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Catalytic esterification of benzyl alcohol with acetic acid by zirconia-loaded on mesoporous material

机译:负载在介孔材料上的氧化锆催化苄醇与乙酸的酯化反应

摘要

This research focuses on the synthesis and characterization of metalcontaining mesoporous silica for catalytic esterification of benzyl alcohol with acetic acid. In this study Zr-containing MCM-41 (Zr-MCM-41) with different molar ratios were synthesized successfully, and the influence of the Si/Zr molar ratio on the crystalline structure, textural properties, morphological features and surface acidity of Zr-MCM-41 mesoporous molecular sieves was investigated by X-ray diffraction (XRD), N2 adsorption-desorption measurement, SEM and FTIR (Fourier transform infrared) Spectroscopy, UV-Vis diffuse reflectance (UV-Vis DR), spectroscopy and single point BET. It is observed that the structural ordering of Zr-MCM-41 varies with the Si/Zr ratio, and highly ordered mesoporous molecular sieves could be earned for a Si/Zr molar ratio larger than 5. Calcination may significantly improve the structural regularity. After impregnation with 15 wt % of H3PW12O40 (denoted as HWP hereafter),in esterification reaction of benzyl alcohol with acetic acid, the benzyl alcohol conversion over all the HPW/Zr-MCM-41catalysts linearly increases with increasing the reaction temperature, and selectivity to benzyl acetate was 100 %. The molar ratios of reactants also were investigated for final product yield; the molar ratio of acetic acid to benzyl alcohol can be 2:1 for high yield. The presence of zirconium in tetrahedral coordination was indicated by UV-Vis DR spectra, which shows an absorption band around 220 nm in Zr-MCM41. The catalyst had more active sites than pure Si-MCM-41 due to enhanced hydrophobicity properties and the presence of framework zirconium species as Lewis active sites. Kinetics studies have shown that the esterification reaction follows the Eley-Ridel mechanism. The energy of activation for the reaction follows the order: HPW/Zr-MCM-41(Si/Zr=5) > Zr- MCM-41(Si/Zr=10) > Zr-MCM-41(Si/Zr=20).
机译:这项研究的重点是含金属的介孔二氧化硅的合成和表征,用于苯甲醇与乙酸的催化酯化反应。本研究成功合成了不同摩尔比的含Zr的MCM-41(Zr-MCM-41),并且Si / Zr摩尔比对Zr-的晶体结构,组织性质,形貌特征和表面酸度的影响。通过X射线衍射(XRD),N2吸附-解吸测量,SEM和FTIR(傅里叶变换红外)光谱,UV-Vis漫反射(UV-Vis DR),光谱和单点BET研究了MCM-41介孔分子筛。观察到Zr-MCM-41的结构有序性随Si / Zr比而变化,并且当Si / Zr摩尔比大于5时,可以获得高度有序的中孔分子筛。煅烧可以显着改善结构规则性。在用15 wt%的H3PW12O40(以下称为HWP)浸渍后,在苯甲醇与乙酸的酯化反应中,所有HPW / Zr-MCM-41催化剂上的苯甲醇转化率随反应温度的升高而线性增加,并且对乙酸苄酯为100%。还研究了反应物的摩尔比以得到最终产物。为了高产率,乙酸与苯甲醇的摩尔比可以为2:1。 UV-Vis DR光谱表明锆存在四面体配位,在Zr-MCM41中显示了约220 nm的吸收带。该催化剂具有比纯Si-MCM-41更多的活性位点,这是由于疏水性增强以及骨架锆物种作为Lewis活性位点的缘故。动力学研究表明,酯化反应遵循Eley-Ridel机理。反应的活化能按以下顺序排列:HPW / Zr-MCM-41(Si / Zr = 5)> Zr-MCM-41(Si / Zr = 10)> Zr-MCM-41(Si / Zr = 20 )。

著录项

  • 作者

    Jazi Mehdi Erfani;

  • 作者单位
  • 年度 2010
  • 总页数
  • 原文格式 PDF
  • 正文语种 {"code":"en","name":"English","id":9}
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