Deactivation and regeneration of TS-1/SiO₂ catalyst for epoxidation of propylene with hydrogen peroxide in a fixed-bed reactor

Abstract

TS-1/SiO₂ catalyst for the epoxidation of propylene with hydrogen peroxide in a fixed-bed reactor has been investigated. The catalyst activity decreases gradually with the online reaction time, but the selectivity of propylene epoxide is kept at about 93%. The fresh, deactivated and regenerated catalysts were characterized with X-ray diffraction, Fourier transform infrared spectroscopy, ultra-violet-visible diffuse reflectance, Brunner-Emmett-Teller method and thermogravimetric analysis, and the deactivated catalyst was regenerated with H₂O₂/methanol solution. Compared with the fresh catalyst, both the framework structure and the content of titanium in the framework of the deactivated and regenerated TS-1/SiO₂ catalysts were not changed. The major reason of the catalyst deactivation was the blockage of the channels of the catalyst by bulky organic by-products, which covered the active centers of titanium in TS-1. The deposited materials on the deactivated TS-1/SiO₂ catalyst could be removed by treatment with hydrogen peroxide/methanol solution or pure methanol; the higher the treatment temperature and the higher the concentration of H₂O₂ in methanol, the higher the extent of the regeneration. The regeneration treatment did not influence the product selectivity in the propylene epoxidation.

Keywords

TS-1/SiO₂, epoxidation of propylene, fixed-bed reactor, deactivation / regeneration

References

[1] Kirk R O, Dempsey T J. Kirk-Othmer Encyclopedia of Chemical Technology. New York: Wiley, 1982, 19, 246–248

[2] Zuo Y, Wang M L, Song W C, Wang X S, Guo X W. Characterization and catalytic performance of deactivated and regenerated TS1 extrudates in a pilot plant of propene epoxidation. Industrial & Engineering Chemistry Research, 2012, 51(32): 10586-10594

[3] Huang J H, Takei T, Ohashi H, Haruta M.Propene epoxidation with oxygen over gold clusters: Role of basic salts and hydroxides of alkalis. Applied Catalysis A: General, 2012, 435-436: 115-122

[4] Wang R P, Guo X W, Wang X S, Hao J Q. Propylene epoxidation over silver supported on titanium silicalite zeolite. Catalysis Letters, 2003, 90(1-2): 57-67

[5] Taramasso M, Peregoand G, Notari B. U S. Patent, <patent>4410501</patent>, 1983-10-18

[6] Taramasso M, Manara G, Fattore V, Notari B. U S. Patent, <patent>4666692</patent>, 1987-05-19

[7] Martens J A, Buskens P, Jacobs P A, van der Pol A, van Hooff J H C, Ferrini C, Kouwenhoven H W, Kooyman P J, van Bekkum H. Hydroxylation of phenol with hydrogen peroxide on EUROTS-1 catalyst. Applied Catalysis A, General, 1993, 99(1): 71-84

[8] Clerici M G, Bellussi G, Romano U. Synthesis of propylene oxide from propylene and hydrogen peroxide catalyzed by titanium silicalite. Journal of Catalysis, 1991, 129(1): 159-167

[9] Tvaruzkova Z, Zilkova N. Incorporation of titanium into the framework sites of Na-zeolites using TiCl₄: Catalytic activity in the ammoximation of cyclohexanone to cyclohexanone oxime. Applied Catalysis A, General, 1993, 103(1): L1-L4

[10] Clerici M G. Oxidation of saturated hydrocarbons with hydrogen peroxide, catalysed by titanium silicalite. Applied Catalysis, 1991, 68(1): 249-261

[11] Maspero F, Romano U. Oxidation of alcohols with H₂O₂ catalyzed by titanium silicalite-1. Journal of Catalysis, 1994, 146(2): 476-482

[12] Wang X S, Guo X W. Synthesis, characterization and catalytic properties of low cost titanium silicalite. Catalysis Today, 1999, 51(1): 177-186

[13] Li G, Wang X S, Yan H S, Liu Y H, Liu X W. Epoxidation of propylene using supported titanium silicalite catalysts. Applied Catalysis A, General, 2002, 236(1-2): 1-7

[14] Tullo A H, Short P L. Propylene oxide routes take off. Chemical and Engineering News, 2006, 84(41): 22-23

[15] Perego C, Carati A, Ingallina P, Mantegazza M A, Bellussi G. Production of titanium containing molecular sieves and their application in catalysis. Applied Catalysis A, General, 2001, 221(1-2): 63-72

[16] Thiel G F, Roland E. Propylene epoxidation with hydrogen peroxide and titanium silicalite catalyst: deactivation and regeneratiom of the catalyst. Journal of Molecular Catalysis A Chemical, 1998, 132(2-3): 281-292

[17] Yan H S, Wang X S, Liu J, Guo X W, Li G. Study on the TS-1 deactivation during propylene epoxidation. Acta Petrolei Sinica, 2002, 18(1): 46-51 (Petroleum Processing Section)

[18] Chen J X, Mi Z T, Wu Y L, Li W, Li Z H. Deactivation of the titanium silicalite catalyst in propylene epoxidation. Journal of Fuel Chemistry and Technology, 2003, 31(1): 80-85

