光助非均相Fenton体系用于活性艳红X-3B脱色的研究
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摘要
随着我国染料和印染工业的发展，每年排放的的染料废水给环境造成了严重的污染。在世界范围内，纺织工业废水已经成为全球性的严重污染问题。染料废水，特别是偶氮染料废水，如果直接排放会对当地水环境造成不可估量的损失。本论文以解决目前染料废水处理中的难点之一——染料废水脱色为目的，对光助非均相Fenton体系对活性艳红X-3B的脱色开展了系统的研究，获得的结果如下：
(1) UV／Fe载体／H_2O_2体系对活性艳红X-3B具有较好的脱色效果，在Fe载体0.5g／L，pH=3.0，H_2O_285mg／L，36W UV253.7nm的条件下，活性艳红X-3B(100mg／L)脱色效果显著，30min时活性艳红X-3B脱色率达到100％，10分钟内该脱色反应符合一级反应动力学，k值为0.1225 min~(-1)。相比之下，催化剂制备过程中，在Fe载体中掺杂一定量铈制备成Ce-Fe材料，将此作为催化剂形成的UV／Ce-Fe／H_2O_2体系对活性艳红X-3B具有更有效的脱色效果。当铈的掺杂浓度为0.08mol／L，Ce-Fe 0.5g／L，pH=3.0，H_2O_234mg／L，36W UV253.7nm的条件下，活性艳红X-3B(100mg／L)脱色效果显著，10min时活性艳红X-3B脱色率达到90％，10分钟内该脱色反应符合一级反应动力学，反应速率k值为0.2456min~(-1)。
(2) XRD表征结果表明，铈的加入改变了铁氧化物载体的晶体结构，形成了介于晶体和无定型之间的微晶体结构，利于其表现出较高的催化活性。在UV／Ce-Fe／H_2O_2体系中，Fe~(3+)的溶出可能在一定程度上提高了活性艳红X-3B的脱色速度。单一的Ce-Fe材料，Ce-Fe／H_2O_2体系，UV／Ce-Fe体系对活性艳红X-3B的脱色作用主要是Ce-Fe材料吸附作用，其对染料分子的降解作用不明显。UV／H_2O_2体系和UV／Ce-Fe／H_2O_2体系对活性艳红X-3B具有降解作用，后者效果更为明显。UV／Ce-Fe／H_2O_2体系对活性艳红X-3B有一定的矿化效果。
本研究首次将Ce-Fe材料作为一种非均相催化剂对染料废水进行处理，对体系的反应条件进行了系统研究，为解决染料废水的脱色问题奠定了坚实的基础。同时，本研究也在一定程度上推理了UV／Ce-Fe／H_2O_2体系的反应机理。
With the development of domestic dye and dye printing industry, environment is polluted seriously by the dyeing wastewater let each year. The dyeing wastewater has been a serious global problem. If dyeing wastewater, especially azo dye wastewater is let, it will seriously do harm to local aquatic environment. The object of the paper is to study the one of problems of the dyeing treatment, the discoloration of dyeing wastewater, and the results are as following.
1. UV/Fe carrier /H202 system is effective for Reactive Brilliant Red X-3B color removal, Experimental results show that the heterogeneous photo-Fenton reaction was in conformity with first-order kinetics equation within 10 minutes and rate constant equaled to 0.1225 min" . The discoloration of the dyes relates to pH and H2O2 concentration. The optimal discoloration for 100 mg/L RBR X-3B was obtained under the condition that pH and H202 concentration are 3.0 and 85mg/L respectively. In this study, discoloration of RBR X-3B was studied by using the iron oxides doped with cerium (Ce-Fe) as a heterogeneous catalyst in the presence of H2O2 and UV light (253.7nm). Compared with UV/Fe carrier /H202 system, UV/Ce-Fe /H2O2 system is more effective for RBR X-3B color removal. Experimental results show that the heterogeneous photo-Fenton reaction was in conformity with first-order kinetics equation within 10 minutes and rate constant equaled to 0.1225 min-1. The discoloration of the dyes relates to the doping dose of
cerium for Ce-Fe preparation, pH and H202 concentration. The optimal discoloration for 100 mg/1 RBR X-3B was obtained under the condition that the doping dose of cerium, pH and H2O2 concentration are 0.08mol/L, 3.0 and 34mg/L respectively.
