Dissertations / Theses on the topic 'Quench water'

The function of a flue-gas quench is to remove additional contaminants from flue-gas and to reduce the wastewater from a waste incineration plant. The aim of this degree project is to find how the system is affected by using a quench and what factors limits the performance. This is done by modelling and simulating a waste incineration plant in Aspen Plus. Data and plant schematics were obtained by a study visit to Mälarenergi Plant 6 situated in Västerås, Sweden, which were used as model input and for model validation. The results have shown that the amount of wastewater can be reduced by more than half compared to a plant without a quench. The heat produced in the condenser, when discharging water to the boiler, would be lowered by up to 20%. For systems with a quench present when more water was discharged to the boiler both the heat production and the pollutant capturing became better. However, the system has limits regarding the amount that could be recirculated, in the form of temperature limits in different parts of the system. In addition, if the heat load is low there is an insufficient amount of wastewater generated in the condenser to run the quench. In that situation, clean (fresh) water needs to be used instead. Using clean water is unwanted since the plant will then consume more resources while still producing less heat than a plant without a quench would.

This thesis presents original research: it examines the constructs of duty and obedience in post-World War II Greek-Australian and Chinese Australian literature and compares the strategies these first- and second-generation authors use to make their fictional characters deal with these concepts while living in Australia, the problems their characters face and the solutions they encounter. This thesis analyses ten texts: six written by Greek-Australian authors and four by Chinese Australian writers. It aims to examine how the above-mentioned cultural concepts appear in these texts and influence the behaviour and thoughts of the characters. In doing so, this thesis aims to state and compare the strategies used. This study looks at texts published in English by first- and second-generation Greek-Australian and first-generation Chinese Australian migrants during the period 1971- 2005. The date 1971 is significant because that year Australia saw the publication of the first English-language book written by a Greek-Australian. It was the poetry collection A Tree at the Gate, by Aristides George Paradissis. Also, it was the year when the People’s Republic of China and Australia re-established diplomatic relations twenty years after all ties between the two nations had been suspended. Likewise, the year 2005 is relevant as the racist Cronulla riots took place in December. The riots marked the end of the spirit of the 2000 Sydney Olympic Games and of the 2001 centennial celebrations of the Federation of Australia… This thesis begins with an analysis of the immigration policies in Australia from the British invasion of the country in 1788 until 2011 and an analysis of the policy of multiculturalism. It then looks at the concepts of duty and obedience in Greek culture and in Chinese culture, how these concepts evolved especially during the nineteenth and twentieth centuries and how they affect marriage and divorce, interpersonal and intergenerational relations, patriotism and migration. This historical-cultural section is followed by a theoretical chapter where the concept of “identity” is explored. The final step is to analyse these notions in the literary texts chosen and compare the strategies used by the authors to make the characters confront (or not) certain specific situations.

The United States holds the world's largest estimated reserves of coal and is also a net exporter of it. Coal gasification provides a cleaner way to utilize coal than directly burning it. Gasification is an incomplete oxidation process that converts various carbon-based feedstocks into clean synthetic gas (syngas), which can be used to produce electricity and mechanical power with significantly reduced emissions. Syngas can also be used as feedstock for making chemicals and various materials. A Computational Fluid Dynamics (CFD) scheme has been used to simulate the gasification process for many years. However, many sub-models still need to be developed and improved. The objective of this study is to use the improved CFD modeling to understand the thermal-flow behavior and the gasification process and to provide guidance in the design of more efficient and cheaper gasifiers. Fundamental research has been conducted to improve the gasification sub-models associated with the volatile thermal cracking, water-gas-shift (WGS) reaction, radiation effect, low-rank-coal gasification, coal to synthetic-natural-gas (SNG), and ash deposition mechanisms. The improved volatile thermal cracking model includes H2S and COS contents. A new empirical WGS reaction model is developed by matching the result with experimental data. A new coal demoisturization model is developed for evaporating the inherent moisture inside the coal particles during low-rank-coal gasification. An ash deposition model has also been developed. Moreover, the effect of different radiation models on the simulated result has been investigated, and the appropriate models are recommended. Some improved model tests are performed to help modify an industrial entrained-flow gasifier. A two-stage oxygen feeding scheme and a unique water quench design are investigated. For the two-stage oxygen feeding design, both experimental data and CFD predictions verify that it is feasible to reduce the peak temperature and achieve a more uniform temperature distribution in the gasifier by controlling the injection scheme without changing the composition and production rate of the syngas. Furthermore, the CFD simulation can acceptably approximate the thermal-flow and reaction behaviors in the coal gasification process, which can then be used as a preliminary screening tool for improving existing gasifiers’ performance and designing new gasifiers.

