Dimethoxymethane carbonylation and disproportionation over extra-large pore zeolite ZEO-1: Reaction network and mechanism

doi:10.1016/S1872-2067(24)60187-7

Abstract

Abstract:

Methyl methoxyacetate (MMAc) and methyl formate (MF) can be produced directly by heterogeneous zeolite-catalyzed carbonylation and disproportionation of dimethoxymethane (DMM), with near 100% selectivity for each process. Despite continuous research efforts, the insight into the reaction mechanism and kinetics theory are still in their nascent stage. In this study, ZEO-1 material, a zeolite with up to now the largest cages comprising 16×16-MRs, 16×12-MRs, and 12×12-MRs, was explored for DMM carbonylation and disproportionation reactions. The rate of MMAc formation based on accessible Brönsted acid sites is 2.5 times higher for ZEO-1 (Si/Al = 21) relative to the previously investigated FAU (Si/Al = 15), indicating the positive effect of spatial separation of active sites in ZEO-1 on catalytic activity. A higher MF formation rate is also observed over ZEO-1 with lower activation energy (79.94 vs. 95.19 kJ/mol) compared with FAU (Si/Al = 30). Two types of active sites are proposed within ZEO-1 zeolite: Site 1 located in large cages formed by 16×16-MRs and 16×12-MRs, which is active predominantly for MMAc formation, and Site 2 located in smaller cages for methyl formate/dimethyl ether formation. Kinetics investigation of DMM carbonylation over ZEO-1 exhibit a first-order dependence on CO partial pressure and a slightly inverse-order dependence on DMM partial pressure. The DMM disproportionation is nearly first-order dependence on DMM partial pressure, while it reveals a strongly inverse dependence with increasing CO partial pressure. Furthermore, ZEO-1 exhibits good catalytic stability, and almost no deactivation is observed during the more than 70 h test with high carbonylation selectivity of above 89%, due to the well-enhanced diffusion property demonstrated by intelligent-gravimetric analysis.

Key words: Dimethoxymethane carbonylation, Dimethoxymethane disproportionation, Zeolite, In-situ IR, Kinetic, Reaction mechanism

Shaolei Gao, Peng Lu, Liang Qi, Yingli Wang, Hua Li, Mao Ye, Valentin Valtchev, Alexis T. Bell, Zhongmin Liu. Dimethoxymethane carbonylation and disproportionation over extra-large pore zeolite ZEO-1: Reaction network and mechanism[J]. Chinese Journal of Catalysis, 2025, 68: 230-245.

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Figures/Tables 16

Fig. 1. The DMM conversion pathways for the production of MEG, GA, MG, and MF from syngas. DMM carbonylation process for new C?C bond formation is outlined in blue.

Fig. 2. Crystal structure and physical properties of ZEO-1 zeolite. XRD pattern (a), N2 adsorption-desorption isotherms (b), and low and high-resolution TEM images (c,d) of ZEO-1 zeolite.

Fig. 3. DMM disproportionation over ZEO-1 as a function of reaction temperature (a,b), space velocity (c,d), and DMM partial pressure (e,f). Reaction conditions: (a,b): 0.05 g ZEO-1, 343?423 K, PDMM = 27 kPa, space velocity = 36 L gcat?1 h?1 at total pressure of 1 MPa (balanced with N2); (c,d): 0.05 g ZEO-1, 373 K, PDMM= 17 kPa, space velocity = 36-108 L gcat?1 h?1 at total pressure of 1 MPa (balanced with N2); (e,f): 0.05 g ZEO-1, 373 K, PDMM= 10?27 kPa, space velocity = 36 L gcat?1 h?1 at total pressure of 1 MPa (balanced with N2).

Fig. 4. DMM carbonylation and disproportionation over ZEO-1 as a function of reaction temperature (a,b), total pressure (c,d) and space velocity (e,f). Reaction conditions: (a,b) 0.05 g zeolite, 373?443 K, PDMM = 43 kPa, space velocity = 36 L gcat?1 h?1 at 3 MPa; (c,d) 0.05 g zeolite, 383 K, PDMM = 14.3?43 kPa, space velocity = 36 L gcat?1 h?1 at 1-3 MPa; (e,f) 0.02 g zeolite, 383 K, PDMM = 43 kPa, space velocity = 45?360 L gcat?1 h?1 at 3 MPa.

