高级氧化法在烟气脱硫脱硝脱汞中的应用研究进展

doi:10.16085/j.issn.1000-6613.2016.10.042

摘要/Abstract

摘要： 近年来，面对大气污染日益严峻的现状，用于燃煤烟气中SO₂、NO_x和Hg⁰的控制技术的研发显得尤为关键。鉴于高级氧化法在污水处理领域较好的应用效果，对于将其用于烟气处理的研究也已展开。本文主要从高级氧化法用于单独脱硝、脱汞和同时脱硫脱硝以及三者联合脱除这4个方面进行了较为详细的综述。重点分析了光催化氧化、蒸发Fenton试剂、多相催化剂、UV/Fenton技术等氧化法在烟气处理领域的研究现状。分析表明，通过对诸多影响因素以及催化剂选择和改性等方面的试验与调控，可使SO₂、NO_x和Hg⁰的脱除率达到90%左右甚至更高的水平，但仍然存在着·OH自由基量难控制以及脱除效率难维持等问题。由此指出，在今后对于将高级氧化法用于燃煤烟气联合脱除的研究中，需要进一步尝试基于多方法融合的完整、稳定、高效脱硫脱硝脱汞的新思路。

关键词: 氧化, 催化, 烟道气, 自由基

Abstract: In recent years,the situation of air pollution becomes more and more serious. Therefore,the technologies of removing SO₂,NO_x and Hg⁰ from coal-fired flue gas need to be deeply developed. Advanced oxidation process(AOPs)has been successively applied in wastewater treatment. Some researches flue gas treatment have already been begun,including removing NO_x and Hg⁰ respectively and simultaneous removal of SO₂ and NO_x. Based on these achievements,technologies for simultaneous removal of SO₂,NO_x and Hg⁰ have been developed,such as photocatalytic oxidation,vapor Fenton reagent,heterogeneous catalyst and UV/Fenton,et al. Therefore,a lot of experiments about the regulation of various factors and the selection and modification of catalyst have been done. As a result,the removal rate of SO₂,NO_x and Hg⁰ is 90% or higher. However,some problems about controlling the quantity of·OH radical and maintaining the removal rates at a higher level still remain. Based on the combination of multiple methods,new ideas for applying AOPs in the integral,stable and effective simultaneous removal of SO₂,NO_x and Hg⁰ from coal-fired flue gas will be needed in the future.

Key words: oxidation, catalysis, flue gas, radical

中图分类号:

X701.7

苑鹏, 卢凤菊, 梅雪, 沈伯雄. 高级氧化法在烟气脱硫脱硝脱汞中的应用研究进展[J]. 化工进展, 2016, 35(10): 3313-3322.

YUAN Peng, LU Fengju, MEI Xue, SHEN Boxiong. Recent progress on application of advanced oxidation processes (AOPs) to remove SO₂,NO_x and Hg⁰ from flue gas[J]. Chemical Industry and Engineering Progree, 2016, 35(10): 3313-3322.

