WO3/TiO2-ZrO2脱硝催化剂制备及其NH3活化机理

doi:10.11949/j.issn.0438-1157.20150277

化工学报 ›› 2015, Vol. 66 ›› Issue (10): 3903-3910.DOI: 10.11949/j.issn.0438-1157.20150277

• 催化、动力学与反应器 • 上一篇下一篇

WO₃/TiO₂-ZrO₂脱硝催化剂制备及其NH₃活化机理

王龙飞¹, 张亚平¹, 郭婉秋¹, 沈凯¹, 郑鹏飞², 杨林军¹

1 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;
2 郑州大学化工与能源学院, 河南郑州 450000

收稿日期:2015-03-09 修回日期:2015-05-19 出版日期:2015-10-05 发布日期:2015-10-05
通讯作者: 张亚平
基金资助:
江苏省自然科学基金项目(BK2012347);国家自然科学基金项目(51306034);国家重点基础研究发展计划项目(2013CB228505)。

Preparation of WO₃/TiO₂-ZrO₂ catalyst for selective catalytic reduction and mechanism of NH₃ activation

WANG Longfei¹, ZHANG Yaping¹, GUO Wanqiu¹, SHEN Kai¹, ZHENG Pengfei², YANG Linjun¹

1 Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, Jiangsu, China;
2 School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450000, Henan, China

Received:2015-03-09 Revised:2015-05-19 Online:2015-10-05 Published:2015-10-05
Supported by:
supported by the Natural Science Foundation of Jiangsu Province (BK2012347), the National Natural Science Foundation of China(51306034) and the National Basic Research Program of China (2013CB228505).

摘要/Abstract

摘要：

采用共沉淀法制备了WO₃/TiO₂-ZrO₂脱硝催化剂,并用固定床反应器进行活性评价,采用BET、XRD、TPD、氨气吸附漫反射FT-IR进行表征。结果显示,ZrO₂掺杂增强了TiO₂的Lewis酸性;负载WO₃之后,位于3.1~1.7 nm之间孔隙的稳定性显著增强;NH₃的吸附与活化分别由TiO₂-ZrO₂载体和WO₃完成;WO₃中W元素强大的电负性,促进了NH₃的N—H键由共价键向离子键过渡,进而导致了NH₃的活化。脱硝活性结果显示:当WO₃含量为9%(质量)时,催化剂脱硝活性最高,并在320~420℃的温度窗口保持94%以上。(9%)WO₃/TiO₂-ZrO₂具有更加稳定的孔隙结构(4.4~1.7 nm),表面Brønsted酸中心数量增加,Lewis酸中心的强度和酸量增加的幅度最大,NH₃-SCR过程中的活性中间产物NH₂的吸收峰更加明显,这些特征可能是其脱硝活性最好的原因。

关键词: 催化剂, 载体, 原位氨气吸附漫反射红外, 三氧化钨, 活化

Abstract:

(x)WO₃/TiO₂-ZrO₂ catalysts with different WO₃ content were prepared by the impregnation method and the catalytic performance for the selective catalytic reduction of NO_x with NH₃ (NH₃-SCR) was investigated in a fixed-bed stainless steel reactor. The catalysts were characterized by BET, XRD, NH₃-TPD and in situ DRIFTS analysis of NH₃ adsorption, and revealed the change of the structural property and acidic capacity. The characterization results showed that WO₃ was in a well-dispersed state and WO₃ addition enhanced the thermal stability of catalysts obviously. The adsorption and activation of NH₃ were caused by TiO₂-ZrO₂ and WO₃, respectively. It was found that W displayed a huge electronegativity and prompted the transfer of the N—H bond of NH₃ from covalent bond to ionic bond, which could incur the NH₃ activation. The results of catalytic activity indicated that the catalyst with 9%(mass) WO₃ content exhibited 94% NO conversion within the wide temperature range of 320℃ to 420℃. (9%)WO₃/TiO₂-ZrO₂ possessed comparatively higher intensity of Lewis acidity and larger amount of Brønsted acidity as well as more stable pore structure (4.4—1.7 nm). Besides, the absorption peak of the active intermediate species NH₂ was more obvious. All these characters probably accounted for its better catalytic performance.

Key words: catalyst, support, in situ DRIFTS analysis of NH₃ adsorption, tungsten, activation

中图分类号:

O643.36

王龙飞, 张亚平, 郭婉秋, 沈凯, 郑鹏飞, 杨林军. WO₃/TiO₂-ZrO₂脱硝催化剂制备及其NH₃活化机理[J]. 化工学报, 2015, 66(10): 3903-3910.

WANG Longfei, ZHANG Yaping, GUO Wanqiu, SHEN Kai, ZHENG Pengfei, YANG Linjun. Preparation of WO₃/TiO₂-ZrO₂ catalyst for selective catalytic reduction and mechanism of NH₃ activation[J]. CIESC Journal, 2015, 66(10): 3903-3910.

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WO₃/TiO₂-ZrO₂脱硝催化剂制备及其NH₃活化机理

Preparation of WO₃/TiO₂-ZrO₂ catalyst for selective catalytic reduction and mechanism of NH₃ activation

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