阿维菌素废水厌氧出水深度处理实验研究
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摘要
阿维菌素废水属于较难生物处理的高浓度发酵类抗生素废水。目前研究结果表明采用厌氧处理技术能够对阿维菌素废水中污染物取得较好的处理效果,系统出水可以满足《污水综合排放标准》(GB 8978-1996)的要求。2008年8月1日,国家环保部和国家质量监督检验检疫总局制订实施《发酵类制药工业水污染物排放标准》(GB 21903-2008)规定:将现有发酵类抗生素制药企业废水COD的排放标准由300 mg·L~(-1)提高到200 mg·L~(-1)。进一步提高了抗生素生产企业的废水排放标准,由于现有工艺处理效果不能满足新标准的要求,因此,阿维菌素生产企业亟待研发高效经济的阿维菌素废水处理工艺。
结合河北省某阿维菌素生产企业实际运行情况,本课题以阿维菌素废水厌氧出水为研究对象,针对阿维菌素废水厌氧出水的水质特点开展试验研究,拟采用“磷酸铵镁化学沉淀+生物接触氧化+Fenton高级氧化”对废水进行处理,本课题研究了组合工艺处理阿维菌素废水的可行性及运行性能,在实现达标排放的基础上,对主要工艺参数进行优化,所得结论如下:
1)根据阿维菌素废水的特点,采用磷酸铵镁化学沉淀工艺(MAP)对废水进行脱氮处理,研究表明搅拌强度、反应物质的摩尔配比、pH值、静沉时间对于MAP晶粒的成长和氨氮的去除效果影响比较明显。试验得到的最佳工艺条件为:pH 8.0～8.5;Mg~(2+):NH_4~+:H_2PO_4-的摩尔配比1.3:1:1。快速(150 r·min~(-1))搅拌2 min;然后慢速(50 r·min~(-1))搅拌5 min;反应时间20 min。在最佳工艺运行条件下,厌氧出水经过磷酸铵镁化学沉淀脱氮处理后,氨氮去除率达到85%以上,出水氨氮浓度为35～50 mg·L~(-1)。
2)阿维菌素废水厌氧出水经MAP脱氮以后,出水残留的COD仍然较高,实验选用生物接触氧化法进行处理。反应器经过85 d运行,COD容积负荷达到1.05 kgCOD·(m~3·d)~(-1)时,出水COD达到415～450 mg·L~(-1),COD去除率达到50%。系统运行稳定。试验确定出的工艺参数为:HRT为24 h;容积负荷:1.05 kgCOD·(m~3·d)~(-1);溶解氧控制在1.0～2.0 mg·L~(-1)。
3)由于废水经生物接触氧化处理后,出水COD不能满足国家排放标准的要求,因此,采用Fenton高级氧化技术进一步深度处理。试验考查了初始pH值、H_2O_2投加量以及FeSO_4投加量的影响、反应温度和反应时间等因素对Fenton试剂反应的影响,并对这些影响因子作了单因素分析。试验确定的最佳反应条件为:pH值为5.0,30%的H_2O_2投加量2.0 mL·L~(-1),FeSO_4投加量为50.0 mg·L~(-1),反应时间2.0 h,COD的去除率可以达到55.4%,系统出水COD为175.0 mg·L~(-1),出水COD和NH_3-N均达到了国家对发酵类抗生素废水排放标准的要求。
综上所述,采用“磷酸铵镁化学沉淀+生物接触氧化+Fenton高级氧化”工艺处理阿维菌素废水,能够满足国家《发酵类制药工业水污染物排放标准》(GB 21903-2008)的相关要求,并能够稳定运行,在技术上具有一定的可行性。本课题为实际工业推广应用,积累了相关的经验数据,对今后该行业废水的深度处理具有一定的借鉴意义。
Avermectin wastewater which is high concentration of antibiotic wastewater is difficult to treatment by biological technology. The study shows that the anaerobic technology for avermectin wastewater treatment has been achieved a level, which can meet the standard of the“Integrated wastewater discharge standard”(GB 8978-1996). But in august of 2008 the discharge standards of water pollutants for pharmaceutical industry was developed and carried out by the Ministry of Environmental Protection of the People’s republic of China. The COD of the pharmaceutical wastewater became 200 mg·L~(-1) instead of 300 mg·L~(-1). Because of new standard the COD of the avermectin wastewater can not meet the request. So the companies which produce avermectin are urgently need the new technology which can treatment the avermectin wastewater effectively and meet the new standard.