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are by-products emitted from combustion sources such as municipal solid waste (MSW) incineration plants. These organic compounds are recognized as toxic, bioaccumulative and persistent in the environment. PCDD/Fs are removed from flue gases before released from MSW incineration. However, the PCDD/Fs are not destroyed but retained in the residues, thus in the environment. Understanding the pathways that lead to their formation is important in order to develop ways to suppress their formation and prevent their release into the environment. Suppressing the formation can also allow less expensive air pollution control system to be used, and/or the costs of thermally treating the residues to be reduced. The main objective of the studies underlying this thesis was to elucidate process, combustion and fuel parameters that substantially affect the emission levels and formation of PCDD/Fs in flue gases from MSW incineration. The experiments were conducted under controllable, realistic combustion conditions using a laboratory-scale reactor combusting artificial MSW. The parameter found to most strongly reduce the PCDD/F emissions, was prolonging the flue gas residence time at a relatively high temperature (460°C). Increasing the sulfur dioxide (SO2) to hydrogen chloride (HCl) ratio to 1.6 in the flue gas was also found to reduce the PCDF levels, but not the PCDD levels. Fluctuations in the combustion process (carbon monoxide peaks), high chlorine levels in the waste (1.7%) and low temperatures in the secondary combustion zone (660°C) all tended to increase the emission levels. The PCDD/PCDF ratio in the flue gas was found to depend on the chlorine level in the waste, fluctuations in the combustion process and the SO2:HCl ratio in the flue gas. The formation pathways were found to be affected by the quench time profiles in the post-combustion zone, fluctuations in the combustion process and addition of sulfur. In addition, increased levels of chlorine in the waste increased the chlorination degrees of both PCDDs and PCDFs. A tendency for increased SO2 levels in the flue gas to increase levels of polychlorinated dibenzothiophenes (sulfur analogues of PCDFs) was also detected, however the increases were much less significant than the reduction in PCDF levels.

Trace component analysis in gasification processes are important part of elemental component balances in order to understand the fate of these participating compounds in the feedstock. Residual traces in the raw synthesis gas after quench could bring about the poisoning of catalysts and corrosion effects on plant facilities. The objective of this work is to investigate the effects of quenching operation on the trace components during test campaigns of the autothermal non-catalytic reforming of natural gas (Gas-POX) mode in the HP POX (high pressure partial oxidation) test plant. In order to achieve this, Aspen Plus simulation model of the quench chamber of the HP POX test plant was developed to re-calculate the quench chamber input amount of different trace compounds from their output amount measured during test points of the Gas-POX campaigns. Variation in quench water temperatures from 130 °C to 220 °C and pH value of quench water as well as the resulting variation in Henry´s and Dissociation constant of the traces (CO2, H2S, NH3 and HCN) changed the distribution of traces calculated in the quench water. The formation of traces of organic acid (formic acid and acetic acid) and traces of BTEX, PAHs and soot in the quench water effluent were discussed. The discrepancies between equilibrium constant and reaction quotient (non-equilibrium or real) for the formation of NH3 and HCN at the exit of the gasifier were discussed. The assessment of the results in this work should lead to the improvement in the understanding of trace components and concepts that could be employed to influence their formation and reduction.

