WO3掺杂对V2O5/TiO2-SnO2催化剂NH3选择性催化还原NOx的影响

doi:10.16085/j.issn.1000-6613.2017.03.024

化工进展 ›› 2017, Vol. 36 ›› Issue (03): 951-956.DOI: 10.16085/j.issn.1000-6613.2017.03.024

WO₃掺杂对V₂O₅/TiO₂-SnO₂催化剂NH₃选择性催化还原NO_x的影响

廖永进¹, 张亚平², 朱一闻², 余岳溪¹, 王龙飞²

1 广东电网有限责任公司电力科学研究院, 广东广州 510080;
2 东南大学能源与环境学院, 能源热转换及其过程测控教育部重点实验室, 江苏南京 210096

收稿日期:2016-08-02 修回日期:2016-11-14 出版日期:2017-03-05 发布日期:2017-03-05
通讯作者: 张亚平,副教授,从事大气污染控制方面的研究。
作者简介:廖永进(1971-),男,工学硕士,教授级高级工程师,主要从事火电厂脱硫、脱硝系统的优化与研究工作。E-mail:lyj23455@163.com。
基金资助:
国家自然科学基金（51306034）、江苏省重点研发计划（BE2015677）及国家重点基础研究发展计划（2013CB228505）项目。

Influence of WO₃ doping on properties of V₂O₅/TiO₂-SnO₂ catalysts for selective catalytic reduction of NO_x by NH₃

LIAO Yongjin¹, ZHANG Yaping², ZHU Yiwen², YU Yuexi¹, WANG Longfei²

1 Electric Power Research Institute of Guangdong Power Grid Co., Ltd., Guangzhou 510080, Guangdong, China;
2 Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, Jiangsu, China

Received:2016-08-02 Revised:2016-11-14 Online:2017-03-05 Published:2017-03-05

摘要/Abstract

摘要：

采用共沉淀法制备TiO₂-SnO₂固溶体，浸渍法负载WO₃和V₂O₅得到一系列V₂O₅-（x%）WO₃/TiO₂-SnO₂脱硝催化剂。利用比表面积测定（BET）、X射线衍射（XRD）、原位漫反射傅里叶变换红外光谱（in situ DRIFTS）、程序升温脱附（NH₃-TPD）、高分辨率透射电子显微镜（HRTEM）等表征技术，结合脱硝性能测试，研究催化剂的表面特性、微观结构及脱硝活性。结果表明：V₂O₅-12% WO₃/TiO₂-SnO₂催化剂在250～400℃的温度窗口具有95%的NO_x转换率；随着WO₃负载量增加，催化剂比表面积有所减小；WO₃以无定形态存在于催化剂表面；催化剂表面Brønsted酸中心强度随WO₃负载量增加逐渐增大，这是V₂O₅-（12%）WO₃/TiO₂-SnO₂催化剂具有最佳脱硝活性的主要原因。

关键词: 三氧化钨, 五氧化二钒, TiO₂-SnO₂固溶体, 载体, 选择催化还原, 催化剂

Abstract:

TiO₂-SnO₂ solid solution was prepared by a co-precipitation method and V₂O₅-(x%)WO₃/TiO₂-SnO₂ catalysts were prepared by the impregnation method. The physicochemical properties were investigated by BET specific surface area,X-ray diffraction(XRD),in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS), NH₃ temperature-programmed desorption (NH₃-TPD) and high-resolution transmission electron microscopy(HRTEM). Their catalytic performance for the selective catalytic reduction of NO_x was also tested. The results indicate that the catalyst with 12% WO₃ exhibits 95% NO conversion within the wide temperature range of 250~400℃. The characterization results show that the specific surface area decreases with the load of WO₃ which is in a well-dispersed state. The strength of Brønsted acid sites are intensified after adding WO₃ which could account for the best catalytic performance of the catalyst V₂O₅-12%WO₃/TiO₂-SnO₂.

Key words: WO₃, V₂O₅, TiO₂-SnO₂ solid solution, support, selective catalytic reduction(SCR), catalyst

中图分类号:

O643.36

廖永进, 张亚平, 朱一闻, 余岳溪, 王龙飞. WO₃掺杂对V₂O₅/TiO₂-SnO₂催化剂NH₃选择性催化还原NO_x的影响[J]. 化工进展, 2017, 36(03): 951-956.

