Chemical-looping combustion – a thermodynamic study

The poor performance of internal combustion (IC) engines can be attributed to the departure from equilibrium in the combustion process. This departure is expressed numerically, as the difference between the working fluid’s temperature and an ideal ‘combustion temperature’, calculated using a simple expression. It is shown that for combustion of hydrocarbons to be performed reversibly in a single reaction, impractically high working fluid temperatures are required — typically at least 3500 K. Chemical-looping combustion (CLC) is an alternative to traditional, single-stage combustion that performs the oxidation of fuels using two reactions, in separate vessels: the oxidizer and reducer. An additional species circulates between the oxidizer and reducer carrying oxygen atoms. Careful selection of this oxygen carrier can reduce the equilibrium temperature of the two redox reactions to below current metallurgical limits. Consequently, using CLC it is theoretically possible to approach a reversible IC engine without resorting to impractical temperatures. CLC also lends itself to carbon capture, as at no point is N2 from the air allowed to mix with the CO2 produced in the reduction process and therefore a post-combustion scrubbing plant is not required. Two thermodynamic criteria for selecting the oxygen carrier are established: the equilibrium temperature of both redox reactions should lie below present metallurgical limits. Equally, both reactions must be sufficiently hot to ensure that their reaction velocity is high. The key parameter determining the two reaction temperatures is the change in standard state entropy for each reaction. An analysis is conducted for an irreversible CLC system using two Rankine cycles to produce shaft work, giving an overall efficiency of 86.5 per cent. The analysis allows for irreversibilites in turbine, boiler, and condensers, but assumes reactions take place at equilibrium. However, using Rankine cycles in a CLC system is considered impractical because of the need for high-temperature, indirect heat exchange. An alternative arrangement, avoiding indirect heat exchange, is discussed briefly.