Thesis (M. Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2008.

In this study, the feasibility of a NaA zeolite membrane for the gas phase separation of steam and hydrogen mixtures was determined. The Fischer-Tropsch (FT) process, which produces high value fuels and chemicals from coal and natural gas, can be greatly improved upon by the selective removal of water from the FT reactor product stream. According to the FT reaction kinetics, the rate of reaction increases with the partial pressure of hydrogen but is adversely affected the presence of water in the reactor product stream. Chemisorbed water on the surface of the metal catalysts also enhances deactivation due to sintering and fouling. The use of a zeolite membrane reactor is well equipped to serve the purpose of in-situ water removal as it can facilitate the separation of chemical components from one another in the presence of catalytic reactions. The LTA type zeolite membrane NaA or zeolite 4A, in particular, is well suited for the separation of polar (H2O) from non-polar (H2) molecules because of its high hydrophilicity. NaA has also been identified as an excellent candidate for selective water removal applications due its high adsorption affinity and capacity for water. The NaA membrane used in this study was manufactured by means of the in-situ crystallisation method where the growth of crystals on the inside surface of a centrifugally casted a-alumina support was favoured. Scanning electron microscopy (SEM) analyses performed on the membrane after a double hydrothermal synthesis indicated that the surface topology was rough and that the zeolite crystals formed were not uniform in size. Overall, the membrane thickness varied between 6.5 and 8.0 flm. An evaluation of the membrane quality was made possible through permeation experiments involving SF6 and Hz. The calculated Hz/SF6 permselectivity in this study was found to be 9.78, which despite being higher than the Knudsen diffusion selectivity of 8.54, confirmed the presence of intercrystalline defects or non-zeolitic pores in the membrane. Experiments concerning pure component and binary mixture permeation of steam and hydrogen through the supported NaA membrane were conducted over a temperature range of 115°C to 160 °c for binary hydrogen/steam mixtures, 25°C to 160°C for pure hydrogen and 130°C to 170°C for pure steam. For the permeation of pure component hydrogen, a local maximum in its permeance having a value of 224 x 10'°8 mol.m,z.s'!.Pa'! was reached at a system pressure and temperature of 6.875 bar and 75°C respectively. For the permeation of pure component steam through NaA, the effects of capillary condensation in the pores and defects of the zeolite membrane resulted in a decrease in steam permeance as a function of absolute pressure for temperatures lower than 160 °c. Once the effects of capillary condensation had receded, maxima in the steam permeances as a function of temperature corresponding to values of 70 x 10,08, 65 X 10,08 and 75 x 10,08 mol.m•2.s'I.Pa'l were found for the 182.5, 197.5 and 222.5 kPa isobars respectively. These observations collaborated well with the description of surface diffusion with permeation taking place in the Langmuir (strong adsorption) regime. Permeation experiments through NaA as function of temperature were conducted for a 90 mol% steam -10 mol% hydrogen (90-10) binary mixture as well as for a 60-40 mixture of these two. At low temperatures the permeation of hydrogen was completely suppressed by the condensed steam resulting in an almost perfect separation. The Kelvin equation was used to estimate the pore size of the defects which was found to range between 1.86 and 2.45 nm. The temperature range over which these defects in the membrane were assumed to become unblocked (i.e. assuming when the first breakthrough of hydrogen occurred), were determined to be between 140 to 148 °c and between 128 to 130 °c for the 90-10 and 60-40 mixtures respectively. The mixture selectivities (towards water) between 115 °c and 130 °c were found to be immensely high (much greater than 1000) for both the 90-10 and 60-40 mixtures, while the ideal selectivities were calculated to be less than lover the same temperature range. At 140 °c, the selectivity towards water for the 9010 mixture was still greater than 1000; however for the 60-40 mixture at this temperature, an inversion of selectivity towards H2 had already taken place. The breakthrough in H2 permeance occurs at a much lower temperature when the feed mixture contains a lower concentration of water. Since the partial pressure of steam will be reduced, larger pores will become unblocked at lower temperatures according to the Kelvin equation. / Thesis (M. Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2008.

