Tin promoted palladium catalysts for nitrate removal from drinking water

Abstract

Hydrogenation of nitrate to nitrogen using Pd/Al2O3 catalysts promoted by a second metal offers a promising process for nitrate removal in drinking water treatment. This study was aimed to elucidate the nature and function of promoting tin species in PdSn/Al2O3 catalysts obtained in different preparation routes. On one hand, a parent Pd/Al2O3 catalyst was doped via impregnation with aqueous solutions of SnCl2 of different concentrations. On the other hand, the palladium surface of the same parent Pd/Al2O3 catalyst was modified via controlled surface reaction (CSR) with hexane solutions of Sn(C4H9)4. The structure of the different PdSn/Al2O3 catalysts was investigated by 119Sn-Mössbauer spectroscopy and by means of various chemisorption techniques (static and pulse chemisorption of H2 or CO, measurement of the differential heat of CO chemisorption, FTIR spectroscopy of CO chemisorption). Catalytic properties were studied in batch experiments under atmospheric pressure. Promoting of the Pd/Al2O3 catalyst by CSR resulted in catalysts with a significantly higher activity compared to PdSn/Al2O3 catalysts obtained via incipient wetness method. Obviously, Sn(II)-species being present in the latter in high portion inhibit the nitrate reduction on bimetallic PdSn ensembles.CO chemisorption reflected a ‘palladium site blocking’ by tin species in both kinds of catalysts and indirectly indicated the generation of palladium–tin ensembles. In case of the CSR preparation the palladium is alloyed by metallic tin.The palladium surface is diluted by tin atoms, i.e. bimetallic PdSnx ensembles are generated which are able to adsorb and activate nitrate ions. There is an optimum of tin loading, i.e. the activity decreases and the undesired ammonium production in a site reaction increases when the surface becomes too tin rich. Sn(II) species, being preferentially present in catalysts obtained by SnCl2 impregnation also strongly modify the chemisorption properties of the palladium surface, but obviously these species inhibit the nitrate reduction on the bimetallic PdSn ensembles, which are also present in these catalysts.