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The present study approaches the pertinent subject to the Enterprise Hot Rio Resorts in what it refers to the use of potentials hídricos of the State of Goiás and the degradation operated in the areas explored with the construction of the enterprise being analyzed the performance of the collectivity and of the Public Power in the execution of the constitutional beginnings that treat of the protection of the environment as well of use common of the people of the presents and future generations. Among the treated subjects, they are the environmental subject in Brazil, level of importance of the environment, the mobilization degree and participation of the collectivity in the knowledge of the subjects of difficult solution that you/they involve the environment, being discussed, still, the existent tensions in the in the facts and in the experience of rules and your it executes application in the environmental protection. Of the context, they are had that measured of the juridical sphere they are adopted before the conflict of interests characterized by the wide action of the initiative deprived in the materialization of your objectives, inside of the possibility of exploration of resources hídricos, doing with that the Public Administration, so much in the acts entrusted of commission as the ones that are stopped accomplishing it suffers several types of controls of the law and the ones that are not accomplished due to the judiciary authority.
O presente estudo aborda a questão pertinente ao Empreendimento Rio Quente Resorts no que se refere ao aproveitamento de potenciais hídricos do Estado de Goiás e a degradação operada nas áreas exploradas com a construção do empreendimento analisando-se a atuação da coletividade e do Poder Público no cumprimento dos princípios constitucionais que tratam da proteção do meio ambiente como bem de uso comum do povo das presentes e futuras gerações. Dentre os assuntos tratados, encontram-se a questão ambiental no Brasil, nível de importância do meio ambiente, o grau de mobilização e participação da coletividade no conhecimento das questões de difícil solução que envolvem o meio ambiente, discutindo-se, ainda, as tensões existentes nos fatos e na experiência de regras e sua efetiva aplicação na proteção ambiental. Do contexto, têm-se que medidas da esfera jurídica são adotadas diante do conflito de interesses caracterizado pela ação ampla da iniciativa privada na concretização de seus objetivos, dentro da possibilidade de exploração de recursos hídricos, fazendo com que a Administração Pública, tanto nos atos encarregados de comissão quanto os que se deixam de cumprir sofra vários tipos de controles da lei e os que não são realizados diante da autoridade judiciária.

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In Hydraulic and Sanitary Building Systems there are nonconformance issues that can occur when user begins occupying and interacting with the building. Among other systems, the Hot Water Building System is responsible to offer to user important activities to human being such as bath and dish washing. The performance of the systems that constitute the housing buildings along its life is connected to the conditions of use for it was designed, to the execution of the construction according to the technical regulations, to the use of materials and components free of imperfections and to the programs and techniques of regular auditing and building maintenance. Even though the field of nonconformance is a subject not so explored in Brazil, it can be inferred as causes of nonconformance issues in the Hot Water Building System: technical regulations out-of-date, project mistakes, inadequate specifications, manufacture problems, execution errors, lack of maintenance or inadequate maintenance. This dissertation, based on the user's requirements as established by NBR 15575-1, objects the identification of performance requirements and criteria, to multistoried residential buildings. This theoretical study was applied to two multistoried residential buildings to find out probable s nonconformance.
Nos Sistemas Prediais Hidráulicos e Sanitários (SPHS) inúmeras são as não conformidades que podem ocorrer quando o usuário passa a ocupar e interagir com a edificação. Dentre esses sistemas, o Sistema Predial de Água Quente (SPAQ) é o responsável por oferecer ao usuário as condições de conforto e higiene em atividades tão importantes para o ser humano como banho e lavagem de louças. O desempenho dos sistemas que compõem o edifício habitacional durante a sua vida útil está vinculado às condições do uso para o qual foi projetado, à execução da obra de acordo com as normas técnicas, à utilização de elementos e componentes sem defeito de fabricação e a programas e técnicas de inspeções periódicas e de manutenção predial. Apesar do estudo das não conformidades nas construções, na área de SPHS, ser um tema pouco estudado no Brasil, pode-se admitir como causas das mesmas no SPAQ: norma técnica desatualizada, erros de projeto, especificações inadequadas, defeitos de fabricação, falhas na execução, falta de manutenção ou manutenção inadequada. Esta dissertação, baseando-se nas exigências do usuário estabelecidas na NBR 15575-1, teve como objetivo a identificação dos requisitos e dos critérios de desempenho do SPAQ, em edifícios habitacionais de múltiplos pavimentos. Esse estudo teórico foi posteriormente aplicado em dois edifícios residenciais para serem encontradas possíveis não conformidades.

