Effect of Mesoporosity, Acidity and Crystal Size of Zeolite ZSM-5 on Catalytic Performance during the Ex-situ Catalytic Fast Pyrolysis of Biomass

Ana M. Hernández-Giménez; Eleni Heracleous; Eleni Pachatouridou; Andrej Horvat; Héctor Hernando; David P. Serrano; Angelos A. Lappas; Pieter C.A. Bruijnincx; Bert M. Weckhuysen

doi:10.1002/cctc.202001778

Effect of Mesoporosity, Acidity and Crystal Size of Zeolite ZSM-5 on Catalytic Performance during the Ex-situ Catalytic Fast Pyrolysis of Biomass

Ana M. Hernández-Giménez, Eleni Heracleous, Eleni Pachatouridou, Andrej Horvat, Héctor Hernando, David P. Serrano, Angelos A. Lappas, Pieter C.A. Bruijnincx, Bert M. Weckhuysen^*

^*Corresponding author for this work

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

Abstract

The catalytic performance of a set of technical, zeolite ZSM-5 extruded materials have been studied in a bench scale unit for the ex-situ Catalytic Fast Pyrolysis (CFP) of lignocellulosic biomass. The set of catalysts include micro- and mesoporous materials, with and without ZrO₂-promotion, with different Si/Al ratios and with micro- and nanosized zeolite crystals. Mesoporosity, acidity and crystal size play a key role on the overall catalytic performances in terms of activity and selectivity (i. e., in their ability to obtain the highest bio-oil fraction with the lowest oxygen content), and also importantly, stability. Detailed post-mortem bulk and micro-spectroscopic studies of the solid catalysts complement the catalytic testing. The obtained results point towards coke deposits as the main cause for catalyst deactivation. Details of the nature, formation and evolution of these coke deposits revealed essential insights, which serve to evaluate the design of catalysts for the ex-situ CFP of biomass. In particular the mesoporous catalysts are overall better preserved with increasing time-on-stream and deactivate later than their microporous counterparts, which suffer from pore blockage. Likewise, it was seen that ZrO₂-promotion contributed positively in the prevention against deactivation by hard coke spreading, thanks to its enhanced Lewis acidity. The zeolite's crystal size is another important characteristic to combine the different components within catalyst bodies, ensuring the proper interaction between zeolite, promoter and binder. This is illustrated by the nanocrystalline ZrO₂/n-ZSM-5-ATP material, which shows the best catalytic performance.

Original language	English
Pages (from-to)	1207-1219
Number of pages	13
Journal	ChemCatChem
Volume	13
Issue number	4
DOIs	https://doi.org/10.1002/cctc.202001778
Publication status	Published - 18 Feb 2021

Bibliographical note

Funding Information:
The work was conducted with support from the EU under the frame of the FP7 funded ?CAScade deoxygenation process using tailored nanoCATalysts for the production of BiofuELs from lignocellullosic biomassCASCATBEL? project (Grant agreement No. 604307). Dr. A. Horvat, Dr. T. Fakin and M. Zmazek (all from Silkem d.o.o) are thanked for providing the catalyst materials.

Funding Information:
The work was conducted with support from the EU under the frame of the FP7 funded “CAScade deoxygenation process using tailored nanoCATalysts for the production of BiofuELs from lignocellullosic biomassCASCATBEL” project (Grant agreement No. 604307). Dr. A. Horvat, Dr. T. Fakin and M. Zmazek (all from Silkem d.o.o) are thanked for providing the catalyst materials.

Publisher Copyright:
© 2020 The Authors. ChemCatChem published by Wiley-VCH GmbH

Funding

The work was conducted with support from the EU under the frame of the FP7 funded ?CAScade deoxygenation process using tailored nanoCATalysts for the production of BiofuELs from lignocellullosic biomassCASCATBEL? project (Grant agreement No. 604307). Dr. A. Horvat, Dr. T. Fakin and M. Zmazek (all from Silkem d.o.o) are thanked for providing the catalyst materials. The work was conducted with support from the EU under the frame of the FP7 funded “CAScade deoxygenation process using tailored nanoCATalysts for the production of BiofuELs from lignocellullosic biomassCASCATBEL” project (Grant agreement No. 604307). Dr. A. Horvat, Dr. T. Fakin and M. Zmazek (all from Silkem d.o.o) are thanked for providing the catalyst materials.

