The Different Roles between Sodium and Potassium Ions in Ion Exchange of WO3/SiO2 Catalysts

WO3/SiO2 catalysts were modified by an ion exchange method with sodium hydroxide or potassium hydroxide solution. The performance of the modified catalysts was tested in the metathesis of ethylene and trans-2-butene to propylene. During ion exchange, sodium and potassium ions played different roles. Sodium modified catalysts revealed constant trans-2-butene conversion and propylene selectivity when the concentrations of sodium in the solution were varied. In contrast, potassium modified catalysts showed reduction of the conversion and increase of the selectivity. From these results, potassium hydroxide may affect the transformation of tungsten oxide active species, resulting in the decrease in conversion whereas sodium hydroxide did not. Moreover, the modification of catalysts by this method improved the catalyst stability by lowering the amount of coke deposited on the catalyst surface.

Kinetic Study of 1-Butene Isomerization over Hydrotalcite Catalyst

This work studied the isomerization of 1-butene over hydrotalcite catalyst. The experiments were conducted at various gas hourly space velocity (GHSV), reaction temperature and feed concentration. No catalyst deactivation was observed over the reaction time of 16 hours. Two major reaction products were trans-2- butene and cis-2-butene. The reaction temperature played an important role on the reaction selectivity. At high operating temperatures, the selectivity of trans-2-butene was higher than the selectivity of cis-2-butene while it was opposite at lower reaction temperature. In the range of operating condition, the maximum conversion of 1-butene was found at 74% when T = 673 K and GHSV = 4 m3/h/kg-cat with trans- and cis-2-butene selectivities of 54% and 46%, respectively. Finally, the kinetic parameters of the reaction were determined.

Effect of N2 Pretreatment on the Properties of Tungsten-Based Catalysts in Metathesis of Ethylene and 2-Butene

The effect of N2 pretreatment on the catalytic activity of tungsten-based catalysts was investigated in the metathesis of ethylene and trans-2-butene at 450oC and atmospheric pressure. The presence of tungsten active species was confirmed by UV-Vis and Raman spectroscopy. Compared to the WO3-based catalysts treated in air, higher amount of WO4 2-tetrahedral species and lower amount of WO3 crystalline species were observed on the N2-treated ones. These contribute to the higher conversion of 2-butene and propylene selectivity during 10 h time-on-stream. Moreover, N2 treatment led to lower amount of coke formation as revealed by TPO of the spent catalysts.

Propylene Self-Metathesis to Ethylene and Butene over WOx/SiO2, Effect of Nano-Sized Extra Supports (SiO2 and TiO2)

Propylene self-metathesis to ethylene and butene was studied over WOx/SiO2 catalysts at 450oC and atmospheric pressure. The WOx/SiO2 catalysts were prepared by incipient wetness impregnation of ammonium metatungstate aqueous solution. It was found that, adding nano-sized extra supports (SiO2 and TiO2) by physical mixing with the WOx/SiO2 enhanced propylene conversion. The UV-Vis and FT-Raman results revealed that WOx could migrate from the original silica support to the extra support, leading to a better dispersion of WOx. The ICP-OES results also indicate that WOx existed on the extra support. Coke formation was investigated on the catalysts after 10 h time-on-stream by TPO. However, adding nano-sized extra supports led to higher coke formation which may be related to acidity as characterized by NH3-TPD.

Propane Dehydrogenation with Better Stability by a Modified Pt-Based Catalyst

The effect of transition metal doping on Pt/Al2O3 catalyst used in propane dehydrogenation reaction at 500°C was studied. The preparation methods investigated were sequential impregnation (Pt followed by the 2nd metal or the 2nd metal followed by Pt) and co-impregnation. The metal contents of these catalysts were fixed as the weight ratio of Pt per the 2nd metal of around 0.075. These catalysts were characterized by N2-physisorption, TPR, COchemisorption and NH3-TPD. It was found that the impregnated 2nd metal had an effect upon reducibility of Pt due to its interaction with transition metal-containing structure. This was in agreement with the CO-chemisorption result that the presence of Pt metal, which is a result from Pt species reduction, was decreased. The total acidity of bimetallic catalysts is decreased but the strong acidity is slightly increased. It was found that the stability of bimetallic catalysts prepared by co-impregnation and sequential impregnation where the 2nd metal was impregnated before Pt were better than that of monometallic catalyst (undoped Pt one) due to the forming of Pt sites located on the transition metal-oxide modified surface. Among all preparation methods, the sequential impregnation method- having Pt impregnated before the 2nd metal gave the worst stability because this catalyst lacked the modified Pt sites and some fraction of Pt sites was covered by the 2nd metal.