稠油污水回用于热采锅炉处理技术研究
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摘要
我国在稠油污水回用于热采锅炉方面作了大量的研究工作,部分污水处理装置已投入运行,但由于稠油污水存在水质变化大、油水密度差小、乳化严重等难点,再加上处理工艺流程不成熟等原因,稠油污水处理在回用方面尚未取得实质性的进展。
针对以上问题,本文的研究目的是以胜利油田陈庄站稠油污水回用处理为例,设计一套适合稠油污水特点的污水回用处理工艺,为稠油污水回用于热采锅炉实现工业化提供理论基础和技术支撑。室内模拟和现场中试的主要创新性研究成果和结论如下:
1.室内模拟研究
1)采用限制性培养方法,针对陈庄稠油污水,构建了一组石油降解菌群SL-16。通过室内摇瓶实验测得该菌群在最佳条件下对陈庄稠油的降解率可达68 %,其适宜的生长及降解温度为35～45℃,pH值为7.0～9.0,矿化度为4000～14000 mg/L,接种量为2 %,原油初始浓度为1 %,摇床转速为140 r/min。
2)在污水回用处理的模拟研究中,采用气浮和生物接触氧化除油,过滤除悬浮物,超滤和反渗透双膜法脱盐淡化、除硬度。气浮出水平均含油量低于20 mg/L。生物接触氧化的最佳运行条件为:温度35～45℃;停留时间为16 h;营养配比COD_(Cr):N:P=100:5:1,N源为硝酸铵,P源为磷酸氢二钾;在此条件下,生物接触氧化后出水中的含油量低于1 mg/L。在0.6 MPa的最佳过滤压力下,砂滤出水的悬浮物降低于5 mg/L。0.3 MPa进水压力下,超滤能够为反渗透提供浊度为0.19、SDI为2.6的给水。制水压力为1.5 MPa条件下,反渗透脱盐率高于90 %,钙离子去除率94 %,镁离子去除率100 %,出水水质优于热采锅炉所用清水。实验证明,采用气浮、生物接触氧化除油,过滤器去除悬浮物,双膜法脱盐淡化、除硬度的稠油污水回用处理工艺技术是可行的。
2.现场中试研究
1)采用换热器、冷却塔、气浮、生物接触氧化、杀菌、絮凝沉降、双介质过滤、保安过滤、超滤、反渗透等设备单元组成的污水回用处理工艺进行现场中试。稠油污水通过换热器对反渗透产水进行加温,反渗透产水可提高10℃,利用冷却塔可以将污水温度降低10～15℃,保证生化进水的温度不高于45℃;气浮可以满足生物接触氧化进水含油量低于30 mg/L的进水要求;在进水量为8.3m3/h的条件下,生物接触氧化反应器出水水质不仅达到GB8978-1996国标规定的二级排放标准,而且出水含油量低于1 mg/L;为防止生化出水中细菌对超滤膜产生污堵,采用次氯酸钠杀菌,投加量为100 ml/L(有效氯含量为10 %);生化出水中残余污染物采用絮凝、沉降、双介质过滤进一步去除,经过实验筛选确定絮凝剂为聚合氯化铝,投加量为80 mg/L,助凝剂为聚丙烯酰胺,投加量为1.25 mg/L;利用精细过滤器作为超滤的保安过滤器,避免大的颗粒物对超滤膜造成伤害;超滤作为反渗透的预处理,可以为反渗透提供SDI小于3,浊度小于0.23 NTU,悬浮物接近0 mg/L的稳定给水,能够满足反渗透的进水要求;反渗透平均脱盐率92.5 %,钙离子平均去除率93 %,镁离子的去除率100 %,产水水质优于清水,完全可以代替清水用于热采锅炉。
2)多级生物接触氧化反应器的除油机理主要为曝气气浮、生物氧化、截留吸附和食物链分级捕食。在系统稳定运行时,随着水流方向,生物膜上的细菌群落结构发生变化,群落结构主要由生物膜上吸附的原油组分决定。经过分子生物学方法分析确认,菌群SL-16为优势菌时,生物接触氧化反应器对污水的处理效果较好。
本论文的研究成果为稠油污水回用于热采锅炉处理实现工业化提供了理论基础和技术支撑,为超滤-反渗透在采油污水回用处理中建立了有效的预处理技术,为油田采油污水实现资源化处理有积极的指导意义。
A lot of research work has been done about reusing the heavy oil sewage in thermal steam generators in china. Part of sewage treatment equipment has been in use. No substantive progress has beeen made in research of reusing heavy oil sewage, because of the serious emulsification of heavy oil effluent and great changes happened usually to water quality and little density difference between water and oil.
