H2SO4 poisoning of Ru-based and Ni-based catalysts for HI decomposition in Sulfur Iodine cycle for hydrogen production

The sulfur–iodine (SI) cycle is deemed to be one of the most promising alternative methods for large-scale hydrogen production by water splitting, free of CO2 emissions. Decomposition of hydrogen iodide is a pivotal reaction that produces hydrogen. The homogeneous conversion of hydrogen iodide is only 2.2% even at 773 K [1]. A suitable catalyst should be selected to reduce the decomposition temperature of HI and attain reaction yields approaching to the thermodynamic equilibrium conversion. However, residual H2SO4 could not be avoided in the SI cycle because of incomplete purification. The H2SO4 present in the HI feeding stream may lead to the poisoning of HI decomposition catalysts. In this study, the activity and sulfur poisoning of Ru and Ni catalysts loaded on carbon and alumina, respectively, were investigated at 773 K. HI conversion efficiency markedly decreased from 21% to 10% with H2SO4 (3000 ppm) present, which was reversible when H2SO4 was withdrawn in the case of Ru/C. In the case of Ru/C and Ni/Al2O3, catalyst deactivation depends on the concentration of H2SO4; the higher the concentration of H2SO4, the greater the severity of deactivation. Catalysts before and after sulfur poisoning were characterized by transmission electron microscopy (TEM), energy-dispersive X-Ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). Experimental results and characterization of poisoned and fresh catalysts indicate that the catalyst deactivation could be ascribed to the competitive adsorption of sulfur species and change in its surface properties.