饮用水深度处理工艺的优化研究
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摘要
臭氧-生物活性炭技术作为饮用水的深度处理技术之一在国内有着很好的应用前景,但针对我国的水质特点还缺乏相应成熟的经验,许多方面还有待进一步完善。本论文以黄浦江原水为处理对象,对臭氧-生物活性炭技术去除水中污染物的机理和性能进行了全面系统的研究,得到了以下主要结论:
改进和完善了三卤甲烷生成潜能及DOC构成测定方法,提出了测定微生物活性的新方法:呼吸势能法。
对臭氧化技术的研究表明,臭氧能够有效降低水体的有机负荷,并在一定程度上改善水质的可生化性。本文在国内首次采用DOC分类测定方法分析臭氧对水中溶解性有机物的影响以及对水质可生化性的改善情况,试验发现,砂滤出水中溶解性有机物80%以上都是NB&ADOC,B&ADOC约为10～13%,NA&BDOC和NRDOC的含量均不超过5%。臭氧后NB&ADOC,NA&BDOC和NRDOC均呈减少趋势,A&BDOC增加,而且提高的幅度随臭氧投加量和接触时间的增加而上升。在确定的最佳臭氧化条件下,臭氧氧化后水中B&ADOC的绝对含量增加了49%,BDOC的绝对含量增加了22%,但BDOC在总DOC中所占比例(BDOC/DOC)只增加了3～4%。首次将分子量分布测定与水质深度处理研究相结合,分析不同工艺单元出水分子量变化规律,得出前处理工艺对分子量在3kD以上的有机物有较好的去除效果。臭氧对分子量大于10kD的有机物氧化分解作用明显,臭氧化后水中分子质量在3kD～1kD以及<0.5kD区间的有机物增加。生物活性炭滤池主要去除分子量分布在10kD～3kD和3kD～1kD以及<0.5kD区间的有机物,炭池出水中分子量在100kD～10kD的有机物会明显增加。通过研究臭氧对三卤甲烷生成潜能的去除规律发现,臭氧对三氯甲烷和二氯一溴甲烷生成潜能都有很好的去除,对一氯二溴甲烷生成潜能的去除效果较差,对溴仿生成潜能基本没有去除。当水中溴化物含量较高时臭氧对溴仿的生成反而具有促进作用。首次结合紫外差分光谱和水中溴化物与臭氧及氯间的化学反应原理探讨了臭氧对三卤甲烷生成潜能的去除机理。在确定的最佳臭氧投加条件下,从降低水体污染负荷和提高水质可生化性两个方面比较分析了臭氧和充氧单元对水质的改变程度。
对生物活性炭滤池除污染能力的研究表明:空气和臭氧对后续生物活性炭滤池挂膜时间没有明显影响。臭氧后生物活性炭柱的运行效果略好于空气后生物活性炭柱。首次结合DOC分类测定和分子量分布测定研究炭池在不同运行阶段对溶解性有机物的去除机理及去除规律。考察了两生物活性炭滤池对三卤甲烷生成潜能去除规律的四季变化,发现炭池对氯仿生成潜能的去除效果较好,对溴代三卤甲烷生成潜能的去除效果较差,去除率随溴化程度的加深而降低。深入探讨了炭池的主要工艺参数(空床接触时间和滤速)和除污染能力间的关系,通过对大量数据的拟合分析,认为空床接触时间是炭池运行的关键参数,并建立了空床接触时间和炭池除污染能力间的相关关系。通过研究不同反冲洗方式、冲洗强度对炭池生物量、净水效能等多项指标的影响确定了炭池的最佳反冲洗模式,在此基础上进一步分析比较了反冲洗对两生物活性炭滤池的影响规律。
通过对“前处理工艺”,“前处理工艺+臭氧+BAC”,“前处理工艺+充氧+BAC”三种处理工艺出水水质的分析表明:两条深度处理工艺都能进一步改善前处理工艺的出水水质。“臭氧+BAC”工艺对CODMn的全年平均去除率为31%左右,“充氧+BAC”为21%左右,前者比后者高出10%左右。对UV254的去除,前者要比后者平均高出20%以上。对两条深度处理工艺出水的水质安全性分析表明:无论是在生物稳定性还是出水携带细菌总数上,“臭氧+BAC”都优于前者。GC/MS检测结果表明,“前处理工艺+臭氧+BAC+氯化消毒”工艺使原水中有机物的种类减少了46种,色谱峰总面积减少了33%。“前处理工艺+充氧+BAC+消毒”工艺使原水中有机物的种类减少了33种,色谱峰总面积减小了13%。进一步证明“臭氧+BAC”出水水质明显好于“充氧+BAC”工艺。
在国内首次利用紫外差分光谱分析了三卤甲烷氯化反应生成机理及生成规律,建立了三卤甲烷生成的预测模式。结合大量试验数据分析了TOC、CODMn和UV254三者间的关联性,建立了UV254来预测TOC的数学模式。
The process of ozone-biological activated carbon which is one of advanced treatment technologies will be applied on a large scale in our country in the future, but there is still no enough experience in using it according to Chinese water characters. Systematical research was done acording to the raw water quality of Huangpu River from the mechanism and performance to remove polutant in this article, and draw the following conclusions:
The analytical methods of trihalomethane formation potential(THMFP) and different kinds of DOC was improved, and a new method was established: respiration potential method.
