Chemical-looping with oxygen uncoupling (CLOU) is a novel method to burn fuels in gas-phase oxygen without the need for an energy-intensive air separation unit. The carbon dioxide from the combustion is obtained separated from the nitrogen in the combustion air. The technique is based on chemical-looping combustion (CLC) but does not involve any direct reaction between the fuel and oxygen carrier. Instead, the CLOU process uses three steps in two reactors, one air reactor where a metal oxide captures oxygen from the combustion air (step 1), and a fuel reactor where the metal oxide releases oxygen (step 2) and where this oxygen reacts with a fuel (step 3). This means that the fuel burns directly with gaseous O 2 . In this work CaMn 0.875 Ti 0.125 O 3 will be used as oxygen carrier. Experiments were first performed with a thermogravimetric analyzer (TGA). Here the sintering temperature, and thereby the porosity, for the produced granulates was varied and optimized. The substitution of Ti on Mn sites in CaMnO 3 was chosen since this material showed no coke formation even in dry CH 4 at high temperatures. This was followed by fluidized bed experiments with both methane and petroleum coke as fuel. The CaMn 0.875 Ti 0.125 O 3 particles showed promising results both for the tests performed in TGA and in fluidized bed experiments. CaMn 0.875 Ti 0.125 O 3 released O 2 both in inert and reducing atmosphere, making it a possible candidate as oxygen carrier in CLOU.

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The present review focuses on links between structure, energetics and ion transport in oxygen-deficient perovskite oxides, ABO(3-delta). The perfect long-range order, convenient for interpretations of the structure and properties of ordered materials, is evidently not present in disordered materials and highly defective perovskite oxides are spatially inhomogeneous on an intermediate length scale. Although this makes a fundamental description of these and other disordered materials very difficult, it is becoming increasingly clear that this complexity is often essential for the functional properties. In the present review we advocate a potential energy barrier description of the disordered state in which the possible local (or inherent) structures are seen to correspond to separate local minima on the potential energy surface. We interpret the average structure observed experimentally at any temperature as a time and spatial average of the different local structures which are energetically accessible. The local structure is largely affected by preferences for certain polyhedron coordinations and the oxidation state stability of the transition metals, and the strong long-range electrostatic interactions present in non-stoichiometric oxides imply that only a small fraction of the local energy minima on the potential energy surface are accessible at most temperatures. We will show that models neglecting the spatial inhomogeneity and thus the local structure serve as useful empirical tools for particular purposes, e.g. for understanding the main features of the complex redox properties that are so crucial for many applications of these oxides. The short-range order is on the other hand central for understanding ionic transport. Oxide ion transport involves the transformation of one energetically accessible local structure into another. Thus, strongly correlated transport mechanisms are expected; in addition to the movement of the oxygen ions giving rise to the transport, other ions are involved and even the A and B atoms move appreciably in a cooperative fashion along the transition path. Such strongly correlated or collective ionic migration mechanisms should be considered for fast oxide ion conductors in general and in particular for systems forming superstructures at low temperatures. Structural criteria for fast ion conduction are discussed. A high density of low-lying local energy minima is certainly a prerequisite and for perovskite-related A(2)B(2)O(5) oxides, those containing B atoms that have energetic preference for tetrahedral coordination geometry are especially promising.

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