Visualizing Dealumination of a Single Zeolite Domain in a Real‐Life Catalytic Cracking Particle

Abstract Fluid catalytic cracking (FCC) catalysts play a central role in the chemical conversion of crude oil fractions. Using scanning transmission X‐ray microscopy (STXM) we investigate the chemistry of one fresh and two industrially deactivated (ECAT) FCC catalysts at the single zeolite domain level. Spectro‐microscopic data at the Fe L3, La M5, and Al K X‐ray absorption edges reveal differing levels of deposited Fe on the ECAT catalysts corresponding with an overall loss in tetrahedral Al within the zeolite domains. Using La as a localization marker, we have developed a novel methodology to map the changing Al distribution of single zeolite domains within real‐life FCC catalysts. It was found that significant changes in the zeolite domain size distributions as well as the loss of Al from the zeolite framework occur. Furthermore, inter‐ and intraparticle heterogeneities in the dealumination process were observed, revealing the complex interplay between metal‐mediated pore accessibility loss and zeolite dealumination.

[1]  Anna M. Wise,et al.  Nanoscale Chemical Imaging of an Individual Catalyst Particle with Soft X-ray Ptychography , 2016, ACS catalysis.

[2]  B. Weckhuysen,et al.  Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis , 2015, Chemical Society reviews.

[3]  B. Weckhuysen,et al.  X-ray Fluorescence Tomography of Aged Fluid-Catalytic-Cracking Catalyst Particles Reveals Insight into Metal Deposition Processes , 2015, ChemCatChem.

[4]  A. Beale,et al.  In Situ Microfocus Chemical Computed Tomography of the Composition of a Single Catalyst Particle During Hydrogenation of Nitrobenzene in the Liquid Phase , 2015, Angewandte Chemie.

[5]  J. Weker,et al.  Agglutination of single catalyst particles during fluid catalytic cracking as observed by X-ray nanotomography† †Electronic supplementary information (ESI) available: Supporting information, Movies S1 and S2. See DOI: 10.1039/c5cc00401b Click here for additional data file. Click here for additional , 2015, Chemical communications.

[6]  Yijin Liu,et al.  Life and death of a single catalytic cracking particle , 2015, Science Advances.

[7]  Yijin Liu,et al.  Mapping Metals Incorporation of a Whole Single Catalyst Particle Using Element Specific X-ray Nanotomography , 2015, Journal of the American Chemical Society.

[8]  B. Weckhuysen,et al.  Hexane cracking over steamed phosphated zeolite H-ZSM-5: promotional effect on catalyst performance and stability. , 2014, Chemistry.

[9]  M. Roeffaers,et al.  High-Resolution Single-Molecule Fluorescence Imaging of Zeolite Aggregates within Real-Life Fluid Catalytic Cracking Particles** , 2014, Angewandte Chemie.

[10]  B. Weckhuysen,et al.  Aluminum-phosphate binder formation in zeolites as probed with X-ray absorption microscopy. , 2014, Journal of the American Chemical Society.

[11]  J. Bokhoven,et al.  Structure of aluminum, iron, and other heteroatoms in zeolites by X-ray absorption spectroscopy , 2014 .

[12]  Andrew M. Beale,et al.  Progress towards five dimensional diffraction imaging of functional materials under process conditions , 2014 .

[13]  B. Lai,et al.  Back Cover: Characterization of a Fluidized Catalytic Cracking Catalyst on Ensemble and Individual Particle Level by X‐ray Micro‐ and Nanotomography, Micro‐X‐ray Fluorescence, and Micro‐X‐ray Diffraction (ChemCatChem 5/2014) , 2014 .

[14]  B. Lai,et al.  Characterization of a Fluidized Catalytic Cracking Catalyst on Ensemble and Individual Particle Level by X‐ray Micro‐ and Nanotomography, Micro‐X‐ray Fluorescence, and Micro‐X‐ray Diffraction , 2014 .

[15]  B. Weckhuysen,et al.  Dispersion and orientation of zeolite ZSM-5 crystallites within a fluid catalytic cracking catalyst particle. , 2014, Chemistry.

[16]  B. Weckhuysen,et al.  Phosphatation of zeolite H-ZSM-5: a combined microscopy and spectroscopy study. , 2014, Chemphyschem : a European journal of chemical physics and physical chemistry.

