纳米级聚合氯化铝制备及提纯分离研究
摘要
本文在总结前期已有研究工作的基础上，采用了多种方法在不同条件下制备了聚合氯化铝絮凝剂PAC，并使用Al-Ferron逐时络合比色法对其中的聚合形态分布特征进行了分析；采用硫酸根沉淀／钡盐置换的方法对PAC中的有效成分Al_b进行了提纯分离实验，主要实验结果如下：
1．本文中主要使用NaOH中和AlCl_3的方法制备聚合氯化铝。制得的PAC的形态组成及分布不仅受到碱化度的影响，其制备方法及制备条件对Al_b组分的含量也有重要的影响。如果使用较慢而且速率均匀的滴碱方式，同时保证液滴的细小及分散的快速，就不易出现局部碱浓度过高而导致Al(OH)_3沉淀的现象；在制备较高碱化度(B=2.5左右)的PAC时，使用较高的反应温度(80℃)有利于聚合体结构重排形成Al_b中的Ferron慢反应部分而不是Al(OH)_3沉淀，从而提高产物中Al_b组分的含量。
2．聚合氯化铝与硫酸根的沉淀反应的实验结果表明，碱化度对PAC／SO_4~(2-)反应体系有较大影响，随着碱化度(B值)的增加，沉淀／结晶的析出速率加快，结晶析出物中SO_4~(2-)／Al的比率下降，由不同形态聚合铝生成的沉淀物的表面形貌也存在着较大的差异。各聚合铝水解形态与SO_4~(2-)反应速率上存在明显差异，从而为其混凝优势形态的分离纯化创造了条件；在不同碱化度以及Al／SO_4~(2-)摩尔比的条件下，使用含有较高Al_b含量的B=2.2的PAC与硫酸根按照1∶1左右的比例投加对Al_b，Al_c的沉淀效果最佳。
3．前驱体PAC形态分布的复杂性，导致了它与硫酸根反应必然产生各种形貌，物化性质存在差异的沉淀／结晶物质，这些物质与Ba~(2+)的反应也是一个复杂的过程。反应物摩尔比，超声时间，反应温度乃至沉淀物分散状况均会影响到Al_b的产率。使用低温烘干的粉末虽然在超声反应中较易分散，但是由于烘干过程会加速聚合铝的熟化，因此前处理使用离心分离更有利于保证最终产物中Al_b组分的含量；实验结果证明Ba~(2+)／SO_4~(2-)为1∶1足以最大限度的将Al_b组分从沉淀物中提纯出来。
Based on the previous research achievements in this laboratory, the preparation, characterization, and purification of Alo were investigated in detail in this thesis. Various methods have been carried out on the preparation of PAC, which has been characterized for the speciation distribution by using Perron assay. Further experiments were then carried out on the optimum separation of the most important species-Al13 in PAC. The main results have been reached as following:
1. The PAC samples were prepared using alkalinity titration method under normal laboratory conditions. The speciation and quantity of Al13 were decided largely by basicity. It was also favorable for the yield of Al13 under slow titration rate by avoiding the local high concentration of alkalinity. As result, the base drop could be dissolved rapidly without forming A1(OH)3 precipitation. It is observed that the quantity of Alb could be largely improved at B=2.5 under moderate high temperature (80@). The low speed reaction part in PAC during Perron assay is formed through aggregation of Alb instead of Al(OH)3.
2. The basicity exhibits significant role in the reaction of PAC with sulfate. Increase the basicity, the speed of precipitation/crystallization is largely increased. The SO42-7/Al in the solids formed decreases with the increase of basicity. The morphology of solids formed differs markedly among the various PAC. The various species in PAC exhibit quite different ratio in reacting with sulfate. It is therefore possible to separate the various species in PAC by reacting with sulfate. It is observed that the SO4/Al ratio of 1:1 is optimum for the separation of Al13 from the B=2.2 PAC.
3. The complicated components of PAC species result in the complicated reaction pathways of sulfate with PAC and reaction products as well. The purification of Al13 is then different for the subsequent reaction of Ba with the various precipitates. The mole ratio of Ba2+/SO42-, ultrasonic reaction time, temperature and dispersion of precipitates have significant influence on the yield of Al13. The wet method exhibits some efficiency against the power method. A Ba2+/SO42" ratio of 1:1 is enough to separate the Al13 in the precipitates.
