负载TiO_2催化剂光催化降解萘系化合物的研究
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摘要
本文以粒状活性炭为载体,冰醋酸(HAc)为修饰剂,用溶胶-凝胶法制备负载TiO_2催化剂,以亚甲蓝为研究对象,确定溶胶-凝胶法制备负载TiO_2催化剂的最佳工艺条件:钛酸丁酯:乙醇:水:冰醋酸=1:4:0.13:0.1(体积比)。
     用XRD、FT-IR、比表面积、亚甲蓝吸附值、催化剂表面的二氧化钛负载量、使用寿命等对催化剂及载体的性能进行了表征,以亚甲蓝水溶液为对象,研究了负载TiO_2催化剂的催化性能。
     探讨在负载工艺中加入冰醋酸和聚乙二醇(PEG)为修饰剂制备负载催化剂,并用XRD、FT-IR、比表面积、亚甲蓝吸附值、催化剂表面的二氧化钛负载量对其进行表征,结果表明由此制得的催化剂有较好的分散度,亚甲蓝吸附值、二氧化钛负载量和光催化活性。
     采用自制负载TiO_2催化剂,研究了在250W高压汞灯照射下,几种萘系化合物废水的光催化降解行为,试验了光催化降解条件和控制因素,研究结果表明:
     (1) 萘系化合物水溶液的初始浓度对其降解率有影响,随着初始浓度的增加,光催化降解率下降明显,扣除吸附后,In(C_0/C_t)~t基本符合线性关系即光催化降解反应是一级动力学反应。
     (2) 萘系化合物水溶液光催化降解时,pH值对降解率的影响与萘系化合物的种类有关。
     (3) 在起始溶液中加入双氧水可明显提高降解效果。
TiO2 catalyst was desposited on granular activated carbon modified with acetic acid by sol-gel method. The optimum process condition of the preparation of the catalyst was determined with methylene blue as experimental object. The ratio of volume was 1 : 4 : 0.13 : 0.1 (butyl titanate, ethanol,liquid and acetic acid).
    TiO2 catalyst supported on granular activated carbon was characterized by XRD, SEM,FT-IR,BET,adsorption value of methylene blue,quanity of titania and photocatalytic activity on methylene blue.
    The preparation of TiO2 catalyst modified with acetic acid and poly ethylene glycol was discussed in this paper, characterized by XRD, SEM, FT-IR, BET, adsorption value of methylene blue,quanity of titania.The results show that pore-size distribution, adsorption value of methylene blue,quanity of titania and photocatalytic activity were higher than of modification by acetic acid.
    Photocatalytic degradation of naphthalene compounds in water were studied by TiO2 catalyst supported on granular activated carbon under irradiation of 250W mercury lamp of high pressure. The condition of photocatalytic degradation and manipulative factors were studied in this paper.
    The results of photocatalytic degradation of naphthalene compound were as follows:
    (1)The degradation ratio of naphthalene compounds was greatly affected by initial concentration. While initial concentration increased, the degradation ratio decreased in evidence. The reaction of photocatalytic degradation accorded with one-step dynamics kinetics deducting adsorption.
    (2)pH value of solution influenced differently on the degradation ratio for the species of naphthalene compound.
    (3)When hydrogen peroxide existed in initial solution, the degradation efficiency can improve in evidence.
