低溫SCR煙氣脫硝催化劑開發(fā)

低溫SCR煙氣脫硝催化劑開發(fā)

劉越浙江大學(xué)環(huán)境與資源學(xué)院環(huán)境高技術(shù)青年論壇，廈門，2010.41煤炭是我國(guó)的主要能源年度消耗量（億噸）在一次能源中的比例200617.169.4%20202560%20503350%探明可采儲(chǔ)量分布Coal92.6%Oil5.35%Naturalgas2.05%我國(guó)可持續(xù)發(fā)展必須注重煤炭的高效潔凈利用2燃煤是我國(guó)主要的污染源80％硫(SO2),60％硝(NOX),60％煙塵,CO2等排放量（萬(wàn)噸）2000201020200100020003000400050006000NOX

2000201020200100020003000400050006000

SO2

3NOx排放全球分布情況4煙氣脫硝技術(shù)現(xiàn)狀NOx控制燃燒前燃燒中煙氣脫硝SCR法SNCR法催化分解法

等離子體法

吸收法吸附法

選擇性催化還原脫硝（SCR）技術(shù)是脫硝效率最高以及應(yīng)用最廣泛的消除煙氣NOx的工藝。

5選擇性催化還原脫硝（SCR）工藝6傳統(tǒng)高溫SCR煙氣脫硝工藝

催化劑體系：V2O5/TiO2

、WO3-V2O5/TiO2

和MoO3-V2O5/TiO2

低溫SCR操作溫度范圍353~523K脫硫除塵裝置之后傳統(tǒng)SCR操作溫度范圍623~673K能耗較大，易中毒脫硫除塵裝置之前7MnOxCrOxV2O5CuONiO等TiO2Al2O3活性炭沸石等對(duì)活性物質(zhì)的保護(hù)作用；硫酸根的穩(wěn)定度低溫SCR催化劑的開發(fā)是目前的研究重點(diǎn)低溫SCR研究現(xiàn)狀8低溫SCR研究現(xiàn)狀目前低溫SCR技術(shù)實(shí)現(xiàn)工業(yè)應(yīng)用的瓶頸

低溫下催化活性不夠理想：國(guó)內(nèi)電廠和工業(yè)鍋爐大部分采用濕法脫硫技術(shù)，脫硫后煙氣溫度均低于80?C，目前報(bào)道的低溫SCR催化劑在該溫度段活性不理想。催化劑抗硫性較差：脫硫后的煙氣中仍含有低濃度的SO2，對(duì)現(xiàn)有催化劑的毒化作用較明顯9ThevariationoftheNOconversionforthecatalystspreparedbydifferentmethodsPublishedin“JournalofHazardousMaterials145(2007)488–494”MnOx/TiO2ThevariationofNOconversionwithMnOx/TiO2catalystswithdifferentratioofMn/Tiat423K>90%10Fe-Mn/TiO2Publishedin“Environ.Sci.Technol.2007,41,5812-5817”55%95%11Fe-Mn/TiO2publishedby《AppliedcatalysisB:environmental》Mn2pXPSspectraTi2pXPSspectra

12publishedby《AppliedcatalysisB:environmental》Fe-Mn/TiO213Publishedby“Environ.Sci.Technol.2007,41,5812-5817”Fe-Mn/TiO2FTIRspectraofMn(0.4)/TiO2pretreatedbyexposuretoNO+O2followedbyexposuretoNH3FTIRspectraofFe（0.1)-Mn(0.4)/TiO2pretreatedbyexposuretoNO+O2followedbyexposuretoNH314Fe-Mn/TiO2

第二種反應(yīng)途徑：Publishedby“Environ.Sci.Technol.2007,41,5812-5817”15SO2氣氛下的反應(yīng)機(jī)理Publishedin

“J.Phys.Chem.C”.

16Ce-Mn/TiO2samplesBETSurfaceArea(m2/g)NOconversionat90℃NOconversionat110℃Mn/TiO253.4753.262.1CeMn1/TiO264.1878.0896.4CeMn2/TiO279.7788.7896.8CeMn3/TiO274.8181.4695.6Ce/TiO2115.8122.8727.8Publishedin

“Catalysiscommunications9(2008)2217-2220”.

17Ce-Mn/TiO2NOconversionofCemodifiedMnOx/TiO2catalystsatdifferenttemperatures

Publishedin

“Catalysiscommunications9(2008)2217-2220”.

18Ce-Mn/TiO2H2-TPRprofilesforvariouscatalysts.1-Ce(0)MnTi,2-Ce(0.07)MnTi,3-Ce(0.1)MnTi,4-Ce(0.2)MnTiPublishedin

“Catalysiscommunications9(2008)2217-2220”.

19Ce-Mn/TiO2NH3-TPDprofilesforCe(0)MnTiandCe(0.07)MnTi.

Publishedin

“Catalysiscommunications9(2008)2217-2220”.

20Ce-Mn/TiO2SCRactivitiesofMn/TiO2andCedopedMn/TiO2inthepresenceofSO2.Publishedin

“Catalysiscommunications10(2009)935-939”.

21SEMmicrographsoffreshandSO2poisonedcatalysts.(A)MnTi,(B)MnTi-S,(C)MnCeTi,(D)MnCeTi-S.Ce-Mn/TiO2Publishedin

“Catalysiscommunications10(2009)935-939”.

22Ce-Mn/TiO2TGandDSCcurvesofNH4HSO4depositedonMn/TiO2(A)andMn-Ce/TiO2

(B)catalysts.Waterevaporation

Waterevaporation

NH4HSO4

decompositionNH4HSO4

decompositionPublishedin

“Catalysiscommunications10(2009)935-939”.

23X-raydiffractionspectraofMn/TiO2andCedopedMn/TiO2beforeandafterSCRreaction(■-Anatase,●-Rutile,○-MnTiO3,□-Ti(SO4)2,▼-(NH4)2SO4).Ce-Mn/TiO2Publishedin

“Catalysiscommunications10(2009)935-939”.

24XPSspectraforundopedandCedopedMn/TiO2catalystsbeforeandafterSCRreactioninthepresenceofSO2(A:Mn2p,B:Ti2p).

Ce-Mn/TiO2Publishedin

“Catalysiscommunications10(2009)935-939”.

25Mn-Ce復(fù)合氧化物負(fù)載于不同載體Publishedin

“Chemosphere78(2010)1160-1166”.

26Mn-Ce復(fù)合氧化物負(fù)載于不同載體Publishedin

“Chemosphere78(2010)1160-1166”.

NH3-TPDprofilesofMn-Ce/TiO2andMn-Ce/Al2O327Mn-Ce復(fù)合氧化物負(fù)載于不同載體Publishedin

“Chemosphere78(2010)1160-1166”.

28Mn-Ce復(fù)合氧化物負(fù)載于不同載體Publishedin

“Chemosphere78(2010)1160-1166”.

反應(yīng)途徑2：反應(yīng)途徑3：反應(yīng)途徑1：常規(guī)的E-R型SCR反應(yīng)，已被R.T.Yang等人所報(bào)道29NOconversionsofMn-Ce/TiO2inthepresenceofSO2atvarioustemperatures.NOconversionsofvariousregeneratedMn-Ce/TiO2samples.

反應(yīng)溫度對(duì)SO2抗性的影響30NH3-TPDprofilesforvariousMn-Ce/TiO2

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