title: The mechanism of vapor phase hydration of calcium oxide: implications for CO2 capture.
abstract: Lime-based sorbents are used for fuel- and flue-gas capture, thereby representing an economic and effective way to reduce CO2 emissions. Their use involves cyclic carbonation/calcination which results in a significant conversion reduction with increasing number of cycles. To reactivate spent CaO, vapor phase hydration is typically performed. However, little is known about the ultimate mechanism of such a hydration process. Here, we show that the vapor phase hydration of CaO formed after calcination of calcite (CaCO3) single crystals is a pseudomorphic, topotactic process, which progresses via an intermediate disordered phase prior to the final formation of oriented Ca(OH)2 nanocrystals. The strong structural control during this solid-state phase transition implies that the microstructural features of the CaO parent phase predetermine the final structural and physicochemical (reactivity and attrition) features of the product hydroxide. The higher molar volume of the product can create an impervious shell around unreacted CaO, thereby limiting the efficiency of the reactivation process. However, in the case of compact, sintered CaO structures, volume expansion cannot be accommodated in the reduced pore volume, and stress generation leads to pervasive cracking. This favors complete hydration but also detrimental attrition. Implications of these results in carbon capture and storage (CCS) are discussed.
authors.affiliation: Dept. Mineralogy and Petrology, University of Granada , Fuentenueva s/n, 18002 Granada, Spain.
authors.forename: Krzysztof
authors.initials: K
authors.lastname: Kudłacz
authors.forename: Carlos
authors.initials: C
authors.lastname: Rodriguez-Navarro
mesh_terms: D002119:Calcium Carbonate / Q000737:chemistry*; D017610:Calcium Compounds / Q000737:chemistry*; D002244:Carbon; D002245:Carbon Dioxide / Q000302:isolation & purification; D002254:Carbonates; D005740:Gases; D008855:Microscopy, Electron, Scanning; D046529:Microscopy, Electron, Transmission; D010087:Oxides / Q000737:chemistry*; D014867:Water / Q000737:chemistry; D014961:X-Ray Diffraction
chemical_list: D017610:Calcium Compounds; D002254:Carbonates; D005740:Gases; D010087:Oxides; D014867:Water; D002245:Carbon Dioxide; D002244:Carbon; C016538:lime; D002119:Calcium Carbonate