ASBR法处理高浓度硫酸盐废水技术的研究
摘要
目前我国的水污染十分严重，硫酸盐污染就是一种重要的组成部分，对硫酸盐污染的治理是一项十分迫切的任务。硫酸盐还原菌(SRB)法作为一种很有潜力的治理硫酸盐污染的技术也就逐渐地成为学者们所研究的热点。
高浓度硫酸盐废水等容易造成水体的pH值降低，土壤变酸，重金属浓度境加，严重影响周边的生态环境。研究硫酸盐废水中硫酸根离子去除影响因素：温度，pH，C／S，微量元素等，寻找含硫酸盐废水脱硫的最佳条件和参数，研究硫酸盐废水生物脱硫过程中反应器的改进。
ASBR反应器是近年来新提出的新型高效厌氧反应器，本文也着重对其进行讨论，并利用单片机设计制作了相关控制系统。在厌氧序批式活性污泥反应器(ASBR)中对几个影响硫酸盐还原菌(SRB)生物技术的重要因素——PH、温度，COD／SO_4~(2-)进行了较细致调整和选取，利用实验室自配废水，获取了有关的硫酸盐浓度的变化规律，并对实际生产中的废水钛白粉废水的生物治理可行性进行了探索。最后本文还着重探讨了硫酸盐还原菌生物技术中的机理方面的问题，并在此基础上建立了一个硫酸盐还原系统的生物行为模型，并且运用模型解释了一些实际污染治理过程中所遇到的和可能遇到的问题
The water pollution is very serious in China now, which the sulfate pollution is predominant factor to contribute to it. Then it is urgent to solve the problem of sulfate pollution. The researchers are paying increasingly attention to the technique of the SRB (sulfate reduction bacteria), which is very potential.
The Wastewater of sulfate are ready to degradation pH.to the water , acid the soil, and increase the concentration of heavy metal. All of these effect our environment. The influence of pH, temperature, C/S, microelement etc. are studied in the treatment on the waste water of sulfate. In order to achieve the best result of the treatment, the good parameter are found in the experiment. In the same time we make effort to improve the reactor.
At the same time we discuss the competent between the SRB and MPB. Anaerobic Sequencing Batch Reactor(SRB) was a high efficient reactor which was designed recently yeas. The character and the development was discussed and Single Chip was used to realization the control system. Then, in the laboratory-scale study two parts of work was done. The different variations of the sulfate concentration under the different parameters of PH, temperature , COD/SO42- are given out and choosed, especially some results by using the TiO2 -producing wastewater were given out. At last the principle of the SRB's behaviors were discussed and a model about it was given out and was also used to solve some problems that sulfate reduction leads to.
高浓度硫酸盐废水等容易造成水体的pH值降低，土壤变酸，重金属浓度境加，严重影响周边的生态环境。研究硫酸盐废水中硫酸根离子去除影响因素：温度，pH，C／S，微量元素等，寻找含硫酸盐废水脱硫的最佳条件和参数，研究硫酸盐废水生物脱硫过程中反应器的改进。
ASBR反应器是近年来新提出的新型高效厌氧反应器，本文也着重对其进行讨论，并利用单片机设计制作了相关控制系统。在厌氧序批式活性污泥反应器(ASBR)中对几个影响硫酸盐还原菌(SRB)生物技术的重要因素——PH、温度，COD／SO_4~(2-)进行了较细致调整和选取，利用实验室自配废水，获取了有关的硫酸盐浓度的变化规律，并对实际生产中的废水钛白粉废水的生物治理可行性进行了探索。最后本文还着重探讨了硫酸盐还原菌生物技术中的机理方面的问题，并在此基础上建立了一个硫酸盐还原系统的生物行为模型，并且运用模型解释了一些实际污染治理过程中所遇到的和可能遇到的问题
The water pollution is very serious in China now, which the sulfate pollution is predominant factor to contribute to it. Then it is urgent to solve the problem of sulfate pollution. The researchers are paying increasingly attention to the technique of the SRB (sulfate reduction bacteria), which is very potential.
The Wastewater of sulfate are ready to degradation pH.to the water , acid the soil, and increase the concentration of heavy metal. All of these effect our environment. The influence of pH, temperature, C/S, microelement etc. are studied in the treatment on the waste water of sulfate. In order to achieve the best result of the treatment, the good parameter are found in the experiment. In the same time we make effort to improve the reactor.
