Conversion of syngas into lower olefins over a hybrid catalyst system

doi:10.1007/s11705-024-2467-4

Front. Chem. Sci. Eng.

2024, Vol. 18

Issue (10) : 116 https://doi.org/10.1007/s11705-024-2467-4

Conversion of syngas into lower olefins over a hybrid catalyst system

Qiao Zhao^1,²(

), Hongyu Wang^1,³, Haoting Liang¹, Xiaoxue Han¹, Chongyang Wei¹, Shiwei Wang⁴, Yue Wang¹, Shouying Huang^1,⁴(

), Xinbin Ma¹

¹. Key Laboratory for Green Chemical Technology of Ministry of Education, Haihe Laboratory of Sustainable Chemical Transformations, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
². School of Materials Science and Engineering, National Institute for Advanced Materials, TKL of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin 300350, China
³. State Key Laboratory of Chemical Safety, SINOPEC Research Institute of Safety Engineering Co., Ltd., Qingdao 266104, China
⁴. Zhejiang Institute of Tianjin University, Ningbo Key Laboratory of Green Petrochemical Carbon Emission Reduction Technology and Equipment, Ningbo 315200, China

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Abstract

Lower olefins, produced from syngas through Fischer-Tropsch synthesis, has been gaining worldwide attention as a non-petroleum route. However, the process demonstrates limited selectivity for target products. Herein, a hybrid catalyst system utilizing Fe-based catalyst and SAPO-34 was shown to enhance the selectivity toward lower olefins. A comprehensive study was conducted to examine the impact of various operating conditions on catalytic performance, such as space velocity, pressure, and temperature, as well as catalyst combinations, including loading pattern, and mass ratio of metal and zeolite. The findings indicated that the addition of SAPO-34 was beneficial for enhancing catalytic activity. Furthermore, compared with AlPO-34 zeolite, the strong-acid site on SAPO-34 was identified to crack the long-chain hydrocarbons, thus contributing to the lower olefin formation. Nevertheless, an excess of strong-acid sites was found to detrimentally impact the selectivity of lower olefins, attributed to the increased aromatization and polymerization of lower olefins. The detailed analysis of a hybrid catalyst in Fischer-Tropsch synthesis provides a practical strategy for improving lower olefins selectivity, and has broader implications for the application of hybrid catalyst in diverse catalytic systems.

Keywords Fischer-Tropsch synthesis lower olefins SAPO-34 hybrid catalyst Fe-based catalyst

Corresponding Author(s): Qiao Zhao,Shouying Huang

Just Accepted Date: 29 April 2024 Issue Date: 08 July 2024

Cite this article:

Qiao Zhao,Hongyu Wang,Haoting Liang, et al. Conversion of syngas into lower olefins over a hybrid catalyst system[J]. Front. Chem. Sci. Eng., 2024, 18(10): 116.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2467-4
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I10/116

Fig.1 XRD patterns of AlPO-34, SAPO-34-1, SAPO-34-2, and SAPO-34-3 zeolites.

Fig.2 Effect of space velocity on catalytic performance. (a) Product distribution, TOS = 15 h; (b) catalyst stability. Reaction condition: WHSV = 27000–54000 mL?g^–1?h^–1, P = 2.0 MPa, T = 400 °C, FeKS/Al₂O₃: SAPO-34-2 = 1:5, granules (40–60 mesh).

Fig.3 Effect of reaction pressure on catalytic performance. (a) Product distribution, TOS = 20 h; (b) catalyst stability. Reaction condition: WHSV = 27000 mL?g^–1?h^–1, P = 0.5–2.0 MPa, T = 360 °C, FeKS/Al₂O₃: SAPO-34-2 = 1:5, granules (40–60 mesh).

Fig.4 Effect of temperature on catalytic performance. (a) Product distribution, TOS = 30 h; (b) catalyst stability. Reaction condition: WHSV = 27000 mL?g^–1?h^–1, P = 1.0 MPa, T = 340–360 °C, FeKS/Al₂O₃: SAPO-34-2 = 1:5, granules (40–60 mesh).

Fig.5 Investigation of two-component loading method. (a) Schematic diagram of loading method; (b) product distribution; (c) catalyst stability; (d) SEM image of powder mixing. Reaction condition: WHSV = 27000 mL?g^–1?h^–1, P = 1.0 MPa, T = 340 °C, FeKS/Al₂O₃:SAPO-34-2 = 1:5.

Fig.6 Effect of different ratios on catalytic performance. (a) Product distribution, TOS = 30 h; (b) calculation of chain growth probability α. Reaction condition: WHSV = 27000 mL?g^–1?h^–1, P = 2.0 MPa, T = 340 °C, FeKS/Al₂O₃:SAPO-34-2 = 1:0–1:7, granules (40–60 mesh).

Tab.1 Catalytic performance of different catalysts

Fig.7 Comparison of catalytic performance of different catalysts. (a) Catalyst stability; (b) selectivity of lower olefins and the ratio of olefin to paraffin. Reaction condition: WHSV = 27000 mL?g^–1?h^–1, P = 1.0 MPa, T = 340 °C, FeKS/Al₂O₃:quartz or zeolite = 1:7, granules (40–60 mesh).

Fig.8 NH₃-TPD profiles of zeolites.

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