This thesis is concerned with the thermodynamic analyses of ion and proton-conducting solid oxide fuel cells (SOFC) fed with ammonia and urea as fuels. A multi-level approach was used to determine the feasibility and the performance of the fuel cells. First, the cell-level thermodynamics were examined to capture the effect of various operating parameters on the cell voltage under open-circuit conditions. Second, electrochemical studies were conducted to characterize the cell-level performance under closed-circuit conditions. Third, the fuel cells were individually integrated in a combined-cycle power generation system and parametric studies were performed to assess the overall performance as well as the thermal and exergy efficiencies. The findings of this study showed that the overall performance and efficiency of the ammonia fed SOFC is superior in comparison to that of the urea fed counterpart. In particular, the ammonia fed system combined with proton-conducting SOFC achieved a thermal efficiency as high as 85% and exergy efficiency as high as 75%. The respective efficiencies of the ammonia fed system combined with ion-conducting SOFC were lower by 5-10%. However, the urea fed system combined with ion or proton-conducting SOFC demonstrated much lower performance and efficiencies due to higher thermodynamic irreversibilities. / UOIT

Today, energy has become one of the most indispensable necessities in the world. Most of the wars and the disputes between the countries have been arising because of the increasing scarcity of energy resources. Therefore, like most country, Turkey has also started to develop new energy policies for more efficient production and utilization of energy. In order to help the understanding of more efficient energy utilization, so far there have been some researches made about energy and exergy (available energy) utilization efficiencies of Turkey with the viewpoint of the quality of energy. In this study, it is aimed to examine energy system of Turkey by computing energy and exergy utilization efficiencies between 1990 and 2006 using the first and the second laws of thermodynamics. The utility sector energy efficiencies are found to range from 41% to 47% and the exergy efficiencies to range from 42% and 48% between 1990 and 2006. The energy efficiencies of the end use sectors of Turkey , namely Industrial, Transportation, Agricultural and Residential-Commercial sectors, are respectively 62%, 22%, 27% and 55% on the average with respect to years. On the other hand, their average exergy efficiencies are 33%, 23%, 27% and 7% between the examined years. The total end use energy and exergy efficiencies are 49% and 21% on the average. Overall energy efficiencies of Turkey range between 37% and 41%, whereas overall exergy efficiencies range between 16% and 17%. Within all the sectors, Residential&ndash / Commercial sector is found as the sector having the highest exergetic improvement potential.

Master of Science / Department of Mechanical and Nuclear Engineering / Hitesh Bindra / Storing excess thermal energy in a storage media that can later be extracted during peak-load times is one of the better economical options for nuclear power in future. Thermal energy storage integration with light water-cooled and advanced nuclear power plants is analyzed to assess technical feasibility of different storage media options. Various choices are considered in this study; molten salts, synthetic heat transfer fluids, and packed beds of solid rocks or ceramics. In-depth quantitative assessment of these integration possibilities are then analyzed using exergy analysis and energy density models. The exergy efficiency of thermal energy storage systems is quantified based on second law thermodynamics. The packed bed of solid rocks is identified as one of the only options which can be integrated with upcoming small modular reactors. Directly storing thermal energy from saturated steam into packed bed of rocks is a very complex physical process due to phase transformation, two phase flow in irregular geometries and percolating irregular condensate flow. In order to examine the integrated physical aspects of this process, the energy transport during direct steam injection and condensation in the dry cold randomly packed bed of spherical alumina particles was experimentally and theoretically studied. This experimental setup ensures controlled condensation process without introducing significant changes in the thermal state or material characteristics of heat sink. Steam fronts at different flow rates were introduced in a cylindrical packed bed and thermal response of the media was observed. The governing heat transfer modes in the media are completely dependent upon the rate of steam injection into the system. A distinct differentiation between the effects of heat conduction and advection in the bed were observed with slower steam injection rates. A phenomenological semi-analytical model is developed for predicting quantitative thermal behavior of the packed bed and understanding physics. The semi-analytical model results are compared with the experimental data for the validation purposes. The steam condensation process in packed beds is very stable under all circumstances and there is no effect of flow fluctuations on thermal stratification in packed beds. With these experimental and analytical studies, it can be concluded that packed beds have potential for thermal storage applications with steam as heat transfer fluid. The stable stratification and condensation process in packed beds led to design of a novel passive safety heat removal system for advanced boiling water reactors.

