修饰SAPO-18分子筛的笼结构以调变甲醇制烯烃反应的产物选择性

doi:10.1016/S1872-2067(19)63281-X

催化学报 ›› 2019, Vol. 40 ›› Issue (4): 477-485.DOI: 10.1016/S1872-2067(19)63281-X

修饰SAPO-18分子筛的笼结构以调变甲醇制烯烃反应的产物选择性

钟家伟^a,b,d, 韩晶峰^a, 魏迎旭^a, 徐舒涛^a, 孙毯毯^a, 曾姝^a, 郭新闻^b, 宋春山^b,c, 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, 能源材料化学协同创新中心, 辽宁大连 116023, 中国;
b 大连理工大学化工学院, 宾州州立大学-大连理工大学联合能源研究中心, 精细化工国家重点实验室, 辽宁大连 116024, 中国;
c 宾州州立大学, 宾夕法尼亚州 16802, 美国;
d 中国科学院大学, 北京 100049, 中国

收稿日期:2018-11-13 修回日期:2018-12-19 出版日期:2019-04-18 发布日期:2019-03-14
通讯作者: 刘中民, 魏迎旭
基金资助:
中国科学院前沿科学重点研究计划（QYZDY-SSW-JSC024）；国家自然科学基金（21603223，21473182，91334205，91545104）；中国科学院青年创新促进会（2014165）.

Tuning the product selectivity of SAPO-18 catalysts in MTO reaction via cavity modification

Jiawei Zhong^a,b,d, Jingfeng Han^a, Yingxu Wei^a, Shutao Xu^a, Tantan Sun^a, Shu Zeng^a, Xinwen Guo^b, Chunshan Song^b,c, 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, iChEM(Collaborative Innovation Center of Chemistry for Energy Materials), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China;
c EMS Energy Institute, Departments of Energy and Mineral Engineering, and of Chemical Engineering, The Pennsylvania State University, University Park, PA 16802, USA;
d University of Chinese Academy of Sciences, Beijing 100049, China

Received:2018-11-13 Revised:2018-12-19 Online:2019-04-18 Published:2019-03-14
Supported by:
This work was supported by the Key Research Program of Frontier Sciences, CAS (QYZDY-SSW-JSC024), the National Natural Science Foundation of China (21603223, 21473182, 91334205, 91545104), and the Youth Innovation Promotion Association of the CAS (2014165).

摘要/Abstract

摘要：

低碳烯烃（乙烯、丙烯）是重要化工材料的基础原料.甲醇制烯烃（MTO）技术是重要的非石油路线制取低碳烯烃技术.SAPO-34分子筛在MTO反应中表现出优异的低碳烯烃选择性，而笼结构尺寸较大的SAPO-18分子筛的MTO反应产物以丙烯为主.乙烯具有比丙烯更高的经济附加值，因此提升SAPO-18分子筛MTO反应中乙烯的选择性有着重要的工业意义.
本文采用离子交换法对SAPO-18分子筛进行金属Zn改性，修饰SAPO-18分子筛的笼结构.利用多种手段对Zn改性SAPO-18分子筛的物理结构、金属物种状态及分布、酸性、扩散性质等进行表征，对积碳物种的种类、积炭量等进行分析，从而关联SAPO-18分子筛笼结构的修饰与MTO反应产物选择性的关系.
首先，我们对Zn改性SAPO-18分子筛的物理结构进行分析.X射线衍射表明，所采用的SAPO-18为不含杂晶的纯相分子筛.N₂物理吸附-脱附表明，离子交换法法保持SAPO-18分子筛比表面积和孔体积.其次，我们考察了Zn改性SAPO-18分子筛中金属物种的状态及分布.X射线光电子能谱（XPS）表明，Zn物种主要以孤立态的Zn²⁺阳离子形式存在.XPS和X射线荧光结合表明，Zn阳离子改性SAPO-18分子筛表层富Si富Zn，呈类核壳结构.氨气-程序升温脱附与核磁共振氢谱结合表明，Zn改性SAPO-18分子筛酸性位点的酸量降低.继而对Zn改性SAPO-18分子筛的扩散性质进行分析.色谱法和智能重量分析表明，Zn阳离子的引入增加探针分子的扩散限制，从而推断增加MTO反应产物的扩散限制.色质谱联用表明，Zn阳离子的引入促进低甲基苯的生成，利于乙烯产物的生成；同时促进双环芳烃的形成，增加MTO反应产物的扩散限制.热重表明，Zn阳离子改性SAPO-18分子筛以更低的积炭量达到同样的MTO反应催化效果，符合碳原子经济性.
Zn阳离子改性有效修饰SAPO-18分子筛的笼结构，表层富Si和Zn，呈现类核壳结构，增加了对MTO反应产物的扩散限制，尤其对分子尺寸较大的反应产物，从而调变MTO反应选择性.因此，Zn阳离子改性有效修饰了SAPO-18分子筛的笼结构，增加乙烯选择性和乙烯/丙烯比，将产物分布以丙烯为主调变为乙烯和丙烯选择性相近.

关键词: SAPO-18, 甲醇制烯烃, 产物选择性, 笼结构修饰

Abstract:

The AEI cavity of SAPO-18 catalyst was modified with zinc cations with the conventional ion exchange procedure. The cavity modification effectively tunes the product selectivity, and shifts the products from mainly propylene to comparable production of ethylene and propylene in methanol to olefin (MTO) reaction. The incorporation of zinc ions and the generation of bicyclic aromatic species in the AEI cavity of SAPO-18 catalysts introduce additional diffusion hindrance that exert greater influence on the relatively bulky products (e.g. propylene and higher olefins), which increase the selectivity to small-sized products (e.g. ethylene). It appears that the incorporated zinc cations facilitate the generation of lower methylbenzenes which promote the generation of ethylene. The cavity modification via incorporating zinc ions effectively tunes the product selectivity over SAPO molecular sieves with relatively larger cavity, which provides a novel strategy to develop the potential alternative to SAPO-34 catalysts for industrial MTO reaction.

Key words: SAPO-18, Methanol to olefin, Cavity modification, Product selectivity

钟家伟, 韩晶峰, 魏迎旭, 徐舒涛, 孙毯毯, 曾姝, 郭新闻, 宋春山, 刘中民. 修饰SAPO-18分子筛的笼结构以调变甲醇制烯烃反应的产物选择性[J]. 催化学报, 2019, 40(4): 477-485.

Jiawei Zhong, Jingfeng Han, Yingxu Wei, Shutao Xu, Tantan Sun, Shu Zeng, Xinwen Guo, Chunshan Song, Zhongmin Liu. Tuning the product selectivity of SAPO-18 catalysts in MTO reaction via cavity modification[J]. Chinese Journal of Catalysis, 2019, 40(4): 477-485.

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修饰SAPO-18分子筛的笼结构以调变甲醇制烯烃反应的产物选择性

Tuning the product selectivity of SAPO-18 catalysts in MTO reaction via cavity modification

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