Thermodynamics of CeO₂ thermochemical fuel production

In this work the thermodynamics of thermochemical fuel production using a CeO₂ redox cycle are studied. The need to reduce the oxygen partial pressure in order to improve efficiency is investigated, with both sweep gas and vacuum pumping considered as methods of achieving this. At ambient pressure the cycles can be maximized with respect to the temperature swing, the minimum oxygen partial pressure, and the extent of the oxidation reaction. For reduction at 1500 °C the maximum efficiency was found to be 4.5%, which is significantly lower than the values found in previous studies. In addition isothermal operation had very low efficiency (less than 2%) under all of the conditions considered. If the system is operated at lower than ambient pressure, the pumping efficiency will depend on the pressure. From an investigation of commercially available pumps the pressure dependence was given an analytical expression. The results showed the cycles have an optimal operating pressure and that using sweep gas, as well as pumping, only reduced the overall efficiency. The efficiency was maximized with respect to the temperature swing, the reduction pressure, and the extent of oxidation, giving a peak efficiency of 7.5% for a reduction temperature of 1500 °C. Reducing the pressure during reduction could also be beneficial due to improved reaction kinetics at lower pressure and an increased yield due to lower oxygen partial pressures. Recovering heat from both the high temperature ceria and the oxidation reaction, and using it as process heat, was also considered. With 60% of this heat being recovered, the peak efficiency for the 1500 °C pumped cycle increased to 11%. Finally the practicality of the cycles, in terms of the quantity of ceria required to maintain continuous operation, are considered, and some suggestions for improving the cycle are given.