Dry-bed adsorptive desulfurization of biomass-based syngas with a low- to medium sulfur content using ZnO was studied as an alternative to conventional wet-scrubbing processes for a small- to medium-scale biomass-to-liquid process concept. Following laboratory-scale long-term H2S breakthrough experiments in a previous study, desulfurization tests were scaled-up to bench-scale with actual bio-syngas to verify the lab-scale results under more realistic process conditions. A desulfurization unit was constructed and connected to a steam-blown atmospheric pilot-scale fluidized bed gasifier. Two successful 70+ h test campaigns were conducted with H2S removal below the breakthrough limit using full-sized ZnO adsorbent particles. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy elemental analysis, and Brunauer-Emmett-Teller (BET) surface area characterization of the fresh and spent adsorbent pellets were performed. SEM micrographs displayed the outward enlarging particle size in the sulfided layer. Characterization showed significant core-shell sulfidation behavior with a few hundred micron-thick sulfided layer leaving the majority of ZnO unutilized. Adsorbents lost most of their porosity in use, which was evident from BET surface area results. Simultaneous COS removal was found possible by the hydrolysis reaction to H2S. Furthermore, evidence of minor chlorine adsorption was found, thus highlighting the need for a dedicated HCl removal step upstream of desulfurization.
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