2. XRD experimental results show that the doping of Cerium change the crystal assembling and it turn out to be a kind of minicrystal which is an intergradation from crystal to unformed structure, and this structure makes the material more active catalyze
performance. Fe dissolved can improve the discoloration rate of RBR X-3B in UV/Ce-Fe /H2O2 system. Adsorption is the discoloration mechanism for RBR X-3B of Ce-Fe, Ce-Fe/HO system and UV/Ce-Fe system. UV/HO system and UV/Ce-Fe/H0 system have the degradation effect on RBR X-3B, and the latter is more prominent.
In this paper, Ce-Fe was studied as a heterogeneous catalyst for the first time and it was used to treat the dyeing wastewater in UV/Ce-Fe /HOsystem. The above results not only provided a possible strategy for the color removal of dyeing wastewater, but also elucidated the reaction mechanisms to some extend.
(1) UV／Fe载体／H_2O_2体系对活性艳红X-3B具有较好的脱色效果，在Fe载体0.5g／L，pH=3.0，H_2O_285mg／L，36W UV253.7nm的条件下，活性艳红X-3B(100mg／L)脱色效果显著，30min时活性艳红X-3B脱色率达到100％，10分钟内该脱色反应符合一级反应动力学，k值为0.1225 min~(-1)。相比之下，催化剂制备过程中，在Fe载体中掺杂一定量铈制备成Ce-Fe材料，将此作为催化剂形成的UV／Ce-Fe／H_2O_2体系对活性艳红X-3B具有更有效的脱色效果。当铈的掺杂浓度为0.08mol／L，Ce-Fe 0.5g／L，pH=3.0，H_2O_234mg／L，36W UV253.7nm的条件下，活性艳红X-3B(100mg／L)脱色效果显著，10min时活性艳红X-3B脱色率达到90％，10分钟内该脱色反应符合一级反应动力学，反应速率k值为0.2456min~(-1)。
(2) XRD表征结果表明，铈的加入改变了铁氧化物载体的晶体结构，形成了介于晶体和无定型之间的微晶体结构，利于其表现出较高的催化活性。在UV／Ce-Fe／H_2O_2体系中，Fe~(3+)的溶出可能在一定程度上提高了活性艳红X-3B的脱色速度。单一的Ce-Fe材料，Ce-Fe／H_2O_2体系，UV／Ce-Fe体系对活性艳红X-3B的脱色作用主要是Ce-Fe材料吸附作用，其对染料分子的降解作用不明显。UV／H_2O_2体系和UV／Ce-Fe／H_2O_2体系对活性艳红X-3B具有降解作用，后者效果更为明显。UV／Ce-Fe／H_2O_2体系对活性艳红X-3B有一定的矿化效果。
本研究首次将Ce-Fe材料作为一种非均相催化剂对染料废水进行处理，对体系的反应条件进行了系统研究，为解决染料废水的脱色问题奠定了坚实的基础。同时，本研究也在一定程度上推理了UV／Ce-Fe／H_2O_2体系的反应机理。
With the development of domestic dye and dye printing industry, environment is polluted seriously by the dyeing wastewater let each year. The dyeing wastewater has been a serious global problem. If dyeing wastewater, especially azo dye wastewater is let, it will seriously do harm to local aquatic environment. The object of the paper is to study the one of problems of the dyeing treatment, the discoloration of dyeing wastewater, and the results are as following.
