The utilisation of alternate sources of energy has reached critical levels due to the constantly growing demand for energy and the diminishing of fossil fuels. The production of hydrogen through the Hybrid Sulphur process is a possible alternative that may contribute towards alleviating the pressure on the world's energy resources. The two-step thermochemical cycle for decomposing water into hydrogen and oxygen offers the potential to obtain acceptable thermal efficiencies, while still using common and inexpensive chemicals. The process mainly makes use of two unit process operations: an electrolyser and a chemical decomposition reactor. This research project focuses on the concept design of the decomposition reactor operated adiabatically as a multi-stage reactor system with inter-stage heating, in order to simplify the reactor design. This approach allows for the independent evaluation of the reaction kinetics and the heat transfer mechanism. / Thesis (M.Ing. (Nuclear Engineering))--North-West University, Potchefstroom Campus, 2009.

The Hybrid Sulphur process is one technology out of a multitude of known technologies responsible for hydrogen production. Within the latter hydrogen production cycle, it is pivotal to recover O2 as a by-product from a sulphuric acid decomposition reaction that produces SO2, H2O and O2. It is assumed that a simple phase separation stage carried out on the reaction products would liberate SO2 and O2 as a gaseous mixture leaving behind H2O in the liquid state. Several separation technologies are available to effect SO2/O2 separation, but membrane technology has proved to be dearer due to simplicity of the technology, low capital and energy costs. It is a pity though that insignificant work has been done that considers the SO2/O2 binary system in the membrane technology context. Of the insignificant work done, non – commercial membranes were employed. It is on the latter background that the present study was proposed. Six commercial membranes were selected from literature, two (Udel Polysulfone and Teflon AF 2400) of which are currently used in gas separation applications and the remainder (Hyflon M, Hyflon F, Halar and Nafion 117) not necessarily used as gas separation membranes but present a potential of separating SO2/O2. The inclusion of the latter four membranes sought to unearth unknown gas separation potentials of the membranes based on hypothetical 1 μm thick membranes. A screening technique was employed to eliminate poor performing membranes through pure component permeation of SO2, O2, N2 and CO2. The use of the additional gases (N2 and CO2) was meant to allow the generation of a pool of data that would be used as a yardstick to compare to literature and thus validate the authenticity of the designed set up. The single permeation experiments were carried out at 25°C and at absolute gas feed pressures of 1 bar, 2 bar and 3 bar, with the exception of Hyflon F experiments that were carried out at 3.85 bar, 2.85 bar and 1.85 bar also at 25°C. The effect of pressure on gas permeability and ideal selectivity of all gases against O2 was investigated. Udel Polysulfone and Nafion 117 presented clearly evident pressure dependant SO2 permeabilities whilst CO2, N2 and O2 permeabilities were sluggishly dependant on pressure in all membranes. Gas flux in general increased with increasing pressure as pressure is essentially the driving force for permeability. Membrane screening for further investigation was then performed based on a compromise between SO2/O2 ideal selectivity and SO2 flux in hypothetical 1 μm thick membranes. Membranes that presented the best SO2/O2 selectivity include, Udel Polysulfone with SO2/O2 selectivities of 46, 58 and 314 at 1 bar, 2 bar and 3 bar respectively, Nafion 117 with SO2/O2 selectivities of 30, 35 and 40 at 1 bar, 2 bar and 3 bar respectively and Halar with a SO2/O2 selectivity of 17 at 3 bar. The best SO2 flux through hypothetical 1 μm thick membranes was manifested in Teflon AF 2400 with SO2 fluxes of 3.6 m3.m-2.hr-1, 5.9 m3.m-2.hr-1 and 9.9 m3.m-2.hr-1 at trans-membrane pressures of 1 bar, 2 Bar and 3 Bar respectively, Udel Polysulfone with SO2 fluxes of 0.13 m3.m-2.hr-1, 0.32 m3.m-2.hr-1 and 2.56 m3.m-2.hr-1 at trans-membrane pressures of 1 bar, 2 bar and 3 bar respectively and Nafion 117 with SO2 fluxes of 0.48 m3.m-2.hr-1, 1.03 m3.m-2.hr-1 and 1.79 m3.m-2.hr-1 