A COMPARATIVE STUDY OF MICROWAVE AND BARRIER DISCHARGE PLASMA FOR THE REGENERATION OF SPENT ZEOLITE CATALYSTS

Due to their acid characteristics and pore structure, which can induce high product selectivity; zeolite catalysts are used extensively in industry to catalyse reactions involving hydrocarbons. However, these catalysts can suffer from deactivation due to cracking reactions that result in the deposition of carbon leading to poisoning of the acid sites and blocking of the pores [1]. Depending upon the reaction and the particular catalyst involved this deactivation may take place over several months or even years but in some cases occurs in minutes. Therefore, zeolite catalysts are frequently reactivated / regenerated. This generally involves a thermal treatment involving air which results in oxidation of the carbon [2]. However, the oxidation of carbon is highly exothermic, and if not carefully controlled, results in the generation of exceedingly high localized temperatures which can destroy the zeolite structure and result in subsequent loss of catalyst activity. More conservative thermal treatments can result in incomplete regeneration and again a catalyst displaying inferior activity. This paper explores the use of non-thermal plasma which had been either generated using microwaves or via a barrier discharge to regenerate spent zeolite catalysts. The catalyst, H-mordenite, was tested for the disproportionation of toluene (Figure 1) using conventional heating. The spent catalyst was then regenerated using a plasma or conventional thermal treatment before having its activity re-evaluated for the toluene disproportionation reaction as previous. Fig. 1. Reaction Scheme for Toluene Disproportionation. Interestingly, not only is plasma regeneration highly effective but also catalysts can be regenerated in greatly reduced times. There is an additional advantage in that plasma regeneration can impart physical properties that result in a zeolite that is resistant to further deactivation. However, the results are highly dependent upon the experimental conditions involved for plasma regeneration. References Wu J, Leu L., Appl. Catal., 1983; 7:283-294. M. Guisnet and P. Magnoux, Deactivation of Zeolites by Coking. Prevention of Deactivation and Regeneration. In: Zeolite Microporous Solids: Synthesis, Structure, and Reactivity. E.G. Derouane, F Lemos, C. Naccache, F. Ramôa Ribeiro, Eds. Pages 437-456. Springer 1992.

Behavior of Molybdenum–Vanadium Mixed Oxides in Selective Oxidation and Disproportionation of Toluene

This study deals with the behavior of molybdenum–vanadium (Mo/V) mixed oxides catalysts in both disproportionation and selective oxidation of toluene. Samples containing different Mo/V ratios were prepared by a modified method using tetradecyltrimethylammonium bromide and acetic acid. The catalysts were characterized using several techniques: nitrogen adsorption–desorption isotherms, X-Ray diffraction (XRD), ammonia temperature-programmed desorption (TPD-NH3), temperature-programmed reduction by hydrogen (H2-TPR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, Fourier-transform infrared-spectroscopy (FTIR) and ultraviolet-visible spectroscopies (UV–VIS). The XRD results evidenced the presence of orthorhombic α-MoO3 and V2O5 phases, as well as monoclinic β-MoO3 and V2MoO8 phases, their abundance depending on the Mo to V ratio, while the TPD-NH3 emphasized that, the total amount of the acid sites diminished with the increase of the Mo loading. The TPR investigations indicated that the samples with higher Mo/V ratio possess a higher reducibility. The main findings of this study led to the conclusion that the presence of strong acid sites afforded a high conversion in toluene disproportionation (Mo/V = 1), while a higher reducibility is a prerequisite to accomplishing high conversion in toluene oxidation (Mo/V = 2). The catalyst with Mo/V = 1 acquires the best yield to xylenes from the toluene disproportionation reaction, while the catalyst with Mo/V = 0.33 presents the highest yield to benzaldehyde.