The research on ozonation technology showed that ozonation can decrease effectively organic pollutant burden and improve biodegradability of water. It was the first time to analyze the effect of ozone on dssovled organic matter and the biodegradability of water by determining different sorts of DOC. The experiment results indicated that for effluent of sand filter there were above 80% of NOM is belong to NB&ADOC, B&ADOCis about 10~13%, the amout of NA&BDOC and NRDOC were both below 5%. After ozonation the content of NB&ADOC, NA&BDOC and NRDOC all decrease but the amount of A&BDOC increase,moreover,the extent of increase for A&BDOC went up with the ozone dosage and contaction time. Under the optimal ozone conditions, the absolute content of B&ADOC increased by 49% and BDOC increased by 22% after ozonation, but proportion of BDOC to the total DOC (BDOC/DOC) increased 3-4%. It was also the first time to combine the molecular weight distribution of organic matter with water advanced treatment research, the molecular weight distribution for different effluent was analyzed and concluded that pretreatment process can effectively remove those organic pollutant whose molecular weight were above 3kD, and those pollutant whose molecular weight were above 10kD would be decomposed and those whose molecular weight were 3kD~1kD and below 0.5kD would increase after ozonation. BAC filter has a good removal ability for those organic matter whose molecular weight were 10kD~3kD, 3kD~1kD and <0.5kD, but the content would increase for those pollutant whose molecular weight was 100kD～10kD after BAC filter.The reduction of trihalomethane formation potential(THMFP) was discussed, which indicated that ozonation has a good removal for chlorofom and bromodichloromethane formation potential, but for dibromochloromethane formation potential the removal efficiency was undesirable and there was almost no removal for bromoform forming potential, Furthermore, when there was enough bromide in water, ozonation would have a promotion effect for bromoform formation potential. For the first time the removal mechanism of THMFP for ozone was demonstrated Combining differential UV spectroscopy and chemical reaction principle of ozone and chlorine. Under the optimal conditions for ozonation,change of water quality before and after ozonation and air was discussed from the following aspects: reducing pollutant burden and improving biodegradablity.
The study on operational performance of BAC filter showed that there was no evident diference on biofilm forming time of BAC filters which following ozonation and air stage. BAC filter following ozone contacting column has a better performance than that following air contacting column. For the first time combining the analytical method of DOC composing and molecular weight distribution to study the removal mechanism and rule of organic matter for BAC filter in different runing phase. In addition, the removal mechanism and rule of THMFP for both of BAC filters in for seasons were discussed and found that BAC filter could reduce chloroform formation potential effectively, but couldn’t effectivly remove bromizing trihalomethane, and the removal efficiency decline with further bromizing. the ralationship of main parameters of BAC filter (EBCT and filtration rate) and the removal ability were discussed , according to the correlative analysis for lots of data, it was concluded that EBCT was the key parameterand the relationship between EBCT and removal ability of filter was founded. Based on the study for backwashing technology, the most optimal backwashing strategy was established, on the base of which to compare the effective rule of backwashing on both of BAC filters.
Effluent water quality of three treatment process which include“pretreatment process”,“pretreatment process + ozonation + BAC”and“pretreatment process + air+BAC”was dicussed, experimental results showed both of two advanced treatment process could improve water quality of pretreatment process. The process of“ozone + BAC”could averagely reduce about 31% of CODMn annually, and about 21% for the process of“air + BAC”. For CODMn the former has a higher removal than the latter by about 10% and for UV254 by about 20%. The security of effluent water quality for both two advanced treatment process was assessed and results showed that the process of“ozone+BAC”has a better performance no matter the biostability or bacteria population for effluent. GC/MS test showed that total organic species number was reduced 59.7% and total spectrum aera was reduced 33% after treatment by“pretreatment+ozone+BAC+chlorination”, on the other hand, total organic species number was reduced 44% and total spectrum aera was reduced 13% after treatment by“pretreatment+air+BAC+chlorination”. All these demonstrated that the process“ozone + BAC”could produce higher quality of water than that of“air + BAC”.
