TiO_2膜光催化降解水中有机污染物的研究
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摘要
作为新的环境净化材料，TiO_2光催化剂可广泛用于废水处理、空气净化、杀菌、除臭、表面自清洁等方面。为了更快地将这种处理技术用于大规模生产当中，本文以焦化废水中的邻甲酚作为目标污染物，试图从催化剂薄膜的制备、反应器的设计、反应条件的影响等各方面来深入研究TiO_2膜催化剂的催化降解作用以便促进提高其实际应用中的经济技术可行性。
溶胶-凝胶法在紫外灯管表面制备TiO_2薄膜催化剂稳定性较高，可重复利用，经过30批次的反应后，催化降解效率仍在85％以上。不仅克服了悬浮相光催化剂的缺点，而且便于改进和放大后应用于工业废水处理。采用P25溶胶来制备TiO_2薄膜催化剂具有经济与技术的双重可行性。
设计了一种新型光催化反应器。对新型光催化反应器模型进行严格控制污染物邻甲酚的光催化降解，效果良好，为酚类废水的处理提供了一种工艺简单、成本低、不会造成二次污染的方法。
选用紫外灯管为载体的UR光催化反应器对紫外光的利用率提高了，对邻甲酚的光催化降解效率很高，反应的过程符合一级动力学规律，研究了反应速率与邻甲酚的初始浓度、光强度和反应温度等反应条件的关系。利用该反应器对具有芳醚结构的农药克百威和残杀威进行光催化降解，表现了良好的降解效率，60min内可降解80％以上。
考察了介质水中常见金属离子Fe~(2+)、Fe~(3+)、Cu~(2+)、Mn~(2+)及酸碱度pH值对紫外灯管负载TiO_2膜催化剂性能的影响。结果表明，适量的Fe~(2+)对反应有促进作用，Fe~(3+)、Cu~(2+)对反应影响很小，Mn~(2+)对反应有抑制作用。溶液的pH值在5.5左右降解效率最高，偏低或偏高的pH值对光催化降解均产生不利的影响。
As a new environmental matrial, TiO2 photocatalyst has the attractive applications to waste water treating, air purifying, bactericide,deodorization and surface, self-cleaning. In order to increase the practical application of this waster water treating technology, in this text, we tried to improvement the feasible on economy and technology from preparation of photocatalysists, design of reactor and the influence of different reaction conditions etc.
A P25 TiO2 film supported on UV light surface was prepared using sol-gel method at 200℃ calcinations temperature, and the photocatalyst has shown a good stability and performance for the photodegradation of orthocresol solution irradiated with UV light of 254nm, when reaction for 30min, the photodegradation still more then 85%. which not only avoid the filtration and resuspension of the photocatalysts, also has advantage for the design of photocatalytic reactor. the efficiencies of photocatalytic degradation of orthocresol increased than the reactor with glass tube as support.
A novel high-efficiencies photocatalytic reactor with the P25 TiO2 film supported on UV light surface was designed. This reactor has shown a good performance with the photodegradation of orthocresol solution. It offered us a method to degradation of aromaticity , this method technics is simple, cost is low and can be avoid the repollution.
The novel photocatalytic reactor with the P25 TiO2 film
supported on UV light surface(UR) have increased the utilance because Light energy transmitted to TiO2 particals without any refraction on the UV light tube. The kinetic study led to one -order reactions,and the efficicency was influenced by prel--iminary concentration, intensity of light and the temperature of reaction as so on. This reactor has shown a good performance with the photodegradation of aether configuration pesticide such as carbofuran and propoxur,the photodegradation rate of 60min achieved 80%.
The influence of common cations (Fe2+, Fe3+, Cu2+, Mn2+) and the pH in water was studied. It is shown that add Fe2+ aptly can accelerate the reaction, Fe3+, Cu2+ have little influence to reaction, but Mn2+ can restrain the rate of reaction. The aptitude pH of solution is 5. 5, on the low side or on the high side will restrain the photocatalystic reaction.
