城市复合污染水体修复的初步研究
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摘要
随着城市化的发展,许多城市的河道、湖泊等水体都受到了污染,不仅氮、磷超标引起富营养化,而且还受到了难降解有机物的污染,表现为复合污染与低碳氮比的特征。对于这类复合污染水体,采用单一物理、化学或生物等方法,都难以修复或控制。鉴于这种情况,我们研制一种集光催化与生物降解一体化的反应器,分别对模拟和实际的复合污染水体进行处理。
实验首先研制了TiO_2光催化膜的制备方法,确定使用TiO_2溶胶-凝胶法制备的光催化板是具有催化氧化效果的,并确定载体为玻璃,镀膜8次,在500℃左右下煅烧时,所得的光催化薄膜具有最佳的催化氧化效果。
其次,实验采用TiO_2光催化剂对受到复合污染的城市河道水进行处理,发现水中的COD出现大幅升高的现象。通过对吡啶进行光催化氧化,验证了其COD上升的原因,并结合紫外分光光谱分析,发现其结构发生变化,由最初不能被重铬酸钾氧化转变为可以被氧化,其COD先逐步升高后又下降,从而说明城市复合污染水体中存在类似的有机物。
在采用光催化氧化和生物降解一体式反应器对该水体进行修复过程中,水中的总氮和COD呈现相对变化的关系,即当COD变化率为负值时,TN的变化率则基本为正值。反之COD变化率为正值时,TN的变化率则基本呈负值。结果表明在光催化氧化和生物降解的协同作用下,总氮和有机物得到同步去除。
最后进一步的反硝化实验中又发现,水中这些有机物污染物在经过光催化氧化之后,可以转变为容易被微生物所利用的有机碳源,从而提高水中的碳氮比。实验证明,经过光催化氧化处理后的河道水,其总氮去除率比未经过光催化氧化的河道水提高30%以上。
With the development of urbanization, many rivers and lakes are polluted simultaneously by nitrogen,phosphate and recalcitrant chemicals. For this kind of water, it is difficult to get repaired by complying single physical, chemical, or biological methods.
In this case,we treat the simulated and actual water with complex pollution by using integrated photocatalytic-biological internal circulating reactor.
At the beginning of the research, we study the method of TiO_2 sol-gel for making TiO_2 film, and the effect of photocatalytic film. The results show that the best film should be coated on groundglass,for eight times, in 500 degrees Celsius.
In the study of groundwater(composite polluted) treatment by TiO_2 photocatalyst, we found that COD could be increasing greatly, and we get the same result in the photocatalytic treatment of water containing pyridine, which indicates that the urban river water contains the similar chemicals like pyridine. The structure of pyridine was changed after photocatalytic oxidation according to ultra violet spectrum analysis. Verified the rise of COD ,and original pyridine could not be oxidized by potassium dichromate, but it could be oxidized after photocatalytic oxidation. Experimental results suggested that there were some recalcitrant organics in urban river water with complex pollution.
It can be indicated that the change of TN was relative to the change of COD. The removal rate of COD was opposite to the removal rate of TN, by using integrated photocatalytic-biological internal circulating reactor.TN and chemicals are removed at the same time by integrated photocatalytic-biological internal circulating reactor.
After photocatalytic oxidation,the chemicals might be transferred into utilizable organic carbon source uses by microorganism and increase of carbon/nitrogen ratio. It is indicated that total nitrogen removal rate increased more than 30 percent by photocatalytic oxidation compared with the river treat that without photocatalysis.
实验首先研制了TiO_2光催化膜的制备方法,确定使用TiO_2溶胶-凝胶法制备的光催化板是具有催化氧化效果的,并确定载体为玻璃,镀膜8次,在500℃左右下煅烧时,所得的光催化薄膜具有最佳的催化氧化效果。
其次,实验采用TiO_2光催化剂对受到复合污染的城市河道水进行处理,发现水中的COD出现大幅升高的现象。通过对吡啶进行光催化氧化,验证了其COD上升的原因,并结合紫外分光光谱分析,发现其结构发生变化,由最初不能被重铬酸钾氧化转变为可以被氧化,其COD先逐步升高后又下降,从而说明城市复合污染水体中存在类似的有机物。
在采用光催化氧化和生物降解一体式反应器对该水体进行修复过程中,水中的总氮和COD呈现相对变化的关系,即当COD变化率为负值时,TN的变化率则基本为正值。反之COD变化率为正值时,TN的变化率则基本呈负值。结果表明在光催化氧化和生物降解的协同作用下,总氮和有机物得到同步去除。
最后进一步的反硝化实验中又发现,水中这些有机物污染物在经过光催化氧化之后,可以转变为容易被微生物所利用的有机碳源,从而提高水中的碳氮比。实验证明,经过光催化氧化处理后的河道水,其总氮去除率比未经过光催化氧化的河道水提高30%以上。
With the development of urbanization, many rivers and lakes are polluted simultaneously by nitrogen,phosphate and recalcitrant chemicals. For this kind of water, it is difficult to get repaired by complying single physical, chemical, or biological methods.