at 1 bar, 2 bar and 3 bar trans-membrane pressures respectively. Despite Teflon AF 2400 presenting the highest SO2 flux, the poor SO2/O2 ideal selectivity ≈ 1 rendered the membrane unfit for further investigation. The low SO2 flux (0.02 m3.m-2.hr-1) presented by Halar also rendered the membrane unfit for further investigation despite the relatively fair SO2/O2 ideal selectivity of 17. Binary permeation experiments were then performed on Udel Polysulfone and Nafion 117 after passing the single permeation screening test. Gas mixture compositions of (25 wt %:75 wt %, SO2:O2), (50 wt %:50 wt %, SO2:O2) and (75 wt %:25 wt %, SO2:O2) were employed. The binary permeation experiments were carried out at a temperature range of 15°C to 55°C and a SO2 feed partial pressure range of 1.1 ± 0.1 bar to 2.3 ± 0.1 bar. The SO2 permeate composition increased with pressure and decreased with temperature in both Udel Polysulfone and Nafion 117. Udel Polysulfone presented a superior SO2/O2 separation potential, concentrating a (25 wt %:75 wt %, SO2:O2) gas mixture to (94 wt %:6 wt %, SO2:O2) in a single step at 15°C and 2.2 ± 0.1 bar SO2 feed partial pressure. Nafion 117 concentrated the same gas mixture to (87 wt %:13 wt %, SO2:O2) also in a single step at 15 °C and 2.4 ± 0.1 bar SO2 feed partial pressure. Based on hypothetical 1 μm thick membranes, Nafion 117 presented generally high SO2 molar fluxes in mixture with O2 of about a magnitude higher than the SO2 molar fluxes presented in Udel Polysulfone. Also, Nafion 117 proved to be less prone to plasticisation within the pressure range considered. Despite Udel Polysulfone presenting generally lower SO2 molar fluxes, Udel Polysulfone was deemed to be the ideal membrane for the current SO2/O2 separation application as thicknesses of 1 μm of Nafion the perfluorosulfonic acid based membrane are currently unknown and also Udel Polysulfone presented the best SO2/O2 separation capability. The latter findings are envisaged to prompt further research on the production of ultra-thin perfluoro-sulfonic acid based membranes for the current application. / Thesis (MIng (Chemical Engineering))--North-West University, Potchefstroom Campus, 2013

The Hybrid Sulphur process is one technology out of a multitude of known technologies responsible for hydrogen production. Within the latter hydrogen production cycle, it is pivotal to recover O2 as a by-product from a sulphuric acid decomposition reaction that produces SO2, H2O and O2. It is assumed that a simple phase separation stage carried out on the reaction products would liberate SO2 and O2 as a gaseous mixture leaving behind H2O in the liquid state. Several separation technologies are available to effect SO2/O2 separation, but membrane technology has proved to be dearer due to simplicity of the technology, low capital and energy costs. It is a pity though that insignificant work has been done that considers the SO2/O2 binary system in the membrane technology context. Of the insignificant work done, non – commercial membranes were employed. It is on the latter background that the present study was proposed. Six commercial membranes were selected from literature, two (Udel Polysulfone and Teflon AF 2400) of which are currently used in gas separation applications and the remainder (Hyflon M, Hyflon F, Halar and Nafion 117) not necessarily used as gas separation membranes but present a potential of separating SO2/O2. The inclusion of the latter four membranes sought to unearth unknown gas separation potentials of the membranes based on hypothetical 1 μm thick membranes. A screening technique was employed to eliminate poor performing membranes through pure component permeation of SO2, O2, N2 and CO2. The use of the additional gases (N2 and CO2) was meant to allow the generation of a pool of data that would be used as a yardstick to compare to literature and thus validate the authenticity of the designed set up. The single permeation experiments were carried out at 25°C and at absolute gas feed pressures of 1 bar, 2 bar and 3 bar, with the exception of Hyflon F experiments that were carried out at 3.85 bar, 2.85 bar and 1.85 bar also at 25°C. The effect of pressure on gas permeability and ideal selectivity of all gases against O2 was investigated. Udel Polysulfone and Nafion 117 presented clearly evident pressure dependant SO2 permeabilities whilst CO2, N2 and