基于流化床结构的电—多相催化装置研究
详细信息    本馆镜像全文|  推荐本文 |  |   获取CNKI官网全文
摘要
本文以初始浓度为200 mg/L水相2,4-二氯酚(2,4-DCP)降解为评价指标,开展了基于流化床结构的筒式无隔膜电.多相催化反应器研究,着重考察了粒子密度、粒子电极膨胀率、反应器有效高径比、流化介质等因素对有机物分解效率的影响,为一种新型的膨化床电解装置及其用于水相有机物分解的处理工艺提供了数据支撑。
     实验结果表明,γ/-Al_2O_3/Sb_2O_4+SnO_2作为复极性三维电极对反应器的运行效果具有较显著的影响,填充粒子量的增多,可以增加复极化的粒子电极数量从而提高反应器对废水的处理效果,实验证明64 mL/L~80 mL/L为最佳粒子电极密度;对不同粒子电极床层膨胀率考察发现,当膨胀率增大到1时,反应器对水相2,4-DCP有很好的去除效果,而后去除效果受膨胀率增大影响变小;通过三组不同高径比的反应器实验比较,综合考虑水相2,4-DCP去除速率及能耗,以高径比为6的反应器为最优,反应60 min有85.8%2,4-DCP被去除,能耗为40.6 kWh/kg2,4-DCP;在同一反应器中,以空气和水流为流化介质时,2,4-DCP都有较好的去除效果,但气流流化的能耗远高于水流流化,并且曝气对2,4-DCP有吹脱作用,造成污染转移。
     在上述实验基础上形成一种膨化床电分解装置,以及相应的处理工艺,克服了粒子电极污染及堵塞,粒子及其表面活性物质流失,流化动力不足等现有电-多相反应器中存在的问题。对两种实际工业废水小试,获得得良好的处理效果及很高的电流效率。
The electricity-heterogeneous catalysis reactor without septum based on fluidized bed was investigated using the degradation of 2,4-dichlorophenol(2,4-DCP) with a concentration of 200 mg/L as evaluating index in this thesis.The effects of structural parameters including the density of particle electrode,the ratio of bed expansion,height-diameter ratio,fluidizing agent on 2,4-DCP removal were investigated.The experimental provided the data to support a new kind of expanded-bed electrolysis device and its treatment process of organic decomposition in aqueous.
     The experimental results show that the density ofγ-Al_2O_3/Sb_2O_4 +SnO_2 particle is a notable factor on the reaction and the oxidation ratio can be improved rapidly with the increasing of theγ-Al_2O_3/Sb_2O_4+SnO_2 particle bipolarized.64 mL/L~80 mL/L is an appropriate particle density. When the particle bed expansion ratio of 1,a better removal efficiency of 2,4-DCP was got than a lower expansion ratio.General consider the degradation rate and energy consumption of 2,4-DCP,the reactor with a height-diameter ratio of 6 is the optimal,after 60min reaction 85.8% 2,4-DCP was removed with a energy consumption of 40.6 kWh/kg2,4-DCP. When use gas as fluidizing agent,got a better removal efficiency of 2,4-DCP than liquid did.But larger energy consumption was needed at remove the same 2,4-DCP.Aeration can cause the transfer of pollutants.
     A new kind of expanded-bed electrolysis device and its treatment process of organic decomposition in aqueous was formed based on the experimental results.The problems existing in current reactor such as the pollution and congestion of particle electrode,the loss of particle or its surface component,lower impetus were conquered.Small-scale test of two kinds of industrial wastewater were performed.A well removal efficiency and high current efficiency were got.
引文
[1]周明华,戴启洲,雷乐成,等.活性炭吸附-电化学高级氧化再生法处理难降解有机污染物[J].科学通报.2005,50(3):303-304.
    [2]刘福兴,李义久.电化学催化氧化降解有机物的机理及研究进展[J].四川环境.2005,24(1):52-56.
    [3]孙德智,于秀娟,冯玉杰.环境工程中的高级氧化技术[M].北京:化学工业出版社,2002:307-308.
    [4]Bickhurst J R,Electrochem Soc[J].1969,116:1600.
