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

doi:10.11949/0438-1157.20200539

Abstract

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

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

CLC Number:

TQ 032

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.

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.

Figures/Tables 11

References 37

1	秦萱, 尹德嘉,余丽泽,等. 硅铝比对Cu/SSZ-13的SCR活性位影响规律研究[J]. 中国环境科学, 2020, 40(2): 591-599.
	Qin X, Yin D J, Yu L Z, et al. Effect of Si/Al ratio on the SCR active sites of Cu/SSZ-13[J]. China Environmental Science, 2020, 40(2): 591-599.
2	高岩. 选择性催化还原脱硝催化剂的实验与机理研究[D]. 济南: 山东大学, 2013.
	Gao Y. Experiment and mechanism analysis on selective catalytic reduction deNOx catalyst[D]. Jinan: Shandong University, 2013.
3	Roy S, Baiker A. NOx storage-reduction catalysis: from mechanism and materials properties to storage-reduction performance[J]. Chemical Reviews, 2009, 109(9): 4054-4091.
4	Hong Z, Wang Z, Liu X B. Catalytic oxidation of nitric oxide (NO) over different catalysts: an overview[J]. Catalysis Science & Technology, 2017, 7: 3440.
5	左建良. 氮氧化物低温选择性催化还原锰基催化剂研究[D]. 广州: 华南理工大学, 2014.
	Zuo J L. Study on Mn-based catalysts for low-temperature selective catalytic reduction of NOx[D]. Guangzhou: South China University of Technology, 2014.
6	郭星萌. 船用柴油机尾气后处理系统的优化设计[D]. 贵阳: 贵州民族大学, 2019.
	Guo X M. Optimization design and policy simulation of marine diesel engine post-processing system[D]. Guiyang: Guizhou Minzu University, 2019.
7	翁端, 王蕾, 吴晓东, 等. 铜基小孔分子筛柴油车尾气脱硝催化材料研究进展[J]. 科技导报, 2013, 31(24): 68-73.
	Weng D, Wang L, Wu X D, et al. Progress for Cu-based small pore molecular sieves as disel De-NOx catalysts[J]. Science & Technology Review, 2013, 32(24): 68-73.
8	张秋林, 徐海迪,邱春天,等. Cu-ZSM-5的NH3选择性催化还原NO性能及其稳态动力学[J]. 物理化学学报, 2012, 28(5): 1230-1236.
	Zhang Q L, Xu H D, Qiu C T, et al. Catalytic performance and steady-state kinetics of Cu-ZSM-5 for selective catalytic reduction of NO with NH3[J]. Acta Physico-Chimica Sinica, 2012, 28(5): 1230-1236.
9	汪宗御, 邝海浪, 张继锋, 等. 基于 DOC+SCR 的船用柴油机尾气污染物脱除实验[J]. 化工学报, 2018, 69(7): 3249-3256.
	Wang Z Y, Kuang H L, Zhang J F, et al. Removal of marine diesel engine exhaust pollutants with DOC+SCR technologies[J]. CIESC Journal, 2018, 69(7): 3249-3256.
10	Hu H, Cai S X, Li H R, et al. Mechanistic aspects of deNOx processing over TiO2 supported Co-Mn oxide catalysts: structure-activity relationships and in situ DRIFTs analysis[J]. ASC Catalysis, 2015, 5: 6069-6077.
11	刘建华, 杨晓博, 张琛, 等. Fe2O3对V2O5-WO3/TiO2催化剂表面性质及其性能的影响[J]. 化工学报, 2016, 67(4): 1287-1293.
	Liu J H, Yang X B, Zhang C, et al. Effect of Fe2O3 on surface properties and activities of V2O5-WO3/TiO2 catalysts[J]. CIESC Journal, 2016, 67(4): 1287-1293.
12	Wang Z Y, Guo R T, Shi X, et al. The enhanced performance of Sb-modified Cu/TiO2 catalyst for selective catalytic reduction of NOx with NH3[J]. Applied Surface Science, 2019, 475: 334-341.
13	郭凤, 余剑, Tran Tuyet-Suong, 等. 溶胶-凝胶原位合成钒钨钛催化剂及NH3-SCR性能[J]. 化工学报, 2017, 68(7): 3747-3754.
	Guo F, Yu J, Tran T S, et al. In situ preparation of mesoporous V2O5-WO3/TiO2 catalyst by sol-gel method and its performance for NH3-SCR reaction[J]. CIESC Journal, 2017, 68(7): 3747-3754.
14	宿文康. Cu/CHA分子筛选择性催化还原柴油车尾气NOx的机理研究[D]. 北京: 清华大学, 2016.
	Su W K. Fundamental research on SCR of NOx by NH3 over Cu/CHA zeolite for diesel vehicle emission control[D]. Beijing: Tsinghua University, 2016.
15	Prodinger S, Derewinski M A, Wang Y L, et al. Sub-micron Cu/SSZ-13: synthesis and application as selective catalytic reduction (SCR) catalysts[J]. Applied Catalysis B: Environmental, 2017, 201: 461-469.
16	Ye Y Z, Shen F, Wang H N, et al. SSZ-13-supported manganese oxide catalysts for low temperature selective catalytic reduction of NOx by NH3[J]. Journal of Chemical Sciences, 2017, 129(6): 765-774.
17	Wang C, Wang J, Wang J Q, et al. The role of impregnated sodium ions in Cu/SSZ-13 NH3-SCR catalysts[J]. Catalysts, 2018, 8(12): 593.
18	Gao F, Szanyi J. On the hydrothermal stability of Cu/SSZ-13 SCR catalysts[J]. Applied Catalysis A: General, 2018, 560: 185-194.
