Development and Evaluation of Materials for Thermochemical Heat Storage Based on the CaO/CaCO_3 Reaction Couple

摘要

The current work relates to the development of synthetic calcium oxide (CaO) based compositions as candidate materials for energy storage under a cyclic carbonation/decarbonation reaction scheme. Although under such a cyclic scheme the energy density of natural lime based CaO is high (～ 3MJ/kg), the particular materials suffer from notable cycle-to-cycle deactivation. To this direction, pure CaO and CaO/Al_2O_3 composites have been prepared and preliminarily evaluated under the suggested cyclic carbonation/decarbonation scheme in the temperature range of 600-800°C. For the composite materials, Ca/Al molar ratios were in the range between 95/5 and 52/48 and upon calcination the formation of mixed Ca/Al phases was verified. The preliminary evaluation of materials studied was conducted under 3 carbonation/decarbonation cycles and the loss of activity for the case of natural CaO was obvious. Synthetic materials with superior stability/capture c.f. natural CaO were further subjected to multi-cyclic carbonation/decarbonation, via which the positive effect of alumina addition was made evident. Selected compositions exhibited adequately high CO_2 capture capacity and stable performance during multi-cyclic operation. Moreover, this study contains preliminary experiments referring to proof-of-principle validation of a concept based on the utilization of a CaO-based honeycomb reactor/heat exchanger preliminary design. In particular, cordierite monolithic structures were coated with natural CaO and in total 11 cycles were conducted. Upon operation, clear signs of heat dissipation by the imposed flow in the duration of the exothermic reaction step were identified.