基于NH3-SCR反应铜基小孔分子筛催化剂Na中毒对比研究

doi:10.11949/0438-1157.20200408

化工学报 ›› 2020, Vol. 71 ›› Issue (12): 5551-5560.DOI: 10.11949/0438-1157.20200408

• 催化、动力学与反应器 • 上一篇下一篇

基于NH₃-SCR反应铜基小孔分子筛催化剂Na中毒对比研究

王晨^1,²(),陈泽翔¹(),王建强¹,沈美庆^1,³,王军¹()

^1.天津大学化工学院，天津 300350
^2.中北大学环境与安全工程学院，山西太原 030051
^3.天津大学内燃机国家重点实验室，天津 300072

收稿日期:2020-04-17 修回日期:2020-07-12 出版日期:2020-12-05 发布日期:2020-12-05
通讯作者: 王军
作者简介:王晨（1987—），男，博士，讲师，chenwang@tju.edu.cn|陈泽翔（1992—），男，博士研究生，tjuczx@tju.edu.cn
基金资助:
国家重点研发计划项目(2017YFC0211302);国家自然科学基金青年基金项目(21908207);中国博士后科学基金项目(2020M670659)

Comparison study of Na poisoning effect on copper-based chabazite micropore catalysts for NH₃-SCR reaction

WANG Chen^1,²(),CHEN Zexiang¹(),WANG Jianqiang¹,SHEN Meiqing^1,³,WANG Jun¹()

^1.School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
^2.School of Environmental and Safety Engineering, North University of China, Taiyuan 030051, Shanxi, China
^3.State Key Laboratory of Engines, Tianjin University, Tianjin 300072, China

Received:2020-04-17 Revised:2020-07-12 Online:2020-12-05 Published:2020-12-05
Contact: WANG Jun

摘要/Abstract

摘要：

以浸渍法模拟碱金属中毒NH₃-SCR催化剂过程，制备不同Na含量（质量分数）的铜基小孔分子筛Cu/SSZ-13和Cu/SAPO-34，对比研究了二者的碱金属中毒机理。结果表明，外引Na离子均可严重影响两种催化剂的NH₃-SCR催化活性，造成催化剂的晶相结构坍塌，酸性量减少，活性物种减少。不同的是，Na引入量较低（<1.82%）时，Cu/SAPO-34比Cu/SSZ-13具有更强的Na离子耐受性，而当Na含量高于3.48%时，Cu/SAPO-34几乎完全丧失NH₃-SCR催化活性。通过催化剂的结构表征（BET、XRD和SEM）和酸性位表征（DRIFTS、NH₃-TPD和H₂-TPR），研究表明随着Na中毒程度的加深，Cu/SSZ-13的结构破坏是渐变式的，而Cu/SAPO-34的结构破坏是突变式的；Na中毒的机理研究表明，酸性位的减少是Cu/SSZ-13的SCR活性下降的主导原因，结构坍塌是Cu/SAPO-34的SCR活性下降的主导原因。

关键词: 选择性催化还原, 碱金属, 分子筛, 催化剂, 氮氧化物, 中毒机理

Abstract:

Using wet impregnation method to mimic alkali metal poison of ammonia-selective catalytic reduction (NH₃-SCR) catalysts, Cu-based micropore zeolites Cu/SSZ-13 and Cu/SAPO-34 with different Na contents(mass fraction) were prepared, and the Na poisoning mechanism on them was studied. The results show that the externally introduced Na ions can severely affect the NH₃-SCR catalytic activity of the two catalysts, resulting in the collapse of the crystal structure of the catalyst, the decrease of acidity and the reduction of active species. In detail, when Na content was less than 1.82%, Cu/SAPO-34 has higher resistance of Na ions than Cu/SZZ-13; while when Na> 3.48%, Cu/SAPO-34 catalysts almost deactivated thoroughly. By structural characterization (BET, XRD and SEM) and acidity characterization (DRIFTS, NH₃-TPD and H₂-TPR), it was found that with Na poisoning deeper and deeper, Cu/SSZ-13 took a gradual style of the structural destruction, but Cu/SAPO-34 adopted a sudden way. Studies on the mechanism of Na poisoning show that the decrease of acid sites is the main reason for the decrease of SCR activity of Cu/SSZ-13, and the structural collapse is the main reason for the decrease of SCR activity of Cu/SAPO-34.

