三维网状结构而实现助留助滤目的的,拓宽了凝胶助留助滤机理的应用范围。
In this thesis, gel retention and drainage mechanism was put forward on the basis of many experiments, and a mechanism model was established too. Polyethylene oxide(PEO)-phenolic resin(PR) retention system was used to inspect and verify gel retention and drainage mechanism. A new dual PEO-silica sol two-component retention and drainage aids system was successfully developed along the idea of gel retention mechanism. In the end of the thesis, gel retention and drainage mechanism was summarized and popularized, it will gain a broader range of applications and provide a reference direction for future researches.
1. Experiments showed that the materials which could gelate all had a flocculation effect on pulp under the same conditions. But their flocculation effects were different due to various influence factors. For example PEO-PR gel system, PEO-silica gel system and PEO-bentonite gel system had good flocculation effect. And they can/have become effective retention systems. Polyacrylate sodium(PAAS)-PEO system and methylcellulose(MC) both had perfect flocculation effect on pulp too, but PAAS was very sensitive to metallic ion and MC didn't gain a good flocculation before the pulp temperature reached the gelatum temperature of MC(which is about 63℃) or above, so PAAS-PEO system and MC used for retention system was more difficult than PEO-PR system. And flocculation effect of PAAS-PEG gel system was poor.
2. Retention and drainage effect of PEO-PR resin system was related to the nature of PEO-phenolic resin gel itself: if the consistency of PEO was assured most gel amount was gained when the dosage of PR was about 5 times as much as the amount of PEO; and the biggest fines retention was obtained as phenolic resin was just 5 times the dosage of PEO. In acidic condition, strength of PEO-PR gel was poor, while in neutral and alkaline conditions the shear resistance of PEO-PR retention system was preferred to in acidic condition.
3. According to gel retention and drainage mechanism, PEO-silica system was found obvious flocculation effects on pulp; further research showed that this system had good retention and drainage effects at low dosage. When the dosage of PEO was 0.01% and silica was 0.1%, the beating degree reduced from 54°SR to 31°SR; fines retention and filler retention reached 90%. In addition, this retention system affected little on the paper evenness, strength and whiteness.
4. It is known that changes in the external environment are the root cause of dehydration and shrinkage of gel and the gel retention mechanism. However, under the given external environment, gel retention mechanism is directly related to gel amount the systems produce (amount of gel is related to concentration, molecular weight and mixture ratio of gel components and so on), the gel contraction and dehydration time, gel strength and elasticity and other factors. From this point of view, humid part of paper is suitable for thermo-responsive hydro gel and pH sensitive gel which respond to changes of temperature or pH and then dehydrate and shrink, such as Hydroxypropylcellulose(HPC) which gelatum temperature is 40-45℃is likely to produce a flocculation effect as MC, and polyvinyl pyrrolidone (PVP) forms complex compound with many chemical compound in neutral or acidic condition. These gels are the new research directions of retention and drainage mechanism.
5. During the gel retention and drainage retention mechanism, cationic retention systems and particulate retention systems work with fiber and filler to form a special three-dimensional network structure via electrostatic coupling or chelating, which achieve the filtering purposes and broaden application ranges of gel retention and drainage mechanism.
引文
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