Cu-MFI催化剂上Cuδ+催化乙醇脱氢制乙醛

doi:10.1016/S1872-2067(23)64431-6

催化学报 ›› 2023, Vol. 49: 91-101.DOI: 10.1016/S1872-2067(23)64431-6

Cu-MFI催化剂上Cu^δ⁺催化乙醇脱氢制乙醛

李显泉^a^,^b, 庞纪峰^a, 赵于嘉^a^,^b, 吴鹏飞^a, 于文广^c, 颜佩芳^c, 苏扬^a, 郑明远^a^,^d^,^*()

^a中国科学院大连化学物理研究所, 中国科学院应用催化科学技术重点实验室, 辽宁大连 116023
^b中国科学院大学, 北京 100049
^c中国科学院大连化学物理研究所, 洁净能源国家实验室(筹), 能源研究技术平台, 辽宁大连 116023
^d中国科学院大连化学物理研究所, 洁净能源国家实验室(筹), 辽宁大连 116023

收稿日期:2023-01-20 接受日期:2023-03-17 出版日期:2023-06-18 发布日期:2023-06-05
通讯作者: ^*电子信箱: myzheng@dicp.ac.cn
基金资助:
国家自然科学基金(21721004);国家自然科学基金(22108274);中国科学院战略重点研究项目“清洁能源转化技术与示范”(XDA 21060200)

Ethanol dehydrogenation to acetaldehyde over a Cu^δ⁺-based Cu-MFI catalyst

Xianquan Li^a^,^b, Jifeng Pang^a, Yujia Zhao^a^,^b, Pengfei Wu^a, Wenguang Yu^c, Peifang Yan^c, Yang Su^a, Mingyuan Zheng^a^,^d^,^*()

^aChinese Academy of Science Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China
^cDalian National Laboratory for Clean Energy, Division of Energy Research Resources, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^dDalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2023-01-20 Accepted:2023-03-17 Online:2023-06-18 Published:2023-06-05
Contact: ^*E-mail: myzheng@dicp.ac.cn (M. Zheng).
Supported by:
National Natural Science Foundation of China(21721004);National Natural Science Foundation of China(22108274);‘‘Transformational Technologies for Clean Energy and Demonstration”, Strategic Priority Research Program of the Chinese Academy of Sciences(XDA 21060200)

摘要/Abstract

摘要：

作为一种清洁的可再生能源产品, 乙醇可用于制造乙醛、丙烯、正丁醇、1,3-丁二烯和芳香烃等高值化学品. 对于大多数的乙醇催化转化过程, 第一步是乙醇脱氢生成乙醛, 因而该反应具有重要的研究意义和应用价值. 铜基催化剂因在乙醇脱氢反应中具有高活性和高选择性, 受到广泛关注与研究. 然而, 由于催化剂上铜配位结构较为复杂, 价态多变, 催化剂的关键活性位点目前仍难以确定. 此外, 铜的Tamman温度较低, 在反应条件下因铜活性位容易烧结或团聚而导致催化剂失活, 因此需要进一步提升铜催化剂的稳定性. 构筑具有明确结构和高稳定性的铜基催化剂是获得高性能乙醇脱氢反应的关键, 也是深入认识该反应中催化剂结构与性能构效关系的前提.

本文首先采用蒸氨法制备了一系列的Cu-MFI催化剂, 再通过酸处理将催化剂上不稳定的CuO_x物种除去, 留下与MFI载体强相互作用的Cu物种. 通过优选Cu负载量和优化反应条件, 发现在250 °C和WHSV = 0.64 h^‒1的反应条件, 在最佳催化剂5%Cu-MFI-deCu上实现了95%的乙醛选择性和约87%的乙醇转化率, 且可稳定运行120 h. 系统表征(氢气程序升温还原、高分辨扫描透射电镜、氘代乙腈红外光谱和X射线吸收光谱)结果表明: 催化剂中稳定的Cu物种以(SiO)₃Cu-OH的形式高度分散在载体上, 在反应过程中被反应物或H₂部分还原为[≡SiO-Cu]^δ⁺ (1 < δ < 2). 不同于之前广泛报道的Cu催化活性中心以Cu⁺和Cu⁰物种存在, 本文中[≡SiO-Cu]^δ⁺物种被证实是乙醇脱氢制乙醛反应的高活性位点. 飞行时间二次离子质谱结果表明, [≡SiO-Cu]^δ⁺数量与乙醇转化率之间存在较好的线性关系. 吡啶红外光谱结果进一步表明, 路易斯酸(LAS)密度与乙醇转化率之间也存在相似的线性关系. 据此可知, 5%Cu-MFI-deCu催化剂上的LAS位点来自于高度分散在载体上的Cu^δ⁺物种. 动力学实验结果表明, 与同时存在Cu²⁺, Cu⁺和Cu⁰的5%Cu-MFI催化剂相比, 仅含有Cu^δ⁺的5%Cu-MFI-deCu催化剂在乙醇脱氢反应中表现出更低的表观活化能, 因而具有更好的催化性能. 综上, 本文构建的具有明确结构的高活性、高稳定性Cu催化剂的策略, 将为发展更多的新型高效乙醇转化催化剂提供有价值的参考.