引文
[1] 姜义华,胡岗,潘毅等.多孔二氧化钛对三氯甲烷光催化氧化的影响[J],催化学报,1999,20 (3):381~383
    [2] 胡岗,姜义华.载TiO_2膜多孔催化剂光催化氧化三氯甲烷的研究[J],太阳能学报,2000,21 (1):114~116
    [3] 陈士夫,赵梦月,陶跃武等.玻璃纤维附载TiO_2光催化降解有机磷农药[J],环境科学,1996,17 (4):33~35
    [4] 陈士夫,梁新,陶跃武等.空心玻璃微球附载TiO_2光催化降解有机磷农药[J],感光科学和光化学,1999,17 (1):85~91
    [5] Ho Te-Fu L.; Bolton James R. Toxicity changes during the UV treatment of pentachlorophenol in dilute aqueous solution[J]. Water Research, 1998, 32(2):489~497
    [6] Linder M. Solar water detoxification: novel TiO_2 powder as highly active photocatalysts[J]. J Solar Energy Engineering, 1997,119:120~125
    [7] Birringer R, Gleiter H, Klein H P et al. Nanocystalline materials-an approach to a novel solid structure with gas-like disorder[J].Physics Letters A,1984, 102A (8):365~369
    [8] 罗裕基.超微细合成技术[J],广东化工,1997,(3):4~7
    [9] 杨修春,韩高荣,杜丕一等.化学气相反应法合成SiC超细粉的成核和生长过程的研究[J],硅酸盐学报1997,25 (3):332~338
    [10] 董利国,高荫本,陈诵英.纳米TiO_2粉体的制备研究[J],无机化学学报,1998,14 (3):327~332
    [11] 黄艳娥,刘冬莲.纳米TiO_2在水处理中的应用[J],河北化工,2000,(2):8~11
    
    
    [12] Ollis D F, Plizzetti E, Serpone N. Destruction of water contaminants[J]. Envrion.sci. & Technol., 1991,25(9) 1523~1529
    [13] Haarstrick A,Kut O M,Heinzle E. TiO_2—assisted degradation of environmentally relevant organic compounds in wastewater using a novel fluidized bed photoreactor[J]. Environ.Sci.& Technol, 1996,30:817~824
    [14] 蔡乃才,王亚平,曹锡良.负载型Pt-TiO_2光催化剂的研究[J],催化学报,1999,20(2):177~180
    [15] Sopyan I, Murasawa S, Hashimoto K et al. Highly efficient TiO_2 film photocatalyst degradation of gaseous acetaldehyde [J]. Chem. lett., 1994,723~726
    [16] Kikuchi Y, Sunada K, Iyoda T et al. Photocatalytic bactericidal effect of TiO_2 thin films: dynamic view of the active oxygen species responsible for the effect[J]. J.Photochem. & Photobiol. A: chem., 1997,106:51~56
    [17] 曹亚安,陈咏梅,管自生等.纳米TiO_2粒子膜的表面性质及其光催化活性研究[J],感光科学和光化学[J],1999,17(2):100~103
    [18] 符小荣,宋世庚,王学燕等.纳米TiO_2/Si薄膜的制备与光催化性能的研究[J],感光科学和光化学,1999,15(3):234~240
    [19] 符小荣,张校刚,宋世庚等.TiO_2/Pt/glass纳米薄膜的制备及对可溶性染料的光电催化降解[J],应用化学,1997,14(4):77~79
    [20] Kumara G R R A, Sultanbawa F M, Continuous flow photochemical reactor for solardecontamination of water using immobilized TiO_2[J]. Solar Energy Materials & Solar Cells, 1999(58): 167~171
    [21] 魏宏斌,严煦世.二氧化钛膜光催化氧化苯酚[J],上海环境科学,1995,14 (10):31~34
    [22] 方佑龄,赵文宽,张国华等.用浸涂法制备漂浮负载型TiO_2薄膜光催化降解辛烷[J],环境化学,1997,16(5):413~417
    [23] Rosenberg I, Brock J R, Heller A. Collection optics of TiO_2 photocatalyst on hollow glass microbeads floating on oil slicks[J]. J. Phys. Chem., 1992,96:3423~3428
    [24] 陈士夫,梁新,赵梦月.不同制备条件对TiO_2/beads光催化活性的影响[J],感光科学和光化学,1999,17 (1):25~31
