No abstract

The aim of the present study is to investigate the influence of the support and composition of the active bimetallic phase on both the physicochemical and catalytic properties of catalysts for use in glycerol hydrogenolysis reaction. Two series of catalysts with different amounts of copper oxide and/or silver supported on Al 2 O 3 or TiO 2 oxides were prepared. To determine the physicochemical properties of the catalysts, the following techniques were used: Brunauer-Emmett-Teller, reactive N 2 O adsorption, X-ray diffraction, and temperature-programmed reduction TPR-H 2 . Physicochemical characterization revealed that addition of silver modifies the redox properties of the catalysts containing copper oxide and influences their specific surface area. It was found that the type of carrier determines the catalytic activity and selectivities for desired products, strongly influencing their distribution. The Al 2 O 3 -supported catalysts were much more selective for 1,2-propanediol, whereas 1-propanol was the main reaction product for the titania-supported catalysts. The best catalysts (6Cu/Al and 2Cu/Ti) achieved 38 % glycerol conversion with 71 % selectivity for 1,2-propanediol and 44 % conversion with 62 % selectivity for 1-propanol, respectively.

Dimethyl ether synthesis was performed from syngas over hybrid catalysts comprising a Cu/Zn/Al as metallic function and K10-montorillonite (K10) as acidic function. The acidic properties of K10 were tuned by deposition of one monolayer of tungstophosphoric acid (H 3 PW 12 O 40 Á23.5 H 2 O, TPA). The changes in acidity were determined based on pyridine adsorption with FTIR detection. Due to the fact that TPA does not possess Lewis acid sites, deposition of TPA on the K10 surface (TPA-K10) resulted only in increase in Brønsted acid site concentrations and in increase in their strength in comparison with unmodified K10. Since both modified and unmodified K10 exhibited the same Lewis acid site concentrations and their strength, it was possible to investigate solely the impact of Brønsted acidity differences of acidic functions on the hybrid catalysts activity in syngas-to-DME process (STD). Additionally, the effect of TPA supported on K10 was investigated in methanol dehydration to DME under atmospheric pressure. In order to prepare metallic functions which differed in activity in CO hydrogenation to methanol (first step of STD), two synthesis methods were used: co-precipitation method (metallic function CZA) and decomposition of citrate complexes of metals (metallic function CZA citric). The hybrid catalysts (CZA/K10, CZA/ TPA-K10, CZA citric /K10, CZA citric /TPA-K10) for STD were prepared by physical mixing of metallic and acidic function in volume ratio equal to 2:1. The impact of K10 substitution with TPA-10 in hybrid catalysts depended on whether STD process was controlled by methanol synthesis step or dehydration methanol step. When K10 possessed adequate acidity to dehydrate methanol formed on metallic function (i.e. CZA citric), it substitution with TPA-K10 in hybrid catalyst did not improve DME yield. On the other hand, when metallic function (i.e. CZA) exhibited higher methanol activity and methanol dehydration rate was limited by insufficient acidity of K10 then usage of TPA-K10 of higher acidity in hybrid catalyst was found to increase significantly DME yield without light parrafins formation.

No abstract

No abstract