恶草酮生产废水的生物降解研究及其工程分析
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摘要
安徽科立华化工有限公司300t/a恶草酮生产项目污水排放量为40t/d,该废水含盐份高、COD浓度高,是恶草酮农药生产的主要污染源,其对环境造成的危害逐渐引起人们的关注。因此,本课题开展了以下研究:
1.对恶草酮项目背景及现有废水处理工艺进行了调查分析。以2,4—二氯苯酚为原料,经酯化、硝化、水解、醚化、还原、重氮化等十步反应合成了原药恶草酮。目前,公司对该废水的处理工序为:先经预处理(三效蒸发器蒸发浓缩)分出盐份,再经微电解后,以提高废水的可生化性。但此处理工序复杂,需要蒸汽量多,能耗高,成本高。
2.驯化筛选恶草酮优势降解菌并采用共代谢与种间协同代谢的方式来降解恶草酮废水。首先从好氧生化池中筛选到两株细菌oxaW、oxaY,一株真菌oxaG,经过复筛得到细菌oxaW为高效降解菌;然后对卤代酚高效降解菌P.aeruginosa TBPY(合肥工业大学生物化工与制药工程研究所保藏)进行驯化,得到能够耐受并能够降解恶草酮废水的菌株P.aeruginosa TBPY。降解试验表明,共代谢方式能促进各菌株对含盐恶草酮废水和蒸馏恶草酮废水的降解。外来营养物质存在时,对含盐恶草酮废水来说,P.aeruginosa TBPY的降解能力最强,而混合菌种间的协同代谢作用能明显促进蒸馏恶草酮废水的降解。
3.根据安徽科立华化工有限公司300t/a恶草酮项目生产废水排放情况的调查分析,制定相应的工程技术方案,即采用化学氧化、微电解以及生化(A/O)工艺,最终使废水的COD降到500mg/L,达到排放要求。
本研究根据现有恶草酮污水处理工艺的分析结果,进行恶草酮废水优势降解菌的筛选,将降解菌用于废水的生化处理,并制定了相应的工程技术方案。本课题的研究将为恶草酮废水的治理提供参考。
Chemical Co., Ltd. Anhui Kelihua discharge oxadiazon production capacity of sewage disposal 401 /d, of the high salinity of the wastewater and COD concentration are the main sources of oxadiazon pesticide production, and human aware of its environment against increasingly. According to the above, the present study the following topics:
1. Oxadiazon items on the background and on the existing wastewater treatment processes were investigated and analyzed. 2,4 - dichloro-phenol as a raw material, esterification, nitration, hydrolysis, etherification, reduction, diazotization and other 10-step reaction synthesis of the original drug oxadiazon. At present, the wastewater treatment processes as follows: first, by preconditioning (three-effect evaporator evaporation) separation of salt, and then by micro-electrolysis, the increase of biodegradability of wastewater. But the handling of process complexity, high cost.
2. Acclimatization screening of oxadiazon degrading bacteria and the use of co-metabolism and cometabolism of inter-species approach to dealing with Oxadiazon wastewater. Two bacterias oxaW and oxaY, a fungal oxaG are screened from the aerobic biochemical pool. High degradation ability bacteria oxaW has been screened though degradation test; the strain P. aeruginosa TBPY (from engineering research institute of bio-chemical and pharmaceutical, Hefei University of Technology to collection) presered from the laboratory has been domesticated, make it can degradate oxadiazon wastewater. Then degradation tests showed that the way to the promotion of co-metabolism of the strains oxadiazon salt wastewater and distilled wastewater oxadiazon degradation. Nutrients in the external existence was most suitable for TBPY oxadiazon salt wastewater degradation, hybrid synergy between bacteria metabolism can significantly promote oxadiazon distillation wastewater degradation.
3. In accordance with Chemical Co., Ltd. Anhui Kelihua clever 300t/a production oxadiazon waste water project survey analysis, engineering and technology to develop the corresponding program, that is, the use of chemical oxidation, micro-electrolysis method, Biochemistry (A/O) technology, down to the end, the COD of wastewater 500mg/L below the emission requirements to meet.
