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

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.

Key words： titanosilicates; Ti-MWW; propylene epoxidation; structured catalyst; KF modification

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

We gratefully acknowledge the financial support from the National Key R&D Program of China (Grant Nos. 2021YFA1501401 and 2023YFB3810602) and the National Natural Science Foundation of China (Grant No. 22222201).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2441-1 and is accessible for authorized users.

References

1 Xu H , Wu P . Two-dimensional zeolites in catalysis: current state-of-the-art and perspectives. Catalysis Reviews: Science and Engineering, 2021, 63(2): 234–301

2 Smeets V , Gaigneaux E M , Debecker D P . Titanosilicate epoxidation catalysts: a review of challenges and opportunities. ChemCatChem, 2022, 14(1): e202101132

3 WangRXiaCPengB. Fundamental understanding and catalytic applications of hollow MFI-type zeolites. Catalysis Today, 2022, 405–406: 111–124

4 Li Y , Yi Y , Wang X , Gao B , Guo Y , Wu G , Feng Z , Guo H . Regeneration of a spent TS-1 zeolite catalyst for liquid-phase epoxidation of propylene and H₂O₂. Industrial & Engineering Chemistry Research, 2023, 62(31): 12152–12173

5 Wang G , Li Y , Zhu Q , Li G , Zhang C , Guo H . Influence of impurities in a methanol solvent on the epoxidation of propylene with hydrogen peroxide over titanium silicalite-1. Catalysts, 2019, 10(1): 15

6 Sulimov A V , Ovcharova A V , Ovcharov A , Flid V R , Leont’eva S V , Bruk L G , Pastukhova Z Y , Flid M R . Study of alkene epoxidation in the presence of extruded silicalite titanium. Russian Chemical Bulletin, 2016, 65(12): 2845–2849

7 Song F , Liu Y , Wang L , Zhang H , He M , Wu P . Highly efficient epoxidation of propylene over a novel Ti-MWW catalyst. Studies in Surface Science and Catalysis, 2007, 170(07): 1236–1243

8 Wu P , Tatsumi T , Komatsu T , Yashima T . A novel titanosilicate with MWW structure. I. Hydrothermal synthesis, elimination of extraframework titanium, and characterizations. Journal of Physical Chemistry B, 2001, 105(15): 2897–2905

9 Yu Y , Fang N , Chen Z , Liu D , Liu Y , He M . Greening oxidation catalysis: water as a solvent for efficient alkene epoxidation over a titanosilicate/H₂O₂ system. ACS Sustainable Chemistry & Engineering, 2022, 10(35): 11641–11654

10 Torres C , Pottis D S , Flaherty D W . Solvent mediated interactions on alkene epoxidations in Ti-MFI: effects of solvent identity and silanol density. ACS Catalysis, 2023, 13(13): 8925–8942

11 Potts D S , Komar J K , Locht H , Flaherty D W . Understanding rates and regioselectivities for epoxide methanolysis within zeolites: mechanism and roles of covalent and non-covalent interactions. ACS Catalysis, 2023, 13(22): 14928–14944

12 Tan J Z , Bregante D T , Torres C , Flaherty D W . Transition state stabilization depends on solvent identity, pore size, and hydrophilicity for epoxidations in zeolites. Journal of Catalysis, 2022, 405: 91–104

13 Serrano D P , Sanz R , Pizarro P , Moreno I , Blázquez S . Preparation of extruded catalysts based on TS-1 zeolite for their application in propylene epoxidation. Catalysis Today, 2013, 143(1): 151–157

14 Zhou J , Teng J , Ren L , Wang Y , Liu Z , Liu W , Yang W , Xie Z . Full-crystalline hierarchical monolithic ZSM-5 zeolites as superiorly active and long-lived practical catalysts in methanol-to-hydrocarbons reaction. Journal of Catalysis, 2016, 340: 166–176

15 Li Z , Jiang X , Xiong G , Nie B , Liu C , He N , Liu J . Towards the preparation of binderless ZSM-5 zeolite catalysts: the crucial role of silanol nests. Catalysis Science & Technology, 2020, 10(23): 7829–7841

