阳离子型聚丙烯酰胺类絮凝剂的合成及性能研究
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摘要
絮凝法是废水处理中简单经济、应用广泛的方法,絮凝效果的好坏取决于絮凝剂的种类及性质。由于废水中的悬浮物表面带负电荷的微粒居多,所以阳离子型的丙烯酰胺絮凝剂成为研究的重点。对阳离子型丙烯酰胺絮凝剂进行改性,可以降低成本、减少环境污染。
本文在分析总结已有絮凝剂的基础上以丙烯酰胺(AM)、二甲基二烯丙基氯化铵(DMDAAC)、玉米淀粉为原料,采用复合引发剂,通过水溶液聚合法制备了阳离子聚丙烯酰胺(CPAM)及淀粉接枝阳离子聚丙烯酰胺(St-g-CPAM)两种絮凝剂。系统分析了引发剂种类及用量、反应温度、反应时间、单体质量分数及配比等对产物分子量、转化率、接枝率等方面的影响；通过浊度去除率表征了絮凝剂的絮凝效果；采用热重分析(TG)、红外光谱(IR)和电子扫描显微镜(SEM)对产物的热行为和微观结构进行了表征。
通过实验得到了阳离子丙烯酰胺的最佳聚合条件：聚合温度55℃,甲醛次硫酸氢钠与过硫酸铵(质量比为4：3)总质量分数0.0125%,偶氮二异丁脒盐酸盐(V-50)的质量分数0.0125%,单体质量分数35%,阳离子单体质量分数35%；在最佳工艺条件下,所得阳离子聚丙烯酰胺絮凝剂的分子量为2.5×106。淀粉接枝阳离子聚丙烯酰胺絮凝剂的最佳工艺条件为：反应温度60℃,硝酸铈铵质量分数0.5%,V-50质量分数为0.0125%,AM和DMDAAC(质量比为7：3)的总单体质量分数20%;在最佳工艺条件下制得的淀粉接枝丙烯酰胺阳离子共聚物,其单体转化率为46.7%,接枝率为92.5%,接枝效率为99.7%。两种絮凝剂都具有良好的絮凝效果。
Flocculation is a simple, economic and widely adopted method in wastewater treatment. Because most of the wastewater's suspensions are negative charges, the cationic polyacrylamide (CPAM) flocculant has attracted much attention both in research and industry. Efforts have been made to modify CPAM with starch in order to reduce the high prices and slove its environmental pollution problems.
CPAM has been synthesized by acrylamide (AM), dimethyl diallyl ammonium chloride (DMDAAC) with solution polymerization. Cationic polyacrylamide grafted starch (St-g-CPAM) has been synthesized by acrylamide (AM), dimethyl diallyl ammonium chloride (DMDAAC) and starch with a multiple initiator with solution polymerization. The effects of initiator ratio, reaction temperature, the monomer concentration and proportion of AM and DMDAAC on the molecular weight, the efficiency of grafting and the yield of grafting were investigated. The flocculation capability has been evaluated by turbidity reduction. The thermal behavior, chemical structure and microstructure of CPAM and St-g-CPAM were also characterized by thermal gravimetric (TG), IR and SEM.
The results show that the optimal conditions of the polymerization on CPAM are as follows:the reaction temperature is 55℃, total mass fraction of (NH4)2S2O8 and NaHSO3.CH2O.2H2O is 0.0125%, mass ratio of NaHSO3.CH2O.2H2O/(NH4)2S2O8 is 4:3, mass fraction of C8H18N6.2HCl(V-50) compounds is 0.0125%, monomer concentration is 35%, cationic monomer concentration is 35%. The optimal conditions of the polymerization on St-g-CPAM are:the concentration of ceric ammonium nitrate is 0.5%, the mass fraction of C8H18N6.2HCl(V-50) compounds is 0.0125%, the reaction temperature is 60℃, the concentration of total monomer is 20%, the monomer ratio between acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) is 7:3. It is suggested that CPAM with a molecular weight of 2.5×106 and St-g-CPAM with a grafting percentage of 92.5% and grafting efficiency of 99.7% have strong flocculation capability.
