Partial oxidation of propene using solid electrolyte membrane reactors
thesisposted on 01.11.2010, 11:58 by Abdullah Abdulaziz Al-Musa
This study investigates the efficiency of a calcia stabilised zirconia (CaSZ) solid electrolyte as an oxygen ion conductor. The study also examines the behaviour of the oxygen species conducted by the solid electrolyte compared to species provided in the gas phase for partial oxidation of hydrocarbons. In this work, an electrochemical cell of the form Air, AgHCaSZ//Ag, Carrier gas was used to investigate the electrochemical efficiency and stability of the solid electrolyte CaSZ conducting of oxygen ions under atmospheric pressure conditions at 500 degrees C by applying a range of electrical potentials from I to 16 volts across the electrochemical cell. Due to the applied potential oxygen anions are transferred across the solid electrolyte from the cathode side of the cell to the anode side. It was found that the employed electrolyte is approximately a 100% purely ionic conductor of oxygen ions in the range of electrical voltage applied from I to 10 volts. Above that range the cell started to degrade and loose its ionic efficiency. It was possible to generate gas mixtures containing trace quantities of oxygen. The viscosity of these gas mixtures as a function of oxygen concentration was determined using an established flow perturbation technique (Flux Response Technology). Partial oxidation of propene was used to investigate the difference between the oxygen species produced electrochemically via electrical potential application across the electrochemical cell Air, AgHCaSZ//Ag, Propene, Ar and oxygen provided in the gaseous state co-fed with propene over silver electrode under atmospheric pressure and 450 degrees C and 500 degrees C. It was found that the method of electrochemical provision of oxygen caused the silver catalyst to be more selective to 1,5-hexadeine, whereas the gaseous oxygen provision produced acrolein as the major product. Carbon dioxide formation was not affected by the method of oxygen provision. The Ag electrode was compared to an Au-rich Ag alloy electrode for propene partial oxidation using electrochemical provision. It was found that 1,5-hexadiene was the major product over both electrodes, but the Au-rich alloy was more selective for acrolein than the Ag electrode. This might be due to the gold serving as a separator between Ag particles which hinder the back-spill over of oxygen and allow desorption of molecular oxygen in the gas phase, which then re-adsorb molecularly on silver sites producing acrolein. The effect of the sequence of the method of oxygen provision on the partial oxidation of propene was tested using the electrochemical cell Y-BiMoHAg//CaSZ//Ag at 450 degrees C and atmospheric pressure. A sharp decrease in acrolein selectivity was found when oxygen was provided in the gas phase after treatment with electrochemical oxygen, while no significant effect was noticed when the electrochemical oxygen was used after treatment with gaseous oxygen. This large decrease in acrolein selectivity might be attributed to the severe reduction of the catalyst, which is probably caused by high electrical potential application. A temperature increase from 450 to 500 degrees C seemed to suppress the formation of acrolein for both methods of oxygen provision and enhance the 1,5-hexadiene formation.
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