Preparation of halloysite nanotubes-encapsulated magnetic microspheres for elemental mercury removal from coal-fired flue gas

Halloysite nanotubes (HNTs) as a natural and inexpensive clay mineral with hollow nanotubular structures, good biocompatibility and active surfaces have been ubiquitously applied in many fields. In this work, a novel multifunctional core-shell sorbent based on HNTs, CuCl₂-HNTs encapsulated magnetic microspheres (SiO₂@Fe₃O₄), was successfully fabricated and applied for Hg⁰ removal from flue gas with good performance for the first time. The core-shell structure prevented the composites from aggregating but kept their magnetism, which enabled the adsorbents being easily separated for reuse by an external magnetic field. In addition, the special structure also significantly enhanced the adsorption capacity of the composites by dispersing the CuCl₂ modified HNTs on the prepared magnetic microspheres. The adsorption performance was comprehensively investigated and fitted by dynamic models. The adsorption followed surface adsorption, particle diffusion and chemisorption with very good SO₂ tolerance. The Cu⁺, Cl^- and lattice oxygen were the crucial components for Hg⁰ removal. In order to further understand the possible mechanism, an online home-made coupling system of temperature-programmed decomposition (TPD) was used to investigate the mercury species on the spent adsorbent in addition to X-ray photoelectron spectroscopy analysis. The results confirmed the mercury species adsorbed were primarily Hg⁰, HgO and HgCl₂.