通过SAPO-34分子筛笼中引入金属物种提升甲醇制烯烃反应中乙烯选择性

doi:10.1016/S1872-2067(18)63141-9

催化学报 ›› 2018, Vol. 39 ›› Issue (11): 1821-1831.DOI: 10.1016/S1872-2067(18)63141-9

通过SAPO-34分子筛笼中引入金属物种提升甲醇制烯烃反应中乙烯选择性

钟家伟^a,b,d, 韩晶峰^b, 魏迎旭^b, 徐舒涛^b, 孙毯毯^b, 郭新闻^a, 宋春山^a,c, 刘中民^b

a 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;
b 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), 能源材料化学协同创新中心, 辽宁大连 116023, 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:2018-06-08 修回日期:2018-07-23 出版日期:2018-11-18 发布日期:2018-09-01
通讯作者: 魏迎旭, 宋春山, 刘中民
基金资助:
国家自然科学基金（21603223，91745109，91545104，21473182）；中国科学院青年创新促进会（2014165）；中国科学院前沿科学重点研究计划（QYZDY-SSW-JSC024）.

Enhancing ethylene selectivity in MTO reaction by incorporating metal species in the cavity of SAPO-34 catalysts

Jiawei Zhong^a,b,d, Jingfeng Han^b, Yingxu Wei^b, Shutao Xu^b, Tantan Sun^b, Xinwen Guo^a, Chunshan Song^a,c, Zhongmin Liu^b

a 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;
b 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;
c EMS Energy Institute, Departments of Energy and Mineral Engineering, and of Chemical Engineering, Pennsylvania State University, University Park, PA 16802, USA;
d University of Chinese Academy of Sciences, Beijing 100049, China

Received:2018-06-08 Revised:2018-07-23 Online:2018-11-18 Published:2018-09-01
Contact: 10.1016/S1872-2067(18)63141-9
Supported by:
This work was supported by the National Natural Science Foundation of China (21603223, 91745109, 91545104, 21473182), the Youth Innovation Promotion Association of the Chinese Academy of Sciences (2014165), and the Key Research Program of Frontier Sciences, CAS (QYZDY-SSW-JSC024).

摘要/Abstract

摘要：

低碳烯烃（乙烯、丙烯）是化学工业极其重要的基本原料.甲醇制烯烃（MTO）反应是重要的烯烃生产石油替代路线.其中，磷酸硅铝类SAPO-34分子筛在MTO反应中表现出优异的低碳烯烃选择性.与丙烯相比，乙烯具有更高的经济附加值，因此提升MTO反应中乙烯的选择性有着重要的意义.
本文采用传统离子交换法（CIE）、模板辅助离子引入法（TⅡ）和醇相离子交换法（AIE）对SAPO-34分子筛进行金属Zn、Cu改性，利用多种表征手段对金属Zn、Cu改性SAPO-34分子筛的物理结构、化学组成、金属物种状态与分布、酸性及扩散性质等进行表征.
首先，对金属Zn、Cu改性SAPO-34分子筛的物理结构和化学组成进行分析.X射线衍射表明，相比AIE法，CIE法和TⅡ法改性基本保持SAPO-34分子筛的结晶度.X射线荧光分析表明，相比Co、Ni，金属Zn、Cu更易引入SAPO-34分子筛.N₂物理吸附-脱附表明，CIE法改性能够保持SAPO-34分子筛的BET比表面积和微孔孔容.其次，考察了金属Zn、Cu改性SAPO-34分子筛中金属物种的状态.氢气-程序升温还原（H₂-TPR）和X射线光电子能谱（XPS）结果表明，Zn物种主要以孤立态的Zn²⁺阳离子形式存在.H₂-TPR、XPS、紫外-可见光谱和电子顺磁共振谱结果表明，Cu物种主要以孤立态的Cu²⁺阳离子以及部分CuO形式存在.继而对金属Zn、Cu改性SAPO-34分子筛中金属物种的分布进行表征.XPS表明，Zn阳离子改性的SAPO-34表层富硅、富Zn，呈类核壳结构；XPS和扫描式电镜-能量色散X射线光谱结果表明，Cu物种在Cu改性SAPO-34分子筛中均匀分布.进一步研究了金属Zn、Cu改性SAPO-34分子筛中酸性的变化.氨气-程序升温脱附和核磁共振氢谱结果表明，Zn、Cu改性SAPO-34酸性位点的酸量降低.最后，对金属Zn、Cu改性SAPO-34分子筛的扩散性质进行分析.智能重量分析表明，Zn、Cu阳离子的引入降低探针分子（乙烷、丙烷）的扩散系数，推断Zn、Cu阳离子的引入增加对MTO反应产物的扩散限制.热重表明，Zn阳离子改性SAPO-34分子筛反应初期积炭量略微增加.
综上所述，Zn阳离子改性SAPO-34催化剂表层富硅、富Zn，呈现类核壳结构.Zn阳离子的引入增加对MTO反应产物的扩散限制，而且Zn阳离子的引入促进MTO反应初始阶段的碳沉积.因此，Zn阳离子改性SAPO-34分子筛显著增加MTO反应产物的扩散限制，对分子尺寸较大的反应产物的扩散限制更为明显，从而提高MTO反应初始阶段的乙烯选择性，增大乙烯/丙烯比.

关键词: 甲醇制烯烃, 产物选择性, 金属改性, 扩散限制, 类核壳

Abstract:

The SAPO-34 catalysts were modified with metal cations by different processes (conventional ion exchange (CIE), template-assisted ion incorporation (TⅡ) and alcoholic ion exchange (AIE)), systematically characterized by XRD, XRF, N₂ adsorption-desorption, UV-VIS, H₂-TPR, EPR, SEM, EDX, XPS, NH₃-TPD, ¹H NMR and IGA, and applied in MTO reaction. The metal cations incorporation introduces extra diffusion hindrance by metallic species located in the cavity of SAPO-34. In particular, the Zn cations-modified SAPO-34 catalysts exhibit core-shell like structure, with Si-rich and Zn-rich sublayer near the external surface, which favors the coke deposition at the beginning of MTO reaction, exerts marked impact on the diffusion of the generated products with relatively large molecular size (e.g. propylene), and significantly increases the selectivity to ethylene and the ratio of ethylene to propene in the MTO reaction.

Key words: Methanol to olefin (MTO), Product selectivity, Metal modification, Diffusion hindrance, Core-shell like

钟家伟, 韩晶峰, 魏迎旭, 徐舒涛, 孙毯毯, 郭新闻, 宋春山, 刘中民. 通过SAPO-34分子筛笼中引入金属物种提升甲醇制烯烃反应中乙烯选择性[J]. 催化学报, 2018, 39(11): 1821-1831.

Jiawei Zhong, Jingfeng Han, Yingxu Wei, Shutao Xu, Tantan Sun, Xinwen Guo, Chunshan Song, Zhongmin Liu. Enhancing ethylene selectivity in MTO reaction by incorporating metal species in the cavity of SAPO-34 catalysts[J]. Chinese Journal of Catalysis, 2018, 39(11): 1821-1831.

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通过SAPO-34分子筛笼中引入金属物种提升甲醇制烯烃反应中乙烯选择性

Enhancing ethylene selectivity in MTO reaction by incorporating metal species in the cavity of SAPO-34 catalysts

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