Thermal energy storage (TES) is an advanced technology for storing thermal energy that can mitigate environmental impacts and facilitate more efficient and clean energy systems. Thermochemical TES is an emerging method with the potential for high energy density storage. Where space is limited, therefore, thermochemical TES has the highest potential to achieve the required compact TES. Principles of thermochemical TES are presented and thermochemical TES is critically assessed and compared with other TES types. The integration of TES systems with heating, ventilating and air conditioning (HVAC) applications is examined and reviewed accounting for various factors, and recent advances are discussed. Thermodynamics assessments are presented for general closed and open thermochemical TES systems. Exergy and energy analyses are applied to assess and compare the efficiencies of the overall thermochemical TES cycle and its charging, storing and discharging processes. Examples using experimental data are presented to illustrate the analyses. Some important factors related to design concepts of thermochemical TES systems are considered and preliminary design conditions for them are investigated. Parametric studies are carried out for the thermochemical storage systems to investigate the effects of selected parameters on the efficiency and behavior of thermochemical storage systems. / UOIT

O presente trabalho propõe uma metodologia científica, com critérios bem definidos, para avaliar e quantificar o desempenho ambiental e a renovabilidade de processos de tratamento de esgoto, numa base única: a exergia. O desempenho ambiental é quantificado através do cálculo da eficiência exergética ambiental, definida como a razão da exergia do efeito útil do processo pela exergia total consumida dos recursos humanos e naturais, incluindo todas as entradas exergéticas. O cálculo da renovabilidade é feito por meio do índice exergético de renovabilidade definido como como a razão entre a exergia dos produtos pela soma das exergias não renováveis, a exergia destruída, a exergia de desativação e a exergia das emissões e residuos. A metodologia foi aplicada a três processos de tratamento de esgoto: dois biológicos (aeróbio e anaeróbio) e um físico-químico (TQA). O cálculo dos indicadores exergéticos foi realizado para cada um destes processos e foi observado que o processo com maiores valores de desempenho ambiental e renovabilidade, considerando o metano e o lodo do processo como efeito útil, foi o processo RAFA Lagoa Facultativa, com valores respectivamente de n<exerg,amb> (0,983) e lâmbda(7,060). A análise dos resultados mostrou que a metodologia proposta é uma ferramenta útil na avaliação e comparação do desempenho ambiental e da renovabilidade de processos de tratamento de esgoto. / This work proposes a scientific methodology, with well defined criteria, to assess and quantify the environmental performance and renewability of wastewater treatment processes on a single base: the exergy. The environmental performance was measured by calculating the environmental exergy efficiency defined as the exergy ratio of the useful effect of the process to the total exergy consumed by human and natural resources, including all the exergy inputs. The renewability calculation was done using the renewability exergy index defined as the exergy ratio of the products to the sum of the non-renewable exergy, destroyed exergy, deactivation exergy and the emissions and waste exergy. The methodology was applied to three wastewater treatment processes: biological (aerobic and anaerobic) and physicochemical (CEPT) processes. The exergy indicators were calculated for each of these processes and it was observed that the process with the higher environmental performance and renewability values, considering the methane and sludge of process as useful effect, was the Facultative Lagoon UASB process, with values, respectively, of n<env,exerg>(0.983) and lambda(7.060). The results analysis showed that the proposed methodology is a useful tool in the evaluation and comparison of environmental performance and renewability of wastewater treatment processes.

