Cu-SAPO-17:一种新颖的NOx选择性催化还原催化剂

doi:10.1016/S1872-2067(20)63609-9

催化学报 ›› 2020, Vol. 41 ›› Issue (11): 1715-1722.DOI: 10.1016/S1872-2067(20)63609-9

Cu-SAPO-17:一种新颖的NO_x选择性催化还原催化剂

刘晓娜^a,b, 曹毅^a,c, 闫娜娜^a,b, 马超^a,b,d, 曹磊^a, 郭鹏^a, 田鹏^a, 刘中民^a

a 中国科学院大连化学物理研究所, 甲醇制烯烃国家工程实验室, 国家能源低碳催化与工程研发中心, 洁净能源国家实验室(筹), 辽宁大连 116023;
b 中国科学院大学, 北京 100049;
c 宁波大学材料科学与化学工程学院, 浙江宁波 315211;
d 大连理工大学张大煜学院, 辽宁大连 116024

收稿日期:2020-02-21 修回日期:2020-03-29 出版日期:2020-11-18 发布日期:2020-08-15
通讯作者: 郭鹏, 田鹏, 刘中民
基金资助:
国家自然科学基金（21972136，21676262，21606221，21991091）；中国科学院前沿科学重点研究计划（QYZDB-SSW-JSC040）.

Cu-SAPO-17: A novel catalyst for selective catalytic reduction of NO_x

Xiaona Liu^a,b, Yi Cao^a,c, Nana Yan^a,b, Chao Ma^a,b,d, Lei Cao^a, Peng Guo^a, Peng Tian^a, Zhongmin Liu^a

a National Engineering Laboratory for Methanol to Olefins, State Energy Low Carbon Catalysis and Engineering R&D Center, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b University of Chinese Academy of Sciences, Beijing 100049, China;
c School of Material Science and Chemical Engineering, Ningbo University, Ningbo 315211, Zhejiang, China;
d Zhang Dayu School of Chemistry, Dalian University of Technology, Dalian 116024, Liaoning, China

Received:2020-02-21 Revised:2020-03-29 Online:2020-11-18 Published:2020-08-15
Supported by:
This work was supported by the National Natural Science Foundation of China (21972136, 21676262, 21606221, 21991091) and the Key Research Program of Frontier Sciences, CAS (QYZDB-SSW-JSC040).

摘要/Abstract

摘要： 在柴油机排放后处理系统中，颗粒捕捉器经常放在氨气选择性催化还原（NH₃-SCR）催化剂附近.在颗粒捕捉器的再生环节中，其需要加热到873K以上.同时，在柴油机存储和冷启动阶段，NH₃-SCR催化剂需要暴露在低温（373K以下）条件下.因此，NH₃-SCR催化剂需要同时具备优异的高温水热稳定性和低温水热稳定性.在现有NH₃-SCR催化剂中，铜交换的磷酸硅铝（SAPO）分子筛由于具有优异的高温水热稳定性而受到广泛关注.到目前为止，在现有41种SAPO分子筛中，仅有Cu-SAPO-34，Cu-SAPO-18，Cu-SAPO-35，MnO_x-SAPO-11和Cu-SAPO STA-7被应用到NH₃-SCR反应中.在这些SAPO分子筛中，除SAPO-11外，其他分子筛都具有小孔大笼的特征.然而，SAPO分子筛在NH₃-SCR反应中的广泛应用一直受到其低温水热稳定性的限制.因此，研究者们一直致力于研发其他具有小孔大笼特征的SAPO分子筛，以实现低温水热稳定性和高温水热稳定性兼备.
本文报道了一个新颖的Cu-SAPO-17催化剂的合成，并首次将其应用于NH₃-SCR反应中.SAPO-17具有三维8 x 8 x 8孔道结构，由沿着c轴的eri笼和can-d6r构成.首先采用廉价的环己胺（CHA）作为模板剂制备SAPO-17原粉，随后对SAPO-17原粉进行铜离子交换和焙烧，得到Cu-SAPO-17催化剂.通过优化催化剂的硅含量和铜含量，我们发现Cu-SAPO-17-8.0%-0.22催化剂表现出优异的低温水热稳定性和高温水热稳定性.该催化剂在353K和10% H₂O的氮气气氛下老化24h后（低温水热老化），可以保持90%以上的新鲜活性；在973K和10% H₂O的空气气氛下老化16h后（高温水热老化），在473K下仍然可以达到50%以上的NO转化率.通过X射线粉末精修（Rietveld精修）SAPO-17-8.0%（未焙烧）确定了模板剂环己胺的落位、分子筛中的主客体相互作用以及Brönsted酸位点分布.精修结果显示：1）一个eri笼子中包含两个质子化的环己胺；2）环己胺上的N原子与骨架上的O4形成了经典的氢键（N-H...O4=2.96Å）.这意味着催化剂焙烧之后，与氢键相连的O4即是Brönsted酸位点.因为O4与P1相连，所以在忽略硅岛的影响时，可以认为Si在SAPO-17-8.0%中主要取代P1位点.结合EPR结果，我们推测出两种Cu²⁺的可能落位.

关键词: SAPO-17分子筛, Rietveld精修, 主客体相互作用, 氨气选择性催化还原(NH₃-SCR), 水热稳定性, Cu²⁺落位

Abstract: The high-temperature (HT) and low-temperature (LT) hydrothermal stabilities of molecular-sieve-based catalysts are important for the selective catalytic reduction of NO_x with ammonia (NH₃-SCR). In this paper, we report a catalyst, Cu²⁺ loading SAPO-17, synthesized using cyclohexylamine (CHA), which is commercially available and inexpensive and is utilized in NH₃-SCR reduction for the first time. After systematic investigations on the optimization of Si and Cu²⁺ contents, it was concluded that Cu-SAPO-17-8.0%-0.22 displays favorable catalytic performance, even after being heated at 353 K for 24 h and at 973 K for 16 h. Moreover, the locations of CHAs, host-guest interaction and the Brönsted acid sites were explored by Rietveld refinement against powder X-ray diffraction data of as-made SAPO-17-8.0%. The refinement results showed that two CHAs exist within one eri cage and that the protonated CHA forms a hydrogen bond with O4, which indicates that the proton bonding with O4 will form the Brönsted acid site after the calcination.

Key words: SAPO-17 molecular sieve, Rietveld refinement, Host-guest interaction, Selective catalytic reduction by ammonia (NH₃-SCR), Hydrothermal stability, Location of Cu²⁺

刘晓娜, 曹毅, 闫娜娜, 马超, 曹磊, 郭鹏, 田鹏, 刘中民. Cu-SAPO-17:一种新颖的NO_x选择性催化还原催化剂[J]. 催化学报, 2020, 41(11): 1715-1722.

Xiaona Liu, Yi Cao, Nana Yan, Chao Ma, Lei Cao, Peng Guo, Peng Tian, Zhongmin Liu. Cu-SAPO-17: A novel catalyst for selective catalytic reduction of NO_x[J]. Chinese Journal of Catalysis, 2020, 41(11): 1715-1722.

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Cu-SAPO-17:一种新颖的NO_x选择性催化还原催化剂

Cu-SAPO-17: A novel catalyst for selective catalytic reduction of NO_x

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Cu-SAPO-17:一种新颖的NOx选择性催化还原催化剂

Cu-SAPO-17: A novel catalyst for selective catalytic reduction of NOx

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Cu-SAPO-17:一种新颖的NO_x选择性催化还原催化剂

Cu-SAPO-17: A novel catalyst for selective catalytic reduction of NO_x