L'hydrogène n'étant pas une énergie primaire, il faut donc le produire, le transporter et le stocker avant de l'utiliser. Il peut être produit par des procédés chimiques, électrolytiques ou biologiques à partir de ressources renouvelables, ou non. Les énergies fossiles représentent la première ressource d'hydrogène, avec 96% de la production totale mondiale, dont 48% se fait à base de gaz naturel qui contient essentiellement du méthane. Dans cette thèse, nous nous intéressons à la génération de l'hydrogène par le procédé de vaporeformage du méthane qui reste le procédé le plus utilisé pour sa conversion. Les objectifs consistent premièrement à explorer, par des études numériques, les performances thermiques et massiques d'un vapo-reformeur à parois catalytiques, dans lequel une répartition discrète du catalyseur est adoptée, combinée ou non, avec une insertion d'un matériau cellulaire à haute porosité, de type mousse métallique, et deuxièmement à analyser, par une approche expérimentale complétée par une procédure numérique inverse, afin d'estimer le flux de chaleur inconnu reçu par le mélange gazeux. Les configurations géométriques adoptées dans les études numériques sont modélisées par les équations deconservation et complétées par les conditions aux limites. La cinétique de la réaction est régie par un modèle basé sur les lois de puissance, et le système d'équations est résolu par la méthode des volumes finis. Pour l'estimation du flux de chaleur, un dispositif expérimental approchant le système de chauffage du réacteur est conçu afin de mesurer la distribution de la température et un code de calcul inverse basé sur la méthode spécification de fonctions. Les résultats montrent que les performances du procédé de vaporeformage peuvent être améliorées en adoptant une bonne distribution du catalyseur sur les parois du réacteur muni d'une mousse métallique dans sa région catalytique. Les améliorations obtenues en termes de conversion de méthane, par rapport à une configuration classique, sont de l'ordre de 44.6%. De plus, la combinaison des approches expérimentale et numérique a permis de déterminer la quantité de chaleur nette transférée par le système de chauffage du vaporeformeur. / Hydrogen is not a primary energy; we must produce it, transport it and store it before use. It cans be produced by chemical, biological or electrolytic processes from renewable resources or not. Fossil fuels represent the first hydrogen resource, with 96% of total world production, which 48% is made from natural gas containing methane. In this thesis, we focus on the generation of hydrogen by the steam-methane reforming process, which is the most used conversion method. The aims consist first to explore, through numerical studies, the thermal and mass performances of a wall coated steam-methane reformer, wherein a discrete distribution of the catalyst is adopted, combined or not, with an insertion of a highly porous metal foam, and secondly to analyze, by an experimental approach completed by a numerical inverse procedure to estimate the unknown heat flux received by the gas mixture. The geometric configurations adopted in the numerical studies are modeled by the conservation equations and the boundary conditions. The kinetic reaction is governed by a model based on power laws, and the system of equations is solved by the finite volume method. For the estimation of heat flux, an experimental device approachingthe reactor heating system is designed to measure the temperature distribution, and an inverse code based on the function specification method. The results show that the steam methane reforming process performances can be improved by adopting a good distribution of the catalyst on the walls of the reactor fitted on its catalytic region with metal foam. The improvements obtained in terms of methane conversion, compared to a conventional configuration, are of the order of 44.6%. In addition, the combination of experimental and numerical approaches was used to determine the net quantity of heat transferred from the heating system to the steam reformer.

