The removal of sulfur compounds such as ethyl mercaptan from natural gas remains a critical challenge due to their detrimental effects on downstream processes, catalyst poisoning, and environmental emissions. In this study, a series of halloysite-supported transition metal oxide catalysts was synthesized and evaluated for the removal of sulfur compounds from natural gas at 25 °C, 200 psi, and 36 mL/min, using 0.5 g of the catalyst. The nanotubular structure and dual surface chemistry of halloysite promote enhanced metal dispersion and improved mass transfer. Single-metal (manganese, copper, zinc, and nickel) catalysts were developed and tested, after which a multi-metal oxide (base) catalyst comprising a composite of the single metals (Zn-Cu-Mn-Ni) was developed as a base catalyst to combine adsorption-active and redox-active functionalities, and its performance was further enhanced by the addition of palladium as promoter. A combination of analytical techniques, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infra-red spectroscopy (FTIR), Brunauer–Emmett–Teller (BET) analysis, scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS), provided evidence that highly dispersed metal oxide phases were formed and the halloysite structure was preserved. XPS data showed the presence of oxidation states of metals that were active (Zn2+, Cu2+, Ni2+, Mn3+/Mn4+ and Pd2+), an indication of a redox-active surface for sulfur interaction. Results from the breakthrough experiments showed that the base catalyst significantly improved sulfur removal compared to single-metal catalysts, while the Pd-promoted catalyst exhibited the highest performance, with a breakthrough time of 630 min. Palladium was incorporated at low loading as a promoter, enhancing adsorption performance while maintaining a favorable balance between efficiency and material cost. This enhancement is attributed to synergistic interactions between adsorption-active sites and redox-active species, as well as improved electron transfer facilitated by palladium. The results demonstrate that rational design of multi-metal oxide catalysts supported on naturally occurring halloysite provides an effective and scalable approach for sulfur removal from natural gas, with strong potential for industrial applications.
Antwi et al. (Tue,) studied this question.