Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts

Autores
Vaschetto, Eliana Gabriela; Casuscelli, Sandra Graciela; Eimer, Griselda Alejandra
Año de publicación
2016
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The Beckmann rearrangement of cyclohexanone oxime (CHO) into e-Caprolactam (e-C) at 300e380 C and W/F ¼ 1e60 gh/mol over a Al-MCM-41 catalyst was studied in a flow reactor at atmospheric pressure. Different reaction conditions as well as the nature of the solvents employed in the feed were evaluated. The e-C was the main product on the whole reaction conditions, but temperatures above 360 C favored its decomposition. A reaction pathway was proposed in order to explain the results obtained at 360 C. The stability and the possibility of recycling of the catalyst were checked by XRD, N2 adsorption, FTIR, pyridine adsorption coupled with FTIR and catalytic activity tests. Thus, the catalyst could be used during 3600 min and then recovered and reused three times without significant changes in the active species, catalytic activity and e-C yield. In addition, a modification in the operating conditions, which consisted in pretreating the catalyst with 1-hexanol, allowed to improve the yield to caprolactam by blocking the terminal silanols responsible of the byproduct formation. Thus, the better catalytic performance was observed at 350 C and W/F ¼ 40 gh/mol, immediately after a catalyst pretreatment with 1-hexanol during 3 h with 1-hexanol, which was also used as reaction solvent. Such conditions allowed us to achieve a high CHO conversion (95%) with a e-C selectivity of around 100%, improving thus results previously reported.
Fil: Vaschetto, Eliana Gabriela. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Cordoba. Centro de Investigacion y Tecnologia Quimica; Argentina. Universidad Tecnologica Nacional. Facultad Regional Cordoba; Argentina
Fil: Casuscelli, Sandra Graciela. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Cordoba. Centro de Investigacion y Tecnologia Quimica; Argentina. Universidad Tecnologica Nacional. Facultad Regional Cordoba; Argentina
Fil: Eimer, Griselda Alejandra. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Cordoba. Centro de Investigacion y Tecnologia Quimica; Argentina. Universidad Tecnologica Nacional. Facultad Regional Cordoba; Argentina
Materia
Beckmann Rearrangement
E-Caprolactam
Reaction Conditions
Stability the Catalyst
Al-Mcm-41
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/10960
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalystsVaschetto, Eliana GabrielaCasuscelli, Sandra GracielaEimer, Griselda AlejandraBeckmann RearrangementE-CaprolactamReaction ConditionsStability the CatalystAl-Mcm-41https://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2The Beckmann rearrangement of cyclohexanone oxime (CHO) into e-Caprolactam (e-C) at 300e380 C and W/F ¼ 1e60 gh/mol over a Al-MCM-41 catalyst was studied in a flow reactor at atmospheric pressure. Different reaction conditions as well as the nature of the solvents employed in the feed were evaluated. The e-C was the main product on the whole reaction conditions, but temperatures above 360 C favored its decomposition. A reaction pathway was proposed in order to explain the results obtained at 360 C. The stability and the possibility of recycling of the catalyst were checked by XRD, N2 adsorption, FTIR, pyridine adsorption coupled with FTIR and catalytic activity tests. Thus, the catalyst could be used during 3600 min and then recovered and reused three times without significant changes in the active species, catalytic activity and e-C yield. In addition, a modification in the operating conditions, which consisted in pretreating the catalyst with 1-hexanol, allowed to improve the yield to caprolactam by blocking the terminal silanols responsible of the byproduct formation. Thus, the better catalytic performance was observed at 350 C and W/F ¼ 40 gh/mol, immediately after a catalyst pretreatment with 1-hexanol during 3 h with 1-hexanol, which was also used as reaction solvent. Such conditions allowed us to achieve a high CHO conversion (95%) with a e-C selectivity of around 100%, improving thus results previously reported.Fil: Vaschetto, Eliana Gabriela. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Cordoba. Centro de Investigacion y Tecnologia Quimica; Argentina. Universidad Tecnologica Nacional. Facultad Regional Cordoba; ArgentinaFil: Casuscelli, Sandra Graciela. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Cordoba. Centro de Investigacion y Tecnologia Quimica; Argentina. Universidad Tecnologica Nacional. Facultad Regional Cordoba; ArgentinaFil: Eimer, Griselda Alejandra. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Cordoba. Centro de Investigacion y Tecnologia Quimica; Argentina. Universidad Tecnologica Nacional. Facultad Regional Cordoba; ArgentinaElsevier2016-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/10960Vaschetto, Eliana Gabriela; Casuscelli, Sandra Graciela; Eimer, Griselda Alejandra; Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts; Elsevier; Microporous And Mesoporous Materials; 221; 1-2016; 175-1811387-1811enginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.micromeso.2015.09.038info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S1387181115005272info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:50:46Zoai:ri.conicet.gov.ar:11336/10960instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 09:50:46.934CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts
title Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts
spellingShingle Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts
Vaschetto, Eliana Gabriela
Beckmann Rearrangement
E-Caprolactam
Reaction Conditions
Stability the Catalyst
Al-Mcm-41
title_short Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts
title_full Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts
title_fullStr Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts
title_full_unstemmed Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts
title_sort Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts
dc.creator.none.fl_str_mv Vaschetto, Eliana Gabriela
Casuscelli, Sandra Graciela
Eimer, Griselda Alejandra
author Vaschetto, Eliana Gabriela
author_facet Vaschetto, Eliana Gabriela
Casuscelli, Sandra Graciela
Eimer, Griselda Alejandra
author_role author
author2 Casuscelli, Sandra Graciela
Eimer, Griselda Alejandra
author2_role author
author
dc.subject.none.fl_str_mv Beckmann Rearrangement
E-Caprolactam
Reaction Conditions
Stability the Catalyst
Al-Mcm-41
topic Beckmann Rearrangement
E-Caprolactam
Reaction Conditions
Stability the Catalyst
Al-Mcm-41
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv The Beckmann rearrangement of cyclohexanone oxime (CHO) into e-Caprolactam (e-C) at 300e380 C and W/F ¼ 1e60 gh/mol over a Al-MCM-41 catalyst was studied in a flow reactor at atmospheric pressure. Different reaction conditions as well as the nature of the solvents employed in the feed were evaluated. The e-C was the main product on the whole reaction conditions, but temperatures above 360 C favored its decomposition. A reaction pathway was proposed in order to explain the results obtained at 360 C. The stability and the possibility of recycling of the catalyst were checked by XRD, N2 adsorption, FTIR, pyridine adsorption coupled with FTIR and catalytic activity tests. Thus, the catalyst could be used during 3600 min and then recovered and reused three times without significant changes in the active species, catalytic activity and e-C yield. In addition, a modification in the operating conditions, which consisted in pretreating the catalyst with 1-hexanol, allowed to improve the yield to caprolactam by blocking the terminal silanols responsible of the byproduct formation. Thus, the better catalytic performance was observed at 350 C and W/F ¼ 40 gh/mol, immediately after a catalyst pretreatment with 1-hexanol during 3 h with 1-hexanol, which was also used as reaction solvent. Such conditions allowed us to achieve a high CHO conversion (95%) with a e-C selectivity of around 100%, improving thus results previously reported.
Fil: Vaschetto, Eliana Gabriela. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Cordoba. Centro de Investigacion y Tecnologia Quimica; Argentina. Universidad Tecnologica Nacional. Facultad Regional Cordoba; Argentina
Fil: Casuscelli, Sandra Graciela. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Cordoba. Centro de Investigacion y Tecnologia Quimica; Argentina. Universidad Tecnologica Nacional. Facultad Regional Cordoba; Argentina
Fil: Eimer, Griselda Alejandra. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Cordoba. Centro de Investigacion y Tecnologia Quimica; Argentina. Universidad Tecnologica Nacional. Facultad Regional Cordoba; Argentina
description The Beckmann rearrangement of cyclohexanone oxime (CHO) into e-Caprolactam (e-C) at 300e380 C and W/F ¼ 1e60 gh/mol over a Al-MCM-41 catalyst was studied in a flow reactor at atmospheric pressure. Different reaction conditions as well as the nature of the solvents employed in the feed were evaluated. The e-C was the main product on the whole reaction conditions, but temperatures above 360 C favored its decomposition. A reaction pathway was proposed in order to explain the results obtained at 360 C. The stability and the possibility of recycling of the catalyst were checked by XRD, N2 adsorption, FTIR, pyridine adsorption coupled with FTIR and catalytic activity tests. Thus, the catalyst could be used during 3600 min and then recovered and reused three times without significant changes in the active species, catalytic activity and e-C yield. In addition, a modification in the operating conditions, which consisted in pretreating the catalyst with 1-hexanol, allowed to improve the yield to caprolactam by blocking the terminal silanols responsible of the byproduct formation. Thus, the better catalytic performance was observed at 350 C and W/F ¼ 40 gh/mol, immediately after a catalyst pretreatment with 1-hexanol during 3 h with 1-hexanol, which was also used as reaction solvent. Such conditions allowed us to achieve a high CHO conversion (95%) with a e-C selectivity of around 100%, improving thus results previously reported.
publishDate 2016
dc.date.none.fl_str_mv 2016-01
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/10960
Vaschetto, Eliana Gabriela; Casuscelli, Sandra Graciela; Eimer, Griselda Alejandra; Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts; Elsevier; Microporous And Mesoporous Materials; 221; 1-2016; 175-181
1387-1811
url http://hdl.handle.net/11336/10960
identifier_str_mv Vaschetto, Eliana Gabriela; Casuscelli, Sandra Graciela; Eimer, Griselda Alejandra; Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts; Elsevier; Microporous And Mesoporous Materials; 221; 1-2016; 175-181
1387-1811
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.micromeso.2015.09.038
info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S1387181115005272
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.13397

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