<p>Hydrogen is considered to be an important potential energy carrier; however, its advantages are unlikely to be realized unless efficient means can be found to produce it without generation of CO₂. Sorption-enhanced steam methane reforming (SE-SMR) represent a novel, energy-efficient hydrogen production route with <i>in situ</i><b> </b>CO₂ capture, shifting the reforming and water gas shift reactions beyond their conventional thermodynamic limits.</p><p>The use of fluidized bed reactors for SE-SMR has been investigated. Arctic dolomite, a calcium-based natural sorbent, was chosen as the primary CO₂-acceptor in this study due to high absorption capacity, relatively high reaction rate and low cost. An experimental investigation was conducted in a bubbling fluidized bed reactor of diameter 0.1 m, which was operated cyclically and batchwise, alternating between reforming/carbonation conditions and higher-temperature calcination conditions. Hydrogen concentrations of >98 mole% on a dry basis were reached at 600°C and 1 atm, for superficial gas velocities in the range of ~0.03-0.1 m/s. Multiple reforming-regeneration cycles showed that the hydrogen concentration remained at ~98 mole% after four cycles. The total production time was reduced with an increasing number of cycles due to loss of CO₂-uptake capacity of the dolomite, but the reaction rates of steam reforming and carbonation seemed to be unaffected for the conditions investigated.</p><p>A modified shrinking core model was applied for deriving carbonation kinetics of Arctic dolomite, using experimental data from a novel thermo gravimetric reactor. An apparent activation energy of 32.6 kJ/mole was found from parameter fitting, which is in good agreement with previous reported results. The derived rate expression was able to predict experimental conversion up to ~30% very well, whereas the prediction of higher conversion levels was poorer. However, the residence time of sorbent in a continuous reformer-calciner system is likely to be rather low, so that only a fraction of the sorbent is utilized, highlighting the importance of the carbonation model at lower conversions.</p><p>A dual fluidized bed reactor for the SE-SMR system was modeled by using a simple two-phase hydrodynamic model, the experimentally derived carbonation kinetics and literature values for the kinetics of steam reforming and water gas shift reactions. The model delineates important features of the process. Hydrogen concentrations of >98 mole% were predicted for temperatures ~600°C and a superficial gas velocity of 0.1 m/s. The reformer temperature should not be lower than 540°C or greater than 630°C for carbon capture efficiencies to exceed 90%. Operating at relatively high solid circulation rates to reduce the need for fresh sorbent, is predicted to give higher system efficiencies than for the case where fresh solid is added. This finding is attributed to the additional energy required to decompose both CaCO₃ and MgCO₃ in fresh dolomite. Moreover, adding fresh sorbent is likely to result in catalyst loss in the purge stream, requiring sorbents with lifetimes comparable to those of the catalyst.</p><p>Thermo gravimetric analysis (TGA) was used to study the reversible CO₂-uptake of sorbents. In general, the multi-cycle capacity of the dolomite was found rather poor. Therefore, synthetic sorbents that maintain their capacities upon multiple reforming-calcination cycles were investigated. A low-temperature liquid phase co-precipitation method was used for synthesis of Li₂ZrO₃ and Na₂ZrO₃. Li₂ZrO₃ showed a superior multi-cycle capacity compared to Arctic dolomite in TGA, but the rate of reaction in diluted CO₂ atmospheres was very slow. The synthesized Na₂ZrO₃ proved to have both fast carbonation kinetics and stable multi-cycle performance. However, regeneration in the presence of carbon dioxide was not easily accomplished.</p><p>The findings of this thesis suggest that the bubbling fluidized bed reactor is an attractive reactor configuration for SE-SMR. Low gas throughput is the major disadvantage for this configuration, and operation in the fast fluidization regime is most likely to be preferred on an industrial scale of the process. Future work should focus on developing sorbents and catalysts that are suited for high velocity operation, with respect to reactivity and mechanical strength.</p>

This thesis encompasses CO2 mitigation using three different processes: i) natural gas-fired combined cycle with chemical looping combustion (CLC), ii) trigeneration of electrical power, hydrogen and district heating with extended CLC, iii) steam-based gasification of biomass integrated in an advanced power cycle. In CLC, a solid oxygen carrier circulates between two fluidised-bed reactors and transports oxygen from the combustion air to the fuel; thus, the fuel is not mixed with air and an inherent CO2 separation occurs. In this thesis, CLC has been studied as an alternative process for CO2 capture in a natural gas-fired combined cycle (NGCC). The potential efficiency of such a process using a turbine inlet temperature of 1200 °C and a pressure ratio of 13 is between 52 and 53 % when including the penalty for CO2 compression to 110 bar. It is shown that this efficiency cannot be further improved by including an additional CO2 turbine. Two conceivable reactor designs for CLC in an NGCC are presented. Top-firing has been studied as an option to overcome a temperature limitation in the CLC reactor system. The degree of CO2 capture is shown versus the temperature in the CLC reactor and its combustion efficiency. CLC has the potential to reach both a higher efficiency and a higher degree of CO2 capture than conventional post combustion CO2 capture technique. However, further research is needed to solve technical problems as, for example, temperature limitations in the reactor to reach this potential. Extended CLC (exCLC) is introduced, in which hydrogen is not only produced but also inherently purified. The potential efficiency of a novel tri-generation process for hydrogen, electricity and district heating using exCLC for CO2 capture is investigated. The results show that a thermal efficiency of about 54% might be achieved. A novel power process named evaporative biomass air turbine (EvGT-BAT) for biomass feedstock is presented. This process contains a steam-based gasification of biomass, which is integrated in an externally fired gas turbine cycle with top-firing. In the EvGT-BAT process, the steam-based gasification is conducted in an entrained-flow tubular reactor that is installed in the SFC as a heat exchanger. The EvGT-BAT process has the potential to generate electrical power from biomass with an efficiency of 41 %.

