腈纶废水处理工艺节能减排技术研究
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摘要
腈纶生产过程中产生的废水水质复杂,尽管外观无色、透明,但低聚物含量高,生物降解性差,且含有有毒物质,污水可生化性差,属难生物降解废水。应用现有的混凝、气浮等预处理及各种生化处理工艺,耗电量大且不能满足达标排放的要求。严重污染了环境,并威胁人类健康。
自1905年臭氧应用于水处理以来,在实际应用中取得了明显的成效。现已开发出O3/OH-、03/UV、03/H2O2/UV、O3/固体催化剂(如活性炭、金属及其氧化物)等高级氧化技术(AOPs)。本文介绍了腈纶废水处理国内外研究现状,并例举了处理难降解废水的先进工艺及简要原理,通过比较提出本实验研究原理及具体方法。本实验分别应用多相催化臭氧实验装置及曝气生物滤池装置对腈纶废水进行处理。对多相催化臭氧实验中降解COD的影响因素及动力学进行了研究,并对废水中的有机物形态演化进行了分析。在应用曝气生物滤池处理废水部分,研究了活性炭与陶粒载体生物降解性能；降解COD、氮素特性；pH值变化特性。最后应用多相催化臭氧-曝气生物滤池进行连续试验,得到了实验最佳参数,并对实验应用于工业做了节能减排分析。
经处理COD去除率可达75%。多相催化臭氧工艺和升降曝气活性滤池工艺两者的协同作用较好,COD去除效能之比近似为1：1,升降曝气活性滤池工艺对氨氮去除率为90%以上。预计每年减少向松花江排放532.6吨COD,减少300万吨新鲜水补充量,节电400万度,为企业节省1000多万元。
The quality of wastewater which occurred in the process of Acrylic is complex, although appearance is colorless, transparent, but oligomer content is high, biodegradability is poor and contain toxic substances. The biodegradability of sewage is poor, belongs to difficult biodegradable waste water. Apply the existing coagulation, air flotation etc. preprocessing and various biochemical process, power consumption is big and cannot meet the requirements of emissions. Seviously pollute environment, and it is a threat to mankind health.
Since ozone used in water treatment in 1905, in practical applications made the obvious effect. Has developed O3/OH-, O3/UV, O3/H2O2/UV, O3/solid catalyst (such as activated carbon, metal and its oxides) and advanced oxidation processes (AOPs). This paper introduced domestic and international research status of acrylic wastewater treatment, and enumerated the advanced technology and brief principle of hard-degradation waste water. By comparing, put forward study principle and specific methods of the experiment. The experiment respectively applied heterogeneous catalysis ozone experiment device and lift aeration active filter device to treat acrylic wastewater. Studied dynamics and the affecting factors of COD degradation in the experiments of heterogeneous catalysis ozone, and analyzed the organic form of wastewater. In the application of lifting aeration activity filter to handle wastewater, we studied the activated carbon and ceramsite carrier biodegradability; degradation of COD, nitrogen characteristics; variation characteristics of PH. And analyzed the backwash effect of filter and biological carrier biological phase. Finally applied heterogeneous catalysis ozone-lift aeration active filter to proceed continuous test and got the optimum parameters.
After processing COD removal rate would up to 75%. Both synergy of heterogeneous catalysis ozone craft and lift aeration active filter technology is better. The removal efficiency ratio of COD is approximate 1:1, while the removal efficiency of lifting aeration active filter technology on ammonia nitrogen is above 90%.