1. UV/Fe carrier /H202 system is effective for Reactive Brilliant Red X-3B color removal, Experimental results show that the heterogeneous photo-Fenton reaction was in conformity with first-order kinetics equation within 10 minutes and rate constant equaled to 0.1225 min" . The discoloration of the dyes relates to pH and H2O2 concentration. The optimal discoloration for 100 mg/L RBR X-3B was obtained under the condition that pH and H202 concentration are 3.0 and 85mg/L respectively. In this study, discoloration of RBR X-3B was studied by using the iron oxides doped with cerium (Ce-Fe) as a heterogeneous catalyst in the presence of H2O2 and UV light (253.7nm). Compared with UV/Fe carrier /H202 system, UV/Ce-Fe /H2O2 system is more effective for RBR X-3B color removal. Experimental results show that the heterogeneous photo-Fenton reaction was in conformity with first-order kinetics equation within 10 minutes and rate constant equaled to 0.1225 min-1. The discoloration of the dyes relates to the doping dose of
cerium for Ce-Fe preparation, pH and H202 concentration. The optimal discoloration for 100 mg/1 RBR X-3B was obtained under the condition that the doping dose of cerium, pH and H2O2 concentration are 0.08mol/L, 3.0 and 34mg/L respectively.
2. XRD experimental results show that the doping of Cerium change the crystal assembling and it turn out to be a kind of minicrystal which is an intergradation from crystal to unformed structure, and this structure makes the material more active catalyze
performance. Fe dissolved can improve the discoloration rate of RBR X-3B in UV/Ce-Fe /H2O2 system. Adsorption is the discoloration mechanism for RBR X-3B of Ce-Fe, Ce-Fe/HO system and UV/Ce-Fe system. UV/HO system and UV/Ce-Fe/H0 system have the degradation effect on RBR X-3B, and the latter is more prominent.
In this paper, Ce-Fe was studied as a heterogeneous catalyst for the first time and it was used to treat the dyeing wastewater in UV/Ce-Fe /HOsystem. The above results not only provided a possible strategy for the color removal of dyeing wastewater, but also elucidated the reaction mechanisms to some extend.
引文
1．岑沛霖，雷乐成．纺织印染废水的湿式空气氧化处理．浙江大学学报(工学版)，2001，35(1)
2．曹瑾．光化学概念．北京：高等教育出版社，1985
3．邓南圣，吴峰．铁羟基络合物体系对水溶性染料的光催化氧化降解．环境与开发．1997，12(3)
4．胡春．TiO_2光催化固定化及染料化合物光催化降解的研究．中国科学院博士论文，2001
5．何锋．UV-Fenton处理难降解废水的研究．浙江大学硕士论文．2002
6．雷乐成，汪大晕．水处理高级氧化技术．北京：化学工业出版社，2001
7．李薇．电光源条件下光催化降解染料化合物的研究．中国科学院博士论文，2003
8．钱易，汤鸿霄，文湘华．水体颗粒物和难降解有机物的特性与控制技术原理(下)．北京：中国环境科学出版社，2000
9．三井纪一郎等．触媒湿式酸化排水处理法．触媒．1991，35(5)：351
10．谢银德，陈锋等．photo-Fenton反应研究进展．感光科学与光化学．2000，18(4)
11．岳林海．稀土元素掺杂二氧化钛催化剂光降解久效磷的研究．上海环境科学，1998，17(9)：17-19
12．周连江，乐志强．无机盐工业手册(下)．北京：化学工业工出版社，1996
13．张彭义，祝万鹏．臭氧水处理技术的进展．环境科学进展．1994，2(3)：50
14．张昱．新型阴离子吸附材料及吸附机理研究．中国科学院博士论文，2003
15．张昱，杨敏等，利用新型稀土铈复合吸附剂去除水体腐殖质的研究．环境科学，2004，25(1)：83—86
16．祝万鹏，杨志华，王利．亚铁-过氧化氢法处理染料中间体H酸生产废液的研究．中国环境科学．1995，15(5)：368-372
17. Beltran F J, Garaia-Araya J F, acedo B. Advanced oxidation of atrazine in water-Ⅱ. ozonation combined with'ultraviolet radiation. Wat Res. 1994, 28(10): 2156
18. Bishop D F. Hydrogen peroxide catalytic oxidation of refractory organics in municipal wastewaters. Industryial and Engineering Chemistry. Process design and development. 1968, 7:110-117
19. Bossmarm S H, Oliveros E, Gob S. New evidence against hydroxyl radicals as reactive intermediates in the thermal and photochemically enhanced Fenton reaction.