LIAO Yongjin, ZHANG Yaping, ZHU Yiwen, YU Yuexi, WANG Longfei. Influence of WO₃ doping on properties of V₂O₅/TiO₂-SnO₂ catalysts for selective catalytic reduction of NO_x by NH₃[J]. Chemical Industry and Engineering Progress, 2017, 36(03): 951-956.

参考文献

[1] 中国环境保护协会脱硫脱硝委员会. 脱硫脱硝行业2014年发展综述[J].中国环保产业,2015,12:4-23. Desulfurization and Denitration Committee of CAEPI. China development report on desulfurization and denitration industries in 2014[J]. China Environmental Protection Industry,2015,12:4-23.
[2] 中国环境保护产业协会脱硫脱硝委员会.我国脱硫脱硝行业2012年发展综述[J].中国环保产业,2013(7):8-20. Desulfurization and Denitration Committee of CAEPI. Development report on China desulfurization and denitration industries in 2012[J].China Environmental Protection Industry,2013(7):8-20.
[3] GB 13223-2011.火电厂大气污染物排放标准[S].北京:中国环境科学出版社,2011. GB 13223-2011.Emission standard of air pollutants for thermal power plants[S].Beijing:China Environmental Science Press,2011.
[4] 谭青,冯雅晨.我国烟气脱硝行业现状与前景及SCR脱硝催化剂的研究进展[J].化工进展,2011,30(s1):709-713. TAN Q,FENG Y C.Prensent status and perspective of China's flue gas denitration industry and research of SCR catalysts[J].Chemical Indusrty and Engineering Progress,2011,30(s1):709-713.
[5] LI K,WANG Y,WANG S,et al. A comparative study of CuO/TiO₂-SnO₂,CuO/TiO₂ and CuO/SnO₂ catalysts for low-temperature CO oxidation[J].Journal of Natural Gas Chemistry,2009,18(4):449-452.
[6] 贾彦荣,蒋晓原,郑小明. CuO/Sn_0.8Ti_0.2O₂催化剂的表征及对NO+CO反应活性研究[J].无机化学学报, 2006,22(3):525-532. JIA Y R,JIANG X Y,ZHENG X M.CuO/Sn_0.8Ti_0.2O₂ catalyst:characterization catalytic performance in NO + CO reaction[J]. Chinese Journal of Inorganic Chemistry,2006,22(3):525-532.
[7] 顾卫荣,周明吉,马薇,等.选择性催化还原脱硝催化剂的研究进展[J].化工进展,2012,31(7):1493-1500. GU W R,ZHOU M J,MA W,et al.Research progress on selective catalytic reduction de-NO_x catalysts[J]. Chemical Indusrty and Engineering Progress,2012,31(7):1493-1500.
[8] NOVA I,LIETTI L,TRONCONI E,et al. Dynamics of SCR reaction over a TiO₂ supported vanadia-tungsta commercial catalyst[J].Catalysis Today,2000,60(1):73-82.
[9] WU Z B,JIN R B,WANG H Q,et al. Effect of ceria doping on SO₂ resistance of Mn/TiO₂ for selective catalytic reduction of NO with NH₃ at low temperature[J].Catalysis Communications,2009,10(6):935-939
[10] 闫志勇,胡建飞,徐鸿.SCR烟气脱硝催化剂V₂O₅-WO₃/TiO₂性能研究[J].中国计量学院学报,2011,22(1):68-72. YAN Z Y,HU J F,XU H.Preparation of V₂O₅-WO₃/TiO₂ catalyst and properties of reduction NO_x[J].Journal of China University of Metrology,2011,22(1):68-72.
[11] DOS SANTOS V C,WILSON K,LEE A F,et al.Physicochemical properties of WOx/ZrO₂ catalysts for palmitic acid esterification[J]. Applied Catalysis B:Environmental,2015,162:75-84.
[12] FOO R,VAZHNOVA T,LUKYANOV D B,et al.Formation of reactive Lewis acid sites on Fe/WO₃-ZrO₂ catalysts for higher temperature SCR applications[J]. Aplied Catalysis B:Environmental, 2015,162:174-179.