At the same time we discuss the competent between the SRB and MPB. Anaerobic Sequencing Batch Reactor(SRB) was a high efficient reactor which was designed recently yeas. The character and the development was discussed and Single Chip was used to realization the control system. Then, in the laboratory-scale study two parts of work was done. The different variations of the sulfate concentration under the different parameters of PH, temperature , COD/SO42- are given out and choosed, especially some results by using the TiO2 -producing wastewater were given out. At last the principle of the SRB's behaviors were discussed and a model about it was given out and was also used to solve some problems that sulfate reduction leads to.
引文
[1] 高廷耀，水污染控制工程，高等教育出版社，1989
[2] 缪应祺，水污染控制工程，东南大学出版社，2002
[3] 金儒霖，陈颂原，房田军；硫酸盐对两相厌氧消化过程的影响；中国环境科学
[4] 杨景亮，左剑恶，胡纪萃；两相厌氧工艺处理含硫酸盐有机废水的研究；环境科学，1994，16(3)：8-12
[5] 孙剑辉，樊国锋，侯杰：含硫酸盐有机废水厌氧消化影响因素的探讨；工业水处理，1999，05，18(3)，10—12
[7] 康宁，伦世仪；硫酸盐还原—甲烷化两相厌氧工艺中的相分离；工业水处理，1996，16(4)：22—24
[8] Janssen .AJH Sleyster R .Kaa C vd .Jochensen A .Bontsema J .Lettinga G; Biological sulfide oxidation in a fed-batch reactor. Biotechnol Bioeng; 1995, 47:327-333
[9] James M. Castro, et al; Stimulation of sulfate-Reducing Bacteria in Lake Water from a former Open-pit Mine Through Addition of organic Waste; Water Environ Res 1999,71:218-223
[10] Widddel F. and Prennig N. Dissimilatory sulphate or surfur-Reducing Bacteria. In Bergey's Manual of Systematic Bacteriology, 1984, 1:633
[11] Pogate, J.R. The Sulphate Reducing Bacteria, Cambridge University Press, UK 1984.
[12] Van Houten, R.T. et al.; Thermophilic sulfat and Sulphite Reduction in Lab-Sacle Gas-Lift Reactor Using H2 and CO2 as Energy and Carbon Source; Biotechnol Bioeng,1997,55:807-814,
[13] Vikas Uberoi, Sanjoy K; Effects of Chlorophenols on the Kinetics of Propionate Degradation in Sulfate-Reducing Anerobic System; Environ. Sci. Technol. 1997,31,1607-1614
[14] Andy ve Smul, Willy, verstraete; Retention of sulfate neducing Bacterria in Expanded Greinular-sludge-blanket Reacter; Water Environ.Res 71:421 (1999): 427-482.
[15] Postage JR. The sulfate-reducing bacteria. Cambridge:Cambridge University.1979Bhattadcharya S.K. Uberoi V. Drnamrajv M.M.; Interaction between acetate fed sulfate reducers and methanogens; Wat. Res: 1996,30:22390-2246
[16] David M Bagley, Toby S Brodkorb; Modeling Microbial Kinetics in an Anaerobic Sequencing Batch Reactor- Model Development and Experimental Validation; Water Environment
[17] 贺延龄；废水的厌氧生物处理；中国轻工业出版社，1999，9
[18] 马晓航，华尧熙，叶雪明；硫酸盐生物还原法处理含锌废水；环境科学，1995，16(4)：19-21
[19] Jan Weijma; Alfons J.M. Stams, Look W. Hwlshoff Pol; Gatte Lettinga; Thermophilic Sulfate Reduction and Methangenesis with Methanol in a High Rate Anaerobic Reactor;Biotechnol Bioeng, 2000,67:354-363
[20] Omil ,F; Lens,P; Hulshoff Pol,L.W; and letting,G: Effect of Upward velocity and sulphitle concentration on Volatile Fatty Acid Degradation in a Sulphidogenic Granular Slndge Reacetor;Process Biochem ,31,699
[21] 冀滨弘，章非娟；高硫酸盐有机废水厌氧处理技术的进展；中国沼气 1999，17(3)
[22] FOmil, P Lens, A Visser, L W Hulshoff Pol, G Lettinga; Long-term Competition between Sulfate Reducing and Methanogenic Bacteria in UASB Reactors Treating Volating Fatty Acids;Biotechnol Bioeng, 1998, 3, 57(6):676-685
[23] 张希衡等；废水厌氧生物处理工程；中国环境出版社，1996
[24] 许保玖，龙腾锐；当代给水与废水处理原理；高等教育出版社，2000，9
[25] 史平，章非娟；厌氧法处理含硫酸盐有机废水的探讨；污染防治技术，1999，9，12(3)：134-138
[26] Vikas Uberoi et al.. Water Environ. Res., 1995, 67(3); 331
[27] 闵航等，厌氧微生物学，浙江大学出版社，1992
[28] Pogate, J. R.. The Sulphate Reducing Bacteria. Cambridge University Press,UK 1984
[29] 俞汉青等 工业废水处理，1991，11(5)：12-14
[30] Motoyoki Yoda et al.. Wat. Res., 1987, 21(12): 1547
[31] R.R. Dague cd., Anerobic activated, J. Water Poll Control Fed., 1996, 38(2): 220-226.
