四磺酸铁酞菁催化材料的制备及其光降解染料废水的研究
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摘要
水环境污染已成为全球性普遍关注的重要课题。随着印染行业的不断发展,其排放的印染废水具有水量大、色度高、可生化性差、组分复杂等特点,传统的废水处理方法很难经济有效地进行处理。
利用光催化氧化技术处理水中难降解有机污染物的方法已经引起了国内外水处理专家的广泛关注。四磺酸铁酞菁作为一种低能耗,高效率的光催化剂,具有可见光响应范围宽、催化效率高、不易受外界干扰、光热稳定性好等特点,将其用于处理印染废水,从环境可持续发展角度来看,具有十分重要的意义。
在本课题中,我们首先通过苯酐-尿素路线,以邻苯二甲酸酐、金属盐、尿素为原料,以钼酸铵为催化剂,用固相法合成了铁酞菁(FePc),并用浓硫酸沉淀法提纯产物,铁酞菁(FePc)经氯磺酸磺化后制备得到具有四个磺酸基的水溶性酞菁化合物四磺酸铁酞菁(FePcS),采用凯式定氮法、红外对最终合成产物的结构进行表征,证明四磺酸铁酞菁已经成功合成。
将四磺酸铁酞菁(FePcS)通过负载技术负载于改性纤维素纤维上,制备得到水溶性铁酞菁负载型催化纤维(FePcS-F),然后将该负载光催化剂应用于可见光下催化降解印染废水,基于光催化氧化理论,以典型商品染料活性红K-2G为研究对象,开展光催化氧化降解模拟染料废水的实验研究,探讨分析了影响光催化氧化降解效果的基本因素、工艺条件以及光降解产物等方面内容。
Environmental contamination in groundwater involving a variety of nonbiodegradable toxic organic pollutants from industrial effluents is a matter of concern. With the development of textile industry, the amount of discharged wastewater in dyeing and printing industry is very high and could not be treated effectively with traditional methods for its deep color, poor biochemical degradation and complicated components.
Photocatalytic oxidation technology has been successfully used to degrade the organic pollutants in wastewater and many water treatment experts pay more attention to study the photocatalytic oxidation technology. Iron phthalocyanine sulfonates(FePcS) can response to a wide range of visiblelight high catalytic efficiency and optical characteristics of a good thermal stability, FePcS as a low-power, high-efficiency catalyst for the treatment of dyeing effluent, has a prefect perspective usage in the field of photo-degradation of dyeing effluent.
This paper used phthalicanhydride、metal-salt、carbamide as raw materials, used (NH_4)_2Mo as catalyzer for the synthesis of Iron phthalocyanine (FePc) by the way of solid phrase. And then use chlorosulfonic acid synthesized Iron phthalocyanine quasulfonates. Produets were characterized by FT-IR and the nitrogen content was determined by the micro-Kjeldahl method. By those methods it proved that the FePcS was successfully synthesized.
Then the Iron phthalocyanine quasulfonates were supported by modified cellulose fibers in acidic condition to obtain loading FePcS fibers (FePcS-F), and then used as a heterogeneous catalyst for the photocatalytic degradation of Reactive Red K-2G in water. Base on the photocatalytic oxidation theory, regard the representative merchandise dyes reactive red K-2G as the object, we developed the researches of photocatalytic oxidation degradation of dye effluent Some basic factors including the condation of processing and the products of photocatalytic oxidation affecting the degradation of Reactive Red K-2G were investigated with respect to the decoloration rate.
