基于钛盐的无机高分子复合絮凝剂的制备及其结构和性能研究
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摘要
基于新型絮凝剂聚硅硫酸钛(PTSS)的亲生物性,制备了多种基于钛盐的无机高分子复合絮凝剂(Ti-IPF)。筛选出适合工业化应用的聚硅硫酸钛铝(PTAS)和聚硅硫酸钛铁(PTFS)。通过实验得出合成PTAS和PTFS的最佳配比分别为n(Ti+Al):n(Si)=1:3、n(Ti):n(Al)=1:5和n(Ti+Fe):n(Si)=1:3、n(Ti):n(Fe)=1:5。
采用X-射线衍射、红外光谱、紫外漫反射光谱分析了PTSS、PTAS与PTFS的成键情况。分析表明:PTSS、PTAS与PTFS均具有框架钛结构(Ti-O-Si)。其中,PTSS是以Ti-O-Si作为骨架单元,与聚硅酸键合形成高分子分枝长链结构,分子量大。最佳配比的PTAS中的Ti4+、Al3+和PTFS中的Ti4+、Fe3+分别取代Si-O-Si中的Si或通过金属离子水解形成的表面的羟基与聚硅酸的Si-O-Si结合,形成具有一定分子量的分枝链状结构单元,分子量较聚硅酸大。通过絮凝剂PTSS、PTAS与PTFS聚合过程中的粒度变化以及Zeta电位测定,推断出PTSS的混凝机理主要是高分子链的架桥网捕与络合物表面的羟基吸附作用。而PTAS和PTFS的混凝机理主要是吸附电中和与络合物表面的羟基吸附网捕卷扫作用,桥联网捕作用均起辅助作用。
论文通过对模拟江水、乳化油废水和磷化废水的混凝实验表明:模拟江水的初始pH值为5.26～9.32、PTFS的投加量为0.3mmol/L时,除浊率达到99.8%。乳化油废水的初始pH值为7.15,PTAS和PTFS的投加量为0.4mmol/L时,对乳化油废水的除浊率分别达到92.5%和99.8%,CODCr的去除率分别达到99.6%和99.3%。采用中和絮凝沉淀法,磷化废水的最佳pH值中和至10.18时,总磷去除率达到99.8%。
In this work, According to a new type of inorganic polymer, poly-silicic titanium sulfate (PTSS), a variety of new inorganic polymeric flocculant titanium-based(Ti-IPF) were prepared by co-polymerization. Poly-silicic titanium-aluminum sulfate(PTAS) and poly-silicic titanium-iron sulfate(PTFS) were selected by industrial applications, The results showed that when the molar ratio of n(Ti+Al):n(Si) or n(Ti +Fe):n(Si) equal to 0.3, the molar ratio of n(Ti):n(Al) or n(Ti):n(Fe) equal to 0.2, the flocculants PTAS and PTFS were optimal.
Bonding mechanism of optimal PTSS, PTAS, PTFS was probed by XRD, IR, UV/Vis measurement. The analysis results shows that the framework titanium structure, Ti-O-Si was existed in PTSS, PTAS and PTFS. The flocculant PTSS possessed long-chain branched structure and big molecular weight, which was composed of the framework titanium structure Ti-O-Si and poly silicate bonded. In the strcture of optimal flocculants PTAS and PTFS,the silicon of Si-O-Si was replaced by metal ions, such as titanium ions, iron ions, and aluminum ions, or poly-hydroxy adsorption which was formed by metal ions hydrolysis, the molecular weight was larger than the poly-silicic acid. Then, the particle size in the polymerization process and the Zeta potential of the optimal PTSS, PTAS and PTFS were investigated, thereby conjectures that the coagulation mechanism of PTSS was mainly chain bridging, sweeping and surface poly-hydroxy adsorption. The coagulation mechanism of PTAS and PTFS were mainly adsorption-charge neutralization and the surface poly-hydroxy adsorption, other mechanisms play a supporting roles, such as the chain bridging, sweeping, and so on.
The optimal PTSS, PTAS and PTFS were used to treat simulation river water, emulsified oil wastewater and phosphating wastewater, coagulation experiments show that turbidity removal rate reached 99.8%, when the initial pH value of simulation river water was 5.26 to 9.32, the dosage of PTAS and PTFS were respectively 0.3 millimoles percent litre. when the initial pH value of emulsified oil wastewater was 7.15, the dosage of PTAS and PTFS was 0.4 millimoles percent litre, of emulsified oil wastewater turbidity removal rates were respectively 92.5% and 99.8%, the removal rate of CODCr were respectively 99.6% and 99.3%. The pH value of phosphating wastewater increased to 10.18 by neutralization of lime and coagulate of PTFS, the removal rate of phosphorus reached 99.8%.
