Recovery and Recycling of Ti Supported Bimodal Mesoporous Catalysts Prepared via Ship-in-a-bottle Method in the Epoxidation of Cyclohexene

doi:10.1016/j.cjche.2014.06.016

Abstract

Abstract: Ti/BMMs (Ti supported bimodal mesoporous silica) catalysts have been prepared via self-assembly route combined with ship-in-a-bottle method. The recovery and recycling performances of Ti/BMMs were investigated in the epoxidation of cyclohexene. In order to the evaluate the regeneration methods and to examine the deactivation behaviors, the deactivated Ti/BMMs catalysts were washed in chloroform or calcinated at 450℃ for 6 h and then activity of the recovery catalysts were examined.Meanwhile, the structure features and surface properties of the regenerated catalysts were characterized by X-ray diffraction, N₂-sorption analysis, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, UV visible spectroscopy and X-ray photoelectron spectroscopy. The results showed that the typical bimodal mesoporous structure of recycled Ti/BMMs catalysts was still maintained, and the phenomenon of Ti leaching during the catalytic process and recovery was negligible. In particular, spectroscopic observations indicated that the effects of the regeneration methods on the tetrahedrally-coordinated Ti species and catalytic deactivation were remarkable. The main reasons were related to the polarities of used solvents during recovery tests, the environment medium of adsorbed water inside mesopore channels and the deposition of bulky molecules of by-products on the mesoporous surface.

Key words: Ti/BMMs, Ship-in-a-bottle method, Recovery, Recycling, Epoxidation of cyclohexene

摘要： Ti/BMMs (Ti supported bimodal mesoporous silica) catalysts have been prepared via self-assembly route combined with ship-in-a-bottle method. The recovery and recycling performances of Ti/BMMs were investigated in the epoxidation of cyclohexene. In order to the evaluate the regeneration methods and to examine the deactivation behaviors, the deactivated Ti/BMMs catalysts were washed in chloroform or calcinated at 450℃ for 6 h and then activity of the recovery catalysts were examined.Meanwhile, the structure features and surface properties of the regenerated catalysts were characterized by X-ray diffraction, N₂-sorption analysis, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, UV visible spectroscopy and X-ray photoelectron spectroscopy. The results showed that the typical bimodal mesoporous structure of recycled Ti/BMMs catalysts was still maintained, and the phenomenon of Ti leaching during the catalytic process and recovery was negligible. In particular, spectroscopic observations indicated that the effects of the regeneration methods on the tetrahedrally-coordinated Ti species and catalytic deactivation were remarkable. The main reasons were related to the polarities of used solvents during recovery tests, the environment medium of adsorbed water inside mesopore channels and the deposition of bulky molecules of by-products on the mesoporous surface.

关键词: Ti/BMMs, Ship-in-a-bottle method, Recovery, Recycling, Epoxidation of cyclohexene

Shiyang Bai, Xintao Hu, Jihong Sun, Bo Ren, Jinpeng Wang. Recovery and Recycling of Ti Supported Bimodal Mesoporous Catalysts Prepared via Ship-in-a-bottle Method in the Epoxidation of Cyclohexene[J]. Chin.J.Chem.Eng., 2014, 22(8): 914-920.

References

[1] A. Ruperta, Y. Shihy, “Process for making phenoxycycloalkanols”, US Pat. 4754076(1988).

[2] Y.D. Zhang, X.L.Gao, X. Chen, C.J.Wang,D.G. Jiang, Study on synthesis, characterizationand catalytic activity of polystyrene-supported Mo (VI) complex in epoxidation ofcyclohexene, Chin. J. Chem. Eng. 11 (3) (2003) 318-325.

[3] M. Tamarasso, C. Perego,B.Notari, “Preparation of porous crystalline syntheticmaterialcomprised of silicon and titanium oxides”, US Pat. 4410501 (1983).

[4] M.A. Camblor, A. Corma, A. Martínez, J. Pérez-Pariente, Synthesis of atitaniumsilicoaluminate isomorphous to zeolite beta and its application as a catalystfor the selective oxidation of large organic molecules, J. Chem. Soc. Chem. Commun. 8(1992) 589-590.

[5] J.M. Thomas, Design, synthesis, and in situ characterization of new solid catalysts,Angew. Chem. Int. Ed. 38 (24) (1999) 3588-3628.

[6] L.L. Wang, Y.M. Liu, W. Xie, H.H. Wu, X.H. Li, M.Y. He, P. Wu, Improving the hydrophobicityand oxidation activity of Ti-MWWby reversible structural rearrangement,J. Phys. Chem. C 112 (15) (2008) 6132-6138.

[7] A. Corma,M.T. Navarro, J.P. Pariente, Synthesis of an ultralarge pope titaniumsilicateisomorphous to MCM-41 and its application as a catalyst for selective oxidation ofhydrocarbons, J. Chem. Soc. Chem. Commun. 2 (1994) 147-148.

