电解-SBR联合处理高盐高浓度制药废水工艺技术研究
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摘要
本文系统地分析了制药废水的种类和特性。通过实际工程项目的经验了解到单独的生化法难以处理高浓度制药废水，甚至导致污泥死亡。本文以杭州市神鹰医药化工有限公司生产废水(COD_(Cr) 4100～7800mg／L，TN60～95mg／L，NH_4~+-N35～40mg／L，pH2.0～4.0)作为研究对象，考虑到制药废水成分复杂、COD高且难降解的特点和电解法处理废水的高效、易操作且能提高废水可生化性等优点，设计了以电解法为预处理联合SBR法处理制药废水的方案。论文主要研究结果如下：
1、通过测定电解槽中制药废水COD_(Cr)、色度、可生物降解性的变化，考察了停留时间、反应温度、废水浓度、电解电压、pH值、电解质、阴阳极转换频率、电极联接方式等电解主要操作条件对制药废水处理效果的影响。并通过同Na_2SO_4、NaNO_3等电解质作对比实验来说明NaCl产生的电解阳极间接氧化的存在。实验结果表明，Cl~-所导致的阳极间接氧化促进了COD_(Cr)的去除，且阳极间接氧化在电解过程中占主导地位。
2、实验所用废水本身Cl~-含量较高，因此无需添加NaCl即可发生电解阳极间接氧化。在本实验中，以30伏直流电压为电解电压，调节废水pH为7.5，电解时间为60min，测得废水COD_(Cr)降低41.4％，色度去除率为96.9％，废水的B／C比从原来的0.17提高到0.34，说明废水的可生化性得到提高，并通过对处理前后的废水组分进行的色质联用分析得到进一步的验证。
3、耐盐微生物的培养驯化是高含盐量废水SBR法处理的最重要的步骤，可使废水中盐对该系统所产生的不利影响降到最低程度。采用限制性曝气方式和非限制性曝气方式进行的对比试验发现，非限制性曝气方式取得较为理想的COD处理效果。
4、本试验分别开展了恒温和变温度条件下DO和ORP作为过程控制参数的可行性研究。采用SBR法研究了不同曝气量、初始MLSS浓度和进水COD浓度等条件下温度对反应过程中DO和ORP变化的影响。结果表明，恒温条件下DO作为过程控制参数是可行的；环境温度的波动极大地影响了反应器内DO的
浙江大学硕士毕业论文
变化趋势，而ORP的变化趋势基本不受影响。提出当环境温度变化时，采用O即
作为控制参数更能反映有机物的降解情况。试验中还发现，ORP凹点出现的时
间与进水COD浓度有关，O即的上升速率与COD降解程度有关。通过以上实
验研究可以实现SBR法处理制药废水的在线控制，合理安排曝气量和曝气时间，
最终达到节约能源的目的。
在通过电解预处理后，废水经中和和稀释后加入到SBR反应器中生化，平
均出水eonc， 230mg/L，SBR出水再经絮凝沉淀CODe，降到loomg几以下，色度
由最初的200降低到10以下。
Systematic analysis of the varieties and characteristics of the pharmaceutical wastewater was conducted. Based on the experience of practical projects, we found that it was unfeasible to treat the pharmaceutical wastewater only with biological methods, it even caused the death of sludge. Considering high COD, complex composition and recalcitrant organic compounds in pharmaceutical wastewater and effectiveness and ease in operation of electrolysis, an schemes of electrolysis-SBR was established.
Experiments were conducted to study the changes in chromaticity, COD and the biodegradability of pharmaceutical wastewater. The objective of this paper is to advance the knowledge of the influence of residence time, polar distance, initial reaction temperature, initial wastewater concentration, voltage, pH and electrolyte , electrode sort, switching frequency of anode and cathode, polar coupling type on the electrolysis efficiency. Chloride is widely presented in many wastewater, so it's worth studying the increase of chromaticity and COD removal by anode indirect oxidation without filling in any other electrolyte. Compared with the effects of Na2SO4, NaNO3 on the electrolysis efficiency, the results of the experiment showed that the COD removal can be mainly attributed to the indirect oxidation effect of NaCl in electrolysis process. The results indicate that the presence of Cl-can achieve higher COD removal because of anode indirect oxidation.