In this case,we treat the simulated and actual water with complex pollution by using integrated photocatalytic-biological internal circulating reactor.
At the beginning of the research, we study the method of TiO_2 sol-gel for making TiO_2 film, and the effect of photocatalytic film. The results show that the best film should be coated on groundglass,for eight times, in 500 degrees Celsius.
In the study of groundwater(composite polluted) treatment by TiO_2 photocatalyst, we found that COD could be increasing greatly, and we get the same result in the photocatalytic treatment of water containing pyridine, which indicates that the urban river water contains the similar chemicals like pyridine. The structure of pyridine was changed after photocatalytic oxidation according to ultra violet spectrum analysis. Verified the rise of COD ,and original pyridine could not be oxidized by potassium dichromate, but it could be oxidized after photocatalytic oxidation. Experimental results suggested that there were some recalcitrant organics in urban river water with complex pollution.
It can be indicated that the change of TN was relative to the change of COD. The removal rate of COD was opposite to the removal rate of TN, by using integrated photocatalytic-biological internal circulating reactor.TN and chemicals are removed at the same time by integrated photocatalytic-biological internal circulating reactor.
After photocatalytic oxidation,the chemicals might be transferred into utilizable organic carbon source uses by microorganism and increase of carbon/nitrogen ratio. It is indicated that total nitrogen removal rate increased more than 30 percent by photocatalytic oxidation compared with the river treat that without photocatalysis.
引文
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[14]王健,王方华,吴虹.小清河底泥污染物释放对西水东调水质的影响研究[J].重庆环境科学,2003,25(12):59-61.
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[16]金春姬,佘宗莲等.低C/N比污水生物脱氮所需外加碳源量的确定[J].环境科学研究,2003,16(5):37-40.
[17]李兰贵.地表水环境恶化的危害及治理对策[J].地下水,2002.24(4):243-245.
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[21]丁志斌,程婷婷等.潜流人工湿地与其他工艺组合处理低浓度生活污水[J].中国给水排水, 2007, 15(8):86-89.
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[24]Skladany,G.J.Microbio logical and Engineering Considerations Hazardous Waste[J]. Hazardous Materials,1989, 6 (2) : 213-215.
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[26]Rittmann B. E. Biofilm Technology Used to Improve Water Quality[J], Journal of Shanghai Normal University, 2004. 33(4):1-8.
[27]Rittmann B. E. and McCarty P. L. Environmental Biotechnology: Principles and Applications[M], McGraw-Hill Book Co., New York. 2001.
[28]牛天新,张永明.生物膜法在去除城市地表水中氨氮的应用研究[J].环境科学与技术,2007,30(4):81-83.
[29]曹国民,赵庆祥等.生物除磷脱氮工艺技术研究[J].中国环境学,1996,16(1):68-72.
[30]马军,邱立平.曝气生物滤池及其研究进展[J].环境工程,2002,20(3):7-11.
[31]周大佐.污染水源水的生物与处理[J].上海环境科学,1997,16(4):23-26.
[32]Scott, J.P.,Ollis, D. F., (1995). Integration of chemical and biological oxidation processes for water treatment; review and recommendations, Environmental Progress. 14(2): 88-103.
[33]Carey J H, Lawrence J. Photodechlorination of PCB’s in the Presence of Titanium Dioxide in Aqueous Suspension[J].Bulletin Environment Contamination Toxicology,1976,16:697-701.
[34]Han, W.Y.,Zhu, W.P., Zhang, P.Y.,Zhang,Y.,Li, L.S. (2004). Photocatalytic degradation of phenols in aqueous solution under irradiation of 254 and 185 nm UV light. Catalysis Today. 90(3-4): 319-324.
[35]Agrios, A.G., Gray, K.A.,Weitz, E.K. (2004). Narrow-band irradiation of a homologous series of chlorophenols on TiO2: Charge-transfer complex formation and reactivity. Langmuir. 20(14): 5911-5917.