O presente estudo teve por objetivo avaliar a qualidade de painéis de partículas de média densidade (MDP), manufaturados a partir de bagaço de cana-de-açúcar e bambu (Dendrocalamus asper). A massa específica nominal foi 0,65 g.cm-3 e utilizou-se adesivo à base de uréia-formaldeído. O delineamento consistiu em 16 tratamentos, divididos em quatro Experimentos. Foram avaliadas as propriedades físicas (Massa Específica Aparente - MEA, Absorção de Água - AA, Inchamento em Espessura - IE e Taxa de Não-Retorno em Espessura - TNRE), mecânicas (Flexão Estática - MoR e MoE, Arrancamento de Parafuso de Superficie e Topo - APS e APT e Ligação Interna - LI, além do Perfil de Densidade, Molhabilidade e Resistência Natural. Os objetivos foram: I - Avaliar painéis de partículas de bagaço de cana com duas granulometrias (0,50 mm e 0,85 mm), tratadas e não tratadas em água quente; II - Avaliar os painéis adotando as mesmas variáveis do experimento anterior, porém, empregando partículas de bambu; III - Avaliar os painéis gerados a partir da mistura de ambos materiais nas proporções de 100%, 75%, 50%, 25% e 0%; IV - Avaliar os painéis constituídos com partículas termorretificadas de bagaço e bambu encoladas com três teores de adesivo (10, 12 e 14%). Os resultados do Experimento I mostraram que propriedades físicas (IE2h, IE24h, AA24h e TNRE), mecânicas (MoR, MoE, APS, APT e LI) e molhabilidade não foram influenciadas pelos fatores (granulometria e condição de partículas). Os fatores influenciaram de forma interativa o perfil de densidade de massa específica aparente da camada externa. A resistência natural foi influenciada pelos fatores e os painéis foram inclusos na categoria \"resistência moderada\". Os resultados do Experimento II mostraram que as partículas tratadas em água quente resultaram em aumento significativo dos valores de IE2h, IE24h e TNRE. O APS, APT e LI apresentaram melhorias significativas para os painéis manufaturados com partículas tratadas em água quente. Os fatores avaliados influenciaram a massa específica aparente da camada externa dos painéis. Houve interação significativa entre os fatores para o ângulo inicial obtido com água. O fungo G. trabeum causou maiores perdas de massa nos painéis constituídos com partículas tratadas em água quente e o T. versicolor evidenciou maior índice de ataque em chapas confeccionadas com partículas controle. No Experimento III o aumento da razão de compactação apresentou tendência significativa de aumento de valores da AA24h, IE2h, IE24h e TNRE, além do MoR. Tal variável reduziu a AA2h, APT e LI, proporcionou picos mais acentuados de massa específica nas faces dos painéis, reduziu significativamente a molhabilidade e aumentou a perda de massa dos painéis submetidos aos fungos P. placenta e G. trabeum. No Experimento IV o tratamento térmico promoveu melhorias significativas para AA2h, AA24h, IE2h e IE24h, porém reduziu o MoR, MoE, APS, APT e LI, que foram melhoradas com o aumento no teor de adesivo, além do perfil de densidade. Não houve influência significativa na molhabilidade, comparando os painéis com mesmo teor de adesivo e nem considerando diferentes teores de adesivo. De forma geral, os painéis apresentaram melhorias significativas na resistência biológica com a termorretificação e aumento no teor de adesivo. Bagaço de cana-de-açúcar e bambu representam boas alternativas de matérias-primas para confecção de chapas aglomeradas. Os painéis podem ser utilizados para forros, isolamento térmico e acústico, revestimentos, painéis decorativos, componentes para construção civil, substrato para piso, embalagens, pequenos objetos entre outras aplicações.
