饮用水应急处理技术集成研究
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摘要
近年来，由于化学品和石油泄漏、工业事故排放等造成的突发性水污染事件的发生频率不断上升，成为威胁城市饮用水安全的主要来源。而我国的城市供水行业普遍不具备应对突发性水污染的应急处理能力、缺乏系统、全面应对突发性水污染的应急处理技术，供水行业迫切需要进行饮用水应急处理技术的研究。
本文选取粉末活性炭吸附、化学沉淀、化学还原和强化消毒四种应急处理技术，采用先小试确定基本控制参数再中试动态模拟的方法，针对不同特性的污染物，选择其中较为典型的若干种进行研究，并对操作参数进行了优化。主要研究成果和结论如下。
通过小试和中试对应急处理技术的研究，建立了粉末活性炭对五种农药类有机物、一种芳香族化合物和两种氯代烃类有机污染物的吸附动力学方程、吸附等温线模型，并确定了粉末活性炭技术可应对的最大污染物浓度；针对金属类金属污染物不同性质，采用相应的化学沉淀技术进行去除，确立了混凝剂种类和投加量、硫化钠投加量、pH等操作参数；按还原剂与污染物反应的化学计量比进行投加，研究了化学还原技术对三种氧化性污染物的去除效果，确定了较佳的化学计量比投加方案。
强化消毒应急处理研究表明：随着pH值的上升，自由氯和一氯胺的灭活率减小，二氧化氯的灭活率则增大；温度对一氯胺的影响较小，自由氯和二氧化氯的影响较显著；将灭活速率常数表示为pH和温度的函数，带入Chick-Watson模型，拟合出含有pH和温度两参数的消毒剂灭活模型，增强了模型的通用性；加入有机物后，三种消毒剂的灭活效果下降；粪肠球菌的灭活率随着颗粒粒径的增大而降低，增加消毒剂投加量可减小颗粒对消毒效果的影响。
用灰色关联方法分析粉末活性炭吸附2,4-二氯苯氧基乙酸、化学沉淀法除镉和氯灭活粪肠球菌过程中各因素的关联性大小，得出关联性大小的顺序为：活性炭投加量>吸附时间>污染物浓度>CODMn；滤后pH>污染物原始浓度>混凝剂种类>混凝剂投加量；Ct值>消毒接触时间>温度>消毒剂浓度>pH。
使用BP神经网络模型对各应急处理工艺的处理效果进行了预测，结果显示粉末活性炭工艺、化学沉淀工艺和消毒工艺的相关系数分别为0.976、0.996和0.943，均方标准差分别为0.0100、0.0033和0.0050，证明该BP神经网络模型对三种应急处理工艺的去除效果有较好的预测能力。
以BP神经网络为基础，采用遗传算法对所建的BP神经网络模型进行寻优。结果显示，粉末活性炭投加量为67mg/L，吸附时间为45min时，即可将初始浓度为0.67mg/L的2,4-二氯苯氧基乙酸去除至0.027mg/L；投加4.3mg/L的三氯化铁混凝剂，在反应前投加NaOH调节pH，控制反应后pH值为9.0，即可将初始浓度为0.9mg/L的镍去除到0.018mg/L。
对饮用水应急处理技术进行集成，并将课题成果应用到了天津市某水厂的示范工程中。
In recent years, emergent water pollution caused by chemicals and oil spills,industrial accidents frequently happened, become the main threat to the city drinkingwater safety. China's urban water supply industry is generallly lack of emergencytreatment capacity, systematic and comprehensive emergent treatment technology todeal with the emergent water pollution incident. This makes the industry an urgent needfor drinking water emergent treatment technology.
Powdered activated carbon adsorption, chemical precipitation, chemical redox anddisinfection were chosen to deal with the typical pollutants of different property, andoperating parameters were optimized. Bench-scale experiment was applied to determinethe basic control parameters and then pilot-scale experiment for dynamic simulation.The main results and conclusions are as follows.
The adsorption kinetics equation and adsorption isotherm model of powderedactivated carbon were established and the maximum concentrations of pollutantspowdered activated carbon can deal with were obtained based on the investigation ofemergent treatment technology carried in bench and pilot scale experiment. Thecorresponding chemical precipitation technology was chosen to deal with the metal andmetalloid pollutants of different property. The operating parameters including the kindof coagulant, coagulant dose, sodium sulfide dose and pH were established. Chlorite canbe removed greatly using ferrous sulfate, and the maximum removal efficiency at morethan98%arrived with reaction time of5minutes, but it could not be effectivelyremoved with sodium sulfide. Neither sodium sulfide nor ferrous sulfate had goodefficiecy on removing bromate and chlorate.
