Élimination sélective d'un mélange d'hydrocarbures imbrûlés Diesel par adsorption sur des matériaux zéolithiques

Actuellement, environ 80% de la pollution par les hydrocarbures (HC) imbrûlés est émise durant la période de démarrage à froid des moteurs (période dite de "cold-start"), d'une durée approximative de 120 s. Pour les véhicules Diesel, une méthode particulièrement prometteuse pourrait consister à piéger les HC sur un adsorbant à des températures inférieures à 200-250 C, pour les oxyder ensuite à plus haute température grâce à un catalyseur d'oxydation conventionnel. Cependant, peu d'études dans la littérature traitent de l'adsorption/désorption d'un mélange complexe d'HC, notamment en présence d'inhibiteurs. Dans cette étude, nous avons cherché à évaluer dans quelle mesure les propriétés structurales et chimiques d'adsorbants zéolithiques pouvaient affecter les caractéristiques d'adsorption et désorption d'un mélange modèle d'HC (propène, toluène, décane) en absence/présence d'inhibiteurs (NOx, H2O, COx..). Dans ce but, 3 séries de tests ont été menées pour mesurer les influences respectives: (i) de la composition du mélange d'HC (binaire/ternaire) ainsi que la présence d'eau sur la zéolithe HY de structure faujasite (pour différents rapports Si/Al); (ii) de l'incorporation d'un cation métallique (Cu, Pt, Ce, Cs) pour la zéolithe HY (rapport Si/Al = 5); (iii) de la topologie et de la porosité de zéolithes protonées (structures FAU, BEA, MOR, MFI, FER, LTA). Les propriétés texturales, structurales et chimiques des zéolithes étudiées ont été systématiquement caractérisées par porosimétrie à l'azote, DRX, FTIR/ATR, DRS-UV-Vis, FTIR du CO, NO et de la pyridine adsorbée. D'une manière générale, les courbes de percée obtenues avec différentes compositions indiquent que la diffusion de chaque HC est fortement affectée par la présence d'autres composés présents simultanément dans le réseau poreux. Pour les zéolithes Y protonées, les faibles rapports Si/Al favorisent la sélectivité pour l'adsorption des insaturés alors que les zéolithes plus hydrophobes (Si/Al élevés) adsorbent préférentiellement le décane. Parmi les différents inhibiteurs testés (CO, NOx, H2O), seul l'eau impacte fortement les capacités d'adsorption aux faibles rapports Si/Al, en raison d'une compétition avec les HC sur les sites acides. L'incorporation d'espèces métalliques dans la zéolithe HY-5 améliore la sélectivité d'adsorption pour les insaturés, notamment les plus légers (propène). Les expériences de TPSR sous atmosphère réactive ont montré que la présence de nouveaux sites acides de Lewis Cu+ et/ou Cu2+ en position d'échange améliore fortement la réduction des NOx par les HC pré-adsorbés. La zéolithe modifiée au Pt a un comportement typique d'un catalyseur d'oxydation, l'intégralité des composés carbonés (HC, CO,...) étant totalement convertie en CO2 à partir de 300C. L'étude des caractéristiques d'adsorption/désorption des HC pour différentes structures zéolithiques a permis de montrer que la topologie ainsi que la force des sites acides sont également des paramètres déterminants pour le piégeage des HC. L'ensemble de ces résultats permet d'envisager l'utilisation de certaines des formulations testées pour une application "cold-start"Currently, about 80% of the pollution from unburnt hydrocarbons (HC) is emitted during the cold-start period, for an approximate duration of 120 s. For Diesel vehicles, a promising approach might be to trap the HC onto an adsorbent below 200-250 C, and then to oxidize them at higher temperatures over a conventional oxidation catalyst. However, few publications in the literature deal with the adsorption / desorption of a complex mixture of HC, especially in the presence of inhibitors. In this study, we tried to assess in which extent structural and chemical properties of zeolite adsorbents could affect the adsorption and desorption characteristics of a model mixture of HC (propene, toluene, decane) in the absence/presence of inhibitors (NOx, H2O, COx ..). For this purpose, three sets of tests were performed in order to measure the respective influences of: (i) the composition of the HC mixture (ternary/binary) and the presence of water on the HY zeolite (with the faujasite structure) for several Si/Al ratios; (ii) the incorporation of a metallic cation (Cu, Pt, Ce, Cs) in the HY zeolite (Si/Al = 5); (iii) the topology and porosity of protonated zeolite (FAU, BEA, MOR, MFI, FER, LTA structures). The textural, structural and chemical properties of the studied zeolites were systematically characterized by nitrogen porosimetry, XRD, FTIR / ATR, DRS-UV-Vis, FTIR of CO, NO and adsorbed pyridine. In general, the breakthrough curves obtained with different compositions indicate that the distribution of each HC is strongly affected by the presence of other compounds present simultaneously in the porous network. For protonated Y zeolites, low Si/Al ratios promote selectively the adsorption of unsaturated HC while the more hydrophobic zeolites (for higher Si/Al ratios) preferentially adsorb decane. Among the various tested inhibitors (CO, NOx, H2O), only water has a strong influence on the adsorption capacities at low Si/Al ratios, due to a competitive adsorption with HC on acid sites. The incorporation of metallic species in the HY-5 zeolite enhances the selectivity for the adsorption of unsaturated hydrocarbons and especially the light ones (propene). TPSR experiments under reactive atmosphere showed that the presence of new Lewis acid sites Cu+ and/or Cu2+ on an exchange site strongly improves the NOx reduction by pre-adsorbed HC. The impregnated Pt-zeolite has a typical behaviour of an oxidation catalyst, all of the carboneous compounds (HC, CO,...) being completely converted to CO2 from 300 C. The study of adsorption/desorption characteristics of HC among different zeolitic structures show that the topology and the strength of acid sites are also critical for the HC trapping. All these results allow to consider using some of these tested formulations for a "cold-start" applicationNANCY-INPL-Bib. électronique (545479901) / SudocSudocFranceF