    [5]冯玉杰,李晓岩,龙宏,等.电化学技术在环境工程中的应用[M].北京:化学工业出版社,2002,76-80.
    [6]谢茂松,王学林,徐桂芬,等.用电-多相催化反应处理二硝基苯酚工业废水的方法[P].中国专利,961155.45.0.
    [7]李炳焕,黄艳娥,刘会媛.电化学催化降解水中有机污染物的研究进展[J].环境污染治理技术与设备,2002,3(2):23-27.
    [8]谢茂松,王学林,徐桂芬,等.治理难降解有机工业废水新技术电多相催化技术[J].大连铁道学院学报,1998,19(2):35-37.
    [9]Comninellis C,Nerini A.Anodic oxidation of penol in the presence of NaCl for wastewater treatment[J].J.Appl.Electrochem.,1995,25(1):23-28.
    [10]孙晓君,冯玉杰.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.
    [11]Ding Z,Weimin C,Qunhui W.A study on the use of bipolar particles-electrodes in decolorization of dyeing effluents and its principle[J].Water Sci Tech,1986,19(3-4):391-400.
    [12]周定,汪群慧.复极性电极中填充材料选择的研究[J].哈尔滨工业大学学报,1984,(增刊):1-4.
    [13]吴辉煌.水中有机污染物电化学清除的研究进展[J].环境污染与防治,2000,22(4):39-42.
    [14]Wang J,Angnes L,Tobias H,et al,Carbon Aerogel Composite Electrodes[J].Anal Chem,1993,65(17):2300-2303
    [15]Kohler D,Zabasajja J,Krishnagopalan,et al,A Metal-carbon composite materials from fiber precursors I.Preparation of stainless steel-carbon composite electrodes[J].J Electrochem Soc,1990,137:136-141.
    [16]Wang J,Brennsteiner A,Angnes L,et al.Composite electrodes based on carbonized poly (acrylonitrile) foams[J].Anal Chem,1990,62(10):1102-1104.
    [17]Sleszynski N,Osteryoung J,Carter M.Arrays of very small voltammetric electrodes based on reticulated vitreous carbon[J].Anal Chem,1984,56(2):130-135.
    [18]熊英健,范娟,朱锡海.三维电极电化学水处理技术研究现状及方向[J].工业水处理,1998,18(1):5-8.
    [19]李保山,牛玉舒,翟玉春,等.发泡金属电极的宏观反应速率及电势分布[J].化工学报,2001,52(7):593-600.
    [20]董献堆,陈平安,陆君涛,等.电解用三维电极体系的研究与发展[J].化学通报,1997,(5):12-19.
    [21]Leroux F,Coeuret F.Flow-by electrodes of ordered sheets of expand metal[J].Electrochim Acta,1985,30(2):167-172.
    [22]Stock A,Enriquez-Granados M A,Roger M,eta.Behaviour of porous electrodes in a flow-by regime-1,theoretical study[J].Electrochim Acta,1982,27(2):293-301.
    [23]朱宏丽,王书惠.三元电极电解在水处理中的应用[J].环境科学,1985,6(6):36-40.
    [24]Bockris J O M,Kim J,Effect of contact resistance between particles on the current distribution in a packed bed electrode[J].J Appl Electrochem,1997,27(8):890-901
    [25]Brown C J,Pletcher D,Walsh F C,et al,Studies of three-dimensional electrodes in the FMO1-LC laboratory electrolyser[J].J Appl Electrochem,1994,24(2):95-106.
    [26]Gaehr F,Hermanutz F,Oppermann W.Ozonation-an important technique to comply with new Germany laws for textile wastewater treatment[J].Water Sci Technol,1994,30(3-3):255-263.
    [27]Ogutveren U B,Gonen N,Koparal S.Removal of chromium from aqueous solutions and plating bath rinse by an electrochemical method[J].,Int J Environ Stud Sect A,1994,45(2):81-87.
    [28]Hutint D,Coeuret F.Experimental study of coper deposition in a fluidized bed electrode[J].J Appl Electrochem,1977,7:463-471.
    [29]Shewood W Queneau G,P B,Nikolic C,D R Hodges.Fluid bed electrolysis of nicke[J].Metallurgical Transactions B,1979,10B:659-66.