自1905年臭氧应用于水处理以来,在实际应用中取得了明显的成效。现已开发出O3/OH-、03/UV、03/H2O2/UV、O3/固体催化剂(如活性炭、金属及其氧化物)等高级氧化技术(AOPs)。本文介绍了腈纶废水处理国内外研究现状,并例举了处理难降解废水的先进工艺及简要原理,通过比较提出本实验研究原理及具体方法。本实验分别应用多相催化臭氧实验装置及曝气生物滤池装置对腈纶废水进行处理。对多相催化臭氧实验中降解COD的影响因素及动力学进行了研究,并对废水中的有机物形态演化进行了分析。在应用曝气生物滤池处理废水部分,研究了活性炭与陶粒载体生物降解性能；降解COD、氮素特性；pH值变化特性。最后应用多相催化臭氧-曝气生物滤池进行连续试验,得到了实验最佳参数,并对实验应用于工业做了节能减排分析。
经处理COD去除率可达75%。多相催化臭氧工艺和升降曝气活性滤池工艺两者的协同作用较好,COD去除效能之比近似为1：1,升降曝气活性滤池工艺对氨氮去除率为90%以上。预计每年减少向松花江排放532.6吨COD,减少300万吨新鲜水补充量,节电400万度,为企业节省1000多万元。
The quality of wastewater which occurred in the process of Acrylic is complex, although appearance is colorless, transparent, but oligomer content is high, biodegradability is poor and contain toxic substances. The biodegradability of sewage is poor, belongs to difficult biodegradable waste water. Apply the existing coagulation, air flotation etc. preprocessing and various biochemical process, power consumption is big and cannot meet the requirements of emissions. Seviously pollute environment, and it is a threat to mankind health.
Since ozone used in water treatment in 1905, in practical applications made the obvious effect. Has developed O3/OH-, O3/UV, O3/H2O2/UV, O3/solid catalyst (such as activated carbon, metal and its oxides) and advanced oxidation processes (AOPs). This paper introduced domestic and international research status of acrylic wastewater treatment, and enumerated the advanced technology and brief principle of hard-degradation waste water. By comparing, put forward study principle and specific methods of the experiment. The experiment respectively applied heterogeneous catalysis ozone experiment device and lift aeration active filter device to treat acrylic wastewater. Studied dynamics and the affecting factors of COD degradation in the experiments of heterogeneous catalysis ozone, and analyzed the organic form of wastewater. In the application of lifting aeration activity filter to handle wastewater, we studied the activated carbon and ceramsite carrier biodegradability; degradation of COD, nitrogen characteristics; variation characteristics of PH. And analyzed the backwash effect of filter and biological carrier biological phase. Finally applied heterogeneous catalysis ozone-lift aeration active filter to proceed continuous test and got the optimum parameters.
After processing COD removal rate would up to 75%. Both synergy of heterogeneous catalysis ozone craft and lift aeration active filter technology is better. The removal efficiency ratio of COD is approximate 1:1, while the removal efficiency of lifting aeration active filter technology on ammonia nitrogen is above 90%.
引文
[1]欧阳丽,王晓明,赵建夫.我国腈纶废水生化法处理进展.工业水处理.2001,21(9)：11-14.
[2]胡万昌.含腈污水脱除氨氮中型试验.石油化工环境保护.1993,(3)：35-38.
[3]杜赦林.软性填料膜法A/O脱氮系统处理腈纶废水.给水排水.1996,22(6)：23-25.
[4]Sui, M. and Mz, J. Study on NB removal by ozone/GAC process. Zhong guo Ji shui Pai shui.2006,17(10):70-73.
[5]Li, L. Peishi, C. and Earnest, F. G. Generalized kinetic model for wet oxidation of organic compounds.1991,36(11):1687-1697.
[6]Koo, C. and Lee, D. S. Supercritical water oxidation of nitrogen containing aromatic compounds. Hwahak Kongshak.1994:32(3):385-392.
[7]Lee, D. S. Gloyne, E. F. and Li, L. Efficiency of hydrogen peroxide and oxygen in supercritical water oxidation of 2,4-dichlorophenol and acetic acid. Journal of Supercritical Fluids.1990,3(4):249-255
[8]Walling, C. Fenton'sreagent reviseted. Acc. Chem. Res.1975,8:125-131.
[9]Glaze, W. H. and Kang, J. W. Advanced oxidation processes test of a kinetic model for the oxidation of organec compounds with ozone and hydrogen peroxide in a semibatch reactor. Ind. Eng. Chem. Res.1989,28(11):1580-1587.
[10]Bigda, R. J. Conseder Fenton'Chemistry for Wastewater Treatment. Chem. Eng. Progr. 1995,91(12):62-66.
[11]Gimenez, J. Cural, M. A. Photocatalytic treatment of phenoland 2,4-dichlorophenol in a solar plant in the way to scaling-up. Catalysis Today.1999,54:229-243.
[12]Beltran, F. J. Gonzalez, M. Rivas, J. et al. Oxidation of mecoprop in water with ozone andozone combined with hydrogen peroxide. Ind. Eng. Chem. Res.1994,33:125-136.
