电镀铜镍合金废水中铜、镍离子的去除研究
摘要
本文以钢芯电镀铜镍合金漂洗废水为研究对象,针对合金电镀时加入了大量络合剂导致铜镍络离子溶解度升高,不易沉淀的特点,探讨了可能的废水处理方法。先破除络合剂再沉淀金属离子理论上虽可行,但针对工厂废水来源广的具体情况,这一工艺路线很难实施且成本过高。故本文探讨了在电镀车间内先除去金属离子至达到国家排放标准,而后再将主要含络合剂的废水排入总厂生化池内破除络合剂等有机物,COD达标后安全排放的处理方案。
由于含柠檬酸、三乙醇胺等络合剂的废水中铜镍离子不能通过调节pH生成氢氧化物沉淀,故必须使用特定的化学药剂将金属离子从柠檬酸、三乙醇胺的络合物中置换出来,才可进一步进行处理。故本文使用大(高)分子胺和二硫化碳合成了二硫化甲酸一胺类复合物(本文称作金属离子沉淀剂),具有如下特点:1)含二硫代基团,可从原络离子中置换金属离子;2)沉淀中含有疏水性的有机基团,与重金属离子络合后不溶于水;3)沉淀剂的分子量均较大,且一个沉淀剂分子可络合多个重金属离子,并具适度有絮凝性,可保证沉淀物易分离。
本文开发的三种新型重金属离子沉淀剂,可用于含中等强度络合剂的重金属废水处理。试验结果表明,本文开发的三种重金属沉淀剂均可有效地去除铜镍电镀废水中的重金属离子。尤以二硫化甲酸一聚亚乙基亚胺复合物(B剂)去除铜镍电镀废水中的重金属离子效果更好。在pH=8左右,用二硫化甲酸一聚亚乙基亚胺复合物处理电镀铜镍废水5分钟,可使重金属离子含量降至国家排放标准以下,该工艺运行简单,加药方便,不会对环境造成二次污染,具有良好的应用前景。
This paper will focus on the research of rinsing water of Cu-Ni alloy plating. Plenty of complex agents are added in the alloy plating, which makes solubility of copper(II) and nickel(II) rise and therefore, ions difficult to deposit. According to this feature, the paper discusses some possible solution. Although the method of realizing ion deposition by decomplexation is feasible in theory, the technology is difficult to put into practice and demands high cost. Therefore, this paper focuses on the treatment schemes that firstly remove metal ions according to National Emission Standard, secondly discharge the waste water which include complex agents into biochemical pool for decomplexation aswell as other organic compounds, and eventually discharge up to the COD standard.
Because copper (II) and nickel (II) ions in the waste water can not turn into hydroxid by adjusting pH value if the waste water includes citric acid, triethanolamine or some other organic compounds, we must use special chemical to decomplex metal ions from complex agents which include citric acid and triethanolamine, and then move into next step. So by using polyamidoamine and CS_2, we make formate disulfide - amine compound (called metal ions precipitants in this paper), whose feature are as follows: 1) It has dithio group, which can decomplex metal ions from complex agents; 2) There are hydrophobic organic group, which doesn't dissolve in water after complex with metal ions; 3) The molecular weight of precipitants is big. Besides, one precipitant molecule can complex several metal ions, and has flocculability, which can make deposit easy to separate.
The three new heavy metal ions precipitants mentioned in this paper can be used to treat heavy metal ions of medium complex property. The result of experiments shows that the three new heavy metal ions precipitants mentioned in this paper can effectively remove heavy metal ions of Cu-Ni alloy plating, and the complex of formate disulfide and polyethylidene imine is most useful. If using the complex to treat waste water of Cu-Ni alloy plating for 5 minutes on the condition that pH value is approximately 8, we can make the content of heavy metal ions up to National Emission Standard. This technology is easy to approach, convenient for addition, and with no secondary pollution, so has wide application prospect.
