Direct conversion of syngas into methyl acetate by relay catalysis: From fabrication of active sites to process control

Suhan Liu; Gongli Wu; Yuqing Chen; Yaoyao Han; Mingchao Zhang; Jincan Kang; Min Tang; Krijn P. de Jong; Qinghong Zhang; Ye Wang; Kang Cheng

doi:10.1002/aic.18664

Direct conversion of syngas into methyl acetate by relay catalysis: From fabrication of active sites to process control

Suhan Liu
, Gongli Wu
, Yuqing Chen
, Yaoyao Han
, Mingchao Zhang
, Jincan Kang
, Min Tang^*
, Krijn P. de Jong
, Qinghong Zhang
, Ye Wang
, Kang Cheng^*

^*Corresponding author for this work

Xiamen University
extern

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

The direct and selective conversion of syngas into C₂₊ oxygenates is challenging due to the complex reaction network. Here, we report a robust relay system for the direct synthesis of methyl acetate (MA) from syngas, which combines CuZnAlO_x/H-ZSM-5 for syngas to dimethyl ether (DME) with modified H-MOR for DME carbonylation. The dehydration of methanol to DME on H-ZSM-5 significantly enhanced the hydrogenation of CO on CuZnAlO_x, because of high DME equilibrium yields. Blocking of Brönsted acid sites with basic molecules or selective dealumination of 12-membered rings in H-MOR suppressed the zeolite coking. Besides, reaction temperatures above 240°C avoided H₂O poisoning of carbonylation sites inside 8-MR side pockets of H-MOR, further benefiting the catalytic stability. Eventually, this relay system provided a high MA selectivity of 75% and an acetic acid selectivity of 13% at a CO conversion of 65%, outperforming reported catalysts.

Original language	English
Article number	e18664
Journal	AICHE Journal
Volume	71
Issue number	3
Early online date	30 Nov 2024
DOIs	https://doi.org/10.1002/aic.18664
Publication status	Published - Mar 2025

Bibliographical note

Publisher Copyright:
© 2024 American Institute of Chemical Engineers.

Funding

This work was supported by the National Key Research and Development Program of Ministry of Science and Technology (No. 2022YFA1504600), the National Natural Science Foundation of China (Nos. 22121001, 91945301, 22222206, U22A20392, 22072120 and 22172123), and Fundamental Research Funds for the Central Universities (20720220008 and 20720220021).

Funders	Funder number
National Key Research and Development Program of Ministry of Science and Technology
National Natural Science Foundation of China	22121001, 91945301, 22222206, U22A20392, 22072120, 22172123
Fundamental Research Funds for the Central Universities	20720220008, 20720220021
???publication-publication-funding-organisation-not-added???	2022YFA1504600

Keywords

C–C coupling
proximity
relay catalysis
syngas
zeolites

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AIChE Journal - 2024 - Liu - Direct conversion of syngas into methyl acetate by relay catalysis From fabrication of activeFinal published version, 3.93 MBLicence: Taverne

Cite this

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title = "Direct conversion of syngas into methyl acetate by relay catalysis: From fabrication of active sites to process control",

abstract = "The direct and selective conversion of syngas into C2+ oxygenates is challenging due to the complex reaction network. Here, we report a robust relay system for the direct synthesis of methyl acetate (MA) from syngas, which combines CuZnAlOx/H-ZSM-5 for syngas to dimethyl ether (DME) with modified H-MOR for DME carbonylation. The dehydration of methanol to DME on H-ZSM-5 significantly enhanced the hydrogenation of CO on CuZnAlOx, because of high DME equilibrium yields. Blocking of Br{\"o}nsted acid sites with basic molecules or selective dealumination of 12-membered rings in H-MOR suppressed the zeolite coking. Besides, reaction temperatures above 240°C avoided H2O poisoning of carbonylation sites inside 8-MR side pockets of H-MOR, further benefiting the catalytic stability. Eventually, this relay system provided a high MA selectivity of 75\% and an acetic acid selectivity of 13\% at a CO conversion of 65\%, outperforming reported catalysts.",

keywords = "C{\textendash}C coupling, proximity, relay catalysis, syngas, zeolites",

author = "Suhan Liu and Gongli Wu and Yuqing Chen and Yaoyao Han and Mingchao Zhang and Jincan Kang and Min Tang and \{de Jong\}, \{Krijn P.\} and Qinghong Zhang and Ye Wang and Kang Cheng",

note = "Publisher Copyright: {\textcopyright} 2024 American Institute of Chemical Engineers.",

year = "2025",

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doi = "10.1002/aic.18664",

language = "English",

volume = "71",

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T1 - Direct conversion of syngas into methyl acetate by relay catalysis

T2 - From fabrication of active sites to process control

AU - Liu, Suhan

AU - Wu, Gongli

AU - Chen, Yuqing

AU - Han, Yaoyao

AU - Zhang, Mingchao

AU - Kang, Jincan

AU - Tang, Min

AU - de Jong, Krijn P.

AU - Zhang, Qinghong

AU - Wang, Ye

AU - Cheng, Kang

PY - 2025/3

Y1 - 2025/3

N2 - The direct and selective conversion of syngas into C2+ oxygenates is challenging due to the complex reaction network. Here, we report a robust relay system for the direct synthesis of methyl acetate (MA) from syngas, which combines CuZnAlOx/H-ZSM-5 for syngas to dimethyl ether (DME) with modified H-MOR for DME carbonylation. The dehydration of methanol to DME on H-ZSM-5 significantly enhanced the hydrogenation of CO on CuZnAlOx, because of high DME equilibrium yields. Blocking of Brönsted acid sites with basic molecules or selective dealumination of 12-membered rings in H-MOR suppressed the zeolite coking. Besides, reaction temperatures above 240°C avoided H2O poisoning of carbonylation sites inside 8-MR side pockets of H-MOR, further benefiting the catalytic stability. Eventually, this relay system provided a high MA selectivity of 75% and an acetic acid selectivity of 13% at a CO conversion of 65%, outperforming reported catalysts.

AB - The direct and selective conversion of syngas into C2+ oxygenates is challenging due to the complex reaction network. Here, we report a robust relay system for the direct synthesis of methyl acetate (MA) from syngas, which combines CuZnAlOx/H-ZSM-5 for syngas to dimethyl ether (DME) with modified H-MOR for DME carbonylation. The dehydration of methanol to DME on H-ZSM-5 significantly enhanced the hydrogenation of CO on CuZnAlOx, because of high DME equilibrium yields. Blocking of Brönsted acid sites with basic molecules or selective dealumination of 12-membered rings in H-MOR suppressed the zeolite coking. Besides, reaction temperatures above 240°C avoided H2O poisoning of carbonylation sites inside 8-MR side pockets of H-MOR, further benefiting the catalytic stability. Eventually, this relay system provided a high MA selectivity of 75% and an acetic acid selectivity of 13% at a CO conversion of 65%, outperforming reported catalysts.

KW - C–C coupling

KW - proximity

KW - relay catalysis

KW - syngas

KW - zeolites

UR - https://www.scopus.com/pages/publications/85210565788

U2 - 10.1002/aic.18664

DO - 10.1002/aic.18664

M3 - Article

AN - SCOPUS:85210565788

SN - 0001-1541

VL - 71

JO - AICHE Journal

JF - AICHE Journal

IS - 3

M1 - e18664

ER -

Direct conversion of syngas into methyl acetate by relay catalysis: From fabrication of active sites to process control

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