制药厂有机废水处理技术研究及工程实践
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摘要
采用铁炭微电解技术和Fenton试剂氧化法联合处理某维生素C(VC)制药厂排放的有机废水。通过正交实验确定铁炭微电解处理的最佳反应条件是：铁屑和焦炭体积比为1：1,铁屑和焦炭粉与水的体积比为0.435,反应时间为3小时,pH值为2.2。铁炭微电解反应后废水的CODCr(重铬酸钾法)去除率和脱色率分别达到56%和25%；再进一步采用Fenton试剂氧化法处理经铁炭微电解处理后的废水,通过正交试验确定Fenton试剂氧化法的最佳反应条件是：H202投加量为0.4ml/L, Fenton试剂投加量为10mg/L,反应时间为2小时。Fenton试剂氧化反应处理后废水的CODcr去除率和脱色率分别达到36%和83%。最终处理后出水测定CODcr值由245mg/l降至50-70mg/l,色度由200倍(稀释比对法)降至25倍(稀释比对法)。
根据实验研究阶段得出的最佳反应条件和制药厂的实际生产情况,制定处理能力强、投资运行成本低且操作灵活,管理方便的技术方案和工艺流程,并在可行性研究阶段,通过技术经济分析得出工程投资预算和操作运行费用。在项目实施阶段,各设计专业根据工艺要求,进行相应的工程设计和制定相关的工程技术规定。项目管理部门在保证安全、进度和环境的基础上进行土建施工及设备、仪表电气等安装工作。工程质量和投资成本在整个项目运行过程中得到了良好的控制,经过系统调试及开车试运行,达到建设单位预期,最终顺利交工。
By applying of iron-carbon micro-electrolysis with Fenton reagent oxidation technical process to treat organic wastewater from a Vitamin C pharmaceutical plant by means of orthogonal experimental design to determine the optimal operating condition of iron-carbon micro electrolysis technique is:Volume ratio of ferrous versus carbon powder as 1:1, Volume ratio of ferrous and carbon powder versus water as 0.435, reaction duration as 3 hours and pH value as 2.2. CODCr removal rate and colourity rate after Iron-carbon micro electrolysis treatment is 56% and 25%. Optimal operating condition for Fenton reagent oxidation process is:quantity of H2O2 as 0.4ml/L, ferrous iron concentration as 10mg/L and reaction duration as 2 hours. CODCr removal rate and colourity rate after Fenton reagent oxidation process is 36% and 83%. The final effluent CODCr after overall treatment was from 245 mg/1 down to 50～70 mg/l. Colourity was from 200 times down to 25 times.
According to the optimal operating condition from laboratory and the actual plant operation situation with client's expectation, perform basic engineering as well as detail engineering further to define wastewater treatment methodology. Deliver engineering deliverables including technical specification, drawings and lists as well as project execution cost estimation and operation cost forecast. During project construction management phase, keep on tracking the construction quality, progress and cost in the same time by ensuring Health, Safety and Environment rules. Handover the waste water extension plant to client with in-spec effluent as technical requirement.
根据实验研究阶段得出的最佳反应条件和制药厂的实际生产情况,制定处理能力强、投资运行成本低且操作灵活,管理方便的技术方案和工艺流程,并在可行性研究阶段,通过技术经济分析得出工程投资预算和操作运行费用。在项目实施阶段,各设计专业根据工艺要求,进行相应的工程设计和制定相关的工程技术规定。项目管理部门在保证安全、进度和环境的基础上进行土建施工及设备、仪表电气等安装工作。工程质量和投资成本在整个项目运行过程中得到了良好的控制,经过系统调试及开车试运行,达到建设单位预期,最终顺利交工。
By applying of iron-carbon micro-electrolysis with Fenton reagent oxidation technical process to treat organic wastewater from a Vitamin C pharmaceutical plant by means of orthogonal experimental design to determine the optimal operating condition of iron-carbon micro electrolysis technique is:Volume ratio of ferrous versus carbon powder as 1:1, Volume ratio of ferrous and carbon powder versus water as 0.435, reaction duration as 3 hours and pH value as 2.2. CODCr removal rate and colourity rate after Iron-carbon micro electrolysis treatment is 56% and 25%. Optimal operating condition for Fenton reagent oxidation process is:quantity of H2O2 as 0.4ml/L, ferrous iron concentration as 10mg/L and reaction duration as 2 hours. CODCr removal rate and colourity rate after Fenton reagent oxidation process is 36% and 83%. The final effluent CODCr after overall treatment was from 245 mg/1 down to 50～70 mg/l. Colourity was from 200 times down to 25 times.
