钒基催化剂降解实际烟气中的二噁英研究
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摘要
为开发高效降解实际烟气中二噁英的新型催化剂,在钒基催化剂中加入Mn和Cu,研究200℃时不同催化剂对二噁英的降解效率,并添加臭氧辅助催化,分析二噁英不同氯代同系物的降解规律。结果表明:催化剂中添加MnO_x或同时添加MnO_x和CuO_x时,催化剂降解效率明显提升;催化剂中仅添加CuO_x则会导致二噁英的大量生成;反应气氛中添加臭氧,能提升催化剂对二噁英的降解效率,特别是VO_x-CuO_x/TiO_2,二噁英由生成转变为降解。分析二噁英同系物的脱除效率发现,催化剂对二噁英的吸附效率随着氯代数增加而增加,降解效率随氯代数增加而降低。
To develop new catalysts to destroy PCDD/Fs in real flue gas,the vanadium based catalysts were dipped with Mn and Cu.PCDD/Fs destruction efficiencies for different catalyst with or without ozone at 200 ℃ was studied.And the decomposition on congeners were also analyzed.Results showed that when MnO_x was added,or MnO_x and CuO_x were added at the same time,the destruction efficiencies increased significantly.But when only CuO_x was added into the catalyst,much amount of PCDD/Fs were synthesized.The addition of ozone in the reaction atmosphere could promote the destruction efficiency,especially for VOx-CuO_x/TiO_2,the formation changed to destruction.With the chlorine number of the PCDD/Fs increasing the adsorption efficiencies on the catalysts raised while the destruction efficiencies decreased.
To develop new catalysts to destroy PCDD/Fs in real flue gas,the vanadium based catalysts were dipped with Mn and Cu.PCDD/Fs destruction efficiencies for different catalyst with or without ozone at 200 ℃ was studied.And the decomposition on congeners were also analyzed.Results showed that when MnO_x was added,or MnO_x and CuO_x were added at the same time,the destruction efficiencies increased significantly.But when only CuO_x was added into the catalyst,much amount of PCDD/Fs were synthesized.The addition of ozone in the reaction atmosphere could promote the destruction efficiency,especially for VOx-CuO_x/TiO_2,the formation changed to destruction.With the chlorine number of the PCDD/Fs increasing the adsorption efficiencies on the catalysts raised while the destruction efficiencies decreased.
引文
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[3]WACHS I E,DEO G,WECKHUYSEN B M,et al.Selective catalytic reduction of NO with NH3over supported vanadia catalysts[J].Journal of Catalysis,1996,161(1):211-221.
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[5]KANG M,PARK E D,KIM J M,et al.Cu-Mn mixed oxides for low temperature NO reduction with NH3[J].Catalysis Today,2006,111(3/4):236-241.
[6]BELKOUCH J,OULD DRIS A,TAOUK B.Removal of hazardous chlorinated VOCs over Mn-Cu mixed oxide based catalyst[J].Journal of Hazardous Materials,2009,169(1/2/3):758-765.
[7]DHANDAPANI B,OYAMA S T.Gas phase ozone decomposition catalysts[J].Applied Catalysis B:Environmental,1997,11(2).
[8]KONOVA P,STOYANOVA M,NAYDENOV A,et al.Catalytic oxidation of VOCs and CO by ozone over alumina supported cobalt oxide[J].Applied Catalysis A:General,2006,298.
[9]LIU J,YU C,ZHAO P,et al.Comparative study of supported CuOxand MnOxcatalysts for the catalytic wet air oxidation ofβ-naphthol[J].Applied Surface Science,2012,258(22):9096-9102.
[10]KANG M,PARK E D,KIM J M,et al.Manganese oxide catalysts for NOx reduction with NH3at low temperatures[J].Applied Catalysis A:General,2007,327(2):261-269.
[11]LI Q,YANG H,QIU F,et al.Promotional effects of carbon nanotubes on V2O5/TiO2 for NOx removal[J].Journal of Hazardous Materials,2011,192(2):915-921.
[12]FANG J,BI X,SI D,et al.Spectroscopic studies of interfacial structures of CeO2-TiO2 mixed oxides[J].Applied Surface Science,2007,253(22):8952-8961.
[13]YU M F,LI X D,REN Y,et al.Low temperature oxidation of PCDD/Fs by TiO2-based V2O5/WO3catalyst[J].Environmental Progress&Sustainable Energy,2016,35(5):1265-1273.
[14]LU S Y,WANG Q L,STEVENS W R,et al.Study on the decomposition of trace benzene over V2O5-WO3/TiO2-based catalysts in simulated flue gas[J].Applied Catalysis B:Environmental,2014,147:322-329.
[15]TANG X,CHEN J,HUANG X,et al.Pt/MnOx-CeO2catalysts for the complete oxidation of formaldehyde at ambient temperature[J].Applied Catalysis B:Environmental,2008,81(1/2):115-121.
[16]WANG Q L,HUANG Q X,WU H F,et al.Catalytic decomposition of gaseous 1,2-dichlorobenzene over CuOx/TiO2and CuOx/TiO2-CNTs catalysts:mechanism and PCDD/Fs formation[J].Chemosphere,2016,144:2343-2350.
[17]FORTUNATO G,OSWALD H,RELLER A.Spinel-type oxide catalysts for low temperature CO oxidation generated by use of an ultrasonic aerosol pyrolysis process[J].Journal of Materials Chemistry,2001,11(3):905-911.
[18]纪莎莎,李晓东,俞明锋,等.V2O5-WO3/TiO2催化剂降解气相二噁英的研究[J].浙江大学学报(工学版),2014,48(10):1746-1751.
[19]DELAIGLE R,DEBECKER D P,BERTINCHAMPS F,et al.Revisiting the behaviour of vanadia-based catalysts in the abatement of(chloro)-aromatic pollutants:towards an integrated understanding[J].Topics in Catalysis,2009,52(5):501-516.
[20]ZHAO R,JIN D,YANG H,et al.Low-temperature catalytic decomposition of 130tetra-to octa-PCDD/Fs congeners over CuOxand MnOx modified V2O5/TiO2-CNTs with the assistance of O3[J].Environmental Science&Technology,2016,50(20):11424-11432.
[21]NAYDENOV A,MEHANDJIEV D.Complete oxidation of benzene on manganese dioxide by ozone[J].Applied Catalysis A:General,1993,97(1):17-22.