[8] T. Blasco, A. Corma, M.T. Navarro, J. Perez-Pariente, Synthesis, characterization, andcatalytic activity of Ti-MCM-41 structures, J. Catal. 156 (1) (1995) 65-74.

[9] T. Maschmeyer, F. Rey, G. Sankar, J.M. Thomas, Heterogeneous catalysts obtained bygrafting metallocene complexes onto mesoporous silica, Nature 378 (6553) (1995)159-162.

[10] K.A. Koyano, T. Tatsumi, Synthesis of titanium-containing mesoporous molecularsieves with a cubic structure, J. Chem. Soc. Chem. Commun. 2 (1996)145-146.

[11] M. Morey, A. Davidson, G. Stucky, A new step toward transition metal incorporationin cubic mesoporous materials: preparation and characterization of Ti-MCM-48,Microporous. Mater. 6 (2) (1996) 99-104.

[12] M.S. Morey, S. O'Brien, S. Schwarz, G.D. Stucky, Hydrothermal and postsynthesissurface modification of cubic, MCM-48, and ultralarge pore SBA-15 mesoporoussilica with titanium, Chem. Mater. 12 (4) (2000) 898-911.

[13] M.L. Peña, V. Dellarocca, F. Rey, A. Corma, S. COluccia, L. Marchese, Elucidatingthe local environment of Ti (IV) active sites in Ti-MCM-48: a comparison betweensilylated and calcined catalysts, Microporous Mesoporous Mater. 44 (2001) 345-356.

[14] A. Vinu, P. Srinivasu, M. Miyahara, K. Ariga, Preparation and catalytic performancesof ultralarge-pore TiSBA-15mesoporousmolecular sieves with very high Ti content,J. Phys. Chem. B 110 (2) (2006) 801-806.

[15] Y. Chen, Y. Huang, J. Xiu, X. Han, X. Bao, Direct synthesis, characterization andcatalytic activity of titanium-substituted SBA-15 mesoporous molecular sieves,Appl. Catal. A Gen. 273 (1-2) (2004) 185-191.

[16] W.H. Zhang, J. Lu, B. Han, M. Li, J. Xiu, P. Ying, C. Li, Direct synthesis and characterizationof titanium-substituted mesoporousmolecular sieve SBA-15, Chem.Mater. 14(8) (2002) 3413-3421.

[17] S. Wu, Y. Han, Y.C. Zou, J. Song, W.L. Zhao, Y. Di, S.Z. Liu, F.S. Xiao, Synthesis ofheteroatom substituted SBA-15 by the pH-adjusting” method, Chem. Mater. 16(3) (2004) 486-492.

[18] B.L. Newalkar, J. Olanrewaju, S. Komarneni, Direct synthesis of titanium-substitutedmesoporous SBA-15 molecular sieve under microwave-hydrothermal conditions,Chem. Mater. 13 (2) (2001) 552-557.

[19] F. Bérubé, F. Kleitz, S. Kaliaguine, A comprehensive study of titanium-substitutedSBA-15 mesoporous materials prepared by direct synthesis, J. Phys. Chem. C 112(37) (2008) 14403-14411.

[20] F. Bérubé, F. Kleitz, S. Kaliaguine, Surface properties and epoxidation catalyticactivity of Ti-SBA15 prepared by direct synthesis, J. Mater. Sci. 44 (24) (2009)6727-6735.

[21] P. Wu, T. Tatsumi, Direct formation of pinacols from olefins over various titanosilicates,Chem. Mater. 14 (4) (2002) 1657-1664.

[22] F. Bérubé, B. Nohair, F. Kleitz, S. Kaliaguine, Controlled postgrafting of titaniumchelates for improved synthesis of Ti-SBA-15 epoxidation catalysts, Chem. Mater.22 (6) (2010) 1988-2000.

[23] F. Bérubé, A. Khadhraoui, M.T. Janicke, F. Kleitz, S. Kaliaguine, Optimizing silicasynthesis for the preparation of mesoporous Ti-SBA-15 epoxidation catalysts, Ind.Eng. Chem. Res. 49 (15) (2010) 6977-6985.

[24] M.C. Capel-Sanchez, G. Blanco-Brieva, J.M. Campos-Martin, M.P. De Frutos,W.Wen,J.A. Rodriguez, J.L.G. Fierro, Grafting strategy to develop single site titanium on anamorphous silica surface, Langmuir 25 (12) (2009) 7148-7155.

[25] S.Y. Bai, X.T. Hu, J.H. Sun, B. Ren, Preparation and characterization of Ti supported bimodalmesoporouscatalysts using a self-assembly route combined with a ship-in-abottlemethod, New J. Chem. 38 (5) (2014) 2128-2134.

