| Sulfur is a natural contaminant in nearly all fossil fuel supplies. When a fuel stream is gasified or reformed, the sulfur manifests itself in the form of hydrogen sulfide, H2S. Extraordinary effort is put forth to remove H2S to at least ppm levels before the fuel can be used for power generation. To compete with current methods, an electrochemical membrane system (EMS) is now being studied to remove H2S in one step at high temperature. This process offers continuous H2S removal at an estimated operating cost of {dollar}0.32/kg H2S removed and a capital cost that is roughly half that of a Claus plant with tail-gas clean-up. Other advantages are the considerable savings in energy and space compared to current methods.; A bench scale set-up was constructed to test the cell performance at 600–700°C and 1 atm. The typical fuel stream inlet proportions were 34% CO, 22% CO2, 35% H2, 8% H2O, and 450–2000 ppm H2S. The fundamental transport restrictions for sulfur species in an electrochemical cell were examined. Temperature and membrane thickness were varied to examine how these parameters affect the maximum flux of H 2S removal. It was found that higher temperature allows more sulfide species to enter the electrolyte, thus increasing the sulfide flux across the membrane and raising the maximum flux of H2S removal. Also, membrane thickness was found to be a critical parameter in cell design. A thinner membrane decreases the distance that sulfide ions must travel to be oxidized at the anode. These results identify sulfide diffusion across the membrane as the rate-limiting step in H2S removal. The maximum H2S removal flux of 1.1 × 10−6 gmol H2S min−1 cm−2 (or 3.5 mA cm−2) was obtained at 650°C, with a membrane that was 0.9 mm thick, 36% porous, and had an estimated tortuosity of 3.6.; Another focus of this thesis was to examine the stability of cathode materials in full cell trials. A major hurdle that remains in process scale-up is cathode selection, as the lifetime of the cell will depend heavily on the lifetime of the cathode material, which is exposed to very sour gas. Materials that showed success in the past (i.e cobalt sulfides and Y0.9Ca 0.1FeO3) were examined but were seen to have limitations in operating environment and temperature. Therefore, other novel metal oxide compounds were studied to find possible candidates for full cell trials.; Gd2TiMoO7 and La0.7Sr0.3VO 3 were the compounds that retained their structure best even when exposed to high H2S, CO2, and H2O concentrations. They also showed no sign of melting at operating temperatures. But Gd 2TiMoO7 was seen to have better stability with electrolyte present, whereas La0.7Sr0.3VO3 was seen to have better stability in the pure sour gas stream without electrolyte present. A layered electrode that could help preserve a stable environment for each of these compounds should be explored in future research. |
