Synthesis Of Modified Mesoporous Molecular Sieve By Functionalized Ionic Liquid And Its Application In The Acid Catalysis

Mesoporous molecular sieves are type of species with large specific surface area and large pore diameter and have an outstanding advantage in the heterogeneous reaction.Nevertheless,their pool hydrothermal stability and weak acidity vastly limit the wide application.Therefore,it is worthy to modified and change the property of mesoporous melocular sevies to enhance their performance in the catalysis.The mainly studies are as follow:?1?The mesoporous SBA-15,MCM-41 and MCM-48 were synthesized by hydrothermal process using different Si and metal source.Meanwhile,the chlorine-aluminate acidic ionic liquid of 1-butyl-3-methylimidazolium chloride-aluminum chloride?denoted as Al-ILs?was prepared by two-step method.The immobilized ionic liquid?Al-IL/SBA-15,Al-IL/MCM-41,Al-IL/MCM-48?was prepared through impregnating Al-ILs,and was characted by XRD,BET,TEM,XPS,FT-IR.The ketalization between cyclohexanone and ethanediol was used as the model reaction to test the catalytic activities of the composite catalysts.The influences of molar ratio of the reactants,reaction time,the catalyst dose,as well as the reaction temperature were discussed in detail.Under comparable conditions,the Al-IL/SBA-15 composite catalyst exhibited much high catalytic activity and gave a maximum cyclohexanone conversion was 85.1%.?2?Zirconium-incorporated SBA-15 mesoporous materials?Zr-SBA-15?with different Si/Zr mole ratio are one-pot synthesized using ZrOCl₂ as the metal source.The Br?nsted-Lewis acidic ionic liquids?[mim-ps]Cl-ZnCl₂?is prepared by hydrothermal process using ZnCl₂ as the lewis acidic site and sulfo group as Br?nsted acidic site.And the acidity is measured by FT-IR spectra using acetonitrile and pyridine as probe.The immobilized[mim-ps]Cl-ZnCl₂ on Zr-SBA-15 catalysts?Zr-SBA-15/[mim-ps]Cl-ZnCl₂?are prepared and characterized by the XRD,BET,FT-IR,TEM,XPS and TG.Furthermore,the catalytic activity of Zr-SBA-15 and Zr-SBA-15/[mim-ps]Cl-ZnCl₂ is studied in the esterification of acetic acid with n-butyl alcohol?n-BuOH?,benzyl alcohol?BnOH?and cyclohexanol?Nxaol?.The results shows that[mim-ps]Cl-ZnCl₂ enhances the catalytic property of Zr-SBA-15 greatly.Under optimal condition,the acetic acid conversion reaches to 89.7,93.6,and 84.9%for n-BuOH,BnOH and Nxaol respectively using Zr-SBA-15/[mim-ps]Cl-ZnCl₂ as catalyst.And after 5 times of recycling,the acetic acid conversion decreases slightly.?3?The Fe-SBA-15 mesoporous materials with different Si/Fe mole ratios were prepared by direct synthesis methods using Fe?NO₃?₃.9H₂O as the metal source.A novel Br?nsted and Lewis acid ionic liquid butyrolactam chlorozincinate?CPCl-ZnCl₂?was synthesized by a hydrothermal process using butyrolactam and ZnCl₂ as the reactants and characterized by FT-IR and ¹HNMR.The supported ionic liquid?IL/Fe-SBA-15?with various IL contents were prepared by a wet impregnation method and characterized by the XRD,BET,FT-IR,TEM,XPS.The catalytic property was tested in the various acetalizations.The results demonstrated that the IL/Fe-SBA-15 is a outstanding catalyst of acetalization of cyclohexanone and ethanediol.And under optimal conditions,the acetalization could reach to 92.6%cyclohexanone conversion with 99.3%acetal selectivity.After 5 cycles,the cyclohexanone conversion decreased slightly.