In this study, the feasibility of a NaA zeolite membrane for the gas phase separation of steam and hydrogen mixtures was determined. The Fischer-Tropsch (FT) process, which produces high value fuels and chemicals from coal and natural gas, can be greatly improved upon by the selective removal of water from the FT reactor product stream. According to the FT reaction kinetics, the rate of reaction increases with the partial pressure of hydrogen but is adversely affected the presence of water in the reactor product stream. Chemisorbed water on the surface of the metal catalysts also enhances deactivation due to sintering and fouling. The use of a zeolite membrane reactor is well equipped to serve the purpose of in-situ water removal as it can facilitate the separation of chemical components from one another in the presence of catalytic reactions. The LTA type zeolite membrane NaA or zeolite 4A, in particular, is well suited for the separation of polar (H2O) from non-polar (H2) molecules because of its high hydrophilicity. NaA has also been identified as an excellent candidate for selective water removal applications due its high adsorption affinity and capacity for water. The NaA membrane used in this study was manufactured by means of the in-situ crystallisation method where the growth of crystals on the inside surface of a centrifugally casted a-alumina support was favoured. Scanning electron microscopy (SEM) analyses performed on the membrane after a double hydrothermal synthesis indicated that the surface topology was rough and that the zeolite crystals formed were not uniform in size. Overall, the membrane thickness varied between 6.5 and 8.0 flm. An evaluation of the membrane quality was made possible through permeation experiments involving SF6 and Hz. The calculated Hz/SF6 permselectivity in this study was found to be 9.78, which despite being higher than the Knudsen diffusion selectivity of 8.54, confirmed the presence of intercrystalline defects or non-zeolitic pores in the membrane. Experiments concerning pure component and binary mixture permeation of steam and hydrogen through the supported NaA membrane were conducted over a temperature range of 115°C to 160 °c for binary hydrogen/steam mixtures, 25°C to 160°C for pure hydrogen and 130°C to 170°C for pure steam. For the permeation of pure component hydrogen, a local maximum in its permeance having a value of 224 x 10'°8 mol.m,z.s'!.Pa'! was reached at a system pressure and temperature of 6.875 bar and 75°C respectively. For the permeation of pure component steam through NaA, the effects of capillary condensation in the pores and defects of the zeolite membrane resulted in a decrease in steam permeance as a function of absolute pressure for temperatures lower than 160 °c. Once the effects of capillary condensation had receded, maxima in the steam permeances as a function of temperature corresponding to values of 70 x 10,08, 65 X 10,08 and 75 x 10,08 mol.m•2.s'I.Pa'l were found for the 182.5, 197.5 and 222.5 kPa isobars respectively. These observations collaborated well with the description of surface diffusion with permeation taking place in the Langmuir (strong adsorption) regime. Permeation experiments through NaA as function of temperature were conducted for a 90 mol% steam -10 mol% hydrogen (90-10) binary mixture as well as for a 60-40 mixture of these two. At low temperatures the permeation of hydrogen was completely suppressed by the condensed steam resulting in an almost perfect separation. The Kelvin equation was used to estimate the pore size of the defects which was found to range between 1.86 and 2.45 nm. The temperature range over which these defects in the membrane were assumed to become unblocked (i.e. assuming when the first breakthrough of hydrogen occurred), were determined to be between 140 to 148 °c and between 128 to 130 °c for the 90-10 and 60-40 mixtures respectively. The mixture selectivities (towards water) between 115 °c and 130 °c were found to be immensely high (much greater than 1000) for both the 90-10 and 60-40 mixtures, while the ideal selectivities were calculated to be less than lover the same temperature range. At 140 °c, the selectivity towards water for the 9010 mixture was still greater than 1000; however for the 60-40 mixture at this temperature, an inversion of selectivity towards H2 had already taken place. The breakthrough in H2 permeance occurs at a much lower temperature when the feed mixture contains a lower concentration of water. Since the partial pressure of steam will be reduced, larger pores will become unblocked at lower temperatures according to the Kelvin equation. / Thesis (M. Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2008.

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The present work focuses on the study of biomass gasification process for generating hydrogen rich synthetic gas with oxy-steam as reactants using experiments and modeling studies. Utilization of the syngas as a fuel in general applications like fuel cells, Fischer-Tropsch FT) process and production of various chemicals like DME, etc. are being considered to meet the demand for clean energy. This study comprises of experiments using an open top down draft reactor with oxygen and steam as reactants in the co-current configuration. Apart from the standard gasification performance evaluation; parametric study using equivalence ratio, steam-to-biomass ratio as major variables towards generation of syngas is addressed towards controlling H2/CO ratio. The gasification process is modeled as a packed bed reactor to predict the exit gas composition, propagation rate, bed temperature as a function of input reactants, temperature and mass flux with variation in thermo-physical properties of biomass. These results are compared with the present experiments as well as those in literature. Experiments are conducted using modified open top downdraft configuration reactor with lock hoppers and provision for oxy-steam injection, and the exit gas is connected to the cooling and cleaning system. The fully instrumented system is used to measure bed temperatures, steam and exit gas temperature, pressures at various locations, flow rates of fuel, reactants and product gas along with the gas composition. Preliminary investigations focused on using air as the reactant and towards establishing the packed bed performance by comparing with the experimental results from the literature and extended the study to O2-N2 mixtures. The study focuses on determining the propagation rate of the flame front in the packed bed reactor for various operating