Kinetic study of phenol hydroxylation by H<inf>2</inf>O<inf>2</inf> in 3D Fe/SiC honeycomb monolithic reactors: Enabling the sustainable production of dihydroxybenzenes

The chemical kinetics of phenol hydroxylation by hydrogen peroxide (H2O2) to produce dihydroxybenzenes was studied using a 3D printed monolithic reactor. The monoliths were manufactured by the Robocasting technique. They consisted on honeycomb-structured Fe/SiC nanoparticles (13.5 mm in diameter and...

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Autores: Vega, Gonzalo, Belmonte, Manuel, Quintanilla Gómez, María Asunción, Casas de Pedro, José Antonio
Tipo de recurso: artículo
Fecha de publicación:2021
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/714797
Acceso en línea:http://hdl.handle.net/10486/714797
https://dx.doi.org/10.1016/j.cej.2021.131128
Access Level:acceso abierto
Palabra clave:3D printing
Dihydroxybenzenes
Heterogeneous kinetic model
Monolithic reactor
Phenol hydroxylation
Robocasting
Química
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spelling Kinetic study of phenol hydroxylation by H<inf>2</inf>O<inf>2</inf> in 3D Fe/SiC honeycomb monolithic reactors: Enabling the sustainable production of dihydroxybenzenesVega, GonzaloBelmonte, ManuelQuintanilla Gómez, María AsunciónCasas de Pedro, José Antonio3D printingDihydroxybenzenesHeterogeneous kinetic modelMonolithic reactorPhenol hydroxylationRobocastingQuímicaThe chemical kinetics of phenol hydroxylation by hydrogen peroxide (H2O2) to produce dihydroxybenzenes was studied using a 3D printed monolithic reactor. The monoliths were manufactured by the Robocasting technique. They consisted on honeycomb-structured Fe/SiC nanoparticles (13.5 mm in diameter and 14.8 mm in length) with triangle cell geometry and staggered interconnected channels (71 cells per cm2). The isothermal reactor was constituted by three stacked monoliths and was operated as an ideal plug flow reactor, according to the measured residence time distribution. The hydroxylation experiments were carried out at CPHENOL,0 = 0.33 M, phenol:H2O2 molar ratio 1:1, τ(space time) = 0–254 g h L-1, T = 80, 85 and 90 °C and water as unique solvent. Experimental results showed no mass transfer limitations. The best fits were obtained for H2O2 decomposition with a Langmuir-Hinshelwood-Hougen-Watson kinetic model and for phenol hydroxylation, as well as, catechol and hydroquinone production, with an Eley-Rideal kinetic model. The hydroxylation reaction mechanism underling to the developed model involved three elementary reactions: (1) adsorption of H2O2 molecules on the iron active sites, (2) chemical surface H2O2 decomposition into the hydroxyl radical species, and (3) reaction between adsorbed radical species and phenol in solution leading to the dihydroxybenzene formation and freeing the iron catalytic active sites (rds). This work contributes to the implementation of outstanding 3D Fe/SiC honeycomb monolithic reactors, with a dihydroxybenzene selectivity above 99% at 80 °C, for the sustainable production of hydroxylated aromaticsThe authors thank the financial support by the Community of Madrid through the project S2018/EMT-4341 and the Government of Spain through the projects: PID2019-105079RB-I00, PGC2018-095642-B-I00 and RTI2018-095052-B-I00 (MCIU/AEI/FEDER, UE). Also, G. Vega acknowledges the Universidad Autonoma de Madrid for the Predoctoral contract FPI/UAM2021ElsevierDepartamento de Ingeniería QuímicaFacultad de CienciasUAM. Departamento de Ingeniería Química20212021-07-06research articlehttp://purl.org/coar/resource_type/c_2df8fbb1AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/714797https://dx.doi.org/10.1016/j.cej.2021.131128reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/7147972026-06-23T12:46:27Z
dc.title.none.fl_str_mv Kinetic study of phenol hydroxylation by H<inf>2</inf>O<inf>2</inf> in 3D Fe/SiC honeycomb monolithic reactors: Enabling the sustainable production of dihydroxybenzenes
title Kinetic study of phenol hydroxylation by H<inf>2</inf>O<inf>2</inf> in 3D Fe/SiC honeycomb monolithic reactors: Enabling the sustainable production of dihydroxybenzenes
spellingShingle Kinetic study of phenol hydroxylation by H<inf>2</inf>O<inf>2</inf> in 3D Fe/SiC honeycomb monolithic reactors: Enabling the sustainable production of dihydroxybenzenes
