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Silicon redistribution, acid site loss and the formation of a core-shell texture upon steaming SAPO-34 and their impact on catalytic performance in the methanol-to-olefins (MTO) reaction

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Silicon redistribution, acid site loss and the formation of a core-shell texture upon steaming SAPO-34 and their impact on catalytic performance in the methanol-to-olefins (MTO) reaction. / Minova, Ivalina B.; Barrow, Nathan S.; Sauerwein, Andrea C.; Naden, Aaron B.; Cordes, David B.; Slawin, Alexandra M.Z.; Schuyten, Stephen J.; Wright, Paul A.

In: Journal of Catalysis, Vol. 395, 03.2021, p. 425-444.

Research output: Contribution to journalArticlepeer-review

Harvard

Minova, IB, Barrow, NS, Sauerwein, AC, Naden, AB, Cordes, DB, Slawin, AMZ, Schuyten, SJ & Wright, PA 2021, 'Silicon redistribution, acid site loss and the formation of a core-shell texture upon steaming SAPO-34 and their impact on catalytic performance in the methanol-to-olefins (MTO) reaction', Journal of Catalysis, vol. 395, pp. 425-444. https://doi.org/10.1016/j.jcat.2021.01.012

APA

Minova, I. B., Barrow, N. S., Sauerwein, A. C., Naden, A. B., Cordes, D. B., Slawin, A. M. Z., Schuyten, S. J., & Wright, P. A. (2021). Silicon redistribution, acid site loss and the formation of a core-shell texture upon steaming SAPO-34 and their impact on catalytic performance in the methanol-to-olefins (MTO) reaction. Journal of Catalysis, 395, 425-444. https://doi.org/10.1016/j.jcat.2021.01.012

Vancouver

Minova IB, Barrow NS, Sauerwein AC, Naden AB, Cordes DB, Slawin AMZ et al. Silicon redistribution, acid site loss and the formation of a core-shell texture upon steaming SAPO-34 and their impact on catalytic performance in the methanol-to-olefins (MTO) reaction. Journal of Catalysis. 2021 Mar;395:425-444. https://doi.org/10.1016/j.jcat.2021.01.012

Author

Minova, Ivalina B. ; Barrow, Nathan S. ; Sauerwein, Andrea C. ; Naden, Aaron B. ; Cordes, David B. ; Slawin, Alexandra M.Z. ; Schuyten, Stephen J. ; Wright, Paul A. / Silicon redistribution, acid site loss and the formation of a core-shell texture upon steaming SAPO-34 and their impact on catalytic performance in the methanol-to-olefins (MTO) reaction. In: Journal of Catalysis. 2021 ; Vol. 395. pp. 425-444.