1．本文中主要使用NaOH中和AlCl_3的方法制备聚合氯化铝。制得的PAC的形态组成及分布不仅受到碱化度的影响，其制备方法及制备条件对Al_b组分的含量也有重要的影响。如果使用较慢而且速率均匀的滴碱方式，同时保证液滴的细小及分散的快速，就不易出现局部碱浓度过高而导致Al(OH)_3沉淀的现象；在制备较高碱化度(B=2.5左右)的PAC时，使用较高的反应温度(80℃)有利于聚合体结构重排形成Al_b中的Ferron慢反应部分而不是Al(OH)_3沉淀，从而提高产物中Al_b组分的含量。
2．聚合氯化铝与硫酸根的沉淀反应的实验结果表明，碱化度对PAC／SO_4~(2-)反应体系有较大影响，随着碱化度(B值)的增加，沉淀／结晶的析出速率加快，结晶析出物中SO_4~(2-)／Al的比率下降，由不同形态聚合铝生成的沉淀物的表面形貌也存在着较大的差异。各聚合铝水解形态与SO_4~(2-)反应速率上存在明显差异，从而为其混凝优势形态的分离纯化创造了条件；在不同碱化度以及Al／SO_4~(2-)摩尔比的条件下，使用含有较高Al_b含量的B=2.2的PAC与硫酸根按照1∶1左右的比例投加对Al_b，Al_c的沉淀效果最佳。
3．前驱体PAC形态分布的复杂性，导致了它与硫酸根反应必然产生各种形貌，物化性质存在差异的沉淀／结晶物质，这些物质与Ba~(2+)的反应也是一个复杂的过程。反应物摩尔比，超声时间，反应温度乃至沉淀物分散状况均会影响到Al_b的产率。使用低温烘干的粉末虽然在超声反应中较易分散，但是由于烘干过程会加速聚合铝的熟化，因此前处理使用离心分离更有利于保证最终产物中Al_b组分的含量；实验结果证明Ba~(2+)／SO_4~(2-)为1∶1足以最大限度的将Al_b组分从沉淀物中提纯出来。
Based on the previous research achievements in this laboratory, the preparation, characterization, and purification of Alo were investigated in detail in this thesis. Various methods have been carried out on the preparation of PAC, which has been characterized for the speciation distribution by using Perron assay. Further experiments were then carried out on the optimum separation of the most important species-Al13 in PAC. The main results have been reached as following:
1. The PAC samples were prepared using alkalinity titration method under normal laboratory conditions. The speciation and quantity of Al13 were decided largely by basicity. It was also favorable for the yield of Al13 under slow titration rate by avoiding the local high concentration of alkalinity. As result, the base drop could be dissolved rapidly without forming A1(OH)3 precipitation. It is observed that the quantity of Alb could be largely improved at B=2.5 under moderate high temperature (80@). The low speed reaction part in PAC during Perron assay is formed through aggregation of Alb instead of Al(OH)3.
2. The basicity exhibits significant role in the reaction of PAC with sulfate. Increase the basicity, the speed of precipitation/crystallization is largely increased. The SO42-7/Al in the solids formed decreases with the increase of basicity. The morphology of solids formed differs markedly among the various PAC. The various species in PAC exhibit quite different ratio in reacting with sulfate. It is therefore possible to separate the various species in PAC by reacting with sulfate. It is observed that the SO4/Al ratio of 1:1 is optimum for the separation of Al13 from the B=2.2 PAC.
3. The complicated components of PAC species result in the complicated reaction pathways of sulfate with PAC and reaction products as well. The purification of Al13 is then different for the subsequent reaction of Ba with the various precipitates. The mole ratio of Ba2+/SO42-, ultrasonic reaction time, temperature and dispersion of precipitates have significant influence on the yield of Al13. The wet method exhibits some efficiency against the power method. A Ba2+/SO42" ratio of 1:1 is enough to separate the Al13 in the precipitates.
引文
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