PDMDAAC与一氯胺的反应动力学研究
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摘要
以中国微污染原水的预氯氧化和复合混凝剂强化混凝过程条件为背景,以聚二甲基二烯丙基氯化铵(PDMDAAC)与一氯胺反应生成N-二甲基亚硝胺(NDMA)的过程为对象,采用隔离法和初始浓度法,在15～35℃间,研究了二者反应的初始阶段、PDMDAAC开环降解反应过程的动力学。结果表明:对于PDMDAAC与一氯胺的反应,总反应级数均在1.99以上,接近于2,对反应物一氯胺和PDMDAAC的反应级数均在0.9971以上;相关系数R~2>0.9976。25℃时,反应速率常数为1.23×10~(–5)L/(mol·h),在15～35℃间反应活化能E_a约为44.22 kJ/mol。由此得到了PDMDAAC与一氯胺反应生成消毒副产物NDMA初始过程的动力学描述。
The prechlorination of tiny-polluted raw water in China and the conditions of coagulation strengthening by composite coagulants were taken as the background. The reaction of poly(dimethyldiallylammonium) chloride(PDMDAAC) with monochloramine to generate N-nitrosodimethylamine(NDMA) was taken as the research object. The reaction kinetics of initial degradation process of monochloramine with PDMDAAC were studied by means of initial reactant concentration and isolation independently within the range of 15～35 ℃. The results showed that the general reaction order was more than 1.99, close to 2, and the reaction order for both monochloramine and PDMDAAC was above 0.9971.The coefficients of correlation R~2 were more than 0.9976. The reaction rate constant was 1.23×10~(–5)L/(mol·h)at 25 ℃.And the reactive activation energy E_a was about 44.22 kJ/mol in the temperature range 15 ℃ to35 ℃. Thus, a kinetic description of the initial stage reaction of PDMDAAC with monochloramine to form NDMA, a disinfection by-product was obtained.
The prechlorination of tiny-polluted raw water in China and the conditions of coagulation strengthening by composite coagulants were taken as the background. The reaction of poly(dimethyldiallylammonium) chloride(PDMDAAC) with monochloramine to generate N-nitrosodimethylamine(NDMA) was taken as the research object. The reaction kinetics of initial degradation process of monochloramine with PDMDAAC were studied by means of initial reactant concentration and isolation independently within the range of 15～35 ℃. The results showed that the general reaction order was more than 1.99, close to 2, and the reaction order for both monochloramine and PDMDAAC was above 0.9971.The coefficients of correlation R~2 were more than 0.9976. The reaction rate constant was 1.23×10~(–5)L/(mol·h)at 25 ℃.And the reactive activation energy E_a was about 44.22 kJ/mol in the temperature range 15 ℃ to35 ℃. Thus, a kinetic description of the initial stage reaction of PDMDAAC with monochloramine to form NDMA, a disinfection by-product was obtained.
引文
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[10]Dai Xingman(代杏满).Characteristics and kinetics study of chloramines and NDMA formation under the condition of chlorination and congulation for the raw water[D].Nanjing:Nanjing University of Technology(南京理工大学),2016.
[11]Jia Xu(贾旭).Synthesis technology,polymerization mechanism and relationshipbetweenstructures andproperties of PDMDAAC[D].Nanjing:Nanjing University of Technology(南京理工大学),2011.
[12]Standardization Administration of the People's Republic of China(中国国家标准化管理委员会).GB 5750.10-2006:Preparation of Chemical Reagent Standard Titration Solution(化学试剂标准滴定溶液的制备)[S].Beijing Standards Press of China,2007:1-2.
[13]Wichaya T,Apiwat C,Weerakanya M,et al.A simple and rapid method based on anti-aggregation of silver nanoparticles for detection of poly(diallyldimethylammonium chloride)in tap water[J].Anal Chem,2016,32(1):769-773.
[2]Richardson S D.Water analysis:emerging contaminants and current issuses[J].Anal Chem,2009,81(12):4645-4647.
[3]Zhu Wenqian(朱文倩),Xu Bin(徐斌),Lin Lin(林琳),et al.The dissolved organic nitrogen composition regulation and water treatment characteristics of tiny-polluted raw water[J].China Environ Sci(中国环境科学),2014,34(1):130-135.
[4]Chen Z,Valentine R L.Formation of N-nitrosodimethylammine from humic substances in natural water[J].Environ Sci Technol,2007,41(7):6059-6065.
[5]Meric S,Daekyun K.The roles of tertiary amine structure,background organic matter and chloramine species on NDMAformation[J].Water Res,2013,47(23):945-953.
[6]Charrois J W A,Hrudey S E.Breakpoint chlorination and free chlorine contact time:implications for drinking water N-nitrosodimethylamine concentrations[J].Water Res,2007,41(3):674-682.
[7]Park S H,Wei S,Mizaikoff B,et al.Degradation of amine-based water treatment polymers during chloramination as N-nitrosodimethylamine(NDMA)precursors[J].Environ Sci Technol,2009,43(5):1360-1366.
[8]Padhye L,Luzinova Y,Cho M,et al.PolyDADMAC and dimethylamine as precursors of N-nitrosodimethylamine during ozonation:reaction kinetics and mechanisms[J].Environ Sci Technol,2011,45(4):4353-4359.
[9]Qian Weiling(钱伟玲).The N-nitrosodimethylamine formation as a disinfection by-product during the enhanced cogulation treatment of micro-polluted waters[D].Nanjing:Nanjing University of Technology(南京理工大学),2016.
[10]Dai Xingman(代杏满).Characteristics and kinetics study of chloramines and NDMA formation under the condition of chlorination and congulation for the raw water[D].Nanjing:Nanjing University of Technology(南京理工大学),2016.
[11]Jia Xu(贾旭).Synthesis technology,polymerization mechanism and relationshipbetweenstructures andproperties of PDMDAAC[D].Nanjing:Nanjing University of Technology(南京理工大学),2011.
[12]Standardization Administration of the People's Republic of China(中国国家标准化管理委员会).GB 5750.10-2006:Preparation of Chemical Reagent Standard Titration Solution(化学试剂标准滴定溶液的制备)[S].Beijing Standards Press of China,2007:1-2.
[13]Wichaya T,Apiwat C,Weerakanya M,et al.A simple and rapid method based on anti-aggregation of silver nanoparticles for detection of poly(diallyldimethylammonium chloride)in tap water[J].Anal Chem,2016,32(1):769-773.
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