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Catalytic Ethylene Production from Ethanol Dehydration over Non-Modified and Phosphoric Acid Modified Zeolite H-Y (80) Catalysts

机译:非改性和磷酸改性沸石H-Y(80)催化剂上乙醇脱水制乙烯的催化作用

摘要

The present work reports on the effects of phosphoric acid-modified Zeolites-Y towards the ethylene formation from ethanol dehydration. The catalyst was impregnated with different H3PO4 loadings from 10 to 30wt%. All the catalysts were characterized using N2-physisorption, thermogravimetric analysis, NH3-TPD, FTIR, SEM-EDX, X-ray diffraction and XPS techniques. The non-modified Zeolite-Y with Si/Al 80:1, H-Y (80) was found to exhibit excellent catalytic activity owing to the presence of weak acid sites that was able to protonate the hydroxyl group of ethanol. Although ethanol conversion dropped with phosphorus modified catalysts, it was found that the modified Zeolite-Y with 10wt% H3PO4 can achieve 99% selectivity to ethylene at 723 K and ethanol partial pressure of 16 kPa. Overall, ethanol conversion and ethylene selectivity decreased in the order of H-Y (80)> 10P/H-Y (80) > 20P/H-Y (80) > 30P/H-Y (80). The decrease in ethanol dehydration activity of phosphorus modified catalysts can be ascribed to the reduced BET specific surface area and pore volume due to the surface coverage by layers of H3PO4, consequently, hindered ethanol access to the active site However, the spent phosphorus modified Zeolite-Y catalyst consistently showed less carbon formation compared to the undoped catalyst. This could be due to the reduction in strong acid site and also hindrance of C2H5OH from travelling deep into the pore networks of H-Y (80), therefore reducing the residence time with a consequence of minimizing the carbon laydown.
机译:本工作报道了磷酸改性的Zeolites-Y对乙醇脱水形成乙烯的影响。催化剂浸渍有10至30 wt%的不同H3PO4负载量。使用N 2物理吸附,热重分析,NH3-TPD,FTIR,SEM-EDX,X射线衍射和XPS技术对所有催化剂进行了表征。发现具有Si / Al 80:1,H-Y(80)的未改性沸石-Y表现出优异的催化活性,这归因于弱酸性位点的存在,能够使乙醇的羟基质子化。尽管用磷改性的催化剂降低了乙醇的转化率,但是发现具有10wt%H3PO4的改性Zeolite-Y在723 K和16 kPa的乙醇分压下可以实现99%的乙烯选择性。总体而言,乙醇转化率和乙烯选择性以H-Y(80)> 10P / H-Y(80)> 20P / H-Y(80)> 30P / H-Y(80)的顺序降低。磷改性催化剂的乙醇脱水活性降低可归因于H3PO4层的表面覆盖导致BET比表面积和孔体积降低,因此阻碍了乙醇进入活性位。但是,用过的磷改性沸石-与未掺杂的催化剂相比,Y催化剂始终显示较少的碳形成。这可能是由于强酸位点的减少以及C2H5OH深入进入H-Y的孔网络(80)的阻碍,因此减少了停留时间,从而使碳沉积最小。

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