In this study, based on the results of the analysis process of the sewage treatment, the oxadiazon degrading bacteria was screened, and the degrading bacteria screened been used for the biological treatment of wastewater, so as to formulate of the corresponding engineering technology program. This will harm wastewater treatment oxadiazon reference.
1.对恶草酮项目背景及现有废水处理工艺进行了调查分析。以2,4—二氯苯酚为原料,经酯化、硝化、水解、醚化、还原、重氮化等十步反应合成了原药恶草酮。目前,公司对该废水的处理工序为:先经预处理(三效蒸发器蒸发浓缩)分出盐份,再经微电解后,以提高废水的可生化性。但此处理工序复杂,需要蒸汽量多,能耗高,成本高。
2.驯化筛选恶草酮优势降解菌并采用共代谢与种间协同代谢的方式来降解恶草酮废水。首先从好氧生化池中筛选到两株细菌oxaW、oxaY,一株真菌oxaG,经过复筛得到细菌oxaW为高效降解菌;然后对卤代酚高效降解菌P.aeruginosa TBPY(合肥工业大学生物化工与制药工程研究所保藏)进行驯化,得到能够耐受并能够降解恶草酮废水的菌株P.aeruginosa TBPY。降解试验表明,共代谢方式能促进各菌株对含盐恶草酮废水和蒸馏恶草酮废水的降解。外来营养物质存在时,对含盐恶草酮废水来说,P.aeruginosa TBPY的降解能力最强,而混合菌种间的协同代谢作用能明显促进蒸馏恶草酮废水的降解。
3.根据安徽科立华化工有限公司300t/a恶草酮项目生产废水排放情况的调查分析,制定相应的工程技术方案,即采用化学氧化、微电解以及生化(A/O)工艺,最终使废水的COD降到500mg/L,达到排放要求。
本研究根据现有恶草酮污水处理工艺的分析结果,进行恶草酮废水优势降解菌的筛选,将降解菌用于废水的生化处理,并制定了相应的工程技术方案。本课题的研究将为恶草酮废水的治理提供参考。
Chemical Co., Ltd. Anhui Kelihua discharge oxadiazon production capacity of sewage disposal 401 /d, of the high salinity of the wastewater and COD concentration are the main sources of oxadiazon pesticide production, and human aware of its environment against increasingly. According to the above, the present study the following topics:
1. Oxadiazon items on the background and on the existing wastewater treatment processes were investigated and analyzed. 2,4 - dichloro-phenol as a raw material, esterification, nitration, hydrolysis, etherification, reduction, diazotization and other 10-step reaction synthesis of the original drug oxadiazon. At present, the wastewater treatment processes as follows: first, by preconditioning (three-effect evaporator evaporation) separation of salt, and then by micro-electrolysis, the increase of biodegradability of wastewater. But the handling of process complexity, high cost.
2. Acclimatization screening of oxadiazon degrading bacteria and the use of co-metabolism and cometabolism of inter-species approach to dealing with Oxadiazon wastewater. Two bacterias oxaW and oxaY, a fungal oxaG are screened from the aerobic biochemical pool. High degradation ability bacteria oxaW has been screened though degradation test; the strain P. aeruginosa TBPY (from engineering research institute of bio-chemical and pharmaceutical, Hefei University of Technology to collection) presered from the laboratory has been domesticated, make it can degradate oxadiazon wastewater. Then degradation tests showed that the way to the promotion of co-metabolism of the strains oxadiazon salt wastewater and distilled wastewater oxadiazon degradation. Nutrients in the external existence was most suitable for TBPY oxadiazon salt wastewater degradation, hybrid synergy between bacteria metabolism can significantly promote oxadiazon distillation wastewater degradation.
3. In accordance with Chemical Co., Ltd. Anhui Kelihua clever 300t/a production oxadiazon waste water project survey analysis, engineering and technology to develop the corresponding program, that is, the use of chemical oxidation, micro-electrolysis method, Biochemistry (A/O) technology, down to the end, the COD of wastewater 500mg/L below the emission requirements to meet.
In this study, based on the results of the analysis process of the sewage treatment, the oxadiazon degrading bacteria was screened, and the degrading bacteria screened been used for the biological treatment of wastewater, so as to formulate of the corresponding engineering technology program. This will harm wastewater treatment oxadiazon reference.
