Synthesis of mesoporous titanium silicalite-1 with high stability in cyclohexanone ammoximation

Abstract

Mesoporous titanium silicalite-1(TS-1)was hydrothermally synthesized with the addition of triethanolamine( TEA)in the conventional process, and used in the cyclohexanone ammoximation in a continuous slurry reactor. The as-prepared TS-1 was characterized with X-ray diffraction(XRD), scanning electron microcopy( SEM), N₂ adsorption-desorption, Fourier transform infrared (FT-IR)spectroscopy, UV-Visible(UV-Vis) diffuse reflectance spectra and UV Raman spectroscopy. The results indicated that the addition of TEA resulted in the formation of mesopores and the slight increase of framework titanium in TS-1. TS-1 synthesized with the addition of TEA exhibited a higher stability in the cyclohexanone ammoximation than that without the addition of TEA, attributing to the increase of mesopore volumes and the slight increase of the framework titanium in TS-1. However, when the addition of TEA was up to TEA/SiO₂ ratio of 0.24, the crystallinity and framework titanium of TS-1 decreased markedly, and the average crystal sizes of TS-1 increased, with the catalyst stability becoming poor.

Keywords

TS-1 / triethanolamine / cyclohexanone ammoximation / mesopore / stability

References

[1] Khouw C B, Dartt C B, Labinger J A, et al. Studies on the catalytic-oxidation of alkanes and alkenes by titanium silicates [J]. Journal of Catalysis, 1994, 149(1): 195-205.

[2] Park S, Cho K M, Youn M H, et al. Direct epoxidation of propylene with hydrogen peroxide over TS-1 catalysts: Effect of hydrophobicity of the catalysts [J]. Catalysis Communications, 2008, 9(15): 2485-2488.

[3] Wróblewska A, Rzepkowska M, Milchert E. Epoxidation of methallyl alcohol with hydrogen peroxide over TS-1 catalyst [J]. Applied Catalysis A: General, 2005, 294(2): 244-250.

[4] Tanev P T, Chibwe M, Pinnavaia T J. Titanium-containing mesoporous molecular sieves for catalytic oxidation of aromatic compounds [J]. Nature, 1994, 368(6469): 321-323.

[5] Tatsumi T, Jappar N. Ammoximation of cyclic ketones on TS-1 and amorphous SiO₂-TiO₂[J]. Journal of Catalysis, 1996, 161(2): 570-576.

[6] Taramasso M, Perego G, Notari B. Preparation of Porous Crystalline Synthetic Material Comprised of Silicon and Titanium Oxides: US, 1983.

[7] Roffia P, Leofanti G, Cesana A, et al. Cyclohexanone ammoximation: A break through in the 6-caprolactam production process [J]. Studies in Surface Science and Catalysis, 1990, 55: 43-52.

[8] Borin M F, Da Silva T, Felisbino R F, et al. Synthesis of TS-1 molecular sieves using a new Ti source [J]. The Journal of Physical Chemistry B, 2006, 110(31): 15080-15084.

[9] Chandra D, Mal N K, Mukherjee M, et al. Titanium-rich highly ordered mesoporous silica synthesized by using a mixed surfactant system [J]. Journal of Solid State Chemistry, 2006, 179(6): 1802-1807.

[10] Fan W, Duan R, Yokoi T, et al. Synthesis, crystallization mechanism, and catalytic properties of titaniumrich TS-1 free of extraframework titanium species [J]. Journal of the American Chemical Society, 2008, 130(31): 10150-10164.

[11] Fang Y, Hu Haoquan. Mesoporous TS-1: Nanocasting synthesis with CMK-3 as template and its performance in catalytic oxidation of aromatic thiophene [J]. Catalysis Communications, 2007, 8(5): 817-820.

[12] Ok D, Jiang N, Prasetyanto E A, et al. Epoxidation of cyclic-olefins over carbon template mesoporous TS-1 [J]. Microporous and Mesoporous Materials, 2011, 141(1): 2-7.

[13] Wang W, Li G, Liu L, et al. Synthesis and catalytic performance of hierarchical TS-1 directly using agricultural products sucrose as meso/macropores template[J]. Microporous and Mesoporous Materials, 2013, 179: 165-171.

[14] Cheneviere Y, Chieux F, Caps V, et al. Synthesis and catalytic properties of TS-1 with mesoporous/microporous hierarchical structures obtained in the presence of amphiphilic organosilanes [J]. Journal of Catalysis, 2010, 269(1): 161-168.

[15] Schmidt I, Krogh A, Wienberg K, et al. Catalytic epoxidation of alkenes with hydrogen peroxide over first mesoporous titanium-containing zeolite [J]. Chemical Communications, 2000, 21: 2157-2158.

[16] Wang Y, Lin M, Tuel Alain. Hollow TS-1 crystals formed via a dissolution-recrystallization process [J]. Microporous and Mesoporous Materials, 2007, 102(1): 80-85.