采用X-射线衍射、红外光谱、紫外漫反射光谱分析了PTSS、PTAS与PTFS的成键情况。分析表明:PTSS、PTAS与PTFS均具有框架钛结构(Ti-O-Si)。其中,PTSS是以Ti-O-Si作为骨架单元,与聚硅酸键合形成高分子分枝长链结构,分子量大。最佳配比的PTAS中的Ti4+、Al3+和PTFS中的Ti4+、Fe3+分别取代Si-O-Si中的Si或通过金属离子水解形成的表面的羟基与聚硅酸的Si-O-Si结合,形成具有一定分子量的分枝链状结构单元,分子量较聚硅酸大。通过絮凝剂PTSS、PTAS与PTFS聚合过程中的粒度变化以及Zeta电位测定,推断出PTSS的混凝机理主要是高分子链的架桥网捕与络合物表面的羟基吸附作用。而PTAS和PTFS的混凝机理主要是吸附电中和与络合物表面的羟基吸附网捕卷扫作用,桥联网捕作用均起辅助作用。
论文通过对模拟江水、乳化油废水和磷化废水的混凝实验表明:模拟江水的初始pH值为5.26～9.32、PTFS的投加量为0.3mmol/L时,除浊率达到99.8%。乳化油废水的初始pH值为7.15,PTAS和PTFS的投加量为0.4mmol/L时,对乳化油废水的除浊率分别达到92.5%和99.8%,CODCr的去除率分别达到99.6%和99.3%。采用中和絮凝沉淀法,磷化废水的最佳pH值中和至10.18时,总磷去除率达到99.8%。
In this work, According to a new type of inorganic polymer, poly-silicic titanium sulfate (PTSS), a variety of new inorganic polymeric flocculant titanium-based(Ti-IPF) were prepared by co-polymerization. Poly-silicic titanium-aluminum sulfate(PTAS) and poly-silicic titanium-iron sulfate(PTFS) were selected by industrial applications, The results showed that when the molar ratio of n(Ti+Al):n(Si) or n(Ti +Fe):n(Si) equal to 0.3, the molar ratio of n(Ti):n(Al) or n(Ti):n(Fe) equal to 0.2, the flocculants PTAS and PTFS were optimal.
Bonding mechanism of optimal PTSS, PTAS, PTFS was probed by XRD, IR, UV/Vis measurement. The analysis results shows that the framework titanium structure, Ti-O-Si was existed in PTSS, PTAS and PTFS. The flocculant PTSS possessed long-chain branched structure and big molecular weight, which was composed of the framework titanium structure Ti-O-Si and poly silicate bonded. In the strcture of optimal flocculants PTAS and PTFS,the silicon of Si-O-Si was replaced by metal ions, such as titanium ions, iron ions, and aluminum ions, or poly-hydroxy adsorption which was formed by metal ions hydrolysis, the molecular weight was larger than the poly-silicic acid. Then, the particle size in the polymerization process and the Zeta potential of the optimal PTSS, PTAS and PTFS were investigated, thereby conjectures that the coagulation mechanism of PTSS was mainly chain bridging, sweeping and surface poly-hydroxy adsorption. The coagulation mechanism of PTAS and PTFS were mainly adsorption-charge neutralization and the surface poly-hydroxy adsorption, other mechanisms play a supporting roles, such as the chain bridging, sweeping, and so on.
The optimal PTSS, PTAS and PTFS were used to treat simulation river water, emulsified oil wastewater and phosphating wastewater, coagulation experiments show that turbidity removal rate reached 99.8%, when the initial pH value of simulation river water was 5.26 to 9.32, the dosage of PTAS and PTFS were respectively 0.3 millimoles percent litre. when the initial pH value of emulsified oil wastewater was 7.15, the dosage of PTAS and PTFS was 0.4 millimoles percent litre, of emulsified oil wastewater turbidity removal rates were respectively 92.5% and 99.8%, the removal rate of CODCr were respectively 99.6% and 99.3%. The pH value of phosphating wastewater increased to 10.18 by neutralization of lime and coagulate of PTFS, the removal rate of phosphorus reached 99.8%.
引文
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[2] R.I.L.Eggen, R.Behra, P.Burkhardt-Hoolm, et al. Challenges in ecotoxicology[J]. Environ.Sci. Technol., 2004, 38(3): 58-64.
[3] E.Silva, N.Rajapakse, A.Kortenkamp. Something from"nothing"--eight weak estrogenic chemicals combined at concentrations below NOEC's produce significant mixture effects[J]. Environ.Sci.Technol., 2002, 36(8): 1751-1756.
[4] Maria Tomaszewska, Sylwia Mozia, Antoni W. Morawski. Removal of organic matter by coagulation enhaneed with adsorption on PAC[J]. Desalination, 2004, 6(1): 79-87.
[5]何铁林.水处理絮凝剂产业发展现状与趋势[J].中国水污染防治技术装备论文,2002,2(8):224-234.
[6] J. Withgott.. Amphibian decline: ubiquitous herbicide emasculates frogs, Science[J]. Environ.Sci.Technol., 2002, 29(6): 447-448.
[7]奕兆坤,汤鸿霄.我国无机高分子絮凝剂产业发展现状与规划[J].工业水处理,2000,20(11):1-6.
[8]王九思.水处理化学[M].北京:化学工业出版社,2002.
[9]肖锦,杞永亮.我国絮凝剂发展的现状与对策[J].现代化工,1997,17(12):6-9.
[10]徐晓军.化学絮凝剂作用机理[M].北京:科学出版社,2005.
[11] Lievitski. Preparation of 5/6 aluminum oxychloride and the development for industrial application[J]. Chemical Industry, 1960, 10(7): 220-230.
[12] Sychev A. V. , Getmantsev S. V., The use of aluminum oxychloride for treatment of water with low alkali reserve[J]. Water Supply and Sanitaty Technology, 2005, 6(8): 14-15.
[13] Linevich S. N. , Bogdanov S. S. , Getmantsev S. V.. Experunental, theoretical and full scale tests of aluminium polyoxychloride on the Don river’s Water[J]. Water Supply and Sanitaty Technology, 2004, 8(1): 15-18.
[14]三上八州家,柳井正彦,森田博野,等.聚合硫酸铁的混凝特性应用实例[J].PPM,1980,4(5):24-30.
[15]徐祖信,陈漩,李霞.聚氯化铝及其在工业废水处理中的应用与展望[J].上海环境科学,2003,22(5):353-357.
[16]李润生.水处理新药剂碱式氯化铝[M].北京:中国建筑工业出版社,1981.
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