MBR-BAF处理采油废水研究
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摘要
辽河油田作为我国的第三大油田，原油产量为1500万吨／年，在我国的国民经济和能源战略上具有举足轻重的地位。但是，随着原油开采技术的发展和原油产量的提高，相应产生的废水水量也在逐年增加，不达标废水的任意排放对外界环境造成了严重的污染问题。
本课题的主要目的在于设计一套适合采油废水特点的污水处理工艺，实现采油废水的达标排放。研究以辽河油田兴一联合站的采油废水为试验对象，通过为期6个月的实验室小试和将近3个月的现场中试(处理规模为1m~3／h)，验证了“气浮(加药)—MBR—BAF—排放”工艺流程在采油废水处理中的有效性和适用性。
在实验室小试阶段，考察了污泥的培养驯化阶段(间歇进水)污泥的性状，并以反应器出水中的污染物指标合格作为污泥驯化成功的标志；还考察了试验稳定运行阶段(连续进水)，不同的HRT(水力停留时间)下，各种污染物的去除效果和膜的连续出水情况。试验结果表明，HRT=10h是膜生物反应器的最佳运行参数，在原水水质COD-400mg／L，BOD-80～100mg／L，SS-100mg／L，油-50mg／L的条件下，COD去除率可达到80％，BOD、SS和石油类物质的去除率均在90％以上，出水可以直接排放。同时，该水力停留时间能够保证膜在较长时间内连续出水，反应器运行稳定。
在小试基础上，于现场进行了处理规模为1m~3／h的中试研究，首先进行污泥的培养驯化，之后在HRT=10h的参数下运行，试验出水仍然保持较高的污染物去除率，系统出水COD基本保持在90mg／L左右，BOD为2～3mg／L，SS、NH_3-N和石油类等均在1mg／L以下，完全能够达到国家规定的污水排放标准。
The amount of crude oil that is recovered in Liaohe Oil Field each year can reach 1.5 107 ton. However, with the development of the oil recovery technology and the exaltation of the crude oil yield, the amount of the accompanying wastewater (produced water) begin to increase year after year and the arbitrarily discharged wastewater has caused serious environmental problem.
The main object of this paper is to design a set of rational technological process that is suitable for produced water to achieve environmentally acceptable disposal of this kind of water. On the basis of current produced water treatment methods, we took the technological flow - "air-floatation (adding chemical) - MBR - BAF -discharging" to treat produced water from Xingyilian (the name of an oil recovery site) and obtained satisfactory results.
In laboratory experiment, we observed the properties of the sludge during cultivation (discontinuous influent mode) and took the concentration values of pollutants in the supernatant fluid which had been treated by microbes as the indication of domestic active sludge. And since the set of devices had began to run steadily (continuous influent mode), we reviewed the disposing effect of the pollutants and the state of the membrane. From the experiment, we concluded that when the COD of raw water was about 400 mg/L, BOD 80-100 mg/L, SS about 100 mg/L and oil content about 50 mg/L, the rate of COD removal could reach 80%, and removal of BOD, SS, oil content were all above 90%, effluent could be discharged to surfaces directly. And HRT = 10h was the best working parameter for the system, under which decent removal effect could be achieved and also the membrane kept fine state.
On the basis of laboratory experiment, we carried on field pilot-plant-scale test (disposal quantity was 1 m3/h). After the sludge cultivation, the system was operated with the parameter of HRT =10h, achieving effluent with following characters -COD was about 90mg/L, BOD was about 2-3 mg/L, SS, NH3-N and oil content were all less than 1 mg/L. The quality of the system effluent could fully fit the national required discharged wastewater quality.