It is first time in our country to analyze the generating mechanics and rules of trihalomethane by utlizing differential UV spectroscopy and founded a predictive model of forming trihalomethane. On the base of lots of data, the correlative analysis for TOC, CODMn and UV254 were done, and a model is established that can rapidly calculate TOC on the base of UV254.
改进和完善了三卤甲烷生成潜能及DOC构成测定方法,提出了测定微生物活性的新方法:呼吸势能法。
对臭氧化技术的研究表明,臭氧能够有效降低水体的有机负荷,并在一定程度上改善水质的可生化性。本文在国内首次采用DOC分类测定方法分析臭氧对水中溶解性有机物的影响以及对水质可生化性的改善情况,试验发现,砂滤出水中溶解性有机物80%以上都是NB&ADOC,B&ADOC约为10～13%,NA&BDOC和NRDOC的含量均不超过5%。臭氧后NB&ADOC,NA&BDOC和NRDOC均呈减少趋势,A&BDOC增加,而且提高的幅度随臭氧投加量和接触时间的增加而上升。在确定的最佳臭氧化条件下,臭氧氧化后水中B&ADOC的绝对含量增加了49%,BDOC的绝对含量增加了22%,但BDOC在总DOC中所占比例(BDOC/DOC)只增加了3～4%。首次将分子量分布测定与水质深度处理研究相结合,分析不同工艺单元出水分子量变化规律,得出前处理工艺对分子量在3kD以上的有机物有较好的去除效果。臭氧对分子量大于10kD的有机物氧化分解作用明显,臭氧化后水中分子质量在3kD～1kD以及<0.5kD区间的有机物增加。生物活性炭滤池主要去除分子量分布在10kD～3kD和3kD～1kD以及<0.5kD区间的有机物,炭池出水中分子量在100kD～10kD的有机物会明显增加。通过研究臭氧对三卤甲烷生成潜能的去除规律发现,臭氧对三氯甲烷和二氯一溴甲烷生成潜能都有很好的去除,对一氯二溴甲烷生成潜能的去除效果较差,对溴仿生成潜能基本没有去除。当水中溴化物含量较高时臭氧对溴仿的生成反而具有促进作用。首次结合紫外差分光谱和水中溴化物与臭氧及氯间的化学反应原理探讨了臭氧对三卤甲烷生成潜能的去除机理。在确定的最佳臭氧投加条件下,从降低水体污染负荷和提高水质可生化性两个方面比较分析了臭氧和充氧单元对水质的改变程度。
对生物活性炭滤池除污染能力的研究表明:空气和臭氧对后续生物活性炭滤池挂膜时间没有明显影响。臭氧后生物活性炭柱的运行效果略好于空气后生物活性炭柱。首次结合DOC分类测定和分子量分布测定研究炭池在不同运行阶段对溶解性有机物的去除机理及去除规律。考察了两生物活性炭滤池对三卤甲烷生成潜能去除规律的四季变化,发现炭池对氯仿生成潜能的去除效果较好,对溴代三卤甲烷生成潜能的去除效果较差,去除率随溴化程度的加深而降低。深入探讨了炭池的主要工艺参数(空床接触时间和滤速)和除污染能力间的关系,通过对大量数据的拟合分析,认为空床接触时间是炭池运行的关键参数,并建立了空床接触时间和炭池除污染能力间的相关关系。通过研究不同反冲洗方式、冲洗强度对炭池生物量、净水效能等多项指标的影响确定了炭池的最佳反冲洗模式,在此基础上进一步分析比较了反冲洗对两生物活性炭滤池的影响规律。
通过对“前处理工艺”,“前处理工艺+臭氧+BAC”,“前处理工艺+充氧+BAC”三种处理工艺出水水质的分析表明:两条深度处理工艺都能进一步改善前处理工艺的出水水质。“臭氧+BAC”工艺对CODMn的全年平均去除率为31%左右,“充氧+BAC”为21%左右,前者比后者高出10%左右。对UV254的去除,前者要比后者平均高出20%以上。对两条深度处理工艺出水的水质安全性分析表明:无论是在生物稳定性还是出水携带细菌总数上,“臭氧+BAC”都优于前者。GC/MS检测结果表明,“前处理工艺+臭氧+BAC+氯化消毒”工艺使原水中有机物的种类减少了46种,色谱峰总面积减少了33%。“前处理工艺+充氧+BAC+消毒”工艺使原水中有机物的种类减少了33种,色谱峰总面积减小了13%。进一步证明“臭氧+BAC”出水水质明显好于“充氧+BAC”工艺。
在国内首次利用紫外差分光谱分析了三卤甲烷氯化反应生成机理及生成规律,建立了三卤甲烷生成的预测模式。结合大量试验数据分析了TOC、CODMn和UV254三者间的关联性,建立了UV254来预测TOC的数学模式。
The process of ozone-biological activated carbon which is one of advanced treatment technologies will be applied on a large scale in our country in the future, but there is still no enough experience in using it according to Chinese water characters. Systematical research was done acording to the raw water quality of Huangpu River from the mechanism and performance to remove polutant in this article, and draw the following conclusions:
The analytical methods of trihalomethane formation potential(THMFP) and different kinds of DOC was improved, and a new method was established: respiration potential method.
