无模板法合成的Phi分子筛在NO选择性催化还原中的应用

doi:10.11949/0438-1157.20200539

化工学报 ›› 2020, Vol. 71 ›› Issue (12): 5578-5588.DOI: 10.11949/0438-1157.20200539

• 催化、动力学与反应器 • 上一篇下一篇

无模板法合成的Phi分子筛在NO选择性催化还原中的应用

杨润农¹(),余林¹(),赵向云²,杨晓波^1,²(),高梓寒¹,傅广赢³,姜久兴³,练纬琳²,刘武源^1,²,范群^1,²

^1.广东工业大学轻工化工学院，广州市清洁交通能源化学重点实验室，广东广州 510006
^2.广州市威格林环保科技有限公司，广东广州 511441
^3.中山大学化学学院，广东广州 510275

收稿日期:2020-05-09 修回日期:2020-07-08 出版日期:2020-12-05 发布日期:2020-12-05
通讯作者: 余林,杨晓波
作者简介:杨润农（1989—），女，博士研究生，Yangrn0814@163.com
基金资助:
国家自然科学基金项目(21576054);广东省省级科技计划项目(2016B020241003)

Phi zeolite synthesized by template-free method for selective catalytic reduction of NO

YANG Runnong¹(),YU Lin¹(),ZHAO Xiangyun²,YANG Xiaobo^1,²(),GAO Zihan¹,FU Guangying³,JIANG Jiuxing³,LIAN Weilin²,LIU Wuyuan^1,²,FAN Qun^1,²

^1.Guangzhou Key Laboratory of Clean Transportation Energy Chemistry, School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, Guangdong, China
^2.Waygreen Environmental Protection Technology Co. , Ltd. , Guangzhou 511441, Guangdong, China
^3.School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, Guangdong, China

Received:2020-05-09 Revised:2020-07-08 Online:2020-12-05 Published:2020-12-05
Contact: YU Lin,YANG Xiaobo

摘要/Abstract

摘要：

氮氧化物（NO_x）是大气中的一种主要污染物。采用具有菱沸石结构（CHA）的铜基分子筛作为催化剂，通过选择性催化还原（SCR）技术可有效去除NO_x。采用一种经济环保的制备方法，在不使用模板剂的条件下水热合成一种具有结构缺陷的低硅铝比CHA型分子筛（Phi，Si/Al=4.7）。结果表明，经Cu离子交换制备的Cu/Phi具有最丰富的表面酸性与孤立态Cu²⁺，表现出较好的低温活性、较宽的工作温度窗口以及良好的水热稳定性。Na或Mg的存在降低了Cu/Phi的表面酸性及孤立态Cu²⁺的含量，水热老化后的Na，Cu/Phi和Mg，Cu/Phi均呈现出不同程度的骨架坍塌，相应导致了催化剂失活。

关键词: 分子筛, 催化剂, 碱/碱土金属离子, 水热稳定性, 失活, NH₃-SCR

Abstract:

Nitrogen oxide (NO_x) is one of the major air pollutants. Using a copper-based zeolite with a chabazite structure (CHA) as a catalyst, the selective catalytic reduction (SCR) technology can effectively remove NO_x. This work introduces a low silica CHA type zeolite with structural defects (zeolite Phi, with Si/Al of 4.7). The zeolite Phi is synthesized through a hydrothermal method without adding any template, which is low-cost and environment-friendly. The Cu-exchanged Phi is abundant of surface acidity and isolated Cu²⁺, showing a superior low-temperature activity, a wide work temperature window and a good hydrothermal stability. The presence of Na or Mg decreases the surface acidity and isolated Cu²⁺. The hydrothermally aged Na,Cu/Phi and Mg,Cu/Phi present different levels of framework collapse, which correspondingly induces catalyst deactivation.

Key words: zeolite, catalyst, alkali/alkaline earth metal, hydrothermal stability, deactivation, NH₃-SCR

中图分类号:

TQ 032

杨润农,余林,赵向云,杨晓波,高梓寒,傅广赢,姜久兴,练纬琳,刘武源,范群. 无模板法合成的Phi分子筛在NO选择性催化还原中的应用[J]. 化工学报, 2020, 71(12): 5578-5588.

YANG Runnong,YU Lin,ZHAO Xiangyun,YANG Xiaobo,GAO Zihan,FU Guangying,JIANG Jiuxing,LIAN Weilin,LIU Wuyuan,FAN Qun. Phi zeolite synthesized by template-free method for selective catalytic reduction of NO[J]. CIESC Journal, 2020, 71(12): 5578-5588.

