Inorganic Chemicals Industry >

2025 , Vol. 57 >Issue 5: 71 - 78

DOI: https://doi.org/10.19964/j.issn.1006-4990.2024-0204

Research & Development

Mechanism study on influence of zeolite topology on dimethoxymethane carbonylation reaction

  • GAO Shaolei ,
  • WANG Yingli ,
  • QI Liang
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  • 1. National Engineering Research Center of Lower?Carbon Catalysis Technology，Dalian Institute of Chemical Physics，Chi? nese Academy of Sciences，Dalian 116023，China
    2. University of Chinese Academy of Sciences，Beijing 100049，China

Received date: 2024-04-09

  Online published: 2024-06-18

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Abstract

Dimethoxymethane（DMM） carbonylation over zeolites to methyl methoxyacetate（MMAc） is currently one of the most promising C1 chemical reactions for both fundamental research and industrialization.Zeolite topology influences DMM carbonylation evidently.In this work，zeolites with different topology including MFI，MOR and FAU were chosen to compare their DMM carbonylation activity and selectivity.As the increase of reaction space，both DMM carbonylation activity and selectivity were increased gradually.The improved DMM carbonylation selectivity could be attributed to the inhibition of DMM disproportionation and DMM carbonylation activity was rate⁃limited by both the generation and conversion of acyl intermediate.The low conversion kinetics conditions test excluding the influence of diffusion revealed that DMM carbonylation activity for FAU was about 9 times higher than that for MFI.Methoxy acetyl intermediate over MFI and FAU in the process of DMM carbonylation was directly observed by in⁃situ IR，and the relative intensity of carbonylation acyl and disproportionation acyl was positive to DMM carbonylation selectivity.Finally，a possible DMM carbonylation and disproportionation mechanism over zeolites was proposed and a DMM carbonylation kinetic formula was deduced based on the in⁃situ IR results and the understanding of the reaction mechanism.

Key words： carbonylation reaction; dimethoxymethane; zeolite; in?situ IR; kinetic

Cite this article

GAO Shaolei , WANG Yingli , QI Liang . Mechanism study on influence of zeolite topology on dimethoxymethane carbonylation reaction[J]. Inorganic Chemicals Industry, 2025 , 57(5) : 71 -78 . DOI: 10.19964/j.issn.1006-4990.2024-0204

