·928 北京科技大学学报 第35卷 在100200℃的低温区间内10%Mn/TiO2-Zr02 ters,2001,72(1/2):115 (4:1)的活性优于10%1Mn/Ti02-Zr02(1:1)和 [7]Das D,Mishra H K,Parida K M,et al.Preparation, 10%Mn/Ti02.结合扫描电镜像可知，10%Mn/Ti02 physico-chemical characterization and catalytic activity of sulphated ZrO2-TiO2 mixed oxides.J Mol Catal A,2002, ZrO2(4:1)中Zr的掺杂促进了载体上活性组分的均 189(2):271 匀分布，从而促进反应物与活性组分的接触，进而 [8]Wu B J,Liu X Q,Wang X G,et al.Investigation and 提高催化剂的低温选择性催化还原活性. characterization on MnO/TiO2 for low-temperature se- (4)TiO2-ZrO2(4:1)负载Mn时，随着Mn负载 lective catalytic reduction of NO with NHs.J Combust 量（质量分数）由5%增大到20%，N0的转化率先增 Sci Technol,.2008,13(3):221 (吴碧君，刘晓勤，王述刚，等.MnOx/TiO2低温NH3选择 大后降低.最佳负载量为10%，该负载量下MnOz 性催化还原NOx的研究与表征.燃烧科学与技术，2008： 较好地分散在载体表面.该催化剂催化O的转化 13(3):221) 率在100℃时为61.7%，130℃时为92.6%，150℃ [9]Jiang X Y,Dong G H,Lou L P,et al.Catalytic activities 时为96.9%. of CuO/TiO2and CuO-ZrO2/TiO2 in NO+CO reaction (5)考察反应温度150℃时模拟烟气中加入体 J Mol Catal A,2004,218(2:187 [10]Zhang QL,Lin T,Li W,et al.Catalytic performance of 积分数为10%的水蒸气对10%Mn/Ti02-Zr02(4:1) MnO2-CeO2/Tio.25Zro.25Alo.5-01.75 monolith catalyst 活性的影响.通入水蒸气后NO转化率逐渐降低， for low temperature selective catalytic reduction of NO 大约在通入水蒸气1h后NO转化率降至最低且达 with NH3.Chin J Inorg Chem,2009,25(3):485 到稳定，由未通入时的96.9%降至88.7%，停止通 (张秋林，林涛，李伟，等.MnO2-Cc02/Ti0.25Zr0.25Al0.501.75 入水蒸气2h后N0转化率逐渐回升到96.0%.反 整体式催化剂的低温NH3选择性催化还原NO性能研究 无机化学学报，2009,25(3)：485) 应温度为200℃时10%Mn/Ti02-Zr02(4:1)的活性 [11]Mao D S,Lu G Z,Chen Q L.Preparation and physico- 基本不受H20的影响.可知H20对10%Mn/Ti02 chemical properties of titanium-zirconium mixed oxide ZrO2(4:1)的毒性作用是可逆的 and its application as a catalyst support.Chin J Catal, 2005,25(6):1 (毛东森，卢冠忠，陈庆龄.钛锆复合氧化物载体的制备、物 参考文献 化性质及在催化反应中的应用.催化学报，2005,25(6)：1) [12]Perez-Hernandez R,Gomez-Cortes A,Arenas-Alatorre J, [1]Fan E Y,Wei P B,Sui G R,et al.Preparation of Mn-Ce- et al.SCR of NO by CH4 on Pt/ZrO2-TiO2 sol-gel cata- O denitration catalyst and its regeneration performance. lysts.Catal Today,2005,107/108:149 Environ Sci Technol,2012,35(9):40 [13]Gao LL,Wang H Y,Ma J,et al.Preparation of Pt- (樊恩亚，卫平波，眭国荣，等.锰铈脱硝催化剂的制备及 Pd/TiO2-ZrO2 catalyst and study of its hydrodearomat- 其再生性能研究.环境科学与技术，2012,35(9)：40) ics performance.Chem Eng Oil Gas,2009,38(5):378 [2]Liu C X,Chen L,Li J H,et al.Enhancement of activity (高琳琳，王海彦，马骏，等.钛锆复合载体负载Pt-Pd and sulfur resistance of CeO2 supported on TiO2-SiO2for 催化剂的制备及加氢脱芳性能的研究.石油与天然气化工， the selective catalytic reduction of NO by NHg.Environ 2009,38(5):378) Sci Technol,2012,46(11):6182 [14]Yang J,Ferreira J M F.On the titania phase transition by [3]Penia DA,Uphade B S,Smirniotis P G.TiO2-supported zirconia additive in a sol-gel-derived powder.Mater Res metal oxide catalysts for low-temperature selective cat- BulL,1998.33(3):389 alytic reduction of NO with NH3:I.Evaluation and char- [15 Tang Y Q,Xie Y C,Gui LL.Study and application of acterization of first row transition metals.J Catal,2004, spontaneous monolayer dispersion of oxides and salts on 221(2):421 supports.Prog Nat Sci,1994,4(6):642 [4]Liu F D,He H,Zhang C B,et al.Mechanism of (唐有祺，谢有畅，桂琳琳.