干法腈纶废水处理技术研究及应用
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摘要
针对干法腈纶废水不能达标排放的问题,对目前腈纶生产装置的工艺、规模、废水排放及处理状况进行了深入细致的调查,找出了影响干法腈纶废水不能达标排放的主要原因,在广泛查阅文献资料及调研的基础上,对干法腈纶废水处理进行实验研究,找出干法腈纶废水的处理方法。采用化学氧化、高效絮凝沉淀、缺氧、动态氧化、硝化、活性碳吸附等处理技术和组合处理技术对干法腈纶废水进行了试验、中试和工业化应用;现场采用将干法腈纶废水单独处理和处理原污水场出水的方案分别进行实验,最后基于以干法腈纶废水达标排放为目的,根据现场中试的结果,提出采用“化学氧化+混凝沉淀+缺氧+动态氧化+硝化+活性碳吸附”的组合处理新工艺,并对腈纶废水处理进行工业化应用研究。
经过对干法腈纶废水分析和研究的结果表明,干法腈纶废水中主要含有机腈类、酯类、烷烃类、醇类等多种有机物,其中某些长碳链有机物及其聚合反应形成的难生物降解的低聚物是导致废水可生化性差的主要原因,处理干法腈纶废水必须采用物化和生化组合技术处理。现场中试研究结果表明,各单元处理技术对干法腈纶废水均有一定的作用和效果,但也存在一些不足,如化学氧化混凝沉淀的技术主要优势在于采用内电解技术,提高腈纶废水的可生化性能,腈纶废水通过内电解技术,使废水的BOD5/COD_(cr)可提高到0.4以上,COD_(cr)去除率可达45.39%;缺氧氧化技术主要优势在于废水经过水解酸化后,将大分子物质、难于降解的物质转化为易于生物降解的小分子有机物质,COD_(cr)去除率可达33.58%;动态氧化结合高效新型菌种,可很好地去除可生化性良好的废水中的有机物,活性碳吸附技术适合于较低浓度废水的处理活,性碳吸附起到最后的出水把关作用,使出水达到排放标准。只有将这些技术合理的组合,才能有效地达到净化废水的目的,优化选择的组合工艺为“化学氧化+混凝沉淀+缺氧+动态氧化+硝化+活性碳吸附”。采用该组合工艺对干法腈纶废水进行工业化应用取得了良好效果,通过控制相应的工艺参数,使废水COD_(cr)由800mg/L降至250mg/L以下,满足了废水达标排放的要求,为腈纶废水处理提供了新的处理方法和研究方向。
The dry-spun polyacrylonitrile (PAN) fiber wastewater cannot be discharged directly before treatment. In this paper, the treatment of PA fiber wastewater was studied after a lot of investigation of the industrial technology and discharge status. Based on the analysis and summary of the research methods and present situation of this treatment both domestic and abroad, it is concluded that all the technologies applied to industrialization for treating highly concentrated PA fiber wastewater have not been ideally effective. It is very difficult to make PA fiber wastewater reach the discharge standard. The ways to deal with the problem include internal electrolysis, chemical oxidation, flocculation experiment, anaerobic process, aerobic process, nitration, active-carbon adsorption and so on. Experiments of laboratory-scale and pilot-scale on treating PA fiber wastewater with chemical oxidation, flocculation experiment, anaerobic process, aerobic process, nitration, active-carbon adsorption have been conducted.
The main pollutants in the dry-spun PA fiber wastewater include nitrile, ester, alkane, phenol and so on. The organic compound with long carbon chain and some polymer will depress the biochemical capacity of the acrylic fiber wastewater. It is necessary to treat the wastewater with both physicochemical method and biochemical treatment. All the above measures are effective to the acrylic fiber wastewater. The methods of chemical oxidation and flocculation experiment have effect on improving the biochemical capacity of wastewater; COD removal rate can increase to 45.39%. The advantage of anaerobic process is making the macromolecule into small molecule which can be degraded easily by hydrolysis-acidification, the COD removal rate can be 33.58%. The aerobic process with microorganism can remove the organic compound effectively. The active-carbon adsorption is suitable to the diluent PA fiber wastewater. The degradation of COD can be decreased 250mg/L from 800mg/L with the multiplex technologies of chemical oxidation, flocculation, anaerobic process, aerobic process, nitration and active-carbon adsorption, which can meet the discharge standard of PA fiber industry.