溶胶-凝胶法在紫外灯管表面制备TiO_2薄膜催化剂稳定性较高，可重复利用，经过30批次的反应后，催化降解效率仍在85％以上。不仅克服了悬浮相光催化剂的缺点，而且便于改进和放大后应用于工业废水处理。采用P25溶胶来制备TiO_2薄膜催化剂具有经济与技术的双重可行性。
设计了一种新型光催化反应器。对新型光催化反应器模型进行严格控制污染物邻甲酚的光催化降解，效果良好，为酚类废水的处理提供了一种工艺简单、成本低、不会造成二次污染的方法。
选用紫外灯管为载体的UR光催化反应器对紫外光的利用率提高了，对邻甲酚的光催化降解效率很高，反应的过程符合一级动力学规律，研究了反应速率与邻甲酚的初始浓度、光强度和反应温度等反应条件的关系。利用该反应器对具有芳醚结构的农药克百威和残杀威进行光催化降解，表现了良好的降解效率，60min内可降解80％以上。
考察了介质水中常见金属离子Fe~(2+)、Fe~(3+)、Cu~(2+)、Mn~(2+)及酸碱度pH值对紫外灯管负载TiO_2膜催化剂性能的影响。结果表明，适量的Fe~(2+)对反应有促进作用，Fe~(3+)、Cu~(2+)对反应影响很小，Mn~(2+)对反应有抑制作用。溶液的pH值在5.5左右降解效率最高，偏低或偏高的pH值对光催化降解均产生不利的影响。
As a new environmental matrial, TiO2 photocatalyst has the attractive applications to waste water treating, air purifying, bactericide,deodorization and surface, self-cleaning. In order to increase the practical application of this waster water treating technology, in this text, we tried to improvement the feasible on economy and technology from preparation of photocatalysists, design of reactor and the influence of different reaction conditions etc.
A P25 TiO2 film supported on UV light surface was prepared using sol-gel method at 200℃ calcinations temperature, and the photocatalyst has shown a good stability and performance for the photodegradation of orthocresol solution irradiated with UV light of 254nm, when reaction for 30min, the photodegradation still more then 85%. which not only avoid the filtration and resuspension of the photocatalysts, also has advantage for the design of photocatalytic reactor. the efficiencies of photocatalytic degradation of orthocresol increased than the reactor with glass tube as support.
A novel high-efficiencies photocatalytic reactor with the P25 TiO2 film supported on UV light surface was designed. This reactor has shown a good performance with the photodegradation of orthocresol solution. It offered us a method to degradation of aromaticity , this method technics is simple, cost is low and can be avoid the repollution.
The novel photocatalytic reactor with the P25 TiO2 film
supported on UV light surface(UR) have increased the utilance because Light energy transmitted to TiO2 particals without any refraction on the UV light tube. The kinetic study led to one -order reactions,and the efficicency was influenced by prel--iminary concentration, intensity of light and the temperature of reaction as so on. This reactor has shown a good performance with the photodegradation of aether configuration pesticide such as carbofuran and propoxur,the photodegradation rate of 60min achieved 80%.
The influence of common cations (Fe2+, Fe3+, Cu2+, Mn2+) and the pH in water was studied. It is shown that add Fe2+ aptly can accelerate the reaction, Fe3+, Cu2+ have little influence to reaction, but Mn2+ can restrain the rate of reaction. The aptitude pH of solution is 5. 5, on the low side or on the high side will restrain the photocatalystic reaction.
引文
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[4] 刘敬肖等．离子束合成TiO_2薄膜对医用NiTi合金表面的改性[J]．材料研究学报，2001，15(4)：445
[5] 曹亚安等．Sn~(4+)掺杂对TiO_2纳米颗粒膜光催化降解苯酚活性的影响[J]．高等学校化学学报，2001，22(11)：1910
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[7] D. Matthews, et al. Electrophoretically deposited titanium dioxide thin films for photovoltaic cells[J]. Aust. J. Chem., 1994,47:1869
[8] C. Kavan, et al. Preparation of TiO_2(anatase) films on electrodes by anodic oxidative hydrolysis of TiCl_3[J].Electroanal. Chem., 1993,346:291
[9] C. Natarajan and G. Nogami, Cathodic electrodeposition of nanocrystalline titanium dioxide thin films[J]. Soc. Electrochem., 1995,143(5):1547
[10] 黄怀国等．TiO_2-聚苯胺复合膜的光电化学[J]．电化学，2001，7(1)：102
[11] M. Shirkhanzadeh. Fabrication and characterization of alkoxy-derived nanophase TiO2 coatings[J]. Mater. Med., 1995, 6:206
[12] Harada Keoji, Hisanaga Teruaki, et al. Photodegradation of dye pollution on TiO_2nanoparticales [J]. Water Res, 1990,24(11):
1415-1417
[13] Li Z X, Zhang M. Decolorization and biodegradability of dyeing wastewater treated by a TiO_2-sensitezed photo-oxidation process[J]. War. Sci. Tech., 1996, 34(9):49-55