[32] Kennedy J.K, Sanchez. A. W, Hamoda F.M, Doroste L.R, "Performance of anaerobic sludge blanker sequencing batch reactor", Research J WPCF, Vol.63.Jan/Fed. 1991, 75～83.
[33] 傅大放等人，厌氧序批式活性工工艺(ASBR)特性研究，中国给水排水，2000，Vol，16。
[34] Dague,Richard R. ASBR treatment of low strength industrial wastewater at psychrophilic temperature, Water Science and Technology. 1997, 36(2-3): 337—344.
[35] Dague Richard R. Effects of temperature and hydraulic retention time on anaerobic sequencing batch rector treament of low-strength wastewater; Water Research V31 n. 10.Oct 1997.
[36] Banik, Gouranga C., Sung Shihwu et al., Granule Size distribution of an ASBR operated at psychrophilic temperatures Adv. Filtr. Sep. Technol., 1997,11,608-613.
[37] Shihwu Sung, Rchard R.Dague, laboratory studies on the anaerobic sequencing batch
reactor, water Enviroment Research, 67(3):294-301.
[38] 李亚新，李玉瑛，厌氧生物处理新工艺—厌氧序批式反应器，工业用水与废水，2002，Vol．33 No．1
[39] Sung S W and Dague R R. Fundamental Principles of the ASBR process. In Proceedings of the 47th Annual Industrial Waste Conference. Lewis publishers, Inc., Chelsea, MI, 1992.393-407.
[40] 孙剑辉 ASBR反应器快速启动的研究，环境工程 2001，2，第19卷第1期。
[41] Trgyer Steve J., Sung, Shihwu; et al. Effects of ammonia on an ASBR treating Swine waster, Adv. Filter. Sep. Technol. 1997,11,590-595.
[42] 郑一新、王宏、何跃，DAF—ASBR处理香料废水工艺研究，给水排水，Vol．26 No．11 2000．
[43] 冯孝善等。厌氧消化技术，杭州：浙水科学技术出版社，1989年，118-119。
[44] 张学元，王凤平，杜元龙，等．石油工业中的细菌腐蚀和预防[J]石油和天然气化工，1999，28(1)：53～56
[45] Starkey R L. The general physilolgy of the sulfate-reducing bacteria in relation to corrosion[j]. Producers Monthly, 1958,22:12-16.
[46] 竺建荣 胡纪萃 顾夏生 二相厌氧消化工艺硫酸盐还原细菌的研究 环境科学 1997．11
[47] 张克强 朱文亭等 硫酸盐还原细菌(SRB)的筛选培养及在两相厌氧工艺中试验研究 农业环境保护 2000，19(6)：347-349
[48] 张小兰 陈志听等 环境因素对硫酸盐还原菌生长的影响，中国腐蚀与防腐学报 Vol．20 No．4 Aug 2000 224-230．
[49] Chen L, liu MY, Call JL. Characterication of electron transfer proteins [A]. Larry L Barton.Sulfate-Reducing Bacteria[c]. NewYork: Plenum Press, 1995, 113-149
[50] Stackebrandt E, Sthl D.A, Devereux R. Taxonomic relationships[A]. Lang L Barton.Sulfate-Reducing Bacteria[c] New York: Plenum Press, 1995.48-87.
