In situ gasification of a lignite coal and CO2 separation using chemical looping with a Cu-based oxygen carrier

Chemical looping combustion (CLC) has the inherent property of separating CO2 from flue gases. This paper is concerned with the application of chemical looping to the combustion of a solid fossil fuel (a lignite and its char) in a technique whereby the fuel is gasified in situ using CO2 in the presence of a batch of supported copper oxide (the "oxygen carrier") in a single reactor. As the metal oxide becomes depleted, the feed of fuel is discontinued, the inventory of fuel is reduced by further gasification and then the contents are re-oxidised by the admission of air to the reactor, to begin the cycle again. The choice of oxides is restricted because it requires an oxide which is exothermic during reduction to balance the endothermic gasification reactions. Copper has such oxides, but a key question is whether or not it can withstand temperatures at which gasification rates are significant (similar to 1173 K), particularly from the point of view of avoiding sintering and deactivation of the carrier in its reduced form. It was found that an impregnated carrier, made by impregnating a theta-alumina catalyst support (BET area 157 m(2)/g) with a saturated solution of copper and aluminium nitrates, acted as a durable carrier over 20 cycles of reduction and oxidation, using both Hambach lignite coal, and its char, and with air as the oxidising agent. During the course of the experiments, the BET surface area of the support fell from similar to 60 m(2)/g, just after preparation, to around 6 m(2)/g after 20 cycles. However, this fall did not appear to affect the overall capacity of the oxygen carrier to react with fuels and its effect on the kinetics of the reaction with CO did not influence the outcome of the experiments, since the overall performance of the looping scheme is dominated by the much slower kinetics of the gasification reaction. The apparent kinetics of the gasification are faster in the presence of the looping agent: this is because the bulk concentration of CO in the presence of the looping agent is lower, and partly because the destruction of CO in the vicinity of a gasifying particle enhances the rate of removal of CO by mass transfer (and increases the local concentration of CO2). There was little evidence to suggest a direct reaction between carbonaceous and carrier solids, other than via a gaseous intermediate. However, the observation of finite rates of conversion in a bed of active carrier, fluidised by nitrogen, is a scientific curiosity, which we have not been able to explain satisfactorily. At 1173 K, as used here, rates of gasification of Hambach lignite, and its char, are significant. The CuO in the carrier decomposes at 1173 K to produce gas-phase O-2 and Cu2O: both can react with CO produced by gasification, whilst the O-2 can react directly with the char. (C) 2009 Elsevier Ltd. All rights reserved.