Key words: selective catalytic reduction, alkali metal, zeolite, catalysts, nitric oxide, poison mechanism

中图分类号:

TQ 028.8

王晨,陈泽翔,王建强,沈美庆,王军. 基于NH₃-SCR反应铜基小孔分子筛催化剂Na中毒对比研究[J]. 化工学报, 2020, 71(12): 5551-5560.

WANG Chen,CHEN Zexiang,WANG Jianqiang,SHEN Meiqing,WANG Jun. Comparison study of Na poisoning effect on copper-based chabazite micropore catalysts for NH₃-SCR reaction[J]. CIESC Journal, 2020, 71(12): 5551-5560.

图/表 11

表1 不同Na负载量的Cu/SSZ-13催化剂和Cu/SAPO-34催化剂的BET比表面积

Table 1 BET specific surface areas of Cu/SSZ-13 and Cu/SAPO-34 with different Na contents

样品	比表面积^①/(m²/g)	下降率^②/%	Cu含量/ %（质量）
Cu-SZ before aging	806	—	—
Cu-SZ	792	—	2.07
1.82Na-SZ	526	34	1.99
3.69 Na-SZ	363	54	2.00
6.04 Na-SZ	107	86	1.81
7.27 Na-SZ	4	99	1.68
Cu-SP before aging	795	—	—
Cu-SP	790	—	1.40
1.82 Na-SP	633	20	1.32
3.48 Na-SP	96	88	1.42
6.33 Na-SP	47	94	1.40
7.75 Na-SP	4	99	1.36

图1 不同Na含量催化剂的NH3-SCR起燃特性曲线

Fig.1 NH3-SCR light-off curves of catalysts with different Na contents

图2 Cu(Na)/SSZ-13与Cu(Na)/SAPO-34 BET比表面积损失与Na含量的关系

Fig.2 BET specific surface area loss ratio function of Na content

图3 不同Na含量催化剂的X射线衍射谱图

Fig.3 XRD patterns of catalysts with different Na contents

图4 不同Na含量催化剂的SEM图

Fig.4 SEM images of catalysts with different Na contents

图5 不同Na含量催化剂的NH3-TPD结果

Fig.5 NH3-TPD results of catalysts with different Na contents

表2 不同Na含量的Cu/SSZ-13和Cu/SAPO-34催化剂的酸总量（基于NH3-TPD积分结果）

Table 2 Acidity quantification of Cu/SSZ-13 and Cu/SAPO-34 catalysts based on NH3-TPD results

样品	酸总量/μmol	样品	酸总量/μmol
Cu-SZ	65.9	Cu-SP	66.1
1.82Na-SZ	24.1	1.82Na-SP	49.0
3.69Na-SZ	13.8	3.48Na-SP	5.6
6.04Na-SZ	7.7	6.33Na-SP	1.5
7.27Na-SZ	1.4	7.75Na-SP	0.7

图6 不同Na含量催化剂的傅里叶离位红外漫反射光谱图

Fig.6 Ex-situ DRIFTS of catalysts with different Na contents

图7 不同Na含量催化剂的H2-TPR结果

Fig.7 H2-TPR results of catalysts with different Na contents

表3 Cu物种的积分定量结果

Table 3 Quantification results of Cu containing species based on H2-TPR

样品	Cu含量/%
样品	8MR Cu²⁺	6MR Cu²⁺	CuO	CuAlO₂
Cu-SZ	35	61	4	—
1.82Na-SZ	18	76	6	—
3.69Na-SZ	14	46	4	36
Cu-SP	46	43	11	—
1.82Na-SP	35	50	15	—

图8 不同Na含量催化剂的结构、酸量和SCR活性（250℃）的关联图

Fig.8 Correlation of BET surface area, acidity and SCR activity at 250℃

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基于NH₃-SCR反应铜基小孔分子筛催化剂Na中毒对比研究

Comparison study of Na poisoning effect on copper-based chabazite micropore catalysts for NH₃-SCR reaction

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