Oxydation en voie humide de la pollution organique aqueuse par le peroxyde d'hydrogène Procédé « Wet Peroxide Oxidation » (WPO®) Étude de nouveaux catalyseurs

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.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

Intercomparison of methods of coupling between convection and large-scale circulation. 2: comparison over non-uniform surface conditions

As part of an international intercomparison project, the weak temperature gradient (WTG) and damped gravity wave (DGW) methods are used to parameterize large-scale dynamics in a set of cloud-resolving models (CRMs) and single column models (SCMs). The WTG or DGW method is implemented using a configuration that couples a model to a reference state defined with profiles obtained from the same model in radiative-convective equilibrium. We investigated the sensitivity of each model to changes in SST, given a fixed reference state. We performed a systematic comparison of the WTG and DGW methods in different models, and a systematic comparison of the behavior of those models using the WTG method and the DGW method. The sensitivity to the SST depends on both the large-scale parameterization method and the choice of the cloud model. In general, SCMs display a wider range of behaviors than CRMs. All CRMs using either the WTG or DGW method show an increase of precipitation with SST, while SCMs show sensitivities which are not always monotonic. CRMs using either the WTG or DGW method show a similar relationship between mean precipitation rate and column-relative humidity, while SCMs exhibit a much wider range of behaviors. DGW simulations produce large-scale velocity profiles which are smoother and less top-heavy compared to those produced by the WTG simulations. These large-scale parameterization methods provide a useful tool to identify the impact of parameterization differences on model behavior in the presence of two-way feedback between convection and the large-scale circulation

Intercomparison of methods of coupling between convection and large-scale circulation: 1. Comparison over uniform surface conditions

As part of an international intercomparison project, a set of single column models (SCMs) and cloud-resolving models (CRMs) are run under the weak temperature gradient (WTG) method and the damped gravity wave (DGW) method. For each model, the implementation of the WTG or DGW method involves a simulated column which is coupled to a reference state defined with profiles obtained from the same model in radiative-convective equilibrium. The simulated column has the same surface conditions as the reference state and is initialized with profiles from the reference state. We performed systematic comparison of the behavior of different models under a consistent implementation of the WTG method and the DGW method and systematic comparison of the WTG and DGW methods in models with different physics and numerics. CRMs and SCMs produce a variety of behaviors under both WTG and DGW methods. Some of the models reproduce the reference state while others sustain a large-scale circulation which results in either substantially lower or higher precipitation compared to the value of the reference state. CRMs show a fairly linear relationship between precipitation and circulation strength. SCMs display a wider range of behaviors than CRMs. Some SCMs under the WTG method produce zero precipitation. Within an individual SCM, a DGW simulation and a corresponding WTG simulation can produce different signed circulation. When initialized with a dry troposphere, DGW simulations always result in a precipitating equilibrium state. The greatest sensitivities to the initial moisture conditions occur for multiple stable equilibria in some WTG simulations, corresponding to either a dry equilibrium state when initialized as dry or a precipitating equilibrium state when initialized as moist. Multiple equilibria are seen in more WTG simulations for higher SST. In some models, the existence of multiple equilibria is sensitive to some parameters in the WTG calculations

Understanding the West African Monsoon from the analysis of diabatic heating distributions as simulated by climate models

International audienceVertical and horizontal distributions of diabatic heating in the West African monsoon (WAM) region as simulated by four model families are analyzed in order to assess the physical processes that affect the WAM circulation. For each model family, atmosphere-only runs of their CMIP5 configurations are compared with more recent configurations which are on the development path toward CMIP6. The various configurations of these models exhibit significant differences in their heating/moistening profiles, related to the different representation of physical processes such as boundary layer mixing, convection, large-scale condensation and radiative heating/cooling. There are also significant differences in the models' simulation of WAM rainfall patterns and circulations. The weaker the radiative cooling in the Saharan region, the larger the ascent in the rainband and the more intense the monsoon flow, while the latitude of the rainband is related to heating in the Gulf of Guinea region and on the northern side of the Saharan heat low. Overall, this work illustrates the difficulty experienced by current climate models in representing the characteristics of monsoon systems, but also that we can still use them to understand the interactions between local subgrid physical processes and the WAM circulation. Moreover, our conclusions regarding the relationship between errors in the large-scale circulation of the WAM and the structure of the heating by small-scale processes will motivate future studies and model development