SnOx-CeO2-MnOx/球状活性炭催化剂低温选择性催化还原NO

王艳莉; 何自国; 詹亮; 葛梦

SnO_x-CeO₂-MnO_x/球状活性炭催化剂低温选择性催化还原NO

华东理工大学, 化学工程联合国家重点实验室, 上海 200237

基金项目: 国家自然科学基金(51472086,20806024,51002051);上海市自然科学基金(12ZR1407200).

详细信息

作者简介:
王艳莉,博士,副教授.E-mail:ylwang@ecust.edu.cn

通讯作者:
詹亮,教授.E-mail:zhanliang@ecust.edu.cn

中图分类号: TQ127.1⁺1
计量
- 文章访问数: 555
- HTML全文浏览量: 101
- PDF下载量: 623
- 被引次数: 0
出版历程
- 收稿日期: 2015-11-09
- 录用日期: 2016-01-05
- 修回日期: 2015-12-04
- 刊出日期: 2015-12-28

SnO_x-CeO₂-MnOx-loaded spherical activated carbons for the selective catalytic reduction of NO

State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Funds: National Science Foundation of China (51472086, 20806024, 51002051); Natural Science Foundation of Shanghai City (12ZR1407200).

摘要

摘要: 制备了系列锡氧化物改性SnO_x-CeO₂-MnO_x/球状活性炭(SAC)催化剂,研究了锡氧化物对催化剂脱硝活性的影响机制,并结合N₂吸附、XRD、XPS和NH₃-TPD等技术对催化剂物理化学性质进行表征。结果表明,向CeO₂-MnO_x/SAC中添加适量SnO_x后明显降低催化剂在低温区80~120 ℃的脱硝活性,但在200~280 ℃温度范围内Sn/Mn摩尔比为0.25的SnO_x-CeO₂-MnO_x/SAC催化剂对NO的转化率高于95.8%。添加适量SnO₂不仅不影响锰氧化物在载体表面的高分散性,而且可以改善CeO₂分散性;添加SnO₂提高了催化剂表面酸性,尤其是增加了催化剂表面中强酸位,有利于促进NH₃的吸附和活化脱氢,从而提高SnO_x-CeO₂-MnO_x/SAC较高温区SCR活性。
- 球状活性炭 /
- SnO_x /
- CeO₂-MnO_x /
- 选择性催化还原 /
- NO
Abstract: A series of SnO_x-CeO₂-MnO_x-loaded spherical activated carbons (SACs) with different Sn/Mn molar ratios were preparedas catalysts for the selective reduction of NO and the influence of the SnO_x contenton their catalytic activities was investigated. The physicochemical properties of the catalysts were characterized by nitrogen adsorption, X-ray diffraction, X-ray photoelectron spectroscopy and temperature-programmed NH₃ desorption. Results indicate that the addition of an appropriate amount of SnO_x to the CeO₂-MnO_x-loaded SACs significantly reduces NO reduction activity in the low temperature range 80-120 ℃. However, the NO conversion is higher than 95.8% in the temperature range 200-280 ℃ when the Sn/Mn ratio of the catalyst is 0.25. The SnO_x addition increasesthe acidity of the catalyst surface, especially the number of the medium-strong acid sites, which favors the adsorption anddehydrogenation of NH₃. An appropriate amount of SnO₂ increasesthe dispersion of CeO₂ on the support with out sacrificing the high dispersion of MnO_x. These factors jointly contribute to the increaseof NO reduction activity over the SnO_x-CeO₂-MnOx-loaded SACs at temperatures from 200 to 280 ℃.
- Spherical activated carbon /
- SnO_x /
- CeO₂-MnO_x /
- Selective catalytic reduction /
- NO

HTML全文

参考文献(22)

胡省三, 成玉琪. 走新型工业化道路,实现高效、安全、洁净、结构优化的煤炭工业[J]. 煤矿机电,2003, (5): 1-3. (HU Sheng-san,CHENG Yu-qi. Taking the Way of New Industrialization;realizing high-efficiency, safety, cleanness and structural optimization coal industry[J]. Colliery Mechanical & Electrical Technology, 2003, (5): 1-3.)

中华人民共和国环境保护部等. 第一次全国污染源普查公报[I]. 国家统计局,2010-02-11.

环保部. 将加大火电厂氮氧化物排放控制力度[N]. 中国环境报, 2010-02-08.

Wang Y L, Ge C Z, Zhan L, et al. MnO_x-CeO₂/activated carbon honeycomb catalyst for selective catalytic reduction of NO with NH₃ at low temperature[J]. Ind Eng Chem Res, 2012, 51(36): 11667-11673.

王艳莉, 李晓晓, 詹亮, 等. 金属助剂对蜂窝MnO_x-CeO₂/ACH催化剂低温脱硝行为的影响[J]. 燃料化学学报, 2014, 42(11): 1365-1371. (WANG Yan-li, LI Xiao-xiao, ZHAN Liang, et al. Effect of metal additives on the catalytic performance of MnO_x-CeO₂ supported on activated carbon honeycomb in NO removal at low temperature[J]. J Fuel Chem Techn, 2014, 42(11): 1365-1371.)

