Sulfur behavior in chemical looping combustion with NiO/Al2O3 oxygen carrier

Chemical looping combustion (CLC) is a novel technology where CO2 is inherently separated during combustion. Due to the existence of sulfur contaminants in the fossil fuels, the gaseous products of sulfur species and the interaction of sulfur contaminants with oxygen carrier are a big concern in the CLC practice. The reactivity of NiO/Al2O3 oxygen carrier reduction with a gas mixture of CO/H2 and H2S is investigated by means of a thermogravimetric analyzer (TGA) and Fourier Transform Infrared spectrum analyzer in this study. An X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscope (SEM) are used to evaluate the phase characterization of reacted oxygen carrier, and the formation mechanisms of the gaseous products of sulfur species are elucidated in the process of chemical looping combustion with a gaseous fuel containing hydrogen sulfide. The results show that the rate of NiO reduction with H2S is higher than the one with CO. There are only Ni and Ni3S2 phases of nickel species in the fully reduced oxygen carrier, and no evidence for the existence of NiS or NiS2. The formation of Ni3S2 is completely reversible during the process of oxygen carrier redox. A liquid phase sintering on the external surface of reduced oxygen carriers is mainly attributed to the production of the low melting of Ni3S2 in the nickel-based oxygen carrier reduction with a gaseous fuel containing H2S. Due to the sintering of metallic nickel grains on the external surface of the reduced oxygen carrier, further reaction of the oxygen carrier with H2S is constrained, and there is no increase of the sulfidation index of the reduced oxygen carrier with the cyclical reduction number. Also, a continuous operation with a syngas of carbon monoxide and hydrogen containing H2S is carried out in a 1 kWth CLC prototype based on the nickel-based oxygen carrier, and the effect of the fuel reactor temperature on the release of gaseous products of sulfur species is investigated.