Estudo da influência da temperatura na desativação de catalisadores automotivos comerciais

• Autor(a) principal: Fernandes, Daniela Meyer
• Data de Publicação: 2007
• Tipo de documento: Dissertação
• Idioma: por
• Título da fonte: Biblioteca Digital de Teses e Dissertações da UERJ
• Texto Completo: http://www.bdtd.uerj.br/handle/1/11956
• topic: ssss; Combustíveis diesel; Oxidação; Sedimentos e depósitos; CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA

The influence of the temperature on the deactivation of two commercial automotive catalysts from different suppliers was studied. Textural and physico-chemical caracterization techniques were employed, such as XRF, AAS, N2 fisisorption, TG-DTA, XRD, TPR, H2 chemisorption and SEM-EDX. The catalysts were evaluated in terms of CO and propane oxidation with a stoichiometric gas mixture similar to the exaust gas. The Pt/Rh catalyst was nominated G and the Pd/Rh one, V. They were aged at 900ºC in stoichiometric conditions, and at 1200ºC in air, for determined periods of time. Concerning aging at 900ºC, even though the caracterization analysis showed better results for catalyst G, the comparison with fresh catalysts indicated that this catalyst suffered a larger deactivation than catalyst V. The aging in oxidizing conditions at 1200ºC was quite harmful to the performance of both catalysts. The diffractograms of the catalysts aged in these conditions showed important fenomena like alumina phase transitions and signs of formation of new mixed oxide phases. TPR profiles presented great decay on reducibility for both catalysts after this aging. SEM-EDS micrographs presented largely sintered structures and several spots of palladium agglomerates on catalyst V. This catalyst also presented particles of unusual texture. Besides, both catalysts presented signs of loss of catalytic material in the samples aged for 72h at 1200ºC.Concerning catalytic activity results, catalyst G presented worse performance than catalyst V. The aging in oxidizing atmosphere may justify this behavior because this procedure leads to the formation of platinum oxides, which are less active than metallic platinum for these reactions. Besides, this catalyst presented a much lower platinum content than those reported in the literature for commercial automotive catalysts. On the other hand, for palladium catalysts, oxidizing aging leads to the formation of PdO, which is more active than metallic Pd.Another relevant point about catalytic evaluation was the fact that fresh catalyst G presented a poor activity, especially for propane oxidation, which tended to enhance with thermal aging. It was suggested that this catalyst would need a thermal activation. It seems that catalyst V was submitted to such activation during its fabrication. This hypothesis is based on the signs of a slight thermal degradation found in the fresh catalyst, as showed by N2 Fisisorption, XRD, TG-DTA, TPR and SEM-EDX.Although it was not possible to determine metal dispersion though H2 chemisorption results, they appeared to correlate well with catalytic activity, expressed in T50 or T20. It was observed that catalytic activity was improved when the quantity of desorbed H2 was enhanced.Finally, it can be concluded that thermal aging is harmful to commercial catalysts peformance, principally in drastic situations like oxidizing aging at 1200ºC