参考文献

[1] 戴彦德,吕斌,冯超."十三五"中国能源消费总量控制与节能[J].北京理工大学学报(社会科学版),2015,17(1):1-7.
[2] 韩恒超,刘伟军,曹伟武.燃煤烟气联合脱硫脱氮除尘技术研究进展[J].上海环境科学,2011,30(5):224-230.
[3] 史亚微,白中华,姜军清,等.中国烟气脱汞技术研究现状及发展趋势[J].洁净煤生产技术,2014,20(2):104-108.
[4] 毛吉献,王凡,王红梅,等.燃煤烟气脱汞技术研究进展[J].能源环境保护,2010,24(2):1-5.
[5] 张运洲,程路.中国电力"十三五"及中长期发展的重大问题研究[J].中国电力,2015,48(1):1-5.
[6] 吴舜泽,贾杰林,孙宁.重金属污染防治当前形势与未来展望[C]//第十届环境与发展论坛论文集,北京,2014:115-119.
[7] 赵毅,郝润龙,齐萌,等.同时脱硫脱硝脱汞技术研究概述[J].中国电力,2013,46(10):155-158.
[8] 刘晶冰,燕磊,白文荣,等.高级氧化技术在水处理的研究进展[J].水处理技术,2011,37(3):11-17.
[9] 李花,沈耀良.废水高级氧化技术现状与研究进展[J].水处理技术,2011,37(6):6-9.
[10] HU Y,SONG X,JIANG S M,et al.Enhanced photocatalytic activity of Pt doped TiO₂ for NO_x oxidation both under UV and visiable light irradiation:a synergistic effect of lattice Pt⁴⁺ and surface PtO[J].Chemical Engineering Journal,2015,274:102-112.
[11] HASHIMOTO K,SUMIDA K,KITANO S,et al.Photo-oxidation of nitrogen oxide over titanium (Ⅳ) oxide modified with platinum or rhodium chlorides under irradiation of visible light or UV light[J].Catalysis Today,2009,144:37-41.
[12] TODOROVAL N,GIANNAKOPOULOU T,POMONI K,et al.Photocatalytic NO_x oxidation over modified ZnO/TiO₂ thin films[J].Catalysis Today,2015,252:41-46.
[13] MATSUDA S,HATANO H.Photocatalytic removal of NO_x in a circulating fluidized bed system[J].Powder Technology,2005,151:61-67.
[14] 刘杨先,潘剑锋,刘勇.UV/H₂O₂氧化联合CaO吸收脱除NO的传质-反应动力学[J].化工学报,2013,64(3):1062-1068.
[15] LIU Y X,ZHANG J,SHENG C D.Kinetic model of NO removal from SO₂-containing simulated flue gas by wet UV/H₂O₂ advanced oxidation process[J].Chemical Engineering Journal,2011,168:183-189.
[16] LIU Y X,PAN J F,TANG A K,et al.A studay on mass transfer-reaction kinetic of NO absorption by using UV/H₂O₂/NaOH process[J].Fuel,2013,108:254-260.
[17] LIU Y X,ZHANG J,SHENG C D,et al.Simultaneous removal of NO and SO₂ from coal-fired flue gas by UV/H₂O₂ advanced oxidation process[J].Chemical Engineering Journal,2010,162:1006-1011.
[18] 刘杨先,张军,王助良.UV/H₂O₂氧化联合Ca (OH)2吸收同时脱硫脱硝[J].化工学报,2012,63(10):3277-3283.
[19] LIU Y X,WANG Q,YIN Y S,et al.Advanced oxidation removal of NO and SO₂ from flue gas by using ultraviolet/H₂O₂/NaOH process[J].Chemical Engineering Research and Design,2014,92:1907-1914.
[20] LIU H,WU H,BAO J J,et al.Photochemical removal of NO and SO₂ from flue gas using UV irradiation[J].Asia-Pacific Journal of Chemical Engineering,2014,9:775-781.
[21] DING J,ZHANG Q,ZHANG S L,et al.Simultaneous removal of NO_x and SO₂ from coal-fired flue gas by catalytic oxidation-removal process with H₂O₂[J].Chemical Engineering Journal,2014,243:176-182.
[22] BAI M D,ZHANG Z T,BAI M D.Simultaneous desulfurization and denitrification of flue gas by ·OH radicals produced from O₂-and water vapor in a duct[J].Environmental Science&Technology,2012,46(18):10161-10168.
[23] TSENG C H,KEENER T C,LEE J Y,et al.Enhanced effect of in-situ generated ammonium salts aerosols on the removal of NO_x from simulated flue gas[J].Environmental Science&Technology,2001,35(15):3219-24.
[24] ZHAO Y,HAO R L,GUO Q,et al.Simultaneous removal of SO₂ and NO by a vaporized enhanced-Fenton reagent[J].Fuel Processing Technology,2015,137:8-15.
[25] LIU Y X,ZHANG J,YIN Y S,et al.Study on absorption of elemental mercury from flue gas by UV/H₂O₂:process parameters and reaction mechanism[J].Chemical Engineering Journal,2014,249:72-78.
[26] WU J,LI C E,ZHAO X Y,et al.Photocatalytic oxidation of gas-phase Hg⁰ by CuO/TiO₂[J].Applied Catalysis B:Environmental,2015,176/177:559-569.
