An investigation of catalyt preparation conditions and promoter loading (Sn) effects on activity and selectivity of Pt catalyists in citiral hydrogenation

Abstract

In this study, citral hydrogenation reaction in liquid phase over silica gel supported Pt and PtSn catalysts were studied. It was desired to hydrogenate carbonyl group (C.O) selectively to produce valuable unsaturated alcohols, namely nerol, geraniol and citronellol. Pt/SiO2 catalysts were prepared by impregnation method while PtSn/SiO2 catalysts were prepared by catalytic reduction (CR), co-impregnation (CI) and successive impregnation (SI) methods. Pt loading over silica gel support was 1 % (w/w). For bimetallic catalysts, the (Sn/Pt) loading ratios were varied as 0.3, 0.5 and 0.7. The effects of parameters investigated in the present study included catalyst activation temperature (350 °C, 450 °C), calcination temperature (400 °C, 500 °C), solvent type (ethanol, 2-pentanol), catalyst activation without calcination, washing of catalyst with 0.1 M NaOH solution, Pt precursor type (hexachloroplatinic acid, platinum II acetylacetonate (PAA)) and Sn loading ratio. For Pt/SiO2 catalysts, maximum citral conversion (89 %) was achieved at lower activation (350 °C) and calcination (500 °C) temperatures when PAA was used. Increasing the activation temperature to 450 °C decreased the citral conversion to 52 % but increased the selectivity to unsaturated alcohols (nerol and geraniol) (SNE+GE) from 8 % to 60 %. It was observed that the lower activation temperature provided higher citral conversion but lower selectivity to unsaturated alcohols. Washing of catalyst and using of 2-pentanol prevented the acetal formation. Catalyst activated without calcination step gave lower conversion (20 %) and SNE+GE of 30 %. For bimetallic catalyst (PtSn/SiO2), maximum citral conversion was observed as 91.1 % when catalyst was prepared by CR method and calcined at 500 °C. Higher citral conversion and selectivity to unsaturated alcohols were achieved at the higher calcination temperature and higher reduction temperature. CR method was the most appropriate preparation method for bimetallic catalysts compared to CI and SI. An optimum of activity (91.1 %) and selectivity (89.7 %) was found at a Sn/Pt ratio 0.5.