Synthesis and Characterization of Zirconium Silicalite-1

Ko YS; Ahn WS

Korean Journal of Chemical Engineering, Vol.15, No.4, 423-428, July, 1998

Zirconium silicalite-1 (ZS-1) catalysts with MFI structure were prepared using a hydrothermal synthesis method. XRD, SEM, IR, ²⁹Si MAS NMR, UV-VIS DRS, physical adsorption of nitrogen, and elemental analysis were then performed to evaluate its physico-chemical properties, and evidences of Zr⁴⁺ incorporation into the zeolite framework were provided : The unit cell volume of zirconium silicalite-1 increased linearly with increases in zirconium content, and the characteristic framework i.r. spectra shifted to lower frequencies as Zr⁴⁺ was incorporated into the silicalite-1 lattice. For its catalytic reaction test, liquid phase 2-butanol oxidation using hydrogen peroxide as an oxidant was carried out. All of the zirconium silicalite-1 samples synthesized were active for the 2-butanol oxidation, but activities obtained using ZS-1 catalysts were lower than TS-1 catalyst. Zirconium in the zeolite framework was found to be the active site for the 2-butanol oxidation.

Keywords:Zirconium Silicalite-1;Hydrothermal Synthesis;IR;UV-VIS DRS;2-Butanol Oxidation

[References]

Blasco T, Camblor MA, Corma A, Perez-Pariente J, J. Am. Chem. Soc., 115, 11806 (1993)
Boccuti MR, Rao KM, Zecchina A, Leofanti G, Petrini G, "Spectroscopic Characterization of Silicalite and Titanium Silicalite," Stud. Surf. Sci. Catal., 48, Morterra, C. et al., eds., Elsevier, Amsterdam, 133 (1989)
Breck DW, "Structure of Zeolites by Infrared Spectroscopy," Zeolite Molecular Sieves, Wiley, New York, 415 (1974)
Clerici MG, Ingallina P, J. Catal., 140, 71 (1993)
Corma A, Navarro MT, Perez-Pariente J, J. Chem. Soc.-Chem. Commun., 147 (1994)
Dongare MK, Singh P, Moghe PP, Ratnasamy P, Zeolites, 11, 690 (1991)
Engelhardt G, Michel D, "High-Resolution Solid-State NMR of Silicates and Zeolites," John Wiley & Sons, New York (1987)
Esposito A, Neri C, Buonomo F, "Process for Oxidizing Alcohols to Aldehydes and/or Ketones," U.S. Patent, 4,480,135 (1984)
Fricke R, Kosslick H, Tuan VA, Grohmann I, Pilz W, Storek W, Walther G, "Study on the Isomorphous Substitution of Silicon by Tetravalent Elements (Zr, Ge, Ti) in the Framework of MFI Type Zeolites," Stud. Surf. Sci. Catal., 83, Hattori, T. and Yashima, T., eds., Elsevier, Amsterdam, 57 (1993)
Huybrechts DRC, DeBruycker L, Jacobs PA, Nature, 345, 240 (1990)
Ko YS, Ahn WS, Korean J. Chem. Eng., 15(2), 182 (1998)
Ko YS, Ahn WS, Microporous Mater., 9, 131 (1997)
Kraushaar B, van Hooff JHC, Catal. Lett., 1, 81 (1988)
Kraushaar B, vanHooff JHC, Catal. Lett., 2, 43 (1989)
Perego G, Bellussi G, Corno C, Taramasso M, Buonomo F, Esposito A, "Titanium Silicalite: A Novel Derivativein the Pentasil Family," Stud. Surf. Sci. Catal., 28, Murakami, Y., eds., Elsevier, Amsterdam, 129 (1986)
Reddy JS, Kumar R, Ratnasamy P, Appl. Catal., 58, L1 (1990)
Serrano DP, Li HX, Davis ME, J. Chem. Soc.-Chem. Commun., 745 (1992)
Tangaraj A, Kumar R, Mirajkar SP, Ratnasamy P, J. Catal., 130, 1 (1991)
Taramasso M, Perego G, Notari B, "Preparation of Porous Crystalline Synthetic Material Comprised of Silicon and Titanium Oxides," U.S. Patent, 4,410,501 (1983)
Tatsumi T, Nakamura M, Negishi S, Tominaga H, J. Chem. Soc.-Chem. Commun., 476 (1990)
vander Pol AJHP, van Hooff JHC, Appl. Catal. A: Gen., 106, 97 (1993)
Wang GR, Wang XQ, Wang XS, Yu SX, "Synthesis and Catalytic Reaction of [Zr] ZSM--5," Stud. Surf. Sci. Catal., 83, Hattori, T. and Yashima, T., eds., Elsevier, Amsterdam, 67 (1993)