经过对干法腈纶废水分析和研究的结果表明,干法腈纶废水中主要含有机腈类、酯类、烷烃类、醇类等多种有机物,其中某些长碳链有机物及其聚合反应形成的难生物降解的低聚物是导致废水可生化性差的主要原因,处理干法腈纶废水必须采用物化和生化组合技术处理。现场中试研究结果表明,各单元处理技术对干法腈纶废水均有一定的作用和效果,但也存在一些不足,如化学氧化混凝沉淀的技术主要优势在于采用内电解技术,提高腈纶废水的可生化性能,腈纶废水通过内电解技术,使废水的BOD5/COD_(cr)可提高到0.4以上,COD_(cr)去除率可达45.39%;缺氧氧化技术主要优势在于废水经过水解酸化后,将大分子物质、难于降解的物质转化为易于生物降解的小分子有机物质,COD_(cr)去除率可达33.58%;动态氧化结合高效新型菌种,可很好地去除可生化性良好的废水中的有机物,活性碳吸附技术适合于较低浓度废水的处理活,性碳吸附起到最后的出水把关作用,使出水达到排放标准。只有将这些技术合理的组合,才能有效地达到净化废水的目的,优化选择的组合工艺为“化学氧化+混凝沉淀+缺氧+动态氧化+硝化+活性碳吸附”。采用该组合工艺对干法腈纶废水进行工业化应用取得了良好效果,通过控制相应的工艺参数,使废水COD_(cr)由800mg/L降至250mg/L以下,满足了废水达标排放的要求,为腈纶废水处理提供了新的处理方法和研究方向。
The dry-spun polyacrylonitrile (PAN) fiber wastewater cannot be discharged directly before treatment. In this paper, the treatment of PA fiber wastewater was studied after a lot of investigation of the industrial technology and discharge status. Based on the analysis and summary of the research methods and present situation of this treatment both domestic and abroad, it is concluded that all the technologies applied to industrialization for treating highly concentrated PA fiber wastewater have not been ideally effective. It is very difficult to make PA fiber wastewater reach the discharge standard. The ways to deal with the problem include internal electrolysis, chemical oxidation, flocculation experiment, anaerobic process, aerobic process, nitration, active-carbon adsorption and so on. Experiments of laboratory-scale and pilot-scale on treating PA fiber wastewater with chemical oxidation, flocculation experiment, anaerobic process, aerobic process, nitration, active-carbon adsorption have been conducted.
The main pollutants in the dry-spun PA fiber wastewater include nitrile, ester, alkane, phenol and so on. The organic compound with long carbon chain and some polymer will depress the biochemical capacity of the acrylic fiber wastewater. It is necessary to treat the wastewater with both physicochemical method and biochemical treatment. All the above measures are effective to the acrylic fiber wastewater. The methods of chemical oxidation and flocculation experiment have effect on improving the biochemical capacity of wastewater; COD removal rate can increase to 45.39%. The advantage of anaerobic process is making the macromolecule into small molecule which can be degraded easily by hydrolysis-acidification, the COD removal rate can be 33.58%. The aerobic process with microorganism can remove the organic compound effectively. The active-carbon adsorption is suitable to the diluent PA fiber wastewater. The degradation of COD can be decreased 250mg/L from 800mg/L with the multiplex technologies of chemical oxidation, flocculation, anaerobic process, aerobic process, nitration and active-carbon adsorption, which can meet the discharge standard of PA fiber industry.