    [30]Morooka S,Kusakabe K,et al.Effective specific resistance of a particle phase in a fluidized-bed electrode[J].International chemical engineering,1981,21(3):465-472.
    [31]阎桂蕃,郝修德,张蕴壁.金属流化床电沉积研究(Ⅰ)[J].高等学校化学学报,1987,8(11):1033-1034.
    [32]孙小华,荫福棠.利用流化床电极从铜隔渣中回收有价成份[J].化工环保,1989,9(1):14-17.
    [33]孙小华,荫福棠.利用流化床电积法从镍阳极泥中分离回收有价成份[J].化工环保,1988,8(8):130-132.
    [34]安成强,王民惠,刘秀晨,等.非金属导体流态化电极的研究及应用[J].沈阳化工,1996(1):7-9.
    [35]于德龙,刘国会,等.流态化电极从酸性废水中电沉积铜的研究[J].沈阳化工,1992(5):39-42.
    [36]张红波,徐仲榆,莫孝文.流态化电极电解法处理含氰废水[J].化工环保,1995,15(4):224-227.
    [37]张红波,徐仲榆,莫孝文.细粒膨胀石墨流态化电极处理含铬废水研究[J].电镀与环保, 1992,12(6):20-23
    [38]许文林,王雅琼,孙彦平.流化床电化学反应器回收铜电解液中的银[J].化工冶金,1995,16(1):77-80.
    [39]朱宏丽,王书惠.三元电极电解在水处理中的应用[J].环境科学,1985,6(6):36-40
    [40]Paidar M.,Bouzek K.,Bergmannb H..Influence of cell construction on the electrochemical reduction of nitrate[J].Chem Eng J,2002,85:99-109.
    [41]何春,安太成,熊亚等,三维电极电化学反应器对有机废水的降解研究[J].电化学,2002,8(3):327-332.
    [42]管玉江,杨卫身.复极性固定床电解槽脱色研究[J].印染,1998,24(11):12-14.
    [43]许海梁,杨卫身.葱酮染料的电解处理研究[J].环境保护科学,1998,24(4):14-16.
    [44]周抗寒,周定,用涂膜活性炭提高复极性电解槽电解效率[J].环境科学,1994,15(2):38-40.
    [45]Ya X,Stunk P.J.et al.Treatment of dye wastewater containing acid orange Ⅱ using a cell with three-phase three-dimensional electrode[J].Wat.Res,2001,35(17):4226-4230.
    [46]Ya X,Karlssonb H T.An experimental investigation of chemical oxygen demand removal from the wastewater containing oxalic acid using three-phase three-dimensional electrode reactor[J].Adv Environ Res,2002,7:139-145.
    [47]Ya X et al.Performance of three-phase three-dimensional electrode reactor for the reduction of COD in simulated wastewater-containing phenol[J].Chemosphere,2003,50:131-136.
    [48]Ya X et al.Removal of formic acid from wastewater using three-phase three- dimensional electrode reactor[J].Water Air Soil Poll,2003,144:67-79.
    [49]Minghua Z,Zucheng W,Xiangjuan M.A novel fluidized electrochemical reactor for organic pollutant abatement[J].Sep Purif Tech,2004,34:81-88.
    [50]曹敬华,张希衡,活性炭固定床电解槽处理苯酚废水[J].中国给水排水,2003,18(5):45-47
    [51]杨松.复极性三维电极反应器的改进研究[D].大连理工大学硕士论文,2004.
    [52]Maluleke M A,Linkov V M.Partial electrochemical oxidation of phenol on ceramic-based flat-sheet type electorlnembrane reactors[J].Sep Purif Technol,2003,32(1-3):377-385.
    [53]Sharifian H,Kirk D W.Electrochemical oxidation of phenol[J].J Electrochem Soc,1986,133(5):921-925.
    [54]刘会娟,曲久辉,雷鹏举,锰砂催化电化学方法对染料K2G脱色效果的研究[J].环境化学,2002,21(1):68-71.
    [55]Fockedey E,Lierde A V.Coupling of anodic and cathodic reactions for phenol electro-oxidation using three-dimensional electrodes[J].Water Res,2002,36(16):4169-4175.