[27] JED C,GRETELL O,JOHN C,et al.PCE oxidation by sodium persulfate in the presence of solids[J].Environmental Science&Technology,2010,44(24):9445-9450.
[28] FURMAN O S,TEEL A L,WATTS R J.Mechanism of base activation of persulfate[J].Environmental Science&Technology,2010,44(16):6423-6428.
[29] ZHAO Y,HAO R L,ZHANG P,et al.An integrative process for Hg⁰ removal using vaporized H₂O₂/Na₂S₂O₈[J].Fuel,2014,136:113-121.
[30] LU D,ANTHONY E J,TAN Y W,et al.Mercury removal from coal combustion by Fenton reactions——Part A:bench-scale tests[J].Fuel,2007,86(s17/s18):2789-2797.
[31] DENG J H,JIANG J Y,ZHANG Y Y,et al.FeVO₄ as a highly active heterogeneous Fenton-like catalyst towards the degradation of Orange Ⅱ[J].Applied Catalysis B:Environmental,2008,84(3):468-473.
[32] RAMIREZ J H,MALDONADO-HÓDAR F J,PÉREZ-CADENAS A F,et al.Azo-dye Orange Ⅱ degradation by heterogeneous Fenton-like reaction using carbon-Fe catalysts[J].Applied Catalysis B:Environmental,2007,75(s3/4):312-323.
[33] AI L,ZHOU Y,JIANG J.Removal of methylene blue from aqueous solution by montmorillonite/CoFe₂O₄ composite with magnetic separation performance[J].Desalination,2011,266(1):72-77.
[34] CUZZOLA A,BERNINI M,SALVADORI P.A preliminary study on iron species as heterogeneous catalysts for the degradation of linear alkylbenzene sulphonic acids by H₂O₂[J].Applied Catalysis B:Environmental,2002,36(3):231-237.
[35] ZHOU C S,SUN L S,ZHANG A C,et al.Elemental mercury (Hg⁰) removal from containing SO₂/NO flue gas by magnetically separable Fe_2.45Ti_0.55O₄/H₂O₂ advanced oxidation processes[J].Chemical Engineering Journal,2015,273:381-389.
[36] NIKSA S,HELBLE J J,FUJIWARA N.Kinetic modeling of homogeneous mercury oxidation:the importance of NO and H₂O in predicting oxidation in coal-derived systems[J].Environmental Science&Technology,2001,35(18):3701-3706.
[37] ZHAO Y,HAO R L,YUAN B,et al.Simultaneous removal of SO₂,NO and Hg⁰ through an integrative process utilizing a cost-effective complex oxidant[J].Journal of Hazardous Materials,2016,301:159-167.
[38] ZHAN F M,LI C T,ZENG G M,et al.Experimental study on oxidation of elemental mercury by UV/Fenton system[J].Chemical Engineering Journal,2013,232(9):81-88.
[39] PRESTO A A,GRANITE E J.Survey of catalysts for oxidation of mercury in flue gas[J].Environmental Science&Technology,2006,40(18):5601-9.
[40] CAO Y,CHEN B,WU J,et al.Study of mercury oxidation by a selective catalytic reduction catalyst in a pilot-scale slipstream reactor at a utility boiler burning bituminous coal[J].Energy&Fuels,2007,21(1):145-156.
[41] LI H L,WU C Y,LI Y,et al.Superior activity of MnO_x-CeO₂/TiO₂ catalyst for catalytic oxidation of elemental mercury at low flue gas temperatures[J].Applied Catalysis B:Environmental,2012,111(3):381-388.
[42] YUAN Y,ZHANG J Y,LI H L,et al.Simultaneous removal of SO₂,NO and mercury using TiO₂-aluminum silicate fiber by photocatalysis[J].Chemical Engineering Journal,2012,192(2):21-28.
[43] LIU H,YU X Q,YANG H M.The integrated photocatalytic removal of SO₂ and NO using Cu doped titanium dioxide supported by multi-walled carbon nanotubes[J].Chemical Engineering Journal,2014,243:465-472.
[44] 叶林静,关卫省,李宇亮.高级氧化技术降解双酚A的研究进展[J].化工进展,2013,32(4):909-918.
[45] 包木太,王娜,陈庆国,等.Fenton法的氧化机理及在废水处理中的应用进展[J].化工进展,2008,27(5):660-665.
[46] 俸志荣,焦纬洲,刘有智,等.铁碳微电解处理含硝基苯废水[J].化工学报,2015,66(3):1150-1155.