This paper take the avermectin wastewater anaerobic effluent as the research object. The aim of the research is making the avermectin wastewater meet the request of new standard. For this aim we choose the "chemical sedimentation of magnesium ammonium phosphate + biocontacting oxidation + Fenton oxidation" process to treatment the avermectin wastewater. The research studied the treatment technology and optimize the main operation date in Avermectin wastewater treatment. The conclusions are as follows:
1) According to the characteristics of Avermectin wastewater, using the Chemical sedimentation of magnesium ammonium phosphate (MAP) for wastewater nitrogen removal treatment, the research have shown that mixing intensity, reaction material molar ratio, pH, time for the MAP grain growth and ammonia nitrogen removal effect are more obvious. The optimum conditions of the reaction were determined as follows: pH 8.0~8.5, the reaction molar ratio of Mg~(2+):NH_4~+:H_2PO_4-=1.3:1:1. Fast (150 r·min~(-1)) mixing 2 min; and then slow (50 r·min~(-1)) mixing 5 min; the reaction time is 20 min. In the optimum operating conditions, the anaerobic effluent treatment through the magnesium ammonium phosphate precipitation and its ammonia removal rate reached 85%, and the remaining ammonia concentration of 35~50 mg·L~(-1).
2) Avermectin wastewater anaerobic effluent by denitrification of MAP, the residual COD of the effluent is still high. The experiment use biological contact oxidation method. The bio-contact oxidation reactor after 85 days running, COD volumetric loading reached 1.05 kgCOD·(m3·d)~(-1), the effluent COD reached 415~450 mg·L~(-1), COD removal rate reached 50%. The system is running stable. Running conditions: HRT, 24 h; volume load: 1.05 kgCOD·(m3·d)~(-1); dissolved oxygen controlled at 1.0~2.0 mg·L~(-1).
3) As the wastewater by biological contact oxidation treatment, the effluent COD can not meet the requirements of the national emission standards, therefore, using Fenton oxidation technology to further advanced treatment. Experiment examined the influences of reaction in the initial pH value, H_2O_2 dosage, as well as the impact of FeSO4·7H2O dosage, reaction temperature and reaction time on the Fenton reagent, and these effects were made by single-factor analysis. Testing to determine the optimal reaction conditions: when the pH value of 5.0, 30% of H_2O_2 dosage of 2.0mL·L~(-1), FeSO_4dosage of 50.0mg·L~(-1), reaction time 2.0 h, the reaction temperature 20~30℃, COD removal rate reached 55.4%, the effluent COD is 175.0 mg·L~(-1), the effluent COD and NH3-N reached a state of fermentation antibiotic wastewater discharge requirements of the standard.
In conclusion, the process of "chemical sedimentation of magnesium ammonium phosphate + biological contact oxidation + Fenton Oxidation" can meet the relevant requirements of the discharge standards of water pollutants for pharmaceutical industry (GB 21903-2008). In this condition the system can be operated stablely. This research accumulated the relevant data for the practical industrial application, which plays an important role in the advanced treatment of avermectin wastewater.
结合河北省某阿维菌素生产企业实际运行情况,本课题以阿维菌素废水厌氧出水为研究对象,针对阿维菌素废水厌氧出水的水质特点开展试验研究,拟采用“磷酸铵镁化学沉淀+生物接触氧化+Fenton高级氧化”对废水进行处理,本课题研究了组合工艺处理阿维菌素废水的可行性及运行性能,在实现达标排放的基础上,对主要工艺参数进行优化,所得结论如下:
1)根据阿维菌素废水的特点,采用磷酸铵镁化学沉淀工艺(MAP)对废水进行脱氮处理,研究表明搅拌强度、反应物质的摩尔配比、pH值、静沉时间对于MAP晶粒的成长和氨氮的去除效果影响比较明显。试验得到的最佳工艺条件为:pH 8.0～8.5;Mg~(2+):NH_4~+:H_2PO_4-的摩尔配比1.3:1:1。快速(150 r·min~(-1))搅拌2 min;然后慢速(50 r·min~(-1))搅拌5 min;反应时间20 min。在最佳工艺运行条件下,厌氧出水经过磷酸铵镁化学沉淀脱氮处理后,氨氮去除率达到85%以上,出水氨氮浓度为35～50 mg·L~(-1)。
2)阿维菌素废水厌氧出水经MAP脱氮以后,出水残留的COD仍然较高,实验选用生物接触氧化法进行处理。反应器经过85 d运行,COD容积负荷达到1.05 kgCOD·(m~3·d)~(-1)时,出水COD达到415～450 mg·L~(-1),COD去除率达到50%。系统运行稳定。试验确定出的工艺参数为:HRT为24 h;容积负荷:1.05 kgCOD·(m~3·d)~(-1);溶解氧控制在1.0～2.0 mg·L~(-1)。
3)由于废水经生物接触氧化处理后,出水COD不能满足国家排放标准的要求,因此,采用Fenton高级氧化技术进一步深度处理。试验考查了初始pH值、H_2O_2投加量以及FeSO_4投加量的影响、反应温度和反应时间等因素对Fenton试剂反应的影响,并对这些影响因子作了单因素分析。试验确定的最佳反应条件为:pH值为5.0,30%的H_2O_2投加量2.0 mL·L~(-1),FeSO_4投加量为50.0 mg·L~(-1),反应时间2.0 h,COD的去除率可以达到55.4%,系统出水COD为175.0 mg·L~(-1),出水COD和NH_3-N均达到了国家对发酵类抗生素废水排放标准的要求。