[34]崔玉民.用光催化剂TiO2深度处理西清河废水的研究[J].水处理技术,2004 ,30(10):283-284.
[37]张英仙,崔建升等.纳米TiO2的光催化活性及其在废水处理中的应用进展[J].河北化工,2007,30(4):9-12.
[38]Wang, C.X.,Yediler, A.,Lienert, D., Wang, Z.J. Kettrup, A., (2003). Ozonation of an azo dye Cl Remazol Black 5 and toxicological assessment of its oxidation products. Chemosphere. 52(7): 1225-1232.
[39]Enriquez, R.; Beaugiraud, B.; Pichat, P., (2004). Mechanistic implications of the effect of TiO2 accessibility in TiO2-SiO2 coatings upon chlorinated organics photocatalytic removal in water. Water Science and Technology. 49(4): 147-152.
[40]Sakthivel, S.; Neppolian, B.; Palanichamy, M.; Arabindoo, B.; Murugesan, V., (2001). Photocatalytic degradation of leather dye over ZnO catalyst supported on alumina and glass surfaces, Water Science and Technology. 44(5): 211-218.
[41]Michael D,Marsolek.Photobiocatalvsis:Coupled photocatalytic-biologic treatment for recalcitrant and inhibitory wasterwater.Dissertation for the degree of Doctor[D]. The U.S.A: Northwestern University,2005,11.
[42]Hess T F,Lew is T A,Crawford R L,et al Combined photocatalytic and fungal treatment for the destruction of 2,4,6-trinitrotoluene(TNT)[J].Water Research,1998,32:1481-1491.
[43]Zhang Z, et al. Photocatalytic pretreatment of contaminated groundwater for biological nitrification enhancement[J]. Chem.Technol.Biotechnol,2002,77:190-194.
[44]文晟.水体中多环芳烃的TiO2光催化降解研究[D].中国科学院研究生院,2002.
[45]沈钢,张祖麟,余刚.夏季海河与渤海湾中壬基酚和辛基酚污染的状况[J].中国环境科学2005,25(6):733-736.
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[2]郭培章,宋群等主编.中外节水技术与政策案例研究[M].北京:中国计划出版社,2003.
[3]李圭白.饮用水水质及处理技术[A].面向21世纪的水科学与水工程技术高级研修班论文集[C].哈尔滨,1999:3-4.
[4]王琳,王宝贞.优质饮用水净化技术[M].北京:科学出版社,2000:3.
[5]P.A.Chadik.Removing Trihalomenthane Precursors from Various Natural-waters by Metal Coagulants[J].J.AWWA.1983,75(10):532-536.
[6]H.Sonthimer.Experience with Riverbank Filtration Along the Rhine River[J].J.AWWA.1980,72(7):386-390.
[7]中华人民共和国国家环境保护部.《2007年全国环境统计公报》.www.envir.gov.cn.
[8]中华人民共和国国家环境保护部.《2007年中国环境状况公报》.www.zhb.gov.cn.
[9]潘碌亭.中国微污染水源水处理技术研究现状与进展[J].工业水处理,2006.26(6):6-9.
[10]曲久辉.我国水体复合污染与控制[J].科学对社会的影响,2000,1:35-39.
[11]Ollis D F, Pelizzetti E, Serpone N, Photocatalysis, Fundamentals and Applications. Ed. By Serpone N, Pelizzetti E[J]. New York: John Wiley &Sons, 1998:609-637.
[12]林建伟.地表水底泥氮磷污染原位控制技术机理的研究[D].同济大学,2006.
[13]Rydin E.,Brunberg A..Seasonal dynamics of phosphorus in Lake Erken surface sediments [J].Arch.Hydrobiol.Spec.Issues Advanc.Limnol.1998,51:157-167.
[14]王健,王方华,吴虹.小清河底泥污染物释放对西水东调水质的影响研究[J].重庆环境科学,2003,25(12):59-61.
[15]曲久辉,李圭白.对地下水水质的GC/MS评价[J].哈尔滨建筑工程学院学报,1991,24(2):48-53.
[16]金春姬,佘宗莲等.低C/N比污水生物脱氮所需外加碳源量的确定[J].环境科学研究,2003,16(5):37-40.
[17]李兰贵.地表水环境恶化的危害及治理对策[J].地下水,2002.24(4):243-245.
[18]Conover, Brett R. Method of treating lake water with aluminum hydroxide sulfate:US,5039427[P].1991-08-13.