The aiming of this study was to evaluate the quality of medium density particleboard (MDP) manufactured with particles of sugarcane bagasse and bamboo with nominal density of 0.65 g.cm-3 and urea-formaldehyde adhesive. The experimental design was composed of 16 treatments divided in four experiments. The physical properties (apparent density, water absorption, thickness swelling and the nonrecoverable tax, mechanical (static bending - modulus of elasticity and modulus of rupture, screw withdrawal strength and internal bonding) were evaluated, as well as the density profile, wettability and natural resistance. The objectives were: I - To evaluate panels of sugarcane bagasse particles with two granulometries (0.50 mm and 0.85 mm) treated and not treated in hot water; II - To evaluate the panels using the same variables of the previous experiment, however using bamboo particles; III - Evaluate the panels origin from the mixture of both materials in proportions of 100%, 75%, 50%, 25% and 0%; IV - Evaluate the panels constituted with heat treatment particles of bamboo and bagasse and glued with three adhesive contents (10, 12 and 14%). The results of the Experiment I showed that physical (IE2h, IE24h, AA24h and TNRE) and mechanical properties (MoR, MoE, APS, APT and LI) and wettability were not influenced by the factors (grain size and particle condition). The factors influenced the apparent specific bulk density profile of the outer layer. Natural resistance was influenced by the factors and the panels were included in the \"moderate resistance\" category. The results of Experiment II showed that the particles treated in hot water resulted in a significant increase in the values of IE2h, IE24h and TNRE. APS, APT and LI showed significant improvements for panels manufactured with hot water treated particles. The evaluated factors influenced the apparent specific mass of the outer layer of the panels. There was a significant interaction between the factors for the initial angle obtained with water. The G. trabeum fungus caused greater mass losses in the panels constituted with particles treated in hot water and T. versicolor evidenced a higher attack rate in plates made with control particles. In Experiment III the increase in compaction ratio showed a significant tendency to increase values of AA24h, IE2h, IE24h and TNRE, in addition to MoR. This variable reduced AA2h, APT and LI, provided more pronounced peaks of specific mass in the faces of the panels, significantly reduced wettability and increased the mass loss of the panels submitted to P. placenta and G. trabeum fungi. In Experiment IV the heat treatment promoted significant improvements for AA2h, AA24h, IE2h and IE24h, but reduced MoR, MoE, APS, APT and LI, which were improved with the increase of the adhesive content, as well as the density profile. There was no significant influence on wettability, comparing the panels with the same adhesive content and different adhesive contents. In general, the panels showed significant improvements in the biological resistance with thermortification and increase in the adhesive content. Sugarcane bagasse and bamboo represent good alternatives of raw materials for confection of agglomerated sheets. The panels can be used for linings, thermal and acoustic insulation, coatings, decorative panels, components for civil construction, substrate for flooring, packaging small objects among other applications.

