X-ray nanotomography uncovers morphological heterogeneity in a polymerization catalyst at multiple reaction stages

Maximilian J. Werny; Roozbeh Valadian; Leon M. Lohse; Anna Lena Robisch; Silvia Zanoni; Coen Hendriksen; Bert M. Weckhuysen; Florian Meirer

doi:10.1016/j.checat.2021.10.008

X-ray nanotomography uncovers morphological heterogeneity in a polymerization catalyst at multiple reaction stages

Maximilian J. Werny
, Roozbeh Valadian
, Leon M. Lohse
, Anna Lena Robisch
, Silvia Zanoni
, Coen Hendriksen
, Bert M. Weckhuysen^*
, Florian Meirer

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

During olefin polymerization on supported catalysts, the controlled morphological evolution of the catalyst particle is vital for ensuring optimal product properties and high catalyst activity. We employed non-destructive hard X-ray holotomography to quantitatively assess the 3D morphology of multiple silica-supported hafnocene-based catalyst particles during the early stages of gas-phase ethylene polymerization. Image processing and pore network modeling revealed clear variations in the dimensions and interconnectivity of pristine particles' macropore networks. This, together with apparent differences in the fragmentation behavior of pre-polymerized particles, suggests that the reactivity and morphological evolution of individual particles are largely dictated by their unique support and pore space architectures. By minimizing the structural heterogeneity among pristine catalyst particles, more uniform particle morphologies may be obtained. Significant polymerization activity, observed in the particles' interiors, further implies that appropriate polymerization conditions and catalyst kinetics can guarantee sufficiently high particle accessibilities and thus more homogeneous support fragmentation.

Original language	English
Pages (from-to)	1413-1426
Number of pages	14
Journal	Chem Catalysis
Volume	1
Issue number	7
DOIs	https://doi.org/10.1016/j.checat.2021.10.008
Publication status	Published - 16 Dec 2021

Bibliographical note

Funding Information:
This research was funded by a grant from the Dutch Polymer Institute (DPI, PO Box 902, 5600 AX Eindhoven, the Netherlands) and represents a part of the Research Program of DPI project 813. F.M. and R.V. acknowledge additional funding from a Netherlands Organization for Scientific Research (NWO) VIDI grant (723.015.007). The research was also supported by the project CALIPSOplus under Grant Agreement 730872 from the EU Framework Program for Research and Innovation Horizon 2020. The holotomography experiments were carried out at the GINIX end station of the Coherence Beamline P10 at PETRA III, DESY, a member of the Helmholtz Association (HGF). We gratefully acknowledge Tim Salditt (University of Göttingen) for his guidance and assistance in performing the holotomography experiments. Our sincere appreciation also goes to Michael Sprung (DESY), Fabian Westermeier (DESY), and Markus Osterhoff (University of Göttingen) for their experimental support at P10, as well as Marina Eckermann (University of Göttingen) and Marianna Gambino (Utrecht University) for their assistance during sample preparation. Delft Solids Solutions are acknowledged for the mercury porosimetry measurements. We would also like to thank Nicolaas Friederichs (SABIC) for his feedback on the collected data and manuscript. Conceptualization, M.J.W. and F.M.; investigation, M.J.W. R.V. L.M.L. A.R. and S.Z.; resources, C.H.; software, R.V. L.M.L. and A.R.; formal analysis, R.V. M.J.W. L.M.L. and A.R.; writing – original draft, M.J.W. and R.V.; writing – review & editing, all authors; funding acquisition, B.M.W. and F.M.; supervision, F.M. and B.M.W. The authors declare no competing interests.

Funding Information:
This research was funded by a grant from the Dutch Polymer Institute (DPI, PO Box 902, 5600 AX Eindhoven, the Netherlands) and represents a part of the Research Program of DPI project 813. F.M. and R.V. acknowledge additional funding from a Netherlands Organization for Scientific Research ( NWO ) VIDI grant ( 723.015.007 ). The research was also supported by the project CALIPSOplus under Grant Agreement 730872 from the EU Framework Program for Research and Innovation Horizon 2020 . The holotomography experiments were carried out at the GINIX end station of the Coherence Beamline P10 at PETRA III, DESY, a member of the Helmholtz Association (HGF). We gratefully acknowledge Tim Salditt (University of Göttingen) for his guidance and assistance in performing the holotomography experiments. Our sincere appreciation also goes to Michael Sprung (DESY), Fabian Westermeier (DESY), and Markus Osterhoff (University of Göttingen) for their experimental support at P10, as well as Marina Eckermann (University of Göttingen) and Marianna Gambino (Utrecht University) for their assistance during sample preparation. Delft Solids Solutions are acknowledged for the mercury porosimetry measurements. We would also like to thank Nicolaas Friederichs (SABIC) for his feedback on the collected data and manuscript.