In the light of the problems above mentioned, the main purpose of this paper is to design a set of sewage treatment techniques which offer theoretical basis and technical support for realizing industrialization of reusing of heavy oil sewage in thermal steam generator.The innovative research results and conclusions of laboratory simulation test and field pilot scale test are summarized as follows:
1. Laboratory simulation test
1) A bacteria community SL-16 with capacity of heavy oil degradation was constructed by the techniques of limited cultivation. Through shaking experiments, the best degradation conditions of bacteria community presented as follows: the temperature was 35～45°C, the pH was 7.0～9.0, the mineralized rate was 4 000～14 000 mg/L, the inoculation was 2 %,the initial crude oil concentration was lower than 1000mg/L,and the rotating speed was 140 r/min. In the best degradation conditions, the oil removal rate of the heavy oil reached 68 %.
2) In the laboratory simulation, oil was removed by gas floatation and biological contact oxygen method; suspend solid was removed by sand filter; salinity was removed by double membrane of ultra-filtration and reverse osmosis. Oil content of gas floatation effluent was lower than 20 mg/L averagely. The best operating condition of biological oxygen method presented as follows: the temperature was 35～45°C, HRT was 16 h; The optimum fertilization proportions (COD_(Cr):N:P) was 100:5:1 when nitrogen was ammonium nitrate and phosphorus source was dipotassium hydrogen phosphate. In this conditions oil content of effluent of biological reactor was lower than 1mg/L.The residual suspend solids was less than 5 mg/L after filtrated by sand filtration under the filtration pressure of 0.6 MPa. SDI of producing water of ultra-filtration was 2.6, turbidity of producing water of ultra-filtration was 0.19 NTU under the operating pressure of 0.3 MPa, which can meet the request of reverse osmosis. Reverse osmosis can removed scaling ions and most of salinity, the removal rate of Ca2+ reached 94 % and the removal rate of Mg2+ reached 100 %, desalination rate was 90 %.the quality of producing water of reverse osmosis was better than fresh water. The experiment showed that the process was feasible to realize the reusing treatment of heavy oil waste water, which including gas floatation, biological contact oxygen method, sand filtration, ultrafiltration and reverse osmosis.
2. Field pilot scale test
1)The design of reusing treatment adopts heat exchanger, cooling tower, gas floatation, biological contact oxygen method, sterilization, flocculation sedimentation, two media filter, ultrafiltration and reverse osmosis. Heavy oil waste water heated the producing water of RO by heat exchanger, and the temperature of producing water increased 10°C.The cooling extent of cooling tower was from 10°C to 15°C, which could ensure the temperature of influent of biological contact oxygen method was not higher than 45°C.The oil concentration of gas floatation effluent was less than 30mg/L, which meet the request of biological contact oxygen method. Under the conditions of influent flow was 8.3 m3/h, the quality of effluent of biological contact oxygen method reached secondary discharge standard of national standard GB8978-1996, and oil concentration was less than 1mg/L. Sodium hypochlorite containing available chlorine 10 % was used to kill bacteria and it’s amount was 100 mL/L. the residual pollutants was removed by flocculation sedimentation and two medias filter, inputting amount of poly aluminium chloride was 80 mg/L and Polyacrylamide was 1.25 mg/L .Fine filter as security filter could avoid the damage of suspend solid to ultrafiltration membrane. SDI of producing water of ultrafiltration was no more than 3, turbidity of producing water of ultra-filtration was no more than 0.23 NTU under the operating pressure of 0.24 MPa, which could offer influent with stable quality for reverse osmosis. Reverse osmosis could remove scaling ions and most of salinity, the average removal rate of Ca~(2+) reached 93 % and the removal rate of Mg~(2+) reached 100 %, the average desalination rate was 92.5 %.The quality of producing water of reverse osmosis is better than fresh water, producing water can be used to replace fresh water.
2) Degreasing mechanism of multilevel biological contact oxygen reactor includs the Aeration Flotation, biological oxygen, interception and adsorption, and food chain grade predator prey. Bacterial community structure was determined by component of oil in biofilm, which changed along the flow direction. The molecular biological analysis results showed that the effluent of biological contact oxygen reactor was of good quality when dominant bacteria community was SL-16 community.