References

1 倪友明.甲缩醛羰基化制甲氧基乙酸甲酯及水解制乙醇酸甲酯技术［Z］.大连：中国科学院大连化学物理研究所，2022-12-01.
2 HENDRIKSEN D.Intermediates to ethylene glycol：Carbonylation of formaldehyde catalyzed by Nafion solid perfluorosulfonic acid resin［J］.Preprint Papers，American Chemical Society，Division of Fuel Chemistry，1983，28：176.
3 SHI Qiqi， GUO Heqin， CHEN Congbiao，et al.An efficient Br?nsted acidic polymer resin for the carbonylation of formaldehyde to glycolic acid［J］.Reaction Kinetics，Mechanisms and Catalysis，2020，130（2）：1027-1042.
4 CAO Xuemin， ZHANG Kun， WANG Yu，et al.Boosting the production of glycolic acid from formaldehyde carbonylation via the bifunctional PdO/ZSM-5 catalyst［J］.Industrial & Engineering Chemistry Research，2023，62（43）：17671-17680.
5 ZHU Zhihao， SUN Ying， YU Haijun，et al.Effect of polytetrafluoroethylene hollow fiber microstructure on formaldehyde carbonylation performance in membrane contactor［J］.Chinese Journal of Chemical Engineering，2023，55：148-155.
6 WANG Di， LV Jiangang.Synthesis of precursors to ethylene glycol via the acid?catalyzed carbonylation of formaldehyde［J］.Catalysts，2023，13（10）：1327.
7 CELIK F E， KIM T J， BELL A T.Vapor-phase carbonylation of dimethoxymethane over H-faujasite［J］.Angewandte Chemie，2009，48（26）：4813-4815.
8 CHEUNG P， BHAN A， SUNLEY G J，et al.Selective carbonylation of dimethyl ether to methyl acetate catalyzed by acidic zeolites［J］.Angewandte Chemie，2006，45（10）：1617-1620.
9 CHEUNG P， BHAN A， SUNLEY G J，et al.Site requirements and elementary steps in dimethyl ether carbonylation catalyzed by aci?dic zeolites［J］.Journal of Catalysis，2007，245（1）：110-123.
10 XIE Mingguan， FANG Xudong， LIU Hongchao，et al.Cyclic oxygenate?based deactivation mechanism in dimethyl ether carbonylation reaction over a pyridine?modified H-MOR catalyst［J］.ACS Catalysis，2023，13（21）：14327-14333.
11 XIE Mingguan， FANG Xudong， CHEN Zhiyang，et al.Insights into the CO-mediated deactivation mechanism for dimethyl ether carbonylation reaction over a H-MOR catalyst［J］.Applied Catalysis A：General，2024，677：119701.
12 FAN Dong， CHEN Nan， HAN Songyue，et al.H2-promoted benign coke strategy for dimethyl ether carbonylation with long?term stability and high activity［J］.ACS Applied Materials & Interfaces，2024，16（15）：18745-18753.
13 LIU Junlong， XUE Huifu， HUANG Xiumin，et al.Stability enhancement of H-mordenite in dimethyl ether carbonylation to methyl acetate by pre?adsorption of pyridine［J］.Chinese Journal of Catalysis，2010，31（7）：729-738.
14 CELIK F E， KIM T J， BELL A T.Effect of zeolite framework type and Si/Al ratio on dimethoxymethane carbonylation［J］.Journal of Catalysis，2010，270（1）：185-195.
15 SHAPOVALOV V， BELL A.Theoretical study of zeolite?catalyzed dimethoxymethane carbonylation to methyl methoxyaceta?te［J］.Journal of Physical Chemistry C，2010，114：17753-17760.
16 RASMUSSEN D B， CHRISTENSEN J M， TEMEL B，et al.Ketene as a reaction intermediate in the carbonylation of dimethyl ether to methyl acetate over mordenite［J］.Angewandte Chemie，2015，54（25）：7261-7264.
17 LIU Shiping， ZHU Wenliang， SHI Lei，et al.A highly efficient Nafion-H catalyst for vapour phase carbonylation of dimethoxymethane［J］.RSC Advances，2014，4（77）：40999-41002.
18 LIU Shiping， ZHU Wenliang， SHI Lei，et al.Activity enhancement of nafion resin：Vapor?phase carbonylation of dimethoxymethane over nafion?silica composite［J］.Applied Catalysis A：General，2015，497：153-159.
19 CHEN Fei， SHI Lei， YAO Jie，et al.A highly efficient sulfonic acid resin for liquid?phase carbonylation of dimethoxymethane［J］.Catalysis Science & Technology，2018，8（2）：580-590.
20 YAO Jie， WANG Yan， BELLO S S，et al.Regulation of Br?nsted acid sites in H-MOR for selective methyl methoxyacetate synthesis［J］.Applied Organometallic Chemistry，2020，34（11）：e5925.
21 SHEIKH K A， ZAGHINI FRANCESCONI V， ZEVACO T A，et al.Carbonylation of dimethoxymethane：A study on the reactivity of different solid acid catalysts［J］.Catalysis Science & Technology，2024，14（5）：1148-1166.
22 CHEN Fei， SHI Lei， BELLO S，et al.Excellent prospects in methyl methoxyacetate synthesis with a highly active and reusable sulfonic acid resin catalyst［J］.New Journal of Chemistry，2020，44（4）：1346-1353.
23 ZHANG Dongxi， SHI Lei， WANG Yan，et al.Effect of mass?transfer control on HY zeolites for dimethoxymethane carbonylation to methyl methoxyacetate［J］.Catalysis Today，2018，316：114-121.
24 CHEN Fei， ZHANG Dongxi， SHI Lei，et al.Optimized pore structures of hierarchical HY zeolites for highly selective production of methyl methoxyacetate［J］.Catalysts，2019，9（10）：865.
25 XIE Zhiqiang， CHEN Congbiao， HOU Bo，et al.Study of the nature of high?silica H-Y acid sites in dimethoxymethane carbonylation by NH3 poisoning［J］.The Journal of Physical Chemistry C，2018，122（18）：9909-9917.
26 梁瑞康，刘卓，孙泽平，等.铝源对HZSM-5分子筛中骨架铝落位及其甲缩醛气相羰基化性能的影响［J］.工业催化，2023，31（7）：23-31.
  LIANG Ruikang， LIU Zhuo， SUN Zeping，et al.Effects of aluminium sources on the framework aluminum siting of HZSM-5 zeolite and its catalytic performance in dimethoxymethane carbonylation［J］.Industrial Catalysis，2023，31（7）：23-31.
27 孙泽平，武建兵，李鹏，等.柠檬酸处理对ZSM-5分子筛甲缩醛气相羰基化性能的影响［J］.分子催化，2021，35（1）：22-30.
  SUN Zeping， WU Jianbing， LI Peng，et al.Effect of citric acid modification of ZSM-5 zeolite on vapor?phase dimethoxymethane carbonylation［J］.Journal of Molecular Catalysis（China），2021，35（1）：22-30.
28 WU Jianbing， ZHANG Xiaoyan， SUN Zeping，et al.Effect of NaOH content in the synthesis gel on the catalytic performance of H-ZSM-5 zeolites in the gas phase carbonylation of dimethoxymethane［J］.Journal of Fuel Chemistry and Technology，2019，47（10）：1226-1234.
29 张晓艳，武建兵，周玮，等.ZSM-5分子筛形貌及硅铝比对甲缩醛气相羰基化反应性能的影响［J］.工业催化，2019，27（8）：52-59.
  ZHANG Xiaoyan， WU Jianbing， ZHOU Wei，et al.Effect of morphology and Si/Al ratio of ZSM-5 on gas phase carbonylation of dimethoxymethane［J］.Industrial Catalysis，2019，27（8）：52-59.
30 ZHU Dali， WANG Linying， ZHANG Wenna，et al.Realizing fast synthesis of high?silica zeolite Y with remarkable catalytic performance［J］.Angewandte Chemie International Edition，2022，61（23）：e202117698.
31 EMEIS C A.Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts［J］.Journal of Catalysis，1993，141（2）：347-354.
32 CELIK F E， KIM T， MLINAR A N，et al.An investigation into the mechanism and kinetics of dimethoxymethane carbonylation over FAU and MFI zeolites［J］.Journal of Catalysis，2010，274（2）：150-162.
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