利用光催化氧化技术处理水中难降解有机污染物的方法已经引起了国内外水处理专家的广泛关注。四磺酸铁酞菁作为一种低能耗,高效率的光催化剂,具有可见光响应范围宽、催化效率高、不易受外界干扰、光热稳定性好等特点,将其用于处理印染废水,从环境可持续发展角度来看,具有十分重要的意义。
在本课题中,我们首先通过苯酐-尿素路线,以邻苯二甲酸酐、金属盐、尿素为原料,以钼酸铵为催化剂,用固相法合成了铁酞菁(FePc),并用浓硫酸沉淀法提纯产物,铁酞菁(FePc)经氯磺酸磺化后制备得到具有四个磺酸基的水溶性酞菁化合物四磺酸铁酞菁(FePcS),采用凯式定氮法、红外对最终合成产物的结构进行表征,证明四磺酸铁酞菁已经成功合成。
将四磺酸铁酞菁(FePcS)通过负载技术负载于改性纤维素纤维上,制备得到水溶性铁酞菁负载型催化纤维(FePcS-F),然后将该负载光催化剂应用于可见光下催化降解印染废水,基于光催化氧化理论,以典型商品染料活性红K-2G为研究对象,开展光催化氧化降解模拟染料废水的实验研究,探讨分析了影响光催化氧化降解效果的基本因素、工艺条件以及光降解产物等方面内容。
Environmental contamination in groundwater involving a variety of nonbiodegradable toxic organic pollutants from industrial effluents is a matter of concern. With the development of textile industry, the amount of discharged wastewater in dyeing and printing industry is very high and could not be treated effectively with traditional methods for its deep color, poor biochemical degradation and complicated components.
Photocatalytic oxidation technology has been successfully used to degrade the organic pollutants in wastewater and many water treatment experts pay more attention to study the photocatalytic oxidation technology. Iron phthalocyanine sulfonates(FePcS) can response to a wide range of visiblelight high catalytic efficiency and optical characteristics of a good thermal stability, FePcS as a low-power, high-efficiency catalyst for the treatment of dyeing effluent, has a prefect perspective usage in the field of photo-degradation of dyeing effluent.
This paper used phthalicanhydride、metal-salt、carbamide as raw materials, used (NH_4)_2Mo as catalyzer for the synthesis of Iron phthalocyanine (FePc) by the way of solid phrase. And then use chlorosulfonic acid synthesized Iron phthalocyanine quasulfonates. Produets were characterized by FT-IR and the nitrogen content was determined by the micro-Kjeldahl method. By those methods it proved that the FePcS was successfully synthesized.
Then the Iron phthalocyanine quasulfonates were supported by modified cellulose fibers in acidic condition to obtain loading FePcS fibers (FePcS-F), and then used as a heterogeneous catalyst for the photocatalytic degradation of Reactive Red K-2G in water. Base on the photocatalytic oxidation theory, regard the representative merchandise dyes reactive red K-2G as the object, we developed the researches of photocatalytic oxidation degradation of dye effluent Some basic factors including the condation of processing and the products of photocatalytic oxidation affecting the degradation of Reactive Red K-2G were investigated with respect to the decoloration rate.
引文
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[4]俞亦政.纺织印染废水处理新技术,“Bio-Uniout"研究和应用[J].染整科技,2007,No.6:38-39.
[5]丁忠浩.有机废水处理技术及应用.化学工业出版社.2002:317-319.
[6]梁志荣.染料废水物理化学处理技术的现状与进展.四川环境.2003,22(6):25-29.
[7]丁忠浩.有机废水处理技术及应用.化学工业出版社.北京.2002:108-143.
[8]Bolton JR.Solar Detoxification[J].Solar Engergy,1996,56(5):375-379.
[9]余颖.有机絮凝剂对水中染料的絮凝作用探讨.环境化学,2000,19(2):142-148.
[10]Canjidoust H.Effect of synthetic and natural coagulant on lignin removal from pulp and paper wastewater.Water Science and Technology,1995,31(3):285-294.
[11]苏玉萍.以活性染料为主要成分的印染废水的混凝实验.化工环保,2000,2(20):7-11.
[12]张凯松.新合成复合絮凝剂HEGES絮凝性能的研究.应用生态学报,2003,14(5):789-793.
[13]吴开芬.用超滤法处理靛蓝废水.环境科学进展,1998,6增刊):124-127.
[14]王振余.炭膜处理染料水溶液的研究.膜科学与技术,1997,17(5):7-1O.