Keywords

Biomass Catalytic Fast Pyrolysis
Coke
Crystal Size
Mesoporosity
Micro-spectroscopy

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Hernández-Giménez, A. M., Heracleous, E., Pachatouridou, E., Horvat, A., Hernando, H., Serrano, D. P., Lappas, A. A., Bruijnincx, P. C. A., & Weckhuysen, B. M. (2021). Effect of Mesoporosity, Acidity and Crystal Size of Zeolite ZSM-5 on Catalytic Performance during the Ex-situ Catalytic Fast Pyrolysis of Biomass. ChemCatChem, 13(4), 1207-1219. https://doi.org/10.1002/cctc.202001778

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abstract = "The catalytic performance of a set of technical, zeolite ZSM-5 extruded materials have been studied in a bench scale unit for the ex-situ Catalytic Fast Pyrolysis (CFP) of lignocellulosic biomass. The set of catalysts include micro- and mesoporous materials, with and without ZrO2-promotion, with different Si/Al ratios and with micro- and nanosized zeolite crystals. Mesoporosity, acidity and crystal size play a key role on the overall catalytic performances in terms of activity and selectivity (i. e., in their ability to obtain the highest bio-oil fraction with the lowest oxygen content), and also importantly, stability. Detailed post-mortem bulk and micro-spectroscopic studies of the solid catalysts complement the catalytic testing. The obtained results point towards coke deposits as the main cause for catalyst deactivation. Details of the nature, formation and evolution of these coke deposits revealed essential insights, which serve to evaluate the design of catalysts for the ex-situ CFP of biomass. In particular the mesoporous catalysts are overall better preserved with increasing time-on-stream and deactivate later than their microporous counterparts, which suffer from pore blockage. Likewise, it was seen that ZrO2-promotion contributed positively in the prevention against deactivation by hard coke spreading, thanks to its enhanced Lewis acidity. The zeolite's crystal size is another important characteristic to combine the different components within catalyst bodies, ensuring the proper interaction between zeolite, promoter and binder. This is illustrated by the nanocrystalline ZrO2/n-ZSM-5-ATP material, which shows the best catalytic performance.",

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author = "Hern{\'a}ndez-Gim{\'e}nez, {Ana M.} and Eleni Heracleous and Eleni Pachatouridou and Andrej Horvat and H{\'e}ctor Hernando and Serrano, {David P.} and Lappas, {Angelos A.} and Bruijnincx, {Pieter C.A.} and Weckhuysen, {Bert M.}",

note = "Funding Information: The work was conducted with support from the EU under the frame of the FP7 funded ?CAScade deoxygenation process using tailored nanoCATalysts for the production of BiofuELs from lignocellullosic biomassCASCATBEL? project (Grant agreement No. 604307). Dr. A. Horvat, Dr. T. Fakin and M. Zmazek (all from Silkem d.o.o) are thanked for providing the catalyst materials. Funding Information: The work was conducted with support from the EU under the frame of the FP7 funded “CAScade deoxygenation process using tailored nanoCATalysts for the production of BiofuELs from lignocellullosic biomassCASCATBEL” project (Grant agreement No. 604307). Dr. A. Horvat, Dr. T. Fakin and M. Zmazek (all from Silkem d.o.o) are thanked for providing the catalyst materials. Publisher Copyright: {\textcopyright} 2020 The Authors. ChemCatChem published by Wiley-VCH GmbH",

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Hernández-Giménez, AM, Heracleous, E, Pachatouridou, E, Horvat, A, Hernando, H, Serrano, DP, Lappas, AA, Bruijnincx, PCA & Weckhuysen, BM 2021, 'Effect of Mesoporosity, Acidity and Crystal Size of Zeolite ZSM-5 on Catalytic Performance during the Ex-situ Catalytic Fast Pyrolysis of Biomass', ChemCatChem, vol. 13, no. 4, pp. 1207-1219. https://doi.org/10.1002/cctc.202001778

TY - JOUR

T1 - Effect of Mesoporosity, Acidity and Crystal Size of Zeolite ZSM-5 on Catalytic Performance during the Ex-situ Catalytic Fast Pyrolysis of Biomass

AU - Hernández-Giménez, Ana M.

AU - Heracleous, Eleni

AU - Pachatouridou, Eleni

AU - Horvat, Andrej

AU - Hernando, Héctor

AU - Serrano, David P.

AU - Lappas, Angelos A.