综上所述,采用“磷酸铵镁化学沉淀+生物接触氧化+Fenton高级氧化”工艺处理阿维菌素废水,能够满足国家《发酵类制药工业水污染物排放标准》(GB 21903-2008)的相关要求,并能够稳定运行,在技术上具有一定的可行性。本课题为实际工业推广应用,积累了相关的经验数据,对今后该行业废水的深度处理具有一定的借鉴意义。
Avermectin wastewater which is high concentration of antibiotic wastewater is difficult to treatment by biological technology. The study shows that the anaerobic technology for avermectin wastewater treatment has been achieved a level, which can meet the standard of the“Integrated wastewater discharge standard”(GB 8978-1996). But in august of 2008 the discharge standards of water pollutants for pharmaceutical industry was developed and carried out by the Ministry of Environmental Protection of the People’s republic of China. The COD of the pharmaceutical wastewater became 200 mg·L~(-1) instead of 300 mg·L~(-1). Because of new standard the COD of the avermectin wastewater can not meet the request. So the companies which produce avermectin are urgently need the new technology which can treatment the avermectin wastewater effectively and meet the new standard.
This paper take the avermectin wastewater anaerobic effluent as the research object. The aim of the research is making the avermectin wastewater meet the request of new standard. For this aim we choose the "chemical sedimentation of magnesium ammonium phosphate + biocontacting oxidation + Fenton oxidation" process to treatment the avermectin wastewater. The research studied the treatment technology and optimize the main operation date in Avermectin wastewater treatment. The conclusions are as follows:
1) According to the characteristics of Avermectin wastewater, using the Chemical sedimentation of magnesium ammonium phosphate (MAP) for wastewater nitrogen removal treatment, the research have shown that mixing intensity, reaction material molar ratio, pH, time for the MAP grain growth and ammonia nitrogen removal effect are more obvious. The optimum conditions of the reaction were determined as follows: pH 8.0~8.5, the reaction molar ratio of Mg~(2+):NH_4~+:H_2PO_4-=1.3:1:1. Fast (150 r·min~(-1)) mixing 2 min; and then slow (50 r·min~(-1)) mixing 5 min; the reaction time is 20 min. In the optimum operating conditions, the anaerobic effluent treatment through the magnesium ammonium phosphate precipitation and its ammonia removal rate reached 85%, and the remaining ammonia concentration of 35~50 mg·L~(-1).
2) Avermectin wastewater anaerobic effluent by denitrification of MAP, the residual COD of the effluent is still high. The experiment use biological contact oxidation method. The bio-contact oxidation reactor after 85 days running, COD volumetric loading reached 1.05 kgCOD·(m3·d)~(-1), the effluent COD reached 415~450 mg·L~(-1), COD removal rate reached 50%. The system is running stable. Running conditions: HRT, 24 h; volume load: 1.05 kgCOD·(m3·d)~(-1); dissolved oxygen controlled at 1.0~2.0 mg·L~(-1).
3) As the wastewater by biological contact oxidation treatment, the effluent COD can not meet the requirements of the national emission standards, therefore, using Fenton oxidation technology to further advanced treatment. Experiment examined the influences of reaction in the initial pH value, H_2O_2 dosage, as well as the impact of FeSO4·7H2O dosage, reaction temperature and reaction time on the Fenton reagent, and these effects were made by single-factor analysis. Testing to determine the optimal reaction conditions: when the pH value of 5.0, 30% of H_2O_2 dosage of 2.0mL·L~(-1), FeSO_4dosage of 50.0mg·L~(-1), reaction time 2.0 h, the reaction temperature 20~30℃, COD removal rate reached 55.4%, the effluent COD is 175.0 mg·L~(-1), the effluent COD and NH3-N reached a state of fermentation antibiotic wastewater discharge requirements of the standard.
In conclusion, the process of "chemical sedimentation of magnesium ammonium phosphate + biological contact oxidation + Fenton Oxidation" can meet the relevant requirements of the discharge standards of water pollutants for pharmaceutical industry (GB 21903-2008). In this condition the system can be operated stablely. This research accumulated the relevant data for the practical industrial application, which plays an important role in the advanced treatment of avermectin wastewater.
引文
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