J. Phys. Chem. 1998, 102(28):5542-5520
20. Centi G, Perathoner S, Catalytic wet oxidation with H202 of carboxylic acids on homogeneous and heterogeneous Fenton-type catalysts, Catalysis Today, 2000, 55:61-69
21. Chen G H, Lei L C. Treatment of desizing waste water containing poly-vinyl alcohol by wet air oxidation. Industrial Engineering Chemistry Research, 2000, 39
22. Chumg King-Thorn. Degradation of azo dyes by environmental microorganisms and belminthes. Environ Toxical Chem. 1993, 13(11):2121-2132
23. Dimirkou A, Ioannou A, Doula M. Preparation characterization and sorption properties for phosphates of hematite benonite and bentonite-hematite systems. Advanced in Colloid and Interf Sci, 2002(97):31—61
24. Eckenfelder, W. Wesley. Chemical oxidation: technologies for the nineties: proceedings of the first international symposium, chemical oxidation: technology for the nineties. Lancaster, Pa: Technomie Pub Co., 1997
25. Eisenberg G M. Colorimetric determiation of hydrogen peroxide. Ind Eng Chem, 1943, 15(5): 327-328
26. Fajerwerg K, Debellefontaine H, Wet oxidation of phenol by hydrogen peroxide using heterogeneous Catalysis Fe-ZSM-5: a promising catalyst. Applied Calysis B :Envionmental, 1996, 10:229-235
27. Fang X W, Pan X M. Reversibility in the reaction of cyclohexadienyl radicals with oxygen in aqueous solution. Eur J Chem, 1995, 1:423
28. Fenton H G H. On a new reaction of tartaric acid (letter to the editor). Chemical News. 1876, 33:190
29. Fenton H G H and H O Jones. The oxidation of organic acids in the presence of iron. C J Chem Soc. 1900, 77:69-76
30. Fernandez J, Bandara J, Lopez A, Buffar Ph, Kiwi J, Photoassisted Fenton degradation of nonbiodegradable azo dye (Orange Ⅱ) in Fe-free solutions mediated by cation transfer membranes. Langmuir1999, 15(1): 185—92.
31. Gallard H, De Laat J and Legube B. Influence du pH sur la vitesse d'oxydation de composes organieques par FeⅡ/H_2O_2. Mecanismes reactionnels et modelisation. New J Chem. 1998, 263-268
32. Glaze W H, Kang J W, Chapin D H. The chemistry of water and wastewater treatment processes involving ozone, hydrogen peroxide and ultraviolet radiation. Ozine Sei Eng,
1987, 9:335-352
33. Glaze W H, Kang J W, Chapin D H. The chemistry of water and wastewater treatment processes involving ozone, hydrogen peroxide and ultraviolet radiation. Ozine Sci Eng, 1987, 9:335-352
34. Glaze W H, Peyton G R, Lin S, et al. Destruction of pollutants in water with ozone in combination with ultraviolet radiation. 2, natural trihalomethane precursors. Environ Sci Technol. 1982, 16:454
35. Haber F, Weiss J. The catalytic decomposition of hydrogen peroxide by iron salt. Proc R Soc, series A. 1934, 147:332
36. Hoigne J, Bader H. The role of hydroxyl radical reaction in ozonation processes in aqueous solutions. Water Res, 1976, 10, 377～383
37. Hunter T V. The effect of dyes on aerobic systems. In Dyes and Environment, 1973, 1(6)
38. Hu X, Lam FLY, et al., Copper/MCM-41 as catalyst for photochemically enhanced oxidation of phenol by hydrogen peroxide. Catalysis Today, 2001, 68: 29—133.
