1,低温SCR烟气脱硝催化剂开发,刘 越,浙江大学环境与资源学院,环境高技术青年论坛 ，厦门， 2010.4,2,煤炭是我国的主要能源,探明可采储量分布,Coal 92.6%,Oil 5.35%,Natural gas 2.05%,我国可持续发展必须注重煤炭的高效洁净利用,3,燃煤是我国主要的污染源,80硫 (SO2), 60硝 (NOX), 60烟尘, CO2 等,排放量（万吨）,2000,2010,2020,0,1000,2000,3000,4000,5000,6000,NO,X,2000,2010,2020,0,1000,2000,3000,4000,5000,6000,SO,2,4,NOx排放全球分布情况,5,烟气脱硝技术现状,6,选择性催化还原脱硝（SCR）工艺,7,传统高温SCR烟气脱硝工艺,催化剂体系：V2O5/TiO2 、WO3-V2O5/TiO2 和MoO3-V2O5/TiO2,低温SCR 操作温度范围 353523 K,脱硫除尘装置之后,传统SCR操作温度范围 623673 K,能耗较大，易中毒,脱硫除尘装置之前,8,MnOx CrOx V2O5 CuO NiO 等,TiO2 Al2O3 活性炭 沸石 等,低温SCR催化剂的开发是目前的研究重点,低温SCR研究现状,9,低温SCR研究现状,目前低温SCR技术实现工业应用的瓶颈 低温下催化活性不够理想： 国内电厂和工业锅炉大部分采用湿法脱硫技术，脱硫后烟气温度均低于80C，目前报道的低温SCR催化剂在该温度段活性不理想。 催化剂抗硫性较差： 脱硫后的烟气中仍含有低浓度的SO2，对现有催化剂的毒化作用较明显,10,The variation of the NO conversion for the catalysts prepared by different methods,Published in “Journal of Hazardous Materials 145 (2007) 488494”,MnOx/TiO2,The variation of NO conversion with MnOx/TiO2 catalysts with different ratio of Mn/Ti at 423 K,90%,11,Fe-Mn/TiO2,Published in “Environ. Sci. Technol. 2007, 41, 5812-5817”,55%,95%,12,Fe-Mn/TiO2,published byApplied catalysis B : environmental,Mn 2p XPS spectra,Ti 2p XPS spectra,13,published by Applied catalysis B : environmental,Fe-Mn/TiO2,14,Published by “Environ. Sci. Technol. 2007, 41, 5812-5817”,Fe-Mn/TiO2,FTIR spectra of Mn(0.4)/TiO2 pretreated by exposure to NO + O2 followed by exposure to NH3,FTIR spectra of Fe（0.1)- Mn(0.4)/TiO2 pretreated by exposure to NO + O2 followed by exposure to NH3,15,Fe-Mn/TiO2,第二种反应途径：,Published by “Environ. Sci. Technol. 2007, 41, 5812-5817”,16,SO2气氛下的反应机理,Published in “J. Phys. Chem. C”.,17,Ce-Mn/TiO2,Published in “Catalysis communications 9 (2008) 2217-2220”.,18,Ce-Mn/TiO2,NO conversion of Ce modified MnOx/TiO2 catalysts at different temperatures,Published in “Catalysis communications 9 (2008) 2217-2220”.,19,Ce-Mn/TiO2,H2-TPR profiles for various catalysts. 1-Ce(0)MnTi, 2-Ce(0.07)MnTi, 3-Ce(0.1)MnTi, 4- Ce(0.2)MnTi,Published in “Catalysis communications 9 (2008) 2217-2220”.,20,Ce-Mn/TiO2,NH3-TPD profiles for Ce(0)MnTi and Ce(0.07)MnTi.,Published in “Catalysis communications 9 (2008) 2217-2220”.,21,Ce-Mn/TiO2,SCR activities of Mn/TiO2 and Ce doped Mn/TiO2 in the presence of SO2.,Published in “Catalysis communications 10 (2009) 935-939”.,22,SEM micrographs of fresh and SO2 poisoned catalysts. (A) MnTi, (B) MnTi-S, (C) MnCeTi, (D) MnCeTi-S.,Ce-Mn/TiO2,Published in “Catalysis communications 10 (2009) 935-939”.,23,Ce-Mn/TiO2,TG and DSC curves of NH4HSO4 deposited on Mn/TiO2 (A) and Mn-Ce/TiO2 (B) catalysts.,Water evaporation,Water evaporation,NH4HSO4 decomposition,NH4HSO4 decomposition,Published in “Catalysis communications 10 (2009) 935-939”.,24,X-ray diffraction spectra of Mn/TiO2 and Ce doped Mn/TiO2 before and after SCR reaction (-Anatase, -Rutile, -MnTiO3, - Ti(SO4)2, -(NH4)2SO4).,Ce-Mn/TiO2,Published in “Catalysis communications 10 (2009) 935-939”.,25,XPS spectra for undoped and Ce doped Mn/TiO2 catalysts before and after SCR reaction in the presence of SO2 (A: Mn 2p, B: Ti 2p).,Ce-Mn/TiO2,Published in “Catalysis communications 10 (2009) 935-939”.,26,Mn-Ce复合氧化物负载于不同载体,Published in “Chemosphere 78 (2010) 1160-1166”.,27,Mn-Ce复合氧化物负载于不同载体,Published in “Chemosphere 78 (2010) 1160-1166”.,NH3-TPD profiles of Mn-Ce/TiO2 and Mn-Ce/Al2O3,28,Mn-Ce复合氧化物负载于不同载体,Published in “Chemosphere 78 (2010) 1160-1166”.,29,Mn-Ce复合氧化物负载于不同载体,Published in “Chemosphere 78 (2010) 1160-1166”.,反应途径2：,反应途径3：,反应途径1：常规的E-R型SCR反应，已被R.T. Yang等人所报道,30,NO conversions of Mn-Ce/TiO2 in the presence of SO2 at various temperatures.,NO conversions of various regenerated Mn-Ce/TiO2 samples.,反应温度对SO2抗性的影响,31,NH3-TPD profiles for various Mn-Ce/TiO2 samples.,NO-TPD profiles for various Mn-Ce/TiO2 samples.,反应温度对SO2抗性的影响,32,今后的工作计划,催化剂抗性的进一步改进降低硫铵盐在催化剂表面的生成和沉积速率 蜂窝状整体催化剂的制备研究拥有较小的床层阻力、较大的几何比表面积和较高的机械强度与热稳定性 催化剂再生工艺研究使失活后的低温SCR催化剂能够重复利用，节省工艺运行成本,33,谢谢大家！,