Publisher Copyright:
© 2021 Elsevier Inc.

Funding

This research was funded by a grant from the Dutch Polymer Institute (DPI, PO Box 902, 5600 AX Eindhoven, the Netherlands) and represents a part of the Research Program of DPI project 813. F.M. and R.V. acknowledge additional funding from a Netherlands Organization for Scientific Research (NWO) VIDI grant (723.015.007). The research was also supported by the project CALIPSOplus under Grant Agreement 730872 from the EU Framework Program for Research and Innovation Horizon 2020. The holotomography experiments were carried out at the GINIX end station of the Coherence Beamline P10 at PETRA III, DESY, a member of the Helmholtz Association (HGF). We gratefully acknowledge Tim Salditt (University of Göttingen) for his guidance and assistance in performing the holotomography experiments. Our sincere appreciation also goes to Michael Sprung (DESY), Fabian Westermeier (DESY), and Markus Osterhoff (University of Göttingen) for their experimental support at P10, as well as Marina Eckermann (University of Göttingen) and Marianna Gambino (Utrecht University) for their assistance during sample preparation. Delft Solids Solutions are acknowledged for the mercury porosimetry measurements. We would also like to thank Nicolaas Friederichs (SABIC) for his feedback on the collected data and manuscript. Conceptualization, M.J.W. and F.M.; investigation, M.J.W. R.V. L.M.L. A.R. and S.Z.; resources, C.H.; software, R.V. L.M.L. and A.R.; formal analysis, R.V. M.J.W. L.M.L. and A.R.; writing – original draft, M.J.W. and R.V.; writing – review & editing, all authors; funding acquisition, B.M.W. and F.M.; supervision, F.M. and B.M.W. The authors declare no competing interests. This research was funded by a grant from the Dutch Polymer Institute (DPI, PO Box 902, 5600 AX Eindhoven, the Netherlands) and represents a part of the Research Program of DPI project 813. F.M. and R.V. acknowledge additional funding from a Netherlands Organization for Scientific Research ( NWO ) VIDI grant ( 723.015.007 ). The research was also supported by the project CALIPSOplus under Grant Agreement 730872 from the EU Framework Program for Research and Innovation Horizon 2020 . The holotomography experiments were carried out at the GINIX end station of the Coherence Beamline P10 at PETRA III, DESY, a member of the Helmholtz Association (HGF). We gratefully acknowledge Tim Salditt (University of Göttingen) for his guidance and assistance in performing the holotomography experiments. Our sincere appreciation also goes to Michael Sprung (DESY), Fabian Westermeier (DESY), and Markus Osterhoff (University of Göttingen) for their experimental support at P10, as well as Marina Eckermann (University of Göttingen) and Marianna Gambino (Utrecht University) for their assistance during sample preparation. Delft Solids Solutions are acknowledged for the mercury porosimetry measurements. We would also like to thank Nicolaas Friederichs (SABIC) for his feedback on the collected data and manuscript.

Keywords

fragmentation
heterogeneity
metallocene
nanotomography
polymerization
polyolefins
pore network modeling
SDG9: Industry innovation and infrastructure

Access to Document

10.1016/j.checat.2021.10.008

1-s2.0-S2667109321002475-mainFinal published version, 2.92 MBLicence: Taverne

Cite this

@article{0e36fd24c0094b86b75c6a6d1a5b137f,

title = "X-ray nanotomography uncovers morphological heterogeneity in a polymerization catalyst at multiple reaction stages",

abstract = "During olefin polymerization on supported catalysts, the controlled morphological evolution of the catalyst particle is vital for ensuring optimal product properties and high catalyst activity. We employed non-destructive hard X-ray holotomography to quantitatively assess the 3D morphology of multiple silica-supported hafnocene-based catalyst particles during the early stages of gas-phase ethylene polymerization. Image processing and pore network modeling revealed clear variations in the dimensions and interconnectivity of pristine particles' macropore networks. This, together with apparent differences in the fragmentation behavior of pre-polymerized particles, suggests that the reactivity and morphological evolution of individual particles are largely dictated by their unique support and pore space architectures. By minimizing the structural heterogeneity among pristine catalyst particles, more uniform particle morphologies may be obtained. Significant polymerization activity, observed in the particles' interiors, further implies that appropriate polymerization conditions and catalyst kinetics can guarantee sufficiently high particle accessibilities and thus more homogeneous support fragmentation.",

keywords = "fragmentation, heterogeneity, metallocene, nanotomography, polymerization, polyolefins, pore network modeling, SDG9: Industry innovation and infrastructure",

