Halide-free carbonylation of methanol with H-MOR supported CuCeO<sub><i>x</i></sub> catalysts

doi:10.1007/s11705-020-2019-5

Front. Chem. Sci. Eng.

2021, Vol. 15

Issue (5) : 1075-1087 https://doi.org/10.1007/s11705-020-2019-5

RESEARCH ARTICLE

Halide-free carbonylation of methanol with H-MOR supported CuCeO_x catalysts

Chaoli Tong, Jiachang Zuo, Danlu Wen, Weikun Chen, Linmin Ye, Youzhu Yuan(

)

State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

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Abstract

Heterogeneous halide-free carbonylation of methanol to acetates, including methyl acetate (MA) and acetic acid, using non-precious metal catalysts has been a topic of interest for decades. The key issue is that the water produced by methanol dehydration inhibits the formation of acetyl species and reduces the MA selectivity. Here, we report that CuCeO_x/H-mordenite (H-MOR) catalyst can nearly eliminate the inhibiting effect of water on carbonylation by a water-gas shift reaction (WGSR) on-site, and can thus achieve 96.5% methanol conversion with 87.4% MA selectivity for the halide-free carbonylation of methanol. The results of powder X-ray diffraction, transmission electron microscopy, and scanning electron microscopy show that the Cu and Ce species are highly dispersed on H-MOR even when the CuCeO_x contents are as high as 29 wt-%. Fourier transform infrared spectroscopy and CO chemisorption analysis reveal that a small portion of Cu species can migrate into the channel of H-MOR when CuCeO_x/H-MOR is calcined at 500 °C and these Cu species are converted into Cu⁺ sites upon reduction. The Cu⁺ sites facilitate the WGSR and are also active sites for methanol carbonylation. The introduction of Ce benefits the inhibition of coke deposits and thus enhances the catalyst stability.

Keywords methanol carbonylation halide-free methyl acetate H-mordenite copper and cerium oxide

Corresponding Author(s): Youzhu Yuan

Just Accepted Date: 13 January 2021 Online First Date: 10 March 2021 Issue Date: 30 August 2021

Cite this article:

Chaoli Tong,Jiachang Zuo,Danlu Wen, et al. Halide-free carbonylation of methanol with H-MOR supported CuCeO_x catalysts[J]. Front. Chem. Sci. Eng., 2021, 15(5): 1075-1087.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-2019-5
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I5/1075

Fig.1 XRD patterns of different zeolite catalysts: (a) H-MOR; (b) Cu/H-MOR; (c) Ce/H-MOR; (d) CuCeO_x/H-MOR (Cu: 9.2 wt-%; Ce: 19.6 wt-%).

Fig.2 (A–C) TEM images and (D) HR-TEM image of the CuCeO_x/H-MOR catalyst (Cu: 9.2 wt-%; Ce: 19.6 wt-%).

Fig.3 (A and B) SEM images of the CuCeO_x/H-MOR catalyst; (C–H) elemental EDS maps of the CuCeO_x/H-MOR catalyst that correspond to the image (C) and five maps for O (D), Si (E), Al (F), Cu (G), and Ce (H) (Cu: 9.2 wt-%; Ce: 19.6 wt-%).

Tab.1 Catalytic performance of different catalysts for heterogeneous methanol carbonylation^a)

Fig.4 Effect of the calcination temperature on the CuCeO_x/H-MOR catalyst for heterogeneous methanol carbonylation (reaction conditions: T = 200 °C; P_co = 1.0 MPa; CH₃OH/CO= 2.15 mol-%; F = 10 mL·min^–1; time on stream= 3 h).

Fig.5 XRD patterns of the CuCeO_x/H-MOR catalyst treated in air at different calcination temperatures: (a) 300 °C, (b) 350 °C, (c) 400 °C, (d) 500 °C, (e) 600 °C, and (f) 700 °C (Cu: 9.2 wt-%; Ce: 19.6 wt-%).

Fig.6 Catalytic performance of CuCeO_x/H-MOR catalysts with different carriers for the methanol heterogeneous carbonylation reaction (reaction conditions: T = 200 °C; P_co = 1.0 MPa; CH₃OH/CO= 2.15 mol-%; F = 10 mL·min^–1; time on stream= 3 h. Cu: 9.2 wt-%; Ce: 19.6 wt-%).

Fig.7 (A) FTIR spectra of the chemisorbed CO on the as-reduced CuCeO_x/H-MOR catalyst with different calcination temperatures after evacuation for 25 min; (B) H₂—TPR and (C) CO-TPD profiles of the CuCeO_x/H-MOR catalyst treated in air at different calcination temperatures: (a) 300 °C; (b) 350 °C; (c) 400 °C; (d) 500 °C; (e) 600 °C; (f) 700 °C (Cu: 9.2 wt-%; Ce: 19.6 wt-%).

Fig.8 Proposed mechanism for the ketonization reaction.

Fig.9 Proposed reaction mechanism of heterogeneous methanol carbonylation over the CuCeO_x/H-MOR catalyst.

Fig.10 Results of carbonylation stability tests (A) methanol conversion and (B) MA selectivity over different catalysts: (a) CuCeO_x/H-MOR; (b) Cu-H-MOR+CuCeO||Cu-H-MOR; (c) Cu/H-MOR; (d) Ce/H-MOR (reaction conditions: T = 200 °C; P_co = 1.0 MPa; CH₃OH/CO= 2.15 mol-%; F = 10 mL·min^–1).

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