[19]周钰林.城市河道整治与水生态修复工作的若干个思考[J].水利发展研究,2006(11):26-27.
[20]孔繁翔,环境生物学[M],北京:高等教育出版社,2000.
[21]丁志斌,程婷婷等.潜流人工湿地与其他工艺组合处理低浓度生活污水[J].中国给水排水, 2007, 15(8):86-89.
[22] Wagner K, Hempel D C.Biodegradation by immobilized bacteria in an airlift-loop reactor influence of biofilm diffusion limitation [J], Biotechnol. Bioeng., 1988,31:559-566.
[23] Meriem B, Nevenka A, Cesar P, et al. Degradation of sodium anthraquinone sulphonate by free and immobilized bacterial cultures [J], Appl. Microbiol. Biotechnol., 1994,41:110-116.
[24]Skladany,G.J.Microbio logical and Engineering Considerations Hazardous Waste[J]. Hazardous Materials,1989, 6 (2) : 213-215.
[25]Rittmann B. E. Biofilms in the water industry. Chapter 19 in M. A. Ghannoum and G. A. O’Toole, eds., Microbial Biofilms[M], ASM Press, Washington, DC., pp. 359-378. 2004.
[26]Rittmann B. E. Biofilm Technology Used to Improve Water Quality[J], Journal of Shanghai Normal University, 2004. 33(4):1-8.
[27]Rittmann B. E. and McCarty P. L. Environmental Biotechnology: Principles and Applications[M], McGraw-Hill Book Co., New York. 2001.
[28]牛天新,张永明.生物膜法在去除城市地表水中氨氮的应用研究[J].环境科学与技术,2007,30(4):81-83.
[29]曹国民,赵庆祥等.生物除磷脱氮工艺技术研究[J].中国环境学,1996,16(1):68-72.
[30]马军,邱立平.曝气生物滤池及其研究进展[J].环境工程,2002,20(3):7-11.
[31]周大佐.污染水源水的生物与处理[J].上海环境科学,1997,16(4):23-26.
[32]Scott, J.P.,Ollis, D. F., (1995). Integration of chemical and biological oxidation processes for water treatment; review and recommendations, Environmental Progress. 14(2): 88-103.
[33]Carey J H, Lawrence J. Photodechlorination of PCB’s in the Presence of Titanium Dioxide in Aqueous Suspension[J].Bulletin Environment Contamination Toxicology,1976,16:697-701.
[34]Han, W.Y.,Zhu, W.P., Zhang, P.Y.,Zhang,Y.,Li, L.S. (2004). Photocatalytic degradation of phenols in aqueous solution under irradiation of 254 and 185 nm UV light. Catalysis Today. 90(3-4): 319-324.
[35]Agrios, A.G., Gray, K.A.,Weitz, E.K. (2004). Narrow-band irradiation of a homologous series of chlorophenols on TiO2: Charge-transfer complex formation and reactivity. Langmuir. 20(14): 5911-5917.
[34]崔玉民.用光催化剂TiO2深度处理西清河废水的研究[J].水处理技术,2004 ,30(10):283-284.
[37]张英仙,崔建升等.纳米TiO2的光催化活性及其在废水处理中的应用进展[J].河北化工,2007,30(4):9-12.
[38]Wang, C.X.,Yediler, A.,Lienert, D., Wang, Z.J. Kettrup, A., (2003). Ozonation of an azo dye Cl Remazol Black 5 and toxicological assessment of its oxidation products. Chemosphere. 52(7): 1225-1232.
[39]Enriquez, R.; Beaugiraud, B.; Pichat, P., (2004). Mechanistic implications of the effect of TiO2 accessibility in TiO2-SiO2 coatings upon chlorinated organics photocatalytic removal in water. Water Science and Technology. 49(4): 147-152.
[40]Sakthivel, S.; Neppolian, B.; Palanichamy, M.; Arabindoo, B.; Murugesan, V., (2001). Photocatalytic degradation of leather dye over ZnO catalyst supported on alumina and glass surfaces, Water Science and Technology. 44(5): 211-218.
[41]Michael D,Marsolek.Photobiocatalvsis:Coupled photocatalytic-biologic treatment for recalcitrant and inhibitory wasterwater.Dissertation for the degree of Doctor[D]. The U.S.A: Northwestern University,2005,11.
[42]Hess T F,Lew is T A,Crawford R L,et al Combined photocatalytic and fungal treatment for the destruction of 2,4,6-trinitrotoluene(TNT)[J].Water Research,1998,32:1481-1491.
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