RESUMO
A sequential adsorption-plasma oxidation system was used to remove toluene from simulated dry air using γ-Al2O3, HZSM-5, a mixture of the two materials or their supported Mn-Ag catalyst as adsorbents under atmospheric pressure and room temperature. After 120min of plasma oxidation, γ-Al2O3 had a better carbon balance (â¼75%) than HZSM-5, but the CO2 yield of γ-Al2O3 was only â¼50%; and there was some desorption of toluene when γ-Al2O3 was used. When a mixture of HZSM-5 and γ-Al2O3 with a mass ratio of 1/2 was used, the carbon balance was up to 90% and 82% of this was CO2. The adsorption performance and electric discharge characteristics of the mixed supports were tested in order to rationalize this high COx yield. After seven cycles of sequential adsorption-plasma oxidation, support and Mn-Ag catalyst deactivation occurred. The support and catalyst were characterized before and after deactivation by SEM, a BET method, XRD, XPS and GC-MS in order to probe the mechanism of their deactivation. 97.6% of the deactivated supports and 76% of the deactivated catalysts could be recovered by O2 temperature-programmed oxidation.
RESUMO
A series of Ag-Mn/γ-Al2O3 were prepared under different Ag/Mn impregnation sequence and tested in the sequential adsorption-plasma catalytic removal of toluene. When Mn was impregnated first, the resulting catalyst, Ag-Mn(F)/γ-Al2O3, had longer breakthrough time, gave less emission of toluene, had higher CO2 selectivity, and had better carbon balance and COx yield compared to catalysts prepared via other impregnation sequences. After 120 min of NTP treatment, the carbon balance of Ag-Mn(F)/γ-Al2O3 was 91%, with 87% as COx contributions. A Brunauer-Emmett-Teller (BET) analysis and X-ray photoelectron spectroscopy (XPS) results show that, the impregnation sequence impacts the BET surface area and the ratio and existing state of Ag on the surface of the catalysts. The longer breakthrough time when using Ag-Mn(F)/γ-Al2O3 as catalyst is attributed to the large amount of Ag(+) on the surface. Ag(+) is a new active site for toluene adsorption. When Ag was impregnated first (Ag(F)-Mn/γ-Al2O3) or Ag and Mn co-impregnated (Ag-Mn-C/γ-Al2O3), the predominant specie was Ag(+). Both Ag(0) and Ag(+) species were detected on Ag-Mn(F)/γ-Al2O3. Ag(0) cooperation with MnOx may promote the migration of surface active oxygen. This would facilitate the oxidation of adsorbed toluene with CC bond already weakened by Ag(+) and would result in higher CO2 selectivity and better carbon balance as seen in the Ag-Mn(F)/γ-Al2O3 system.