[14] Thornton M H et al. Investigation of TiO_2-based photocatalysts for inactivation of E. Coli in water[J]. (In):Hazardous and Industrial Waters-Proceeding of the Mid-Atlantic Industrial Waste Conference, 1997, Jul.,13-16
[15] Navio A J et al. Photoconductive and photocatalytic properties of ZrTiO_4. Comparison with the parent oxides TiO_2 and ZrO_2[J]. Photochem. Photobiol. A: Chem, 1997,108:179-185
[16] Lea J et al. The photo-oxidative degradation of sodium dodecyl sulphate in aerated aqueous TiO_2 suspension[J]. Photochem. Photobiol. A: Chem., 1998,118:111-122
[17] Ohno T et al. Relay of positive holes from photoirradiated Pt-loaded TiO_2 particles in an aqueous phase to t-butylhydroquinone in an oil phase[J]. Photochem. Photobiol. A: Chem., 1998,117:143-147
[18] Sczechowski G J et al. A taylor vortex reactor for heterogeneous photocatalysis[J]. Noble Chemical Engineering Science, 1995, 50(20):3136-3173
[19] Ray K A et al. Novel swirl-flow reactor for kinetic studies of semiconductor phtocatalysis[J]. Environmental and Energy Engineering, 1997, 43(10):2571-2578
[20] Goslich R et al. Solar water treatment: principles and reactor[J]. Water Science and Technology, 1997, 35(4):137-148
[21] Puma L G et al. Comparison of the effectiveness of photonbased oxidation processes in a pilot falling film photoreactor[J]. Enciron.
Sci. Technol., 1999, 33: 3210-3216
[22] Chester G et al. A jacketed annular membrane photocatalytic reactor for wastewater treatment: degradation of formic acid and atrazine[J]. Photochem. Photobiol. A: Chem., 1993, 71:291-297
[23] Angelidis T M N et al. Kinetic study of the photocatalytic recovery of Pt from aqueous solution by TiO_2, in a closed loop reactor[J]. Applied Catalysis B: Environmental, 1998,16:347-357
[24] Kobayakawa K et al. Continuous-flow photoreactor packed with titanium dioxide immobilized on large silica gel beads to decompose oxalic acid in excess water[J].Photochem. Photobiol. A: Chem., 1998,118:65-69
[25] Burns A R et al. Effect of inorganic ions in heterogeneous photocatalysis of TCE [J]. Environmental Engineering, 1999, Jan., 77-85
[26] Vidal A et al. Mogyorodi. Photocatalytic degradation of thiocarbamate herbicide active ingredients in water[J]. Applied Catalysis B: Environmental, 1999,21:259-267
[27] Crittenden C J et al. Solar detoxification of fuel-contaminated groundwater using fixed-bed photocatalysts[J]. Water Environment Research, 1996, 68(3):270-278
[28] Zhang Y et al. Fixed-bed photocatalysts for solar decontamination of water[J]. Environ. Sci. Technol., 1994,28(3): 435-442
[29] Herrmann J-M et al. TiO_2-based solar photocatalytic detoxification of water containing organic pollutants. Case studies of 2,4-dichlorophenoxyaceticacid(2,4-D) and of benzofuran[J]. Applied Catalysis B: Environmental, 1998, 17:15-23
[30] Wyness P et al. Performance of nonconcentrating solar photocatalytic
oxidation reactors, Part Ⅰ: Flat-plate configuration[J].Solar Energy Engineering, 1994, 116:2-7
[31] Sunada K et al. Bactericidal and detoxification effects of TiO_2 thin film photocatalysts[J]. Environ. Sci. Technol., 1998, 32(5): 726-728
[32] Matthews W R.. Photooxidative degradation of coloured organics in water using supported catalystsTiO_2 on sand[J]. Water Res., 1991, 25(10): 1169-1176
[33] Matthews W R et al. Destruction of phenol in water with sun, sand, and photocatalysis[J]. Solar Energy, 1992,49(6):507-513
[34] Wyness Pet al. Performance of nonconcentrating solar photocatalytic oxidation reactors, Part Ⅱ: shallow pond configuration[J]. Solar Energy Engineering, 1994,116:8-13
[35] Peill J Net al. Iron(Ⅲ)-doped Q-sized TiO_2 coatings in a fiber-optic cable photochemical reactor[J]. Photochem. Photobiol. A: Chem., 1997,108:221-228
[36] Ray K A et al. Novel photocatalytic reactor for water purification[J]. Environmental and Enery Engineering, 1998,44(2):477-483
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