Effect of Temperature on Reduction of CaSO₄ Oxygen Carrier in Chemical-Looping Combustion of Simulated Coal Gas in a Fluidized Bed Reactor

Abstract

Chemical-looping combustion (CLC) is a promising combustion technology for gaseous and solid fuel with efficient use of energy and inherent separation of CO 2 . The concept of a coal-fueled CLC system using calcium sulfate (CaSO 4 ) as oxygen carrier is proposed in this study. Reduction tests of CaSO 4 oxygen carrier with simulated coal gas were performed in a laboratory-scale fluidized bed reactor in the temperature range of 890-950 °C. A high concentration of CO 2 was obtained at the initial reduction period. CaSO 4 oxygen carrier exhibited high reactivity initially and decreased gradually at the late period of reduction. The sulfur release during the reduction of CaSO 4 as oxygen carrier was also observed and analyzed. H 2 and CO conversions were greatly influenced by reduction temperature. The carbon deposition ratio was found to be quite low. The oxygen carrier conversion and mass-based reaction rates during the reduction at typical temperatures were compared. Higher temperatures would enhance reaction rates and result in high conversion of oxygen carrier. An XRD patterns study indicated that CaS was the dominant product of reduction and the variation of relative intensity with temperature is in agreement with the solid conversion. The slight content of CaO in reduced oxygen carrier at high temperatures was due to the formation of SO 2 and H 2 S during the reduction period. ESEM analysis indicated that the surface structure of oxygen carrier particles changed significantly from impervious to porous after reduction. Slight agglomeration of small grains occurred for reduced particles at 950 °C. EDS analysis also demonstrated the transfer of oxygen from the oxygen carrier to the fuel gas and a certain amount of sulfur loss and CaO formation on the surface at higher temperatures. The reduction kinetics of CaSO 4 oxygen carrier was explored with the shrinking unreacted-core model. The apparent kinetic parameters were obtained, and the kinetic equation well predicted the experimental data. Finally, some basic considerations on the use of CaSO 4 oxygen carrier in a CLC system for solid fuels were discussed.

Progress in Chemical-Looping Combustion and Reforming technologies

“…Worse performance was obtained processing syngas in a 120 kW th facility with a natural ilmenite than using a Ni-based oxygen-carrier [191,208], but the low price and the environmental friendly behaviour of ilmenite are the main reasons to be considered as oxygen-carrier. Lower reactivity was found for CaSO 4 based oxygen-carriers [273,275,277,283].…”

“…For example, CaSO 4 from natural anhydrite is a low cost material and has much higher oxygen transport capacity than other proposed materials These reactions have exhibited low reaction rates [274][275][276][277][278]. In addition, simulation results based on chemical equilibrium show that small fractions of CO and H 2 can not be converted [278,279].…”

“…Low reactivity has been shown with all the reducing gases (H 2 , CO and CH 4 ) [274][275][276][277][278]. However, this should not be an important problem in the iG-CLC process because the conversion rate of the fuel is limited by the slow gasification step.…”

“…Thus, different paths can drive to obtain a mixture of CO 2 [275]. By contrast, for a Ni-based material the reaction rate corresponded to that of the gas reacting faster, H 2 or CO, depending on the actual gas concentration [232].…”

Chemical Looping Combustion of Solid Fuels in a Laboratory Fluidized-bed Reactor

“…This means that high temperatures can be targeted since this enhances fuel conversion in a CLC fuel reactor [9,17,28]. Successful CLC experiments were done at temperatures as high as 1100°C (see Fig.…”