本课题的主要目的在于设计一套适合采油废水特点的污水处理工艺，实现采油废水的达标排放。研究以辽河油田兴一联合站的采油废水为试验对象，通过为期6个月的实验室小试和将近3个月的现场中试(处理规模为1m~3／h)，验证了“气浮(加药)—MBR—BAF—排放”工艺流程在采油废水处理中的有效性和适用性。
在实验室小试阶段，考察了污泥的培养驯化阶段(间歇进水)污泥的性状，并以反应器出水中的污染物指标合格作为污泥驯化成功的标志；还考察了试验稳定运行阶段(连续进水)，不同的HRT(水力停留时间)下，各种污染物的去除效果和膜的连续出水情况。试验结果表明，HRT=10h是膜生物反应器的最佳运行参数，在原水水质COD-400mg／L，BOD-80～100mg／L，SS-100mg／L，油-50mg／L的条件下，COD去除率可达到80％，BOD、SS和石油类物质的去除率均在90％以上，出水可以直接排放。同时，该水力停留时间能够保证膜在较长时间内连续出水，反应器运行稳定。
在小试基础上，于现场进行了处理规模为1m~3／h的中试研究，首先进行污泥的培养驯化，之后在HRT=10h的参数下运行，试验出水仍然保持较高的污染物去除率，系统出水COD基本保持在90mg／L左右，BOD为2～3mg／L，SS、NH_3-N和石油类等均在1mg／L以下，完全能够达到国家规定的污水排放标准。
The amount of crude oil that is recovered in Liaohe Oil Field each year can reach 1.5 107 ton. However, with the development of the oil recovery technology and the exaltation of the crude oil yield, the amount of the accompanying wastewater (produced water) begin to increase year after year and the arbitrarily discharged wastewater has caused serious environmental problem.
The main object of this paper is to design a set of rational technological process that is suitable for produced water to achieve environmentally acceptable disposal of this kind of water. On the basis of current produced water treatment methods, we took the technological flow - "air-floatation (adding chemical) - MBR - BAF -discharging" to treat produced water from Xingyilian (the name of an oil recovery site) and obtained satisfactory results.
In laboratory experiment, we observed the properties of the sludge during cultivation (discontinuous influent mode) and took the concentration values of pollutants in the supernatant fluid which had been treated by microbes as the indication of domestic active sludge. And since the set of devices had began to run steadily (continuous influent mode), we reviewed the disposing effect of the pollutants and the state of the membrane. From the experiment, we concluded that when the COD of raw water was about 400 mg/L, BOD 80-100 mg/L, SS about 100 mg/L and oil content about 50 mg/L, the rate of COD removal could reach 80%, and removal of BOD, SS, oil content were all above 90%, effluent could be discharged to surfaces directly. And HRT = 10h was the best working parameter for the system, under which decent removal effect could be achieved and also the membrane kept fine state.
On the basis of laboratory experiment, we carried on field pilot-plant-scale test (disposal quantity was 1 m3/h). After the sludge cultivation, the system was operated with the parameter of HRT =10h, achieving effluent with following characters -COD was about 90mg/L, BOD was about 2-3 mg/L, SS, NH3-N and oil content were all less than 1 mg/L. The quality of the system effluent could fully fit the national required discharged wastewater quality.