The research on ozonation technology showed that ozonation can decrease effectively organic pollutant burden and improve biodegradability of water. It was the first time to analyze the effect of ozone on dssovled organic matter and the biodegradability of water by determining different sorts of DOC. The experiment results indicated that for effluent of sand filter there were above 80% of NOM is belong to NB&ADOC, B&ADOCis about 10~13%, the amout of NA&BDOC and NRDOC were both below 5%. After ozonation the content of NB&ADOC, NA&BDOC and NRDOC all decrease but the amount of A&BDOC increase,moreover,the extent of increase for A&BDOC went up with the ozone dosage and contaction time. Under the optimal ozone conditions, the absolute content of B&ADOC increased by 49% and BDOC increased by 22% after ozonation, but proportion of BDOC to the total DOC (BDOC/DOC) increased 3-4%. It was also the first time to combine the molecular weight distribution of organic matter with water advanced treatment research, the molecular weight distribution for different effluent was analyzed and concluded that pretreatment process can effectively remove those organic pollutant whose molecular weight were above 3kD, and those pollutant whose molecular weight were above 10kD would be decomposed and those whose molecular weight were 3kD~1kD and below 0.5kD would increase after ozonation. BAC filter has a good removal ability for those organic matter whose molecular weight were 10kD~3kD, 3kD~1kD and <0.5kD, but the content would increase for those pollutant whose molecular weight was 100kD～10kD after BAC filter.The reduction of trihalomethane formation potential(THMFP) was discussed, which indicated that ozonation has a good removal for chlorofom and bromodichloromethane formation potential, but for dibromochloromethane formation potential the removal efficiency was undesirable and there was almost no removal for bromoform forming potential, Furthermore, when there was enough bromide in water, ozonation would have a promotion effect for bromoform formation potential. For the first time the removal mechanism of THMFP for ozone was demonstrated Combining differential UV spectroscopy and chemical reaction principle of ozone and chlorine. Under the optimal conditions for ozonation,change of water quality before and after ozonation and air was discussed from the following aspects: reducing pollutant burden and improving biodegradablity.
The study on operational performance of BAC filter showed that there was no evident diference on biofilm forming time of BAC filters which following ozonation and air stage. BAC filter following ozone contacting column has a better performance than that following air contacting column. For the first time combining the analytical method of DOC composing and molecular weight distribution to study the removal mechanism and rule of organic matter for BAC filter in different runing phase. In addition, the removal mechanism and rule of THMFP for both of BAC filters in for seasons were discussed and found that BAC filter could reduce chloroform formation potential effectively, but couldn’t effectivly remove bromizing trihalomethane, and the removal efficiency decline with further bromizing. the ralationship of main parameters of BAC filter (EBCT and filtration rate) and the removal ability were discussed , according to the correlative analysis for lots of data, it was concluded that EBCT was the key parameterand the relationship between EBCT and removal ability of filter was founded. Based on the study for backwashing technology, the most optimal backwashing strategy was established, on the base of which to compare the effective rule of backwashing on both of BAC filters.
Effluent water quality of three treatment process which include“pretreatment process”,“pretreatment process + ozonation + BAC”and“pretreatment process + air+BAC”was dicussed, experimental results showed both of two advanced treatment process could improve water quality of pretreatment process. The process of“ozone + BAC”could averagely reduce about 31% of CODMn annually, and about 21% for the process of“air + BAC”. For CODMn the former has a higher removal than the latter by about 10% and for UV254 by about 20%. The security of effluent water quality for both two advanced treatment process was assessed and results showed that the process of“ozone+BAC”has a better performance no matter the biostability or bacteria population for effluent. GC/MS test showed that total organic species number was reduced 59.7% and total spectrum aera was reduced 33% after treatment by“pretreatment+ozone+BAC+chlorination”, on the other hand, total organic species number was reduced 44% and total spectrum aera was reduced 13% after treatment by“pretreatment+air+BAC+chlorination”. All these demonstrated that the process“ozone + BAC”could produce higher quality of water than that of“air + BAC”.
It is first time in our country to analyze the generating mechanics and rules of trihalomethane by utlizing differential UV spectroscopy and founded a predictive model of forming trihalomethane. On the base of lots of data, the correlative analysis for TOC, CODMn and UV254 were done, and a model is established that can rapidly calculate TOC on the base of UV254.
引文
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