Effect of sodium ions in synthesis of titanium silicalite-1 on its catalytic performance for cyclohexanone ammoximation

Abstract

Titanium silicalite-1 (TS-1) has been hydrothermally synthesized with tetrapropylammonium hydroxide (TPAOH) as the template in the presence of various amounts of Na⁺, characterized by inductively coupled plasma, X-ray diffraction, scanning electron microscope, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and ultro-violet-visible spectroscopy and studied in cyclohexanone ammoximation. The characterization results show that with the increase of Na⁺ concentration in the synthesis, both the crystal sizes of TS-1and extra framework Ti increase but framework Ti decreases. The addition of Na⁺ below 3 mol-% of TPAOH in the synthesis does not influence the catalytic properties with above 98% conversion of cyclohexanone and 99.5% selectivity to cyclohexanone oxime. However, at the concentrations of Na⁺≥3 mol-% of TPAOH in the synthesis, the catalysts are deactivated faster with the increase of Na⁺ addition, which can be attributed to more high molecular weight byproducts deposited in the large TS-1 particles and the loss of the frame-work titanium. The results of this work are of great importance for the industry.

Keywords

titanium silicalite-1 / sodium ion / crystal size / extra framework Ti / cyclohexanone ammoximation

References

[1] RoffiaP, LeofantiG, CesanaA, MantegazzaM, PadovanM, PetriniG, TontiS, GervasuttiP. Cyclohexanone ammoximation: A break through in the 6-caprolactam production process. Studies in Surface Science and Catalysis, 1990, 55: 43-52

[2] DahlhoffG, NiedererJ P M, HoelderichW F. ϵ-Caprolactam: New by-product free synthesis routes. Catalysis Reviews. Science and Engineering, 2001, 43(4): 381-441

[3] Le BarsJ, DakkaJ, SheldonR A. Ammoximation of cyclohexanone and hydroxyaromatic ketones over titanium molecular sieves. Applied Catalysis A, General, 1996, 136(1): 69-80

[4] TvaruzkovaZ, PetrasM, HabersbergerK, JiruP. Surface complexes of cyclohexanone and aqueous solution of NH₃ on Ti-silicalite in liquid phase. Catalysis Letters, 1992, 13(1-2): 117-122

[5] PinelliD, TrifiròF, VaccariA, GiamelloE, PedulliG. Nature of active sites in catalytic ammoximation of cyclohexanone to the corresponding oxime on amorphous silica: E.P.R. investigations. Catalysis Letters, 1992, 13(1-2): 21-26

[6] YipA C K, LamF L Y, HuX J. A heterostructured titanium silicalite-1 catalytic composite for cyclohexanone ammoximation. Microporous and Mesoporous Materials, 2009, 120(3): 368-374

[7] YasuiE, KawaguchiT, MatsubaraT, KatoH. US Patent, 3562328, 1971-<month>09</month>-<day>02</day>

[8] RoffiaP, PadovanM, MorettiE, De AlbertiG. EP 0208311, 1985-<month>07</month>-<day>10</day>

[9] ThangarajA, SivasankerS, RatanasamyP. Catalytic properties of crystalline titanium silicalites III.Ammoximation of cyclohexanone. Journal of Catalysis, 1991, 131(2): 394-400

[10] CesanaA, MantegazzaM A, PastoriM. A study of the organic by-products in the cyclohexanone ammoximation. Journal of Molecular Catalysis A Chemical, 1997, 117(1-3): 367-373

[11] Dal PozzoL, FornsariG, MontiT. TS-1, catalytic mechanism in cyclohexanone oxime production. Catalysis Communications, 2002, 3(8): 369-375

[12] KhouwC B, DavisM E. Catalytic activity of titanium silicates synthesized in the presence of alkali-metal and alkaline-earth ions. Journal of Catalysis, 1995, 151(1): 77-86

[13] LiG, WangX, YanH, ChenY, SuQ. Effect of sodium ions on propylene epoxidation catalyzed by titanium silicalite. Applied Catalysis A, General, 2001, 218(1-2): 31-38

[14] TatsumiT, KoyanoK A, ShimizuY. Effect of potassium on the catalytic activity of TS-1. Applied Catalysis A, General, 2000, 200(1-2): 125-134

[15] TaramassoM, PeregoG, NotariB. US Patent, 4410501, 1983-<month>10</month>-<day>18</day>

