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

J 2024

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

PAMPARARO, Giovanni; Zuzana HLAVENKOVÁ; Aleš STÝSKALÍK a Damien P DEBECKER

Základní údaje

Originální název

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

Autoři

PAMPARARO, Giovanni; Zuzana HLAVENKOVÁ (703 Slovensko, domácí); Aleš STÝSKALÍK (203 Česká republika, domácí) a Damien P DEBECKER

Vydání

Catalysis Science and Technology, Royal Society of Chemistry, 2024, 2044-4753

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10400 1.4 Chemical sciences

Stát vydavatele

Velká Británie a Severní Irsko

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 4.400 v roce 2023

Kód RIV

RIV/00216224:14740/24:00138738

Organizační jednotka

Středoevropský technologický institut

DOI

http://dx.doi.org/10.1039/d4cy00646a

UT WoS

001276569200001

EID Scopus

2-s2.0-85199506964

Klíčová slova anglicky

ACETIC-ACID SYNTHESIS; ETHANOL DEHYDROGENATION; COPPER-CATALYSTS; OXIDE ADDITIVES; ETHYL-ACETATE; CU; OXIDATION; EFFICIENT; SURFACE; NANOPARTICLES

Štítky

CF CRYO, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 15. 3. 2025 18:19, Mgr. Eva Dubská

Anotace

V originále

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.

Návaznosti

EF18_046/0015974, projekt VaV

Název: Modernizace České infrastruktury pro integrativní strukturní biologii

EH22_008/0004572, projekt VaV

Název: Kvantové materiály pro aplikace v udržitelných technologiích

90242, velká výzkumná infrastruktura

Název: CIISB III

Citovat

PAMPARARO, Giovanni; Zuzana HLAVENKOVÁ; Aleš STÝSKALÍK a Damien P DEBECKER. Suppressing on-stream deactivation of CuSiO2 catalysts in the dehydrogenation of bioethanol to acetaldehyde. Catalysis Science and Technology. Royal Society of Chemistry, 2024, roč. 14, č. 17, s. 4912-4926. ISSN 2044-4753. Dostupné z: https://dx.doi.org/10.1039/d4cy00646a.

@article{2473023,
   author = {Pampararo, Giovanni and Hlavenková, Zuzana and Stýskalík, Aleš and Debecker, Damien P},
   article_number = {17},
   doi = {http://dx.doi.org/10.1039/d4cy00646a},
   keywords = {ACETIC-ACID SYNTHESIS; ETHANOL DEHYDROGENATION; COPPER-CATALYSTS; OXIDE ADDITIVES; ETHYL-ACETATE; CU; OXIDATION; EFFICIENT; SURFACE; NANOPARTICLES},
   language = {eng},
   issn = {2044-4753},
   journal = {Catalysis Science and Technology},
   title = {Suppressing on-stream deactivation of CuSiO2 catalysts in the dehydrogenation of bioethanol to acetaldehyde},
   url = {https://pubs.rsc.org/en/content/articlelanding/2024/cy/d4cy00646a},
   volume = {14},
   year = {2024}
}

TY  - JOUR
ID  - 2473023
AU  - Pampararo, Giovanni - Hlavenková, Zuzana - Stýskalík, Aleš - Debecker, Damien P
PY  - 2024
TI  - Suppressing on-stream deactivation of CuSiO2 catalysts in the dehydrogenation of bioethanol to acetaldehyde
JF  - Catalysis Science and Technology
VL  - 14
IS  - 17
SP  - 4912-4926
EP  - 4912-4926
PB  - Royal Society of Chemistry
SN  - 20444753
KW  - ACETIC-ACID SYNTHESIS
KW  - ETHANOL DEHYDROGENATION
KW  - COPPER-CATALYSTS
KW  - OXIDE ADDITIVES
KW  - ETHYL-ACETATE
KW  - CU
KW  - OXIDATION
KW  - EFFICIENT
KW  - SURFACE
KW  - NANOPARTICLES
UR  - https://pubs.rsc.org/en/content/articlelanding/2024/cy/d4cy00646a
N2  - 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.
ER  -

PAMPARARO, Giovanni; Zuzana HLAVENKOVÁ; Aleš STÝSKALÍK a Damien P DEBECKER. Suppressing on-stream deactivation of CuSiO2 catalysts in the dehydrogenation of bioethanol to acetaldehyde. \textit{Catalysis Science and Technology}. Royal Society of Chemistry, 2024, roč.~14, č.~17, s.~4912-4926. ISSN~2044-4753. Dostupné z: https://dx.doi.org/10.1039/d4cy00646a.

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