As the wastewater used in this experiment was rich in chloride, electrolysis anode indirect oxidation occurred without filling in NaCl. The results showed that the use of electrolysis technology could remove about 96.9% of chromaticity and 41.4% of COD and improve the biodegradability of pharmaceutical wastewater from 0.17 to 0.34. volts d.c. of 30 voltages, 7.5 of pH value and a retention time of 60 minutes were recommended for the process design of electrolysis. This was verified ulteriorly by chromatogram-mass spectrum.
Acclimation procedures are of utmost importance when high salinity wastewater was to be treated with SBR treatment. While the process was affected slightly, proper acclimation methods minimize negative effects and the process would yield a good quality effluent. Compared with confined movement way of SBR process, unconfmed way played a more important role in the good removal efficiency of COD.
At present, there are some problems in the study of DO and ORP as control parameters, because the researches are usually developed in the invariable temperature. However, environmental temperature is changing in the wastewater treatment. The effect of environmental temperature on and ORP as control parameter was studied specially in some experiments carried on a sequencing batch reactor(SBR) fed with pharmaceutical wastewater in this paper. It was carried out in the invariable temperature and in the variable temperature, respectively. Results showed that DO as control parameter is valid in the invariable temperature, and the law of variation in DO during organism removal were influenced with the environmental temperature, at different experiment condition of aeration intensity, MLSS concentration or inflow nutrition concentration, but the variation in ORP were not influenced with it. The reason that the DO was influenced was also discussed. This paper brought forward that the control parameter using ORP was
accurate and reliable when environmental temperature changed. In addition, inflow COD concentration and the time that ORP concave value appeared was connected, and the speed that ORP in curve ascended related with the COD concentration during the degradation. So it can be made on-line control of aeration intensity and aeration time.
After the pre-treatment of pharmaceutical wastewater with electrolysis, the supernatant was neutralized and diluted and then was added to SBR reactor. Compared with the pharmaceutical wastewater without electrolysis, results showed that the average CODcr value of SBR effluent was 230mg/L, after flocculent sedimentation, CODcr reduced to le
1、通过测定电解槽中制药废水COD_(Cr)、色度、可生物降解性的变化，考察了停留时间、反应温度、废水浓度、电解电压、pH值、电解质、阴阳极转换频率、电极联接方式等电解主要操作条件对制药废水处理效果的影响。并通过同Na_2SO_4、NaNO_3等电解质作对比实验来说明NaCl产生的电解阳极间接氧化的存在。实验结果表明，Cl~-所导致的阳极间接氧化促进了COD_(Cr)的去除，且阳极间接氧化在电解过程中占主导地位。
2、实验所用废水本身Cl~-含量较高，因此无需添加NaCl即可发生电解阳极间接氧化。在本实验中，以30伏直流电压为电解电压，调节废水pH为7.5，电解时间为60min，测得废水COD_(Cr)降低41.4％，色度去除率为96.9％，废水的B／C比从原来的0.17提高到0.34，说明废水的可生化性得到提高，并通过对处理前后的废水组分进行的色质联用分析得到进一步的验证。
3、耐盐微生物的培养驯化是高含盐量废水SBR法处理的最重要的步骤，可使废水中盐对该系统所产生的不利影响降到最低程度。采用限制性曝气方式和非限制性曝气方式进行的对比试验发现，非限制性曝气方式取得较为理想的COD处理效果。
4、本试验分别开展了恒温和变温度条件下DO和ORP作为过程控制参数的可行性研究。采用SBR法研究了不同曝气量、初始MLSS浓度和进水COD浓度等条件下温度对反应过程中DO和ORP变化的影响。结果表明，恒温条件下DO作为过程控制参数是可行的；环境温度的波动极大地影响了反应器内DO的
浙江大学硕士毕业论文
变化趋势，而ORP的变化趋势基本不受影响。提出当环境温度变化时，采用O即
作为控制参数更能反映有机物的降解情况。试验中还发现，ORP凹点出现的时
间与进水COD浓度有关，O即的上升速率与COD降解程度有关。通过以上实
验研究可以实现SBR法处理制药废水的在线控制，合理安排曝气量和曝气时间，
最终达到节约能源的目的。
在通过电解预处理后，废水经中和和稀释后加入到SBR反应器中生化，平
均出水eonc， 230mg/L，SBR出水再经絮凝沉淀CODe，降到loomg几以下，色度
由最初的200降低到10以下。
Systematic analysis of the varieties and characteristics of the pharmaceutical wastewater was conducted. Based on the experience of practical projects, we found that it was unfeasible to treat the pharmaceutical wastewater only with biological methods, it even caused the death of sludge. Considering high COD, complex composition and recalcitrant organic compounds in pharmaceutical wastewater and effectiveness and ease in operation of electrolysis, an schemes of electrolysis-SBR was established.