Biological hydrogen production is a renewable, carbon-neutral and clean route for hydrogen production. Purple non-sulfur (PNS) bacteria have the ability to produce biohydrogen via photofermentation process. The type of the bacterial strain used in photofermentation is known to have an important effect on hydrogen yield. In this study, the effect of different co-cultures of PNS bacteria on photofermentation process was investigated in search of improving the hydrogen yield. For this purpose, growth, hydrogen production and substrate utilization of single and co-cultures of different PNS bacteria (R. capsulatus (DSM 1710), R. capsulatus hup- v (YO3), R. palustris (DSM 127) and R. sphaeroides O.U.001 (DSM 5864)) were compared on artificial H2 production medium in 150 mL photobioreactors under continuous illumination and anaerobic conditions. In general, higher hydrogen yields were obtained via co-cultivation of two different PNS bacteria when compared with single cultures. Further increase in hydrogen yield was observed with co-cultivation of three different PNS bacteria. Co-cultures of two different PNS bacteria have resulted in up to 1.4 and 2.1 fold increase in hydrogen yield and hydrogen productivity. Whereas co-cultures of three different PNS bacteria have resulted in up to 1.6 and 2.0 fold increase in hydrogen yield and hydrogen productivity compared to single cultures. These results indicate that, defined co-cultures of PNS bacteria produce hydrogen at a higher yield and productivity, due most probably to some synergistic relationship. Further studies regarding the physiological and molecular changes need to be carried out for deeper understanding of the mechanism of hydrogen production in co-cultures.

The reactions between aqueous radiolysis products and oxide surfaces are important in nuclear technology in many ways. In solid-liquid systems, they affect (and at the same time are dependent on) both the solution chemistry and the stability of materials under the influence of ionizing radiation. The stability of surface oxides is a factor that determines the longevity of the materials where such oxides are formed. Additionally, the aqueous radiolysis products are responsible for corrosion and erosion of the materials.   In this study, the reactions between radiolysis products of water – mainly H2O2 and HO radicals – with metal, lanthanide and actinide oxides are investigated. For this, experimental and computational chemistry methods are employed. For the experimental study of these systems it was necessary to implement new methodologies especially for the study of the reactive species – the HO radicals. Similarly, the computational study also required the development of models and benchmarking of methods. The experiments combined with the computational chemistry studies produced valuable kinetic, energetic and mechanistic data.   It is demonstrated here that the HO radicals are a primary product of the decomposition of H2O2. For all the materials, the catalytic decomposition of H2O2 consists first of molecular adsorption onto the surfaces of the oxides. This step is followed by the cleavage of the O-O bond in H2O2 to form HO radicals. The HO radicals are able to react further with the hydroxylated surfaces of the oxides to form water and a surface bound HO• center. The dynamics of formation of HO• vary widely for the different materials studied. These differences are also observed in the activation energies and kinetics for decomposition of H2O2. It is found further that the removal of HO• from the system where H2O2 undergoes decomposition, by means of a scavenger, leads to the spontaneous formation of H2.   The combined theoretical-experimental methodology led to mechanistic understanding of the reactivity of the oxide materials towards H2O2 and HO radicals. This reactivity can be expressed in terms of fundamental properties of the cations present in the oxides. Correlations were found between several properties of the metal cations present in the oxides and adsorption energies of H2O, adsorption energies of HO radicals and energy barriers for H2O2 decomposition. This knowledge can aid in improving materials and processes important for nuclear technological systems, catalysis, and energy storage, and also help to better understand geochemical processes. / <p>QC 20130322</p>

