Investigating the active phase of Ca-based ...
Document type :
Article dans une revue scientifique: Article original
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Title :
Investigating the active phase of Ca-based glycerol polymerization catalysts: On the importance of calcium glycerolate
Author(s) :
Ebadi Pour, Negisa [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Dumeignil, Franck [Auteur]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Katryniok, Benjamin [Auteur]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Delevoye, Laurent [Auteur]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Revel, Bertrand [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
PAUL, Sébastien [Auteur]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Dumeignil, Franck [Auteur]

Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Katryniok, Benjamin [Auteur]

Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Delevoye, Laurent [Auteur]

Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Revel, Bertrand [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
PAUL, Sébastien [Auteur]

Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Journal title :
Molecular Catalysis
Volume number :
507
Pages :
111571
Publication date :
2021-05
ISSN :
24688231
HAL domain(s) :
Chimie/Chimie inorganique
Chimie/Catalyse
Chimie/Catalyse
English abstract : [en]
Ca-based catalysts are of strong interest for glycerol polymerization reaction due to their high catalytic performances, their wide availability and the absence of any toxicity. In the present study, we investigated the ...
Show more >Ca-based catalysts are of strong interest for glycerol polymerization reaction due to their high catalytic performances, their wide availability and the absence of any toxicity. In the present study, we investigated the active phase of CaO, Ca(OH)2, CaCO3 and calcium diglyceroxide used as catalysts for this reaction. The solids were analyzed by XRD, solid-state 13C-NMR and TGA-DSC. XRD evidenced the presence of calcium glycerolate in the spent catalysts when CaO, Ca(OH)2 and calcium diglyceroxide were used as starting materials. This was corroborated by the TGA-DSC results. Further, the SS NMR results showed that the as-formed calcium glycerolate is a mixture of linear Ca(C3H7O3) and cyclic-branched Ca(C3H6O3). Moreover, the recycled catalyst issued, e.g., from CaO was more efficient that the initial catalyst with a glycerol conversion of 47 % (vs. 22 % initially for CaO) and a 70 % (vs. 55 %) selectivity to polyglycerols higher than tetraglycerol at 245 °C after 4 h in the presence of 3.5 mol.% of catalyst. As the main outcome, we have shown that Ca-glycerolate is the actual solid active phase, which is formed in situ from CaO and Ca(OH)2 playing the role of catalyst precursors. A mechanism involving the dissolution of CaO and Ca(OH)2, the formation of Ca-glycerolate and its precipitation followed by crystallization, supported by characterization studies, is proposed.Show less >
Show more >Ca-based catalysts are of strong interest for glycerol polymerization reaction due to their high catalytic performances, their wide availability and the absence of any toxicity. In the present study, we investigated the active phase of CaO, Ca(OH)2, CaCO3 and calcium diglyceroxide used as catalysts for this reaction. The solids were analyzed by XRD, solid-state 13C-NMR and TGA-DSC. XRD evidenced the presence of calcium glycerolate in the spent catalysts when CaO, Ca(OH)2 and calcium diglyceroxide were used as starting materials. This was corroborated by the TGA-DSC results. Further, the SS NMR results showed that the as-formed calcium glycerolate is a mixture of linear Ca(C3H7O3) and cyclic-branched Ca(C3H6O3). Moreover, the recycled catalyst issued, e.g., from CaO was more efficient that the initial catalyst with a glycerol conversion of 47 % (vs. 22 % initially for CaO) and a 70 % (vs. 55 %) selectivity to polyglycerols higher than tetraglycerol at 245 °C after 4 h in the presence of 3.5 mol.% of catalyst. As the main outcome, we have shown that Ca-glycerolate is the actual solid active phase, which is formed in situ from CaO and Ca(OH)2 playing the role of catalyst precursors. A mechanism involving the dissolution of CaO and Ca(OH)2, the formation of Ca-glycerolate and its precipitation followed by crystallization, supported by characterization studies, is proposed.Show less >
Language :
Anglais
Peer reviewed article :
Oui
Audience :
Internationale
Popular science :
Non
Administrative institution(s) :
CNRS
Centrale Lille
ENSCL
Univ. Artois
Université de Lille
Centrale Lille
ENSCL
Univ. Artois
Université de Lille
Collections :
Research team(s) :
RMN et matériaux inorganiques (RM2I)
Valorisation des alcanes et de la biomasse (VAALBIO)
Valorisation des alcanes et de la biomasse (VAALBIO)
Submission date :
2022-03-24T09:02:38Z
2023-10-19T12:31:16Z
2023-10-19T12:31:16Z
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