    [25] 席北斗,刘纯新,孔欣等.负载催化剂光催化氧化五氯苯酚钠的效果[J],环境科学,2001,22 (1):41~44
    
    
    [26] Dionysios D, et al. Continuous-mode photocatalytic degradation of chlorinated phenols and pesticides in water using a bench-scale TiO_2 rotating disk reactor[J]. Applied Catalysis,2000,B(24): 139~155
    [27] 刘鸿,成少安,张鉴清等.泡沫镍载二氧化钛光催化降解磺基水杨酸[J],中国科学环境,1998,6:548~551
    [28] Fernandz A, Lassaletta G; Jimenez V M et al. Preparation and characterization of TiO_2 photocatalysta supported on various rigid supports(glass,quartz, and strainless steel). Comparative studies of photocatalytic activity in water purification[J]. Appl. Catal. B: Environ., 1995,7:49~63
    [29] Zhang Y, Crittenden J C, H, D W et al. Fixed-bed photocatalysts for solar decontamination of water[J]. Environ. Sci. Technol., 1994, 28: 435~442
    [30] 王怡中,胡春.有机物多相光催化降解反应中催化剂固定技术研究[J],环境科学,1998,19 (4):40~44
    [31] Matsumoto A, Tsutsumi K, Kaneko K. Titania coating of a microporous carbon surface by Mmolecular adsorption-deposition[J]. Langmuir, 1992,8:2515~2520
    [32] Uchida H, Itoh S, Yoneyama H. Photocatalytic decomposition of propyzamide using TiO_2 supported on activated carbon[J]. Chem. Lett. 1993,1995~1998
    [33] John C. Decontamination of water using adsorption of photocatalysis[J]. J Water Res, 1997,31(1):411~418
    [34] Sauer M L, Ollis D F. Acetone oxidation in a photocatalytic monolith reactor[J]. J. Catal., 1994,149:L81~99
    [35] 方佑龄,赵文宽,尹少华等.纳米TiO_2载空心陶瓷微球上的固定及光催化降解辛烷[J],应用化学,1997,14 (2):81~83
    [36] Yoneyama H, Haga S, Yamanaka S. Photocatalytic activities of microcrystalline TiO_2 incorporated in sheet silicates of clay[J]. J. Phys. Chem. 1989,93:4833~4837
    [37] Uchida H, Hirao S, Torimoto T et al. Preparation and properties of size-quantized TiO_2 particles immobilized in polyvinylpyrrolidinone gel films[J]. Langmuir, 1995,11:3725~3729
    [38] 赵文宽,覃榆森,方佑龄等.水面石油污染物的光催化降解漂浮负载型TiO_2光催化剂的制备[J],催化学报,1999,20 (3):368~372
    [39] Horikoshi S, Serprone N, Hisamatsu Y et al. Photocatalyzed Degradation of Polymers in Aqueous Semiconductor Suspensions.3. Photooxidation of a Solid Polymer:TiO_2-Blended
    
    Poly(vinyl chloride) Film[J]. Environ Sci. & Technol., 1998,32:4010~4016
    [40] 张彭义,余刚,蒋展鹏.光活性二氧化钛膜的制备与应用[J],环境科学进展,1998,6(5):50~56
    [41] 许宜铭,陈文星,朱志杰.苯酚及氯代苯酚化合物TiO_2催化光致降解[J],环境科学,1990,9(6):13~19
    [42] 陈士夫,赵梦月,陶跃武.太阳光TiO_2薄层光催化降解有机磷农药的研究[J],太阳能学报,1995,16(3):234~239
    [43] 郑巍,刘维屏,宣日成等.附载TiO_2光催化降解咪蚜胺农药[J],环境科学,1999,20(1):73~76
    [44] Sopyan I,Watanable M, Murasawa S et al. A Film-Type Photocatalyst incorporating highly active TiO_2 powder and fluororesin binder: Photocataytic activity and long-term stab ility [J]. Electr oanal. Chem., 1996,415:183~186