Research results of this paper offer theoretical basis and technical supports for realizing industrialization of reusing of heavy oil sewage in thermal steam generators, and the reseach established effective pretreatment technology for ultrafiltration and reverse osmosis. In summary, the results of this reseach have positive guiding significance for resourceful disposal of oil field waste water.
针对以上问题,本文的研究目的是以胜利油田陈庄站稠油污水回用处理为例,设计一套适合稠油污水特点的污水回用处理工艺,为稠油污水回用于热采锅炉实现工业化提供理论基础和技术支撑。室内模拟和现场中试的主要创新性研究成果和结论如下:
1.室内模拟研究
1)采用限制性培养方法,针对陈庄稠油污水,构建了一组石油降解菌群SL-16。通过室内摇瓶实验测得该菌群在最佳条件下对陈庄稠油的降解率可达68 %,其适宜的生长及降解温度为35～45℃,pH值为7.0～9.0,矿化度为4000～14000 mg/L,接种量为2 %,原油初始浓度为1 %,摇床转速为140 r/min。
2)在污水回用处理的模拟研究中,采用气浮和生物接触氧化除油,过滤除悬浮物,超滤和反渗透双膜法脱盐淡化、除硬度。气浮出水平均含油量低于20 mg/L。生物接触氧化的最佳运行条件为:温度35～45℃;停留时间为16 h;营养配比COD_(Cr):N:P=100:5:1,N源为硝酸铵,P源为磷酸氢二钾;在此条件下,生物接触氧化后出水中的含油量低于1 mg/L。在0.6 MPa的最佳过滤压力下,砂滤出水的悬浮物降低于5 mg/L。0.3 MPa进水压力下,超滤能够为反渗透提供浊度为0.19、SDI为2.6的给水。制水压力为1.5 MPa条件下,反渗透脱盐率高于90 %,钙离子去除率94 %,镁离子去除率100 %,出水水质优于热采锅炉所用清水。实验证明,采用气浮、生物接触氧化除油,过滤器去除悬浮物,双膜法脱盐淡化、除硬度的稠油污水回用处理工艺技术是可行的。
2.现场中试研究
1)采用换热器、冷却塔、气浮、生物接触氧化、杀菌、絮凝沉降、双介质过滤、保安过滤、超滤、反渗透等设备单元组成的污水回用处理工艺进行现场中试。稠油污水通过换热器对反渗透产水进行加温,反渗透产水可提高10℃,利用冷却塔可以将污水温度降低10～15℃,保证生化进水的温度不高于45℃;气浮可以满足生物接触氧化进水含油量低于30 mg/L的进水要求;在进水量为8.3m3/h的条件下,生物接触氧化反应器出水水质不仅达到GB8978-1996国标规定的二级排放标准,而且出水含油量低于1 mg/L;为防止生化出水中细菌对超滤膜产生污堵,采用次氯酸钠杀菌,投加量为100 ml/L(有效氯含量为10 %);生化出水中残余污染物采用絮凝、沉降、双介质过滤进一步去除,经过实验筛选确定絮凝剂为聚合氯化铝,投加量为80 mg/L,助凝剂为聚丙烯酰胺,投加量为1.25 mg/L;利用精细过滤器作为超滤的保安过滤器,避免大的颗粒物对超滤膜造成伤害;超滤作为反渗透的预处理,可以为反渗透提供SDI小于3,浊度小于0.23 NTU,悬浮物接近0 mg/L的稳定给水,能够满足反渗透的进水要求;反渗透平均脱盐率92.5 %,钙离子平均去除率93 %,镁离子的去除率100 %,产水水质优于清水,完全可以代替清水用于热采锅炉。
2)多级生物接触氧化反应器的除油机理主要为曝气气浮、生物氧化、截留吸附和食物链分级捕食。在系统稳定运行时,随着水流方向,生物膜上的细菌群落结构发生变化,群落结构主要由生物膜上吸附的原油组分决定。经过分子生物学方法分析确认,菌群SL-16为优势菌时,生物接触氧化反应器对污水的处理效果较好。
本论文的研究成果为稠油污水回用于热采锅炉处理实现工业化提供了理论基础和技术支撑,为超滤-反渗透在采油污水回用处理中建立了有效的预处理技术,为油田采油污水实现资源化处理有积极的指导意义。
A lot of research work has been done about reusing the heavy oil sewage in thermal steam generators in china. Part of sewage treatment equipment has been in use. No substantive progress has beeen made in research of reusing heavy oil sewage, because of the serious emulsification of heavy oil effluent and great changes happened usually to water quality and little density difference between water and oil.