[13] 李娟,张亚平,王文选,等.TiO₂-SnO₂基钨催化剂的表面性质和NH₃吸附特性及脱硝机理[J].东南大学学报(自然科学版),2016(1):92-99. JI J,ZHANG Y P,WANG W X,et al.Surface properties,NH₃ adsorption characteristic and NO_x removal mechanism of TiO₂-SnO₂ supported WO₃ catalysts[J].Journal of Southeast University(Natural Science Edition),2016(1):92-99.
[14] ZHANG L,LI L,CAO Y,et al.Promotional effect of doping SnO₂ into TiO₂ over a CeO₂/TiO₂ catalyst for selective catalytic reduction of NO by NH₃[J].Catalysis Science & Technology,2015,5(4):2188-2196.
[15] 朱崇兵,金保升,仲兆平,等.WO₃对于V₂O₅/TiO₂脱硝催化剂的抗中毒作用[J].锅炉技术,2009,40(1):63-67. ZHU C B,JIN B S,ZHONG Z P,et al.Anti-poisoning effect of WO₃ on V₂O₅/TiO₂ catalysts[J]. Boiler Technology,2009,40(1):63-67.
[16] ZHANG Y P,WANG X L,SHENG K,et al.WO₃ modification of MnO_x/TiO₂ catalysts for low temperature selective catalytic reduction of NO with ammonia[J].Chinese Journal of Catalysis,2012,33(9):1523-1531.
[17] 张亚平,汪小蕾,郑晓红,等.WO₃掺杂对MnO_x/TiO₂催化剂低温选择性催化还原NO_x的影响[J].中南大学学报:自然科学版, 2013,44(12):5165-5172. ZHANG Y P,WANG X L,ZHENG X H,et al.Influence of WO₃ doping on properties of MnO_x/TiO₂ catalyst for low-temperature selective catalytic reduction of NO_x by NH₃[J].Journal of Central South University(Science and Technology),2013,44(12):5165-5172.
[18] 余长林,杨凯,舒庆,等.WO₃/ZnO复合光催化剂的制备及其光催化性能[J].催化学报,2011,32(4):51-61. YU C L,YANG K,SHU Q,et al.Preparation of WO₃/ZnO composite photocatalyst and its photocatalytic performance[J].Chinese Journal of Catalysis,2011,32(4):51-61.
[19] 辛勤,罗孟飞.现代催化研究方法[M].北京:科学出版社,2009:83-88. XIN Q,LUO M F.Modern catalytic research methods[M].Beijing:Science Press,2009:83-88.
[20] RAMIS G,BUSCA G,BREGANI F,et al.Fourier transform-infrared study of the adsorption and coadsorption of nitric oxide,nitrogen dioxide and ammonia on vanadia-titania and mechanism of selective catalytic reduction[J].Applied Catalysis,1990,64:259-278.
[21] PINAEVA L G,SUKNEV A P,BUDNEVA A A,et al.On the role of oxygen in the reaction of NO reduction by NH₃ over monolayer V₂O₅/TiO₂ catalyst[J].Journal of Molecular Catalysis A:Chemical, 1996,112(1):115-124.
[22] SUN C Z,DONG L H,YU W J,et al.Promotion effect of tungsten oxide on SCR of NO with NH₃ for the V₂O₅-WO₃/Ti_0.5Sn_0.5O₂ catalyst:experiments combined with DFT calculations[J].Journal of Molecular Catalysis A,Chemical,2011,346(1):29-38.
[23] FAN Y,BAO X,WANG H,et al.A surfactant-assisted hydrothermal deposition method for preparing highly dispersed W/γ-Al₂O₃ hydrodenitrogenation catalyst[J].Journal of Catalysis,2007,245(2):477-481.
[24] 郭婉秋,张亚平,王文选,等.基于钛锡载体的SCR低温脱硝催化剂的表面性质研究[J].燃料化学学报,2015,11:1393-1401. GUO W Q,ZHANG Y P,WANG W X,et al.Study on the surface properties of TiO₂-SnO₂ supported catalysts for low temperature selective catalytic reduction of NO_x[J].Journal of Fuel Chemistry and Technology,2015,11:1393-1401.

WO₃掺杂对V₂O₅/TiO₂-SnO₂催化剂NH₃选择性催化还原NO_x的影响

Influence of WO₃ doping on properties of V₂O₅/TiO₂-SnO₂ catalysts for selective catalytic reduction of NO_x by NH₃

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