Role of extra-framework aluminum species within MOR zeolites for syngas conversion via OXZEO catalysis

doi:10.1016/S1872-2067(24)60135-X

Abstract

Abstract:

The location of aluminum within the framework or extra-framework of zeolites is a critical factor in determining its catalytic performance. Despite extensive research on the identification and formation mechanism of extra-framework aluminum (EFAl), its impact on catalytic performance requires further investigation. Herein, mordenite (MOR) zeolites with comparable acid density within the 8MR and 12MR channels but different EFAl contents were prepared, and their catalytic roles were examined in syngas conversion. Intelligent gravimetric analysis, model experiment of ethylene conversion and thermogravimetric analysis demonstrate that the existence of EFAl species can inhibit the secondary conversion of ethylene to long chain hydrocarbons (i.e., C₅₊) as well as the over-accumulation of carbonaceous species. However, excessive EFAl species lead to rapid deactivation due to restricted space and thus severe diffusion limitation. MOR zeolite with a moderate amount of EFAl species achieves a superior ethylene selectivity and exhibits an enhanced stability in syngas conversion when combined with ZnAlO_x oxide. The insights gained in this work provide important guidance for the design of more efficient zeolite-based catalysts.

Key words: Syngas conversion, OR zeolite, Extra-framework aluminum, Ethylene selectivity, Diffusion

Haodi Wang, Feng Jiao, Jingyao Feng, Yuting Sun, Guangjin Hou, Xiulian Pan, Xinhe Bao. Role of extra-framework aluminum species within MOR zeolites for syngas conversion via OXZEO catalysis[J]. Chinese Journal of Catalysis, 2024, 67: 135-143.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60135-X

https://www.cjcatal.com/EN/Y2024/V67/I12/135

Figures/Tables 6

Table 1 Analysis of the Al distribution in MOR zeolites.

Sample	Si/Al ^a	Al distribution^b (%)				Al content^b (μmol g^-1)
Sample	Si/Al ^a	EFAl	T₁	T₂+T₄	T₃	EFAl	12MR	8MR
MOR-EFAl-1	9.2	0.21	14.19	45.10	40.49	3.4	978.5	668.2
MOR-EFAl-2	6.2	23.61	10.77	36.54	29.08	562.1	1126.5	692.4
MOR-EFAl-3	4.6	37.84	13.80	24.17	24.20	1146.7	1150.4	733.2

Fig. 1. Identification of aluminum species within MOR. (a) Deconvoluted bands of FT-IR spectra corresponding to the hydroxyls in the EFAl (3660 cm-1), T1 sites (TF, 3620 cm-1), T2+T4 sites (HF, 3607 cm-1) and T3 sites (LF, 3587 cm-1). (b) 27Al MAS NMR spectra.

Fig. 2. Catalytic performance of ZnAlOx-MOR bifunctional catalysts in syngas conversion with time on stream. (a) CO conversion. (b) Hydrocarbon distribution and CO conversion at time on stream of 40 h. (c) Hydrocarbon distribution for MOR-EFAl-1. (d) Hydrocarbon distribution for MOR-EFAl-2. (e) Hydrocarbon distribution for MOR-EFAl-3. Reaction conditions: 375 °C, 2.5 MPa, H2/CO=1, ZnAlOx/MOR=1/1 (mass ratio), 1800 mL g-1 h-1.

Fig. 3. IGA analysis and ethylene conversion as a model reaction. (a) Uptake curves of ethane analyzed by IGA at 30 °C with the pressure increasing from 0 to 10 mbar. (b) Uptake curves of n-butane analyzed by IGA at 30 °C with the pressure increasing from 0 to 5 mbar, the inset is the initial adsorption rate curves. (c) The yield of C3+ and C5+ in ethylene conversion at TOS of 10 h. (d) The selectivity ratio of (C3= + C4=) to C5+ in ethylene conversion at TOS of 10 h. Reaction conditions: 375 °C, 2.5 MPa, 21600 mL g-1 h-1, 0.6% C2H4 + H2 + Ar.

Fig. 4. TGA and DTG profiles of used MOR zeolites in syngas reaction for 4 and 8 h. (a) MOR-EFAl-1; (b) MOR-EFAl-2; (c) MOR-EFAl-3. (d) Carbonaceous species amount calculated from the TGA curves. The range of 200 to 480 °C corresponds to carbonaceous species I, and the range of 480 to 900 °C to carbonaceous species II.

Scheme 1. Schematic diagram of the role of EFAl species within MOR zeolites for syngas conversion.

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