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Catalyst characterization
(2009)
Influence of the of dealumination and porosity on the acid sites of natural zeolite clinoptilolite
(2016)
Heavy feedstock from crude and bio oil is a widely available and renewable resource for production of fuel and starting materials for other organic valuables by cracking or hydrocracking. Catalytic processing of heavy feedstock can meet the increased demand of energy up to a great extent. It requires the application of acidic catalysts like zeolites. However, the used synthetic catalysts are difficult to recover and reuse and are mostly spent.
The use of natural zeolite as spent catalysts may open new perspectives in the chemical use of heavy feed feedstock by chemical conversion. Natural zeolites are not expensive, widely available and environment friendly. Clinoptilolite is the most abundant natural zeolite. Clinoptilolite has a crystalline structure with a defined micropore system of medium size showing unique ion exchange and sorption properties. However, it is catalytically active only in the H-form. Also certain porosity is required for improvement of the accessibility of active sites.
This paper deals with the tuning of acid properties and of the mesoporosity of the clinoptilolite by variation of the Si/Al framework ratio, extra-framework aluminum and modification of the porosity by specific acid and water vapor treatment. The preparation of hierarchical pore structures containing interconnected micro-meso-macropores is an important factor influencing the catalytic performance.
The obtained materials have been characterized by XRD, TEM, FTIR, Raman, TG/DSC. The chemical composition has been determined by ICP-AES. The porosity have been investigated by nitrogen adsorption desorption measurements. The acidity has been measured by Ammonia-TPD. The extent of dealumination, stability of the clinoptilolite against acid treatment and the change in the nature of acid sites and their local structure has been studied by solid state 29Si and 27Al MAS NMR spectroscopy in detail. The catalytic activity has been investigated in the acetalization of benzaldehyde with 1,3-butanediol. The impact of the porosity, change of the Si/Al ratio as well as present Al species on catalytic properties will be discussed.
The catalytic potential of tin(II)acetate, tin(IV)acetate, dibutyltin-bis-acetate and dioctyl tin-bis-acetate was compared based on polymerizations of L-lactide conducted in bulk at 160 or 130°C. With SnAc2 low-Lac/Cat ratios (15/1–50/1) were studied and linear chains having one acetate and one carboxyl end group almost free of cyclics were obtained. Higher monomer/catalyst ratios and lower temperatures favored formation of cycles that reached weight average molecular weights (Mw's) between 100,000 and 2,500,000. SnAc4 yielded mixtures of cycles and linear species under all reaction conditions. Dibutyltin- and dioctyl tin bis-acetate yielded cyclic polylactides under most reaction conditions with Mw's in the range of 20,000–80,000. Ring-opening polymerizations performed with ε-caprolactone showed similar trends, but the formation of COOH-terminated linear chains was significantly more favored compared to analogous experiments with lactide. The reactivity of the acetate catalysts decreased in the following order: SnAc2> SnAc4>Bu2SnAc2~Oct2SnAc2