引文
[1]中华民族共和国水利部编.2005-中国水资源公报.北京:中国水利水电出版社,2006.
[2]中国环境年鉴编辑委员会编.2001年环境年鉴.北京:中国环境年鉴社,2001.
[3]北京化工信息咨询有限责任公司.2004年中国农药市场研究报告.
[4]陈东海,操庆国.中国农药废水处理现状[J].北方环境,2004,29(6):43-46.
[5]邱宇平,陈金龙,张全兴,等.农药废水处理方法与资源化技术[J].环境污染治理技术与设备,2003,4(9):63-67.
[6]迟春娟,施跃锦,张嗣炯.液-液萃取处理高氯难降解有机废水[J].浙江工业大学学报,2001,29(2):204-212.
[7]李林新,曾新昌,陈淑怡,等.高浓度二氯酚钠废水治理[J].工业水处理,1992,12(2):24-27.
[8]李永才,张杰.用N-235萃取工业废水中的二氯酚[J].化学工程师,1998,65(2):18-20.
[9]程迪.化学农药工业废水处理技术[J].环境保护,1993(1):14-17.
[10]姜军清,黄卫红,陆晓华.活性炭纤维处理含酚废水的研究[J].工业水处理,2001,21(3):20-22.
[11]赵光,肖月竹.用活性炭纤维吸附处理十三吗啉农药废水的研究[J].化工环保,1995,15(3):131-135.
[12]张全兴,等.一种废水处理并回收邻苯二胺的方法和装置.国家发明专利,1989.专利号:ZL89104014.5.
[13]张全兴,徐伟,荆和祥,等.树脂吸附—生物接触氧化法处理多菌灵及其中间体工业废水的研究[J].污染防治技术,1992,5(3):17-19.
[14]张全兴,潘丙才,陈金龙.国内农药、医药及其中间体生产废水的树脂吸附法处理与资源化研究[J].江苏化工,2000,28(1):21-23.
[15]郑祖英,朱俭,许志东,等.树脂吸附法处理甲基农药生产过程中产生的对硝基酚钠废水[J].离子交换与吸附,1992,8(4):318-324.
[16]王槐三,寇晓康,刘玉鑫,等.树脂吸附法处理2,4-D丁酯氯化含酚废水[J].石油化工,2002,31(6):468-471.
[17]Zhu Shiyun,Chen jinlong.Study on the treatment of 3—phenoxybenzadehyde industrial waste water with polymeric adsorbent.ChineseJournal of Reactive Polymer,1998,5(2):22-31.
[18]车荣睿,宋宽秀.吸附树脂在治理有机农药废水中的应用[J].工业水处理,1993,13(5):3-7.
[19]Xu,Z.Y.,Zhang,Q.X.,Chen,J.L.,etal.Adsorption of naphthalene derivatives on hypercross linked polymeric adsorbents.Chemosphere,1999,38(9):2003-2011.
[20]Aimin Li,Quanxing Zhang,Gengcheng Zhang,etal.Adsorption of phenolic compouns from aqueous solutions by a water-compatible hypercross linked polymeric adsorbent.Chemosphere,2002,47(9):981-989.
[21]B.C.Pan,Y.Xiong,A.M.li,etal.Adsorption of aromaticacids on an aminated hypercrosslinked macroporous polymer.Reactive & Functional Polymers,2002,53:63-72.
[22]邱宇平,陈金龙,陈一良,等.超高交联树脂吸附处理2,4-D含酚废水的研究[J].工业水处理,2003,23(4):50-52.
[23]刘福强,陈金龙,李爱民,等.超高交联吸附树脂对苯甲酸的吸附研究[J].离子交换与吸附,2002,18(6):522-528.
[24]范建伟,王占宁,包肖文,等.二氧化氯处理含氰废水的工程实践[J].中国给水排水,2005,21(6):59-63.
[25]宋怀俊,韩绿霞,李玉,等.二氧化氯处理农药厂含硫化物废水的研究[J].浙江化工,2005,36(2):38-40.