This research investigates an alternative approach to the use of two wastes from agricultural and livestock activities developed in Colombia. Swinemanure and coffee mucilage were used to evaluatean anaerobic co-digestion process focused on hydrogen production. In addition, the aims covered a further stage in order to close the cycle of the both wastes. The thesis was conducted in three phases : 1. Evaluation of hydrogen production from the co-digestion of coffee mucilage and swine manure during dark fermentation ; 2. Trends over retention time through the monitoring of microorganisms by quantitative PCR and other parameters incluiding pH, oxidation reduction potential, and hydrogen partial pressure ; 3. Treatment of the effluent from hydrogen production process by anaerobic digestion with methane production. The experimental results showed that mixtures of both wastes are able to produce hydrogen. A substrate ratio of 5:5, which was associated with a C/N ratio of 53, was suitable for hydrogen production. Moreover, the stability and optimization of the process were evaluated by increasing the influent organic load rate. This wasthe best experimental condition in terms of average cumulative hydrogen volume, production rate and yield which were 2661 NmL, 760 NmLH2/Lwd and 43 NmL H2/gCOD, respectively. This performance was preserved over time, which was verified through the repetitive batch cultivation during 43 days. Two trends were identified over retention time associated with similar cumulative hydrogen, but with differences in lag-phase time and hydrogen production rate. T.thermosaccharolyticum was the dominating genus during the short trend related to the shortest lag phase time and highest hydrogen production rate. The long trends were associated with a decrease of Bacillus sp. concentration at the beginning of the experiments and with the possible competition for soluble substrates between T.thermosaccharolyticum and Clostridium sp. The third phase showed that the use of a second stage to produce methane was useful enhancing the treatment of both wastes. Finally, the overall energy produced for both biofuels (Hydrogen andmethane) showed similar levels with other process. However, hydrogen was around the 10% of the overall energy produced in the process. In addition, both gases could be mixed to produce biohythane which improves the properties of biogas.

Nuclear-based hydrogen production via thermochemical water decomposition using a copper-chlorine cycle consists of a series of chemical reactions that split water into hydrogen and oxygen. This is accomplished through reactions involving intermediate copper and chlorine compounds, which act as catalysts that are recycled in the process. In this thesis, analytical and numerical solutions are developed to predict the behaviour of aqueous cupric chloride droplets in a solution undergoing spray-drying in the Cu-Cl cycle. The aqueous CuCl2 is present as a slurry within the cycle, which will later generate oxygen and hydrogen as a net result. The efficiency of the cycle can be increased by utilizing low-grade waste heat from any industrial source or nuclear power plant to assist in the drying process. There are many different methods employed in industry for drying of solutions. Each method has its own advantages and disadvantages, depending on the application and conditions. In this thesis, analytical correlations of heat and mass transfer are developed for the aqueous solution, subject to various drying conditions. The analysis is performed for moist air in contact with a sprayed aqueous solution of CuCl2(2H2O). Validation of the model is performed by comparisons with experimental results obtained from a Niro-spray dryer for CuCl2 and previous experimental and theoretical data for different fluids, on the basis of non-dimensional analysis. / UOIT

In this thesis, a number of clean-energy materials for hydrogen generation, hydrogen storage, and Li-ion battery energy storage applications have been investigated through state-of-the-art density functional theory. As an alternative fuel, hydrogen has been regarded as one of the promising clean energies with the advantage of abundance (generated through water splitting) and pollution-free emission if used in fuel cell systems. However, some key problems such as finding efficient ways to produce and store hydrogen have been hindering the realization of the hydrogen economy. Here from the scientific perspective, various materials including the nanostructures and the bulk hydrides have been examined in terms of their crystal and electronic structures, energetics, and different properties for hydrogen generation or hydrogen storage applications. In the study of chemisorbed graphene-based nanostructures, the N, O-N and N-N decorated ones are designed to work as promising electron mediators in Z-scheme photocatalytic hydrogen production. Graphene nanofibres (especially the helical type) are found to be good catalysts for hydrogen desorption from NaAlH4. The milestone nanomaterial, C60, is found to be able to significantly improve the hydrogen release from the (LiH+NH3) mixture. In addition, the energetics analysis of hydrazine borane and its derivative solid have revealed the underlying reasons for their excellent hydrogen storage properties.  As the other technical trend of replacing fossil fuels in electrical vehicles, the Li-ion battery technology for energy storage depends greatly on the development of electrode materials. In this thesis, the pure NiTiH and its various metal-doped hydrides have been studied as Li-ion battery anode materials. The Li-doped NiTiH is found to be the best candidate and the Fe, Mn, or Cr-doped material follows. / <p>QC 20130925</p>