AU - Bruijnincx, Pieter C.A.

AU - Weckhuysen, Bert M.

N1 - Funding Information: The work was conducted with support from the EU under the frame of the FP7 funded ?CAScade deoxygenation process using tailored nanoCATalysts for the production of BiofuELs from lignocellullosic biomassCASCATBEL? project (Grant agreement No. 604307). Dr. A. Horvat, Dr. T. Fakin and M. Zmazek (all from Silkem d.o.o) are thanked for providing the catalyst materials. Funding Information: The work was conducted with support from the EU under the frame of the FP7 funded “CAScade deoxygenation process using tailored nanoCATalysts for the production of BiofuELs from lignocellullosic biomassCASCATBEL” project (Grant agreement No. 604307). Dr. A. Horvat, Dr. T. Fakin and M. Zmazek (all from Silkem d.o.o) are thanked for providing the catalyst materials. Publisher Copyright: © 2020 The Authors. ChemCatChem published by Wiley-VCH GmbH

PY - 2021/2/18

Y1 - 2021/2/18

N2 - The catalytic performance of a set of technical, zeolite ZSM-5 extruded materials have been studied in a bench scale unit for the ex-situ Catalytic Fast Pyrolysis (CFP) of lignocellulosic biomass. The set of catalysts include micro- and mesoporous materials, with and without ZrO2-promotion, with different Si/Al ratios and with micro- and nanosized zeolite crystals. Mesoporosity, acidity and crystal size play a key role on the overall catalytic performances in terms of activity and selectivity (i. e., in their ability to obtain the highest bio-oil fraction with the lowest oxygen content), and also importantly, stability. Detailed post-mortem bulk and micro-spectroscopic studies of the solid catalysts complement the catalytic testing. The obtained results point towards coke deposits as the main cause for catalyst deactivation. Details of the nature, formation and evolution of these coke deposits revealed essential insights, which serve to evaluate the design of catalysts for the ex-situ CFP of biomass. In particular the mesoporous catalysts are overall better preserved with increasing time-on-stream and deactivate later than their microporous counterparts, which suffer from pore blockage. Likewise, it was seen that ZrO2-promotion contributed positively in the prevention against deactivation by hard coke spreading, thanks to its enhanced Lewis acidity. The zeolite's crystal size is another important characteristic to combine the different components within catalyst bodies, ensuring the proper interaction between zeolite, promoter and binder. This is illustrated by the nanocrystalline ZrO2/n-ZSM-5-ATP material, which shows the best catalytic performance.

AB - The catalytic performance of a set of technical, zeolite ZSM-5 extruded materials have been studied in a bench scale unit for the ex-situ Catalytic Fast Pyrolysis (CFP) of lignocellulosic biomass. The set of catalysts include micro- and mesoporous materials, with and without ZrO2-promotion, with different Si/Al ratios and with micro- and nanosized zeolite crystals. Mesoporosity, acidity and crystal size play a key role on the overall catalytic performances in terms of activity and selectivity (i. e., in their ability to obtain the highest bio-oil fraction with the lowest oxygen content), and also importantly, stability. Detailed post-mortem bulk and micro-spectroscopic studies of the solid catalysts complement the catalytic testing. The obtained results point towards coke deposits as the main cause for catalyst deactivation. Details of the nature, formation and evolution of these coke deposits revealed essential insights, which serve to evaluate the design of catalysts for the ex-situ CFP of biomass. In particular the mesoporous catalysts are overall better preserved with increasing time-on-stream and deactivate later than their microporous counterparts, which suffer from pore blockage. Likewise, it was seen that ZrO2-promotion contributed positively in the prevention against deactivation by hard coke spreading, thanks to its enhanced Lewis acidity. The zeolite's crystal size is another important characteristic to combine the different components within catalyst bodies, ensuring the proper interaction between zeolite, promoter and binder. This is illustrated by the nanocrystalline ZrO2/n-ZSM-5-ATP material, which shows the best catalytic performance.

KW - Biomass Catalytic Fast Pyrolysis

KW - Coke

KW - Crystal Size

KW - Mesoporosity

KW - Micro-spectroscopy

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JO - ChemCatChem

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ER -

Effect of Mesoporosity, Acidity and Crystal Size of Zeolite ZSM-5 on Catalytic Performance during the Ex-situ Catalytic Fast Pyrolysis of Biomass

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Keywords

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