氧化物和盐类在载体表面的自 the selective catalytic reduction of NO with NHs over 发单层分散及其应用.自然科学进展.1994,4(6)：642) environmental-friendly iron titanate catalyst.Catal To- [16 Qi G,Yang R T.Low-temperature selective catalytic re- day,2011,175(1):18 duction of NO with NH3 over iron and manganese oxides (5]Machida M,Ikeda S,Kurogi D,et al.Low temperature supported on titania.Appl Catal B,2003,44(3):217 catalytic NO-H2 reactions over Pt/TiO2-ZrO2 in an ex- [17]Kijlstra W S,Daamen J C M L,Graaf J M,et al.In- cess oxygen.Appl Catal B,2001,35(2):107 hibiting and deactivating effects of water on the selec- [6]Maity S K,Rana M S,Bej S K,et al.TiO2-ZrO2mixed tive catalytic reduction of nitric oxide with ammonia over oxide as a support for hydrotreating catalyst.Catal Let- MnO/Al2O3.Appl Catal B,1996,7(3/4):337· 928 · 北 京 科 技 大 学 学 报 第 35 卷 在 100∼200 ℃的低温区间内 10%Mn/TiO2-ZrO2 (4:1) 的 活 性 优 于 10%Mn/TiO2-ZrO2(1:1) 和 10%Mn/TiO2. 结合扫描电镜像可知，10%Mn/TiO2- ZrO2(4:1) 中 Zr 的掺杂促进了载体上活性组分的均 匀分布，从而促进反应物与活性组分的接触，进而 提高催化剂的低温选择性催化还原活性. (4) TiO2-ZrO2(4:1) 负载 Mn 时，随着 Mn 负载 量 (质量分数) 由 5%增大到 20%，NO 的转化率先增 大后降低. 最佳负载量为 10%，该负载量下 MnOx 较好地分散在载体表面. 该催化剂催化 NO 的转化 率在 100 ℃时为 61.7%，130 ℃时为 92.6%，150 ℃ 时为 96.9%. (5) 考察反应温度 150 ℃时模拟烟气中加入体 积分数为 10%的水蒸气对 10%Mn/TiO2-ZrO2(4:1) 活性的影响. 通入水蒸气后 NO 转化率逐渐降低， 大约在通入水蒸气 1 h 后 NO 转化率降至最低且达 到稳定，由未通入时的 96.9%降至 88.7%，停止通 入水蒸气 2 h 后 NO 转化率逐渐回升到 96.0%. 反 应温度为 200 ℃时 10%Mn/TiO2-ZrO2(4:1) 的活性 基本不受 H2O 的影响. 可知 H2O 对 10%Mn/TiO2- ZrO2(4:1) 的毒性作用是可逆的. 参 考 文 献 [1] Fan E Y, Wei P B, Sui G R, et al. Preparation of Mn-Ce￾Ox denitration catalyst and its regeneration performance. Environ Sci Technol, 2012, 35(9): 40 (樊恩亚，卫平波，眭国荣，等. 锰铈脱硝催化剂的制备及 其再生性能研究. 环境科学与技术, 2012, 35(9): 40) [2] Liu C X, Chen L, Li J H, et al. Enhancement of activity and sulfur resistance of CeO2 supported on TiO2-SiO2for the selective catalytic reduction of NO by NH3. Environ Sci Technol, 2012, 46(11): 6182 [3] Pe˜na D A, Uphade B S, Smirniotis P G. 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Investigation and characterization on MnOx/TiO2 for low-temperature se￾lective catalytic reduction of NOx with NH3. J Combust Sci Technol, 2008, 13(3): 221 (吴碧君, 刘晓勤, 王述刚，等. MnOx/TiO2 低温 NH3 选择 性催化还原 NOx 的研究与表征. 燃烧科学与技术, 2008: 13(3):221) [9] Jiang X Y, Dong G H, Lou L P, et al. Catalytic activities of CuO/TiO2and CuO-ZrO2/TiO2 in NO+CO reaction. J Mol Catal A, 2004, 218(2): 187 [10] Zhang Q L, Lin T, Li W, et al. Catalytic performance of MnO2-CeO2/Ti0.25Zr0.25Al0.5-O1.75 monolith catalyst for low temperature selective catalytic reduction of NO with NH3. Chin J Inorg Chem, 2009, 25(3): 485 (张秋林, 林涛, 李伟, 等. MnO2-CeO2/Ti0.25Zr0.25Al0.5O1.75 整体式催化剂的低温 NH3 选择性催化还原 NO 性能研究. 无机化学学报, 2009, 25(3): 485) [11] Mao D S, Lu G Z, Chen Q L. Preparation and physico￾chemical properties of titanium-zirconium mixed oxide and its application as a catalyst support. 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