由于含柠檬酸、三乙醇胺等络合剂的废水中铜镍离子不能通过调节pH生成氢氧化物沉淀,故必须使用特定的化学药剂将金属离子从柠檬酸、三乙醇胺的络合物中置换出来,才可进一步进行处理。故本文使用大(高)分子胺和二硫化碳合成了二硫化甲酸一胺类复合物(本文称作金属离子沉淀剂),具有如下特点:1)含二硫代基团,可从原络离子中置换金属离子;2)沉淀中含有疏水性的有机基团,与重金属离子络合后不溶于水;3)沉淀剂的分子量均较大,且一个沉淀剂分子可络合多个重金属离子,并具适度有絮凝性,可保证沉淀物易分离。
本文开发的三种新型重金属离子沉淀剂,可用于含中等强度络合剂的重金属废水处理。试验结果表明,本文开发的三种重金属沉淀剂均可有效地去除铜镍电镀废水中的重金属离子。尤以二硫化甲酸一聚亚乙基亚胺复合物(B剂)去除铜镍电镀废水中的重金属离子效果更好。在pH=8左右,用二硫化甲酸一聚亚乙基亚胺复合物处理电镀铜镍废水5分钟,可使重金属离子含量降至国家排放标准以下,该工艺运行简单,加药方便,不会对环境造成二次污染,具有良好的应用前景。
This paper will focus on the research of rinsing water of Cu-Ni alloy plating. Plenty of complex agents are added in the alloy plating, which makes solubility of copper(II) and nickel(II) rise and therefore, ions difficult to deposit. According to this feature, the paper discusses some possible solution. Although the method of realizing ion deposition by decomplexation is feasible in theory, the technology is difficult to put into practice and demands high cost. Therefore, this paper focuses on the treatment schemes that firstly remove metal ions according to National Emission Standard, secondly discharge the waste water which include complex agents into biochemical pool for decomplexation aswell as other organic compounds, and eventually discharge up to the COD standard.
Because copper (II) and nickel (II) ions in the waste water can not turn into hydroxid by adjusting pH value if the waste water includes citric acid, triethanolamine or some other organic compounds, we must use special chemical to decomplex metal ions from complex agents which include citric acid and triethanolamine, and then move into next step. So by using polyamidoamine and CS_2, we make formate disulfide - amine compound (called metal ions precipitants in this paper), whose feature are as follows: 1) It has dithio group, which can decomplex metal ions from complex agents; 2) There are hydrophobic organic group, which doesn't dissolve in water after complex with metal ions; 3) The molecular weight of precipitants is big. Besides, one precipitant molecule can complex several metal ions, and has flocculability, which can make deposit easy to separate.
The three new heavy metal ions precipitants mentioned in this paper can be used to treat heavy metal ions of medium complex property. The result of experiments shows that the three new heavy metal ions precipitants mentioned in this paper can effectively remove heavy metal ions of Cu-Ni alloy plating, and the complex of formate disulfide and polyethylidene imine is most useful. If using the complex to treat waste water of Cu-Ni alloy plating for 5 minutes on the condition that pH value is approximately 8, we can make the content of heavy metal ions up to National Emission Standard. This technology is easy to approach, convenient for addition, and with no secondary pollution, so has wide application prospect.
引文
[1]刘天齐.三废处理工程技术手册.北京:化学工业出版社.2001
[2]陈亚主编.现代实用电镀技术.北京:国防工业出版社.2003
[3]王绍文,姜风有.重金属废水治理技术.北京:冶金工业出版社,1993.
[4]张永锋,许振良.重金属废水处理最新进展.工业水处理.2003,23(6):1-5.
[5]马江游,黄代城,王睿.重金属离子脱除技术进展.化学工业与工程技术.2003,24(3):8-11.
[6]李健,张惠源,尔丽珠.电镀重金属废水治理技术的发展现状.2003,25(3):36-42。
[7]李庆伦,陈淑华,王晓鹏.中国有色金属学报.1998,8:551-553.
