On the thermal stabilization of carbon-supported SiO2 catalysts by phosphorus: evaluation in the oxidative dehydrogenation of ethylbenzene to styrene and a comparison with relevant catalysts

Valeriya Zarubina, Hesamoddin Talebi, Harrie Jansma, Kinga Góra-Marek, Christian Nederlof, Freek Kapteijn, Michiel Makkee, Ignacio Melián-Cabrera*

*Corresponding author for this work

Research output: Contribution to journalArticle

Abstract

A strategy to enhance the thermal stability of C/SiO2 hybrids for the O2-based oxidative dehydrogenation of ethylbenzene to styrene (ST) by P addition is proposed. The preparation consists of the polymerization of furfuryl alcohol (FA) on a mesoporous precipitated SiO2. The polymerization is catalyzed by oxalic acid (OA) at 160 °C (FA:OA = 250). Phosphorous was added as H3PO4 after the polymerization and before the pyrolysis that was carried out at 700 °C and will extend the overall activation procedure. Estimation of the apparent activation energies reveals that P enhances the thermal stability under air oxidation, which is a good indication for the ODH tests. Catalytic tests show that the P/C/SiO2 hybrids are readily active, selective and indeed stable in the applied reactions conditions for 60 h time on stream. Coke build-up during the reaction attributed to the P-based acidity is substantial, leading to a reduction of the surface area and pore volume. The comparison with a conventional MWCNT evidences that the P/C/SiO2 hybrids are more active and selective at high temperatures (450–475 °C) while the difference becomes negligible at lower temperature. However, the comparison with reference P/SiO2 counterparts shows a very similar yield than the hybrids but more selective to ST. The benefit of the P/C/SiO2 hybrid is the lack of stabilization period, which is observed for the P/SiO2 to create an active coke overlayer. For long term operation, P/SiO2 appears to be a better choice in terms of selectivity, which is crucial for commercialization.
Original languageEnglish
Pages (from-to)173-181
Number of pages9
JournalApplied Catalysis A: General
Volume514
Early online date21 Jan 2016
DOIs
Publication statusPublished - 25 Mar 2016

Fingerprint

Styrene
Ethylbenzene
Dehydrogenation
Catalyst supports
Phosphorus
Oxalic Acid
Oxalic acid
Carbon
Stabilization
Polymerization
Coke
Catalysts
Alcohols
Thermodynamic stability
Acidity
Pyrolysis
Activation energy
Chemical activation
Oxidation
Temperature

Bibliographical note

© 2015, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/

Keywords

  • ethylbenzene
  • styrene
  • oxidative dehydrogenation
  • carbon-based catalysts
  • phosphorus
  • thermal stability

Cite this

Zarubina, Valeriya ; Talebi, Hesamoddin ; Jansma, Harrie ; Góra-Marek, Kinga ; Nederlof, Christian ; Kapteijn, Freek ; Makkee, Michiel ; Melián-Cabrera, Ignacio. / On the thermal stabilization of carbon-supported SiO2 catalysts by phosphorus : evaluation in the oxidative dehydrogenation of ethylbenzene to styrene and a comparison with relevant catalysts. In: Applied Catalysis A: General. 2016 ; Vol. 514. pp. 173-181.
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On the thermal stabilization of carbon-supported SiO2 catalysts by phosphorus : evaluation in the oxidative dehydrogenation of ethylbenzene to styrene and a comparison with relevant catalysts. / Zarubina, Valeriya; Talebi, Hesamoddin; Jansma, Harrie; Góra-Marek, Kinga; Nederlof, Christian; Kapteijn, Freek; Makkee, Michiel; Melián-Cabrera, Ignacio.

In: Applied Catalysis A: General, Vol. 514, 25.03.2016, p. 173-181.

Research output: Contribution to journalArticle

TY - JOUR

T1 - On the thermal stabilization of carbon-supported SiO2 catalysts by phosphorus

T2 - evaluation in the oxidative dehydrogenation of ethylbenzene to styrene and a comparison with relevant catalysts

AU - Zarubina, Valeriya

AU - Talebi, Hesamoddin

AU - Jansma, Harrie

AU - Góra-Marek, Kinga

AU - Nederlof, Christian

AU - Kapteijn, Freek

AU - Makkee, Michiel

AU - Melián-Cabrera, Ignacio

N1 - © 2015, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/

PY - 2016/3/25

Y1 - 2016/3/25

N2 - A strategy to enhance the thermal stability of C/SiO2 hybrids for the O2-based oxidative dehydrogenation of ethylbenzene to styrene (ST) by P addition is proposed. The preparation consists of the polymerization of furfuryl alcohol (FA) on a mesoporous precipitated SiO2. The polymerization is catalyzed by oxalic acid (OA) at 160 °C (FA:OA = 250). Phosphorous was added as H3PO4 after the polymerization and before the pyrolysis that was carried out at 700 °C and will extend the overall activation procedure. Estimation of the apparent activation energies reveals that P enhances the thermal stability under air oxidation, which is a good indication for the ODH tests. Catalytic tests show that the P/C/SiO2 hybrids are readily active, selective and indeed stable in the applied reactions conditions for 60 h time on stream. Coke build-up during the reaction attributed to the P-based acidity is substantial, leading to a reduction of the surface area and pore volume. The comparison with a conventional MWCNT evidences that the P/C/SiO2 hybrids are more active and selective at high temperatures (450–475 °C) while the difference becomes negligible at lower temperature. However, the comparison with reference P/SiO2 counterparts shows a very similar yield than the hybrids but more selective to ST. The benefit of the P/C/SiO2 hybrid is the lack of stabilization period, which is observed for the P/SiO2 to create an active coke overlayer. For long term operation, P/SiO2 appears to be a better choice in terms of selectivity, which is crucial for commercialization.

AB - A strategy to enhance the thermal stability of C/SiO2 hybrids for the O2-based oxidative dehydrogenation of ethylbenzene to styrene (ST) by P addition is proposed. The preparation consists of the polymerization of furfuryl alcohol (FA) on a mesoporous precipitated SiO2. The polymerization is catalyzed by oxalic acid (OA) at 160 °C (FA:OA = 250). Phosphorous was added as H3PO4 after the polymerization and before the pyrolysis that was carried out at 700 °C and will extend the overall activation procedure. Estimation of the apparent activation energies reveals that P enhances the thermal stability under air oxidation, which is a good indication for the ODH tests. Catalytic tests show that the P/C/SiO2 hybrids are readily active, selective and indeed stable in the applied reactions conditions for 60 h time on stream. Coke build-up during the reaction attributed to the P-based acidity is substantial, leading to a reduction of the surface area and pore volume. The comparison with a conventional MWCNT evidences that the P/C/SiO2 hybrids are more active and selective at high temperatures (450–475 °C) while the difference becomes negligible at lower temperature. However, the comparison with reference P/SiO2 counterparts shows a very similar yield than the hybrids but more selective to ST. The benefit of the P/C/SiO2 hybrid is the lack of stabilization period, which is observed for the P/SiO2 to create an active coke overlayer. For long term operation, P/SiO2 appears to be a better choice in terms of selectivity, which is crucial for commercialization.

KW - ethylbenzene

KW - styrene

KW - oxidative dehydrogenation

KW - carbon-based catalysts

KW - phosphorus

KW - thermal stability

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DO - 10.1016/j.apcata.2016.01.024

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