author = "Werny, \{Maximilian J.\} and Roozbeh Valadian and Lohse, \{Leon M.\} and Robisch, \{Anna Lena\} and Silvia Zanoni and Coen Hendriksen and Weckhuysen, \{Bert M.\} and Florian Meirer",

note = "Funding Information: This research was funded by a grant from the Dutch Polymer Institute (DPI, PO Box 902, 5600 AX Eindhoven, the Netherlands) and represents a part of the Research Program of DPI project 813. F.M. and R.V. acknowledge additional funding from a Netherlands Organization for Scientific Research (NWO) VIDI grant (723.015.007). The research was also supported by the project CALIPSOplus under Grant Agreement 730872 from the EU Framework Program for Research and Innovation Horizon 2020. The holotomography experiments were carried out at the GINIX end station of the Coherence Beamline P10 at PETRA III, DESY, a member of the Helmholtz Association (HGF). We gratefully acknowledge Tim Salditt (University of G{\"o}ttingen) for his guidance and assistance in performing the holotomography experiments. Our sincere appreciation also goes to Michael Sprung (DESY), Fabian Westermeier (DESY), and Markus Osterhoff (University of G{\"o}ttingen) for their experimental support at P10, as well as Marina Eckermann (University of G{\"o}ttingen) and Marianna Gambino (Utrecht University) for their assistance during sample preparation. Delft Solids Solutions are acknowledged for the mercury porosimetry measurements. We would also like to thank Nicolaas Friederichs (SABIC) for his feedback on the collected data and manuscript. Conceptualization, M.J.W. and F.M.; investigation, M.J.W. R.V. L.M.L. A.R. and S.Z.; resources, C.H.; software, R.V. L.M.L. and A.R.; formal analysis, R.V. M.J.W. L.M.L. and A.R.; writing – original draft, M.J.W. and R.V.; writing – review \& editing, all authors; funding acquisition, B.M.W. and F.M.; supervision, F.M. and B.M.W. The authors declare no competing interests. Funding Information: This research was funded by a grant from the Dutch Polymer Institute (DPI, PO Box 902, 5600 AX Eindhoven, the Netherlands) and represents a part of the Research Program of DPI project 813. F.M. and R.V. acknowledge additional funding from a Netherlands Organization for Scientific Research ( NWO ) VIDI grant ( 723.015.007 ). The research was also supported by the project CALIPSOplus under Grant Agreement 730872 from the EU Framework Program for Research and Innovation Horizon 2020 . The holotomography experiments were carried out at the GINIX end station of the Coherence Beamline P10 at PETRA III, DESY, a member of the Helmholtz Association (HGF). We gratefully acknowledge Tim Salditt (University of G{\"o}ttingen) for his guidance and assistance in performing the holotomography experiments. Our sincere appreciation also goes to Michael Sprung (DESY), Fabian Westermeier (DESY), and Markus Osterhoff (University of G{\"o}ttingen) for their experimental support at P10, as well as Marina Eckermann (University of G{\"o}ttingen) and Marianna Gambino (Utrecht University) for their assistance during sample preparation. Delft Solids Solutions are acknowledged for the mercury porosimetry measurements. We would also like to thank Nicolaas Friederichs (SABIC) for his feedback on the collected data and manuscript. Publisher Copyright: {\textcopyright} 2021 Elsevier Inc.",

year = "2021",

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doi = "10.1016/j.checat.2021.10.008",

language = "English",

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T1 - X-ray nanotomography uncovers morphological heterogeneity in a polymerization catalyst at multiple reaction stages

AU - Werny, Maximilian J.

AU - Valadian, Roozbeh

AU - Lohse, Leon M.

AU - Robisch, Anna Lena

AU - Zanoni, Silvia

AU - Hendriksen, Coen

AU - Weckhuysen, Bert M.