[8]三废治理与利用编委会.三废治理与利用.北京:冶金工业出版社,1995
[9]北京环境科学学会.工业企业环境保护手册.北京:中国环境科学出版社,1990
[10]国家环境保护局.工业污染治理技术丛书—废水卷.北京:中国环境科学出版社,1992
[11]涂锦葆.电镀废水治理手册.北京:机械工业出版社,2089
[12]安成强,崔作兴,郝建军.电镀三废治理技术.北京:国防工业出版社,2002
[13]王绍文.重金属废水治理技术.北京:冶金工业出版社.1993
[14]铁道部专业设计院标准处合编.污水处理的基本方法及应用.北京:中国铁道出版社.1982
[15]彭滨.电镀污泥中铜和镍的回收.山东化工,2006,35(1):7-10
[16]冯绍彬.电镀清洁生产工艺.北京:化学工业出版社.2004
[17]张福隆.对含镍铬铜电镀废水的处理.纺织器材.1996,23(1):12-13
[18]陈思宁,方文川,程玉镜.利用硅烷螯合树脂处理重金属废水.广东化工.2001,5
[19]钱湛等.Fenton氧化2混凝联合工艺处理络合铜镍废水的研究.环境污染治理技术与设备.2006,7(5):119-123
[20]王文丰,黄翠萍.螯合沉淀法处理含重金属离子废水.中国给水排水.2002,11
[21]蒋剑虹,曾光明,张盼月,张西林.锌冶炼厂重金属废水处理试验研究.工业水处理.2005,11,
[22]杜仰民.利用腐植酸树脂处理镀镍废水.环境工程.1993,11(3):21-25
[23]余建民,刘时杰.胺类萃取剂在贵金属溶剂萃取中的应用.贵金属.1996年01期
[24]沈品华.电镀废水治理方法探讨[J].电镀与环保.1998,18(5):28-31
[25]Salmen K S,Kowalski A S,Ward W J.Composition and method for simultaneously precipitating metal ions from semiconductor wastewater and enhancing microfilter operation.US 6,258,277.2001
[26]Abdo M D E.A new technique for removing hexavaLent chromium from wastewater and energy generation via galvanic reduction with scrap iron.Energy convers.1998
[27]贾金平.电镀废水处理技术及工程实例.北京:化学工业出版社,2003
[28]曹靓.混合电镀废水处理工艺.城市环境与城市生态.2004,02:34-35
[29]陈惠国.论电镀废水治理技术发展动态.电镀与环保.2001,21:32-35
[30]安瑜.高分子絮凝剂去除废水中铜及浊度的研究[J].净水技术.2004,6(23):4-6
[31]于明泉.高分子重金属絮凝剂的性能及作用机理研究[J].环境科学学报.2005,225:180-185
[32]孟祥和,胡国飞。重金属废水处理[M].北京:化学工业出版社.2000
[33]曾华梁,吴仲达.电镀工艺手册[M].北京:化学工业出版社.1997
[34]黄渭澄.电镀三废处理[M].成都:四川科学技术出版社.1983
[35]张建梅.重金属废水处理技术研究进展.西安联合大学学报.2003,6(2):55-59
[36]贾金平,谢少艾,陈虹锦.电镀废水处理技术及工程实例[M].北京:化学工业出版社,2003
[37]徐红娣,邹群.电镀溶液分析技术[M].北京:化学工业出版社,2003
[38]张福隆.对含镍铬铜电镀废水的处理[J].纺织器材.1996,23(1):12-13.
[39]王文丰,黄翠萍.螯合沉淀法处理含重金属离子废水.中国给水排水.2002
[40]唐受印等.水处理工程.北京:化学工业出版社.1999
[41]李健等.离子交换法治理重金属电镀废水及发展动态.电镀与精饰.2003,25(6):28-29
[42]郭晓滨,李晓池,王晓刚.重金属螯合剂在含铜废水处理重的应用.西安科技学院学报.2003,23(4):422-423
[43]冯爱红,迟大明.重金属螯合剂在印制电路板含铜废水处理中的应用,电镀与环保.2006,26(6):39-40
[44]韩曼,孙来九,王瑛.重金属捕集沉淀剂处理含络合铜废水的工艺研究.化工环保.2003,23(3):177-178
[45]周勤,苏彩燕,袁笑一,吴友明.重金属捕集剂WY5处理综合铜、镍废水的研究.工业水处理.2006,24(4):31-32
[46]于明泉,常青.高分子重金属絮凝剂的性能及作用机理研究.环境科学学报.2005,2(25):180-185
[47]安瑜,常青,于明泉.高分子絮凝剂去除废水重铜及浊度的研究.净水技术.2004,6(23):4-6
[48]胡献舟,张盼月,曾光明,夏耀玲,王金菊.助凝助沉剂在含镍废水化学处理中 的应用.工业水处理.2007,27(4):48-49
[49]聂忠源,陈尚林.印制板蚀刻、微蚀刻废液的再生和铜回收的技术及设备.印制电路信息.2006,11:57-58
[50]罗耀宗.用符合特效絮凝剂处理化学镀镍废水.电镀与环保.2005,25(5):43-44
[51]沈友良,聂基兰.用化学捕收剂处理含镍废水.南昌大学学报.2005,29(4):367-368
[52]孙余凭.一种新型NF膜在含镍废水回用中的应用.电镀与环保.2007,27(1):39
