Pore-mouth catalysis boosting the formation of iso-paraffins from syngas over bifunctional catalysts

doi:10.1016/S1872-2067(20)63770-6

Abstract

Abstract:

Recent studies confirm that the emerging bifunctional catalysts consisting of metal oxide and zeolites can directly convert syngas into high-quality gasoline, however, the formation mechanism of iso-paraffins and the difference with the conventional FT/zeolite catalyst have not been investigated. Herein, three one-dimensional SAPO zeolites with diverse micropore sizes were synthesized and assembled with ZnAlO_x with spinel structure. It was found that ZnAlO_x/SAPO-41 and ZnAlO_x/SAPO-11 with medium micropore sizes favored the formation of C₅-C₁₁ hydrocarbons with a high content of iso-paraffins. The characterizations pointed out that the formation of iso-paraffins over SAPO-11 followed a pore-mouth catalysis mechanism, which means the isomerization of linear hydrocarbons can only take place near the pore mouth region of zeolites. This mechanism only allows the formation of mono-branched iso-paraffins in the C₅-C₁₁ range, which are less prone to be cracked than their di-branched isomers. A careful comparative analysis between ZnAlO_x/SAPO-11 and Co/H-meso-ZSM-5 was also made in terms of product distribution, activity, and stability.

Key words: Pore-mouth catalysis, Shape-selective catalysis, Bifunction, Syngas, Gasoline

Mengheng Wang, Yaoyao Han, Suhan Liu, Zhiming Liu, Dongli An, Zhiqiang Zhang, Kang Cheng, Qinghong Zhang, Ye Wang. Pore-mouth catalysis boosting the formation of iso-paraffins from syngas over bifunctional catalysts[J]. Chinese Journal of Catalysis, 2021, 42(12): 2197-2205.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63770-6

https://www.cjcatal.com/EN/Y2021/V42/I12/2197

Figures/Tables 7

Fig. 1. PXRD patterns of SAPO-41 (a), SAPO-11 (b) and SAPO-5 (c); SEM imaging of SAPO-41 (d), SAPO-11 (e) and SAPO-5 (f).

Table 1 Physiochemical properties of three SAPO zeolites and AlPO-11 zeolite.

Zeolites	Pore size (nm²)	Topology	Si/(Si + Al + P)^a	Peak_HT^b (°C)	D_acid^c (mmol g^-1)	Morphology^d
SAPO-41	0.41 × 0.53	AFO	0.04	308	0.12	Eight prism, 5 µm
SAPO-11	0.40 × 0.65	AEL	0.06	303	0.23	Cuboid, 1-2 µm
SAPO-5	0.73 × 0.73	AFI	0.03	265	0.15	Hexagonal prism, 2 µm
AlPO-11	0.40 × 0.65	AEL	0	—	0	Needle, 1 µm

Fig. 2. Effects of Brönsted acid sites (a), temperature (b) and pressure (c) on the catalytic behaviors of ZnAlOx/SAPO catalyst in CO hydrogenation. Reaction conditions: Wcat = 1.0 g, H2/CO = 1, P = 2-4 MPa, Fsyngas = 25 mL min-1, T = 350-400 °C, time on stream = 10 h. Catalytic performances in detail are listed in Table S5-S7.

Fig. 3. Effect of pore size of 1D SAPO zeolites on the catalytic behaviors of bifunctional ZnAlOx/SAPO catalysts in CO hydrogenation. Reaction conditions: Wcat = 1.0 g, H2/CO = 1, P = 3 MPa, Fsyngas = 25 mL min-1, T = 350 °C, time on stream = 4 h or 10 h. Catalytic performances in detail are listed in Table S9.

Fig. 4. Comparison of catalytic performance between bifunctional ZnAlOx/SAPO-11 and Co/H-meso-ZSM-5 catalyst in syngas conversion reaction after 10 h of reaction. Reaction conditions for ZnAlOx/SAPO-11: Wcat = 1.0 g, H2/CO = 1, P = 3 MPa, Fsyngas = 25 mL min-1, T = 350 °C, time on stream = 10 h. Reaction conditions for Co/H-meso-ZSM-5: Wcat = 0.5 g, H2/CO = 1, P = 2 MPa, Fsyngas = 20 mL min-1, T = 240 °C, time on stream = 10 h. Catalytic performances in detail are listed in Table S10.

Fig. 5. Comparison of (a) ZnAlOx/SAPO-11 and (b) Co/H-meso-ZSM-5 in syngas conversion. Reaction conditions for ZnAlOx/SAPO-11: Wcat = 1.0 g, H2/CO = 1, P = 3 MPa, Fsyngas = 25 mL min-1, T = 350 °C. Reaction conditions for Co/H-meso-ZSM-5: Wcat = 0.5 g, H2/CO = 1, P = 2 MPa, Fsyngas = 20 mL min-1, T = 240 °C.

Fig. 6. (a) GC-MS analysis of the gaseous product in C4-C6 cut over bifunctional ZnAlOx/SAPO-11 catalyst after 10 h of reaction; (b) Adsorption isotherms of n-butane and iso-butane over SAPO-11; (c) Schematic pore-mouth catalysis mechanism in syngas conversion over ZnAlOx/SAPO-11 catalyst.

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