[16] SerranoD P, SanzR, PizarroP, MorenoI, FrutosP D, BlázquezS. Preparation of extruded catalysts based on TS-1 zeolite for their application in propylene epoxidation. Catalysis Today, 2009, 143(1-2): 151-157

[17] KeX B, XuL, ZengC F, ZhangL X, XuN P. Synthesis of mesoporous TS-1 by hydrothermal and steam-assisted dry gel conversion techniques with the aid of triethanolamine. Microporous and Mesoporous Materials, 2007, 106(1-3): 68-75

[18] GrieneisenJ L, KesslerH, FachE, GovicA M L. Synthesis of TS-1 in fluoride medium. A new way to a cheap and efficient catalyst for phenol hydroxylation. Microporous and Mesoporous Materials, 2000, 37(3): 379-386

[19] PerssonA E, SchoemanB J, SterteJ, OtterstedtJ E. Synthesis of stable suspensions of discrete colloidal zeolite (Na, TPA) ZSM-5 crystals. Zeolites, 1995, 15(7): 611-619

[20] GriekenR V, SoteloJ L, MenéndezJ M, MeleroJ A. Anomalous crystallization mechanism in the synthesis of nanocrystalline ZSM-5. Microporous and Mesoporous Materials, 2000, 39(1-2): 135-147

[21] NamH J, AmemiyaT, MurabayashiM, ItohK. The influence of Na⁺ on the crystallite size of TiO₂ and the photocatalytic activity. Research on Chemical Intermediates, 2005, 31(4-6): 365-370

[22] HuybrechtsD R C, VaesenI, LiH X, JacobsP A. Factors influencing the catalytic activity of titanium silicalites in selective oxidations. Catalysis Letters, 1991, 8(2-4): 237-244

[23] BoccutiM R, RaoK M, ZecchinaA, LeofantiG, PetriniG. Spectroscopic characterization of silicalite and titanium-silicalite. Studies in Surface Science and Catalysis, 1989, 48: 133-144

[24] ZecchinaA, SpotoG, BordigaS, PadovanM, LeofantiG, PetriniG. IR spectra of CO adsorbed at low temperature (77 K) on titaniumsilicalite, H-ZSM5 and silicalite. Studies in Surface Science and Catalysis, 1991, 65: 671-680

[25] VayssilovG N. Structural and physicochemical features of titanium silicalites. Catalysis Reviews. Science and Engineering, 1997, 39(3): 209-251

[26] ThangarajA, KumarR, MirajkarS P, RatnasamyP. Catalytic properties of crystalline titanium silicalites I.Synthesis and characterization of titanium-rich zeolites with MFI structure. Journal of Catalysis, 1991, 130(1): 1-8

[27] ZecchinaA, SpotoG, BordigaS, FerreroA, PetriniG, LeofantiG, PadovanM. Framework and extraframework Ti in titanium-silicalite: Investigation by means of physical methods. Studies in Surface Science and Catalysis, 1991, 69: 251-258

[28] KimY L, RileyR L, HuqM J, SalimS. LeA E, MalloukT E. Zeolitic materials as organizing media for semiconductor-based artificial photosynthetic systems. MRS Proceedings, 1991, 233: 145-156

[29] FanW, WuP, NambaS, TatsumiT. A titanosilicate that is structurally analogous to an MWW-type lamellar precursor. Angewandte Chemie International Edition, 2004, 43(2): 236-240

[30] FanW, WuP, NambaS, TatsumiT. Synthesis and catalytic properties of a new titanosilicate molecular sieve with the structure analogous to MWW-type lamellar precursor. Journal of Catalysis, 2006, 243(1): 183-191

[31] FanW, DuanR, YokoiT, WuP, KubotaY, TatsumiT. Synthesis, crystallization mechanism, and catalytic properties of titanium-rich TS-1 free of extraframework titanium species. Journal of the American Chemical Society, 2008, 130(31): 10150-10164

[32] ChoiJ S, KimD J, ChangS H, AhnW S. Catalytic applications of MCM-41 with different pore sizes in selected liquid phase reactions. Applied Catalysis A, General, 2003, 254(2): 225-237

RIGHTS & PERMISSIONS

Higher Education Press and Springer-Verlag Berlin Heidelberg