利用溶胶-凝胶法,采用三种酸性金属氧化物(氧化铌、氧化钨和氧化钼)对锰铈复合氧化物催化剂进行了改性.测试了催化剂的氮氧化物选择性催化还原(SCR)活性,以筛选对应不同温度窗口的合适酸性氧化物改性剂.同时评价了催化剂的NO氧化和NH3氧化活性.利用X射线衍射、BET比表面积测试、H2程序升温还原、NH3/NOx程序升温脱附和NH3/NOx吸附红外光谱等手段对催化剂进行了表征. MnOx-CeO2催化剂表现出良好的低温(100-150°C)活性.酸性金属氧化物的添加削弱了催化剂的氧化还原特性,从而抑制了NH3的活化和NO2辅助的快速SCR反应.与此同时,相对高温(250-350°C)区NH3的氧化也受到了抑制, B酸和L酸上的NH3吸附得以增强.因此,催化剂的SCR脱硝温度窗口向高温移动,改性效果Nb2O5< WO3< MoO3.
A MnOx-CeO2 catalyst was modified with various acidic metal oxides (Nb2O5, WO3, and MoO3) using a sol-gel method. The activities of the obtained catalysts were measured for the selective catalytic reduction (SCR) of NOx with NH3 to screen suitable acidic metal oxides for different temperature windows. The catalytic activities for NO and NH3 oxidation were also evaluated. The catalysts were characterized by X-ray diffraction, N2 adsorption, H2 temperature-programmed reduction, NH3/NOx temperature-programmed desorption analyses, and infrared spectroscopic measurements of NH3/NOx adsorption. The MnOx-CeO2 catalyst exhibited the greatest low-temperature (100-150°C) activity. The addition of acidic metal oxides weakened the redox properties of the catalyst, resulting in inhibition of the partial oxidation of the adsorbed NH3 and NO2-assisted fast SCR reactions. Meanwhile, the oxidation of NH3 at relatively high temperatures (250-350°C) was suppressed, and the adsorption of NH3 on Br?nsted and Lewis acid sites was strengthened. Consequently, the tem-perature window of SCR reaction shifted to higher temperatures in the order Nb2O5
参考文献
[1] | Busca G;Lietti L;Ramis G;Berti F .[J].Applied Catalysis B:Environmental,1998,18:1. |
[2] | Heck R M .[J].Catalysis Today,1999,53:519. |
[3] | Liu ZM;Woo SI .Recent advances in catalytic DeNO(X) science and technology[J].Catalysis Reviews. Science and Engineering,2006(1):43-89. |
[4] | Li J H;Chang H Z;Ma L;Hao J M Yang R T .[J].Catalysis Today,2011,175:147. |
[5] | Gilot P;Guyon M;Stanmore B R .[J].FUEL,1997,76:507. |
[6] | Brandenberger S;Krocher O;Tissler A;Althoff R .The State of the Art in Selective Catalytic Reduction of NOx by Ammonia Using Metal-Exchanged Zeolite Catalysts[J].Catalysis Reviews. Science and Engineering,2008(4):492-531. |
[7] | Burch R.;Breen JP.;Meunier FC. .A review of the selective reduction of NOx, with hydrocarbons under lean-burn conditions with non-zeolitic oxide and platinum group metal catalysts [Review][J].Applied Catalysis, B. Environmental: An International Journal Devoted to Catalytic Science and Its Applications,2002(4):283-303. |
[8] | Zhang L;Pierce J;Leung V L;Wang D Epling W S .[J].J Phys Chem C,2013,117:8282. |
[9] | Qi G S;Yang R T .[J].Journal of Catalysis,2003,217:434. |