O presente trabalho propõe uma metodologia científica, com critérios bem definidos, para avaliar e quantificar o desempenho ambiental e a renovabilidade de processos de tratamento de esgoto, numa base única: a exergia. O desempenho ambiental é quantificado através do cálculo da eficiência exergética ambiental, definida como a razão da exergia do efeito útil do processo pela exergia total consumida dos recursos humanos e naturais, incluindo todas as entradas exergéticas. O cálculo da renovabilidade é feito por meio do índice exergético de renovabilidade definido como como a razão entre a exergia dos produtos pela soma das exergias não renováveis, a exergia destruída, a exergia de desativação e a exergia das emissões e residuos. A metodologia foi aplicada a três processos de tratamento de esgoto: dois biológicos (aeróbio e anaeróbio) e um físico-químico (TQA). O cálculo dos indicadores exergéticos foi realizado para cada um destes processos e foi observado que o processo com maiores valores de desempenho ambiental e renovabilidade, considerando o metano e o lodo do processo como efeito útil, foi o processo RAFA Lagoa Facultativa, com valores respectivamente de n<exerg,amb> (0,983) e lâmbda(7,060). A análise dos resultados mostrou que a metodologia proposta é uma ferramenta útil na avaliação e comparação do desempenho ambiental e da renovabilidade de processos de tratamento de esgoto. / This work proposes a scientific methodology, with well defined criteria, to assess and quantify the environmental performance and renewability of wastewater treatment processes on a single base: the exergy. The environmental performance was measured by calculating the environmental exergy efficiency defined as the exergy ratio of the useful effect of the process to the total exergy consumed by human and natural resources, including all the exergy inputs. The renewability calculation was done using the renewability exergy index defined as the exergy ratio of the products to the sum of the non-renewable exergy, destroyed exergy, deactivation exergy and the emissions and waste exergy. The methodology was applied to three wastewater treatment processes: biological (aerobic and anaerobic) and physicochemical (CEPT) processes. The exergy indicators were calculated for each of these processes and it was observed that the process with the higher environmental performance and renewability values, considering the methane and sludge of process as useful effect, was the Facultative Lagoon UASB process, with values, respectively, of n<env,exerg>(0.983) and lambda(7.060). The results analysis showed that the proposed methodology is a useful tool in the evaluation and comparison of environmental performance and renewability of wastewater treatment processes.

Dans ce travail, la production in-situ d'hydrogène (pur) à partir de vapo-reformage d’éthanol (ESR) dans un réacteur catalytique à membrane (MR) a été étudiée. Un mélange d'éthanol pur et distillé a été utilisé comme combustible. Le réacteur est constitué d’un catalyseur Pd-Rh/CeO2 et d’une membrane Pd-Ag: l’ensemble est désigné par « reformeur ». Les expériences sur ce reformeur ont été effectuées dans diverses conditions de fonctionnement: température, pression, débit de combustible et rapport molaire de l'eau-éthanol (rapportSC). La performance du réacteur catalytique à membrane (CMR) a été étudiée en termes de facteur de production d'hydrogène théorique, d’efficacité de production de l’hydrogène et de la part d’hydrogène récupérée. L’évaluation thermodynamique du reformeur a été présentée. L'analyse exergétique a été réalisée sur la base des résultats expérimentaux visant non seulement à comprendre la performance thermodynamique du reformeur, mais aussi d'introduire l'application de l'analyse exergétique dans les études CMRs. L'analyse exergétique a fourni des informations importantes sur l'effet des conditions d'exploitation et les pertes thermodynamiques, et a donné lieu à la compréhension des meilleures conditions de fonctionnement. Outre les évaluations expérimentales et thermodynamiques du reformeur, la simulation de la dynamique de la production d'hydrogène (perméation) a été effectuée comme la dernière étape pour étudier l'applicabilité d'un tel système dans le cadre d'une utilisation finale réelle, qui peut être l’alimentation d’une pile à combustible. La simulation présentée dans ce travail est semblable aux ajustements de débit d'hydrogène nécessaires pour régler la charge électrique d'une pile à combustible répondant à des besoins variables. / In this work, in-situ production of fuel cell grade hydrogen (pure hydrogen) via catalytic ethanol steam reforming (ESR) in a membrane reactor (MR) was investigated. A mixture of pure ethanol and distilled was used as the fuel. ESR experiments were carried out over a Pd-Rh/CeO2 catalyst in a Pd-Ag membrane reactor – named as the fuel reformer – at variety of operating conditions regarding the operating temperature, pressure, fuel flow rate, and the molar ratio of water-ethanol (S/C ratio). The performance of the catalytic membrane reactor (CMR) was studied in terms of pure hydrogen production, hydrogen yield, andhydrogen recovery.Thermodynamic evaluation of the CMR was presented as a supplement to the comprehensive investigation of the overall performance of the mentioned pure hydrogen generating system. Exergy analysis was performed based on the experimental results aiming not only to understand the thermodynamic performance of the fuel reformer, but also to introduce the application of the exergy analysis in CMRs studies. Exergy analysis provided important information on the effect of operating conditions and thermodynamic losses, resulting in understanding of the best operating conditions.In addition to the experimental and thermodynamic evaluation of the reforming system, the simulation of the dynamics of hydrogen production (permeation) was performed as the last step to study the applicability of such a system in connection with a real end user, which can be a fuel cell. The simulation presented in this work is similar to the hydrogen flow rate adjustments needed to set the electrical load of a fuel cell, if fed on line by the studied pure hydrogen generating system.