Suppressing on-stream deactivation of CuSiO2 catalysts in the dehydrogenation of bioethanol to acetaldehyde

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14740%2F24%3A00138738" target="_blank" >RIV/00216224:14740/24:00138738 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2024/cy/d4cy00646a" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2024/cy/d4cy00646a</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d4cy00646a" target="_blank" >10.1039/d4cy00646a</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Suppressing on-stream deactivation of CuSiO2 catalysts in the dehydrogenation of bioethanol to acetaldehyde

Popis výsledku v původním jazyce

Bioethanol upgrading to valuable platform molecules is a cornerstone of the emerging "integrated biorefinery" concept. Although active catalysts have already been developed for the non-oxidative dehydrogenation of ethanol to acetaldehyde, their rapid deactivation - through coking and sintering - is still an unsolved challenge. Herein, we study a 7.4 wt% Cu-SiO2 catalyst at 573 K for 8 or 24 hours under stable ethanol feed, we report in-depth characterization of the spent catalysts to univocally describe deactivation phenomena, and we propose reaction engineering procedures based on gas co-feed (O-2 or H-2) to decisively enhance the catalyst stability. Under the standard conditions, the pristine catalyst undergoes fast deactivation, as conversion drops from similar to 95% to similar to 25% in about 8 hours. While sintering is shown to occur during the reaction, we demonstrate that the main cause of deactivation is actually the accumulation of carbonaceous deposits. Even if such deactivation is shown to be reversible (regeneration by oxidative treatment), it is more attractive to prevent it from happening. Studying the effect of gas doping, we show that introducing a small fraction of oxygen (0.44 vol%) leads to a marked decrease of the extent of coking and stabilization of catalytic activity at a much higher conversion level (75% after 24 h). A slightly higher O2 concentration (1.77 vol%) leads to complete stabilization of the ethanol conversion (90% after 24 h), but concomitantly provokes a slight drop in acetaldehyde selectivity. With the findings of this study, with optimized reaction conditions and an ameliorated catalyst formulation, an outstanding acetaldehyde productivity (2.9 gaca gcat(-1) h(-1)) was maintained fully stable for 24 h.

Název v anglickém jazyce

Suppressing on-stream deactivation of CuSiO2 catalysts in the dehydrogenation of bioethanol to acetaldehyde

Popis výsledku anglicky

Bioethanol upgrading to valuable platform molecules is a cornerstone of the emerging "integrated biorefinery" concept. Although active catalysts have already been developed for the non-oxidative dehydrogenation of ethanol to acetaldehyde, their rapid deactivation - through coking and sintering - is still an unsolved challenge. Herein, we study a 7.4 wt% Cu-SiO2 catalyst at 573 K for 8 or 24 hours under stable ethanol feed, we report in-depth characterization of the spent catalysts to univocally describe deactivation phenomena, and we propose reaction engineering procedures based on gas co-feed (O-2 or H-2) to decisively enhance the catalyst stability. Under the standard conditions, the pristine catalyst undergoes fast deactivation, as conversion drops from similar to 95% to similar to 25% in about 8 hours. While sintering is shown to occur during the reaction, we demonstrate that the main cause of deactivation is actually the accumulation of carbonaceous deposits. Even if such deactivation is shown to be reversible (regeneration by oxidative treatment), it is more attractive to prevent it from happening. Studying the effect of gas doping, we show that introducing a small fraction of oxygen (0.44 vol%) leads to a marked decrease of the extent of coking and stabilization of catalytic activity at a much higher conversion level (75% after 24 h). A slightly higher O2 concentration (1.77 vol%) leads to complete stabilization of the ethanol conversion (90% after 24 h), but concomitantly provokes a slight drop in acetaldehyde selectivity. With the findings of this study, with optimized reaction conditions and an ameliorated catalyst formulation, an outstanding acetaldehyde productivity (2.9 gaca gcat(-1) h(-1)) was maintained fully stable for 24 h.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10400 - Chemical sciences

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2024

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Catalysis Science and Technology

ISSN

2044-4753

e-ISSN

2044-4761

Svazek periodika

14

Číslo periodika v rámci svazku

17

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

15

Strana od-do

4912-4926

Kód UT WoS článku

001276569200001

EID výsledku v databázi Scopus

2-s2.0-85199506964