Experiments were conducted to study the changes in chromaticity, COD and the biodegradability of pharmaceutical wastewater. The objective of this paper is to advance the knowledge of the influence of residence time, polar distance, initial reaction temperature, initial wastewater concentration, voltage, pH and electrolyte , electrode sort, switching frequency of anode and cathode, polar coupling type on the electrolysis efficiency. Chloride is widely presented in many wastewater, so it's worth studying the increase of chromaticity and COD removal by anode indirect oxidation without filling in any other electrolyte. Compared with the effects of Na2SO4, NaNO3 on the electrolysis efficiency, the results of the experiment showed that the COD removal can be mainly attributed to the indirect oxidation effect of NaCl in electrolysis process. The results indicate that the presence of Cl-can achieve higher COD removal because of anode indirect oxidation.
As the wastewater used in this experiment was rich in chloride, electrolysis anode indirect oxidation occurred without filling in NaCl. The results showed that the use of electrolysis technology could remove about 96.9% of chromaticity and 41.4% of COD and improve the biodegradability of pharmaceutical wastewater from 0.17 to 0.34. volts d.c. of 30 voltages, 7.5 of pH value and a retention time of 60 minutes were recommended for the process design of electrolysis. This was verified ulteriorly by chromatogram-mass spectrum.
Acclimation procedures are of utmost importance when high salinity wastewater was to be treated with SBR treatment. While the process was affected slightly, proper acclimation methods minimize negative effects and the process would yield a good quality effluent. Compared with confined movement way of SBR process, unconfmed way played a more important role in the good removal efficiency of COD.
At present, there are some problems in the study of DO and ORP as control parameters, because the researches are usually developed in the invariable temperature. However, environmental temperature is changing in the wastewater treatment. The effect of environmental temperature on and ORP as control parameter was studied specially in some experiments carried on a sequencing batch reactor(SBR) fed with pharmaceutical wastewater in this paper. It was carried out in the invariable temperature and in the variable temperature, respectively. Results showed that DO as control parameter is valid in the invariable temperature, and the law of variation in DO during organism removal were influenced with the environmental temperature, at different experiment condition of aeration intensity, MLSS concentration or inflow nutrition concentration, but the variation in ORP were not influenced with it. The reason that the DO was influenced was also discussed. This paper brought forward that the control parameter using ORP was
accurate and reliable when environmental temperature changed. In addition, inflow COD concentration and the time that ORP concave value appeared was connected, and the speed that ORP in curve ascended related with the COD concentration during the degradation. So it can be made on-line control of aeration intensity and aeration time.
After the pre-treatment of pharmaceutical wastewater with electrolysis, the supernatant was neutralized and diluted and then was added to SBR reactor. Compared with the pharmaceutical wastewater without electrolysis, results showed that the average CODcr value of SBR effluent was 230mg/L, after flocculent sedimentation, CODcr reduced to le
引文
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