关键词: 铜催化剂, 乙醇脱氢, 乙醛, Cu^δ⁺物种, 活性位点

Abstract:

Copper catalysts have been extensively investigated for the dehydrogenation of ethanol to acetaldehyde. However, identifying the essential active sites for this reaction is difficult because of the complex coordination structure and variable valences of the Cu species during the reaction. The stability of the Cu catalysts in the reaction also needs to be substantially improved. In this study, Cu-MFI, a well-defined Cu-based Lewis acid catalyst, was prepared using a post-acid treatment method for ethanol dehydrogenation. Different from the widely reported Cu⁺ and Cu⁰ species accounting for the activity of Cu catalysts, conditional experiments and in situ characterizations revealed that the highly dispersed Cu^δ⁺ (1 < δ < 2) species on the MFI support are the essential active sites for ethanol dehydrogenation. Due to the strong interaction between Cu and silica via the Cu-O-Si linkage, the Cu^δ⁺ species were very stable in the reaction and played the role of a Lewis acid catalyst in promoting ethanol activation and dehydrogenation. Over the optimal catalyst 5%Cu-MFI-deCu, 95% selectivity of acetaldehyde and approximately 87% ethanol conversion were obtained at 250 °C and a weight hourly space velocity of 0.64 h⁻¹ in 120 h time on stream.

Key words: Copper catalyst, Ethanol dehydrogenation, Acetaldehyde, Cu^δ+ species, Lewis acid

李显泉, 庞纪峰, 赵于嘉, 吴鹏飞, 于文广, 颜佩芳, 苏扬, 郑明远. Cu-MFI催化剂上Cu^δ⁺催化乙醇脱氢制乙醛[J]. 催化学报, 2023, 49: 91-101.

Xianquan Li, Jifeng Pang, Yujia Zhao, Pengfei Wu, Wenguang Yu, Peifang Yan, Yang Su, Mingyuan Zheng. Ethanol dehydrogenation to acetaldehyde over a Cu^δ⁺-based Cu-MFI catalyst[J]. Chinese Journal of Catalysis, 2023, 49: 91-101.

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图/表 7

Fig. 1. (a) Schematic of Cu catalyst preparation. (b) Catalytic performance of Cu-MFI for ethanol conversion to acetaldehyde (300 °C, WHSV = 1.92 h?1); (c) nominal and actual Cu loadings on the Cu-MFI catalysts. (d) Catalytic performance of Cu-MFI-deCu for ethanol conversion to acetaldehyde (300 °C, WHSV = 1.92 h?1). (e) 5%Cu-MFI-deCu stability in the ethanol conversion at 250 °C. ELE and DEE are abbreviations for ethylene and diethyl ether, respectively. C4+ byproducts include crotyl alcohol, ethyl acetate, crotonaldehyde, and butyraldehyde.

Fig. 2. (a) H2-TPR profiles (TCD signals were normalized by the actual Cu loadings). (b) 29Si MAS NMR spectra. (c) 1H MAS NMR spectra. (d) DRIFTS spectra for typical Cu catalysts.

Fig. 3. CD3CN-DRIFTS profiles for (a) 5%Cu-MFI-deCu catalyst, (b) 5%Cu-MFI-deCu-20h catalyst, and (c) 5%Cu-MFI-deCu-200h catalyst at different temperatures.

Fig. 4. (a) XANES profiles of Cu foil, Cu2O, CuO and Cu-MFI, Cu-MFI-deCu catalysts. (b) First derivatives of XANES profiles of Cu foil, Cu2O, CuO and 5%Cu-MFI-deCu-20h catalysts. (c) Mean chemical valence of Cuδ+ species for the 5%Cu-MFI-deCu-20h catalyst. (d) X-ray absorption fine structure (EXAFS) and (e) WT spectra of Cu foil, Cu2O, CuO, Cu-MFI, and Cu-MFI-deCu catalysts.

Fig. 5. (a) Time-of-flight secondary ion mass spectrometry (TOF-SIMS) spectra of 5%Cu-MFI-deCu catalysts at different use stages. (b) Linear relationship between the contents of Cuδ+ species (semi-quantitatively determined by the SIMS signal intensity) and ethanol conversion; and TOF-SIMS images of Cu mapping for fresh 5%Cu-MFI-deCu catalysts (c), 5%Cu-MFI-deCu-20h (d), and 5%Cu-MFI-deCu-200h (e) (The brightest color of scale bar at the right indexes to the highest Cuδ+ intensity in the sample).

Fig. 6. (a) Py-FTIR spectra of 5%Cu-MFI-deCu at different temperatures. (b) Linear relationship between the LAS density and ethanol conversion.

Fig. 7. TPSR profiles in ethanol conversion over 5%Cu-MFI-deCu (a) and 5%Cu-MFI catalysts (b) (Reaction conditions: WHSV = 0.64 h?1, 30-500 °C). (c) in situ DRIFTS for ethanol conversion over 5%Cu-MFI-deCu catalyst. (d) Arrhenius plots of ethanol conversion over 5%Cu-MFI-deCu and 5%Cu-MFI catalysts.

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Cu-MFI催化剂上Cu^δ⁺催化乙醇脱氢制乙醛

Ethanol dehydrogenation to acetaldehyde over a Cu^δ⁺-based Cu-MFI catalyst

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Cu-MFI催化剂上Cuδ+催化乙醇脱氢制乙醛

Ethanol dehydrogenation to acetaldehyde over a Cuδ+-based Cu-MFI catalyst

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Cu-MFI催化剂上Cu^δ⁺催化乙醇脱氢制乙醛

Ethanol dehydrogenation to acetaldehyde over a Cu^δ⁺-based Cu-MFI catalyst