引文
[1] 邓述波．油田采出水的特性及处理技术．工业水处理，2000，20(7)：10-12
[2] 邹启贤，陆正禹．油田废水处理综述．工业水处理，2001，21(8)：1-3
[3] 谢加才，王正江，刘喜林等．稠油产出水深度处理回用于热采锅炉的中试研究．石油学报，2003，24(5)：93-98
[4] 高廷耀．水污染控制工程(下册)．第一版．北京：高等教育出版社，1992年3月
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[6] Arnold et al. Designing oil and gas production systems. World Oil, 1985, 200(6): 91-92,94-95,98
[7] 臧维良等．带翼斜板设备处理石油污水的研究．石油化工环境保护，1997，2：12-15
[8] Carriere et al. Using coalescence to improve efficiency of oil/water separation. Field experiencee. The S.P. Pack free flow coalescer. Adv. Filtr. Sep. Technol., 1990, 1 (Filtr. Sep. Oil Gas Drill. Prod. Oper. ): 266-281
[9] Dotson et al. Report on the start-up of a unique hydro-cyclone-based system for treating produced water. Environmental Science and Research, 1996, 52(Produced Water 2):431-445
[10] Darlington et al., Process for treating produced water from oil recovery for removal of oil and water soluble petroleum components. EP901805 A117 Mar. 1999
[11] Means et al. Process for removing water-soluble organic compounds from produced water. EP432787 A1 Jun 1991
[12] Viraraghavan et al. Use of peat in the removal of oil from produced waters. Environ. Technol. Lett., 1989, 10(4): 385-394
[13] 李化民，苏显举等．油田含油污水处理．石油工业出版社，1992
[14] 张士权，潘红磊．采油污水排放达标面临的问题与对策．油气田环境保护，1996(6)： 20-22
[15] 刘霞等．用单柱离子色谱法测定油田水质．石油学报，1999，20(5)：76-81
[16] 吕开河，郭东荣．油田废水的生物处理．钻井液与完井液，1996，13(6)：9-12
[17] 雷乐成，陈琳，张瑞成．油田废水COD构成分析及生物可降解性研究．给水排水，2002，28(6)：44-47
[18] 陈进富，黄军荣，吴芳云．油田采油污水的CODcr构成分析．工业水处理，2002，22(8)：29-31
[19] Watkinson et al. Biodegradability of produced water effluents. Proc. Inst. Pet., 1987, (1, Microb. Probl. Offshore Oil Ind.): 165-173
[20] Tellez et al. Bioreclamation of oilfield produced wastewater: characterization and feasibility study. Environmental Science Research, 1992, 46 (Produced Water): 523-533
[21] Rajganesh et al. Bio-treatment of produced water for removal of sulfides, organics and toxicity. Applied Bio-chemistry and Bio-technology, 1995, 51 (52): 735-746
[22] Madian et al. Treatment of produced water for surface discharge at the Arun gas condensate field. Proc.-Int. Symp. Oilfield Chem., SPE: Richardson, Tex. USA, 1995, 17-27
[23] Gevertz et al. Microbial oxidation of soluble sulfide in produced water from the Bakken Solving Environmental Problem International Conference (Dallas, 9/11-14/95) Process (US DOE report No.9509173), 1995, 295-309
[24] Dutta et al. Recent developments in hydro-cyclones and bio-treatment of wastes incorporating polymer membrane and activated carbon. 3rd Inst. Gas Technol. (Chicago) Gas, Oil, Coal & Bio-technol. Int. Symp. (New Orleans, 12/3-5/90) Process, 1991, 239-254
[25] 竺建荣．厌—好氧交替工艺处理辽河油田废水试验．环境科学，1999，20(1)；62
[26] Biochemical degradation treats produced water. OGJ, 1997, Jan 20
[27] Biotreating produced water could save costs, benefit environment. OGJ, 1996, May 6
[28] 籍国东等．自由表面流人工湿地处理超稠油废水．环境科学，2001，22(4)：95-99