Bibtex - Download

@article{5d5d6c4362ba4d2c99b60d6c3b517921,
title = "Silicon redistribution, acid site loss and the formation of a core-shell texture upon steaming SAPO-34 and their impact on catalytic performance in the methanol-to-olefins (MTO) reaction",
abstract = "SAPO-34 is a commercially-implemented silicoaluminophosphate catalyst for selective high yield production of ethene and propene from methanol, but high temperature regeneration in the presence of steam leads to its deactivation. A comprehensive investigation of the effect of prolonged hydrothermal treatment on the structure and properties of SAPO 34 explains the changes in its catalytic methanol-to-olefins (MTO) performance. Microcrystalline powdered SAPO-34 (ca. 3 µm crystals, Al17.1P15.6Si3.3O72) and two batches of larger single crystals of SAPO-34 of different Si concentration (20-100 µm; Al17.3P14.7Si4.0O72 and Al17.7P12.3Si5.9O72 ) were steamed (pH2O = 0.95 atm) at 873–1023 K for up to 240 h. The acidity (NH3-TPD), crystallinity (PXRD), framework cation environment (solid-state 27Al, 29Si and 31P MAS NMR) and porosity were followed for all materials; larger crystals were amenable to single crystal X-ray diffraction, FIB-SEM and synchrotron IR microspectroscopy, including operando study during methanol and dimethyl ether conversions. Some level of steaming improved the lifetime of all SAPO-34 materials in MTO catalysis without affecting their olefin selectivity, although more severe conditions led to the formation of core-shell structures, microporosity loss and eventually at 1023 K, recrystallization to a dense phase. All these irreversible changes occurred faster in crystals with higher Si contents. The initial increase in catalytic lifetime results from an activated reduction in acid site density (Eact = 146(18) kJ mol⁻1), a result of redistribution of Si within the SAPO framework without porosity loss. Operando IR with online product analysis during methanol conversion suggests similar reaction pathways in calcined and steamed crystals, but with greatly reduced methoxy group densities in the latter. The gradual development of optically dark crystal cores upon progressive steaming was shown by FIB-SEM to be due to the formation of regions with meso- and macropores, and these were shown by IR mapping to possess low hydroxyl densities.",
keywords = "Steamed SAPO 34, Methanol-to-olefins, IR spectroscopy and microscopy, FIB SEM",
author = "Minova, {Ivalina B.} and Barrow, {Nathan S.} and Sauerwein, {Andrea C.} and Naden, {Aaron B.} and Cordes, {David B.} and Slawin, {Alexandra M.Z.} and Schuyten, {Stephen J.} and Wright, {Paul A.}",
note = "IBM has received funding from the Engineering and Physical Sciences Research Council (EPSRC, Centre for Doctoral Training in Critical Resource Catalysis, EP/I017008/1) and Scotland's Chemistry departments (ScotCHEM). IBM also received a scholarship from the SCI and Santander. Johnson Matthey is thanked for in-kind contributions and hosting IBM in their R&D labs. ABN gratefully acknowledges support from the EPSRC (grants EP/L017008/1 and EP/R023751/1). The research data supporting this publication can be accessed at: https://doi.org/10.17630/09ddc03e-f121-4e79-9b55-674f64d9c8c4 [62].",
year = "2021",
month = mar,
doi = "10.1016/j.jcat.2021.01.012",
language = "English",
volume = "395",
pages = "425--444",
journal = "Journal of Catalysis",
issn = "0021-9517",
publisher = "Academic Press Inc.",

}

RIS (suitable for import to EndNote) - Download

TY - JOUR

T1 - Silicon redistribution, acid site loss and the formation of a core-shell texture upon steaming SAPO-34 and their impact on catalytic performance in the methanol-to-olefins (MTO) reaction

AU - Minova, Ivalina B.

AU - Barrow, Nathan S.

AU - Sauerwein, Andrea C.

AU - Naden, Aaron B.

AU - Cordes, David B.

AU - Slawin, Alexandra M.Z.

AU - Schuyten, Stephen J.

AU - Wright, Paul A.

N1 - IBM has received funding from the Engineering and Physical Sciences Research Council (EPSRC, Centre for Doctoral Training in Critical Resource Catalysis, EP/I017008/1) and Scotland's Chemistry departments (ScotCHEM). IBM also received a scholarship from the SCI and Santander. Johnson Matthey is thanked for in-kind contributions and hosting IBM in their R&D labs. ABN gratefully acknowledges support from the EPSRC (grants EP/L017008/1 and EP/R023751/1). The research data supporting this publication can be accessed at: https://doi.org/10.17630/09ddc03e-f121-4e79-9b55-674f64d9c8c4 [62].

