新型八元环孔结构分子筛Cu/SAPO-35应用于NH3-SCR的研究

doi:10.7503/cjcu20160360

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (10): 1817.doi: 10.7503/cjcu20160360

新型八元环孔结构分子筛Cu/SAPO-35应用于NH₃-SCR的研究

刘宁, 王继琼, 陈标华, 李英霞, 张润铎()

北京化工大学化工资源有效利用国家重点实验室, 北京 100029

收稿日期:2016-05-20 出版日期:2016-10-10 发布日期:2016-09-23
作者简介:联系人简介: 张润铎, 男, 博士, 教授, 博士生导师, 主要从事大气污染催化控制方面的研究. E-mail:zhangrd@mail.buct.edu.cn
基金资助:
国家自然科学基金(批准号: 21477007, 21407007)、江苏省自然科学基金(批准号: BK20140268)、北京化工大学优势学科新增长点”学科提升计划项目(批准号: YS1401)、北京化工大学学科建设项目(批准号: XK1504)和国家“八六三”计划项目(批准号: 2013AA065901)资助

Study of Eight Membered Ring Zeolitic Catalyst of Cu/SAPO-35 over NH₃-SCR^†

LIU Ning, WANG Jiqiong, CHEN Biaohua, LI Yingxia, ZHANG Runduo^*()

State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2016-05-20 Online:2016-10-10 Published:2016-09-23
Contact: ZHANG Runduo E-mail:zhangrd@mail.buct.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21477007, 21407007), the Natural Science Foundation of Jiangsu Province, China(No.BK20140268), the “New Growth Point of Advantage Disciplime” in Beijing University of Chemical Technology-discipline Upgrading Program(No.YS1401), BUCT Fund for Disciplines Construction and Development(No.XK1504) and the National High Technology Research and Development Program of China(No.2013AA065901)

摘要/Abstract

摘要：

采用六亚甲基亚胺(HMI)为模板剂, 合成了新型SAPO-35分子筛, 研究发现SAPO-35的酸性随着硅铝摩尔比增加[n(SiO₂)/n(Al₂O₃)=0.3, 0.5, 0.7]呈现先增加后降低的趋势, 当n(Si)/n(Al)=0.7时, 部分Si将发生SM3取代, 进而降低SAPO-35酸量. 进一步采用旋转浸渍法和离子交换法对SAPO-35进行改性, 制得Cu/SAPO-35催化剂, 并研究了其催化氨气选择性还原(NH₃-SCR)反应的性能. 催化剂表征结果表明, Cu主要以Cu²⁺离子形式存在于离子交换法制备的Cu/SAPO-35中, 因此其NH₃-SCR催化性能更优良. 基于液相离子交换法, 进一步研究了不同硅铝比[n(SiO₂)/n(Al₂O₃)=0.3, 0.5, 0.7]SAPO-35原粉酸性对所制备Cu/SAPO-35催化剂NH₃-SCR反应活性的影响, 结果表明, 分子筛原粉强酸量越大, 制得的Cu基催化剂中Cu²⁺离子含量越高, 从而催化剂的SCR活性、 N₂选择性更优.

关键词: Cu/SAPO-35, 氨气选择性催化还原, 酸性, 硅铝比, 离子交换法

Abstract:

A new type of SAPO-35 zeolite was synthesized utilizing hexamethyleneimine(HMI) as template. It was found that the acidity of SAPO-35 firstly increased and then decreased along with the increasing of SiO₂/Al₂O₃ molar ratio(0.3, 0.5, 0.7). With the molar ratio of SiO₂/Al₂O₃ = 0.7, the SM3 substitution mode occurred for the atomic Si during the SAPO-35 synthesis process, which could decrease the related acidity. The impregnation and wet ion exchange(WIE) method were applied to produce Cu modified SAPO-35 samples of Cu/SAPO-35, which were further evaluated in NH₃-SCR reaction system. According to various characterization results of XRF, NH₃-TPD, and H₂-TPR, it was revealed that the cationic Cu²⁺ constituted the main copper species on WIE method prepared Cu/SAPO-35, which displayed much better NH₃-SCR catalytic performance with respect to that of Cu/SAPO-35 prepared by impregnation method. Finally, various Cu/SAPO-35 with different SiO₂/Al₂O₃ molar ratio(0.3, 0.5, 0.7) were prepared by WIE and further evaluated for NH₃-SCR, wherein the influences of the acidities of parent SAPO-35 were thereafter investigated. It was revealed that the higher acidity of parent SAPO-15 could produce higher amount of exchanged Cu²⁺ cations, which resulted in superior NH₃-SCR activity and N₂ selectivity.