Fig. 5. Dependence of the rates of DMM carbonylation to MMAc and disproportionation to MF over ZEO-1 measured at 353?373 K, on the CO partial pressure (a,c) and DMM partial pressure (b,d). Reaction conditions: (a,c) 0.0065 g ZEO-1, 373 K, PDMM = 43 kPa, PCO = 0.74?2.96 MPa at total pressure of 3 MPa, (b,d) 0.0113 g ZEO-1, 353 K, PDMM = 27?52 kPa at total pressure of 3 MPa.

Fig. 6. Comparison of DMM carbonylation activity over ZEO-1 and FAU under low conversion. For ZEO-1: 0.01 g ZEO-1, 373 K, PDMM = 43 kPa, GHSV = 360 L gcat?1 h?1 at 2 MPa. For FAU (Si/Al = 15): 0.05 g FAU, 373 K, PDMM = 43 kPa, GHSV = 240 L gcat?1 h?1 at 2 MPa. For FAU (Si/Al = 30): 0.02 g FAU, 373 K, PDMM = 43 kPa, GHSV = 600 L gcat?1 h?1 at 2 MPa.

Fig. 7. DMM carbonylation over ZEO-1 and FAU (Si/Al = 30). Reaction conditions: 0.1 g zeolite, 383 K, PDMM = 14 kPa, space velocity = 18 L gcat?1 h?1 at 5 MPa.

Fig. 8. Schematic illustration for the formation of MMZ via the interaction of DMM with Br?nsted acid sites over zeolite (a), MAZ via CO insertion into MMZ (b), and MFZ via a hydrogen transfer reaction between DMM and MMZ (c).

Fig. 9. (a) IR spectrum of surface hydroxyl groups on ZEO-1. In-situ IR spectra of ZEO-1 exposed to 8 kPa DMM/Ar (b,c) and Ar purge after DMM/Ar (d,e). (f) Plots of the IR intensity representing CH2/CH3 versus purging time. Conditions: 0.015 g ZEO-1, 383 K, 100 mL min-1 total flow rate at a total pressure of 0.4 MPa.

Fig. 10. In-situ IR spectra of ZEO-1 collected during exposed to 8 kPa DMM/Ar (a), Ar purging after DMM/Ar (b), exposed to 8 kPa DMM/CO (c) and Ar purging after DMM/CO (d). Conditions: 0.0157 g ZEO-1 for (a,b) and 0.0140 g ZEO-1 for (c,d), 383 K, 100 mL min-1 total flow rate at total pressure of 0.5 MPa.

Table 1 The assignment and area of IR peaks for FAU (Si/Al = 30) and ZEO-1 with identical feed compositions.

Wavenumber (cm^‒1)	Assignment	(Area/μmol_{Brönsted acid})
Wavenumber (cm^‒1)	Assignment	FAU ^f	ZEO-1 ^f	FAU ^g	ZEO-1 ^g
1766 ^a	MF	0.137	0.158	—	—
1759 ^b	MMAc	—	—	8.06	3.30
1753 ^c	MF	0.0263	0.0216	—	—
1744 ^d	MAZ	—	—	10.29	8.21
1733/1736 ^e	MFZ	0.388	0.711	—	—

Fig. 11. In-situ IR spectra of FAU (Si/Al = 30) collected during exposed to 8 kPa DMM/Ar (a) and 8 kPa DMM/CO (b), respectively. Conditions: 0.0115 g FAU for (a) and 0.0134 g FAU for (b), 383 K, 100 mL min?1 total flow rate at total pressure of 0.5 MPa.

Fig. 12. In-situ IR spectrum of ZEO-1 collected during exposed to 8 kPa DMM/13CO. Conditions: 0.015 g ZEO-1, 383 K, 25 mL min?1 total flow rate at total pressure of 0.1 MPa.

Fig. 13. Proposed mechanism for DMM carbonylation and disproportionation over different active sites in ZEO-1 [2,14]. The blue dashed square demonstrates the reaction cycle over DMM carbonylation active site (Site 1), and the orange dashed square demonstrates the reaction cycle over DMM disproportionation active site (Site 2).

Fig. 14. DMM carbonylation and disproportionation apparent activation energy of ZEO-1 exposed to DMM/CO. Reaction conditions: 0.008 g ZEO-1, 363?383 K, PDMM = 43 kPa, GHSV = 750 L gcat?1 h?1 at 2 MPa.

Fig. 15. DMM carbonylation and disproportionation apparent activation energy of FAU (Si/Al = 30) exposed to DMM/CO. Reaction conditions: 0.01 g FAU, 353?383 K, PDMM = 43 kPa, GHSV = 300-1200 L gcat?1 h?1 at 2 MPa.

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