[29] Seybold et al. Demonstration of produced water treatment using a biological GAC-FBR. 9th Inst. Gas Technol. Gas, Oil & Environ. Biotechnol. Int. Symp. (Colorado Springs, Co, 12/9-11/96) Process 1996
[30] Hicky. Reactor combines activated carbon and bio-mass to treat water. Gas-tips, 1995, 1 (1) : 11-13
[31] Simmons. Produced water treatment & disposal options: a technical and economic comparison. 3rd US DOE, Tulsa Univ. et al. Petrl. Environ. Conf. (Albuquergue, NM, 9/24-27/96), 1996
[32] 龚争辉．气浮—生物接触氧化技术在采油废水处理中的应用．黑龙江环境通报，2000，24(4)：26-27
[33] 樊耀波等．膜生物反应器净化石油化工朽水的研究．环境科学学报，1997，17(1)：68-74
[34] 樊耀波．水与废水处理中的膜生物反应器技术．环境科学，1995，16(5)：79-81
[35] BUDD William E, OKAY Robert W. Biological Treatment of Waste Water and Industrial Wastes. US: Dorr Oliver Incorporated, 1969,.3:472-765
[36] 吴开芬．超滤法处理回用印纱厂擦板液的研究．环境科学，1993，14(4)：37-41
[37] 邢传宏．无机膜—生物反应器处理生活污水试验研究．环境科学，1997，18(3)：1-4
[38] 李红兵．中空纤维膜生物反应器处理生活污水的特性．环境科学，1999，20(2)：53-56
[39] Pierre Cote et al. Bubblefree aeration using membranes: process analysis. Journal WPCF,
1988,60 (11): 1986-1992
[40] Muller et al. Aerobic domestic wastewater treatment in a pilot plant with complete sludge retention by cross flow filtration. Wat. Res., 1995, 29(4): 1179-1189
[41] 刘锐，黄霞，刘若鹏．膜—生物反应器和传统活性污泥工艺的比较．环境科学，2001，22(3)：20-24
[42] 邢传宏，钱易等．超滤膜-生物反应器处理生活污水及其水力学研究．环境科学，1997，18(5)：19-22
[43] Davies W J et al. Intensified activated sludge process with submerged membrane micro filtration. Wat. Sci. Tech., 1998, 38(4～5): 421-428
[44] 刘忠洲等．微滤、超滤过程中的膜污染与清洗．水处理技术，1997，23(4)：187-193
[45] 续曙光等．超滤膜污染和清洗方法的研究．环境化学．1998，17(4)：404-406
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[2] 邹启贤，陆正禹．油田废水处理综述．工业水处理，2001，21(8)：1-3
[3] 谢加才，王正江，刘喜林等．稠油产出水深度处理回用于热采锅炉的中试研究．石油学报，2003，24(5)：93-98
[4] 高廷耀．水污染控制工程(下册)．第一版．北京：高等教育出版社，1992年3月
[5] 何桂华．油田采出水处理构筑物．注水及水处理，1992，1：69-74
[6] Arnold et al. Designing oil and gas production systems. World Oil, 1985, 200(6): 91-92,94-95,98
[7] 臧维良等．带翼斜板设备处理石油污水的研究．石油化工环境保护，1997，2：12-15
[8] Carriere et al. Using coalescence to improve efficiency of oil/water separation. Field experiencee. The S.P. Pack free flow coalescer. Adv. Filtr. Sep. Technol., 1990, 1 (Filtr. Sep. Oil Gas Drill. Prod. Oper. ): 266-281
[9] Dotson et al. Report on the start-up of a unique hydro-cyclone-based system for treating produced water. Environmental Science and Research, 1996, 52(Produced Water 2):431-445
[10] Darlington et al., Process for treating produced water from oil recovery for removal of oil and water soluble petroleum components. EP901805 A117 Mar. 1999
[11] Means et al. Process for removing water-soluble organic compounds from produced water. EP432787 A1 Jun 1991
[12] Viraraghavan et al. Use of peat in the removal of oil from produced waters. Environ. Technol. Lett., 1989, 10(4): 385-394
[13] 李化民，苏显举等．油田含油污水处理．石油工业出版社，1992
[14] 张士权，潘红磊．采油污水排放达标面临的问题与对策．油气田环境保护，1996(6)： 20-22
[15] 刘霞等．用单柱离子色谱法测定油田水质．石油学报，1999，20(5)：76-81
[16] 吕开河，郭东荣．油田废水的生物处理．钻井液与完井液，1996，13(6)：9-12
[17] 雷乐成，陈琳，张瑞成．油田废水COD构成分析及生物可降解性研究．给水排水，2002，28(6)：44-47
