Abstract
Fluid catalytic cracking (FCC) is the major conversion process used in oil refineries to produce valuable hydrocarbons from crude oil fractions. Because the demand for oil-based products is ever increasing, research has been ongoing to improve the performance of FCC catalyst particles, which are complex mixtures of zeolite and binder materials. Unfortunately, there is limited insight into the distribution and activity of individual zeolitic domains at different life stages. Here we introduce a staining method to visualize the structure of zeolite particulates and other FCC components. Brønsted acidity maps have been constructed at the single particle level from fluorescence microscopy images. By applying a statistical methodology to a series of catalysts deactivated via industrial protocols, a correlation is established between Brønsted acidity and cracking activity. The generally applicable method has clear potential for catalyst diagnostics, as it determines intra- and interparticle Brønsted acidity distributions for industrial FCC materials.
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References
Brouwer, L. E. L. The Petroleum Handbook (Balding & Mansell Limited, 1966).
Cheng, W-C. et al. in Handbook of Heterogeneous Catalysis (eds Ertl, G., Knözinger, H., Schüth, F. & Weitkamp, J.) 2741–2778 (Wiley-VCH, 2008).
von Balmoos, R., Harris, D. H. & Magee, J. S. in Handbook of Heterogeneous Catalysis (eds Ertl, G., Knözinger, H. & Weitkamp, J.) 1955–1983 (Wiley-VCH, 1997).
Vermeiren, W. & Gilson, J-P. Impact of zeolites on the petroleum and petrochemical industry. Top. Catal. 52, 1131–1161 (2009).
Newsam, J. M. The zeolite cage structure. Science 231, 1093–1099 (1986).
Rigutto, M. in Zeolites and Catalysis: Synthesis, Reactions and Applications (eds Čejka, J., Corma, A. & Zones, S. I.) 547–584 (Wiley-VCH, 2010).
Corma, A. Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions. Chem. Rev. 95, 559–614 (1995).
Bomgardner, M. M. Using pore power. Chem. Eng. News 89, 20–21 (2011).
Rawlence, D. J. & Gosling, K. FCC catalyst performance evaluation. Appl. Catal. 43, 213–237 (1988).
Chao, K. J., Lin, L. H., Ling, Y. C., Hwang, J. F. & Hou, L. Y. Vanadium passivation of cracking catalysts by imaging secondary ion mass spectrometry. Appl. Catal. A 121, 217–229 (1995).
Kugler, E. L. & Leta, D. P. Nickel and vanadium on equilibrium cracking catalysts by imaging secondary ion mass spectrometry. J. Catal. 109, 387–395 (1988).
Cao, H. & Suib, S. L. Spectroscopic studies of the migration of vanadium in the model fluid catalytic cracking process. Appl. Spectrosc. 49, 1454–1462 (1995).
Lappas, A. A., Nalbandian, L., Iatridis, D. K., Voutetakis, S. S. & Vasalos, I. A. Effect of metals poisoning on FCC products yields: studies in an FCC short contact time pilot plant unit. Catal. Today 65, 233–240 (2001).
Haas, A., Suarez, W. & Young, G. W. Evaluation of metals contaminated FCC catalysts. AIChE Symposium Series 133–142 (1992).
Occelli, M. L., Gould, S. A. C. & Stucky, G. D. The study of the surface topography of microporous materials using atomic force microscopy. Stud. Surf. Sci. Catal. 485–492 (1994).
Psarras, A. C., Iliopoulou, E. F., Nalbandian, L., Lappas, A. A. & Pouwels, C. Study of the accessibility effect on the irreversible deactivation of FCC catalysts from contaminant feed metals. Catal. Today 127, 44–53 (2007).
Zhang, J., Campbell, R. E., Ting, A. Y. & Tsien, R. Y. Creating new fluorescent probes for cell biology. Nature Rev. Mol. Cell Biol. 3, 906–918 (2002).
Krutzik, P. O. & Nolan, G. P. Fluorescent cell barcoding in flow cytometry allows high-throughput drug screening and signaling profiling. Nature Methods 3, 361–368 (2006).
Martin, B. R., Giepmans, B. N. G., Adams, S. R. & Tsien, R. Y. Mammalian cell-based optimization of the biarsenical-binding tetracysteine motif for improved fluorescence and affinity. Nature Biotechnol. 23, 1308–1314 (2005).
Rajagopal, J., Anderson, W. J., Kume, S., Martinez, O. I. & Melton, D. A. Development: insulin staining of ES cell progeny from insulin uptake. Science 299, 363 (2003).
Darzynkiewicz, Z., Bedner, E., Li, X., Gorczyca, W. & Melamed, M. R. Laser-scanning cytometry: a new instrumentation with many applications. Exp. Cell Res. 249, 1–12 (1999).
Marks, K. M. & Nolan, G. P. Chemical labeling strategies for cell biology. Nature Methods 3, 591–596 (2006).
Karwacki, L. et al. Morphology-dependent zeolite intergrowth structures leading to distinct internal and outer-surface molecular diffusion barriers. Nature Mater. 8, 959–965 (2009).
Roeffaers, M. B. J. et al. Spatially resolved observation of crystal-face-dependent catalysis by single turnover counting. Nature 439, 572–575 (2006).
Xu, W., Kong, J. S., Yeh, Y. T. E. & Chen, P. Single-molecule nanocatalysis reveals heterogeneous reaction pathways and catalytic dynamics. Nature Mater. 7, 992–996 (2008).