[13]Paillard, H. Brunet, R.and Dore, M. Conditions optimals dapplication du system oxybant ozone-peroxide hydrogene. Wat. Res.1988,22:91-103.
[14]Adams, C. D. Cozzens, R. A. and Kim, B. J. Effects of ozonation on the biodegradability of substituted phenols. Wat. Res.1997,31(10):2655-2663.
[15]Scott, J and Ollis, D. F. Entegration of Chemical and Biological Oxidation Processes for Water Treatment Tecent lustrations and Experiences. Adv. Oxidation Technology.1997, 2:374-381.
[16]竹湘锋,徐新华,王天聪.Fe3+/03体系对草酸的催化氧化.浙江大学学报.2004,5(3)：322-325.
[17]Jan Perkowski, Lech Kos. Treatment of Textile Dyeing Wastewater by Hydrogen Peroxide and Ferrous Ions. Instieute of Knitting Technology and Techniques.2002, 270:90-361.
[18]Peyton, G. R. and Glaze, W. H. Destruction of pollutants in water with ozone in combination with ultraviolet radiation photolysis of aqueous ozone. Environ. Sci.Technol.1988,22:761-767.
[19]Trapido, M. Ozonation ozne/UV and UV/H2O2 degradation of chlorophenols. Ozone Sci. & Eng.1997,19(1):75-96.
[20]Ruppert, G. Bauer, R. and Heisler, G. Comparison of advanced oxidation processes for waste water treatment. Chemosphere.1994,28(8):1447-1454
[21]徐亚明,吴浩汀.气水比回流比及冲击负荷对BAF的影响.环境科学于技术.2004,27(6)：47-49.
[22]王劲松,胡勇有.曝气生物滤池填料的研究进展.工业用水与废水。2002,33(5)：7-9.
[23]齐兵强,王占生.曝气生物滤池在污水处理中的应用.给水排水.2000,26(10)： 4-8
[24]J. Z. Wang, R. S. Summers and R. J. Miltner. Biofiltration Performance:Part1, Relationship to Biomass. Filtration:J. Am. Water Works Association.1995,87:55-63.
[25]R. C. Jin, P. Zheng, Q. Mahmood, et al.Osmotic Stress on Nitrification in an Airlift Bioreactor. Journal of Hazardous Materials.2007,146(1-2):148-154.
[26]Y. Liu. Adhesion Kinetics of Nitrifying Bacteria on Various Thermoplastic Supports. Colloids and Surfaces.1995,5(5):213-219.
[27]A. M. Knezeva, D.van der Kooij. Optimisation and Significance of ATP Analysis for Measuring Active Biomass in Granular Activated Carbon Filters Used in Water Treatment.Water Research.2004,38(18):3971-3979.
[28]S. S.Cheng, Y. N. Chen.Study of a three-stage fluidized bed process treating acrylic synthetic-fiber manufacturing wastewater containing high-strength nitrogenous compounds. Wat.Sci.&Tech.2004:49(5-6),113-119.
[29]J. M. Wyatt and C. J. Knowles. Microbial degradation of acrylonitrile waste effluents:the degradation of effluents and condensates from the manufacture of acrylonitrile. International Biodeterioration & Biodegradation.1995,45:227-248.
[30]J. M. Wyatt and C. J. Knowles. The development of a novel strategy for the microbial treatment of acrylonitrile effluents.Biodegradation.1995,33:93-107.
[31]Young-O Kim, Hai-UK Nam, Etc. Fenton oxidation process control using oxidation-reduction potential measurement for pigment wastewater treatment. korean J. Chem. Eng.2004:21(4):801-805.
[32]J. Herney Ramirez, Carlos A. Costa, Luis M. Madeira. Experimental design to optimize the degradation of the synthetic dye orange Ⅱ using Fenton's reagent.Catalysis Today. 2005,107-108:68-76.
[33]Bao Xiao Jun, Englande Andrew J. Proceedings of IWA-Specialty Confernce of Chemical and Petrochemical Industries Group. Beijing:University of Petroleum Press. 2000,237-244.
[34]杨晓奕,蒋展鹏,师绍琪等.单相厌氧与两相厌氧处理干法腈纶废水研究.工业用水与废水.2002,33(2)：21-24.