According to the optimal operating condition from laboratory and the actual plant operation situation with client's expectation, perform basic engineering as well as detail engineering further to define wastewater treatment methodology. Deliver engineering deliverables including technical specification, drawings and lists as well as project execution cost estimation and operation cost forecast. During project construction management phase, keep on tracking the construction quality, progress and cost in the same time by ensuring Health, Safety and Environment rules. Handover the waste water extension plant to client with in-spec effluent as technical requirement.
引文
[1]韦朝海,何苗.有毒难降解有机物的污染及防治对策.世界环境.1997,1：35-36
[2]韦朝海,焦向东,陈焕钦.有毒难降解有机污染物治理方法的研究进展.重庆环境科学.1998,20(4)：22-27
[3]何德文,王罗春,陆雍森.难降解有机污染物的治理方法及进展.环境与开发.1998,13(4)：4-5
[4]Horikoshi S. Oohta M.Hidaka H. Zhao J. Photo Catalyzed Oxidation of Water-soluble Polyethylene Glycol at TiO2/H2O2 Interfaces. Recent Res.Devel.In Polymerscience.1997,1: 149-150
[5]Hoffmann M.R. Martin S.T.Bahnemann D.W. Environmental Application of Semiconductor Photo Catalysis. Chem. Rev.1995,95:69-96
[6]Bhatkhande D.S. Pangarkar V.G. Beenackets A. Photo Catalytic Degradation for Environmental Application-A Review.Chem. Technology. Biotechnol.2001,77:102-116
[7]罗菊仙,赵中一.半导体多相光催化氧化技术在环境保护中的应用研究进展.地球科学-中国地质大学学报.2005,5：536-541
[8]刘正保,姚清照.光催化氧化技术及其发展.工业水处理.1997,6：7-8
[9]薛向东,金奇庭,黄永勤.紫外光助氧化法处理TNT废水研究.给水排水.2001,27(10)：53-58
[10]王华成吕锡武.微污染水源水饮用水处理研究进展.净水技术.2005,21(01)：30-34
[11]张朝晖,吕锡武.饮用水深度处理技术.电力环境保护.2004,20(2)：41-45
[12]王莉莉.O3-H2O2组合法处理染料中间体废水的研究.环境污染与防治.1994,16(5)：11-15
[13]刘德启等.稀土催化双氧水氧化耦合处理染料中间体废水研究.环境污染与防治.2002,3
[14]朱洪涛UV-Fenton催化氧化处理印染废水的实验研究.工业水处理.2006,3
[15]张乃东,郑威等.铁屑-Fenton法处理焦化含酚废水的研究.哈尔滨建筑科技大学.2002,35(2)：57-60
[16]John A. Bergendahl,Timothy P. Thesis. Fenton's Oxidation of MTBE with Zero-violent Iron. Water Research.2004,34:327-334
[17]黄益宏UV/Fenton法处理高浓度香料废水的试验研究.环境技术.2002,2：29-32
[18]黄君礼等UV/Fe(C2O4)3 3-/H2O2法处理水中的苯胺的研究.哈尔滨建筑大学学报.1999,32(3)：48-51
[19]程沧沧,肖忠海等UV-TiO2/Fenton试剂系统处理制药废水的研究.环境科学研究.2001,14(2)：33-35
[20]袁松虎,王琳玲等.阴极电Fenton法处理硝基笨酚模拟废水的研究.工业水处理.2004,24(4)：33^35
[21]E.Guivarch,N.Oturan, etc. Removal of Organ Phosphorus Pesticides from Water by Electro Generated Fenton's Reagent. Environ Chem. Lett.2003,1:165-168