39. Jiyun Feng, Xijun Hu, et al., Discoloration and mineralization of Reactive Red HE-3B by heterogeneous photo-Fenton reaction. Water Research, 2003, 37: 3776—3784
40. Jiyun Feng, Xijun Hu, et al., Anovel laponite clay-based Fe nanocomposite and its photo-catalytic activity in photo-assisted degradation of Orange Ⅱ. Chemical Engineering Science, 2003, 58:679—685
41. Joseph J, Plgnatello, Dark and Photoassisted Fe3+-Catalyzed Degradation of Chlorophenoxy Herbicides by Hydrogen Peroxide. Environ. Sci. Technol. 1992, 26(5): 944—951
42. Kremer M L, Stein G. The catalytic decomposition of hydrogen peroxise by ferric perchlorate. Trans Faraday Soc. 1959, 55:959-973
43. Legrini O, Olibveros E, Braun A M. Photochemical process for water treatment. Chemical Reviews. 1993, 93(2): 14-31
44. Nomura J, Imai H, Miyake T. R Removal of fluoride ion from wastewater by a hydrous ceriym oxide adsorbent. Am. Chem. Soc. Syrup. Ser, 1990:422
45. Perkins, Michael John. Radical chemistry. New York: Ellis Horwood, 1994
46. R. Bauer, G. Waldner, et al., The photo-fenton reaction and the TiO_2/UV process for waste water treatment - novel developments. Catalysis Today 1999, 53(1): 131—144
47. Sabhi S, Kiwi J, Degradation of 2, 4-dichlorophenol by immobilized iron catalysts, Wat.
Res, 2001, 35:1994-2001
48. Sunstrorm D W, Klei H E, Nalette T A, et al. Hazard Waste Hazard Mater. 1986, 3:101
49. Shyh-Fang Kang, Chih-Hsiang Liao, Hung-Pin Hung, Peroxidation treatment of dye manufacturing wastewater in the presence of ultraviolet light and ferrous ions. Journal of Hazardous Materials, 1999, B65:317—333
50. Tanner, Dennis D. Advances in free radical chemistry: a research annual. Greenwich: JAI Pr Inc, 1990.
51. Weir B A, Sunstrorm D W, Klei H E. Destruction of halogenerated aliphatics by ultraviolet catalyzed oxidation with hydrogen peroxide. Hazard Waste Hazard Mater. 1987, 4:165
52. Wolfgang Gernjak, Thomas Krutzler, et al., Photo-Fenton treatment of water containing natural phenolic pollutants. Chemosphere 2003, 50:71—78
53. Yenkie MKN, Natarajan GS. Adsorption equilibrium studies of some aqueous aromatic pollutants on granulm activated carbon samples. Separ Sci and Tech. 1991 26(5):661—674
54. Yu Zhang, Min Yang, Xia Huang, Arsenic(Ⅴ) removal with a Ce(Ⅳ)-doped iron oxide adsorbent. Chemosphere, 2003, 51: 945—952
55. Zeep, R. G. Hydroxyl radical formation in aqueous reactions of iron(Ⅱ) with hydrogen peroxide: the photo-Fenton reaction. Environ. Sci. Technol. 1992, 26, 313-319
2．曹瑾．光化学概念．北京：高等教育出版社，1985
3．邓南圣，吴峰．铁羟基络合物体系对水溶性染料的光催化氧化降解．环境与开发．1997，12(3)
4．胡春．TiO_2光催化固定化及染料化合物光催化降解的研究．中国科学院博士论文，2001
5．何锋．UV-Fenton处理难降解废水的研究．浙江大学硕士论文．2002
6．雷乐成，汪大晕．水处理高级氧化技术．北京：化学工业出版社，2001
7．李薇．电光源条件下光催化降解染料化合物的研究．中国科学院博士论文，2003