16 Xu H , Tian W , Xu L , Jin X , Xue T , Chen L , He M , Wu P . Crossed intergrowth triggered TS-2 microsphere: formation mechanism, modification and catalytic performance. Chinese Journal of Catalysis, 2020, 41(7): 1109–1117

17 Yin J , Jin X , Xu H , Guan Y , Peng R , Chen L , Jiang J , Wu P . Structured binder-free MWW-type titanosilicate with Si-rich shell for selective and durable propylene epoxidation. Chinese Journal of Catalysis, 2021, 42(9): 1561–1575

18 Lu X , Xu H , Yan J , Zhou W J , Liebens A , Wu P . One-pot synthesis of ethylene glycol by oxidative hydration of ethylene with hydrogen peroxide over titanosilicate catalysts. Journal of Catalysis, 2018, 358: 89–99

19 Wu L , Zhao S , Lin L , Fang X , Liu Y , He M . In-depth understanding of acid catalysis of solvolysis of propene oxide over titanosilicates and titanosilicate/H₂O₂ systems. Journal of Catalysis, 2016, 337: 248–259

20 Sever R R , Root T W . DFT study of solvent coordination effects on titanium-based epoxidation catalysts. Part Ⅰ: formation of the titanium hydroperoxo intermediate. Journal of Physical Chemistry B, 2003, 107(17): 4090–4099

21 Sever R R , Root T W . DFT study of solvent coordination effects on titanium-based epoxidation catalysts. Part two: reactivity of titanium hydroperoxo complexes in ethyleneepoxidation. Journal of Physical Chemistry B, 2003, 107(17): 4090–4099

22 Gordon C P , Engler H , Tragl A S , Plodinec M , Lunkenbein T , Berkessel A , Teles J H , Parvulescu A N , Copéret C . Efficient epoxidation over dinuclear sites in titanium silicalite-1. Nature, 2020, 586(7831): 708–713

23 Wang Y , Yang H , Zuo Y , Tian D , Hou G , Su Y , Feng Z , Guo X , Li C . New penta- and hexa-coordinated titanium sites in titanium silicalite-1 catalyst for propylene epoxidation. Applied Catalysis B: Environmental, 2023, 325: 122396

24 Bregante D T , Chan M C , Tan J Z , Ayla E Z , Nicholas C P , Shukla D , Flaherty D W . The shape of water in zeolites and its impact on epoxidation catalysis. Nature Catalysis, 2021, 4(9): 797–808

25 Clerici M G , Ingallina P . Epoxidation of lower olefins with hydrogen peroxide and titanium silicalite. Journal of Catalysis, 1993, 140(1): 71–83

26 Yang Y , Ding J , Wang B , Wu J , Zhao C , Gao G , Wu P . Influences of fluorine implantation on catalytic performance and porosity of MOR-type titanosilicate. Journal of Catalysis, 2014, 320: 160–169

27 Lu X , Wu H , Jiang J , He M , Wu P . Selective synthesis of propylene oxide through liquid-phase epoxidation of propylene with H₂O₂ over formed Ti-MWW catalyst. Journal of Catalysis, 2016, 342: 173–183

28 Goa Y , Wu P , Tatsumi T . Influence of fluorine on the catalytic performance of Ti-Beta zeolite. Journal of Physical Chemistry B, 2004, 108(14): 4242–4244

29 Fang X , Wang Q , Zheng A , Liu Y , Wang Y , Deng X , Wu H , Deng F , He M , Wu P . Fluorine-planted titanosilicate with enhanced catalytic activity in alkene epoxidation with hydrogen peroxide. Catalysis Science & Technology, 2012, 2(12): 2433

30 Fang X , Wang Q , Zheng A . Post-synthesis, characterization and catalytic properties of fluorine-planted MWW-type titanosilicate. Physical Chemistry Chemical Physics, 2013, 2013,15(14): 4930–4938

