The occurrence of hydrogen sulphide in the environment, the reasons for concern about the levels which may be present, particularly on off-shore installations, and methods for determining the gas in air are reviewed. The original aim of this project was to explain the reasons for the variations in the levels of naturally occurring hydrogen sulphide over the estuary of the Don at Aberdeen. The monitoring work required a reliable method: as the published methods were all problematical, much effort was expended in improving the Ethylene Blue method and investigating the range of trapping solutions. The final optimised method has been published (Analyst 1988, 113, 1635). An alternative method for standardising H2S in air gas mixes has also been developed and used on commercial samples. Microbiological studies have shown that sulphate-reducing bacteria were not present in the sediments of the Don estuary in 1988 (but were present in sediments from the Forth estuary) and further, that the Don sediments would not support growth of SRB's, which in part explains why there has been effectively no release of H2S from the estuary in recent years. Attempts have been made to correlate the H2S emission events with changes in river water quality over the last ten years, but no obvious clues have become evident.

One of the major technical challenges towards a viable H2S//Air SOFC is to identify and develop anode materials that are electronically conductive, chemically and electrochemically stable, and catalytically active when exposed to H2S-rich environments. The corrosive nature of H2S renders most traditional state-of-the-art SOFC anode materials (Ni, Pt, Ag) useless for long-term cell performance even at very low sulfur concentrations. In my doctoral thesis work, a new class of perovskite-based anodes was developed for potential use in SOFCs operating with H2S and sulfur-containing fuels. Cermets from this family of materials have shown excellent chemical stability and electrochemical performance at typical SOFC operating conditions. As an added benefit, they appear to preferentially oxidize H2S over hydrogen, as suggested by open circuit voltage, impedance spectra, and cell performance measurements obtained using various H2S-H2-N2 fuel mixtures. Cell power output values were among the highest reported in the literature and showed no significant deterioration during 48-hour testing periods. Impedance measurements indicated overall cell resistances decreased with increasing temperature and H2S content of the fuel. This behavior is starkly different from that of contemporary SOFC anodes, where the presence of H2S usually increases overall polarization resistance and ultimately destroys the cell. Results are promising due to the drastic improvement in sulfur tolerance compared to the current generation of SOFC power systems.

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Hydrogen sulphide is an environmentally hazardous gas which is present in many gas streams associated with oil and gas industry. Oxidation of H2S to sulphur in air produces no bulky or waste material and requires no further purification. Activated carbon is known as a catalyst for this reaction.<p> In this research, a coal-based precursor (luscar char) and a biomass-based precursor (biochar) were used for production of activated carbons by two common methods of activation: physical and chemical activation in which steam and potassium hydroxide (KOH), respectively, were used. Experiments were designed by the statistical central composite design method. Two models were developed for the BET surface area and reaction yield of each activation process. These models showed the effects of operating conditions, such as activation temperature, mass ratio of activating agent to precursor, activation time, and nitrogen flowrate on the BET surface area and reaction yield for each activation method for each precursor. The optimum operating conditions were calculated using these models to produce activated carbons with relatively large BET surface area (> 500 m2/g) and high reaction yield (> 50 wt %). The BET surface area and reaction yield for activated carbons produced at optimum operating conditions showed maximum 7 and 7.4 % difference, respectively, comparing to the values predicted by models.<p> The activated carbons produced at optimum operating conditions were used as the base catalysts for the direct oxidation of 1 mol % hydrogen sulphide in nitrogen to sulphur at the temperature range of 160-205 oC and pressure of 700 kPa. Originally activated carbons showed a good potential for oxidation of hydrogen sulphide by their selectivity for sulphur product and low amount of sulphur dioxide production. To improve the performance of steam-activated carbons, the catalysts were modified by acid-treatment followed by thermal desorption. This method increased the break-through times for coal-based and biomass-based catalysts to 115 and 141 minutes, respectively. The average amounts of sulphur dioxide produced during the reaction time were 0.14 and 0.03 % (as % of hydrogen sulphide fed to the reactor) for modified activated carbons prepared from biochar and luscar char, respectively. The effects of porous structure, surface chemistry, and ash content on the performances of these activated carbon catalysts were investigated for the direct oxidation reaction of hydrogen sulphide.<p> The acid-treatment followed by thermal desorption of activated carbons developed the porosity which produced more surface area for active sites and in addition, provided more space for sulphur product storage resulting in higher life time for catalyst. Boehm titration and temperature program desorption showed that the modification method increased basic character of carbon surface after thermal desorption in comparison to acid-treated sample. In addition, the effects of impregnating agents (potassium iodide and manganese nitrate) and two solvents for impregnation process were studied on the performance of the activated carbon catalysts for the direct oxidation of H2S to sulphur.<p> Sulphur L-edge X-ray near edge structure (XANES) showed that the elemental sulphur was the dominant sulphur species in the product. The kinetic study for oxidation reaction of H2S over LusAC-O-D(650) was performed for temperature range of 160-190 oC, oxygen to hydrogen sulphide molar ratio of 1-3, and H2S concentration of 6000-10000 ppm at 200 kPa. The values of activation energy were 26.6 and 29.3 kJ.gmol-1 for Eley-Rideal and Langmuir-Hinshelwood mechanisms, respectively.