8．钱易，汤鸿霄，文湘华．水体颗粒物和难降解有机物的特性与控制技术原理(下)．北京：中国环境科学出版社，2000
9．三井纪一郎等．触媒湿式酸化排水处理法．触媒．1991，35(5)：351
10．谢银德，陈锋等．photo-Fenton反应研究进展．感光科学与光化学．2000，18(4)
11．岳林海．稀土元素掺杂二氧化钛催化剂光降解久效磷的研究．上海环境科学，1998，17(9)：17-19
12．周连江，乐志强．无机盐工业手册(下)．北京：化学工业工出版社，1996
13．张彭义，祝万鹏．臭氧水处理技术的进展．环境科学进展．1994，2(3)：50
14．张昱．新型阴离子吸附材料及吸附机理研究．中国科学院博士论文，2003
15．张昱，杨敏等，利用新型稀土铈复合吸附剂去除水体腐殖质的研究．环境科学，2004，25(1)：83—86
16．祝万鹏，杨志华，王利．亚铁-过氧化氢法处理染料中间体H酸生产废液的研究．中国环境科学．1995，15(5)：368-372
17. Beltran F J, Garaia-Araya J F, acedo B. Advanced oxidation of atrazine in water-Ⅱ. ozonation combined with'ultraviolet radiation. Wat Res. 1994, 28(10): 2156
18. Bishop D F. Hydrogen peroxide catalytic oxidation of refractory organics in municipal wastewaters. Industryial and Engineering Chemistry. Process design and development. 1968, 7:110-117
19. Bossmarm S H, Oliveros E, Gob S. New evidence against hydroxyl radicals as reactive intermediates in the thermal and photochemically enhanced Fenton reaction.
J. Phys. Chem. 1998, 102(28):5542-5520
20. Centi G, Perathoner S, Catalytic wet oxidation with H202 of carboxylic acids on homogeneous and heterogeneous Fenton-type catalysts, Catalysis Today, 2000, 55:61-69
21. Chen G H, Lei L C. Treatment of desizing waste water containing poly-vinyl alcohol by wet air oxidation. Industrial Engineering Chemistry Research, 2000, 39
22. Chumg King-Thorn. Degradation of azo dyes by environmental microorganisms and belminthes. Environ Toxical Chem. 1993, 13(11):2121-2132
23. Dimirkou A, Ioannou A, Doula M. Preparation characterization and sorption properties for phosphates of hematite benonite and bentonite-hematite systems. Advanced in Colloid and Interf Sci, 2002(97):31—61
24. Eckenfelder, W. Wesley. Chemical oxidation: technologies for the nineties: proceedings of the first international symposium, chemical oxidation: technology for the nineties. Lancaster, Pa: Technomie Pub Co., 1997
25. Eisenberg G M. Colorimetric determiation of hydrogen peroxide. Ind Eng Chem, 1943, 15(5): 327-328
26. Fajerwerg K, Debellefontaine H, Wet oxidation of phenol by hydrogen peroxide using heterogeneous Catalysis Fe-ZSM-5: a promising catalyst. Applied Calysis B :Envionmental, 1996, 10:229-235
27. Fang X W, Pan X M. Reversibility in the reaction of cyclohexadienyl radicals with oxygen in aqueous solution. Eur J Chem, 1995, 1:423
28. Fenton H G H. On a new reaction of tartaric acid (letter to the editor). Chemical News. 1876, 33:190
29. Fenton H G H and H O Jones. The oxidation of organic acids in the presence of iron. C J Chem Soc. 1900, 77:69-76
30. Fernandez J, Bandara J, Lopez A, Buffar Ph, Kiwi J, Photoassisted Fenton degradation of nonbiodegradable azo dye (Orange Ⅱ) in Fe-free solutions mediated by cation transfer membranes. Langmuir1999, 15(1): 185—92.
