Kinetic study of phenol hydroxylation by H2O2 in 3D Fe/SiC honeycomb monolithic reactors: Enabling the sustainable production of dihydroxybenzenes

[EN] The chemical kinetics of phenol hydroxylation by hydrogen peroxide (HO) 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...

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Detalles Bibliográficos
Autores: Vega, Gonzalo, Quintanilla, Asunción, Belmonte, Manuel, Casas, José A.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2021
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/282679
Acceso en línea:http://hdl.handle.net/10261/282679
Access Level:acceso abierto
Palabra clave:3D printing
Robocasting
Monolithic reactor
Phenol hydroxylation
Dihydroxybenzenes
Heterogeneous kinetic model
Descripción
Sumario:[EN] The chemical kinetics of phenol hydroxylation by hydrogen peroxide (HO) 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 cm). 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 C = 0.33 M, phenol:HO molar ratio 1:1, τ(space time) = 0–254 g h L, T = 80, 85 and 90 °C and water as unique solvent. Experimental results showed no mass transfer limitations. The best fits were obtained for HO 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 HO molecules on the iron active sites, (2) chemical surface HO 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.