引文
[1]高敏惠.我国腈纶工业的发展前景.合成纤维工业,2001,24(1):6～8,42
[2]任玲子.中国腈纶工业现状与前景展望.合成维纤工业,2005,(1):46～49
[3]张震东.我国腈纶工业现状与发展前景.合成维纤工业,2006,(4):49～51
[4]任铃子.我国腈纶工业发展与对策.合成纤维工业,2000,23(1):14～21
[5]张震东.我国腈纶工业现状与发展前景.合成维纤工业,2006,(4):49～51
[6]欧阳丽,王晓明,赵建夫等.我国腈纶废水生化法处理进展.同济大学学报(自然科学版),2001,(3):18～20
[7] Leo H JJ Vredenbregt, et al. Fluid bed biological nitrification and denitrification in high salinity wastewater [J].Water Science & Technology,1997,36(1):93-100
[8] Jensen Jr k A,Houtman C J,Ryan ZC.et al. Pathway for extracellular Fenton chemistry in the brown rot basidiomycete Gloeophyllum trabeum. Applied &Environmental Microbiology,2001,67(6):2705～2711
[9]徐亚同.废水中氮磷的处理.上海:华东师范大学出版社,1994:43～63
[10] Werker Alan G,Becker Jennifer,Huitema Carly.Assessment of activated sludge microbial community analysis in fuii-scale biological wastewater treatment plants using patterns of fatty acid isopropyl esters(FAPEs)[J].Water Res.2003,37(9):2 162
[11]杜赦林.软性填料膜法A/O脱氮系统处理腈纶废水.给水排水,1996,22(6):23～25
[12]杨晓奕,师绍琪,蒋展鹏等.混凝一二相厌氧一缺氧一好氧工艺处理腈纶废水的研究.给水排水,2001,27(6):40～44
[13] Hardik Patel, Datta Madamar. Biomethanation of low pH petrochemical wastewater using up-flow fixed-film anaerobic bioreactors[J].World Journal of Microbiology & Biotechnology,2000,16:69-75
[14] Hulshoff pol,L.W.Fundamentals of anaerobic digestion 5.in:1st Int.Course on Anaerobic and Low Cost Treatment of Wastes and Wastewaters. The Neterlands;IAC and WAU.1994
[15]黄民生,黄升.湿法腈纶生产的含腈废水处理实验研究.工业水处理,2002,22(5):15～18
[16]左剑恶.高浓度硫酸盐有机废水生物处理新工艺的研究:[学位论文] .清华大学,北京:1995
[17]赵朝成,王志伟.臭氧氧化法处理腈纶废水研究化工环保,2004,24:56～59
[18]陆斌,韦鹤平.内电解强化处理腈纶废水的试验研究.同济大学学报(自然科学版),2001,29(11):1294～1298
[19]周培国,傅大放.微电解工艺研究进展.环境污染治理技术与设备,2001,2(4):18～24
[20]韩洪军,刘彦忠,杜冰.铁屑-碳粒法处理纺织印染废水.工业水处理,1997,17(6):15～17
[21]陈水平.铁屑内电解法处理船舶含油废水的研究.水处理技术,1999,25(5):303～30
[22]肖羽堂,许建华,陈静.铁屑强化系统工艺处理难降解印染废水的实践.给水排水,1998,24(4):37～39
[23]郝瑞霞,程水源,黄群贤.铁屑过滤法预处理可生化性差的印染废水.化工环保,1999,19(3):135～139
[24]魏守强.铁屑活性炭内电解法预处理干法腈纶废水的实验研究.沈阳工业学院学报.2003,22(2):49～50
[25]赵朝成,王志伟.臭氧氧化法处理腈纶废水研究.化工环保,2004,24:56～59
[26]汪宏渭,孙在柏,孙国华.干法腈纶废水处理工艺的研究.中国环保产业,2004,(3):30～32
[27]《辽宁省污水与废气排放标准》(污水部分)DB21-60-89
[28]《污水综合排放标准》GB8978-1996
[29]国家环境保护总局.关于发布《污水综合排放标准》(GB8978-1996)中石化工业COD标准值修改单的通知.环发[1999]285号,1999
