SO_4～（2-）和/或SiO_3～（2-）对部分水解铝盐混凝剂性能的影响研究
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摘要
本论文在综合国内外大量相关文献的基础上，对SO_4~(2-)和/或SiO_3~(2-)对部分水解铝盐混凝剂中铝形态及性能的影响进行了研究。同时对含SO_4~(2-)和/或SiO_3~(2-)复合混凝剂的形态的分析表征和定量计算、结构形貌、水解过程以及混凝动态过程等问题进行了较为系统的探讨。主要研究内容及结论如下：
1．Al-Ferron反应动力学曲线可以反映整个反应时间内混凝剂的铝形态与Ferron反应的情况，聚合铝盐混凝剂的Al-Ferron反应动力学曲线符合假一级化学反应方程式，Al-Ferron反应动力学法计算的铝水解形态与Al-Ferron反应过程的实验结果和~(27)Al-NMR法测定结果非常一致，可以很好的反映复合混凝剂的水解形态，避免了人为划分反应时间带来的误差。
2．Al-Ferron法和~(27)Al-NMR法的计算结果表明，在PAC的制备过程中，SO_4~(2-)和/或SiO_3~(2-)的存在都会抑制具有较好混凝性能的Al_b和Al_(13)形态的形成，SO_4~(2-)的抑制作用比SiO_3~(2-)的影响更为明显。其中，SO_4~(2-)的存在使AlCl_3的水解过程向聚合方向进行，趋于形成更大的聚集体，SiO_3~(2-)的存在使AlCl_3的水解过程向水解方向进行，趋于形成较小的聚集体。
3．SO_4~(2-)和/或SiO_3~(2-)与铝水解形态之间的相互作用会影响混凝剂的混凝性能。红外光谱结果表明，少量SO_4~(2-)存在使PAC中H-O-H水分子弯曲振动和Al-O八面体中Al-OH伸缩振动明显增强，分子间氢键O-H伸缩振动随SO_4~(2-)增加而增强至γ_(SO4/Al)=0.2时趋势逆转。SiO_3~(2-)的存在对PAC水解形态H-O-H水分子弯曲振动、Al-O八面体中Al-OH伸缩振动和分子间氢键O-H伸缩振动的影响较SO_4~(2-)弱，但随γ_(Si/Al)增加呈明显增强趋势。
4．混凝剂的透射和扫描电镜观察表明PAC、PASiC_(0.10)和PACS_(0.10)三种混凝剂在贮存初期聚集体均呈枝状分布，其中PACS混凝剂中聚集体尺寸最大，聚集体晶粒在各分枝的外缘排列致密内部排列稍松散；PAC中聚集体尺寸次之，晶粒基本在各分枝的外缘紧密排列，内部晶粒很少；PASiC混凝剂聚集体尺寸最小但数量最多且晶粒排列最紧密。随贮存时间的延长，PAC和PACS
The influence of SO_4~(2-) and /or SiO_3~(2-) on Al (III) properties and flocculation efficiency is explored in this paper. Meanwhile, Al (III) species calculation, interactions of SO_4~(2-) and/or SiO_3~(2-) with Al (III) species, surface morphology, hydrolysis and flocculation dynamic of Polyaluminum flocculants containing SO_4~(2-) and /or SiO_3~(2-) are investigated. The main research and conclusions are as follows:
1. A new Al-Ferron kinetics method was developed to monitor and calculate Al speciation. The results showed that the Al-Ferron kinetics fit a binary pseudo 1st order rate equation. Sulfate and silicate had different influences on Al-Ferron kinetics. Al-Ferron complexation timed spectrophotometry is the commonly used method of determining Al speciation but this new Al-Ferron kinetics calculation method shows different species distributions. For all the flocculants except polyaluminum silicate chloride (PASiC), the new method yielded higher Alb and lower Al_a values. The Al (III) chemical species calculated using Al-Ferron kinetics is more consistent with the Al-Ferron reaction results and ~(27)Al NMR results.
2. The results of Al (III) speciation calculated using Al-Ferron kinetics and ~(27)A1 NMR method showed, on one hand , that the presence of SO_4~(2-) and /or SiO_3~(2-) inhibited forming Al_b/or Al_(13) species during polyaluminum prehydrolysis. And this effect of the presence of SO_4~(2-) was more obvious than that of SiO_3~(2-) On the other hand, the inhibition of SO_4~(2-) and SiO_3~(2-)on Al_b/or Al_(13) formation was in different direction. SO_4~(2-) tended to aggregate and form larger polymers while SiO_3~(2-) tended to disaggregate and form smaller polymers.
