A series of iron oxide sorbents with novel structures of three-dimensionally ordered macropores (3DOM), ranging in size from 60 to 550 nm, were fabricated and creatively used as sorbents for the removal of H2S at medium temperatures of 300–350 °C. Evaluation tests using thermogravimetric analysis (TGA) and a fixed-bed reactor showed that, in comparison to the iron oxide sorbent prepared by a conventional mixing method, the fabricated iron oxide sorbent with a 3DOM structure exhibited much higher reactivity and efficiency, as well as high sorbent utilization with low regeneration temperature. The excellent performance of 3DOM iron oxide as a sulfur sorbent is attributed to its special texture, i.e., the open and interconnected macroporous, large surface area, and nanoparticles of iron oxide, which are revealed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and nitrogen adsorption techniques. The investigation results of the pore effect on the performance of the sorbent show that sorbents with pores size around 150 nm in diameter revealed the best performance. The reason is that pores of this size are large enough to allow gas to pass through even if the channel is partially blocked during the reaction process while remaining a large surface area that can provide more active sites for the reaction.

•The deoxygenation of CMM was fulfilled by passing CMM through heated gangue.•Both temperature and gas flow rate influence the deoxygenation efficiency.•Oxygen can be eliminated completely under condition of 650 °C and 250 mL/min.•Gangue had been activated in the course of deoxygenation process.The deoxygenation of coal mine methane (CMM) is a necessary process for concentrating methane by pressure-swing adsorption technology. Removal of oxygen in CMM by the reaction between oxygen and carbon in coal gangue is a novel solution for simultaneously utilizing two kinds of byproducts of coal mine, CMM and coal gangue. Process conditions for the deoxygenation of CMM were investigated systematically by using a fixed-bed reactor. The results show that higher temperature and lower gas flow rate not only decreased the residual oxygen concentration in the outlet gas but also increased the methane loss, and that the particle size of gangue did not influence deoxygenation within the experimental conditions used. Under optimal conditions (650 °C and 250 mL/min), there was no residual oxygen in the outlet gas and the methane concentration decreased by less than 0.5 mol%. XRD results show that coal gangue was activated during deoxygenation, and that activated gangue was suitable for utilization as a main component in cementitious materials.

The purpose of this study is to investigate the effect of clay binder, an important additive, on the performance of iron oxide sorbent in high temperature coal gas desulfurization. The four clay binders chosen for the study were kaolinite, diatomite, bentonite and brick clay. The sulfidation–regeneration cycles were conducted in a fixed-bed reactor. XRD, DTA and FTIR, together with texture characterizing techniques, such as mercury porosimetry and nitrogen adsorption, were adopted to characterize the sorbents and raw materials. The results obtained show that sorbents prepared from various clay binders exhibit different breakthrough behaviors. In addition, a correlation between pore volume and sulfur capacity reveals that sorbents with a greater number of pores larger than 200 nm (diameter), exhibit higher sulfur capacity. The reason for this is that a greater number of large pores can improve diffusion and provide a larger space for relieving heat impact. However, too many large pores may result in weak strength and very low bulk density, thus a balance between large pores and the density must be achieved. This study also reveals that clay binder can contribute to the modification of a sorbent's texture as gas is released when the mineral structure changes during calcination. In addition, a clay mineral with an active interlayer has been shown to be beneficial in improving the dispersion of active components in the sorbent, because of the existence of an interaction between the mineral and red mud.