Theoretical calculation study on the reaction mechanism of methanol/dimethyl ether carbonylation catalyzed by the B/Al/Ga-MOR zeolites

REN Pengyu; LIU Zhuo; QUAN Yanhong; GUO Junjun; MA Hong; WU Jianbing; WANG Yongzhao

doi:10.1016/S1872-5813(23)60395-0

Volume 52 Issue 3

Mar. 2024

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Article Navigation > Journal of Fuel Chemistry and Technology > 2024 > 52(3): 323-334

REN Pengyu, LIU Zhuo, QUAN Yanhong, GUO Junjun, MA Hong, WU Jianbing, WANG Yongzhao. Theoretical calculation study on the reaction mechanism of methanol/dimethyl ether carbonylation catalyzed by the B/Al/Ga-MOR zeolites[J]. Journal of Fuel Chemistry and Technology, 2024, 52(3): 323-334. doi: 10.1016/S1872-5813(23)60395-0

Citation:

REN Pengyu, LIU Zhuo, QUAN Yanhong, GUO Junjun, MA Hong, WU Jianbing, WANG Yongzhao. Theoretical calculation study on the reaction mechanism of methanol/dimethyl ether carbonylation catalyzed by the B/Al/Ga-MOR zeolites[J]. Journal of Fuel Chemistry and Technology, 2024, 52(3): 323-334. doi: 10.1016/S1872-5813(23)60395-0

Citation:

REN Pengyu, LIU Zhuo, QUAN Yanhong, GUO Junjun, MA Hong, WU Jianbing, WANG Yongzhao. Theoretical calculation study on the reaction mechanism of methanol/dimethyl ether carbonylation catalyzed by the B/Al/Ga-MOR zeolites[J]. Journal of Fuel Chemistry and Technology, 2024, 52(3): 323-334. doi: 10.1016/S1872-5813(23)60395-0

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Theoretical calculation study on the reaction mechanism of methanol/dimethyl ether carbonylation catalyzed by the B/Al/Ga-MOR zeolites

doi: 10.1016/S1872-5813(23)60395-0

REN Pengyu^1
,,
LIU Zhuo^1
,,
QUAN Yanhong^2
,,
GUO Junjun^3
,,
MA Hong^1
,,
WU Jianbing^{1
,
,},
WANG Yongzhao^{1
,
,}

1.
Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
2.
Taiyuan University of Technology, Key Laboratory of Coal Science and Technology, Ministry of Education, Shanxi Research Institute for Clean Energy Tsinghua University, Taiyuan 030024, China
3.
Shanxi Lu'an Carbon One Chemical Co., Ltd., Changzhi 046100, China

Funds: The National Natural Science Foundation of China (22072079, 22302115), the Fundamental Research Program of Shanxi Province (202303021221056), the Open Fund for Key Laboratory of Coal Science and Technology, Ministry of Education, Taiyuan University of Technology (MKX202103).

Received Date: 2023-10-08
Accepted Date: 2023-10-24
Rev Recd Date: 2023-10-24

Available Online: 2023-11-10

Publish Date: 2024-03-10

Abstract

Abstract

The reaction mechanism of methanol/dimethyl ether (DME) carbonylation catalyzed by isomorphously substituted B-, Al-, and Ga-MOR zeolites (B/Al/Ga-MOR) was comparatively investigated by the density functional theory (DFT) calculations. The commonalities and differences between methanol and dimethyl ether as the reactant as well as among various MOR zeolites in the catalytic reaction pathways were disclosed, where one Si atom was substituted by B, Al or Ga at the 8-ring side pockets T3 sites or the 12-ring channels T4 sites of MOR. The results indicate that the insertion of CO into methoxy group to form acetyl groups follows the S_N2 mechanism and is the rate-determining step in the carbonylation reactions. Under 473 K, either methanol or dimethyl ether is used as feedstock, the formed acetyl group prefers to interact with CH₃O in methanol to form methyl acetate. The T3 sites show better carbonylation selectivity, whereas T4 sites display better trimethoxonium ions selectivity which favors the generation of aromatics and leads to the catalyst deactivation. Comparing with Al-MOR, the introduction of Ga and B at the T3 sites increases the free energy barriers of carbonylation, whereas the introduction of Ga and B in particular at the T4 sites can substantially increase the energy barriers of generating trimethyloxonium ions, which can effectively suppress the side reaction and improve the catalyst stability. This work contributes to the understanding of the catalytic roles of various acidic sites in different channels of the MOR zeolites and provides certain theoretical support for tailoring and designing efficient MOR zeolite catalysts for methanol/dimethyl ether carbonylation.
- carbonylation,
- methanol,
- dimethyl ether,
- B/Al/Ga-MOR zeolites,
- DFT calculation,
- reaction mechanism

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References(43)

References

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