As reserves of conventional crude oil are depleted, there is a growing need to develop unconventional oils such as heavy oil and bitumen from oil sands. In terms of recoverable oil, Canadian oil sands are considered to be the second largest oil reserves in the world. However, the upgrading of bitumen from oil sands to synthetic crude oil (SCO) requires nearly ten times more hydrogen (H₂) than the conventional crude oils. The current H₂ demand for oil sands operations is met mostly by steam reforming of natural gas. With the future expansion of oil sands operations, the demand of H₂ for oil sand operations is likely to quadruple in the next decade. As natural gas reforming involves significant carbon dioxide (CO₂) emissions, this sector is likely to be one of the largest emitters of CO₂ in Canada. <br> <br>In the current H₂ plants, CO₂ emissions originate from two sources, the combustion flue gases from the steam reformer furnace and the off-gas from the process (steam reforming and water-gas shift) reactions. The objective of this study is to develop a process that captures CO₂ at minimum energy penalty in typical H₂ plants. <br> <br>The approach is to look at the best operating conditions when considering the H₂ and steam production, CO₂ production and external fuel requirements. The simulation in this study incorporates the kinetics of the steam methane reforming (SMR) and the water gas shift (WGS) reactions. It also includes the integration of CO₂ capture technologies to typical H₂ plants using pressure swing adsorption (PSA) to purify the H₂ product. These typical H₂ plants are the world standard of producing H₂ and are then considered as the base case for this study. The base case is modified to account for the implementation of CO₂ capture technologies. Two capture schemes are tested in this study. The first process scheme is the integration of a monoethanolamine (MEA) CO₂ scrubbing process. The other scheme is the introduction of a cardo polyimide hollow fibre membrane capture process. Both schemes are designed to capture 80% of the CO₂ from the H₂ process at a purity of 98%. <br> <br>The simulation results show that the H₂ plant with the integration of CO₂ capture has to be operated at the lowest steam to carbon (S/C) ratio, highest inlet temperature of the SMR and lowest inlet temperatures for the WGS converters to attain lowest energy penalty. H₂ plant with membrane separation technology requires higher electricity requirement. However, it produces better quality of steam than the H₂ plant with MEA-CO₂ capture process which is used to supply the electricity requirement of the process. Fuel (highvale coal) is burned to supply the additional electricity requirement. The membrane based H₂ plant requires higher additional electricity requirement for most of the operating conditions tested. However, it requires comparable energy penalty than the H₂ plant with MEA-CO₂ capture process when operated at the lowest energy operating conditions at 80% CO₂ recovery. <br> <br>This thesis also investigates the sensitivity of the energy penalty as function of the percent CO₂ recovery. The break-even point is determined at a certain amount of CO₂ recovery where the amount of energy produced is equal to the amount of energy required. This point, where no additional energy is required, is approximately 73% CO₂ recovery for the MEA based capture plant and 57% CO₂ recovery for the membrane based capture plant. <br> <br>The amount of CO₂ emissions at various CO₂ recoveries using the best operating conditions is also presented. The results show that MEA plant has comparable CO₂ emissions to that of the membrane plant at 80% CO₂ recovery. MEA plant is more attractive than membrane plant at lower CO₂ recoveries.

The main objective of this study is exploring the parameters affecting photobiological hydrogen production and developing anaerobic photobioreactor for efficient photofermentative hydrogen production from organic acids in outdoor conditions. Rhodobacter capsulatus and Rhodobacter sphaeroides strains were used as microorganisms. EU project &ldquo / Hyvolution&rdquo / targets to combine thermophilic fermentation with photofermentation for the conversion of biomass to hydrogen. In this study, the effluent obtained by dark fermentation of Miscanthus hydrolysate by T. neapolitana was fed to photobioreactor for photofermentation by R. capsulatus. Hydrogen yield was 1.4 L/Lculture showing that the integration of dark and photofermentation is possible. Innovative elements were introduced to the photobioreactor design such as removal of argon flushing. An online gas monitoring system was developed which became a commercial product. It was found that the light intensity should be at least 270 W/m2 on the bioreactor surface for the highest hydrogen productivity and the hydrogen production decreased by 43 % if infrared light was not provided to the bioreactor. Scale-up of photofermentation process to 25L was achieved yielding 27L hydrogen in 11 days by R. capsulatus on acetate/lactate/glutamate (40/7.5/2 mM) medium. The outdoor application of the system was made. Shading and water spraying were adapted as cooling methods for controlling the temperature of the outdoor bioreactor. It was found that uptake hydrogenase deleted mutant of R. capsulatus show better hydrogen productivity (0.52 mg/L.h) compared to the wild type parent (0.27 mg/L.h) in outdoor conditions. It was also shown that the hydrogen production depended on the sunlight intensity received.