    [56]Tennakoon C L,Bhardwaj R C,Bockris J O.Electrochemical treatment of human wastes in a packed bed reactor[J].J Appl Electrochem,1996,26(1):18-29.
    [57]Gunnar R D,Stanley H L.Comparisons of Ebonex~(?) and graphite supports for platinum and nick elelectro catalysis[J].Electrochim Acta,1998,44(2-3):437-444.
    [58]谢茂松,王学林,杨旭,等.用电-多相催化技术处理二硝基苯酚工业废水[P].中国发明专 利,96115545.0.1996.
    [59]谢茂松,王学林,徐桂芬,等.用电-多相催化新技术处理化肥厂工业废水[J].工业水处理,2001,21(9):15-17
    [60]江琳才,电合成[M].北京:高等教育出版社,1993,29-30
    [61]Tomat R,Rigo A,Electrochemical oxidation of toluene promoted by OH radicals[J].J Appl Electrochem,1984,14(1):1-8
    [62]庄连春,曾迪华.UV/H_2O_2光氧化系统分解苯环类污染物之研究[J].中国环境工程学刊,1997,7(3):253-262.
    [63]Huh and J W Evans.Electrical and electrochemical behavior of fluidized bed electrodes.Ⅰ,Potential transients and time-averaged values.Ⅱ.Effective bed resistivities[J].J Electrochem.Soc.1987,2:308-321.
    [64]J K Lee,L W shemilt,H S Chun.Studies of bipolarity in fluidized bed electrodes[J].J Appl Electrochem,1989,19:877-881.
    [65]Plimley R E,Wright A R.A bipolar mechanism for charge transfer in a fluidized bed electrode [J]..Cheml Eng Sci,1984,39(3):395-405.
    [66]Lee J K,Chun H S,Shemilt L W.Overpotential distribution for nominally monopolar fluidized bed electrodes[J].Journal of ChemicalEngineering of JaPan,1995,28(1):25-30.
    [67]孙启文,朱英,朱炳辰.流化床电化学反应器研究(Ⅰ)理论分析、实验及数据处理方法,(Ⅱ)导电机理及电位波动特性的实验研究,(Ⅲ)电沉积银系统的电位分布与表现性能[J]..化工学报,1991(5):520-540.
    [68]孙启文,朱炳辰.流化床电化学反应器的应用[J].现代化工,1989,9(6):16-20.
    [69]Augusto P,et al.Process for the Electrochemical Decontamination of Water polluted By Pathogenic Germs with Peroxide Formed in Situ[P].US4619745,1986,(19):1-8.
    [70]崔玉虹,冯玉杰,刘峻峰.Sb掺杂钛基SnO_2电极的制备、表征及其电催化性能研究[J].功能材料,2005,36(2):234-237.
    [71]Yujie F,X.Y.Li,Electro-catalytic oxidation of phenol on several metal-oxide electrodes in aqueous solution[J].Wat Res,2003,37(10):2399-2407.
    [72]刘海萍,李宁等,掺锑二氧化锡多孔钛阳极对苯酚的催化氧化[J]..环境科学学报,2005,25(8):1015-1020.
    [73]Yujie F,Yuhong C.Performance of Gd-doped Ti-based Sb-SnO_2 anodes for electrochemical destruction of phenol[J].Chemosphere,2008,70:1629-1636.
    [74]Bo W,Wuping K,Hongzhu M.Electrochemical treatment of paper mill wastewater using three-dimensional electrodes with Ti/Co/SnO_2-Sb_2O_5 anode[J].J Hazard Mater,2007,146:295-301.
    [75]王建龙.生物固定化技术与水污染控制[M].北京:科学出版社,2002.261-267.
    [76]国家环境保护总局《水和废水监测分析方法》编委会.水和废水监测分析方法,第四版[M]. 中国环境科学出版社,2002:211-213.
    [77]冯玉杰,李晓岩,尤宏,等.电化学技术在环境工程中的应用[M].北京:化学工业出版社,2002.132.
    [78]Line S M,Daniel B,Luc V,et al.Evaluation of sodium 4-hydroxylbenzoate as an hydroxyl radical trap using Gas Chromatography-Mass Spectrometry and High-Performance liquid chromatography with electrochemical detection[J].Anal Biochem,1996,241:67-74.
