Post-treatment of Ti-MWW zeolite with potassium fluoride for propylene epoxidation

doi:10.1007/s11705-024-2441-1

Front. Chem. Sci. Eng.

2024, Vol. 18

Issue (8) : 88 https://doi.org/10.1007/s11705-024-2441-1

Post-treatment of Ti-MWW zeolite with potassium fluoride for propylene epoxidation

Xintong Li, Xianchen Gong, Jilong Wang, Shengbo Jin, Hao Xu(

), Peng Wu(

)

State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China

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Abstract

Epoxidation of propylene to propylene oxide (PO) with hydrogen peroxide (HPPO) is an environmentally friendly and cost-efficient process in which titanosilicates are used as catalysts. Ti-MWW is a potential industrial catalyst for this process, which involves the addition of HPPO to PO. The silanol groups generated during secondary crystallization unavoidably result in ring-opening of PO and inefficient decomposition of HPPO, which diminish the PO selectivity and the lifespan of Ti-MWW. To address this issue, we conducted post-treatment modifications of the structured Bf-Ti-MWW catalyst with potassium fluoride aqueous solutions. By quenching the silanol groups with potassium fluoride and implanting electron-withdrawing fluoride groups into the Ti-MWW framework, both the catalytic activity and HPPO utilization efficiency were increased. Moreover, the ring opening reaction of PO was prohibited. In a continuous fixed-bed liquid-phase propylene epoxidation reaction, the KF-treated structured Ti-MWW catalyst displayed an exceptionally long lifespan of 2700 h, with a PO yield of 590 g·kg⁻¹·h⁻¹.

Keywords titanosilicates Ti-MWW propylene epoxidation structured catalyst KF modification

Corresponding Author(s): Hao Xu,Peng Wu

Just Accepted Date: 03 April 2024 Issue Date: 28 May 2024

Cite this article:

Xintong Li,Xianchen Gong,Jilong Wang, et al. Post-treatment of Ti-MWW zeolite with potassium fluoride for propylene epoxidation[J]. Front. Chem. Sci. Eng., 2024, 18(8): 88.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2441-1
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I8/88

Tab.1 Propylene epoxidation over the Ti-MWW catalysts before and after treatment^a)

Fig.1 (a) XRD patterns and (b) N₂ adsorption-desorption isotherms at 77 K for (I) Bf-Ti-MWW, (II) Bf-Ti-MWW-KF, (III) Bf-Ti-MWW-KHCO₃, and (IV) Bf-Ti-MWW-NH₄F.

Tab.2 Textural properties of BF-Ti-MWW before and after treatment with potassium salts and ammonium fluoride

Fig.2 (a) UV-Vis spectra, (b) Ti 2p XPS spectra, and (c) ¹⁹F MAS NMR spectra of (I) Bf-Ti-MWW, (II) Bf-Ti-MWW-KF, (III) Bf-Ti-MWW-KHCO₃, and (IV) Bf-Ti-MWW-NH₄F.

Fig.3 (a) H₂O adsorption isotherms generated at 298 K, (b) spectra in the hydroxyl-stretching region, and (c) pyridine-adsorbed FTIR spectra after evacuation at 523 K for (I) Bf-Ti-MWW, (II) Bf-Ti-MWW-KF, (III) Bf-Ti-MWW-KHCO₃, and (IV) Bf-Ti-MWW-NH₄F. B: Br?nsted acid sites; L: Lewis acid sites; H: hydrogen-bonded pyridine.

Scheme1 Post-treatment of Ti-MWW zeolites with KF for propylene epoxidation and possible structures of the K and F species in Ti-MWW.

Fig.4 (a) Progress of PO hydrolysis over (I) Bf-Ti-MWW, (II) Bf-Ti-MWW-KF, (III) Bf-Ti-MWW-KHCO₃, and (IV) Bf-Ti-MWW-NH₄F in the presence of H₂O₂. Reaction conditions: catalyst, 0.2 g; PO, 40 mmol; H₂O₂ (30 wt %), 10 mmol; H₂O/PO molar ratio, 5; temperature, 313 K. (b) Hydrolysis of PO over different catalysts in H₂O or H₂O/H₂O₂. Reaction conditions: catalyst, 0.2 g; PO, 40 mmol; H₂O₂ (30 wt %), 10 mmol (if added); H₂O/PO molar ratio, 5; temperature, 313 K; time, 12 h.

Fig.5 (a) Dependence of the TOFs on the H₂O₂ concentrations for (I) Bf-Ti-MWW-KF and (II) Bf-Ti-MWW. Reaction conditions: catalyst, 0.01 g; H₂O₂, 30 wt %; solvent, MeCN, 10 mL; temperature, 313 K; time, 4 min. (b) Time-dependent H₂O₂ conversion in propylene epoxidation over (I) Bf-Ti-MWW-KF and (II) Bf-Ti-MWW. Reaction conditions: catalyst, 0.03 g; H₂O₂ (30 wt %), 30 mmol; solvent MeCN, 10 mL; propylene pressure, 0.4 MPa; temperature, 313 K.

Fig.6 Stability of the Bf-Ti-MWW-KF catalyst in continuous liquid-phase propylene epoxidation. Reaction conditions: catalyst, 3 g; temperature, 313–333 K; C₃H₆/H₂O₂ molar ratio, 3; additive, (NH₄)₂CO₃, 15 ppm; pressure, 2–3 MPa; WHSV (H₂O₂), 0.4 h^?1; WHSV (MeCN), 5 h^?1. X: H₂O₂ conversion; S: PO selectivity; Y: PO yield; U: H₂O₂ ultilization efficiency.

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