[26] J.H. Sun, Z.P. Shan, T. Maschmeyer, M.-O. Coppens, Synthesis of bimodal nanostructuredsilicas with independently controlled small and large mesopore sizes,Langmuir 19 (20) (2003) 8395-8402.

[27] J.H. Sun, Z.P. Shan, T. Maschmeyer, J.A.Moulijn, M.-O. Coppens, Synthesis of tailoredbimodal mesoporous materials with independent control of the dual pore sizedistribution, Chem. Commun. 24 (2001) 2670-2671.

[28] Y.Z. Li, J.H. Sun, L. Gao, X.Wu,Grafting fluorescencemolecules into the pore surface ofbimodal mesoporous silicas with different routes, Mater. Lett. 65 (2) (2011) 250-252.

[29] S.J. Qiu, J.H. Sun, Y.Z. Li, L. Gao, Investigation of heterogeneous asymmetricdihydroxylation over OsO4-(QN)2PHAL catalysts of functionalized bimodal mesoporoussilica with ionic liquid, Mater. Res. Bull. 46 (8) (2011) 1197-1201.

[30] L. Gao, J.H. Sun, B. Ren, Y.Z. Li, H. Zhang, Structural characterization and surfaceheterogeneity of bimodal mesoporous silicas functionalized with aminopropylgroups and loaded aspirin, Mater. Res. Bull. 46 (10) (2011) 1540-1545.

[31] J. He, H.Ma, Z.Y. Guo, D.G. Evans, X. Duan, Chemical stability of Ti-modifiedMCM-41catalysts in the hydroxylation of benzene in the liquid phase, Top. Catal. 22 (1-2)(2003) 41-51.

[32] Q.F. Wang, L. Wang, J.X. Chen, Y.L. Wu, Z.T. Mi, Deactivation and regeneration oftitanium silicalite catalyst for epoxidation of propylene, J. Mol. Catal. A Chem. 273(1-2) (2007) 73-80.

[33] M. Guidotti, N. Ravasio, R. Psaro, G. Ferraris, G. Moretti, Epoxidation on titaniumcontainingsilicates: do structural features really affect the catalytic performance?J. Catal. 214 (2) (2003) 242-250.

[34] Y.S. Zhou, G.W. Jiang, Study on properties of composite oxides TiO₂/SiO₂, Chin. J.Chem. Eng. 10 (3) (2002) 349-353.

[35] G.A. Eimer, S.G. Casuscelli, G.E. Ghione, M.E. Crivello, E.R. Herrero, Synthesis, characterizationand selective oxidation properties of Ti-containing mesoporous catalysts,Appl. Catal. A Gen. 298 (2006) 232-242.

[36] R.A. Sheldon, J.A. Van Doorn, Metal-catalyzed epoxidation of olefins with organichydroperoxides: I. A comparison of various metal catalysts, J. Catal. 31 (3) (1973)427-437.

[37] A. Corma, From microporous tomesoporousmolecular sievematerials and their usein catalysis, Rev. Chem. 97 (6) (1997) 2373-2420.

[38] A. Bhaumik, T. Tatsumi, Organically modified titanium-rich Ti-MCM-41, efficientcatalysts for epoxidation reactions, J. Catal. 189 (1) (2000) 31-39.

[39] W.B. Fan, P. Wu, S. Namba, T. Tatsumi, Synthesis and catalytic properties of a newtitanosilicate molecular sieve with the structure analogous to MWW-type lamellarprecursor, J. Catal. 243 (1) (2006) 183-191.

[40] A. Corma, H. Garcia, Lewis acids as catalysts in oxidation reactions: from homogeneousto heterogeneous systems, Chem. Rev. 102 (10) (2002) 3837-3892.

[41] T. Blasco, M.A. Camblor, J.L.G. Fierro, J. Perez-Pariente, X-ray photoelectronspectroscopy of Ti-Beta zeolite, Microporous Mesoporous Mater. 3 (3) (1994)259-263.

[42] M.C. Capel-Sanchez, V.A. Dela Peña-O'Shea, J.M. Campos-Martin, J.L.G. Fierro, TDDFTanalysis of the electronic spectra of Ti-containing catalysts, Top. Catal. 41(1-4) (2006) 27-34.

[43] X.W. Liu, X.S.Wang, X.W. Guo, G. Li, H.S. Yan, Regeneration of lamina TS-1 catalyst inthe epoxidation of propylene with hydrogen peroxide, Catal. Lett. 97 (3-4) (2004)223-229.

[44] Q.C. Yuan, A. Hagen, F. Roessner, An investigation into the Ti-grafting structure onMCM-41 and epoxidation catalysis, Appl. Catal. A Gen. 303 (1) (2006) 81-87.