[35]陆斌,韦鹤平.内电解强化处理腈纶废水的试验研究.同济大学报.2001,29(11)：1294-1298.
[36]赵朝成,王志伟.臭氧氧化法处理腈纶废水研究.化工环保.2005,24：56-59.
[37]Chi-Kan Glin, Tsung-Yueht Sai, Jiunn Ching Liu, Etc. Enhanced biodegrade- tion of petrochemical wastewater using ozonation and BAC advanced treatment system.Water Research.2001,35(3):699-704.
[38]J. Hoigne, H. Bader. Ozonation of water:role of hydroxyl radicals as oxidizing intermediates.science.1975,190(21):782-783.
[39]Barbara Kasprzyk, Hordern, Maria Ziolek, etc.Catalytic ozonation and methods of enhancing molecular ozone reactions in water treatment. Applied Catalysis:B Environmental.2003,46:656-658.
[40]T. ogager, J. Holcman, K. Sehested, T. Pedersen. Oxidation of ferrous ions by ozone in acidic solution. Inorg. Chem.1992,31:3523-3529.
[41]G. R. Peyton, R. F. Christan, K. P. Canto. Significance and treatment of volatile orangnic Lcompounds in water supplies. Lewis Pu.1990,313-326.
[42]Temesgen G, Mirat D. G. Degradation of Tert-Butyl alcohol in dilute aqueous solution by an 03/UV process. Environ. Sci. Technol.2004,38:5246-5252.
[43]Youn-Joo An, R. C. Elizabeth. PAH degradation by UV/H2O2 in perfluorinated surfactant solutions. Wat. Res.2002,36:309-314.
[44]Hou H., Smith D. W. Advanced technologies in water and wastewater treatment. Environ. Sci. Technol.2004,1:247-264.
[45]Regube B., Karpel N., Leitner V. Catalytic ozonation:a promising advanced oxidation technology for water treatment. Catalysis today.1999,53:61-72.
[46]H. Bader, J. Hoigne. Determination of ozone in water by the indigo method. Water Res. 1981,15:449-456.
[47]T. Logager, J. Holcman, K. Sehested, T. Pedersen. Oxidation of ferrous ions by ozone in acidic solution. Inorg. Chem.1992,31:3523-3529.
[48]R.Chen, J. J. Pignatello. Role of quinine intermediates as electron shuttles in Fenton and phtoassisted Fenton oxidation or aromatic compounds. Environ. Sci. Technol.1997, 31(8):2399-2406.
[49]Garoma T., Gurol M. D. Degaradation of Tert-Butyl Alcohol (TBA) in dilute aqueous solution by O3/UV process. Environ. Sci. Technol.2004,38(19):5246-5252.
[50]Zhang Ya Lei, Zhao Jian Fu, Gu Guo Wei.Theoretical Biodegradability of the Organic Pollutants in Acrylic Fiber Waste water of Two-processes Technology. Journal of Tong Ji University.2001,29(6):715-719.
[51]Hoigne J, Bader H. Ozonation of water:role of hydroxyl radicals as oxidizing intermediates [J]. Science,1975,190(21):782-783.
[52]Temesgen G, Mirat D G. Degradation of Tert-Butyl alcohol in dilute aqueous solution by an O3/UV process[J]. Environ Sci Technol.2004,38(8):5246-252
[2]胡万昌.含腈污水脱除氨氮中型试验.石油化工环境保护.1993,(3)：35-38.
[3]杜赦林.软性填料膜法A/O脱氮系统处理腈纶废水.给水排水.1996,22(6)：23-25.
[4]Sui, M. and Mz, J. Study on NB removal by ozone/GAC process. Zhong guo Ji shui Pai shui.2006,17(10):70-73.
[5]Li, L. Peishi, C. and Earnest, F. G. Generalized kinetic model for wet oxidation of organic compounds.1991,36(11):1687-1697.
[6]Koo, C. and Lee, D. S. Supercritical water oxidation of nitrogen containing aromatic compounds. Hwahak Kongshak.1994:32(3):385-392.
[7]Lee, D. S. Gloyne, E. F. and Li, L. Efficiency of hydrogen peroxide and oxygen in supercritical water oxidation of 2,4-dichlorophenol and acetic acid. Journal of Supercritical Fluids.1990,3(4):249-255
[8]Walling, C. Fenton'sreagent reviseted. Acc. Chem. Res.1975,8:125-131.