[53]王刚,常青.高分子重金属絮凝剂处理含镍废水性能研究.安全与环境学报.2007,7(4):61
[54]常青,安瑜,于明泉.高分子重金属絮凝剂的制备及含铜废水处理.环境还学,2006,25(2):176-178
[55]郭仁东,吴昊,张晓颖.高浓度含铜废水处理方法的研究.当代化工.2004,33(5):281
[56]王文丰.螯合沉淀法处理含络合铜废水.印制电路信息.2003,11:62-63
[57]王碧,许桂丽,胡星淇.HW型高分子捕集剂处理含铅铜废水.化工环保.2007,27(5):484-486
[58]王进喜,常青,童敏,王亚军.高分子重金属絮凝剂MAPEI的制备及性能研究.环境科学学报.2007,27(10):1623-1624
[59]胡巧开.含铜废水的吸附处理研究.冶金能源.2005,24(2):59-60
[60]李萌.化学镀镍废水的处理及其利用.技术于研究.2006,5:68-69
[61]徐作鹏.焦磷酸盐镀铜废水的处理.沈阳大学学报.2005,17(2):56-57
[2]陈亚主编.现代实用电镀技术.北京:国防工业出版社.2003
[3]王绍文,姜风有.重金属废水治理技术.北京:冶金工业出版社,1993.
[4]张永锋,许振良.重金属废水处理最新进展.工业水处理.2003,23(6):1-5.
[5]马江游,黄代城,王睿.重金属离子脱除技术进展.化学工业与工程技术.2003,24(3):8-11.
[6]李健,张惠源,尔丽珠.电镀重金属废水治理技术的发展现状.2003,25(3):36-42。
[7]李庆伦,陈淑华,王晓鹏.中国有色金属学报.1998,8:551-553.
[8]三废治理与利用编委会.三废治理与利用.北京:冶金工业出版社,1995
[9]北京环境科学学会.工业企业环境保护手册.北京:中国环境科学出版社,1990
[10]国家环境保护局.工业污染治理技术丛书—废水卷.北京:中国环境科学出版社,1992
[11]涂锦葆.电镀废水治理手册.北京:机械工业出版社,2089
[12]安成强,崔作兴,郝建军.电镀三废治理技术.北京:国防工业出版社,2002
[13]王绍文.重金属废水治理技术.北京:冶金工业出版社.1993
[14]铁道部专业设计院标准处合编.污水处理的基本方法及应用.北京:中国铁道出版社.1982
[15]彭滨.电镀污泥中铜和镍的回收.山东化工,2006,35(1):7-10
[16]冯绍彬.电镀清洁生产工艺.北京:化学工业出版社.2004
[17]张福隆.对含镍铬铜电镀废水的处理.纺织器材.1996,23(1):12-13
[18]陈思宁,方文川,程玉镜.利用硅烷螯合树脂处理重金属废水.广东化工.2001,5
[19]钱湛等.Fenton氧化2混凝联合工艺处理络合铜镍废水的研究.环境污染治理技术与设备.2006,7(5):119-123
[20]王文丰,黄翠萍.螯合沉淀法处理含重金属离子废水.中国给水排水.2002,11
[21]蒋剑虹,曾光明,张盼月,张西林.锌冶炼厂重金属废水处理试验研究.工业水处理.2005,11,
[22]杜仰民.利用腐植酸树脂处理镀镍废水.环境工程.1993,11(3):21-25
[23]余建民,刘时杰.胺类萃取剂在贵金属溶剂萃取中的应用.贵金属.1996年01期
[24]沈品华.电镀废水治理方法探讨[J].电镀与环保.1998,18(5):28-31
[25]Salmen K S,Kowalski A S,Ward W J.Composition and method for simultaneously precipitating metal ions from semiconductor wastewater and enhancing microfilter operation.US 6,258,277.2001
[26]Abdo M D E.A new technique for removing hexavaLent chromium from wastewater and energy generation via galvanic reduction with scrap iron.Energy convers.1998
[27]贾金平.电镀废水处理技术及工程实例.北京:化学工业出版社,2003
[28]曹靓.混合电镀废水处理工艺.城市环境与城市生态.2004,02:34-35
[29]陈惠国.论电镀废水治理技术发展动态.电镀与环保.2001,21:32-35
[30]安瑜.高分子絮凝剂去除废水中铜及浊度的研究[J].净水技术.2004,6(23):4-6
[31]于明泉.高分子重金属絮凝剂的性能及作用机理研究[J].环境科学学报.2005,225:180-185
[32]孟祥和,胡国飞。重金属废水处理[M].北京:化学工业出版社.2000
[33]曾华梁,吴仲达.电镀工艺手册[M].北京:化学工业出版社.1997
[34]黄渭澄.电镀三废处理[M].成都:四川科学技术出版社.1983
[35]张建梅.重金属废水处理技术研究进展.西安联合大学学报.2003,6(2):55-59
[36]贾金平,谢少艾,陈虹锦.电镀废水处理技术及工程实例[M].北京:化学工业出版社,2003
[37]徐红娣,邹群.电镀溶液分析技术[M].北京:化学工业出版社,2003
[38]张福隆.对含镍铬铜电镀废水的处理[J].纺织器材.1996,23(1):12-13.