Naito, K., Tachikawa, T., Fujitsuka, M. & Majima, T. Single-molecule observation of photocatalytic reaction in TiO2 nanotube: importance of molecular transport through porous structures. J. Am. Chem. Soc. 131, 934–936 (2009).
De Cremer, G., Sels, B. F., De Vos, D. E., Hofkens, J. & Roeffaers, M. B. J. Fluorescence micro(spectro)scopy as a tool to study catalytic materials in action. Chem. Soc. Rev. 39, 4703–4717 (2010).
Chen, P. et al. Single-molecule fluorescence imaging of nanocatalytic processes. Chem. Soc. Rev. 39, 4560–4570 (2010).
Tachikawa, T. & Majima, T. Single-molecule, single-particle fluorescence imaging of TiO2-based photocatalytic reactions. Chem. Soc. Rev. 39, 4802–4819 (2010).
Weckhuysen, B. M. Chemical imaging of spatial heterogeneities in catalytic solids at different length and time scales. Angew. Chem. Int. Ed. 48, 4910–4943 (2009).
Denk, W., Strickler, J. H. & Webb, W. W. Two-photon laser scanning fluorescence microscopy. Science 248, 73–76 (1990).
Roeffaers, M. B. J. et al. Morphology of large ZSM-5 crystals unraveled by fluorescence microscopy. J. Am. Chem. Soc. 130, 5763–5772 (2008).
Seebacher, C. et al. Visualization of mesostructures and organic guest inclusion in molecular sieves with confocal microscopy. Adv. Mater. 13, 1374–1377 (2001).
Kox, M. H. F., Mijovilovich, A., Sättler, J. J. H. B., Stavitski, E. & Weckhuysen, B. M. The catalytic conversion of thiophenes over large H-ZSM-5 crystals: an X-ray, UV/vis, and fluorescence microspectroscopic study. ChemCatChem 2, 564–571 (2010).
Kox, M. H. F. et al. Label-free chemical imaging of catalytic solids by coherent anti-Stokes Raman scattering and synchrotron-based infrared microscopy. Angew. Chem. Int. Ed. 48, 8990–8994 (2009).
Rautiainen, E., Pimenta, R., Ludvig, M. & Pouwels, C. Deactivation of ZSM-5 additives in laboratory for realistic testing. Catal. Today 140, 179–186 (2009).
Bendiksen, M., Tangstad, E. & Myrstad, T. A comparison of laboratory deactivation methods for FCC catalysts. Appl. Catal. A 129, 21–31 (1995).
Psarras, A. C., Iliopoulou, E. F., Kostaras, K., Lappas, A. A. & Pouwels, C. Investigation of advanced laboratory deactivation techniques of FCC catalysts via FTIR acidity studies. Microporous Mesoporous Mater. 120, 141–146 (2009).
Mitchell, B. R. Metal contamination of cracking catalysts. 1. Synthetic metals deposition on fresh catalysts. Ind. Eng. Chem. Prod. Res. Dev. 19, 209–213 (1980).
Rust, M. J., Bates, M. & Zhuang, X. Sub-diffraction-limit imaging by stochastic optical reconstruction microscopy (STORM). Nature Methods 3, 793–795 (2006).
Betzig, E. & Trautman, J. K. Near-field optics: microscopy, spectroscopy, and surface modification beyond the diffraction limit. Science 257, 189–195 (1992).
Chen, N. Y., Mitchell, T. O., Olson, D. H. & Pelrine, B. P. Irreversible deactivation of zeolite fluid cracking catalyst. 2. Hydrothermal stability of catalysts containing NH4Y and rare earth Y. Ind. Eng. Chem. Prod. Res. Dev. 16, 247–252 (1977).
Chen, D. et al. Acidity studies of fluid catalytic cracking catalysts by microcalorimetry and infrared spectroscopy. J. Catal. 136, 392–402 (1992).
Farneth, W. E. & Gorte, R. J. Methods for characterizing zeolite acidity. Chem. Rev. 95, 615–635 (1995).
Acknowledgements
The authors thank Albemarle Catalysts for financial support and for providing catalyst materials, catalytic performance data and part of the bulk characterization data. J.R.M. acknowledges the ACTS-Aspect program for funding. The authors thank F. Soulimani (Utrecht University) for help with the IR measurements, M. Versluijs-Helder (Utrecht University) for the XRD measurements, U. Deka (Utrecht University) for the calculations of the unit cell sizes, A. Ruppert (Technical University of Lodz) for the design of Fig. 1a and the graphical abstract and J. Francis (Albemarle Corporation) for fruitful discussions.
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I.L.C.B. and J.R.M. contributed equally to this work. They carried out the experiments, the statistical analysis and wrote the manuscript. W.V.K. contributed to the catalytic activity tests and discussion thereof and participated in manuscript preparation. D.B., J.A.B. and E.T.C.V. contributed to the discussion of the results. B.M.W. designed and directed the research, and contributed to the preparation and writing of the manuscript.
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Buurmans, I., Ruiz-Martínez, J., Knowles, W. et al. Catalytic activity in individual cracking catalyst particles imaged throughout different life stages by selective staining. Nature Chem 3, 862–867 (2011). https://doi.org/10.1038/nchem.1148
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DOI: https://doi.org/10.1038/nchem.1148
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