O2 permeabilities were sluggishly dependant on pressure in all membranes. Gas flux in general increased with increasing pressure as pressure is essentially the driving force for permeability. Membrane screening for further investigation was then performed based on a compromise between SO2/O2 ideal selectivity and SO2 flux in hypothetical 1 μm thick membranes. Membranes that presented the best SO2/O2 selectivity include, Udel Polysulfone with SO2/O2 selectivities of 46, 58 and 314 at 1 bar, 2 bar and 3 bar respectively, Nafion 117 with SO2/O2 selectivities of 30, 35 and 40 at 1 bar, 2 bar and 3 bar respectively and Halar with a SO2/O2 selectivity of 17 at 3 bar. The best SO2 flux through hypothetical 1 μm thick membranes was manifested in Teflon AF 2400 with SO2 fluxes of 3.6 m3.m-2.hr-1, 5.9 m3.m-2.hr-1 and 9.9 m3.m-2.hr-1 at trans-membrane pressures of 1 bar, 2 Bar and 3 Bar respectively, Udel Polysulfone with SO2 fluxes of 0.13 m3.m-2.hr-1, 0.32 m3.m-2.hr-1 and 2.56 m3.m-2.hr-1 at trans-membrane pressures of 1 bar, 2 bar and 3 bar respectively and Nafion 117 with SO2 fluxes of 0.48 m3.m-2.hr-1, 1.03 m3.m-2.hr-1 and 1.79 m3.m-2.hr-1 at 1 bar, 2 bar and 3 bar trans-membrane pressures respectively. Despite Teflon AF 2400 presenting the highest SO2 flux, the poor SO2/O2 ideal selectivity ≈ 1 rendered the membrane unfit for further investigation. The low SO2 flux (0.02 m3.m-2.hr-1) presented by Halar also rendered the membrane unfit for further investigation despite the relatively fair SO2/O2 ideal selectivity of 17. Binary permeation experiments were then performed on Udel Polysulfone and Nafion 117 after passing the single permeation screening test. Gas mixture compositions of (25 wt %:75 wt %, SO2:O2), (50 wt %:50 wt %, SO2:O2) and (75 wt %:25 wt %, SO2:O2) were employed. The binary permeation experiments were carried out at a temperature range of 15°C to 55°C and a SO2 feed partial pressure range of 1.1 ± 0.1 bar to 2.3 ± 0.1 bar. The SO2 permeate composition increased with pressure and decreased with temperature in both Udel Polysulfone and Nafion 117. Udel Polysulfone presented a superior SO2/O2 separation potential, concentrating a (25 wt %:75 wt %, SO2:O2) gas mixture to (94 wt %:6 wt %, SO2:O2) in a single step at 15°C and 2.2 ± 0.1 bar SO2 feed partial pressure. Nafion 117 concentrated the same gas mixture to (87 wt %:13 wt %, SO2:O2) also in a single step at 15 °C and 2.4 ± 0.1 bar SO2 feed partial pressure. Based on hypothetical 1 μm thick membranes, Nafion 117 presented generally high SO2 molar fluxes in mixture with O2 of about a magnitude higher than the SO2 molar fluxes presented in Udel Polysulfone. Also, Nafion 117 proved to be less prone to plasticisation within the pressure range considered. Despite Udel Polysulfone presenting generally lower SO2 molar fluxes, Udel Polysulfone was deemed to be the ideal membrane for the current SO2/O2 separation application as thicknesses of 1 μm of Nafion the perfluorosulfonic acid based membrane are currently unknown and also Udel Polysulfone presented the best SO2/O2 separation capability. The latter findings are envisaged to prompt further research on the production of ultra-thin perfluoro-sulfonic acid based membranes for the current application. / Thesis (MIng (Chemical Engineering))--North-West University, Potchefstroom Campus, 2013

The utilisation of alternate sources of energy has reached critical levels due to the constantly growing demand for energy and the diminishing of fossil fuels. The production of hydrogen through the Hybrid Sulphur process is a possible alternative that may contribute towards alleviating the pressure on the world's energy resources. The two-step thermochemical cycle for decomposing water into hydrogen and oxygen offers the potential to obtain acceptable thermal efficiencies, while still using common and inexpensive chemicals. The process mainly makes use of two unit process operations: an electrolyser and a chemical decomposition reactor. This research project focuses on the concept design of the decomposition reactor operated adiabatically as a multi-stage reactor system with inter-stage heating, in order to simplify the reactor design. This approach allows for the independent evaluation of the reaction kinetics and the heat transfer mechanism. / Thesis (M.Ing. (Nuclear Engineering))--North-West University, Potchefstroom Campus, 2009.