[39]王文丰,黄翠萍.螯合沉淀法处理含重金属离子废水.中国给水排水.2002
[40]唐受印等.水处理工程.北京:化学工业出版社.1999
[41]李健等.离子交换法治理重金属电镀废水及发展动态.电镀与精饰.2003,25(6):28-29
[42]郭晓滨,李晓池,王晓刚.重金属螯合剂在含铜废水处理重的应用.西安科技学院学报.2003,23(4):422-423
[43]冯爱红,迟大明.重金属螯合剂在印制电路板含铜废水处理中的应用,电镀与环保.2006,26(6):39-40
[44]韩曼,孙来九,王瑛.重金属捕集沉淀剂处理含络合铜废水的工艺研究.化工环保.2003,23(3):177-178
[45]周勤,苏彩燕,袁笑一,吴友明.重金属捕集剂WY5处理综合铜、镍废水的研究.工业水处理.2006,24(4):31-32
[46]于明泉,常青.高分子重金属絮凝剂的性能及作用机理研究.环境科学学报.2005,2(25):180-185
[47]安瑜,常青,于明泉.高分子絮凝剂去除废水重铜及浊度的研究.净水技术.2004,6(23):4-6
[48]胡献舟,张盼月,曾光明,夏耀玲,王金菊.助凝助沉剂在含镍废水化学处理中 的应用.工业水处理.2007,27(4):48-49
[49]聂忠源,陈尚林.印制板蚀刻、微蚀刻废液的再生和铜回收的技术及设备.印制电路信息.2006,11:57-58
[50]罗耀宗.用符合特效絮凝剂处理化学镀镍废水.电镀与环保.2005,25(5):43-44
[51]沈友良,聂基兰.用化学捕收剂处理含镍废水.南昌大学学报.2005,29(4):367-368
[52]孙余凭.一种新型NF膜在含镍废水回用中的应用.电镀与环保.2007,27(1):39
[53]王刚,常青.高分子重金属絮凝剂处理含镍废水性能研究.安全与环境学报.2007,7(4):61
[54]常青,安瑜,于明泉.高分子重金属絮凝剂的制备及含铜废水处理.环境还学,2006,25(2):176-178
[55]郭仁东,吴昊,张晓颖.高浓度含铜废水处理方法的研究.当代化工.2004,33(5):281
[56]王文丰.螯合沉淀法处理含络合铜废水.印制电路信息.2003,11:62-63
[57]王碧,许桂丽,胡星淇.HW型高分子捕集剂处理含铅铜废水.化工环保.2007,27(5):484-486
[58]王进喜,常青,童敏,王亚军.高分子重金属絮凝剂MAPEI的制备及性能研究.环境科学学报.2007,27(10):1623-1624
[59]胡巧开.含铜废水的吸附处理研究.冶金能源.2005,24(2):59-60
[60]李萌.化学镀镍废水的处理及其利用.技术于研究.2006,5:68-69
[61]徐作鹏.焦磷酸盐镀铜废水的处理.沈阳大学学报.2005,17(2):56-57