31. Gallard H, De Laat J and Legube B. Influence du pH sur la vitesse d'oxydation de composes organieques par FeⅡ/H_2O_2. Mecanismes reactionnels et modelisation. New J Chem. 1998, 263-268
32. Glaze W H, Kang J W, Chapin D H. The chemistry of water and wastewater treatment processes involving ozone, hydrogen peroxide and ultraviolet radiation. Ozine Sei Eng,
1987, 9:335-352
33. Glaze W H, Kang J W, Chapin D H. The chemistry of water and wastewater treatment processes involving ozone, hydrogen peroxide and ultraviolet radiation. Ozine Sci Eng, 1987, 9:335-352
34. Glaze W H, Peyton G R, Lin S, et al. Destruction of pollutants in water with ozone in combination with ultraviolet radiation. 2, natural trihalomethane precursors. Environ Sci Technol. 1982, 16:454
35. Haber F, Weiss J. The catalytic decomposition of hydrogen peroxide by iron salt. Proc R Soc, series A. 1934, 147:332
36. Hoigne J, Bader H. The role of hydroxyl radical reaction in ozonation processes in aqueous solutions. Water Res, 1976, 10, 377～383
37. Hunter T V. The effect of dyes on aerobic systems. In Dyes and Environment, 1973, 1(6)
38. Hu X, Lam FLY, et al., Copper/MCM-41 as catalyst for photochemically enhanced oxidation of phenol by hydrogen peroxide. Catalysis Today, 2001, 68: 29—133.
39. Jiyun Feng, Xijun Hu, et al., Discoloration and mineralization of Reactive Red HE-3B by heterogeneous photo-Fenton reaction. Water Research, 2003, 37: 3776—3784
40. Jiyun Feng, Xijun Hu, et al., Anovel laponite clay-based Fe nanocomposite and its photo-catalytic activity in photo-assisted degradation of Orange Ⅱ. Chemical Engineering Science, 2003, 58:679—685
41. Joseph J, Plgnatello, Dark and Photoassisted Fe3+-Catalyzed Degradation of Chlorophenoxy Herbicides by Hydrogen Peroxide. Environ. Sci. Technol. 1992, 26(5): 944—951
42. Kremer M L, Stein G. The catalytic decomposition of hydrogen peroxise by ferric perchlorate. Trans Faraday Soc. 1959, 55:959-973
43. Legrini O, Olibveros E, Braun A M. Photochemical process for water treatment. Chemical Reviews. 1993, 93(2): 14-31
44. Nomura J, Imai H, Miyake T. R Removal of fluoride ion from wastewater by a hydrous ceriym oxide adsorbent. Am. Chem. Soc. Syrup. Ser, 1990:422
45. Perkins, Michael John. Radical chemistry. New York: Ellis Horwood, 1994
46. R. Bauer, G. Waldner, et al., The photo-fenton reaction and the TiO_2/UV process for waste water treatment - novel developments. Catalysis Today 1999, 53(1): 131—144
47. Sabhi S, Kiwi J, Degradation of 2, 4-dichlorophenol by immobilized iron catalysts, Wat.
Res, 2001, 35:1994-2001
48. Sunstrorm D W, Klei H E, Nalette T A, et al. Hazard Waste Hazard Mater. 1986, 3:101
49. Shyh-Fang Kang, Chih-Hsiang Liao, Hung-Pin Hung, Peroxidation treatment of dye manufacturing wastewater in the presence of ultraviolet light and ferrous ions. Journal of Hazardous Materials, 1999, B65:317—333
50. Tanner, Dennis D. Advances in free radical chemistry: a research annual. Greenwich: JAI Pr Inc, 1990.
51. Weir B A, Sunstrorm D W, Klei H E. Destruction of halogenerated aliphatics by ultraviolet catalyzed oxidation with hydrogen peroxide. Hazard Waste Hazard Mater. 1987, 4:165
52. Wolfgang Gernjak, Thomas Krutzler, et al., Photo-Fenton treatment of water containing natural phenolic pollutants. Chemosphere 2003, 50:71—78
53. Yenkie MKN, Natarajan GS. Adsorption equilibrium studies of some aqueous aromatic pollutants on granulm activated carbon samples. Separ Sci and Tech. 1991 26(5):661—674
54. Yu Zhang, Min Yang, Xia Huang, Arsenic(Ⅴ) removal with a Ce(Ⅳ)-doped iron oxide adsorbent. Chemosphere, 2003, 51: 945—952
55. Zeep, R. G. Hydroxyl radical formation in aqueous reactions of iron(Ⅱ) with hydrogen peroxide: the photo-Fenton reaction. Environ. Sci. Technol. 1992, 26, 313-319