[9]Glaze, W. H. and Kang, J. W. Advanced oxidation processes test of a kinetic model for the oxidation of organec compounds with ozone and hydrogen peroxide in a semibatch reactor. Ind. Eng. Chem. Res.1989,28(11):1580-1587.
[10]Bigda, R. J. Conseder Fenton'Chemistry for Wastewater Treatment. Chem. Eng. Progr. 1995,91(12):62-66.
[11]Gimenez, J. Cural, M. A. Photocatalytic treatment of phenoland 2,4-dichlorophenol in a solar plant in the way to scaling-up. Catalysis Today.1999,54:229-243.
[12]Beltran, F. J. Gonzalez, M. Rivas, J. et al. Oxidation of mecoprop in water with ozone andozone combined with hydrogen peroxide. Ind. Eng. Chem. Res.1994,33:125-136.
[13]Paillard, H. Brunet, R.and Dore, M. Conditions optimals dapplication du system oxybant ozone-peroxide hydrogene. Wat. Res.1988,22:91-103.
[14]Adams, C. D. Cozzens, R. A. and Kim, B. J. Effects of ozonation on the biodegradability of substituted phenols. Wat. Res.1997,31(10):2655-2663.
[15]Scott, J and Ollis, D. F. Entegration of Chemical and Biological Oxidation Processes for Water Treatment Tecent lustrations and Experiences. Adv. Oxidation Technology.1997, 2:374-381.
[16]竹湘锋,徐新华,王天聪.Fe3+/03体系对草酸的催化氧化.浙江大学学报.2004,5(3)：322-325.
[17]Jan Perkowski, Lech Kos. Treatment of Textile Dyeing Wastewater by Hydrogen Peroxide and Ferrous Ions. Instieute of Knitting Technology and Techniques.2002, 270:90-361.
[18]Peyton, G. R. and Glaze, W. H. Destruction of pollutants in water with ozone in combination with ultraviolet radiation photolysis of aqueous ozone. Environ. Sci.Technol.1988,22:761-767.
[19]Trapido, M. Ozonation ozne/UV and UV/H2O2 degradation of chlorophenols. Ozone Sci. & Eng.1997,19(1):75-96.
[20]Ruppert, G. Bauer, R. and Heisler, G. Comparison of advanced oxidation processes for waste water treatment. Chemosphere.1994,28(8):1447-1454
[21]徐亚明,吴浩汀.气水比回流比及冲击负荷对BAF的影响.环境科学于技术.2004,27(6)：47-49.
[22]王劲松,胡勇有.曝气生物滤池填料的研究进展.工业用水与废水。2002,33(5)：7-9.
[23]齐兵强,王占生.曝气生物滤池在污水处理中的应用.给水排水.2000,26(10)： 4-8
[24]J. Z. Wang, R. S. Summers and R. J. Miltner. Biofiltration Performance:Part1, Relationship to Biomass. Filtration:J. Am. Water Works Association.1995,87:55-63.
[25]R. C. Jin, P. Zheng, Q. Mahmood, et al.Osmotic Stress on Nitrification in an Airlift Bioreactor. Journal of Hazardous Materials.2007,146(1-2):148-154.
[26]Y. Liu. Adhesion Kinetics of Nitrifying Bacteria on Various Thermoplastic Supports. Colloids and Surfaces.1995,5(5):213-219.
[27]A. M. Knezeva, D.van der Kooij. Optimisation and Significance of ATP Analysis for Measuring Active Biomass in Granular Activated Carbon Filters Used in Water Treatment.Water Research.2004,38(18):3971-3979.
[28]S. S.Cheng, Y. N. Chen.Study of a three-stage fluidized bed process treating acrylic synthetic-fiber manufacturing wastewater containing high-strength nitrogenous compounds. Wat.Sci.&Tech.2004:49(5-6),113-119.
[29]J. M. Wyatt and C. J. Knowles. Microbial degradation of acrylonitrile waste effluents:the degradation of effluents and condensates from the manufacture of acrylonitrile. International Biodeterioration & Biodegradation.1995,45:227-248.