[22]E.Brilla; etc Mineralization of Herbicide 3,6-dichloro-2-methoxybenzoic Acid in Aqueous Medium by Anodic Oxidation Electro-Fenton and Photoelectron-Fenton Electrochemical Act 48(2003):1697-1705
[23]Melitas N; etc Understanding Soluble Arsenate Removal Kinetics by Zero-valent Iron Media Enviro. Sci.& Technology 36(9):2074-20812002
[24]Nam Sangkil, Tratnyek Paul G. Reduction of Azo Dyes with Zero-vale Iron Water Research 34(6):1837-1845 2000
[25]Grittini C; etc. Rapid Dechlorination of Polychlorinated Biphenyls on the Surface of Pd/Fe Bimetallic System Environ. Sci.& Technology 29(11):2898-2900 1995
[26]Ghauch A, etc. Reductive Degradation of Carbaryl in Water by Zero-valent Iron Chemosphere 42:419-424 2001
[27]Slater G F; etc Isotopic Fractionation during Reductive Dechlorination of Trichloroethylene by Zero-valent Iron:Influence of Surface Treatment; Chemosphere; 49(3): 589-596; 2002
[28]光大环保水务年度报告2009-01-07
[29]中国工业水处理和污水处理设备市场增长.水处理技术.第34卷第10期
[30]中国行业发展研究报告环境环保服务行业2008-2009
[31]蒋耀新.水环境现状及水污染防治.甘肃环境研究与监测.2003,16(7)：454
[32]杨志清.21世纪水资源展望.水资源保护.2004,20(5)：66-68
[33]彭珂珊.21世纪中国水资源危机Ⅲ.水利水电科技进展.2000,20(5)：14
[34]关亮炯.我国水污染现状及治理对策.科技情报开发与经济.2004,14(6)：80
[35]徐文英,等.催化铁内电解处理难降解废水的方法；CN1382649A；2002
[36]唐文伟,曾新平等.芬顿试剂和湿式过氧化氢氧化法处理乳化液废水研究.环境科学报2006 08 Vol 28,No.8
[37]祝万鹏,杨志华等Fe2+-H2O2法处理DSD酸生产氧化母液的研究.环境科学报199516(1)：19-22
[38]GB 50216-2001建设工程施工项目管理规范
[39]P.Bautista, A.F.Mohedano, Application of Fenton Oxidation to Cosmetic Wastewaters Treatment Journal of Hazardous Materials 143 (2007) 128-134
[40]唐文伟,曾新.芬顿试剂和湿式过氧化氢氧化法处理乳化液废水研究环境科学学报第26卷第8期
[2]韦朝海,焦向东,陈焕钦.有毒难降解有机污染物治理方法的研究进展.重庆环境科学.1998,20(4)：22-27
[3]何德文,王罗春,陆雍森.难降解有机污染物的治理方法及进展.环境与开发.1998,13(4)：4-5
[4]Horikoshi S. Oohta M.Hidaka H. Zhao J. Photo Catalyzed Oxidation of Water-soluble Polyethylene Glycol at TiO2/H2O2 Interfaces. Recent Res.Devel.In Polymerscience.1997,1: 149-150
[5]Hoffmann M.R. Martin S.T.Bahnemann D.W. Environmental Application of Semiconductor Photo Catalysis. Chem. Rev.1995,95:69-96
[6]Bhatkhande D.S. Pangarkar V.G. Beenackets A. Photo Catalytic Degradation for Environmental Application-A Review.Chem. Technology. Biotechnol.2001,77:102-116
[7]罗菊仙,赵中一.半导体多相光催化氧化技术在环境保护中的应用研究进展.地球科学-中国地质大学学报.2005,5：536-541
[8]刘正保,姚清照.光催化氧化技术及其发展.工业水处理.1997,6：7-8
[9]薛向东,金奇庭,黄永勤.紫外光助氧化法处理TNT废水研究.给水排水.2001,27(10)：53-58
[10]王华成吕锡武.微污染水源水饮用水处理研究进展.净水技术.2005,21(01)：30-34