Hydrogen sulphide is an environmentally hazardous gas which is present in many gas streams associated with oil and gas industry. Oxidation of H2S to sulphur in air produces no bulky or waste material and requires no further purification. Activated carbon is known as a catalyst for this reaction.<p> In this research, a coal-based precursor (luscar char) and a biomass-based precursor (biochar) were used for production of activated carbons by two common methods of activation: physical and chemical activation in which steam and potassium hydroxide (KOH), respectively, were used. Experiments were designed by the statistical central composite design method. Two models were developed for the BET surface area and reaction yield of each activation process. These models showed the effects of operating conditions, such as activation temperature, mass ratio of activating agent to precursor, activation time, and nitrogen flowrate on the BET surface area and reaction yield for each activation method for each precursor. The optimum operating conditions were calculated using these models to produce activated carbons with relatively large BET surface area (> 500 m2/g) and high reaction yield (> 50 wt %). The BET surface area and reaction yield for activated carbons produced at optimum operating conditions showed maximum 7 and 7.4 % difference, respectively, comparing to the values predicted by models.<p> The activated carbons produced at optimum operating conditions were used as the base catalysts for the direct oxidation of 1 mol % hydrogen sulphide in nitrogen to sulphur at the temperature range of 160-205 oC and pressure of 700 kPa. Originally activated carbons showed a good potential for oxidation of hydrogen sulphide by their selectivity for sulphur product and low amount of sulphur dioxide production. To improve the performance of steam-activated carbons, the catalysts were modified by acid-treatment followed by thermal desorption. This method increased the break-through times for coal-based and biomass-based catalysts to 115 and 141 minutes, respectively. The average amounts of sulphur dioxide produced during the reaction time were 0.14 and 0.03 % (as % of hydrogen sulphide fed to the reactor) for modified activated carbons prepared from biochar and luscar char, respectively. The effects of porous structure, surface chemistry, and ash content on the performances of these activated carbon catalysts were investigated for the direct oxidation reaction of hydrogen sulphide.<p> The acid-treatment followed by thermal desorption of activated carbons developed the porosity which produced more surface area for active sites and in addition, provided more space for sulphur product storage resulting in higher life time for catalyst. Boehm titration and temperature program desorption showed that the modification method increased basic character of carbon surface after thermal desorption in comparison to acid-treated sample. In addition, the effects of impregnating agents (potassium iodide and manganese nitrate) and two solvents for impregnation process were studied on the performance of the activated carbon catalysts for the direct oxidation of H2S to sulphur.<p> Sulphur L-edge X-ray near edge structure (XANES) showed that the elemental sulphur was the dominant sulphur species in the product. The kinetic study for oxidation reaction of H2S over LusAC-O-D(650) was performed for temperature range of 160-190 oC, oxygen to hydrogen sulphide molar ratio of 1-3, and H2S concentration of 6000-10000 ppm at 200 kPa. The values of activation energy were 26.6 and 29.3 kJ.gmol-1 for Eley-Rideal and Langmuir-Hinshelwood mechanisms, respectively.

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