[30]J. M. Wyatt and C. J. Knowles. The development of a novel strategy for the microbial treatment of acrylonitrile effluents.Biodegradation.1995,33:93-107.
[31]Young-O Kim, Hai-UK Nam, Etc. Fenton oxidation process control using oxidation-reduction potential measurement for pigment wastewater treatment. korean J. Chem. Eng.2004:21(4):801-805.
[32]J. Herney Ramirez, Carlos A. Costa, Luis M. Madeira. Experimental design to optimize the degradation of the synthetic dye orange Ⅱ using Fenton's reagent.Catalysis Today. 2005,107-108:68-76.
[33]Bao Xiao Jun, Englande Andrew J. Proceedings of IWA-Specialty Confernce of Chemical and Petrochemical Industries Group. Beijing:University of Petroleum Press. 2000,237-244.
[34]杨晓奕,蒋展鹏,师绍琪等.单相厌氧与两相厌氧处理干法腈纶废水研究.工业用水与废水.2002,33(2)：21-24.
[35]陆斌,韦鹤平.内电解强化处理腈纶废水的试验研究.同济大学报.2001,29(11)：1294-1298.
[36]赵朝成,王志伟.臭氧氧化法处理腈纶废水研究.化工环保.2005,24：56-59.
[37]Chi-Kan Glin, Tsung-Yueht Sai, Jiunn Ching Liu, Etc. Enhanced biodegrade- tion of petrochemical wastewater using ozonation and BAC advanced treatment system.Water Research.2001,35(3):699-704.
[38]J. Hoigne, H. Bader. Ozonation of water:role of hydroxyl radicals as oxidizing intermediates.science.1975,190(21):782-783.
[39]Barbara Kasprzyk, Hordern, Maria Ziolek, etc.Catalytic ozonation and methods of enhancing molecular ozone reactions in water treatment. Applied Catalysis:B Environmental.2003,46:656-658.
[40]T. ogager, J. Holcman, K. Sehested, T. Pedersen. Oxidation of ferrous ions by ozone in acidic solution. Inorg. Chem.1992,31:3523-3529.
[41]G. R. Peyton, R. F. Christan, K. P. Canto. Significance and treatment of volatile orangnic Lcompounds in water supplies. Lewis Pu.1990,313-326.
[42]Temesgen G, Mirat D. G. Degradation of Tert-Butyl alcohol in dilute aqueous solution by an 03/UV process. Environ. Sci. Technol.2004,38:5246-5252.
[43]Youn-Joo An, R. C. Elizabeth. PAH degradation by UV/H2O2 in perfluorinated surfactant solutions. Wat. Res.2002,36:309-314.
[44]Hou H., Smith D. W. Advanced technologies in water and wastewater treatment. Environ. Sci. Technol.2004,1:247-264.
[45]Regube B., Karpel N., Leitner V. Catalytic ozonation:a promising advanced oxidation technology for water treatment. Catalysis today.1999,53:61-72.
[46]H. Bader, J. Hoigne. Determination of ozone in water by the indigo method. Water Res. 1981,15:449-456.
[47]T. Logager, J. Holcman, K. Sehested, T. Pedersen. Oxidation of ferrous ions by ozone in acidic solution. Inorg. Chem.1992,31:3523-3529.
[48]R.Chen, J. J. Pignatello. Role of quinine intermediates as electron shuttles in Fenton and phtoassisted Fenton oxidation or aromatic compounds. Environ. Sci. Technol.1997, 31(8):2399-2406.
[49]Garoma T., Gurol M. D. Degaradation of Tert-Butyl Alcohol (TBA) in dilute aqueous solution by O3/UV process. Environ. Sci. Technol.2004,38(19):5246-5252.
[50]Zhang Ya Lei, Zhao Jian Fu, Gu Guo Wei.Theoretical Biodegradability of the Organic Pollutants in Acrylic Fiber Waste water of Two-processes Technology. Journal of Tong Ji University.2001,29(6):715-719.
[51]Hoigne J, Bader H. Ozonation of water:role of hydroxyl radicals as oxidizing intermediates [J]. Science,1975,190(21):782-783.
[52]Temesgen G, Mirat D G. Degradation of Tert-Butyl alcohol in dilute aqueous solution by an O3/UV process[J]. Environ Sci Technol.2004,38(8):5246-252