1．Al-Ferron反应动力学曲线可以反映整个反应时间内混凝剂的铝形态与Ferron反应的情况，聚合铝盐混凝剂的Al-Ferron反应动力学曲线符合假一级化学反应方程式，Al-Ferron反应动力学法计算的铝水解形态与Al-Ferron反应过程的实验结果和~(27)Al-NMR法测定结果非常一致，可以很好的反映复合混凝剂的水解形态，避免了人为划分反应时间带来的误差。
2．Al-Ferron法和~(27)Al-NMR法的计算结果表明，在PAC的制备过程中，SO_4~(2-)和/或SiO_3~(2-)的存在都会抑制具有较好混凝性能的Al_b和Al_(13)形态的形成，SO_4~(2-)的抑制作用比SiO_3~(2-)的影响更为明显。其中，SO_4~(2-)的存在使AlCl_3的水解过程向聚合方向进行，趋于形成更大的聚集体，SiO_3~(2-)的存在使AlCl_3的水解过程向水解方向进行，趋于形成较小的聚集体。
3．SO_4~(2-)和/或SiO_3~(2-)与铝水解形态之间的相互作用会影响混凝剂的混凝性能。红外光谱结果表明，少量SO_4~(2-)存在使PAC中H-O-H水分子弯曲振动和Al-O八面体中Al-OH伸缩振动明显增强，分子间氢键O-H伸缩振动随SO_4~(2-)增加而增强至γ_(SO4/Al)=0.2时趋势逆转。SiO_3~(2-)的存在对PAC水解形态H-O-H水分子弯曲振动、Al-O八面体中Al-OH伸缩振动和分子间氢键O-H伸缩振动的影响较SO_4~(2-)弱，但随γ_(Si/Al)增加呈明显增强趋势。
4．混凝剂的透射和扫描电镜观察表明PAC、PASiC_(0.10)和PACS_(0.10)三种混凝剂在贮存初期聚集体均呈枝状分布，其中PACS混凝剂中聚集体尺寸最大，聚集体晶粒在各分枝的外缘排列致密内部排列稍松散；PAC中聚集体尺寸次之，晶粒基本在各分枝的外缘紧密排列，内部晶粒很少；PASiC混凝剂聚集体尺寸最小但数量最多且晶粒排列最紧密。随贮存时间的延长，PAC和PACS
The influence of SO_4~(2-) and /or SiO_3~(2-) on Al (III) properties and flocculation efficiency is explored in this paper. Meanwhile, Al (III) species calculation, interactions of SO_4~(2-) and/or SiO_3~(2-) with Al (III) species, surface morphology, hydrolysis and flocculation dynamic of Polyaluminum flocculants containing SO_4~(2-) and /or SiO_3~(2-) are investigated. The main research and conclusions are as follows:
1. A new Al-Ferron kinetics method was developed to monitor and calculate Al speciation. The results showed that the Al-Ferron kinetics fit a binary pseudo 1st order rate equation. Sulfate and silicate had different influences on Al-Ferron kinetics. Al-Ferron complexation timed spectrophotometry is the commonly used method of determining Al speciation but this new Al-Ferron kinetics calculation method shows different species distributions. For all the flocculants except polyaluminum silicate chloride (PASiC), the new method yielded higher Alb and lower Al_a values. The Al (III) chemical species calculated using Al-Ferron kinetics is more consistent with the Al-Ferron reaction results and ~(27)Al NMR results.
2. The results of Al (III) speciation calculated using Al-Ferron kinetics and ~(27)A1 NMR method showed, on one hand , that the presence of SO_4~(2-) and /or SiO_3~(2-) inhibited forming Al_b/or Al_(13) species during polyaluminum prehydrolysis. And this effect of the presence of SO_4~(2-) was more obvious than that of SiO_3~(2-) On the other hand, the inhibition of SO_4~(2-) and SiO_3~(2-)on Al_b/or Al_(13) formation was in different direction. SO_4~(2-) tended to aggregate and form larger polymers while SiO_3~(2-) tended to disaggregate and form smaller polymers.
引文
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