AU - Meirer, Florian

N1 - Funding Information: This research was funded by a grant from the Dutch Polymer Institute (DPI, PO Box 902, 5600 AX Eindhoven, the Netherlands) and represents a part of the Research Program of DPI project 813. F.M. and R.V. acknowledge additional funding from a Netherlands Organization for Scientific Research (NWO) VIDI grant (723.015.007). The research was also supported by the project CALIPSOplus under Grant Agreement 730872 from the EU Framework Program for Research and Innovation Horizon 2020. The holotomography experiments were carried out at the GINIX end station of the Coherence Beamline P10 at PETRA III, DESY, a member of the Helmholtz Association (HGF). We gratefully acknowledge Tim Salditt (University of Göttingen) for his guidance and assistance in performing the holotomography experiments. Our sincere appreciation also goes to Michael Sprung (DESY), Fabian Westermeier (DESY), and Markus Osterhoff (University of Göttingen) for their experimental support at P10, as well as Marina Eckermann (University of Göttingen) and Marianna Gambino (Utrecht University) for their assistance during sample preparation. Delft Solids Solutions are acknowledged for the mercury porosimetry measurements. We would also like to thank Nicolaas Friederichs (SABIC) for his feedback on the collected data and manuscript. Conceptualization, M.J.W. and F.M.; investigation, M.J.W. R.V. L.M.L. A.R. and S.Z.; resources, C.H.; software, R.V. L.M.L. and A.R.; formal analysis, R.V. M.J.W. L.M.L. and A.R.; writing – original draft, M.J.W. and R.V.; writing – review & editing, all authors; funding acquisition, B.M.W. and F.M.; supervision, F.M. and B.M.W. The authors declare no competing interests. Funding Information: This research was funded by a grant from the Dutch Polymer Institute (DPI, PO Box 902, 5600 AX Eindhoven, the Netherlands) and represents a part of the Research Program of DPI project 813. F.M. and R.V. acknowledge additional funding from a Netherlands Organization for Scientific Research ( NWO ) VIDI grant ( 723.015.007 ). The research was also supported by the project CALIPSOplus under Grant Agreement 730872 from the EU Framework Program for Research and Innovation Horizon 2020 . The holotomography experiments were carried out at the GINIX end station of the Coherence Beamline P10 at PETRA III, DESY, a member of the Helmholtz Association (HGF). We gratefully acknowledge Tim Salditt (University of Göttingen) for his guidance and assistance in performing the holotomography experiments. Our sincere appreciation also goes to Michael Sprung (DESY), Fabian Westermeier (DESY), and Markus Osterhoff (University of Göttingen) for their experimental support at P10, as well as Marina Eckermann (University of Göttingen) and Marianna Gambino (Utrecht University) for their assistance during sample preparation. Delft Solids Solutions are acknowledged for the mercury porosimetry measurements. We would also like to thank Nicolaas Friederichs (SABIC) for his feedback on the collected data and manuscript. Publisher Copyright: © 2021 Elsevier Inc.

PY - 2021/12/16

Y1 - 2021/12/16

N2 - During olefin polymerization on supported catalysts, the controlled morphological evolution of the catalyst particle is vital for ensuring optimal product properties and high catalyst activity. We employed non-destructive hard X-ray holotomography to quantitatively assess the 3D morphology of multiple silica-supported hafnocene-based catalyst particles during the early stages of gas-phase ethylene polymerization. Image processing and pore network modeling revealed clear variations in the dimensions and interconnectivity of pristine particles' macropore networks. This, together with apparent differences in the fragmentation behavior of pre-polymerized particles, suggests that the reactivity and morphological evolution of individual particles are largely dictated by their unique support and pore space architectures. By minimizing the structural heterogeneity among pristine catalyst particles, more uniform particle morphologies may be obtained. Significant polymerization activity, observed in the particles' interiors, further implies that appropriate polymerization conditions and catalyst kinetics can guarantee sufficiently high particle accessibilities and thus more homogeneous support fragmentation.

AB - During olefin polymerization on supported catalysts, the controlled morphological evolution of the catalyst particle is vital for ensuring optimal product properties and high catalyst activity. We employed non-destructive hard X-ray holotomography to quantitatively assess the 3D morphology of multiple silica-supported hafnocene-based catalyst particles during the early stages of gas-phase ethylene polymerization. Image processing and pore network modeling revealed clear variations in the dimensions and interconnectivity of pristine particles' macropore networks. This, together with apparent differences in the fragmentation behavior of pre-polymerized particles, suggests that the reactivity and morphological evolution of individual particles are largely dictated by their unique support and pore space architectures. By minimizing the structural heterogeneity among pristine catalyst particles, more uniform particle morphologies may be obtained. Significant polymerization activity, observed in the particles' interiors, further implies that appropriate polymerization conditions and catalyst kinetics can guarantee sufficiently high particle accessibilities and thus more homogeneous support fragmentation.

KW - fragmentation

KW - heterogeneity

KW - metallocene

KW - nanotomography

KW - polymerization

KW - polyolefins

KW - pore network modeling

KW - SDG9: Industry innovation and infrastructure

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DO - 10.1016/j.checat.2021.10.008

M3 - Article

AN - SCOPUS:85129619324

SN - 2667-1107

VL - 1

SP - 1413

EP - 1426

JO - Chem Catalysis

JF - Chem Catalysis

IS - 7

ER -

X-ray nanotomography uncovers morphological heterogeneity in a polymerization catalyst at multiple reaction stages

Abstract

Bibliographical note

Funding

Keywords

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