Performances of pretreated ceria-zirconia nanomaterials/H<SUB align="right">2</SUB align="right">O<SUB align="right">2</SUB align="right"> system for the degradation of Orange II dye

International audienceIn this work, the parameters affecting the reactivity of non-sulfated and sulfated commercial ceria-zirconia (CexZr1&minus;xO2) nanomaterials with varying Ce content (x = 1, 0.80, 0.50, 0.21, 0) towards the degradation of Orange II dye have been evaluated. Characterisation of the catalysts was performed using nitrogen adsorption, XRD, Raman, TGA thermogravimetry and DR-UV-Vis spectroscopy. Briefly, it can be deduced that the sulfation treatment mostly affects the Ce rich catalysts by increasing the crystallite size and lowering the specific surface area. It is shown that the H2O2 dissociates on Ce (III) surface sites to yield peroxide-like species. Such species played a key role in enhancing the discoloration of the dye under dark and UV-Vis conditions. By contrast, the sulfation treatment is unfavorable for the adsorption of H2O2. Sulfates interfere in the formation and the chemical stability of the surface peroxide species via pre-chelating the cerium surface centers, resulting in reducing the catalytic activity of catalysts, especially for CeO2

Comparative study on different coals from the Lorraine basin (France) by sorption isotherms, thermogravimetric analysis and breakthrough curves for CO2-ECBM recovery

International audienceThe enhanced coalbed methane recovery using CO 2 injection (CO 2 -ECBM) is widely proposed as a way of achieving the energy transition and reducing atmospheric CO 2 in areas such as the Lorrain basin in France, where heavy industry is responsible for huge CO 2 emissions and coal mines have been closed for more than a decade. This paper deals with the feasibility of extracting methane from the Lorraine basin using CO 2 -ECBM by comparing data from sorption isotherms, thermogravimetric analyses and breakthrough curves for two coal samples. One is bituminous (Box 18), from Folschviller (France) and is compared with another sub-bituminous (TH01) from La Houve (France), which is used as a reference because it was identified as a good candidate for CO 2 -ECBM in a previous research program. The quantities of adsorbed gases (CO 2 /CH 4 ) obtained by sorption isotherms, thermogravimetry and CO 2 breakthrough curves showed that Box 18 adsorbs more CO 2 and CH 4 than TH01 due to its higher porosity and good affinity for gases (CO 2 /CH 4 ). Tόth model fits the experimental CH 4 and CO 2 adsorption isotherms better, reflecting the fact that the adsorption surface of the coals studied is heterogeneous. Adsorption enthalpies obtained by calorimetry indicated physisorption for gas-coal interactions, with higher values for CO 2 than for CH 4 . Thermogravimetric analyses and breakthrough curves carried out at up to 50% relative humidity showed that the adsorption capacity of CO 2 decreases with increasing temperature and the presence of water, respectively. The compilation of these experimental data explained the adsorption process of the studied coals and revealed their advantages for CO 2 -ECBM