PY - 2021/3

Y1 - 2021/3

N2 - SAPO-34 is a commercially-implemented silicoaluminophosphate catalyst for selective high yield production of ethene and propene from methanol, but high temperature regeneration in the presence of steam leads to its deactivation. A comprehensive investigation of the effect of prolonged hydrothermal treatment on the structure and properties of SAPO 34 explains the changes in its catalytic methanol-to-olefins (MTO) performance. Microcrystalline powdered SAPO-34 (ca. 3 µm crystals, Al17.1P15.6Si3.3O72) and two batches of larger single crystals of SAPO-34 of different Si concentration (20-100 µm; Al17.3P14.7Si4.0O72 and Al17.7P12.3Si5.9O72 ) were steamed (pH2O = 0.95 atm) at 873–1023 K for up to 240 h. The acidity (NH3-TPD), crystallinity (PXRD), framework cation environment (solid-state 27Al, 29Si and 31P MAS NMR) and porosity were followed for all materials; larger crystals were amenable to single crystal X-ray diffraction, FIB-SEM and synchrotron IR microspectroscopy, including operando study during methanol and dimethyl ether conversions. Some level of steaming improved the lifetime of all SAPO-34 materials in MTO catalysis without affecting their olefin selectivity, although more severe conditions led to the formation of core-shell structures, microporosity loss and eventually at 1023 K, recrystallization to a dense phase. All these irreversible changes occurred faster in crystals with higher Si contents. The initial increase in catalytic lifetime results from an activated reduction in acid site density (Eact = 146(18) kJ mol⁻1), a result of redistribution of Si within the SAPO framework without porosity loss. Operando IR with online product analysis during methanol conversion suggests similar reaction pathways in calcined and steamed crystals, but with greatly reduced methoxy group densities in the latter. The gradual development of optically dark crystal cores upon progressive steaming was shown by FIB-SEM to be due to the formation of regions with meso- and macropores, and these were shown by IR mapping to possess low hydroxyl densities.

AB - SAPO-34 is a commercially-implemented silicoaluminophosphate catalyst for selective high yield production of ethene and propene from methanol, but high temperature regeneration in the presence of steam leads to its deactivation. A comprehensive investigation of the effect of prolonged hydrothermal treatment on the structure and properties of SAPO 34 explains the changes in its catalytic methanol-to-olefins (MTO) performance. Microcrystalline powdered SAPO-34 (ca. 3 µm crystals, Al17.1P15.6Si3.3O72) and two batches of larger single crystals of SAPO-34 of different Si concentration (20-100 µm; Al17.3P14.7Si4.0O72 and Al17.7P12.3Si5.9O72 ) were steamed (pH2O = 0.95 atm) at 873–1023 K for up to 240 h. The acidity (NH3-TPD), crystallinity (PXRD), framework cation environment (solid-state 27Al, 29Si and 31P MAS NMR) and porosity were followed for all materials; larger crystals were amenable to single crystal X-ray diffraction, FIB-SEM and synchrotron IR microspectroscopy, including operando study during methanol and dimethyl ether conversions. Some level of steaming improved the lifetime of all SAPO-34 materials in MTO catalysis without affecting their olefin selectivity, although more severe conditions led to the formation of core-shell structures, microporosity loss and eventually at 1023 K, recrystallization to a dense phase. All these irreversible changes occurred faster in crystals with higher Si contents. The initial increase in catalytic lifetime results from an activated reduction in acid site density (Eact = 146(18) kJ mol⁻1), a result of redistribution of Si within the SAPO framework without porosity loss. Operando IR with online product analysis during methanol conversion suggests similar reaction pathways in calcined and steamed crystals, but with greatly reduced methoxy group densities in the latter. The gradual development of optically dark crystal cores upon progressive steaming was shown by FIB-SEM to be due to the formation of regions with meso- and macropores, and these were shown by IR mapping to possess low hydroxyl densities.

KW - Steamed SAPO 34

KW - Methanol-to-olefins

KW - IR spectroscopy and microscopy

KW - FIB SEM

U2 - 10.1016/j.jcat.2021.01.012

DO - 10.1016/j.jcat.2021.01.012

M3 - Article

AN - SCOPUS:85101206598

VL - 395

SP - 425

EP - 444

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

ER -

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