E. Salminen, S. Bridier, P. Mäki-Arvela, Narendra Kumar, J. Dahl, Jorma Roine, T. Salmi, J. Mikkola
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引用次数: 0
摘要
不同的催化剂合成方法决定了所制备材料的物理化学和催化性能。设计合适的催化活性位点对于提高活性和提高期望产物的选择性是非常重要的。生物质衍生的萜烯及其氧化物(例如α-蒎烯氧化物)是制药和精细化工行业的重要平台构建块。催化剂的刘易斯酸性促进了α-蒎烯氧化物转化为芳香化学品——樟脑醛。研究了α-蒎烯氧化物在共改性β -和y -沸石以及二氧化硅、氧化铝和介孔H-MCM-48催化剂上异构化成樟脑醛的反应。采用粉末x射线衍射(PXRD)、扫描电镜(SEM)、能量色散x射线能谱(EDX)、氮吸附分析(孔隙度分析)、x射线光电子能谱(XPS)研究Co氧化态、程序升温解吸(TPD)-NH3和傅里叶变换红外光谱(FTIR)-吡啶测定催化剂的酸性。co - h - β -150、co - h - β -25、Co-H-Y-12、Co-H-Y-80、Co-H-MCM-48催化剂的α-蒎烯氧化物转化率高达62%。Co-H-Y-80分子筛和Co-MCM-48介孔催化剂的脑烯醛收率分别为51%和45%。
Chapter 4. Design of Metal-modified Zeolites and Mesoporous Aluminosilicates and Application in the Synthesis of Fine Chemicals
Different catalyst synthesis methods determine the physicochemical and catalytic properties of the prepared materials. The design of suitable catalytic active sites is important to increase the activity and to improve selectivity for the desired product. Biomass derived terpenes and their oxides (e.g. α-pinene oxide) are important platform building blocks for the pharmaceutical and fine chemical industries. Transformation of α-pinene oxide to a fragrance chemical, campholenic aldehyde, is promoted by the Lewis acidic nature of the catalyst. The isomerization of α-pinene oxide to campholenic aldehyde was studied over Co-modified Beta- and Y-zeolites as well as over silica, alumina and mesoporous H-MCM-48 catalysts. The Co-modified catalysts were characterized using powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), elemental analysis using energy dispersive X-ray spectroscopy (EDX), nitrogen sorption analysis to analyze the porosity, X-ray photoelectron spectroscopy (XPS) to study the Co oxidation states, temperature programmed desorption (TPD)-NH3 and Fourier transform infrared spectroscopy (FTIR)-pyridine to measure the acidic properties. Co-H-Beta-150, Co-H-Beta-25, Co-H-Y-12, Co-H-Y-80, Co-H-MCM-48 catalysts gave rise to a high conversion (>62%) of α-pinene oxide. The Co-H-Y-80 zeolite and the Co-MCM-48 mesoporous catalysts exhibited a 51% and 45% yield of campholenic aldehyde, respectively.