In the light of the problems above mentioned, the main purpose of this paper is to design a set of sewage treatment techniques which offer theoretical basis and technical support for realizing industrialization of reusing of heavy oil sewage in thermal steam generator.The innovative research results and conclusions of laboratory simulation test and field pilot scale test are summarized as follows:
1. Laboratory simulation test
1) A bacteria community SL-16 with capacity of heavy oil degradation was constructed by the techniques of limited cultivation. Through shaking experiments, the best degradation conditions of bacteria community presented as follows: the temperature was 35～45°C, the pH was 7.0～9.0, the mineralized rate was 4 000～14 000 mg/L, the inoculation was 2 %,the initial crude oil concentration was lower than 1000mg/L,and the rotating speed was 140 r/min. In the best degradation conditions, the oil removal rate of the heavy oil reached 68 %.
2) In the laboratory simulation, oil was removed by gas floatation and biological contact oxygen method; suspend solid was removed by sand filter; salinity was removed by double membrane of ultra-filtration and reverse osmosis. Oil content of gas floatation effluent was lower than 20 mg/L averagely. The best operating condition of biological oxygen method presented as follows: the temperature was 35～45°C, HRT was 16 h; The optimum fertilization proportions (COD_(Cr):N:P) was 100:5:1 when nitrogen was ammonium nitrate and phosphorus source was dipotassium hydrogen phosphate. In this conditions oil content of effluent of biological reactor was lower than 1mg/L.The residual suspend solids was less than 5 mg/L after filtrated by sand filtration under the filtration pressure of 0.6 MPa. SDI of producing water of ultra-filtration was 2.6, turbidity of producing water of ultra-filtration was 0.19 NTU under the operating pressure of 0.3 MPa, which can meet the request of reverse osmosis. Reverse osmosis can removed scaling ions and most of salinity, the removal rate of Ca2+ reached 94 % and the removal rate of Mg2+ reached 100 %, desalination rate was 90 %.the quality of producing water of reverse osmosis was better than fresh water. The experiment showed that the process was feasible to realize the reusing treatment of heavy oil waste water, which including gas floatation, biological contact oxygen method, sand filtration, ultrafiltration and reverse osmosis.
2. Field pilot scale test
1)The design of reusing treatment adopts heat exchanger, cooling tower, gas floatation, biological contact oxygen method, sterilization, flocculation sedimentation, two media filter, ultrafiltration and reverse osmosis. Heavy oil waste water heated the producing water of RO by heat exchanger, and the temperature of producing water increased 10°C.The cooling extent of cooling tower was from 10°C to 15°C, which could ensure the temperature of influent of biological contact oxygen method was not higher than 45°C.The oil concentration of gas floatation effluent was less than 30mg/L, which meet the request of biological contact oxygen method. Under the conditions of influent flow was 8.3 m3/h, the quality of effluent of biological contact oxygen method reached secondary discharge standard of national standard GB8978-1996, and oil concentration was less than 1mg/L. Sodium hypochlorite containing available chlorine 10 % was used to kill bacteria and it’s amount was 100 mL/L. the residual pollutants was removed by flocculation sedimentation and two medias filter, inputting amount of poly aluminium chloride was 80 mg/L and Polyacrylamide was 1.25 mg/L .Fine filter as security filter could avoid the damage of suspend solid to ultrafiltration membrane. SDI of producing water of ultrafiltration was no more than 3, turbidity of producing water of ultra-filtration was no more than 0.23 NTU under the operating pressure of 0.24 MPa, which could offer influent with stable quality for reverse osmosis. Reverse osmosis could remove scaling ions and most of salinity, the average removal rate of Ca~(2+) reached 93 % and the removal rate of Mg~(2+) reached 100 %, the average desalination rate was 92.5 %.The quality of producing water of reverse osmosis is better than fresh water, producing water can be used to replace fresh water.
2) Degreasing mechanism of multilevel biological contact oxygen reactor includs the Aeration Flotation, biological oxygen, interception and adsorption, and food chain grade predator prey. Bacterial community structure was determined by component of oil in biofilm, which changed along the flow direction. The molecular biological analysis results showed that the effluent of biological contact oxygen reactor was of good quality when dominant bacteria community was SL-16 community.
Research results of this paper offer theoretical basis and technical supports for realizing industrialization of reusing of heavy oil sewage in thermal steam generators, and the reseach established effective pretreatment technology for ultrafiltration and reverse osmosis. In summary, the results of this reseach have positive guiding significance for resourceful disposal of oil field waste water.
引文
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