    [45] Berry R J, Mueller M R. Photocatalytic Decomposition of Crude Oil Slicks Using TiO_2 on a Floating Subtrate. Microchem.J.,1994,50:28~32
    [46] 王春云编译.TiO_2光催化剂大气净化涂料的开发,化工新型材料,1998,8:29~30
    [47]徐明霞,徐延献,刘宁.由TiOSO_4水解沉淀制备TiO_2薄膜[J],硅酸盐学报,1997,2:209~213
    [48] 章思规主编.《精细有机化学品技术手册》,科学出版社,北京,1992
    [49] 冯文国,张全兴,陈金龙.萘系染料中间体生产废水的治理方法[J],化工环保,1999,19 (4):208~212
    [50] Borraccino,R.;Pauss A.;Lebeaut. The priority toxicant reference range study: Interion report[J]. Meded-Fac Landbounkd Toegepaste Bio Wet, 1993, 58(4A), 1783~1785
    [51] Kameeya Takashi; Murayama, Takashi; Vrno Kohei. Biodegradation ranks of priority organic compounds under anaerobic conditions A biotic degradation of catechol, 1-naphthol, trichloro phenol and o-nitrophenol [J].Sci Total Environ.,1995,17(1,2),43~51
    [52] 经再英.2-萘酚生产废水的处理[J],化工环保,1991,11(3):157~161
    [53] 李明,朱伟,匡墨南.甲萘酚生产废水处理[J],化工环保,1988,8(6):336~340
    [54] 彭书传,魏风玉,周源祥.2-萘磺酸钠生产废水的处理[J],中国环境科学,1998,18 (5):455~457
    [55] 陈其昌.γ酸和T酸废水综合治理初探[J],江苏化工,1992,(3):44~46
    [56] 许昭怡,张慧春,王勇.大孔树脂吸附法处理萘系中间体生产废水的进展[J],化工环保,
    
    1999,19(1):20~24
    [57] 刘天华.树脂吸附法处理周位酸废水的研究[J],离子交换与吸附,1993,9(5):423~428
    [58] 张全兴,刘天华.我国应用树脂吸附法处理有机废水进展[J],化工环保,1994,14 (6):344~347
    [59] 张全兴,刘天华.我国应用树脂吸附法处理有机废水进展(续)[J],化工环保,1995,15 (1):17~20
    [60] 陶大钧,张玮.大孔树脂吸附处理酚类胺类和再生[J],化工环保,1990,10(5):267~271
    [61] 王勇,张全兴,陈金龙.树脂吸附法处理2-萘酚工业废水的研究[J],离子交换与吸附,1997,13 (6):573~578
    [62] 张乃东.HV/Fe(C_2O_4)_3~(3-)/H_2O_2法处理苯胺类废水的研究[D],哈尔滨:哈尔滨工业大学,1999
    [63] 云桂春,E.吉尔伯特,S.H.艾伯特.用H_2O_2/Fe~(2+)处理含蒽醌-2-磺酸(ASA)染料废水的实验研究[J],水处理技术,1987,13(4):193~199
    [64] Zhu WanPeng, Yang Lihua, Wang Li. Application of ferrous-hydrogen peroxide for the treatment of H-acid manufacturing process wastewater[J]. Wat. Res, 1996,30(12):2949~2954.
    [65] 祝万鹏,杨志华,王利.Fe~(2+)-H_2O氧化法处理染料中间体H酸生产废液的研究[J],中国环境科学,1995,15(5):368~372
    [66] 蒋展鹏,祝万鹏,杨志华等.化学氧化法处理资源回收的丁酸和吐氏酸染料中间体废液[J],环境科学,1997,18(4):35~37
    [67] 彭书传,魏玉风,崔康平.H_2O_2-Fe~(2+)法处理β-磺酸钠生产废水的研究[J],工业水处理,1998,18(1):23~25
    [68] 陶显宏,胡顺兴.高浓度薛佛氏酸生产废水的资源化处理工艺研究[J],环境科学与技术,2001(1):33~35
    [69] 肖羽堂,陈拥军,张晶晶等.Fenton试剂预处理H酸废水的影响因素及其可生化性[J],环境科学,2001,20(3):281~285
    [70] Gilbert E. Biodegradability of ozonation products as a funtion of COD and DOC elimination by example of substituted aromatic substances[J]. Wat Res, 1987,21(10): 1273~1278
    [71] 赵锡武,阎金宏.絮凝沉淀——臭氧氧化法处理有机废水[J],天津化工,2000,5:39~40
    [72] 朱世云,张全兴,王连生等.萘系化合物臭氧化对其COD、DOC及其可生化性影响研究[J],环境科学进展,1999,7(4):48~53
    
    
    [73] 朱世云,张全兴,陈金龙等.臭氧氧化降解水溶液中1-萘酚的动力学研究[J],环境化学,1999,18(3):227~231
    [74] 朱世云.有机染料废水处理研究进展[J],上海环境科学,2000,19(8):396~398.
