Formulation of zeolite-mesoporous silica composite catalysts for light olefin production from catalytic cracking

doi:10.1007/s11705-024-2480-7

Front. Chem. Sci. Eng.

2024, Vol. 18

Issue (11) : 133 https://doi.org/10.1007/s11705-024-2480-7

Formulation of zeolite-mesoporous silica composite catalysts for light olefin production from catalytic cracking

Hassan Alhassawi¹(

), Edidiong Asuquo¹, Shima Zainal¹, Yuxin Zhang¹, Abdullah Alhelali¹, Zhipeng Qie^1,², Christopher M. A. Parlett^1,^3,^4,⁵, Carmine D’Agostino¹, Xiaolei Fan¹, Arthur A. Garforth¹(

)

¹. Department of Chemical Engineering, School of Engineering, The University of Manchester, Manchester M13 9PL, UK
². Faculty of Environment and Life, Beijing University of Technology, Beijing 100124, China
³. Diamond Light Source Harwell Science and Innovation Campus, Oxfordshire OX11 0DE, UK
⁴. University of Manchester at Harwell, Diamond Light Source Harwell Science and Innovation Campus, Oxfordshire OX11 0DE, UK
⁵. UK Catalysis Hub, Research Complex at Harwell, Rutherford Appleton Laboratory, Oxfordshire OX11 0FA, UK

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Abstract

Framework materials such as zeolites and mesoporous silicas are commonly used for many applications, especially catalysis and separation. Here zeolite-mesoporous silica composite catalysts (employing zeolite Y, ZSM-5, KIT-6, SBA-15 and MCM-41 mesoporous silica) were prepared (with different weight percent of zeolite Y and ZSM-5) and assessed for catalytic cracking (using n-heptane, as the model compound at 550 °C) with the aim to improve the selectivity/yield of light olefins of ethylene and propylene from n-heptane. Physicochemical properties of the parent zeolites and the prepared composites were characterized comprehensively using several techniques including X-ray diffraction, nitrogen physisorption, scanning electron microscopy, fourier transform infrared spectroscopy, pulsed-field gradient nuclear magnetic resonance and thermogravimetric analysis. Catalytic cracking results showed that the ZY/ZSM-5/KIT-6 composite (20:20:60 wt %) achieved a high n-heptane conversion of 85% with approximately 6% selectivity to ethylene/propylene. In contrast, the ZY/ZSM-5/SBA-15 composite achieved a higher conversion of 95% and an ethylene/propylene ratio of 8%, indicating a more efficient process in terms of both conversion and selectivity. Magnetic resonance relaxation analysis of the ZY/ZSM-5/KIT-6 (20:20:60) catalyst confirmed a micro-mesoporous environment that influences n-heptane diffusion and mass transfer. As zeolite Y and ZSM-5 have micropores, n-heptane can move and undergo hydrogen transfer reactions, whereas KIT-6 has mesopores that facilitate n-heptane’s accessibility to the active sites of zeolite Y and ZSM-5.

Keywords zeolites mesoporous silica composite catalysts catalytic cracking light olefins

Corresponding Author(s): Hassan Alhassawi,Arthur A. Garforth

Just Accepted Date: 31 May 2024 Issue Date: 29 August 2024

Cite this article:

Hassan Alhassawi,Edidiong Asuquo,Shima Zainal, et al. Formulation of zeolite-mesoporous silica composite catalysts for light olefin production from catalytic cracking[J]. Front. Chem. Sci. Eng., 2024, 18(11): 133.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2480-7
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I11/133

Tab.1 Proportion of components in the formulated composite catalysts

Fig.1 Schematic of the experimental rig for performing the catalytic cracking reaction. 1. pressure regulators for N₂ and air; 2. valves; 3. mass flow controllers; 4. bubblers; 5. chiller bath; 6. pressure gauge; 7. pressure relief valve; 8. reactor tube; 9. furnace; 10. glass wool; 11. catalyst bed; 12. glass beads; 13. GC; 14. data collector.

Fig.2 (a) Small-angle XRD patterns of the mesoporous silicas; wide-angle XRD diffraction patterns of (b) ZY/ZSM-5/KIT-6 group; (c) ZY/ZSM-5/MCM-41 group, and (d) ZY/ZSM-5/SBA-15.

Tab.2 Textural properties of the mesoporous silicas and the composite catalysts

Fig.3 (a) N₂ adsorption-desorption isotherms of ZY/ZSM-5/KIT-6(20:20:60), ZY/ZSM-5/MCM-41(20:20:60), and ZY/ZSM-5/SBA-15(20:20:60), and (b) the associated PSD by the BJH method.

Fig.4 TEM images of the selected composite catalysts: (a) ZY/ZSM-5/KIT-6 (20:20:60); (b) ZY/ZSM-5/SBA-15 (20:20:60), and (c) ZY/ZSM-5/MCM-41 (20:20:60).

Fig.5 (a) Conversions of n-C₇ and (b) total yields of LOs over different composite catalysts (conditions: t = 550 °C, WHSV = 0.4 h^–1, ToS = 4 h, P = atmospheric pressure).

Tab.3 Averaged activity and selectivity data of n-C₇ cracking over the selected composite catalysts at 550 °C, 0.4 h^–1 and atmospheric pressure

Fig.6 Longevity tests of the selected composite catalysts at 550 °C and atmospheric pressure (ToS = 12 h and WHSV = 0.4 h^–1): (a) n-C₇ conversion; (b) total yield of LOs; (c) product distribution of LOs, and (d) distribution of gas yields.

Fig.7 TGA profiles of the used ZY/ZSM-5/KIT-6 (20:20:60), ZY/ZSM-5/SBA-15 (20:20:60), and ZY/ZSM-5/MCM-41 (20:20:60).

Fig.8 Log₁₀ attenuation plots of n-C₇ saturated composite catalysts under investigation.

Tab.4 Relevant diffusion coefficients and calculated tortuosity values by PFG-NMR

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