Ihli J, Jacob R R, Holler M, Guizar-Sicairos M, Diaz A, da Silva J C, Ferreira Sanchez D, Krumeich F, Grolimund D, Taddei M, Cheng W -C, Shu Y, Menzel A, van Bokhoven J A
Paul Scherrer Institut, 5232, Villigen PSI, Switzerland.
European Radiation Synchrotron Facility, 38000, Grenoble, France.
Nat Commun. 2017 Oct 9;8(1):809. doi: 10.1038/s41467-017-00789-w.
Since its commercial introduction three-quarters of a century ago, fluid catalytic cracking has been one of the most important conversion processes in the petroleum industry. In this process, porous composites composed of zeolite and clay crack the heavy fractions in crude oil into transportation fuel and petrochemical feedstocks. Yet, over time the catalytic activity of these composite particles decreases. Here, we report on ptychographic tomography, diffraction, and fluorescence tomography, as well as electron microscopy measurements, which elucidate the structural changes that lead to catalyst deactivation. In combination, these measurements reveal zeolite amorphization and distinct structural changes on the particle exterior as the driving forces behind catalyst deactivation. Amorphization of zeolites, in particular, close to the particle exterior, results in a reduction of catalytic capacity. A concretion of the outermost particle layer into a dense amorphous silica-alumina shell further reduces the mass transport to the active sites within the composite.Catalyst deactivation in fluid catalytic cracking processes is unavoidably associated with structural changes. Here, the authors visualize the deactivation of zeolite catalysts by ptychography and other imaging techniques, showing pronounced amorphization of the outer layer of the catalyst particles.
自四分之三个世纪前商业化引入以来,流化催化裂化一直是石油工业中最重要的转化工艺之一。在这个过程中,由沸石和粘土组成的多孔复合材料将原油中的重质馏分裂解为运输燃料和石化原料。然而,随着时间的推移,这些复合颗粒的催化活性会降低。在此,我们报告了叠层成像断层扫描、衍射和荧光断层扫描以及电子显微镜测量,这些测量阐明了导致催化剂失活的结构变化。综合起来,这些测量揭示了沸石非晶化以及颗粒外部明显的结构变化是催化剂失活的驱动力。特别是靠近颗粒外部的沸石非晶化导致催化能力下降。最外层颗粒层凝结成致密的无定形硅铝壳进一步减少了向复合材料内活性位点的质量传输。流化催化裂化过程中的催化剂失活不可避免地与结构变化相关。在此,作者通过叠层成像和其他成像技术可视化了沸石催化剂的失活,显示出催化剂颗粒外层明显的非晶化。