The emergent treatment technology of strengthen disinfection results of freechlorine, chloramines and chlorine dioxide on Escherichia coli, Enterococcus faecalisand Clostridium perfringens showed that the inactivation rate of free chlorine andchloramine decrease while that of chlorine dioxide increases with the rise of pH.Temperature had more significant influence on free chlorine and chlorine dioxidecompared with chloramines. Expressing inactivation rate constant as a function of pHand temperature and applying to the Chick-Watson model, a disinfection model with thetwo parameters of pH and temperature is established with enhanced versatility. Theinactivation rate constant of the disinfectants declined when adding organic matter. Theinactivation rate of E.faecalis decreased with bigger particle size, and increasing thedosage of disinfectant could reduce the impact of particle.
The relationship of various factors and the remove effect of powdered activatedcarbon adsorption of2,4-D, chemical precipitation of cadmium and chlorineinactivation of E.faecalis by using the grey analysis method were as follows: powderedactivated carbon dosage> adsorption time> pollutant concentration> CODMn, filteredwater pH> initial concentration of pollutants> coagulant type> coagulant dosage, Ctvalue> disinfection contact time> temperature> disinfectant concentration> pH.
BP neural network model was employed to predict the effect of emergencytreatment process. The results showed that the correlation coefficient Rs of powderedactivated carbon, chemical precipitation and the disinfection were0.976,0.996and0.943, respectively, and the RMSE was0.0100,0.0033and0.0050, respectively, whichindicated that the BP neural network model has a good predictive ability of threeemergency treatment processes.
Genetic algorithm (GA) had been used to select the optimal parameters ofemergency treatment process based on BP neural network. The results indicated thatunder the condition of powdered activated carbon dosage at67mg/L and adsorptiontime at45min,2,4-D could be reduced to0.027mg/L from the initial concentration of0.67mg/L. Nickel could be decreased to0.018mg/L from the initial concentration of0.9mg/L when pH of filtered water was9.0and the dosage of ferric chloride was4.3mg/L.
Integration of emergency treatment technology of drinking water was carried out,and research results were applied in a demonstration project at a waterworks in Tianjin.
本文选取粉末活性炭吸附、化学沉淀、化学还原和强化消毒四种应急处理技术，采用先小试确定基本控制参数再中试动态模拟的方法，针对不同特性的污染物，选择其中较为典型的若干种进行研究，并对操作参数进行了优化。主要研究成果和结论如下。
通过小试和中试对应急处理技术的研究，建立了粉末活性炭对五种农药类有机物、一种芳香族化合物和两种氯代烃类有机污染物的吸附动力学方程、吸附等温线模型，并确定了粉末活性炭技术可应对的最大污染物浓度；针对金属类金属污染物不同性质，采用相应的化学沉淀技术进行去除，确立了混凝剂种类和投加量、硫化钠投加量、pH等操作参数；按还原剂与污染物反应的化学计量比进行投加，研究了化学还原技术对三种氧化性污染物的去除效果，确定了较佳的化学计量比投加方案。
强化消毒应急处理研究表明：随着pH值的上升，自由氯和一氯胺的灭活率减小，二氧化氯的灭活率则增大；温度对一氯胺的影响较小，自由氯和二氧化氯的影响较显著；将灭活速率常数表示为pH和温度的函数，带入Chick-Watson模型，拟合出含有pH和温度两参数的消毒剂灭活模型，增强了模型的通用性；加入有机物后，三种消毒剂的灭活效果下降；粪肠球菌的灭活率随着颗粒粒径的增大而降低，增加消毒剂投加量可减小颗粒对消毒效果的影响。
用灰色关联方法分析粉末活性炭吸附2,4-二氯苯氧基乙酸、化学沉淀法除镉和氯灭活粪肠球菌过程中各因素的关联性大小，得出关联性大小的顺序为：活性炭投加量>吸附时间>污染物浓度>CODMn；滤后pH>污染物原始浓度>混凝剂种类>混凝剂投加量；Ct值>消毒接触时间>温度>消毒剂浓度>pH。
使用BP神经网络模型对各应急处理工艺的处理效果进行了预测，结果显示粉末活性炭工艺、化学沉淀工艺和消毒工艺的相关系数分别为0.976、0.996和0.943，均方标准差分别为0.0100、0.0033和0.0050，证明该BP神经网络模型对三种应急处理工艺的去除效果有较好的预测能力。
以BP神经网络为基础，采用遗传算法对所建的BP神经网络模型进行寻优。结果显示，粉末活性炭投加量为67mg/L，吸附时间为45min时，即可将初始浓度为0.67mg/L的2,4-二氯苯氧基乙酸去除至0.027mg/L；投加4.3mg/L的三氯化铁混凝剂，在反应前投加NaOH调节pH，控制反应后pH值为9.0，即可将初始浓度为0.9mg/L的镍去除到0.018mg/L。
对饮用水应急处理技术进行集成，并将课题成果应用到了天津市某水厂的示范工程中。
In recent years, emergent water pollution caused by chemicals and oil spills,industrial accidents frequently happened, become the main threat to the city drinkingwater safety. China's urban water supply industry is generallly lack of emergencytreatment capacity, systematic and comprehensive emergent treatment technology todeal with the emergent water pollution incident. This makes the industry an urgent needfor drinking water emergent treatment technology.