The constantly growing demand for energy and the consequent depletion of fossil fuels have led to a drive for energy that is environmentally friendly, efficient and sustainable. A viable source with the most potential of adhering to the criteria is nuclear-produced hydrogen. The hybrid sulphur cycle (HyS) is the proposed electrothermochemical process that can produce the energy carrier, hydrogen. The HyS consists of two unit operations, namely the electrolyzer and the decomposition reactor, that decomposes water into hydrogen and oxygen. A techno-economic evaluation of the technology is needed to prove the commercial potential of the cycle. This research project focuses on determining the hybrid sulphur cycle’s recommended operating parameter range that will support economic viability whilst maintaining a high efficiency. This is done by comparing the results of an evaluation of four case studies, all operating under different conditions. The technical evaluation of the research project is executed using the engineering tool Aspen PlusTM. The models used to achieve accurate results were OLI Mixed Solvent Electrolyte, oleum data package for use with Aspen PlusTM, which provides an accurate representation of the H2SO4 properties, and ELECNRTL to provide an accurate representation of H2SO4 at high temperature conditions. This evaluation provides insight into the efficiency of the process as well as the operating conditions that deliver the highest efficiency. The economic evaluation of the research project determines the hydrogen production costs for various operating conditions. These evaluations provide a recommended operating parameter range for the HyS to obtain high efficiency and economic viability. / Thesis (M.Ing. (Nuclear Engineering))--North-West University, Potchefstroom Campus, 2010.

The utilisation of alternate sources of energy has reached critical levels due to the constantly growing demand for energy and the diminishing of fossil fuels. The production of hydrogen through the Hybrid Sulphur process is a possible alternative that may contribute towards alleviating the pressure on the world's energy resources. The two-step thermochemical cycle for decomposing water into hydrogen and oxygen offers the potential to obtain acceptable thermal efficiencies, while still using common and inexpensive chemicals. The process mainly makes use of two unit process operations: an electrolyser and a chemical decomposition reactor. This research project focuses on the concept design of the decomposition reactor operated adiabatically as a multi-stage reactor system with inter-stage heating, in order to simplify the reactor design. This approach allows for the independent evaluation of the reaction kinetics and the heat transfer mechanism. / Thesis (M.Ing. (Nuclear Engineering))--North-West University, Potchefstroom Campus, 2009.

