Benefits of H-ZSM-5 zeolite from fluoride-mediated acidic synthesis for liquid-phase conversion of cyclohexanol

doi:10.1016/S1872-2067(25)64718-8

Abstract

Abstract:

The hydrothermal stability of zeolites is essential for their potential applications in biomass conversion, especially in processes involving elevated temperatures alongside the use or generation of H₂O. In this study, we employed F^- ions as mineralizers to synthesize hydrothermally stable ZSM-5 zeolites under acidic conditions. The acidic synthesis system promotes zeolites with fewer silanol-terminated lattice defects (ZSM-5(A)) compared to the traditional basic conditions (ZSM-5(B)), endowing materials with substantially higher structural integrity and hydrophobicity. After 10 days of autoclave treatment at 200 °C in aqueous phase, H-ZSM-5(A) demonstrated nearly unchanged reaction rates in the dehydration of cyclohexanol, while H-ZSM-5(B) lost > 50% of the dehydration activity. Additionally, H-ZSM-5(A) delivered higher initial dehydration rates compared to H-ZSM-5(B). The different measured activation energies further revealed variations in reaction pathways during cyclohexanol dehydration, i.e., the monomer- or dimer-mediated routes depending on the concentration of alcohol molecule within zeolite pores, providing additional evidence for the strengthened hydrophobic nature of H-ZSM-5(A). Beyond this, the zeolite surface properties and the strength of cyclohexanol-zeolite interactions may impose additional transport/adsorption barriers attributed to multi-phase phenomena on the more polar H-ZSM-5(B) zeolite surfaces. More importantly, the hydrothermal treatment did not induce significant desilication and dealumination in H-ZSM-5(A), thereby preserving its active acid sites and ensuring exceptional hydrothermal stability. The present work fundamentally studies the synthesis of hydrothermally stable zeolites in an acidic medium using fluorides and expands the understanding of polar interactions in catalysis, characterized by the dehydration of cyclohexanol, for future application in biomass conversion.

Key words: Biomass conversion, Dehydration, Hydrothermal stability, Kinetics, Zeolites

Qisong Yi, Lu Lin, Huawei Geng, Shaohua Chen, Yuanchao Shao, Ping He, Zhifeng Liu, Haimei Xu, Tiehong Chen, Yuanshuai Liu, Valentin Valtchev. Benefits of H-ZSM-5 zeolite from fluoride-mediated acidic synthesis for liquid-phase conversion of cyclohexanol[J]. Chinese Journal of Catalysis, 2025, 74: 97-107.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64718-8

https://www.cjcatal.com/EN/Y2025/V74/I7/97

Figures/Tables 7

Fig. 1. (a) The schematic diagram of ZSM-5 synthesis under acidic conditions. XRD patterns (b) and SEM images (c,d) of H-ZSM-5(A) and H-ZSM-5(B) zeolites. TEM (e,f, inset: SAED spectrum) and mapping images (g) of H-ZSM-5(A) zeolite.

Table 1 Acidity measurements of ZSM-5 zeolites before and after hydrothermal treatment using Py-IR.

Sample	Si/Al^a	Acidity (μmol·g^-1)			B/L	Si/Al^b
Sample	Si/Al^a	BAS	LAS	Total	B/L	Si/Al^b
H-ZSM-5(A)	75 (± 8)	230	10	240	23	—
H-ZSM-5(A)-H-10d	80 (± 5)	220	11	231	20	579 (± 21)
H-ZSM-5(B)	73 (± 6)	239	22	261	11	—
H-ZSM-5(B)-H-10d	93 (± 8)	174	27	201	6	372 (± 17)

Fig. 2. (a) FT-IR spectra of H-ZSM-5(A) and H-ZSM-5(B). (b) Water adsorption isotherm over two zeolite samples. FT-IR spectra have been calibrated based on the sample mass.

Fig. 3. (a) The catalytic activity of ZSM-5 zeolites for the dehydration of cyclohexanol in decalin before and after the hydrothermal treatment as well as steaming treatment. (b) Apparent activation energies (Ea,app) for dehydration of cyclohexanol over ZSM-5 zeolites. (c) Adsorption isotherms of cyclohexanol from decalin over ZSM-5. (d) The proposed reaction path for dehydration of cyclohexanol over ZSM-5 zeolites. Hydrothermal treatment conditions: 0.5 g zeolite, 50 mL H2O, 200 °C, 15 rpm, 5?10 d. Steaming treatment conditions: 0.4 g zeolite, 0.04 mL·min?1 H2O, 20 mL·min?1 N2, 500 °C, 4 h on a fixed bed reactor. Reaction conditions: 0.1 g zeolite, 5 g cyclohexanol, 100 mL decalin, 180 °C, 3 Mpa H2, 4 h in a stirred batch reactor.

Fig. 4. Py-IR spectra on ZSM-5 samples before and after hydrothermal treatment.

Fig. 5. (a) 29Si MAS NMR spectra of ZSM-5 zeolites before and after hydrothermal treatment. (b) The structure diagram of Q4 and Q3 silica species. The fitted 29Si MAS NMR spectra of H-ZSM-5(A) (c) and H-ZSM-5(B) (d) before and after hydrothermal treatment.

Fig. 6. (a) 27Al MAS NMR spectra of ZSM-5 zeolites before and after hydrothermal treatment. (b) The schematic diagrams of different locations of Al. The fitted 27Al MAS NMR spectra (c-d), and the distribution of Al (e) over ZSM-5 zeolites before and after hydrothermal treatment.

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