Fenton chemistry-based detemplation of an industrially relevant microcrystalline beta zeolite. Optimization and scaling-up studies

A mild template removal of microcrystalline beta zeolite, based on Fenton chemistry, was optimized. Fenton detemplation was studied in terms of applicability conditions window, reaction rate and scale up. TGA and CHN elemental analysis were used to evaluate the detemplation effectiveness, while ICP, XRD, LPHR-Ar physisorption, and 27Al MAS NMR were applied to characterize the structure and texture of the resulting materials. The material properties were compared to calcination. By understanding the interplay of relevant parameters of the Fenton chemistry, the process can be optimized in order to make it industrially attractive for scale-up. The H2O2 utilization can be minimized down to 15 mL H2O2/g (88 °C, 30 ppm Fe), implying a high solid concentration and low consumption of H2O2. When Fe concentration must be minimized, values as low as 5 ppm Fe can be applied (88 °C, 30 mL H2O2/g), to achieve full detemplation. The reaction time to completeness can be reduced to 5 h when combining a Fe-oxalate catalyst with UV radiation. The protocol was scaled up to 100 times larger its original recipe. In terms of the material's properties, the scaled material is structurally comparable to the calcined counterpart (comparable Si/Al and XRD patterns), while it displays benefits in terms of texture and Al-coordination, the latter with full preservation of the tetrahedral Al

Tail gas catalyzed N2O decomposition over Fe-beta zeolite. On the promoting role of framework connected AlO6 sites in the vicinity of Fe by controlled dealumination during exchange

A novel route to prepare highly active and stable N2O decomposition catalysts is presented, based on Fe-exchanged beta zeolite. The procedure consists of liquid phase Fe(III) exchange at low pH. By varying the pH systematically from 3.5 to 0, using nitric acid during each Fe(III)-exchange procedure, the degree of dealumination was controlled, verified by ICP and NMR. Dealumination changes the presence of neighbouring octahedral Al sites of the Fe sites, improving the performance for this reaction. The so-obtained catalysts exhibit a remarkable enhancement in activity, for an optimal pH of 1. Further optimization by increasing the Fe content is possible. The optimal formulation showed good conversion levels, comparable to a benchmark Fe-ferrierite catalyst. The catalyst stability under tail gas conditions containing NO, O2 and H2O was excellent, without any appreciable activity decay during 70 h time on stream. Based on characterisation and data analysis from ICP, single pulse excitation NMR, MQ MAS NMR, N2 physisorption, TPR(H2) analysis and apparent activation energies, the improved catalytic performance is attributed to an increased concentration of active sites. Temperature programmed reduction experiments reveal significant changes in the Fe(III) reducibility pattern with the presence of two reduction peaks; tentatively attributed to the interaction of the Fe-oxo species with electron withdrawing extraframework AlO6 species, causing a delayed reduction. A low-temperature peak is attributed to Fe-species exchanged on zeolitic AlO4 sites, which are partially charged by the presence of the neighbouring extraframework AlO6 sites. Improved mass transport phenomena due to acid leaching is ruled out. The increased activity is rationalized by an active site model, whose concentration increases by selectively washing out the distorted extraframework AlO6 species under acidic (optimal) conditions, liberating active Fe species.