[10] | Qi G S;Yang R T .[J].Journal of Physical Chemistry B,2004,108:15738. |
[11] | Qi G S;Yang R T;Chang R .[J].Applied Catalysis B:Environmental,2004,51:93. |
[12] | Casapu M;Kr?cher O;Elsener M .[J].Applied Catalysis B:Environmental,2009,88:413. |
[13] | Casapu M;Kr?cher O;Mehring M;Nachtegaal M Borca C Har-fouche M Grolimund D .[J].J Phys Chem C,2010,114:9791. |
[14] | Zhang Q L;Qiu C T;Xu H D;Lin T Gong M C Chen Y Q .[J].CATALYSIS COMMUNICATIONS,2011,16:20. |
[15] | Xu H D;Zhang Q L;Qiu C T;Lin T Gong M C Chen Y Q .[J].Chemical engineering science,2012,76:120. |
[16] | Jin R B;Liu Y;Wu Z B;Wang H Q Gu T T .[J].CHEMOSPHERE,2010,78:1160. |
[17] | Shen B X;Zhang X P;Ma H Q;Yao Y Liu T .[J].Journal of Environmental Sciences,2013,25:791. |
[18] | Chang H Z;Chen X Y;Li J H;Ma L Wang C Z Liu C X Schwank J W Hao J M .[J].Environmental Science and Technology,2013,47:5294. |
[19] | Gu T T;Jin R B;Liu Y;Liu H F Weng X L Wu Z B .[J].Applied Catalysis B:Environmental,2013,129:30. |
[20] | Shen B X;Liu T;Zhao N;Yang X Y Deng L D .[J].Journal of Environmental Sciences,2010,22:1447. |
[21] | 李丽,王丽珊,盘思伟,韦正乐,黄碧纯.Ce掺杂对碳纳米管负载Mn催化剂结构及SCR反应性能的影响[J].催化学报,2013(06):1087-1097. |
[22] | Wu X D;Liu S;Weng D;Lin F Ran R .[J].Journal of Hazardous Materials,2011,187:283. |
[23] | Delimaris D;Ioannides T .[J].Applied Catalysis B:Environmental,2008,84:303. |
[24] | Pengpanich S;Meeyoo V;Rirksomboon T;Schwank J .[J].Journal of Natural Gas Chemistry,2007,16:227. |
[25] | Shi C;Zhu AM;Yang XF;Au CT .On the catalytic nature of VN, Mo2N, and W2N nitrides for NO reduction with hydrogen[J].Applied Catalysis, A. General: An International Journal Devoted to Catalytic Science and Its Applications,2004(1/2):223-230. |
[26] | Kijlstra WS.;Poels EK.;Bliek A.;Brands DS. .MECHANISM OF THE SELECTIVE CATALYTIC REDUCTION OF NO BY NH3 OVER MNOX/AL2O3 .1. ADSORPTION AND DESORPTION OF THE SINGLE REACTION COMPONENTS[J].Journal of Catalysis,1997(1):208-218. |
[27] | Chen L;Li J H;Ge M F .[J].Environmental Science and Technology,2010,44:9590. |
[28] | Chen L;Li J H;Ge M F;Zhu R H .[J].Catalysis Today,2010,153:77. |
[29] | Schraml-Marth M;Wokaun A;Baiker A .[J].Journal of Catalysis,1992,138:306. |
[30] | Ramis G;Busca G;Bregani F;Forzatti P .[J].Applied Catalysis,1990,64:259. |
[31] | Eigenmann F;Maciejewski M;Baiker A .[J].Applied Catalysis B:Environmental,2006,62:311. |
[32] | Xu L;Li X S;Crocker M;Zhang Z S Zhu A M Shi C .[J].Journal of Molecular Catalysis A:Chemical,2013,378:82. |
[33] | 陈婷,管斌,林赫,朱霖.原位漫反射傅里叶变换红外光谱研究锰铁基催化剂上低温选择性催化还原反应机理[J].催化学报,2014(03):294-301. |
- 下载量()
- 访问量()
- 您的评分:
-
10%
-
20%
-
30%
-
40%
-
50%