Deactivation by Potassium Accumulation on a Pt/TiO2 Bifunctional Catalyst for Biomass Catalytic Fast Pyrolysis

Biomass-derived feedstocks bring significant challenges to the longevity of the catalysts used for their conversion, and alkali metals, for example, K, in the feedstock have been widely ascribed as one of the important factors causing catalyst deactivation. To address this challenge, it is critical...

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Veröffentlicht in:ACS catalysis 2022-01, Vol.12 (1), p.465-480
Hauptverfasser: Lin, Fan, Lu, Yubing, Unocic, Kinga A, Habas, Susan E, Griffin, Michael B, Schaidle, Joshua A, Meyer, Harry M, Wang, Yong, Wang, Huamin
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container_end_page 480
container_issue 1
container_start_page 465
container_title ACS catalysis
container_volume 12
creator Lin, Fan
Lu, Yubing
Unocic, Kinga A
Habas, Susan E
Griffin, Michael B
Schaidle, Joshua A
Meyer, Harry M
Wang, Yong
Wang, Huamin
description Biomass-derived feedstocks bring significant challenges to the longevity of the catalysts used for their conversion, and alkali metals, for example, K, in the feedstock have been widely ascribed as one of the important factors causing catalyst deactivation. To address this challenge, it is critical to understand the mechanism of catalyst deactivation caused by K accumulation to guide the improvement of catalysts and processes and the development of catalyst regeneration strategies. In this work, we report a deep understanding of the impact of K on a bifunctional Pt/TiO2 catalyst, which is an efficient catalyst for the ex situ catalytic fast pyrolysis of biomass. We simulated the K-poisoning of Pt/TiO2 catalysts by purposely loading different amounts of K (100–6000 ppm by weight) on the catalysts. A series of characterization approaches, including scanning transmission electron microscopy, Fourier transform infrared spectroscopy, and chemical titration, were combined with a kinetic assessment of multiple probe reactions to elucidate the mechanism of Pt/TiO2 deactivation by K accumulation. At low K loadings (800 ppm), K starts to accumulate on the Pt–TiO2 interfacial area, poisoning the interfacial active sites for HDO and CO oxidation reactions. We further found that the poisoning of the Pt/TiO2 catalyst by K is reversible, and water washing can successfully remove the accumulated K and recover the activities for both alcohol dehydration and m-cresol HDO reactions.
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(NREL), Golden, CO (United States) ; Pacific Northwest National Lab. (PNNL), Richland, WA (United States)</creatorcontrib><description>Biomass-derived feedstocks bring significant challenges to the longevity of the catalysts used for their conversion, and alkali metals, for example, K, in the feedstock have been widely ascribed as one of the important factors causing catalyst deactivation. To address this challenge, it is critical to understand the mechanism of catalyst deactivation caused by K accumulation to guide the improvement of catalysts and processes and the development of catalyst regeneration strategies. In this work, we report a deep understanding of the impact of K on a bifunctional Pt/TiO2 catalyst, which is an efficient catalyst for the ex situ catalytic fast pyrolysis of biomass. We simulated the K-poisoning of Pt/TiO2 catalysts by purposely loading different amounts of K (100–6000 ppm by weight) on the catalysts. A series of characterization approaches, including scanning transmission electron microscopy, Fourier transform infrared spectroscopy, and chemical titration, were combined with a kinetic assessment of multiple probe reactions to elucidate the mechanism of Pt/TiO2 deactivation by K accumulation. At low K loadings (&lt;800 ppm), K preferentially poisons the strong Lewis acid sites, leading to significantly reduced activity for acid-catalyzed alcohol dehydration. However, acetone condensation is less sensitive to the poisoning of strong Lewis acid sites. Reactions that occur on Pt sites or at the metal–support interface, including alkene hydrogenation, m-cresol hydrodeoxygenation (HDO), and CO oxidation, were not impacted. At high K loadings (&gt;800 ppm), K starts to accumulate on the Pt–TiO2 interfacial area, poisoning the interfacial active sites for HDO and CO oxidation reactions. 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Reactions that occur on Pt sites or at the metal–support interface, including alkene hydrogenation, m-cresol hydrodeoxygenation (HDO), and CO oxidation, were not impacted. At high K loadings (&gt;800 ppm), K starts to accumulate on the Pt–TiO2 interfacial area, poisoning the interfacial active sites for HDO and CO oxidation reactions. 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subjects 09 BIOMASS FUELS
biomass
catalytic fast pyrolysis
deactivation
potassium
Pt/TiO2
title Deactivation by Potassium Accumulation on a Pt/TiO2 Bifunctional Catalyst for Biomass Catalytic Fast Pyrolysis
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