Contribution of Na/K Doping to the Activity and Mechanism of Low-Temperature COS Hydrolysis over TiO2-Al2O3 Based Catalyst in Blast Furnace Gas

As an organic sulfur pollutant generated in blast furnace gas, carbonyl sulfide (COS) has attracted more attention due to its negative effects on the environment and economy. The TiO₂-Al₂O₃ composite metal oxide (Ti_0.5Al) with uniformly dispersed particles was prepared by the co-precipitation method. And on this basis, a series of Na/K-doped catalysts were prepared separately. The activity evaluation results showed that the introduction of Na/K significantly improved the low-temperature COS hydrolysis activity, which exhibited a COS conversion of 98% and H₂S yield of 95% at 75 °C with 24,000 h^-1. And K showed a better promoting effect than Na. Brunauer-Emmett-Teller (BET) results revealed the increased mesopore proportion of Na/K-modified catalysts. X-ray diffraction (XRD) and scanning electron microscopy (SEM) showed that Na and K formed prismatic and nanorod-like structures, respectively. More weakly basic sites with enhanced intensity and decreased O_ads/O_lat content contributed to the excellent catalytic activity, as certified by the results of CO₂ temperature-programmed desorption (CO₂-TPD) and X-ray photoelectron spectroscopy (XPS). It was also proposed that the decrease of weakly basic sites ultimately deactivated catalyst activity. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that the introduction of Na/K enhanced the dissociation of H₂O, and the generated abundant hydroxyl groups promoted the adsorption of COS and formed surface transition species, such as HSCO₂ ^- and HCO₃ ^-.