[17]  Sharon Mitchell,et al.  From powder to technical body: the undervalued science of catalyst scale up. , 2013, Chemical Society reviews.

[18]  Upakul Deka,et al.  Correlating Metal Poisoning with Zeolite Deactivation in an Individual Catalyst Particle by Chemical and Phase-Sensitive X-ray Microscopy , 2013, Angewandte Chemie.

[19]  Yijin Liu,et al.  3D nanoscale chemical imaging of the distribution of aluminum coordination environments in zeolites with soft X-ray microscopy. , 2013, Chemphyschem : a European journal of chemical physics and physical chemistry.

[20]  B. Weckhuysen,et al.  X-ray imaging of zeolite particles at the nanoscale: influence of steaming on the state of aluminum and the methanol-to-olefin reaction. , 2012, Angewandte Chemie.

[21]  K. Lillerud,et al.  X-ray absorption spectroscopies: useful tools to understand metallorganic frameworks structure and reactivity. , 2010, Chemical Society reviews.

[22]  A. Beale,et al.  Chemical imaging of catalytic solids with synchrotron radiation. , 2010, Chemical Society reviews.

[23]  Christian G. Schroer,et al.  Hard and soft X-ray microscopy and tomography in catalysis: bridging the different time and length scales. , 2010, Chemical Society reviews.

[24]  Anmin Zheng,et al.  Insights into the dealumination of zeolite HY revealed by sensitivity-enhanced 27Al DQ-MAS NMR spectroscopy at high field. , 2010, Angewandte Chemie.

[25]  M. Janousch,et al.  In situ XAS and XRPD parametric rietveld refinement to understand dealumination of Y zeolite catalyst. , 2010, Journal of the American Chemical Society.

[26]  J. Grunwaldt,et al.  Catalysts at work: From integral to spatially resolved X-ray absorption spectroscopy , 2009 .

[27]  Y. Mortazavi,et al.  Synergetic effects of Y-zeolite and amorphous silica-alumina as main FCC catalyst components on triisopropylbenzene cracking and coke formation , 2009 .

[28]  F. R. Ribeiro,et al.  Deactivation of FCC catalysts , 2008 .

[29]  Adam P. Hitchcock,et al.  Soft X-ray spectromicroscopy beamline at the CLS: Commissioning results , 2007 .

[30]  Anmin Zheng,et al.  Brønsted/Lewis acid synergy in dealuminated HY zeolite: a combined solid-state NMR and theoretical calculation study. , 2007, Journal of the American Chemical Society.

[31]  A. Bell,et al.  An in situ Al K-edge XAS investigation of the local environment of H+- and Cu+-exchanged USY and ZSM-5 zeolites. , 2006, The journal of physical chemistry. B.

[32]  R. Prins,et al.  Effect of temperature on aluminum coordination in zeolites H-Y and H-USY and amorphous silica-alumina: an in situ Al K edge XANES study. , 2005, The journal of physical chemistry. B.

[33]  O. Bayraktar,et al.  Visualization of the Equilibrium FCC Catalyst Surface by AFM and SEM–EDS , 2003 .

[34]  J. V. van Bokhoven,et al.  Three-coordinate aluminum in zeolites observed with in situ x-ray absorption near-edge spectroscopy at the Al K-edge: flexibility of aluminum coordinations in zeolites. , 2003, Journal of the American Chemical Society.

[35]  J. Bokhoven,et al.  Influence of Steam Activation on Pore Structure and Acidity of Zeolite Beta: An Al K Edge XANES Study of Aluminum Coordination , 2002 .

[36]  E. Sousa-Aguiar,et al.  Thermal stability of Y zeolites containing different rare earth cations , 2002 .

[37]  J. Bokhoven,et al.  Al K-edge near-edge X-ray absorption fine structure (NEXAFS) study on the coordination structure of aluminum in minerals and Y zeolites , 1999 .

[38]  A. Flank,et al.  Aluminium X-ray absorption Near Edge Structure in model compounds and Earth’s surface minerals , 1998 .

[39]  P. Gallezot,et al.  The nature of the nonframework aluminum species formed during the dehydroxylation of H-Y , 1985 .

[40]  J. Scherzer,et al.  Ion-exchanged ultrastable Y zeolites--3. Gas oil cracking over rare earth-exchanged ultrastable Y zeolites , 1978 .

[41]  M. M. Mitchell,et al.  Fluid catalytic cracking : science and technology , 1993 .