[51] 国家环境保护总局；1998中国环境状况公报；1999，7
[52] 赵宇华，叶央芳，刘学东；硫酸盐还原菌及影响因子；环境污染与防治，1997，19(5)：41-43
[2] 缪应祺，水污染控制工程，东南大学出版社，2002
[3] 金儒霖，陈颂原，房田军；硫酸盐对两相厌氧消化过程的影响；中国环境科学
[4] 杨景亮，左剑恶，胡纪萃；两相厌氧工艺处理含硫酸盐有机废水的研究；环境科学，1994，16(3)：8-12
[5] 孙剑辉，樊国锋，侯杰：含硫酸盐有机废水厌氧消化影响因素的探讨；工业水处理，1999，05，18(3)，10—12
[7] 康宁，伦世仪；硫酸盐还原—甲烷化两相厌氧工艺中的相分离；工业水处理，1996，16(4)：22—24
[8] Janssen .AJH Sleyster R .Kaa C vd .Jochensen A .Bontsema J .Lettinga G; Biological sulfide oxidation in a fed-batch reactor. Biotechnol Bioeng; 1995, 47:327-333
[9] James M. Castro, et al; Stimulation of sulfate-Reducing Bacteria in Lake Water from a former Open-pit Mine Through Addition of organic Waste; Water Environ Res 1999,71:218-223
[10] Widddel F. and Prennig N. Dissimilatory sulphate or surfur-Reducing Bacteria. In Bergey's Manual of Systematic Bacteriology, 1984, 1:633
[11] Pogate, J.R. The Sulphate Reducing Bacteria, Cambridge University Press, UK 1984.
[12] Van Houten, R.T. et al.; Thermophilic sulfat and Sulphite Reduction in Lab-Sacle Gas-Lift Reactor Using H2 and CO2 as Energy and Carbon Source; Biotechnol Bioeng,1997,55:807-814,
[13] Vikas Uberoi, Sanjoy K; Effects of Chlorophenols on the Kinetics of Propionate Degradation in Sulfate-Reducing Anerobic System; Environ. Sci. Technol. 1997,31,1607-1614
[14] Andy ve Smul, Willy, verstraete; Retention of sulfate neducing Bacterria in Expanded Greinular-sludge-blanket Reacter; Water Environ.Res 71:421 (1999): 427-482.
[15] Postage JR. The sulfate-reducing bacteria. Cambridge:Cambridge University.1979Bhattadcharya S.K. Uberoi V. Drnamrajv M.M.; Interaction between acetate fed sulfate reducers and methanogens; Wat. Res: 1996,30:22390-2246
[16] David M Bagley, Toby S Brodkorb; Modeling Microbial Kinetics in an Anaerobic Sequencing Batch Reactor- Model Development and Experimental Validation; Water Environment
[17] 贺延龄；废水的厌氧生物处理；中国轻工业出版社，1999，9
[18] 马晓航，华尧熙，叶雪明；硫酸盐生物还原法处理含锌废水；环境科学，1995，16(4)：19-21
[19] Jan Weijma; Alfons J.M. Stams, Look W. Hwlshoff Pol; Gatte Lettinga; Thermophilic Sulfate Reduction and Methangenesis with Methanol in a High Rate Anaerobic Reactor;Biotechnol Bioeng, 2000,67:354-363
[20] Omil ,F; Lens,P; Hulshoff Pol,L.W; and letting,G: Effect of Upward velocity and sulphitle concentration on Volatile Fatty Acid Degradation in a Sulphidogenic Granular Slndge Reacetor;Process Biochem ,31,699
[21] 冀滨弘，章非娟；高硫酸盐有机废水厌氧处理技术的进展；中国沼气 1999，17(3)
[22] FOmil, P Lens, A Visser, L W Hulshoff Pol, G Lettinga; Long-term Competition between Sulfate Reducing and Methanogenic Bacteria in UASB Reactors Treating Volating Fatty Acids;Biotechnol Bioeng, 1998, 3, 57(6):676-685
[23] 张希衡等；废水厌氧生物处理工程；中国环境出版社，1996
[24] 许保玖，龙腾锐；当代给水与废水处理原理；高等教育出版社，2000，9
[25] 史平，章非娟；厌氧法处理含硫酸盐有机废水的探讨；污染防治技术，1999，9，12(3)：134-138
[26] Vikas Uberoi et al.. Water Environ. Res., 1995, 67(3); 331
[27] 闵航等，厌氧微生物学，浙江大学出版社，1992
[28] Pogate, J. R.. The Sulphate Reducing Bacteria. Cambridge University Press,UK 1984
[29] 俞汉青等 工业废水处理，1991，11(5)：12-14
[30] Motoyoki Yoda et al.. Wat. Res., 1987, 21(12): 1547
[31] R.R. Dague cd., Anerobic activated, J. Water Poll Control Fed., 1996, 38(2): 220-226.