[26]金小元,陈金龙,李爱民,等.二氧化氯催化氧化处理含酚废水的研究[J].离子交换与吸附,2003,19(1):61-66.
[27]周作明,杨仁斌,龚道新,等.含三唑啉农药废水的光降解研究[J].湖南农业大学学报(自然科学版),2005,31(2):210-212.
[28]1994-2008 China Academic Journal Electronic Publishing House.All rights reserved.http://www.cnki.net.
[29]程洁红,李慧蓉.高效降解菌处理多菌灵农药生产废水的研究[J].上海环境科学,2003,22(10):690-694,727.
[30]周湘梅.高明华.两段生物接触氧化法处理甲胺磷生产废水[J].化工环保,1994,14(4):225-229.
[31]夏淑芬.微生物生态学[M].武汉:武汉大学出版社,1988.
[32]王思菊.苯系化合物好氧生物降解性研究[J].环境化学,1993,12(5):394-397.
[33]夏淑芬.微生物生态学[M].武汉:武汉大学出版社,1988.
[34]金志刚,张彤,朱怀兰.污染物生物降解[M].上海:华东理工大学出版社,1997:198-199.
[35]杨骏昌,等.对生态系统中分离获得的菌种进行优势种群测定的方法学探讨:一株优势纤维分解菌的确定[J].应用与环境生物学报,1995,1(2):145-149.
[36]夏淑芬.微生物生态学[M].武汉:武汉大学出版社,1988.
[37]张蔚文,等.混合菌培养在生物降解中的意义[J].环境科学与技术,1993(1):16-22.
[38]李拥军,黄志强,易伟亮.气相色谱—质谱法测定粮谷中恶草酮的残留量[J].色谱,2002,20(2):190-192.
[39]方赤光,周春梅.食品中恶草酮残留量检测过程中条件实验的研究[J].农业与技术,2006,26(1):79-81.
[40]张冠英,方赤光,李青.固相萃取—气相色谱法测定植物性食品中恶草酮残留量方法研究[J].中国卫生检验杂志,2007,17(9):1626-1633.
[41]胡双庆,尹大强,陈良燕.吡虫清等4种新农药的水生态安全性评价[J].农村生态环境,2002,18(4):23-26,34.
[2]中国环境年鉴编辑委员会编.2001年环境年鉴.北京:中国环境年鉴社,2001.
[3]北京化工信息咨询有限责任公司.2004年中国农药市场研究报告.
[4]陈东海,操庆国.中国农药废水处理现状[J].北方环境,2004,29(6):43-46.
[5]邱宇平,陈金龙,张全兴,等.农药废水处理方法与资源化技术[J].环境污染治理技术与设备,2003,4(9):63-67.
[6]迟春娟,施跃锦,张嗣炯.液-液萃取处理高氯难降解有机废水[J].浙江工业大学学报,2001,29(2):204-212.
[7]李林新,曾新昌,陈淑怡,等.高浓度二氯酚钠废水治理[J].工业水处理,1992,12(2):24-27.
[8]李永才,张杰.用N-235萃取工业废水中的二氯酚[J].化学工程师,1998,65(2):18-20.
[9]程迪.化学农药工业废水处理技术[J].环境保护,1993(1):14-17.
[10]姜军清,黄卫红,陆晓华.活性炭纤维处理含酚废水的研究[J].工业水处理,2001,21(3):20-22.
[11]赵光,肖月竹.用活性炭纤维吸附处理十三吗啉农药废水的研究[J].化工环保,1995,15(3):131-135.
[12]张全兴,等.一种废水处理并回收邻苯二胺的方法和装置.国家发明专利,1989.专利号:ZL89104014.5.
[13]张全兴,徐伟,荆和祥,等.树脂吸附—生物接触氧化法处理多菌灵及其中间体工业废水的研究[J].污染防治技术,1992,5(3):17-19.
[14]张全兴,潘丙才,陈金龙.国内农药、医药及其中间体生产废水的树脂吸附法处理与资源化研究[J].江苏化工,2000,28(1):21-23.
[15]郑祖英,朱俭,许志东,等.树脂吸附法处理甲基农药生产过程中产生的对硝基酚钠废水[J].离子交换与吸附,1992,8(4):318-324.