31 Fang X , Sun L , Lin L , Wu L , Liu Y . Enhanced catalytic oxidation performance of F-Ti-MWW through the synergistic effect of anion and cation. Catalysis Communications, 2017, 96: 54–57

32 Kuwahara Y , Nishizawa K , Nakajima T , Kamegawa T , Mori K , Yamashita H . Enhanced catalytic activity on titanosilicate molecular sieves controlled by cation-π interactions. Journal of the American Chemical Society, 2011, 133(32): 12462–12465

33 Lamberti C , Bordiga S , Arduino D , Zecchina A , Geobaldo F , Spanó G , Genoni F , Petrini G , Carati A , Villain F . . Evidence of the presence of two different framework Ti(IV) species in Ti-silicalite-1 in vacuo conditions: an EXAFS and a photoluminescence study. Journal of Physical Chemistry B, 1998, 102(33): 6382–6390

34 Xu L , Huang D D , Li C G , Ji X , Jin S , Feng Z , Xia F , Li X , Fan F , Li C . . Construction of unique six-coordinated titanium species with an organic amine ligand in titanosilicate and their unprecedented high efficiency for alkene epoxidation. Chemical Communications, 2015, 51(43): 9010–9013

35 Lu X , Zhou W J , Guan Y , Liebens A , Wu P . Enhancing ethylene epoxidation of a MWW-type titanosilicate/H₂O₂ catalytic system by fluorine implanting. Catalysis Science & Technology, 2017, 7(12): 2624–2631

36 Bregante D T , Johnson A M , Patel A Y , Ayla E Z , Cordon M J , Bukowski B C , Greeley J , Gounder R , Flaherty D W . Cooperative effects between hydrophilic pores and solvents: catalytic consequences of hydrogen bonding on alkene epoxidation in zeolites. Journal of the American Chemical Society, 2019, 141(18): 7302–7319

37 Bregante D T , Flaherty D W . Impact of specific interactions among reactive surface intermediates and confined water on epoxidation catalysis and adsorption in lewis acid zeolites. ACS Catalysis, 2019, 9(12): 10951–10962

38 Zhang K , Lively R P , Noel J D , Dose M E , Mccool B A , Chance R R , Koros W J . Adsorption of water and ethanol in MFI-type zeolites. Langmuir, 2012, 28(23): 8664–8673

39 Özgür Yazaydın A , Thompson R W . Molecular simulation of water adsorption in silicalite: effect of silanol groups and different cations. Microporous and Mesoporous Materials, 2009, 123(1–3): 169–176

40 Trzpit M , Soulard M , Patarin J , Desbiens N , Cailliez F , Boutin A , Demachy I , Fuchs A H . The effect of local defects on water adsorption in silicalite-1 zeolite: a joint experimental and molecular simulation study. Langmuir, 2007, 23(20): 10131–10139

41 JinXPengRTongWYinJXuHWuP. Investigation of the active centers and structural modifications for TS-1 in catalyzing the Beckmann rearrangement. Catalysis Today, 2022, 405–406(1): 193–202

42 Xu L , Ding J , Yang Y , Wu P . Distinctions of hydroxylamine formation and decomposition in cyclohexanone ammoximation over microporous titanosilicates. Journal of Catalysis, 2014, 309: 1–10

43 Xu H , Guan Y , Lu X , Yin J , Li X , Zhou D , Wu P . Relation of selective oxidation catalytic performance to microenvironment of Ti(IV) active site based on isotopic labeling. ACS Catalysis, 2020, 10(8): 4813–4819

44 Na K , Jo C , Kim J , Ahn W S , Ryoo R . MFI titanosilicate nanosheets with single-unit-cell thickness as an oxidation catalyst using peroxides. ACS Catalysis, 2011, 1(8): 901–907

45 Wang Y , Liu Y , Li X , Wu H , He M , Wu P . Intermolecular condensation of ethylenediamine to 1,4-diazabicyclo[2,2,2]octane over TS-1 catalysts. Journal of Catalysis, 2009, 266(2): 258–267