[2]任玲子.中国腈纶工业现状与前景展望.合成维纤工业,2005,(1):46～49
[3]张震东.我国腈纶工业现状与发展前景.合成维纤工业,2006,(4):49～51
[4]任铃子.我国腈纶工业发展与对策.合成纤维工业,2000,23(1):14～21
[5]张震东.我国腈纶工业现状与发展前景.合成维纤工业,2006,(4):49～51
[6]欧阳丽,王晓明,赵建夫等.我国腈纶废水生化法处理进展.同济大学学报(自然科学版),2001,(3):18～20
[7] Leo H JJ Vredenbregt, et al. Fluid bed biological nitrification and denitrification in high salinity wastewater [J].Water Science & Technology,1997,36(1):93-100
[8] Jensen Jr k A,Houtman C J,Ryan ZC.et al. Pathway for extracellular Fenton chemistry in the brown rot basidiomycete Gloeophyllum trabeum. Applied &Environmental Microbiology,2001,67(6):2705～2711
[9]徐亚同.废水中氮磷的处理.上海:华东师范大学出版社,1994:43～63
[10] Werker Alan G,Becker Jennifer,Huitema Carly.Assessment of activated sludge microbial community analysis in fuii-scale biological wastewater treatment plants using patterns of fatty acid isopropyl esters(FAPEs)[J].Water Res.2003,37(9):2 162
[11]杜赦林.软性填料膜法A/O脱氮系统处理腈纶废水.给水排水,1996,22(6):23～25
[12]杨晓奕,师绍琪,蒋展鹏等.混凝一二相厌氧一缺氧一好氧工艺处理腈纶废水的研究.给水排水,2001,27(6):40～44
[13] Hardik Patel, Datta Madamar. Biomethanation of low pH petrochemical wastewater using up-flow fixed-film anaerobic bioreactors[J].World Journal of Microbiology & Biotechnology,2000,16:69-75
[14] Hulshoff pol,L.W.Fundamentals of anaerobic digestion 5.in:1st Int.Course on Anaerobic and Low Cost Treatment of Wastes and Wastewaters. The Neterlands;IAC and WAU.1994
[15]黄民生,黄升.湿法腈纶生产的含腈废水处理实验研究.工业水处理,2002,22(5):15～18
[16]左剑恶.高浓度硫酸盐有机废水生物处理新工艺的研究:[学位论文] .清华大学,北京:1995
[17]赵朝成,王志伟.臭氧氧化法处理腈纶废水研究化工环保,2004,24:56～59
[18]陆斌,韦鹤平.内电解强化处理腈纶废水的试验研究.同济大学学报(自然科学版),2001,29(11):1294～1298
[19]周培国,傅大放.微电解工艺研究进展.环境污染治理技术与设备,2001,2(4):18～24
[20]韩洪军,刘彦忠,杜冰.铁屑-碳粒法处理纺织印染废水.工业水处理,1997,17(6):15～17
[21]陈水平.铁屑内电解法处理船舶含油废水的研究.水处理技术,1999,25(5):303～30
[22]肖羽堂,许建华,陈静.铁屑强化系统工艺处理难降解印染废水的实践.给水排水,1998,24(4):37～39
[23]郝瑞霞,程水源,黄群贤.铁屑过滤法预处理可生化性差的印染废水.化工环保,1999,19(3):135～139
[24]魏守强.铁屑活性炭内电解法预处理干法腈纶废水的实验研究.沈阳工业学院学报.2003,22(2):49～50
[25]赵朝成,王志伟.臭氧氧化法处理腈纶废水研究.化工环保,2004,24:56～59
[26]汪宏渭,孙在柏,孙国华.干法腈纶废水处理工艺的研究.中国环保产业,2004,(3):30～32
[27]《辽宁省污水与废气排放标准》(污水部分)DB21-60-89
[28]《污水综合排放标准》GB8978-1996
[29]国家环境保护总局.关于发布《污水综合排放标准》(GB8978-1996)中石化工业COD标准值修改单的通知.环发[1999]285号,1999