The constantly growing demand for energy and the consequent depletion of fossil fuels have led to a drive for energy that is environmentally friendly, efficient and sustainable. A viable source with the most potential of adhering to the criteria is nuclear-produced hydrogen. The hybrid sulphur cycle (HyS) is the proposed electrothermochemical process that can produce the energy carrier, hydrogen. The HyS consists of two unit operations, namely the electrolyzer and the decomposition reactor, that decomposes water into hydrogen and oxygen. A techno-economic evaluation of the technology is needed to prove the commercial potential of the cycle. This research project focuses on determining the hybrid sulphur cycle’s recommended operating parameter range that will support economic viability whilst maintaining a high efficiency. This is done by comparing the results of an evaluation of four case studies, all operating under different conditions. The technical evaluation of the research project is executed using the engineering tool Aspen PlusTM. The models used to achieve accurate results were OLI Mixed Solvent Electrolyte, oleum data package for use with Aspen PlusTM, which provides an accurate representation of the H2SO4 properties, and ELECNRTL to provide an accurate representation of H2SO4 at high temperature conditions. This evaluation provides insight into the efficiency of the process as well as the operating conditions that deliver the highest efficiency. The economic evaluation of the research project determines the hydrogen production costs for various operating conditions. These evaluations provide a recommended operating parameter range for the HyS to obtain high efficiency and economic viability. / Thesis (M.Ing. (Nuclear Engineering))--North-West University, Potchefstroom Campus, 2010.

This study introduces an evaluation of the downstream utilization of oxygen produced by the hybrid sulfur process (HYS). Both technical and economic aspects were considered in the production of primarily synthesis gas and hydrogen. Both products could increase the economic potential of the hybrid sulfur process. Based on an assumed 500MWt pebble bed modular nuclear reactor, the volume of hydrogen and oxygen produced by the scaled down HYS was found to be 121 and 959 ton per day respectively. The partial oxidation plant (POX) could produce approximately 1840 ton synthesis gas per day based on the oxygen obtained from the HYS. The capital cost of the POX plant is in the order of $104 million (US dollars, Base year 2008). Compared to the capital cost of the HYS, this seems to be a relatively small additional investment. The production cost varied from a best case scenario $9.21 to a worst case scenario of $19.36 per GJ synthesis gas. The profitability analysis conducted showed favourable results, indicating that under the assumed conditions, and with 20 years of operation, a NPV of $87 mil. and an IRR of 19.5% could be obtained, for the assumed base case. The economic sensitivity analysis conducted, provided insight into the upper and lower limitations of favourable operation. The second product that could be produced was hydrogen. With the addition of a water gas shift and a pressure swing adsorption process to the POX, it was found that an additional 221 ton of hydrogen per day could be produced. The hydrogen could be produced in the best case at $2.34/kg and in the worst case at $3.76/kg. The investment required would be in the order of $50 million. The profitability analysis for the base case analysis predicts an NPV of $206 million and a high IRR of 23.0% under the assumed conditions. On financial grounds it therefore seemed that the hydrogen production process was favourable. The thermal efficiency of the synthesis gas production section was calculated and was in good agreement with that obtained from literature. The hydrogen production section’s thermal efficiency was compared to that of steam methane reforming of natural gas (SMR) and it was found that the efficiencies were comparable but the SMR process was superior. The hydrogen production capacity of the HYS process was increased by a factor of 1.83. This implied that for every 1 kg of hydrogen produced by the HYS an additional 1.83 kg was produced by the proposed process addition. This lowers the cost of hydrogen produced by the HYS from $6.83 to the range of approximately $3.93 - $4.85/kg. In the event of a global hydrogen economy, traditional production methods could very well be supplemented with new and innovative methods. The integration of the wellknown methods incorporated with the new nuclear based methods of hydrogen production and chemical synthesis could facilitate the smooth transition from fossil fuel based to environmentally friendly methods. This study presents one possible integration method of nuclear based hydrogen production and conventional processing methods. This process is technically possible, efficient and economically feasible. / Thesis (M.Ing. (Nuclear Engineering))--North-West University, Potchefstroom Campus, 2009.