[17] Zuo Y, Song W, Dai C, et al. Modification of small-crystal titanium silicalite-1 with organic bases: Recrystallization and catalytic properties in the hydroxylation of phenol [J]. Applied Catalysis A: General, 2013, 453: 272-279.

[18] Xu J, Wang Y, Feng W, et al. Effect of triethylamine treatment of titanium silicalite-1 on propylene epoxidation [J]. Frontiers of Chemical Science and Engineering, 2014, 8(4): 478-487.

[19] Wu X, Wang Y, Zhang T, et al. Effect of TS-1 treatment by tetrapropyl ammonium hydroxide on cyclohexanone ammoximation[J]. Catalysis Communications, 2014, 50: 59-62.

[20] Zhang T, Wang Y, Wang S, et al. Effect of triethylamine treatment of titanium silicalite-1 on cyclohexanone ammoximation in a continuous system [J]. Reaction Kinetics, Mechanisms and Catalysis, 2015, 114(2): 735-752.

[21] Yao P, Wang Y, Zhang T, et al. Effect of sodium ions in synthesis of titanium silicalite-1 on its catalytic performance for cyclohexanone ammoximation [J]. Frontiers of Chemical Science and Engineering, 2014, 8(2): 149-155.

[22] Khomane R B, Kulkarni B D, Paraskar A, et al. Synthesis, characterization and catalytic performance of titanium silicalite-1 prepared in micellar media [J]. Materials Chemistry and Physics, 2002, 76(1): 99-103.

[23] Xia Q H, Gao Z. Crystallization kinetics of pure TS-1 zeolite using quaternary ammonium halides as templates [J]. Materials Chemistry and Physics, 1997, 47(2): 225-230.

[24] Ke X, Xu L, Zeng C, et al. Synthesis of mesoporous TS-1 by hydrothermal and steam-assisted dry gel conversion techniques with the aid of triethanolamine [J]. Microporous and Mesoporous Materials, 2007, 106(1): 68-75.

[25] Shan Z, Jansen J C, Marchese L, et al. Synthesis, characterization and catalytic testing of a 3-D mesoporous titanosilica, Ti-TUD-1 [J]. Microporous and Mesoporous Materials, 2001, 48(1): 181-187.

[26] Shan Z, Gianotti E, Jansen J C, et al. One-step synthesis of a highly active, mesoporous, titanium-containing silica by using bifunctional templating [J]. Chemistry-A European Journal, 2001, 7(7): 1437-1443.

[27] Cundy C S, Forrest J O. Some observations on the preparation and properties of colloidal silicalites(Part ?): Preparation, characterisation and properties of colloidal silicalite-1, TS-1, silicalite-2 and TS-2 [J]. Microporous and Mesoporous Materials, 2004, 72(1): 67-80.

[28] Ricchiardi G, Damin A, Bordiga S, et al. Vibrational structure of titanium silicate catalysts. A spectroscopic and theoretical study[J]. Journal of the American Chemical Society, 2001, 123(46): 11409-11419.

[29] Thangaraj A, Kumar R, Mirajkar S P, et al. Catalytic properties of crystalline titanium silicalites I. Synthesis and characterization of titanium-rich zeolites with MFI structure [J]. Journal of Catalysis, 1991, 130(1): 1-8.

[30] On D T, Kaliaguine S, Bonneviot L. Titanium boralites with MFI structure characterized using XRD, XANES, IR, and UV-visible techniques: Effect of hydrogen peroxide on the preparation [J]. Journal of Catalysis, 1995, 157(1): 235-243.

[31] Ratnasamy P, Srinivas D, Knözinger H. Active sites and reactive intermediates in titanium silicate molecular sieves [J]. Advances in Catalysis, 2004, 48: 1-169.

[32] Song W, Xiong G, Long H, et al. Effect of treatment with different bases on the catalytic properties of TS-1/SiO₂ extrudates in propylene epoxidation [J]. Microporous and Mesoporous Materials, 2015, 212: 48-55.

[33] Song W, Zuo Y, Xiong G, et al. Transformation of SiO₂ in titanium silicalite-1/SiO₂ extrudates during tetrapropylammonium hydroxide treatment and improvement of catalytic properties for propylene epoxidation [J]. Chemical Engineering Journal, 2014, 253: 464-471.

[34] Su J, Xiong G, Zhou J, et al. Amorphous Ti species in titanium silicalite-1: Structural features, chemical properties, and inactivation with sulfosalt [J]. Journal of Catalysis, 2012, 288: 1-7.

[35] Li C, Xiong G, Liu J, et al. Identifying framework titanium in TS-1 zeolite by UV resonance Raman spectroscopy [J]. The Journal of Physical Chemistry B, 2001, 105(15): 2993-2997.

[36] Huang D, Zhang X, Liu T, et al. Synthesis of high-performanced titanium silicalite-1 zeolite at very low usage of tetrapropyl ammonium hydroxide[J]. Industrial & Engineering Chemistry Research, 2013, 52(10): 3762-3772.