[Referenced By]

[1] Blasco T, Camblor MA, Corma A, Perez-Pariente J, J. Am. Chem. Soc., 115, 11806 (1993)

[2] Boccuti MR, Rao KM, Zecchina A, Leofanti G, Petrini G, "Spectroscopic Characterization of Silicalite and Titanium Silicalite," Stud. Surf. Sci. Catal., 48, Morterra, C. et al., eds., Elsevier, Amsterdam, 133 (1989)

[3] Breck DW, "Structure of Zeolites by Infrared Spectroscopy," Zeolite Molecular Sieves, Wiley, New York, 415 (1974)

[4] Clerici MG, Ingallina P, J. Catal., 140, 71 (1993)

[5] Corma A, Navarro MT, Perez-Pariente J, J. Chem. Soc.-Chem. Commun., 147 (1994)

[6] Dongare MK, Singh P, Moghe PP, Ratnasamy P, Zeolites, 11, 690 (1991)

[7] Engelhardt G, Michel D, "High-Resolution Solid-State NMR of Silicates and Zeolites," John Wiley & Sons, New York (1987)

[8] Esposito A, Neri C, Buonomo F, "Process for Oxidizing Alcohols to Aldehydes and/or Ketones," U.S. Patent, 4,480,135 (1984)

[9] Fricke R, Kosslick H, Tuan VA, Grohmann I, Pilz W, Storek W, Walther G, "Study on the Isomorphous Substitution of Silicon by Tetravalent Elements (Zr, Ge, Ti) in the Framework of MFI Type Zeolites," Stud. Surf. Sci. Catal., 83, Hattori, T. and Yashima, T., eds., Elsevier, Amsterdam, 57 (1993)

[10] Huybrechts DRC, DeBruycker L, Jacobs PA, Nature, 345, 240 (1990)

[11] Ko YS, Ahn WS, Korean J. Chem. Eng., 15(2), 182 (1998)

[12] Ko YS, Ahn WS, Microporous Mater., 9, 131 (1997)

[13] Kraushaar B, van Hooff JHC, Catal. Lett., 1, 81 (1988)

[14] Kraushaar B, vanHooff JHC, Catal. Lett., 2, 43 (1989)

[15] Perego G, Bellussi G, Corno C, Taramasso M, Buonomo F, Esposito A, "Titanium Silicalite: A Novel Derivativein the Pentasil Family," Stud. Surf. Sci. Catal., 28, Murakami, Y., eds., Elsevier, Amsterdam, 129 (1986)

[16] Reddy JS, Kumar R, Ratnasamy P, Appl. Catal., 58, L1 (1990)

[17] Serrano DP, Li HX, Davis ME, J. Chem. Soc.-Chem. Commun., 745 (1992)

[18] Tangaraj A, Kumar R, Mirajkar SP, Ratnasamy P, J. Catal., 130, 1 (1991)

[19] Taramasso M, Perego G, Notari B, "Preparation of Porous Crystalline Synthetic Material Comprised of Silicon and Titanium Oxides," U.S. Patent, 4,410,501 (1983)

[20] Tatsumi T, Nakamura M, Negishi S, Tominaga H, J. Chem. Soc.-Chem. Commun., 476 (1990)

[21] vander Pol AJHP, van Hooff JHC, Appl. Catal. A: Gen., 106, 97 (1993)

[22] Wang GR, Wang XQ, Wang XS, Yu SX, "Synthesis and Catalytic Reaction of [Zr] ZSM--5," Stud. Surf. Sci. Catal., 83, Hattori, T. and Yashima, T., eds., Elsevier, Amsterdam, 67 (1993)