Key words: Cu/SAPO-35, NH3-SCR, Acidity, Si/Al ratio, Wet ion exchange method

中图分类号:

O643.3

TrendMD:

刘宁, 王继琼, 陈标华, 李英霞, 张润铎. 新型八元环孔结构分子筛Cu/SAPO-35应用于NH₃-SCR的研究. 高等学校化学学报, 2016, 37(10): 1817.

LIU Ning, WANG Jiqiong, CHEN Biaohua, LI Yingxia, ZHANG Runduo. Study of Eight Membered Ring Zeolitic Catalyst of Cu/SAPO-35 over NH₃-SCR^†. Chem. J. Chinese Universities, 2016, 37(10): 1817.

图/表 14

Fig.1 XRD patterns of SAPO-35 zeolites with the Si/Al molar ratios of 0.3(a), 0.5(b) and 0.7(c)

Fig.2 SEM image of 0.5Si-SAPO-35 zeolite

Table 1 N2 adsorption-desorption test results of SAPO-35 samples with different Si/Al molar ratios

Zeolite	Specific surface area/(m²·g^-1)	Pore volume/(cm³·g^-1)	Pore diameter/nm	Crystallite size^*/nm
0.3Si-SAPO-35	398.8	0.14	4.4	1.9
0.5Si-SAPO-35	443.4	0.10	3.4	2.1
0.7Si-SAPO-35	597.4	0.09	3.8	2.2

Table 2 XRF element analysis data of SAPO-35 samples

Zeolite	Molar ratio		Si substitution method
Zeolite	Al/Si/P		(Si+P)/Al
0.3Si-SAPO-35	1/0.15/0.83	0.98	SM2
0.5Si-SAPO-35	1/0.25/0.82	1.07	SM2
0.7Si-SAPO-35	1/0.36/0.81	1.17	SM2+SM3

Fig.3 Si NMR profiles of SAPO-35 zeolitesa. 0.3Si-SAPO-35; b. 0.5Si-SAPO-35; c. 0.7Si-SAPO-35.

Fig.4 NH3-TPD curves of SAPO-35 zeolitesa. 0.3Si-SAPO-35; b. 0.5Si-SAPO-35; c. 0.7Si-SAPO-35.

Table 3 XRF element analysis data of SAPO-35 samples

Catalyst	Molar ratio of SiO₂/Al₂O₃	Molar fraction of (Si+P)	Mass fraction of Cu(%)
Cu/0.3Si-SAPO-35	0.3	0.98	1.8
Cu/0.5Si-SAPO-35	0.5	1.07	3.1
Cu/0.7Si-SAPO-35	0.7	1.17	2.5

Fig.5 NH3-SCR activities of Cu/SAPO-35 zeolites prepared by ion exchange methodReaction conditions: 1 g/m3 NO, 1 g/m3 NH3, 10%O2 balanced by Ar, GHSV=3×104 h-1.

Fig.6 Comparison of H2-TPR test result between the samples prepared by rotating impregnation method and ion exchange methoda. 3.1%Cu/0.5Si-SAPO-35;b. 4%Cu/0.5Si-SAPO-35.

Fig.7 XPS test result of the 3.1%Cu/0.5Si-SAPO-35 zeolite prepared by ion exchange method

Fig.8 NH3-SCR activities of Cu/SAPO-35 zeolites prepared by ion exchange method with different Si/Al molar ratios Reaction conditions: 1 g/m3 NO, 1 g/m3 NH3, 10%O2 balanced by Ar, GHSV=3×104 h-1.

Fig.9 H2-TPR profiles of Cu/SAPO-35 zeolites prepared by ion exchange methoda. Cu/0.3Si-SAPO-35; b. Cu/0.5Si-SAPO-35; c. Cu/0.7Si-SAPO-35.

Table 4 H2-Consumption of Cu/SAPO-35 zeolites calculated by H2-TPR test result

Catalyst	H₂ Consumption/(mmol·g^-1)	H₂/Cu^*
Cu/0.3Si-SAPO-35	0.185	0.65
Cu/0.5Si-SAPO-35	0.213	0.44
Cu/0.7Si-SAPO-35	0.190	0.49

Fig.10 Possible location site of Cu2+ ions on Cu-SAPO-35 zeolite

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新型八元环孔结构分子筛Cu/SAPO-35应用于NH₃-SCR的研究

Study of Eight Membered Ring Zeolitic Catalyst of Cu/SAPO-35 over NH₃-SCR^†

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