Structured binder-free MWW-type titanosilicate with Si-rich shell for selective and durable propylene epoxidation

doi:10.1016/S1872-2067(20)63759-7

Abstract

Abstract:

Selective and durable fixed-bed catalysts are highly desirable for developing eco-efficient HPPO (hydrogen peroxide propylene oxide) process. The powder titanosilicate catalysts must be shaped before being applied in industrial processes. As the essential additives for preparing formed catalysts, binders are usually the catalytically inert components, but they would cover the surface and pore mouth of zeolite, thereby declining the accessibility of active sites. By recrystallizing the binder (silica)/Ti-MWW extrudates with the assistance of dual organic structure-directing agents, the silica binder was converted into MWW zeolite phase to form a structured binder-free Ti-MWW zeolite with Si-rich shell, which enhanced the diffusion efficiency and maintained the mechanical strength. Meanwhile, due to the partial dissolution of Si in the Ti-MWW matrix, abundant silanol nests formed and part of framework TiO₄ species were transferred into open TiO₆ ones, improving the accumulation and activation ability of H₂O₂ inside the monolith. Successive piperidine treatment and fluoridation of the binder-free Ti-MWW further enhanced the H₂O₂ activation and oxygen transfer ability of the active Ti sites, and stabilized the Ti-OOH intermediate through hydrogen bond formed between the end H in Ti-OOH and the adjacent Si-F species, thus achieving a more efficient epoxidation process. Additionally, the side reaction of PO hydrolysis was inhibited because the modification effectively quenched numerous Si-OH groups. The lifetime of the modified binder-free Ti-MWW catalyst was 2400 h with the H₂O₂ conversion and PO selectivity both above 99.5%.

Key words: Propylene epoxidation, Titanosilicate, Binder-free formed catalyst, Recrystallization, Microenvironment

Jinpeng Yin, Xin Jin, Hao Xu, Yejun Guan, Rusi Peng, Li Chen, Jingang Jiang, Peng Wu. Structured binder-free MWW-type titanosilicate with Si-rich shell for selective and durable propylene epoxidation[J]. Chinese Journal of Catalysis, 2021, 42(9): 1561-1575.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63759-7

https://www.cjcatal.com/EN/Y2021/V42/I9/1561

Figures/Tables 16

Scheme 1. The recrystallization process of shaped Ti-MWW catalyst.

Fig. 1. XRD patterns of P-Ti-MWW (1), S-Ti-MWW (2), as-synthesized Bf-Ti-MWW (3) and calcined Bf-Ti-MWW (4).

Fig. 2. SEM images of P-Ti-MWW (a,d), S-Ti-MWW (b,e), and Bf-Ti- MWW (c,f).

Fig. 3. HR-TEM images of S-Ti-MWW (a,b) and Bf-Ti-MWW (c-f); Edge-on TEM image of Bf-Ti-MWW taken along the directions of [100] (g) and [001] (h); STEM-HAADF image of Bf-Ti-MWW (i) and the corresponding EDX mapping images for Si, O and Ti elements (j-l).

Fig. 4. (a) N2 adsorption-desorption isotherms at 77 K; (b) BJH pore size distribution of P-Ti-MWW (1), S-Ti-MWW (2) and Bf-Ti-MWW (3).

Table 1 Physicochemical properties and catalytic performance for the propylene epoxidation of various titanosilicate catalysts.a

Catalyst	Si/Ti^b	Si/B^b	SSA^c /m² g^-1	Pore volume /cm³ g^-1		Mechanical strength^e /N cm^-1	H₂O₂/%		PO/%
Catalyst	Si/Ti^b	Si/B^b	SSA^c /m² g^-1	V_mic.^d	V_meso.	Mechanical strength^e /N cm^-1	conversion	efficiency	yield	selectivity
P-Ti-MWW	40	97	552	0.14	0.33	—	22.7	86.1	19.5	99.8
S-Ti-MWW	53	128	507	0.12	0.56	13.2	15.2	86.3	13.1	99.9
Bf-Ti-MWW	52	133	633	0.15	0.43	21.8	53.5	90.6	48.4	99.9
RF-Ti-MWW	52	248	638	0.15	0.65	25.3	65.1	93.9	61.1	99.9

Fig. 5. (a) H2O adsorption isotherms at 298 K; (b) FT-IR spectra in the region of hydroxyl stretching vibration for P-Ti-MWW (1), S-Ti-MWW (2) and Bf-Ti-MWW (3).

Fig. 6. 29Si MAS NMR spectra of P-Ti-MWW (1), S-Ti-MWW (2) and Bf-Ti-MWW (3).

Fig. 7. UV-Vis spectra (a) and Ti 2p XPS spectra (b) of P-Ti-MWW (1), S-Ti-MWW (2) and Bf-Ti-MWW (3).

Scheme 2. The possible changes of active Ti sites during recrystallization and subsequence modification of microenvironments of Ti active sites.

Fig. 8. CD3CN (a-c) or pyridine (d-f) adsorbed FT-IR spectra of P-Ti-MWW (a,d), S-Ti-MWW (b,e) and Bf-Ti-MWW (c,f) after evacuation at different temperatures. B: Br?nsted acid sites; L: Lewis acid sites; H: hydrogen-bonded pyridine.

Fig. 9. Dependence of turnover frequency of PO on methylphosphonic acid (MPA)-to-Ti ratio (H2O2 0.1 mol L-1, C3H6 0.4 MPa, solvent MeCN, temperature 313 K) (a), H2O2 concentration (C3H6 0.4 MPa, solvent MeCN, temperature 313 K) (b) and C3H6 pressure (H2O2 1.0 mol L-1, solvent MeCN, temperature 313 K) (c) over various catalysts; Kinetic curves fitted by Arrhenius equation in propylene epoxidation (d).

Fig. 10. Comparison of the lifetime of S-Ti-MWW (1 solid) and Bf-Ti-MWW (2, blank). Reaction conditions: C3=/H2O2 ratio = 3, 313 K, 2 MPa, WHSV (H2O2) = 0.3 h-1, WHSV (MeCN) = 6.5 h-1, WHSV (H2O) = 0.7 h-1.

Fig. 11. XRD patterns (a), N2 adsorption-desorption isotherms at 77 K (b), UV-Vis spectra (c), 19F MAS NMR spectra (d), Ti 2p XPS spectra (e) and 29Si MAS NMR spectra (f) of Bf-Ti-MWW (1) and RF-Ti-MWW (2).

Fig. 12. Dependence of the reaction rate of propylene (PE) epoxidation (left) and PO hydrolysis (right) on reaction temperature over Bf-Ti-MWW and RF-Ti-MWW.

Fig. 13. The stability of RF-Ti-MWW catalyst for the continuous liquid-phase propylene epoxidation in a fixed-bed reactor. Reaction conditions: temperature 313-333 K; C3=/H2O2 molar ratio, 3; pressure, 2 MPa; WHSV (H2O2), 0.35 h-1 and WHSV (MeCN), 2 h-1. X(H2O2), H2O2 conversion; S(PO), PO selectivity; Y(PO), PO yield; U(H2O2), H2O2 utilization efficiency.

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