Temperature variations in the oxygen carrier particles during their reduction and oxidation in a chemical-looping combustion system

A particle reaction model including mass and heat transfer has been developed to know the temperature variations produced inside the oxygen carrier particles during the cyclic reduction and oxidation reactions taking place in a chemical-looping combustion (CLC) system. The reactions of the different oxygen carriers based on Cu, Co, Fe, Mn, and Ni during the reduction with fuel gas (CH4, CO, and H2) and oxidation (O2) have been considered. In these systems, the oxidation reaction is always exothermic with subsequent heat release; however, the reduction reaction can be exothermic or endothermic depending on the metal oxide and the fuel gas. The heat generated inside the oxygen carriers during the exothermic reactions increases the particle temperature, and could affect the particle structure if the temperature increase is near to the melting point of the active materials. Several variables that affect the reaction rate and the heat transport process have been analyzed to know their effect on the internal particle temperature. For a given oxygen carrier and reaction, the maximum temperature of the particles depended mainly on the particle size, the reaction rate, and the external heat transfer resistance, being lower than the effect of the oxygen carrier porosity, type of inert material, and metal oxide content. The highest temperature variations were reached for the oxidation reactions, with the maximum corresponding to the Ni and Co oxygen carriers with values of ∼+90K for 1mm particles. The highest temperature increase observed during the reduction reactions corresponded to the reaction of CuO with CO, with values of ∼+40K for 1mm particles. For the rest of the reactions and metals, the variations in the particle temperature were below 10K for particle sizes below 1mm. Under the typical operating conditions that exist in a CLC system, with particle sizes lower than 0.3mm, 40wt% of metal oxide content, and overall conversion times lower than 30s, the increases of temperature with respect to the bulk conditions were lower than 15K for any reaction of any oxygen carrier. Moreover, the temperature profiles inside the particles were near flat in most of the practical conditions, and no local points with high temperatures were found. Thus, changes in the solid porous structure of the carrier due to sintering during oxidation in fluidized bed reactors are not expected working at typical temperatures of CLC systems (1000-1300K).