Oxydation en voie humide de la pollution organique aqueuse par le peroxyde d'hydrogène Procédé « Wet Peroxide Oxidation » (WPO®) Étude de nouveaux catalyseurs Wet oxidation of organic aqueous pollutants by hydrogen peroxide with the « Wet Peroxide Oxidation » process (WPO®). Investigation of new catalysts

Résumé

Les effluents aqueux pollués par des matières organiques provenant d'industries chimiques présentent souvent une faible biodégradabilité. Dans certains domaines de concentration (DCO = 0,5 - 15 g/l), le procédé WPO® développé au laboratoire se substitue avantageusement à l'incinération pour traiter ce type d'effluents. La réaction, qui met en œuvre le réactif de Fenton à température élevée, conduit parfois à la formation de quantités importantes d'acides carboxyliques légers. Nous avons donc développé des systèmes catalytiques originaux remplaçant les sels de fer et conduisant à une oxydation totale des acides carboxyliques. Le système le plus efficace constitué de sels de fer, de cuivre et de manganèse permet d'obtenir, en 1 h à 100 °C, l'oxydation totale d'un mélange synthétique de ces acides (COT = 5 g/l) avec 1,5 fois la quantité de peroxyde théoriquement nécessaire à l'oxydation. Le catalyseur précipité et séparé en fin de traitement peut être recyclé et conserve la môme activité. Les unités industrielles permettant d'effectuer le traitement WPO® avec les nouveaux catalyseurs, recyclés ou non, seront similaires à celle déjà réalisée pour le traitement de « points noirs » industriels.

Mots-clés:

• Eaux usées industrielles,
• oxydation à haute température,
• peroxyde d'hydrogène,
• pollution organique réfractaire,
• réactif de Fenton,
• synergie catalytique

Abstract

There is an important concern about the problems occuring with wastes elimination, specially the industrial liquid wastes. Te face the problem of organic aqueous wastes coming front various branches of industry, the WPO® (wet peroxide oxidation) process was developed at the laboratory. In the WAO process (wet air oxidation), which uses gaseous oxygen, the limiting step is usually oxygen transfer. In this new process, this problem is suppressed by using a liquid oxidising agent (hydrogen peroxide). This process is adapted from the classical Fenton's reaction and iron salts are used as the catalyst in order to promote the formation of ^•OH radicles which are the main active species. But the reaction is carried out at about 120 °C; so, a very significant TOC (total organic carton) removal efficiency is obtained (60 to 90 %) in comparison with the low efficiency of the classical Fenton's reagent (typically 25 % at room temperature).

Significant amounts of free fatty acids are formed during the reaction. They are namely oxalic, malonic, succinic and acetic acids, which are common by products obtained during audition of most industrial organic pollutants. In order to comply with the regulations requirements, it was necessary to improve the efficiency of the original process. It was also very important to obtain an efficient elimination at a temperature not greater than 100 °C in order to avoid to pressurize the treatment reactor. This could be obtained by using new catalysts which are described in this paper.

Because of the related field, precious metals like Pt and potentially toxic ones like Cr were not considered. One needs a treatment process as cheap and as reliable as possible. So, only Fe, Cu, Co, Ni and Mn were used as salts in order to test their calalytic activity in the treatment by hydrogen peroxide of a synthetical mixture of oxalic, malonic, succinic and acetic acids (O, M, S, A). The experimental device is a stirred tank reactor where the organics and the catalyst are batch loaded. It is continuously fed, for 1 hour, with hydrogen peroxide. The total amount injected is 1.5 the stoechiometric amount. In table 1, it can be seen that any metal has a satisfactory activity when used alone (TOC removal efficiency cannot exceed 22 %). In table 2, it is clear that, in soma cases, the association of two or three metals with each other can lead to very important synergetic effects. When using a mixture of Fe, Cu and Mn, the removal efficiency can increase to 91 %. This Fe/Cu/Mn catalyst is studied with further details in table 4. It appears to have its best efficiency at about 100 °C because of a parasitic decomposition of the peroxide at higher temperatures. For an organic mixture coutaining 5 g TOC/l, 100 ppm of each metal is a convenient concentration. This new catalyst still needs an acidic pH, from 3 to about 5, but the dependency is not so strict than with Fe alone (original process) which needs a value from 3 to 3.5. In addition, it was observed that the treatment time could be easily reduced (down to 45 minutes) as well as the amount of peroxide injected.

Very similar results have been obtained with synthetic solutions of pollutants and with real industrial ones, thus establishing the ability of the Fe/Cu/Mn mixture to catalyse the oxidation of a large variety of species and not only carboxilic acids. The difference between the efficiency of this new catalyst and the conventional one is shown in table 5. Figures 1 and 2 are related to an Industrial WPO® unit which is commonly used with the conventional catalyst (Fe). It has been possible to improve its efficiency by using the new one without any significant modification. The Fe/Cu/Mn catalyst can be easily separated alter reaction (coprecipitation effect). Thus, the treated water meets the regulation requirements and the recovered catalyst can be easily resolubilized and recycled.

Keywords:

• Industrial wastewaters,
• high temperature oxidation,
• hydrogen peroxide,
• refractory organic pollution,
• Fenton 's reagent,
• synergetic effect,
• catalysis