    [75] 杨志华,祝万鹏,王利.H_2O_2-O_3氧化法处理染料中间体H酸和1-氨基蒽醌生产废液的研究[J],环境科学,1994,15(6):4~7
    [76] 王永仪,杨志华,蒋展鹏等.H-酸废母液的湿式空气氧化处理[J],环境科学,1996.17(1):31~33
    [77] 宾月景,祝万鹏,蒋展鹏.H-酸的催化湿式氧化反应过程研究[J],环境污染与防治,2000,22(3):4~7
    [78] 宾月景,祝万鹏,蒋展鹏等.催化湿式氧化剂及处理技术研究[J],环境科学,1999,20(2):42~44
    [79] 孙晓君,冯玉杰,蔡伟民.废水中难降解有机物的高级氧化技术[J],化工环保,2001,21(5):264~269
    [80] 宾月景,祝万鹏,蒋展鹏等.催化湿式氧化处理H酸溶液的反应动力学[J],环境科学,2000,21(3):77~80
    [81] 赵国方,赵宏斌.有机废液湿式氧化处理的现状与进展[J],江苏化工,2000,28(5):23~25
    [82] Helmut S, Johannes A. Supercritical water oxidation: state of the art[J]. Chem Eng Technol,1999,22(11):903~908
    [83] Sealock L J, Elliott D C, Baker E G, et al. Chemical processing in high-pressure aqueous environments.1.Historical perspective and continuing developments[J]. Ind Eng Chem Res, 1993,32(8): 1535~1541
    [84] 丁军委,陈峰秋,吴素芳等.超临界水氧化法处理含酚废水[J],环境污染与防治,2000,22(1):1~3
    [85] 王涛,沈忠耀,杨基础等.环境新技术——超临界水氧化法[J],环境保护,1995,(3):6~7
    [86] 林春锦,周红艺,潘志彦等.超临界水氧化法降解苯酚的研究[J],环境科学研究,2000,13(2):12~13
    [87] Yu JingLi. Savage Phillip E. Kinetics of catalytic supercritical water oxidation of phenol over TiO_2[J].Environ Sci Techonol,2000,34(15):3191~3198
    [88] 林春绵,章渊昶,周红艺等.超临界水中萘酚氧化分解的研究[J],化学反应工程,2000,
    
    16(1):77~81
    [89] 祝万鹏,王利,杨志华等.光催化氧化处理染料中间体H酸水溶液[J],环境科学,1996,17(4):7~10
    [90] 李定邦,修光利,张大年.α-萘酚的催化氧化研究[J],化学世界,2000,S1期:52~54
    [91] Andrzej Sobczynski,Lukasz Duczmal,Anna Dobosz. Photocatalysis by illuminated titania: oxidation of hydro quinone and p-benzo quinone[J]. Monatshefte fǖr Chemie. 1999,130(3):337~384
    [92] Kiwi J. Role of oxygen at the TiO_2 interface during photodegradation of biologically difficult-to-degrade anthraquinone-sulfonate dyes[J]. Environmental Toxcology and Chemistry, 1994,13(10): 1569~1575

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