[19] Crocco G L, Zajacek J G. U S. Patent, <patent>5741749</patent>, 1998-<month>04</month>-<day>21</day>

[20] Catinat J P, Strebelle M. U S. Patent, <patent>6169050</patent>, 2001-<month>01</month>-<day>02</day>

[21] Mantegazza M A, Balducci L, Rivetti F.U S. Patent, <patent>6403514</patent>, 2002-<month>06</month>-<day>11</day>

[22] Grosch G H, Muller U, Walch A, Reiber N, Harder W. U S. Patent, <patent>6710002</patent>, 2004-<month>03</month>-<day>23</day>

[23] Carroll K M, Morales E, Han Y Z.U S. Patent, <patent>5798313</patent>, 1998-08-25

[24] Muller U, Teles J H, Wenzel A, Harder W, Rudolf P, Rehfinger A, Baler P, Reiber N. US Patent, <patent>6790969</patent>, 2004-<month>09</month>-<day>14</day>

[25] Han H Z, Carrol K M.US Patent, <patent>6872679</patent>, 2005-<month>03</month>-<day>29</day>

[26] Wang Q F, Li W, Chen J X, Wu Y L, Mi Z T. Deactivation and regeneration of titanium silicalite catalyst for epoxidation of propylene. Journal of Molecular Catalysis A Chemical, 2007, 273(1-2): 73-80

[27] Carroll K M, Morales E, Han Y Z.US Patent, <patent>5916835</patent>, 1999-<month>06</month>-<day>29</day>

[28] Shaumont D. WO Patent, <patent>9901445</patent>, 1999-<month>01</month>-<day>14</day>

[29] Chang T.EP Patent, <patent>1190770</patent>, 2002-<month>03</month>-<day>27</day>

[30] Thiele G. US Patent, <patent>5620935</patent>, 1997-<month>04</month>-<day>15</day>

[31] Gilbeau P. WO Patent, <patent>9818555</patent>, 1998-<month>05</month>-<day>07</day>

[32] Mantegazza M A, Balducci L, Rivetti F.<patent>US Patent</patent>, <patent>6403514</patent>, 2002-<month>06</month>-<day>11</day>

[33] Wu G Q, Wang Y Q, Wang L N, Feng W P, Shi H N, Lin Y, Zhang T, Jin X, Wang S H, Wu X X, Yao P X. Epoxidation of propylene with H₂O₂ catalyzed by supported TS-1 catalyst in a fixed-bed reactor: experiments and kinetics. Chemical Engineering Journal, 2013, 215-216: 306-314

[34] Li G, Wang X S, Yan H S, Chen Y Y, Su Q S. Effect of sodium ions on propylene epoxidation catalyzed by titanium silicalite. Applied Catalysis A, General, 2001, 218(1): 31-38

[35] Astorino E, Peri J B, Willey R J, Busca G. Spectroscopic characterization of silicalite-1 and titanium silicalite-1. Journal of Catalysis, 1995, 157(2): 482-500

[36] Armaroli T, Milella F, Notari B, Willey R J, Busca G. A spectroscopic study of amorphous and crystalline Ti-containing silicas and their surface acidity. Topics in Catalysis, 2001, 15(1): 63-71

[37] Capel-Sanchez M C, Campos-Martin J M, Fierro J L G. Impregnation treatments of TS-1 catalysts and their relevance in alkene epoxidation with hydrogen peroxide. Applied Catalysis A, General, 2003, 246(1): 69-77

[38] Sanz R, Serrano D P, Pizarro P, Moreno I. Hierarchical TS-1 zeolite synthesized from SiO₂ TiO₂ xerogels imprinted with silanized protozeolitic units. Chemical Engineering Journal, 2011, 171(3): 1428-1438

[39] Marra G L, Artioli G, Fitch A N, Milanesio M, Lamberti C. Orthorhombic to monoclinic phase transition in high-Ti-loaded TS-1: An attempt to locate Ti in the MFI framework by low temperature XRD. Microporous and Mesoporous Materials, 2000, 40(1-3): 85-94

[40] Reddy J S, Sivasanker S, Ratnasamy P. Hydroxylation of phenol over Ts-2, a titanium silicate molecular sieve. Journal of Molecular Catalysis, 1992, 71(3): 373-381

[41] Huybrechts D R C, Buskens P L, Jacobs P A. Physicochemical and catalytic properties of titanium silicalites. Journal of Molecular Catalysis, 1992, 71(1): 129-147

[42] Li G, Wang X S, Guo X W, Liu S, Zhao Q, Bao X H, Lin L W. Titanium species in titanium silicalite TS-1 prepared by hydrothermal method. Materials Chemistry and Physics, 2001, 71(2): 195-201

[43] Liu H, Lu G Z, Guo Y L, Guo Y, Wang J S. Deactivation and regeneration of TS-1/diatomite catalyst for hydroxylation of phenol in fixed-bed reactor. Chemical Engineering Journal, 2005, 108(3): 187-192

Acknowledgments

This work has been supported by the Natural Science Foundation of China (Grant No. 21276183) and Program of Introducing Talents of Discipline to Universities (No. B06006).

RIGHTS & PERMISSIONS

2014 Higher Education Press and Springer-Verlag Berlin Heidelberg