本文在分析总结已有絮凝剂的基础上以丙烯酰胺(AM)、二甲基二烯丙基氯化铵(DMDAAC)、玉米淀粉为原料,采用复合引发剂,通过水溶液聚合法制备了阳离子聚丙烯酰胺(CPAM)及淀粉接枝阳离子聚丙烯酰胺(St-g-CPAM)两种絮凝剂。系统分析了引发剂种类及用量、反应温度、反应时间、单体质量分数及配比等对产物分子量、转化率、接枝率等方面的影响；通过浊度去除率表征了絮凝剂的絮凝效果；采用热重分析(TG)、红外光谱(IR)和电子扫描显微镜(SEM)对产物的热行为和微观结构进行了表征。
通过实验得到了阳离子丙烯酰胺的最佳聚合条件：聚合温度55℃,甲醛次硫酸氢钠与过硫酸铵(质量比为4：3)总质量分数0.0125%,偶氮二异丁脒盐酸盐(V-50)的质量分数0.0125%,单体质量分数35%,阳离子单体质量分数35%；在最佳工艺条件下,所得阳离子聚丙烯酰胺絮凝剂的分子量为2.5×106。淀粉接枝阳离子聚丙烯酰胺絮凝剂的最佳工艺条件为：反应温度60℃,硝酸铈铵质量分数0.5%,V-50质量分数为0.0125%,AM和DMDAAC(质量比为7：3)的总单体质量分数20%;在最佳工艺条件下制得的淀粉接枝丙烯酰胺阳离子共聚物,其单体转化率为46.7%,接枝率为92.5%,接枝效率为99.7%。两种絮凝剂都具有良好的絮凝效果。
Flocculation is a simple, economic and widely adopted method in wastewater treatment. Because most of the wastewater's suspensions are negative charges, the cationic polyacrylamide (CPAM) flocculant has attracted much attention both in research and industry. Efforts have been made to modify CPAM with starch in order to reduce the high prices and slove its environmental pollution problems.
CPAM has been synthesized by acrylamide (AM), dimethyl diallyl ammonium chloride (DMDAAC) with solution polymerization. Cationic polyacrylamide grafted starch (St-g-CPAM) has been synthesized by acrylamide (AM), dimethyl diallyl ammonium chloride (DMDAAC) and starch with a multiple initiator with solution polymerization. The effects of initiator ratio, reaction temperature, the monomer concentration and proportion of AM and DMDAAC on the molecular weight, the efficiency of grafting and the yield of grafting were investigated. The flocculation capability has been evaluated by turbidity reduction. The thermal behavior, chemical structure and microstructure of CPAM and St-g-CPAM were also characterized by thermal gravimetric (TG), IR and SEM.
The results show that the optimal conditions of the polymerization on CPAM are as follows:the reaction temperature is 55℃, total mass fraction of (NH4)2S2O8 and NaHSO3.CH2O.2H2O is 0.0125%, mass ratio of NaHSO3.CH2O.2H2O/(NH4)2S2O8 is 4:3, mass fraction of C8H18N6.2HCl(V-50) compounds is 0.0125%, monomer concentration is 35%, cationic monomer concentration is 35%. The optimal conditions of the polymerization on St-g-CPAM are:the concentration of ceric ammonium nitrate is 0.5%, the mass fraction of C8H18N6.2HCl(V-50) compounds is 0.0125%, the reaction temperature is 60℃, the concentration of total monomer is 20%, the monomer ratio between acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) is 7:3. It is suggested that CPAM with a molecular weight of 2.5×106 and St-g-CPAM with a grafting percentage of 92.5% and grafting efficiency of 99.7% have strong flocculation capability.
引文
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