[11]张朝晖,吕锡武.饮用水深度处理技术.电力环境保护.2004,20(2)：41-45
[12]王莉莉.O3-H2O2组合法处理染料中间体废水的研究.环境污染与防治.1994,16(5)：11-15
[13]刘德启等.稀土催化双氧水氧化耦合处理染料中间体废水研究.环境污染与防治.2002,3
[14]朱洪涛UV-Fenton催化氧化处理印染废水的实验研究.工业水处理.2006,3
[15]张乃东,郑威等.铁屑-Fenton法处理焦化含酚废水的研究.哈尔滨建筑科技大学.2002,35(2)：57-60
[16]John A. Bergendahl,Timothy P. Thesis. Fenton's Oxidation of MTBE with Zero-violent Iron. Water Research.2004,34:327-334
[17]黄益宏UV/Fenton法处理高浓度香料废水的试验研究.环境技术.2002,2：29-32
[18]黄君礼等UV/Fe(C2O4)3 3-/H2O2法处理水中的苯胺的研究.哈尔滨建筑大学学报.1999,32(3)：48-51
[19]程沧沧,肖忠海等UV-TiO2/Fenton试剂系统处理制药废水的研究.环境科学研究.2001,14(2)：33-35
[20]袁松虎,王琳玲等.阴极电Fenton法处理硝基笨酚模拟废水的研究.工业水处理.2004,24(4)：33^35
[21]E.Guivarch,N.Oturan, etc. Removal of Organ Phosphorus Pesticides from Water by Electro Generated Fenton's Reagent. Environ Chem. Lett.2003,1:165-168
[22]E.Brilla; etc Mineralization of Herbicide 3,6-dichloro-2-methoxybenzoic Acid in Aqueous Medium by Anodic Oxidation Electro-Fenton and Photoelectron-Fenton Electrochemical Act 48(2003):1697-1705
[23]Melitas N; etc Understanding Soluble Arsenate Removal Kinetics by Zero-valent Iron Media Enviro. Sci.& Technology 36(9):2074-20812002
[24]Nam Sangkil, Tratnyek Paul G. Reduction of Azo Dyes with Zero-vale Iron Water Research 34(6):1837-1845 2000
[25]Grittini C; etc. Rapid Dechlorination of Polychlorinated Biphenyls on the Surface of Pd/Fe Bimetallic System Environ. Sci.& Technology 29(11):2898-2900 1995
[26]Ghauch A, etc. Reductive Degradation of Carbaryl in Water by Zero-valent Iron Chemosphere 42:419-424 2001
[27]Slater G F; etc Isotopic Fractionation during Reductive Dechlorination of Trichloroethylene by Zero-valent Iron:Influence of Surface Treatment; Chemosphere; 49(3): 589-596; 2002
[28]光大环保水务年度报告2009-01-07
[29]中国工业水处理和污水处理设备市场增长.水处理技术.第34卷第10期
[30]中国行业发展研究报告环境环保服务行业2008-2009
[31]蒋耀新.水环境现状及水污染防治.甘肃环境研究与监测.2003,16(7)：454
[32]杨志清.21世纪水资源展望.水资源保护.2004,20(5)：66-68
[33]彭珂珊.21世纪中国水资源危机Ⅲ.水利水电科技进展.2000,20(5)：14
[34]关亮炯.我国水污染现状及治理对策.科技情报开发与经济.2004,14(6)：80
[35]徐文英,等.催化铁内电解处理难降解废水的方法；CN1382649A；2002
[36]唐文伟,曾新平等.芬顿试剂和湿式过氧化氢氧化法处理乳化液废水研究.环境科学报2006 08 Vol 28,No.8
[37]祝万鹏,杨志华等Fe2+-H2O2法处理DSD酸生产氧化母液的研究.环境科学报199516(1)：19-22
[38]GB 50216-2001建设工程施工项目管理规范
[39]P.Bautista, A.F.Mohedano, Application of Fenton Oxidation to Cosmetic Wastewaters Treatment Journal of Hazardous Materials 143 (2007) 128-134
[40]唐文伟,曾新.芬顿试剂和湿式过氧化氢氧化法处理乳化液废水研究环境科学学报第26卷第8期