The gradual depletion of and dependence on fossil fuels, air pollution and global warming have all accelerated the development of alternative energy systems which use hydrogen as an energy carrier. The hybrid sulphur cycle (HyS) is the foremost electrothermochemical process that can produce hydrogen as the energy carrier. The HyS cycle consists of two units, namely the sulphuric acid decomposition reactor and the sulphur dioxide electrolyser (SDE). The SDE is responsible for the SO2 electrooxidation to sulphuric acid and protons at the anode and the electro–reduction of protons to hydrogen at the cathode. This research study focuses on the kinetic data collected from the prepared catalysts for SO2 electro–oxidation at the anode. Platinum dispersed on carbon, niobium pentoxide, tantalum pentoxide and zirconium dioxide as electrocatalysts were prepared using sodium borohydride as a reducing agent. These electrocatalysts were characterized using transmission electron microscopy and x–ray diffraction. Cyclic voltammetry was used to study the electrochemical active surface area (EAS) and the results showed that Pt/ZrO2–C had a higher EAS area than Pt/Ta2O5–C, Pt/Nb2O5–C and Pt/C. The high EAS of Pt/ZrO2–C can be explained by the low crystal size however after a series of linear polarisation scans Pt/ZrO2–C experiences a much greater area loss than all the other catalysts. Linear polarisation scans for each of the catalysts revealed that the influence of increased temperature and sulphuric acid concentration were showed improved results. Levich and Koutecky–Levich plots revealed that the SO2 oxidation is a multistep reaction on all the prepared catalysts and that there are regions which are kinetic and diffusion controlled and diffusion–only controlled. Pt/Ta2O5–C catalysts exhibited superior catalytic activity and stability compared Pt/Nb2O5–C, Pt/ZrO2–C and Pt/C. The Pt/ZrO2–C exhibited the most inferior catalytic activity and stability. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2011.

This study introduces an evaluation of the downstream utilization of oxygen produced by the hybrid sulfur process (HYS). Both technical and economic aspects were considered in the production of primarily synthesis gas and hydrogen. Both products could increase the economic potential of the hybrid sulfur process. Based on an assumed 500MWt pebble bed modular nuclear reactor, the volume of hydrogen and oxygen produced by the scaled down HYS was found to be 121 and 959 ton per day respectively. The partial oxidation plant (POX) could produce approximately 1840 ton synthesis gas per day based on the oxygen obtained from the HYS. The capital cost of the POX plant is in the order of $104 million (US dollars, Base year 2008). Compared to the capital cost of the HYS, this seems to be a relatively small additional investment. The production cost varied from a best case scenario $9.21 to a worst case scenario of $19.36 per GJ synthesis gas. The profitability analysis conducted showed favourable results, indicating that under the assumed conditions, and with 20 years of operation, a NPV of $87 mil. and an IRR of 19.5% could be obtained, for the assumed base case. The economic sensitivity analysis conducted, provided insight into the upper and lower limitations of favourable operation. The second product that could be produced was hydrogen. With the addition of a water gas shift and a pressure swing adsorption process to the POX, it was found that an additional 221 ton of hydrogen per day could be produced. The hydrogen could be produced in the best case at $2.34/kg and in the worst case at $3.76/kg. The investment required would be in the order of $50 million. The profitability analysis for the base case analysis predicts an NPV of $206 million and a high IRR of 23.0% under the assumed conditions. On financial grounds it therefore seemed that the hydrogen production process was favourable. The thermal efficiency of the synthesis gas production section was calculated and was in good agreement with that obtained from literature. The hydrogen production section’s thermal efficiency was compared to that of steam methane reforming of natural gas (SMR) and it was found that the efficiencies were comparable but the SMR process was superior. The hydrogen production capacity of the HYS process was increased by a factor of 1.83. This implied that for every 1 kg of hydrogen produced by the HYS an additional 1.83 kg was produced by the proposed process addition. This lowers the cost of hydrogen produced by the HYS from $6.83 to the range of approximately $3.93 - $4.85/kg. In the event of a global hydrogen economy, traditional production methods could very well be supplemented with new and innovative methods. The integration of the wellknown methods incorporated with the new nuclear based methods of hydrogen production and chemical synthesis could facilitate the smooth transition from fossil fuel based to environmentally friendly methods. This study presents one possible integration method of nuclear based hydrogen production and conventional processing methods. This process is technically possible, efficient and economically feasible. / Thesis (M.Ing. (Nuclear Engineering))--North-West University, Potchefstroom Campus, 2009.