宋燕, 凌立成, 乔文明, 等. 沥青基球状活性炭气相吸脱附行为研究[J]. 离子交换与吸附, 2001, 17(6): 481-486. (SONG Yan, LING Li-cheng, QIAO Wen-ming, et al. Dynamic adsorption/desorption behavior of pitch based-spherical activated carbon[J]. Ion exchange and adsorption, 2001, 17(6): 481-486.)

刘朝军, 梁晓怿, 滕娜,等.气相氧化处理对沥青基球状活性炭表面化学及吸附性能的影响[J]. 新型炭材料, 2010, 25(6): 460-464. (LIU Chao-jun, LIANG Xiao-yi, TENG Na, et al. The surface chemistry of pitch-based spherical activated carbon (PSAC) and the effect of gas oxidation treatment on its adsorption performance[J]. New Carbon Materials, 2010, 25(6): 460-464.)

Wang Z, Wang Y L, Wang D J, et al. Low-temperature selective catalytic reduction of NO with Urea supported on pitch-based spherical activated carbon[J]. Ind Eng Chem Res, 2010, 49(14): 6317-6322.

邓珊珊, 李永红, 阿荣塔娜,等. MnO_x-SnO₂/TiO₂型催化剂低温NH₃选择性催化还原NO[J]. 化工进展, 2013, 32 (10): 2403-2408. (DENG Shan-shan, LI Yong-hong, A Rong ta-na, et al. Low-temperature selective catalytic reduction of NO with NH₃ over manganese and tin oxides supported on titania[J]. Chemical Industry and engineering Progress, 2013, 32 (10): 2403-2408.)

Zeng X R, Zhang R B, Xu X L, et al. Study on ceria-modified SnO₂ for CO and CH₄oxidation[J]. Journal of Rare Earths, 2012, 30 (10): 1013-1019.

Qi G, Yang R T, Chang R. MnO_x-CeO₂ mixed oxides prepared by co-precipitation for selective catalytic reduction of NO with NH₃ at low temperatures[J]. Appl Catal B, 2004, 51(2): 93-106.

Machida M, Uto M, Kurogi D, et al. Solid-gas ineration of nitrogen oxide adsorbed on MnO_x-CeO₂: A DRIFTS study[J]. J Mater Chem, 2001,11(3): 900-904.

Wang Y L, Li X X, Zhan L, et al. Effect of SO₂ on activated carbon honeycomb supported CeO₂-MnO_x catalyst for NO removal at low temperature[J]. Ind Eng Chem Res, 2015, 54(8): 2274-2278.

Yang S X, Zhu W P, Jiang Z P, et al. The surface properties and the activities in catalytic wet air oxidation over CeO₂-TiO₂ catalysts[J]. Appl Sur Sci, 2006, 252(24): 8499-8505.

Chen L, Li J H, Ge M, et al. Enhanced activity of tungsten modified CeO₂/TiO₂ for selective catalytic reduction of NO_x with ammonia[J]. Catal Today, 2010, 153(3): 77-83.

Zou Z Q, Meng M, Zha Y Q. Surfactant-assisted synthesis, characterizations, and catalytic oxidation mechanisms of the mesoporous MnO_x-CeO₂ and Pd/MnO_x-CeO₂ catalysts used for CO and C₃H₈ oxidation[J]. J Phys Chem C 2010, 114(1), 468-477.

Gu T T, Liu Y, Weng X L, et al. The enhanced performance of ceria with surface sulfation for selective catalyticreduction of NO by NH₃[J]. Catal Commun, 2010, 12(4): 310-313.

Xu X, Zhang R, Zeng X, et al. Effects of La, Ce, and Y oxides on SnO₂ catalysts for CO and CH₄ oxidation[J]. Chem Cat Chem, 2013, 5(7): 2025-2036.

Maffeis T G G, Owen G T, Penny M W, et al. Nano-crystalline SnO₂ gas sensor response to O₂ and CH₄ at elevated temperature investigated by XPS[J]. Surface Science, 2002, 520(1): 29-34.

Ramis G, Li Y, Busca G. Ammonia activation over catalysts for the selective catalytic reduction of NO_x and the selective catalytic oxidation of NH₃: An FT-IR study[J]. Catal Today, 1996, 28 (4): 373-380.

Busca G, Lietti L, Ramis G, et al. Chemical and mechanistic aspects of the selective catalytic reduction of NO_x by ammonia over oxide catalysts: A review[J]. Appl Catal B, 1998, 18(1-2): 1-36.

刘清雅, 刘振宇, 李成岳. NH₃在选择性催化还原NO过程中的吸附与活化[J].催化学报,2006, 27(7): 636-646. ( LIU Qing-ya, LIU Zhen-yu, LI Cheng-yue. Adsorption and activation of NH₃ during selective catalytic reduction of NO by NH₃[J]. Chinese Journal of Catalysis, 2006, 27(7): 636-646.)

施引文献

资源附件(0)

访问统计