Two-dimensional Organic-Inorganic Ti-MWW as Regenerable Catalyst for Fixed-bed Propylene Epoxidation

Abstract

The direct epoxidation of propylene to propylene oxide with hydrogen peroxide, known as the HPPO process, is a highly efficient and eco-friendly route for propylene oxide production. In the present study, the three-dimensional (3D) MWW-type titanosilicate Ti-MWW in shaped form was reconstructed to a 2D organic-inorganic hybrid material through the hydrothermal treatment of piperidine (PI) solution, which serves as a highly active catalyst for the fixed-bed HPPO process. The PI hydrothermal treatment induced chemical modifications on the Ti active centers, fabricating an open hexacoordinated Ti species [Ti(OSi)₂(OH)₂(H₂O)PI], which significantly enhanced the catalytic activity. The solvent effect was also altered after the PI hydrothermal treatment, especially for methanol. In the continuous fixed-bed HPPO reaction, this 2D organic-inorganic Ti-MWW catalyst (RS-Ti-MWW) exhibited exceptional stability, achieving a lifetime of 730 h in MeCN and 216 h in MeOH, with PO selectivity exceeding 99.6% and H₂O₂ utilization above 95%. RS-Ti-MWW can be regenerated through calcination and the subsequent hydrothermal treatment of PI solution, and the regenerated sample remains stable for up to 730 h of continuous operation, demonstrating its strong potential for industrial application.

Keywords

Ti-MWW zeolite / HPPO (propylene to propylene oxide with hydrogen peroxide) process / Organic-inorganic material / Reconstruction / Regeneration

References

[1] Nijhuis T A, Makkee M, Moulijn J A, Weckhuysen B M. Ind. Eng. Chem., 2006, 45: 3447

[2] Climent M J, Corma A, Iborra S. Chem. Rev., 2011, 111: 1072

[3] Zuo Y, Liu M, Hong L, Wu M, Zhang T, Ma M, Song C, Guo X. Ind. Eng. Chem. Res., 2015, 54: 1513

[4] Kapil N, Weissenberger T, Cardinale F, Trogadas P, Nijhuis T A, Nigra M M. Angew. Chem., 2021, 133: 18333

[5] Ghannadzadeh A, Tarighaleslami A H. Int. J. Life. Cycle. Assess., 2022, 27: 20

[6] Lin M, Xia C, Zhu B, Li H, Shu X. Chem. Eng. J., 2016, 295: 370

[7] Bassler P, Weidenbach M, Goebbel H. Chem. Eng. Trans., 2010, 21: 571

[8] Guo Q, Sun K, Feng Z, Li G, Guo M, Fan F, Li C. Chem. Eur. J., 2012, 18: 13854

[9] Xu L, Huang D, Li C, Ji X, Jin S, Feng Z, Xia F, Li X, Fan F, Li C. Chem. Commun., 2015, 51: 9010

[10] Wu L, Tang Z, Yu Y, Yao X, Liu W, Li L, Yan B, Liu Y, He M. Chem. Commun., 2018, 54: 6384

[11] Tang Z, Yu Y, Liu W, Chen Z, Wang R, Liu H, Wu H, Liu Y, He M. Catal. Sci. Technol., 2020, 10: 2905

[12] Wu L, Deng X, Zhao S, Yin H, Zhuo Z, Fang X, Liu Y, He M. Chem. Commun., 2016, 52: 8679

[13] Fang X, Wu L, Yu Y, Sun L, Liu Y. Catal. Commun., 2018, 114: 1

[14] Wu M, Chou L, Song H. Catal. Lett., 2012, 142: 627

[15] Wu M, Song H, Chou L. RSC Adv., 2013, 3: 23562

[16] Wu M, Song H, Wang F, Chou L. J. Mol. Catal. A: Chem., 2013, 379: 207

[17] Lu X, Wu H, Jiang J, He M, Wu P. J. Catal., 2016, 342: 173

[18] Yoon C W, Hirsekorn K F, Neidig M L, Yang X, Tilley T D. ACS Catal., 2011, 1: 1665

[19] Li G, Wang X, Yan H, Chen Y, Su Q. Appl. Catal. A, 2001, 218: 31

[20] Wu L, Zhao S, Lin L, Fang X, Liu Y, He M. J. Catal., 2016, 337: 248

[21] Liu X, Wang X, Guo X, Li G. Catal. Today, 2004, 93: 505

[22] Zhou X, Wang L, Li Y, Ji H. Chin. J. Chem. Eng., 2022, 48: 61

[23] Li J, Gao S, Xi Z. Chin. J. Catal., 2010, 31: 895

[24] Clerici M G, Ingallina P. J. Catal., 1993, 140: 71

[25] Sever R R, Root T W. J. Phys. Chem. B, 2003, 107: 4080

[26] Nie X, Ren X, Ji X, Chen Y, Janik M J, Guo X, Song C. J. Phys. Chem. B, 2019, 123: 7410

[27] Nie X, Ji X, Chen Y, Guo X, Song C. Mol. Catal., 2017, 441: 150

[28] Potts D S, Torres C, Kwon O, Flaherty D W. Chem. Sci., 2023, 14: 3160

[29] Fan W, Wu P, Tatsumi T. J. Catal., 2008, 256: 62

[30] Ji P, Lu K, Lu X, Xu H, Wu P. Dalton Trans., 2017, 46: 5776

[31] Gordon C P, Engler H, Tragl A S, Plodinec M, Lunkenbein T, Berkessel A, Teles J H, Parvulescu A-N, Copéret C. Nature, 2020, 586: 708

[32] Gengenbach T R, Chatelier R C, Griesser H J. Surf. Interface Anal., 1996, 24: 611

[33] Prokes S M, Gole J L, Chen X, Burda C, Carlos W E. Adv. Funct. Mater., 2005, 15: 161

[34] Hasegawa Y, Ayame A. Catal. Today, 2001, 71: 177

[35] Langerame F, Salvi A M, Silletti M, Moretti G. Surf. Interface Anal., 2008, 40: 695

[36] Nogier J P, Millot Y, Man P P, Méthivier C, Che M, Dzwigaj S. Catal. Lett., 2009, 130: 588

[37] Yin J, Xu H, Wang B, Tian W, Yin J, Jiang J, Wu P. Catal. Sci. Technol., 2020, 10: 6050

[38] Ratnasamy P, Srinivas D, Knözinger H. Adv. Catal., 2004, 48: 1

[39] Flaherty D W, Iglesia E. J. Am. Chem. Soc., 2013, 135: 18586

[40] Torres C, Kwon O, Potts D S, Flaherty D W. J. Catal., 2024, 429: 115288

[41] Russo V, Tesser R, Santacesaria E, Di Serio M. Ind. Eng. Chem. Res., 2014, 53: 6274

[42] Shin S B, Chadwick D. Ind. Eng. Chem. Res., 2010, 49: 8125

[43] Yang G, Zhuang J, Ma D, Lan X, Zhou L, Liu X, Han X, Bao X. J. Mol. Struct., 2008, 882: 24

[44] Yin J, Jin X, Xu H, Guan Y, Peng R, Chen L, Jiang J, Wu P. Chin. J. Catal., 2021, 42: 1561

[45] Lu X, Xu H, Yan J, Zhou W, Liebens A, Wu P. J. Catal., 2018, 358: 89

[46] Wu L, Zhao S, Lin L, Fang X, Liu Y, He M. J. Catal., 2016, 337: 248

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Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH