Titanium substituted manganese-ferrite as an oxygen carrier with permanent magnetic properties for chemical looping combustion of solid fuels

- Particles with Mn/(Mn + Fe) = 0.55-0.87 show good performance for CLC with solids.
- (MnxFe1−x)Ti0.15Oz oxygen carriers can show permanent magnetic properties.
- The reactivity with fuel gases (CH4, H2 and CO) increases with the Mn content.
- The magnetic permeability increases as the Mn content decreases.
- Material with Mn/(Mn + Fe) = 0.55 is preferred considering its reactivity and magnetism.

Mixed oxides of Mn-Fe have been identified as suitable materials for Chemical Looping Combustion (CLC) with solid fuels both via in-situ Gasification Chemical Looping Combustion (iG-CLC) and Chemical Looping with Oxygen Uncoupling (CLOU) processes. These materials show the property of react with gaseous fuels as well as release oxygen under given conditions, while cheap metals are used. In addition, these materials can show magnetic properties that can be used for an easy separation from ash in CLC with solid fuels. Thus, losses of oxygen carrier material in the ash drain stream would be reduced. Different cations have been proposed for improving the magnetic properties of manganese ferrites, including Ti4+. In this context, the present work accomplishes a screening of (MnxFe1−x)2O3 doped with 7 wt.% TiO2, with x ranging from 0 to 1. The influence of Mn:Fe ratio on their physical and chemical properties was evaluated. In general, particles with high crushing strength values (>4 N) were obtained, and magnetic characteristics were highlighted when x ⩽ 0.66. The oxygen uncoupling capability depended on the Mn:Fe ratio and the oxidation conditions, i.e. temperature and oxygen partial pressure. Broader oxidation conditions to take advantage of the oxygen uncoupling capability were found for materials with low Mn content. On contrary, the reactivity with fuel gases (CH4, H2 and CO) increased with the Mn content. Thus, oxygen carriers with Mn/(Mn + Fe) molar ratio in the 0.5-0.9 interval showed interesting properties at suitable temperatures for the iG-CLC and CLOU processes (i.e. 850-980 °C). The material with Mn/(Mn + Fe) = 0.55 was preferred considering a trade-off between reactivity and magnetic properties.

The production method of MnFe mixed oxide particles has been developed in order to obtain permanent magnetic properties during redox cycles in CLC, which can be used for separation purposes of oxygen carrier particles in the purge stream of ash.140