Steam hydration is reported to be an effective method for reactivating spent sorbents in calcium looping applications; however, uncertainties remain regarding the optimal method of returning the hydrated sorbent to the CO 2 capture loop. Carbonation conversions were found to be higher when Ca(OH) 2 was directly carbonated at high temperatures compared to conversions reached when Ca(OH) 2 was dehydrated prior to carbonation. This observation can lead to improved hydration based reactivation techniques for calcium looping applications. Upon heating in CO 2 , calcium hydroxide remained stable at temperatures >450 °C and the extent of carbonation was controlled by temperature only. The carbonation mechanism of Ca(OH) 2 at high temperatures appears to be more complex than the expected simple mechanism comprising the dehydration reaction of Ca(OH) 2 and the subsequent carbonation of the resulting CaO. An alternate mechanism was proposed, involving the formation of liquid like layers of water on the surface of Ca(OH) 2 .

Steam hydration of lime is an effective method for restoring CO2 capture activity but gives rise to high particle attrition rates in a fluid bed reactor. This paper describes the phenomenon of Ca(OH)2 superheating, also referred to as superheated dehydration (SD). The potential of an attrition-free lime reactivation process using this phenomenon is also investigated. Attrition rates of the sorbent are measured when a reactivation step using steam hydration is implemented every three carbonation/calcination cycles. It has been shown that the presence of CO2 during the dehydration step reduces attrition during subsequent cycles. Experiments performed in a small fluid bed reactor show that the presence of 40−100% CO2 during the dehydration step increases the initiation temperature of the decomposition of Ca(OH)2 from 445 to 618 °C. The thermodynamic equilibrium water vapor pressure for the dehydration reaction at 618 °C is 516 kPa, whereas no water vapor was detected in the reactor during the dehydration step before the temperature reached 618 °C. Under these circumstances it is proposed that the Ca(OH)2 is in a nonequilibrium “superheated state”. A CO2 capture cycling experiment, with a reactivation step every three carbonation/calcination cycles, maintained an average activity of 60%, creating only 3.25% of fines < 150 μm after 28 carbonations. The reactivation step consisted of hydrating the sorbent at a temperature of 270 °C and dehydrating it in 100% CO2 with a 23 min hold at 520 °C. It is proposed that the SD phenomenon may be a key step in the development of an industrially feasible method of lime reactivation for use in CO2 capture and in thermal energy storage applications.

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Samples of natural limestone and commercial calcium carbonate were subjected to successive calcination and carbonation reactions in a TGA and to repeated activity restoration by steam hydration. Steam hydration of spent lime, followed by heating in CO(2), was shown to be an effective method for repeatedly restoring high CO(2) capture activity to spent lime during a large number of CO(2) capture cycles. Steam hydration was also shown to reduce the decay rate of the CO(2) capture activity by increasing the rate of carbonation in the diffusion controlled regime. Repeated hydration-carbonation-calcination cycles led to a considerable expansion of the particles through the formation of large vesicles, likely to lead to high attrition levels when applied in fluidized beds. Based on SEM observation of the particles during hydration-carbonation-calcination cycling, a model was proposed for their progressive weakening. It was concluded that strategies to reduce this weakening must limit the growth of the cracks in the crystal as they are cycled repeatedly.

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