Utilisation du complexe Fe(III)-EDDS dans des procédés d’oxydation avancée : dégradation du 4-tert-butylphénol

Application of Fe(III)-EDDS complex in advanced oxidation processes : 4-ter-butylphenol degradation

• Auteur / Autrice : Yanlin Wu
• Direction : Gilles Mailhot, Wenbo Dong
• Type : Thèse de doctorat
• Discipline(s) : Chimie-Physique
• Date : Soutenance le 16/05/2014
• Etablissement(s) : Clermont-Ferrand 2 en cotutelle avec Université de Wuhan (Chine)
• Ecole(s) doctorale(s) : École doctorale des sciences fondamentales (Clermont-Ferrand)
• Partenaire(s) de recherche : Equipe de recherche : Institut de Chimie de Clermont-Ferrand (Aubière, Puy-de-Dôme ; 2012-....)
• Jury : Président / Présidente : Jean-Marc Chovelon
• Jury : Examinateurs / Examinatrices : Gilles Mailhot, Wenbo Dong, Marcello Brigante, Hongjing Li
• Jury : Rapporteur / Rapporteuse : Feng Wu

Mots clés

Mots clés contrôlés

Eau -- Épuration

Polluants organiques de l'eau

Oxydation

Mots clés libres

Photochimie

Complexes de fer

Fenton

Fe(III)-EDDS

Radical hydroxyle

Persulfate

Radical sulfate

Perturbateur endocrinien

4-t-BP

Photochemistry

Fe(III)-EDDS

Fenton-like

Hydroxyl radical

Persulfate

Sulfate radical

Endocrine disrupting chemicals

4-t-BP

Résumé

Dans cette étude, un nouveau complexe de fer est utilisé dans des processus d’oxydation avancée pour la dégradation de polluants organiques présents dans l’eau. Le fer ferrique (Fe(III)) et l’acide éthylène diamine-N,N’-disuccinique (EDDS) forment un complexe Fe(III)-EDDS dont la structure a été mise en évidence durant ce travail. Les propriétés photochimiques du complexe ont ensuite été évaluées en fonction de différents paramètres physico-chimiques dont le pH qui est apparu comme un paramètre clé pour l’efficacité des processus testés. Ensuite nous avons donc travaillé sur l’utilisation de ce complexe dans les processus de Fenton modifié, photo-Fenton et comme activateur des persulfates (S2O82-). Nos expériences ont été réalisées en présence du 4-tert-butylphénol (4-t-BP) qui est connu pour être un perturbateur endocrinien. Nous avons ensuite mis en évidence les conditions optimales du traitement pour la dégradation du 4-t-BP. Il est apparu que le pH joue un rôle très important et qu’en présence de ce complexe de fer, l’efficacité est plus importante pour des pH neutre ou légèrement basique. L’identification des radicaux oxydants responsables de la dégradation du polluant a également été réalisée. Dans ce cadre nous avons montré que le radical sulfate joue un rôle plus important que le radical hydroxyle lors du processus d’activation des persulfates.

Advanced Oxidation Processes (AOPs) have been proved to be successfully applied in the treatment of sewage. It can decolorize the wastewater, reduce the toxicity of pollutants, convert the pollutants to be a biodegradable by-product and achieve the completed mineralization of the organic pollutants. The Fenton technologies which are performed by iron-activated hydrogen peroxide (H2O2) to produce hydroxyl radical (HO•) has been widely investigated in the past few decades. Recently, Sulfate radical (SO4•-) which was produced by the activation of persulfate (S2O82-) is applied to the degradation of organic pollutants in water and soil. It is a new technology recently developed. It is also believed to be one of the most promising advanced oxidation technologies.In this study, a new iron complex is introduced to the traditional Fenton reaction. The ferric iron (Fe(III)) and Ethylene diamine-N,N′-disuccinic acid (EDDS) formed the complex named Fe(III)-EDDS. It can overcome the main disadvantage of traditional Fenton technology, which is the fact that traditional Fenton technology can only perform high efficiency in acidic condition. Simultaneously, EDDS is biodegradable and it is one of the best environment-friendly complexing agents. On the other hand, the transition metal is able to activate S2O82- to generate SO4•-. Therefore, Fe(III)-EDDS will also be applied to activate S2O82- in the present study. 4-tert-Butylphenol (4-t-BP) has been chosen as a target pollutant in this study. It is widely used as a chemical raw material and is classified as endocrine disrupting chemicals due to the estrogenic effects. The 4-t-BP degradation rate (R4-t-BP) is used to indicate the efficiency of the advanced oxidation processes which are based on Fe(III)-EDDS utilization. The main contents and conclusions of this research are shown as follows:In the first part, the chemical structure and properties of Fe(III)-EDDS and the 4-t-BP degradation efficiency in UV/Fe(III)-EDDS system were studied. The results showed that Fe(III)-EDDS was a stable complex which was formed by the Fe(III) and EDDS with the molar ratio 1:1. From the photoredox process of Fe(III)-EDDS, the formation of hydroxyl radical was confirmed including that HO• is the main species responsible for the degradation of 4-t-BP in aqueous solution. Ferrous ion (Fe(II)) was also formed during the reaction. With the increasing Fe(III)-EDDS concentration, 4-t-BP degradation rate increased but is inhibited when the Fe(III)-EDDS concentration was too high. Indeed, Fe(III)-EDDS is the scavenger of HO•. pH value had a significant effect on the degradation efficiency of 4-t-BP that was enhanced under neutral or alkaline conditions. On the one hand, Fe(III)-EDDS presented in the FeL-, Fe(OH)L2-, Fe(OH)2L3-, Fe(OH)4- four different forms under different pH conditions and they had different sensitivity to the UV light. On the other hand, pH value affected the cycle between Fe(III) and Fe(II ). The formation of hydroperoxy radicals (HO2•) and superoxide radical anions (O2•-) (pka = 4.88) as a function of pH was also one of the reasons. It was observed that O2 was an important parameter affecting the efficiency of this process. This effect of O2 is mainly due to its important role during the oxidation of the first radical formed on the pollutant. (...)