[16]王槐三,寇晓康,刘玉鑫,等.树脂吸附法处理2,4-D丁酯氯化含酚废水[J].石油化工,2002,31(6):468-471.
[17]Zhu Shiyun,Chen jinlong.Study on the treatment of 3—phenoxybenzadehyde industrial waste water with polymeric adsorbent.ChineseJournal of Reactive Polymer,1998,5(2):22-31.
[18]车荣睿,宋宽秀.吸附树脂在治理有机农药废水中的应用[J].工业水处理,1993,13(5):3-7.
[19]Xu,Z.Y.,Zhang,Q.X.,Chen,J.L.,etal.Adsorption of naphthalene derivatives on hypercross linked polymeric adsorbents.Chemosphere,1999,38(9):2003-2011.
[20]Aimin Li,Quanxing Zhang,Gengcheng Zhang,etal.Adsorption of phenolic compouns from aqueous solutions by a water-compatible hypercross linked polymeric adsorbent.Chemosphere,2002,47(9):981-989.
[21]B.C.Pan,Y.Xiong,A.M.li,etal.Adsorption of aromaticacids on an aminated hypercrosslinked macroporous polymer.Reactive & Functional Polymers,2002,53:63-72.
[22]邱宇平,陈金龙,陈一良,等.超高交联树脂吸附处理2,4-D含酚废水的研究[J].工业水处理,2003,23(4):50-52.
[23]刘福强,陈金龙,李爱民,等.超高交联吸附树脂对苯甲酸的吸附研究[J].离子交换与吸附,2002,18(6):522-528.
[24]范建伟,王占宁,包肖文,等.二氧化氯处理含氰废水的工程实践[J].中国给水排水,2005,21(6):59-63.
[25]宋怀俊,韩绿霞,李玉,等.二氧化氯处理农药厂含硫化物废水的研究[J].浙江化工,2005,36(2):38-40.
[26]金小元,陈金龙,李爱民,等.二氧化氯催化氧化处理含酚废水的研究[J].离子交换与吸附,2003,19(1):61-66.
[27]周作明,杨仁斌,龚道新,等.含三唑啉农药废水的光降解研究[J].湖南农业大学学报(自然科学版),2005,31(2):210-212.
[28]1994-2008 China Academic Journal Electronic Publishing House.All rights reserved.http://www.cnki.net.
[29]程洁红,李慧蓉.高效降解菌处理多菌灵农药生产废水的研究[J].上海环境科学,2003,22(10):690-694,727.
[30]周湘梅.高明华.两段生物接触氧化法处理甲胺磷生产废水[J].化工环保,1994,14(4):225-229.
[31]夏淑芬.微生物生态学[M].武汉:武汉大学出版社,1988.
[32]王思菊.苯系化合物好氧生物降解性研究[J].环境化学,1993,12(5):394-397.
[33]夏淑芬.微生物生态学[M].武汉:武汉大学出版社,1988.
[34]金志刚,张彤,朱怀兰.污染物生物降解[M].上海:华东理工大学出版社,1997:198-199.
[35]杨骏昌,等.对生态系统中分离获得的菌种进行优势种群测定的方法学探讨:一株优势纤维分解菌的确定[J].应用与环境生物学报,1995,1(2):145-149.
[36]夏淑芬.微生物生态学[M].武汉:武汉大学出版社,1988.
[37]张蔚文,等.混合菌培养在生物降解中的意义[J].环境科学与技术,1993(1):16-22.
[38]李拥军,黄志强,易伟亮.气相色谱—质谱法测定粮谷中恶草酮的残留量[J].色谱,2002,20(2):190-192.
[39]方赤光,周春梅.食品中恶草酮残留量检测过程中条件实验的研究[J].农业与技术,2006,26(1):79-81.
[40]张冠英,方赤光,李青.固相萃取—气相色谱法测定植物性食品中恶草酮残留量方法研究[J].中国卫生检验杂志,2007,17(9):1626-1633.
[41]胡双庆,尹大强,陈良燕.吡虫清等4种新农药的水生态安全性评价[J].农村生态环境,2002,18(4):23-26,34.