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

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

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64431-6

https://www.cjcatal.com/EN/Y2023/V49/I6/91

Figures/Tables 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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