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

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.

Graphical abstract

Keywords

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

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (Grant Nos. 2018YFB0604703, 2017YFA0206801, and 2018YFB0604701), the National Natural Science Foundation of China (Grant Nos. 21972113 and 91545115), the Program for Innovative Research Team in Chinese Universities (Grant No. IRT_14R31), and the Fundamental Research Funds for the Central Universities (Grant No.20720190039).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-020-2019-5 and is accessible for authorized users.

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