19	Godiksen A, Stappen F N, Vennestrøm P N R, et al. Coordination environment of copper sites in Cu-CHA zeolite investigated by electron paramagnetic resonance[J]. The Journal of Physical Chemistry C, 2014, 118(40): 23126-23138.
20	Janssens T V W, Falsig H, Lundegaard L F, et al. A consistent reaction scheme for the selective catalytic reduction of nitrogen oxides with ammonia[J]. ACS Catalysis, 2015, 5(5): 2832-2845.
21	Zhao Z C, Yu R, Zhao R R, et al. Cu-exchanged Al-rich SSZ-13 zeolite from organotemplate-free synthesis as NH3-SCR catalyst: effects of Na+ ions on the activity and hydrothermal stability[J]. Applied Catalysis B: Environmental, 2017, 217: 421-428.
22	Gao F, Wang Y L, Washton N M, et al. Effects of alkali and alkaline earth cocations on the activity and hydrothermal stability of Cu/SSZ-13 NH3-SCR catalysts[J]. ACS Catalysis, 2015, 5(11): 6780-6791.
23	Wang C, Yan W J, Wang Z X, et al. The role of alkali metal ions on hydrothermal stability of Cu/SSZ-13 NH3-SCR catalysts[J]. Catalysis Today, 2020, 355: 482-492.
24	Ming S, Pang L, Fan C, et al. Chemical deactivation of Cu-SAPO-18 deNO catalyst caused by basic inorganic contaminants in diesel exhaust[J]. Chinese Journal of Catalysis, 2019, 40(4): 590-599.
25	Cui Y R, Wang Y L, Walter E D, et al. Influences of Na+ co-cation on the structure and performance of Cu/SSZ-13 selective catalytic reduction catalysts[J]. Catalysis Today, 2020, 339: 233-240.
26	Xie L J, Liu F D, Shi X Y, et al. Effects of post-treatment method and Na co-cation on the hydrothermal stability of Cu-SSZ-13 catalyst for the selective catalytic reduction of NOx with NH3[J]. Applied Catalysis B: Environmental, 2015, 179: 206-212.
27	Lin Q J, Liu J Y, Liu S, et al. Barium-promoted hydrothermal stability of monolithic Cu/BEA catalyst for NH3-SCR[J]. Dalton Trans, 2018, 47(42): 15038-15048.
28	Sultana A, Nanba T, Haneda M, et al. Influence of co-cations on the formation of Cu+ species in Cu/ZSM-5 and its effect on selective catalytic reduction of NOx with NH3[J]. Applied Catalysis B: Environmental, 2010, 101(1/2): 61-67.
29	Wang C, Wang C, Wang J, et al. Effects of Na+ on Cu/SAPO-34 for ammonia selective catalytic reduction[J]. Journal of Environmental Sciences, 2018, 70: 20-28.
30	Zhu N, Shan W P, Shan Y L, et al. Effects of alkali and alkaline earth metals on Cu-SSZ-39 catalyst for the selective catalytic reduction of NO with NH3[J]. Chemical Engineering Journal, 2020, 388: 124250.
31	Yang X B, Zhao X Y, Xiao J M, et al. High silica zeolite Phi, a CHA type zeolite with ABC-D6R stacking faults[J]. Microporous and Mesoporous Materials, 2017, 248: 129-138.
32	刘小青, 李时卉, 孙梦婷, 等. MnOx/SAPO-11催化剂的制备、表征及其低温NH3-SCR活性[J]. 物理化学学报, 2016, 32(5): 1236-1246.
	Liu X Q, Li S H, Sun M T, et al. Preparation, characterization and low-temperature NH3-SCR activity of MnOx/SAPO-11 catalysts[J]. Acta Physico-Chimica Sinica, 2016, 32(5): 1236-1246.
33	郝腾. SO2对Cu/SAPO-34催化剂NH3-SCR性能的影响[D]. 天津: 天津大学, 2014.
	He T. The effect of SO2 poisoning on the NH3-SCR performance over Cu/SAPO-34 catalysts[D]. Tianjin: Tianjin University, 2014.
34	Niu C, Shi X Y, Liu F D, et al. High hydrothermal stability of Cu-SAPO-34 catalysts for the NH3-SCR of NOx[J]. Chemical Engineering Journal, 2016, 294: 254-263.
35	Wang Q Y, Liu Z L, Zou H B, et al. Effect of calcinations temperature of Cu/Ti-PILCs for selective catalytic reduction of NO by propylene[J]. Advanced Materials Research, 2012, 396/397/398: 776-781.
36	Bendrich M, Scheuer A, Hayes R E, et al. Unified mechanistic model for standard SCR, fast SCR, and NO2 SCR over a copper chabazite catalyst[J]. Applied Catalysis B: Environmental, 2018, 222: 76-87.
37	Zhang D, Yang R T. NH3-SCR of NO over one-pot Cu-SAPO-34 catalyst: performance enhancement by doping Fe and MnCe and insight into N2O formation[J]. Applied Catalysis A: General, 2017, 543: 247-256.

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]

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]

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

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

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