电化学预氧化—生物转盘联合处理采油污水
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摘要
随着采油技术的不断提高,采油污水成分日趋复杂,直接回注或排放不仅会污染环境,还会造成巨大的浪费。所以,必须对油田采出水进行适当处理然后回注或排放。
本文以采油污水为研究对象,首先采用电化学预氧化工艺来提高污水的可生化性,考察了电解电压、pH值、电解时间、极板间距、阳极材料、阳极极板数等因素对除污效果的影响。利用正交实验设计和单因素验证确定了电化学预氧化最佳工艺参数为:电解电压15V、pH值为5、极板间距2.0cm、阳极材料为Ti/Ir形稳电极、2个阳极极板,此条件下电解30min采油污水COD的去除率达到61%,SRB杀灭率为99.89%。利用BOD_5/COD_(Cr)比值法和微生物呼吸速率法对污水的可生化性进行了研究,两种实验方法均表明处理前采油污水的可生化性较差,而经电化学氧化工艺处理后的污水可进行生化处理,同时在微生物呼吸速率法的基础上探讨了微生物的生化反应动力学,结果表明,实验条件下微生物呼吸速率都严格遵循一级动力学关系式lnC(O)=lnC_0 (O)–Kt。
然后对生物转盘生物膜的载体—活性炭进行了表面氧化改性,借助化学分析、表面形态分析等表征方法研究了化学氧化-Fe~(3+)覆盖技术和HF处理后活性炭的表面形貌、表面官能团、比表面积及其亲水性的变化情况,对比分析了两种改性方法对生物转盘挂膜性能的影响。将两种表面氧化处理的活性炭分别制作成两组生物转盘盘片Ι、Π,用其来处理经电化学氧化法预处理的采油污水。结果表明采用化学氧化-Fe~(3+)覆盖技术改性处理过的活性炭具有更大的比表面积、较高的酸性官能团含量、亲水性更好,挂膜后两组生物转盘的微生物相比较丰富,但是生物转盘II的生物膜厚度更厚一些,挂膜速率也更快,两组生物转盘的微生物含量分别为2.20×10~9cfu/g、2.60×10~9cfu/g,生物膜干重分别为12.7858g/m~2、16.9096g/m~2。在盘片转速4rpm、水温20℃、HRT为6h、pH值为6~8时,三级生物转盘各级COD去除率都在80%以上,最高达到了92.36%,并且生物转盘Π要比Ι的去除效果好。实验还研究了电化学预处理对生物转盘处理效果的影响,结果表明电化学与生物转盘联合处理采油污水的效果要远远好于单独使用生物转盘的效果,处理后污水COD含量为65.8mg/L,达到污水综合排放标准的二级标准。
With the continuous improvement of Oil extraction technology, the increasing complexity of produced water components, direct injection or discharge will not only pollute the environment, but also cause great waste. Therefore, the oilfield produced water must be properly treated then reinjected or let.
This text was based on oilfield produced sewage, first of all, by electrochemical preoxidation process to improve biodegradability of the sewage, inspected the electrolysis voltage, pH value, electrolysis time, plate spacing, the anode material, and the number of the anode plate on the decontamination effect.
Using Orthogonal experiment design and single-factor authentication determine the best electrochemical preoxidation process parameters: electrolysis voltage 15V, pH 5, plate spacing 2.0cm, anode materials for the Ti/Ir dimensionally stable electrode, the anode is 2 board, under these conditions, the removal rate of COD achieve 61% after electrolyzing 30 min, SRB killing rate was 99.89%. The biochemical capacity of sewage treated and untreated was studied by BOD_5/COD_(Cr) and microbial respiration rate method. Both experimental methods show that the former produced water biodegradability is poor, and the electrochemical oxidation treatment can be the biological treatment of sewage, at the same time, on the basis of microbial respiration rate, the microbial reaction kinetics results show that under the experimental conditions microbial respiration rate are strictly abide by a kinetic relationship lnC(O) = lnC_0(O)-Kt.
Then rotating biological contactors biofilm carrier - the surface of activated carbon was modified by the chemical oxidation method - Fe~(3+) coverage technology and HF treatment. In virtue of chemical analysis, analysis of surface morphology characterization studied the changes of surface morphology, surface groups, hydrophilic and specific surface area activated carbon treated.Contrasted the two methods to impact on film properties of rotating biological contactor. Activated carbon dealt with the two surface oxidation was cranked out disces of rotating biological contactorsΙandΠ.Using them to dispose the produced water of being pretreated by electrochemical oxidation.The results showed that the use of chemical oxidation-Fe~(3+) coverage technology modification of activated carbon have greater specific surface area, high levels of acidic functional groups, as well as better link hydrophilic The microbe phase are very abundant of the two rotating biological contactor after attaching biofilm, but the biofilm of II is much thicker and attaching rate is faster. The microbe content are 2.20×10~9cfu/g, 2.60×10~9cfu/g respectively, and the dried weight of biofilm are 12.7858g/m~2,16.9096 g/m~2 respectively of the two rotating biological contactor.The COD removal rates of all the three-stages rotating biological contactor are above 80% with the disc speed of 4rpm, water temperature 20℃, HRT for 6h, pH 6 to 8, the highest level achieves 92.36%, and rotating biological contactorsΠis better thanΙ. Rotating biological contactors are always aerobic running. Also the results show that the electrochemical pretreatment united rotating biological contactors is much better than the separate use of rotating biological contactors on the removal effects. The COD content of sewage disposed is 65.8mg/L and reaches the second-grade standard of the national discharge.