    [79]卞文娟.高压脉冲液相放电技术处理水中难降解有机污染物的研究[D].浙江大学博士学位论文,2005.01.
    [80]陈霞.声辅助电催化处理水相氯酚的研究[D].浙江工业大学硕士学位论文,2007.05.
    [81]张芳,等.Mn-Sn-Sb/γ-Al_2O_3粒子电极对苯酚的降解特性[J].化工学报,2006,57(10):2515-2521.
    [82]孙启文,朱英,朱炳辰.流化床电化学反应器研究(Ⅰ)理论分析、实验及数据处理方法[J].化工学报,1991,5(5):519-525.
    [83]施汉昌,贾立敏.内循环三相流化床的设备化技术.清华大学环境科学与工程系,2000:1-60.
    [84]杜桂荣,孙占学等.催化臭氧氧化法降解2,4-二氯苯酚的研究[J].化工环保,2006,25(2):93-96.
    [85]胡翔,李进,等.臭氧氧化水中壬基酚的反应机理研究[J].环境科学,2007,28(3):584-587.
    [86]曾华冲,杨利芝,等.Fenton试剂氧化法修复2,4-DCP污染土壤的研究[J].生态环境,2008,17(1):221-226.
    [87]Suranjana C,Krishna G.Bhattacharyya.Catalytic wet oxidation of 2-chlorophenol,2,4-dichlorophenol and 2,4,6-trichlorophenol in water with Mn(Ⅱ)-MCM41[J].Chem En Jl 2008,139:575-588.
    [88]朱琨,王海涛,等.UV-H_2O_2系统对水中2,4-DCP氧化降解研究[J].工业用水与废水,2006,37(1):27-31.
    [89]Ormad M.P.,Ovelleiro J.L.,Kiwi J..Photocatalytic degradation of concentrated solutions of 2,4-dichlorophenol using low energy light Identification of intermediates[J].Appl Catal B-Environ,2001,32:157-166.
    [90]Alaton I A,Balcioglu I A,Bahnemann D W,2002.Advanced oxidation of a reactive dyebath effluent:comparison of O_3,H_2O_2/UV-A processes[J],Water Res.36:1143-1154.
    [91]Jiangren F,Houk L.L.,.Johnson D.C.Electrocatalysis of Anodic Oxygen- transfer Reaction:the Electrochemical Incineration of Benzoquinone[J].J.Electrochem.Soc.1995,11(142):3627-3631.
    [92].Azzam M.O,Al-Tarazi M.,Tahboub Y..Anodic Destruction of 4-chlorophenol Solution[J].J Hazaed Mater,2000,75:99-113.
    [93]王海涛,等.UV/H_2O_2降解水中2,4-DCP试验研究[J].兰州铁道学院学报(自然科学版),2003,22(3):31-33.
    [94]胡俊生,等2,4-DCP的电化学降解及影响因素研究[J].沈阳建筑大学学报(自然科学版), 2007,23(6):1012-1016.
    [95]成华,田凯勋.铁炭内电解法处理2,4-DCP研究[J].企业技术开发,2005,24(7):11-12.
    [96]路艳艳,等.超声波/铁粉对废水2,4-DCP的降解研究[J].污染防治技术,2008,21(2):4-9.
    [97]Li X.Z.,Zhao B.X.,Wang P..Degradation of 2,4-dichlorophenol in aqueous solutionby a hybrid oxidation process[J].J Hazaed Mater,2007,147:281-287.
    [98]Walter Z.Tang,C P Huang.Photocatalyzed oxidation pathways of 2,4-dichlorophenol by CdS in basic and acidic aqueous solutions[J].Wat Res.1995,29(2):745-756.
    [99]Comninellis C,Pulgerin C.Anodic oxidation of phenol for wastewater treatment[J].J Appl Electrochem,1991,21(8):703-708.
    [100]潘伟伟.电-多相催化降解2-氯酚的机理研究[D].浙江工业大学硕士学位论文,2008.04.

© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号

地址:北京市海淀区学院路29号 邮编:100083

电话:办公室:(+86 10)66554848;文献借阅、咨询服务、科技查新:66554700