conditions. O2 is varied between 20-100% (vol.) in a mixture of O2-N2 to study the effect of O2 fraction on flame propagation rate and biomass conversion. With the increase in O2 fraction, the propagation rates are found to be very high and reaching over 10 mm/s, resulting in incomplete pyrolysis and poor biomass conversion. The flame propagation rate is found to vary with oxygen volume fraction as XO22.5, and stable operation is achieved with O2 fraction below 30%. Towards introducing H2O as a reactant for enhancing the hydrogen content in the syngas and also to reduce the propagation rates at higher ER, wet biomass is used. Stable operating conditions are achieved using wet biomass with moisture-to-biomass (H2O:Biomass) ratio between 0.6 to 1.1 (mass basis) and H2 yield up to 63 g/kg of dry biomass amounting to 33% volume fraction in the syngas. Identifying the limitation on the hydrogen yield and the criticality of achieving high quality gas; oxy-steam mixture is introduced as reactants with dry biomass as fuel. An electric boiler along with a superheater is used to generate superheated steam upto 700 K and pressure in the range of 0.4 MPa. Steam-to-biomass ratio (SBR) and ER is varied with towards generating hydrogen rich syngas with sustained continuous operation of oxy-steam gasification of dry biomass. The results are analysed with the variation of SBR for flame propagation rates, calorific value of product syngas, energy efficiency, H2 yield per kg of biomass and H2/CO ratio. Hydrogen yield of 104 g per kg of dry casuarina wood is achieved amounting to 50.5% volume fraction in dry syngas through oxy-steam gasification process compared to air gasification hydrogen yield of about 40 g per kg of fuel and 20% volume fraction. First and second law analysis for energy and exergy efficiency evaluation has been performed on the experimental results and compared with air gasification. Individual components of the energy input and output are analysed and discussed. H2 yield is found to increase with SBR with the reduction in energy density of syngas and also energy efficiency. Highest energy efficiency of 80.3% has been achieved at SBR of 0.75 (on molar basis) with H2 yield of 66 g/kg of biomass and LHV of 8.9 MJ/Nm3; whereas H2 yield of 104 g/kg of biomass is achieved at SBR of 2.7 with the lower efficiency of 65.6% and LHV of 7.4 MJ/Nm3. The energy density of the syngas achieved in the present study is roughly double compared to the LHV of typical product gas with air gasification. Elemental mass balance technique has been employed to identify carbon boundary at an SBR of 1.5. Controlling parameters for arriving at the desired H2/CO ratio in the product syngas have been identified. Optimum process parameters (ER and SBR) has been identified through experimental studies for sustained continuous oxy-steam gasification process, maximizing H2 yield, controlling the H2/CO ratio, high energy efficiency and high energy density in the product syngas. Increase in ER with SBR is required to compensate the reduction in O2 fraction in oxy-steam mixture and to maintain the desired bed temperature in the combustion zone. In the range of SBR of 0.75 to 2.7, ER requirement increases from 0.18 to 0.3. The sustained continuous operation is possible upto SBR of 1.5, till the carbon boundary is reached. Operating at high SBR is required for high H2 yield but sustained highest H2 yield is obtained as SBR of 1.5. H2/CO ratio in the syngas increases from 1.5 to 4 with the SBR and depending on the requirement of the downstream process (eg., FT synthesis), suitable SBR and ER combination is suggested. To obtain high energy density in syngas and high energy efficiency, operations at lower SBR is recommended. The modeling study is the extension of the work carried by Dasappa (1999) by incorporating wood pyrolysis model into the single particle and volatile combustion for the packed bed of particles. The packed bed reactor model comprises of array of single particles stacked in a vertical bed that deals with the detailed reaction rates along with the porous char spheres and thermo-physical phenomenon governed by the mass, species and energy conservation equations. Towards validating the pyrolysis and single particle conversion process, separate analysis and parametric study addressing the effects of thermo-physical parameters like particle size, density and thermal conductivity under varying conditions have been studied and compared with the available results from literature. It has been found that the devolatilisation time of particle (tc) follows closely the relationship with the particle diameter (d), thermal conductivity (k), density () and temperature (T) as: The complete combustion of a single particle flaming pyrolysis and char combustion has been studied and validated with the experimental results. For the reactor modeling, energy, mass and species conservation equations in the axial flow direction formulate the governing equations coupled to the detailed single particle analysis. Gas phase reactions involving combustion of volatiles and water gas shift reaction are solved in the packed bed. The model results are compared with the experimental results from wood gasification system with respect to the propagation rate, conversion times, exit gas composition and other bed parameters like conversion, peak bed temperatures, etc. The propagation rates compare well with experimental data over a range of oxygen concentration in the O2- N2 mixture, with a peak at 10 mm/s for 100 % O2. In the case of oxy-steam gasification of dry biomass, the results clearly suggest that the char conversion is an important component contributing to the bed movement and hence the overall effective propagation rate is an important parameter for co-current reactors. This is further analyzed using the carbon boundary points based on elemental balance technique. The model predictions for the exit gas composition from the oxy-steam gasification matches well with the experimental results over a wide range of equivalence ratio and steam to biomass ratio. The output gas composition and propagation rates are found to be a direct consequence of input mass flux and O2 fraction in oxy-steam mixture. The present study comprehensively addresses the oxy-steam gasification towards generating hydrogen rich syngas using experimental and model studies. The study also arrives at the parameters for design consideration towards operating an oxy-steam biomass gasification system. The following flow chart provides the overall aspects that are covered in the thesis chapter wise.