[32] Kennedy J.K, Sanchez. A. W, Hamoda F.M, Doroste L.R, "Performance of anaerobic sludge blanker sequencing batch reactor", Research J WPCF, Vol.63.Jan/Fed. 1991, 75～83.
[33] 傅大放等人，厌氧序批式活性工工艺(ASBR)特性研究，中国给水排水，2000，Vol，16。
[34] Dague,Richard R. ASBR treatment of low strength industrial wastewater at psychrophilic temperature, Water Science and Technology. 1997, 36(2-3): 337—344.
[35] Dague Richard R. Effects of temperature and hydraulic retention time on anaerobic sequencing batch rector treament of low-strength wastewater; Water Research V31 n. 10.Oct 1997.
[36] Banik, Gouranga C., Sung Shihwu et al., Granule Size distribution of an ASBR operated at psychrophilic temperatures Adv. Filtr. Sep. Technol., 1997,11,608-613.
[37] Shihwu Sung, Rchard R.Dague, laboratory studies on the anaerobic sequencing batch
reactor, water Enviroment Research, 67(3):294-301.
[38] 李亚新，李玉瑛，厌氧生物处理新工艺—厌氧序批式反应器，工业用水与废水，2002，Vol．33 No．1
[39] Sung S W and Dague R R. Fundamental Principles of the ASBR process. In Proceedings of the 47th Annual Industrial Waste Conference. Lewis publishers, Inc., Chelsea, MI, 1992.393-407.
[40] 孙剑辉 ASBR反应器快速启动的研究，环境工程 2001，2，第19卷第1期。
[41] Trgyer Steve J., Sung, Shihwu; et al. Effects of ammonia on an ASBR treating Swine waster, Adv. Filter. Sep. Technol. 1997,11,590-595.
[42] 郑一新、王宏、何跃，DAF—ASBR处理香料废水工艺研究，给水排水，Vol．26 No．11 2000．
[43] 冯孝善等。厌氧消化技术，杭州：浙水科学技术出版社，1989年，118-119。
[44] 张学元，王凤平，杜元龙，等．石油工业中的细菌腐蚀和预防[J]石油和天然气化工，1999，28(1)：53～56
[45] Starkey R L. The general physilolgy of the sulfate-reducing bacteria in relation to corrosion[j]. Producers Monthly, 1958,22:12-16.
[46] 竺建荣 胡纪萃 顾夏生 二相厌氧消化工艺硫酸盐还原细菌的研究 环境科学 1997．11
[47] 张克强 朱文亭等 硫酸盐还原细菌(SRB)的筛选培养及在两相厌氧工艺中试验研究 农业环境保护 2000，19(6)：347-349
[48] 张小兰 陈志听等 环境因素对硫酸盐还原菌生长的影响，中国腐蚀与防腐学报 Vol．20 No．4 Aug 2000 224-230．
[49] Chen L, liu MY, Call JL. Characterication of electron transfer proteins [A]. Larry L Barton.Sulfate-Reducing Bacteria[c]. NewYork: Plenum Press, 1995, 113-149
[50] Stackebrandt E, Sthl D.A, Devereux R. Taxonomic relationships[A]. Lang L Barton.Sulfate-Reducing Bacteria[c] New York: Plenum Press, 1995.48-87.
[51] 国家环境保护总局；1998中国环境状况公报；1999，7
[52] 赵宇华，叶央芳，刘学东；硫酸盐还原菌及影响因子；环境污染与防治，1997，19(5)：41-43