[18] 陈进富，黄军荣，吴芳云．油田采油污水的CODcr构成分析．工业水处理，2002，22(8)：29-31
[19] Watkinson et al. Biodegradability of produced water effluents. Proc. Inst. Pet., 1987, (1, Microb. Probl. Offshore Oil Ind.): 165-173
[20] Tellez et al. Bioreclamation of oilfield produced wastewater: characterization and feasibility study. Environmental Science Research, 1992, 46 (Produced Water): 523-533
[21] Rajganesh et al. Bio-treatment of produced water for removal of sulfides, organics and toxicity. Applied Bio-chemistry and Bio-technology, 1995, 51 (52): 735-746
[22] Madian et al. Treatment of produced water for surface discharge at the Arun gas condensate field. Proc.-Int. Symp. Oilfield Chem., SPE: Richardson, Tex. USA, 1995, 17-27
[23] Gevertz et al. Microbial oxidation of soluble sulfide in produced water from the Bakken Solving Environmental Problem International Conference (Dallas, 9/11-14/95) Process (US DOE report No.9509173), 1995, 295-309
[24] Dutta et al. Recent developments in hydro-cyclones and bio-treatment of wastes incorporating polymer membrane and activated carbon. 3rd Inst. Gas Technol. (Chicago) Gas, Oil, Coal & Bio-technol. Int. Symp. (New Orleans, 12/3-5/90) Process, 1991, 239-254
[25] 竺建荣．厌—好氧交替工艺处理辽河油田废水试验．环境科学，1999，20(1)；62
[26] Biochemical degradation treats produced water. OGJ, 1997, Jan 20
[27] Biotreating produced water could save costs, benefit environment. OGJ, 1996, May 6
[28] 籍国东等．自由表面流人工湿地处理超稠油废水．环境科学，2001，22(4)：95-99
[29] Seybold et al. Demonstration of produced water treatment using a biological GAC-FBR. 9th Inst. Gas Technol. Gas, Oil & Environ. Biotechnol. Int. Symp. (Colorado Springs, Co, 12/9-11/96) Process 1996
[30] Hicky. Reactor combines activated carbon and bio-mass to treat water. Gas-tips, 1995, 1 (1) : 11-13
[31] Simmons. Produced water treatment & disposal options: a technical and economic comparison. 3rd US DOE, Tulsa Univ. et al. Petrl. Environ. Conf. (Albuquergue, NM, 9/24-27/96), 1996
[32] 龚争辉．气浮—生物接触氧化技术在采油废水处理中的应用．黑龙江环境通报，2000，24(4)：26-27
[33] 樊耀波等．膜生物反应器净化石油化工朽水的研究．环境科学学报，1997，17(1)：68-74
[34] 樊耀波．水与废水处理中的膜生物反应器技术．环境科学，1995，16(5)：79-81
[35] BUDD William E, OKAY Robert W. Biological Treatment of Waste Water and Industrial Wastes. US: Dorr Oliver Incorporated, 1969,.3:472-765
[36] 吴开芬．超滤法处理回用印纱厂擦板液的研究．环境科学，1993，14(4)：37-41
[37] 邢传宏．无机膜—生物反应器处理生活污水试验研究．环境科学，1997，18(3)：1-4
[38] 李红兵．中空纤维膜生物反应器处理生活污水的特性．环境科学，1999，20(2)：53-56
[39] Pierre Cote et al. Bubblefree aeration using membranes: process analysis. Journal WPCF,
1988,60 (11): 1986-1992
[40] Muller et al. Aerobic domestic wastewater treatment in a pilot plant with complete sludge retention by cross flow filtration. Wat. Res., 1995, 29(4): 1179-1189
[41] 刘锐，黄霞，刘若鹏．膜—生物反应器和传统活性污泥工艺的比较．环境科学，2001，22(3)：20-24
[42] 邢传宏，钱易等．超滤膜-生物反应器处理生活污水及其水力学研究．环境科学，1997，18(5)：19-22
[43] Davies W J et al. Intensified activated sludge process with submerged membrane micro filtration. Wat. Sci. Tech., 1998, 38(4～5): 421-428
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