Vega, Gonzalo
3D printing
Dihydroxybenzenes
Heterogeneous kinetic model
Monolithic reactor
Phenol hydroxylation
Robocasting
Química
title_short Kinetic study of phenol hydroxylation by H<inf>2</inf>O<inf>2</inf> in 3D Fe/SiC honeycomb monolithic reactors: Enabling the sustainable production of dihydroxybenzenes
title_full Kinetic study of phenol hydroxylation by H<inf>2</inf>O<inf>2</inf> in 3D Fe/SiC honeycomb monolithic reactors: Enabling the sustainable production of dihydroxybenzenes
title_fullStr Kinetic study of phenol hydroxylation by H<inf>2</inf>O<inf>2</inf> in 3D Fe/SiC honeycomb monolithic reactors: Enabling the sustainable production of dihydroxybenzenes
title_full_unstemmed Kinetic study of phenol hydroxylation by H<inf>2</inf>O<inf>2</inf> in 3D Fe/SiC honeycomb monolithic reactors: Enabling the sustainable production of dihydroxybenzenes
title_sort Kinetic study of phenol hydroxylation by H<inf>2</inf>O<inf>2</inf> in 3D Fe/SiC honeycomb monolithic reactors: Enabling the sustainable production of dihydroxybenzenes
dc.creator.none.fl_str_mv Vega, Gonzalo
Belmonte, Manuel
Quintanilla Gómez, María Asunción
Casas de Pedro, José Antonio
author Vega, Gonzalo
author_facet Vega, Gonzalo
Belmonte, Manuel
Quintanilla Gómez, María Asunción
Casas de Pedro, José Antonio
author_role author
author2 Belmonte, Manuel
Quintanilla Gómez, María Asunción
Casas de Pedro, José Antonio
author2_role author
author
author
dc.contributor.none.fl_str_mv Departamento de Ingeniería Química
Facultad de Ciencias
UAM. Departamento de Ingeniería Química
dc.subject.none.fl_str_mv 3D printing
Dihydroxybenzenes
Heterogeneous kinetic model
Monolithic reactor
Phenol hydroxylation
Robocasting
Química
topic 3D printing
Dihydroxybenzenes
Heterogeneous kinetic model
Monolithic reactor
Phenol hydroxylation
Robocasting
Química
description The chemical kinetics of phenol hydroxylation by hydrogen peroxide (H2O2) to produce dihydroxybenzenes was studied using a 3D printed monolithic reactor. The monoliths were manufactured by the Robocasting technique. They consisted on honeycomb-structured Fe/SiC nanoparticles (13.5 mm in diameter and 14.8 mm in length) with triangle cell geometry and staggered interconnected channels (71 cells per cm2). The isothermal reactor was constituted by three stacked monoliths and was operated as an ideal plug flow reactor, according to the measured residence time distribution. The hydroxylation experiments were carried out at CPHENOL,0 = 0.33 M, phenol:H2O2 molar ratio 1:1, τ(space time) = 0–254 g h L-1, T = 80, 85 and 90 °C and water as unique solvent. Experimental results showed no mass transfer limitations. The best fits were obtained for H2O2 decomposition with a Langmuir-Hinshelwood-Hougen-Watson kinetic model and for phenol hydroxylation, as well as, catechol and hydroquinone production, with an Eley-Rideal kinetic model. The hydroxylation reaction mechanism underling to the developed model involved three elementary reactions: (1) adsorption of H2O2 molecules on the iron active sites, (2) chemical surface H2O2 decomposition into the hydroxyl radical species, and (3) reaction between adsorbed radical species and phenol in solution leading to the dihydroxybenzene formation and freeing the iron catalytic active sites (rds). This work contributes to the implementation of outstanding 3D Fe/SiC honeycomb monolithic reactors, with a dihydroxybenzene selectivity above 99% at 80 °C, for the sustainable production of hydroxylated aromatics
publishDate 2021
dc.date.none.fl_str_mv 2021
2021-07-06
dc.type.none.fl_str_mv research article
http://purl.org/coar/resource_type/c_2df8fbb1
AM
http://purl.org/coar/version/c_ab4af688f83e57aa
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10486/714797
https://dx.doi.org/10.1016/j.cej.2021.131128
url http://hdl.handle.net/10486/714797
https://dx.doi.org/10.1016/j.cej.2021.131128
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:Biblos-e Archivo. Repositorio Institucional de la UAM
instname:Universidad Autónoma de Madrid
instname_str Universidad Autónoma de Madrid
reponame_str Biblos-e Archivo. Repositorio Institucional de la UAM
collection Biblos-e Archivo. Repositorio Institucional de la UAM
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repository.mail.fl_str_mv
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