[15]Oliveim L.Activated carbon 八 ron oxide magnetic composites for the adsorption of contaminant in water.Carbon,2002,40(12):2177-2183.
[16]Engwall,M.A.,Pignatello,J.J.,Grasso,D.Degradation and detoxification of the wood preservatives creosote and pentachlorophenol in water by the photo-Fenton reaction.Wat.Res.1999.33:1151-1158.
[17]刘琼玉,李太友.难降解有机污染物的高级氧化技术.江汉大学学报.2002.19:56-58.
[18]Esplugas,S.,Gimenez,J,Contreras,S,Pasual,E.,Rodriguez,M.Comparison of different advanced oxidation processes for phenol degradation.Res.2002.36:1034-1042.
[19]Peyton,GR.,Glaze,W.H.Destruction of pollutants in water with ozone in combination with ultraviolet.3.Photolysis of aqueous ozone.Environ.Sci.Technol.1988.22:761-767.
[20]吕锡武,严熙世.光化学氧化处理饮用水中有机优先污染物.中国环境科学.1992.12:71-74.
[21]崔斌.Fe_2O_3搀杂TiO_2薄膜对甲基紫溶液光催化降解.应用化学,2001,18(12):958-961.
[22]白波.纳米TiO_2薄膜光催化降解酸性粒子元青溶液的研究.2002,24(3):140-143.
[23]杨爱丽.负载型光催化剂降解有机废水的研究进展.工业水处理.2003,23(3):1-4.
[24]Lecheng Lei.Homogeneous catalytic wet-air oxidation for the treatment of textile wastewater.Water Environment Research,2000,72(2):147-151.
[25]Pansward T.Decolourization of reactive dyes with different molecular structure under different environmental conditions.WaterResearch,2000,34(17):4177-4184.
[26]Macdonald,D.D.,Kriksunov,L.B.Probing the chemical and electrochemical properties of SCWO Systems.Electrochimica Acta 2001.47:775-790.
[27]佐古猛.超临界水氧化芳香类有机物处理技术的应用.用水与废水,1999,4l(8):38-42.
[28]佐藤政树.芳香类有机物污染物诬害化技术用水与废水,1999,41(8):34-41.
[29]彭继伟.改良厌氧-生物接触氧化处理纺织印染废水.工业水处理,2002,22(7):46-48.
[30]门庆松.偶氮染料废水的厌氧好氧处理工程实例.工业水处理,2001,21(1):44-46.
[31]Shaw G.Anaerobic/aerobic treatment of colored textile effluents using sequencing Batch reactors.Water Research.2002,36(8):1993-2001.
[32]肖利.缺氧—好氧—亚滤—富氧生物炭工艺处理印染废水.环境工程,2002,20(4):33-34.
[33]梁沈平.固定化微生物柱对染料废水的脱色实验.环境科学,1998,19(5):10-14.
[34]Walker G.Biological activated carbon treatment of industrial wastewater in stirred tank reactors.Chemical Engineering Journal,1999,75(3):201-206.
[35]王一平.活性污泥法处理染料废水的研究.环境_!程,1999,6(17):7-10.
[36]蔡惠如.膜生物反应器与SBR法处理染料废水的比较.水处理技术,2002,28(6):347-349.
[37]Lopez C.Enzymatic membrane reactors for biodegradation of recalcitrant compounds.Journal ofbiotechnology,2002,99(3):249-257.
[38]李明玉等.脱氨-催化氧化-吸附联合工艺处理苯胺类废水的研究[J].给水排水.2003,29(1):52.
[39]刘勇弟,徐寿昌.几种类Fenton试剂的氧化特性及在工业废水处理中的应用[J].上海环境科学,1994,13(4):1.
[40]Wang Aimin,Yang Lihong,Zhang Sujuan,Jiang Guilan.[J]Industrial Water Treatment,2001,21(8):4-7.
[41]Lei Lecheng,Wang Dahui.[J]China Environmental Science,1999,19(1):42-46.
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