图/表 11

表1 碱/碱土金属对不同分子筛催化剂的影响

Table 1 Effect of alkali/alkaline earth metals on different zeolite catalysts

Catalyst^①	Cu content /%	M^② content /%	Effect on catalytic activity	Effect on hydrothermal stability	Ref.
Cu-Na-SSZ-13(4)	~2.5	<1.7	slightly enhanced	positive	[21]
Cu-Na-SSZ-13(4)	~2.5	1.7—3.4	negative	negative	[21]
Cu-Li/Na-SSZ-13(6)	1.0	0.4/1.8	positive	positive	[22]
Cu-K/Cs-SSZ-13(6)	0.9/0.6	4.2/15.0	negative	negative	[22]
Cu-Na-SSZ-13(9)	1.0	1.5	slightly enhanced	—	[25]
Cu-Na-SSZ-13(9)	2.0—4.0	1.5	negative	negative	[25]
Cu-Na-SSZ-13	1.7—3.9	<0.8	positive	positive	[26]
Cu-Na-SSZ-13	4.3—5.3	2.5—3.7	negative	negative	[26]
Cu-Ba-BEA(25)	—	2.0	no influence	positive	[27]
Cu-Na-ZSM-5	2.4—3.5	0.04—0.6	positive	—	[28]
Cu-Na-SSZ-13(12)	—	1.2—3.5	negative	negative	[23]
Cu-Na-SSZ-13	—	0.7—3.5	negative	negative	[17]
Cu-Na-SAPO-34	~2.0	0.4—1.8	negative	—	[29]
Cu-K/Na/Ca/Mg-SAPO-18	~2.1	~0.5	negative	negative	[24]
Cu-K/Na/Ca/Mg-SAPO-18	~2.1	~1.0	negative	negative	[24]
Cu-K/Mg/Ca/Na-SSZ-39	~2.3	3.9/2.2/3.1/3.0	negative	negative	[30]

图1 不同催化剂的XRD谱图

Fig.1 XRD patterns of different catalysts

图2 不同催化剂的SEM图（左）和EDS图（右）

Fig.2 SEM (left) and EDS (right) images of different catalysts

表2 催化剂中各元素含量分析

Table 2 Element contents in catalysts

Sample	Mass content/%			Atomic ratio^②
Sample	Cu	Na	Mg	Si/Al	Cu/Al	M^③/Al
Cu/SSZ-13	3.16^①/2.29^②	—	—	10.9	0.36	—
Cu/Phi	4.41^①/3.58^②	—	—	4.65	0.24	—
Na,Cu/Phi	4.83^①/4.07^②	0.81^①/0.80^②	—	4.81	0.26	0.14
Mg,Cu/Phi	4.07^①/3.04^②	—	1.53^①/1.10^②	4.71	0.20	0.20

图3 不同催化剂的NH3-TPD图和对应的不同强度酸的含量

Fig.3 NH3-TPD profiles of different catalysts and the corresponding amounts of acid sites with different strengths

图4 不同催化剂的吡啶红外谱图和相应的不同种类酸的含量

Fig.4 FTIR spectra of pyridine adsorption for different catalysts and the corresponding amounts of acid sites with different natures

图5 不同催化剂的EPR谱图和孤立态Cu2+的含量

Fig.5 EPR spectra and the corresponding amounts of isolated Cu2+ of different catalysts

图6 不同催化剂的NH3-SCR活性图及NO反应速率的Arrhenius数据图

Fig.6 NH3-SCR activities and Arrhenius plots of NO reaction rates over different catalysts

图7 水热老化催化剂的XRD谱图（虚线表示老化前催化剂的XRD谱图）

Fig.7 XRD patterns of hydrothermal aged catalysts (XRD patterns of corresponding fresh catalysts are shown as dashed lines)

图8 不同水热老化催化剂的NH3-SCR活性

Fig.8 NH3-SCR activities over different hydrothermally aged catalysts

图9 不同催化剂的总酸含量、孤立态Cu2+含量与T90及工作温度窗口间的关系

Fig.9 Relationships among total acid amount, isolated Cu2+ amount and T90 or work temperature window for different catalysts

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无模板法合成的Phi分子筛在NO选择性催化还原中的应用

Phi zeolite synthesized by template-free method for selective catalytic reduction of NO

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