Powdered activated carbon adsorption, chemical precipitation, chemical redox anddisinfection were chosen to deal with the typical pollutants of different property, andoperating parameters were optimized. Bench-scale experiment was applied to determinethe basic control parameters and then pilot-scale experiment for dynamic simulation.The main results and conclusions are as follows.
The adsorption kinetics equation and adsorption isotherm model of powderedactivated carbon were established and the maximum concentrations of pollutantspowdered activated carbon can deal with were obtained based on the investigation ofemergent treatment technology carried in bench and pilot scale experiment. Thecorresponding chemical precipitation technology was chosen to deal with the metal andmetalloid pollutants of different property. The operating parameters including the kindof coagulant, coagulant dose, sodium sulfide dose and pH were established. Chlorite canbe removed greatly using ferrous sulfate, and the maximum removal efficiency at morethan98%arrived with reaction time of5minutes, but it could not be effectivelyremoved with sodium sulfide. Neither sodium sulfide nor ferrous sulfate had goodefficiecy on removing bromate and chlorate.
The emergent treatment technology of strengthen disinfection results of freechlorine, chloramines and chlorine dioxide on Escherichia coli, Enterococcus faecalisand Clostridium perfringens showed that the inactivation rate of free chlorine andchloramine decrease while that of chlorine dioxide increases with the rise of pH.Temperature had more significant influence on free chlorine and chlorine dioxidecompared with chloramines. Expressing inactivation rate constant as a function of pHand temperature and applying to the Chick-Watson model, a disinfection model with thetwo parameters of pH and temperature is established with enhanced versatility. Theinactivation rate constant of the disinfectants declined when adding organic matter. Theinactivation rate of E.faecalis decreased with bigger particle size, and increasing thedosage of disinfectant could reduce the impact of particle.
The relationship of various factors and the remove effect of powdered activatedcarbon adsorption of2,4-D, chemical precipitation of cadmium and chlorineinactivation of E.faecalis by using the grey analysis method were as follows: powderedactivated carbon dosage> adsorption time> pollutant concentration> CODMn, filteredwater pH> initial concentration of pollutants> coagulant type> coagulant dosage, Ctvalue> disinfection contact time> temperature> disinfectant concentration> pH.
BP neural network model was employed to predict the effect of emergencytreatment process. The results showed that the correlation coefficient Rs of powderedactivated carbon, chemical precipitation and the disinfection were0.976,0.996and0.943, respectively, and the RMSE was0.0100,0.0033and0.0050, respectively, whichindicated that the BP neural network model has a good predictive ability of threeemergency treatment processes.
Genetic algorithm (GA) had been used to select the optimal parameters ofemergency treatment process based on BP neural network. The results indicated thatunder the condition of powdered activated carbon dosage at67mg/L and adsorptiontime at45min,2,4-D could be reduced to0.027mg/L from the initial concentration of0.67mg/L. Nickel could be decreased to0.018mg/L from the initial concentration of0.9mg/L when pH of filtered water was9.0and the dosage of ferric chloride was4.3mg/L.
Integration of emergency treatment technology of drinking water was carried out,and research results were applied in a demonstration project at a waterworks in Tianjin.
引文
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