本文以采油污水为研究对象,首先采用电化学预氧化工艺来提高污水的可生化性,考察了电解电压、pH值、电解时间、极板间距、阳极材料、阳极极板数等因素对除污效果的影响。利用正交实验设计和单因素验证确定了电化学预氧化最佳工艺参数为:电解电压15V、pH值为5、极板间距2.0cm、阳极材料为Ti/Ir形稳电极、2个阳极极板,此条件下电解30min采油污水COD的去除率达到61%,SRB杀灭率为99.89%。利用BOD_5/COD_(Cr)比值法和微生物呼吸速率法对污水的可生化性进行了研究,两种实验方法均表明处理前采油污水的可生化性较差,而经电化学氧化工艺处理后的污水可进行生化处理,同时在微生物呼吸速率法的基础上探讨了微生物的生化反应动力学,结果表明,实验条件下微生物呼吸速率都严格遵循一级动力学关系式lnC(O)=lnC_0 (O)–Kt。
然后对生物转盘生物膜的载体—活性炭进行了表面氧化改性,借助化学分析、表面形态分析等表征方法研究了化学氧化-Fe~(3+)覆盖技术和HF处理后活性炭的表面形貌、表面官能团、比表面积及其亲水性的变化情况,对比分析了两种改性方法对生物转盘挂膜性能的影响。将两种表面氧化处理的活性炭分别制作成两组生物转盘盘片Ι、Π,用其来处理经电化学氧化法预处理的采油污水。结果表明采用化学氧化-Fe~(3+)覆盖技术改性处理过的活性炭具有更大的比表面积、较高的酸性官能团含量、亲水性更好,挂膜后两组生物转盘的微生物相比较丰富,但是生物转盘II的生物膜厚度更厚一些,挂膜速率也更快,两组生物转盘的微生物含量分别为2.20×10~9cfu/g、2.60×10~9cfu/g,生物膜干重分别为12.7858g/m~2、16.9096g/m~2。在盘片转速4rpm、水温20℃、HRT为6h、pH值为6~8时,三级生物转盘各级COD去除率都在80%以上,最高达到了92.36%,并且生物转盘Π要比Ι的去除效果好。实验还研究了电化学预处理对生物转盘处理效果的影响,结果表明电化学与生物转盘联合处理采油污水的效果要远远好于单独使用生物转盘的效果,处理后污水COD含量为65.8mg/L,达到污水综合排放标准的二级标准。
With the continuous improvement of Oil extraction technology, the increasing complexity of produced water components, direct injection or discharge will not only pollute the environment, but also cause great waste. Therefore, the oilfield produced water must be properly treated then reinjected or let.
This text was based on oilfield produced sewage, first of all, by electrochemical preoxidation process to improve biodegradability of the sewage, inspected the electrolysis voltage, pH value, electrolysis time, plate spacing, the anode material, and the number of the anode plate on the decontamination effect.
Using Orthogonal experiment design and single-factor authentication determine the best electrochemical preoxidation process parameters: electrolysis voltage 15V, pH 5, plate spacing 2.0cm, anode materials for the Ti/Ir dimensionally stable electrode, the anode is 2 board, under these conditions, the removal rate of COD achieve 61% after electrolyzing 30 min, SRB killing rate was 99.89%. The biochemical capacity of sewage treated and untreated was studied by BOD_5/COD_(Cr) and microbial respiration rate method. Both experimental methods show that the former produced water biodegradability is poor, and the electrochemical oxidation treatment can be the biological treatment of sewage, at the same time, on the basis of microbial respiration rate, the microbial reaction kinetics results show that under the experimental conditions microbial respiration rate are strictly abide by a kinetic relationship lnC(O) = lnC_0(O)-Kt.
Then rotating biological contactors biofilm carrier - the surface of activated carbon was modified by the chemical oxidation method - Fe~(3+) coverage technology and HF treatment. In virtue of chemical analysis, analysis of surface morphology characterization studied the changes of surface morphology, surface groups, hydrophilic and specific surface area activated carbon treated.Contrasted the two methods to impact on film properties of rotating biological contactor. Activated carbon dealt with the two surface oxidation was cranked out disces of rotating biological contactorsΙandΠ.Using them to dispose the produced water of being pretreated by electrochemical oxidation.The results showed that the use of chemical oxidation-Fe~(3+) coverage technology modification of activated carbon have greater specific surface area, high levels of acidic functional groups, as well as better link hydrophilic The microbe phase are very abundant of the two rotating biological contactor after attaching biofilm, but the biofilm of II is much thicker and attaching rate is faster. The microbe content are 2.20×10~9cfu/g, 2.60×10~9cfu/g respectively, and the dried weight of biofilm are 12.7858g/m~2,16.9096 g/m~2 respectively of the two rotating biological contactor.The COD removal rates of all the three-stages rotating biological contactor are above 80% with the disc speed of 4rpm, water temperature 20℃, HRT for 6h, pH 6 to 8, the highest level achieves 92.36%, and rotating biological contactorsΠis better thanΙ. Rotating biological contactors are always aerobic running. Also the results show that the electrochemical pretreatment united rotating biological contactors is much better than the separate use of rotating biological contactors on the removal effects. The COD content of sewage disposed is 65.8mg/L and reaches the second-grade standard of the national discharge.
引文
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