Orientador: José Antonio Siqueira Dias
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação
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Resumo: Mais de 90% dos sistemas de aquecimento de água por energia solar instalados no Brasil (número superior a 700.00 instalações) são do tipo convencional por circulação passiva. Esse tipo de instalação apresenta boa performance, aliada à simplicidade de funcionamento. Considerando-se que aproximadamente 8% da energia consumida em nosso país é para o aquecimento de água residencial, trata-se de uma excelente alternativa ecológica de economia de energia. Em períodos de baixa insolação, o usuário pode contar com um aquecimento auxiliar através de um resistor instalado no interior do reservatório (boiler).Nesta situação a temperatura da água até atingir o valor de desligamento do termostato de segurança do sistema.Não havendo o acompanhamento da temperatura, o sistema entra num regime de funcionamento de sucessivos períodos e aquecimento e resfriamento (por perdas de calor), até que o usuário lembre-se de desligar o disjuntor. Este trabalho apresenta uma solução economicamente viável de se melhorar essa situação, fazendo-se uso da eletrônica microcontrolada. Assim, pode-se monitorar o aquecimento da água pelo resistor auxiliar através de sensores do tipo NTC, propiciando uma economia de até 25% na conta mensal, além de outras comodidades. Possuindo três modos de operação : temporizado (atua como timer), termostato (termostato ajustável pelo painel) e programado (o usuário determina o momento de uso e a temperatura desejada da água) , o sistema é constituído por console de controle e unidade de potência. O sistema é de fácil instalação, constituindo uma alternativa viável para se melhorar significativamente a performance dos sistemas atuais
Abstract: Over 90% of heating water by solar energy installed in Brazil today (more than 700,000 facilities ) are of the conventional type passive thermosyphon. This type of installation has good performance and the simplicity of operation. Considering that approximately 8% of energy consumed in our country is for heating domestic water, this is an excellent alternative of ecological energy saving. In periods of low insolation, the user can rely on an auxiliary heating through a resistor installed inside the tank (boiler), powered through a circuit breaker. In this situation, with no one monitoring , the water temperature rises until it reaches the value of shutting down the thermostat's security system, which in most cases is set at 55 ° C. Without the monitoring of temperature, the system enters a regime of operation of successive periods of heating and cooling (for heat loss), until the user remember to turn off the breaker. This paper presents an economically viable solution to improve that, by making use of electronics microcontroller. Thus, one can monitor the water heating aid through the resistor sensor NTC, providing savings of up to 25% on the monthly bill, and other amenities. With three modes of operation: timer (operates as a timer), thermostat (panel adjustable thermostat ) and programmed (the user determines the time of use and temperature of the water), the system consists of the control console and power unit. The system is easy to install, providing a viable alternative to significantly improve the performance of current systems
Mestrado
Eletrônica, Microeletrônica e Optoeletrônica
Mestre em Engenharia Elétrica

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The swine salmonellosis has significant importance in economic and food security, as well as being a cause of food poisoning in humans, is present in large scale in finishing swine, due to the latency in lymph nodes and the rearing conditions. The objective of this study was to evaluate the reduction in the count of Salmonella in pig carcasses at slaughter after being subjected to the same water bath at 80 ° C. Were sampling 90 swine carcasses after slaughter were sampled at four sampling points (ham, loin, belly and jowl), before and after applying water bath at 80 ° C a total of 720 samples and quantitative analysis by NMP. At slaughter 43% of the animals were positive prior to application of the hot water 62 represented by positive samples. After the intervention, 89% of positive counts zeroed in seven samples and no reduction in 11 samples was positive in previously negative animals. Samples with greater reduction in counting samples were jowls and belly with concentration indices 330NMP / g which subsequently zeroed. The treatment bath of hot water in the carcasses was effective, with a significant difference in positivity before and after the intervention. There were cases of cross-contamination after the intervention in animals maintained positive and negative animals. Typing of all positives were Salmonella Typhimurium
A salmonelose suína tem relevante importância econômica e na segurança alimentar, pois além de ser causadora de toxinfecções alimentares em humanos, está presente em larga escala nos suínos de terminação, devido à latência em linfonodos e as condições de criação. O objetivo deste trabalho foi avaliar a redução na contagem de Salmonella spp. em carcaças de suínos ao abate após as mesmas serem submetidas a banho com água a 80°C. Foram amostradas 90 carcaças de suínos após abate em quatro pontos de colheita (pernil, lombo, barriga e papada),antes e após a aplicação de banho com água a 80°C, num total de 720 amostras, com análise quantitativa por NMP. No abatedouro 43% dos animais foram positivos antes da aplicação da água quente representado por 62 amostras positivas. Após a intervenção 89% dos positivos zeraram as contagens, em sete amostras não houve redução e em 11 amostras houve positividade em animais anteriormente negativas. As amostras com maior redução na contagem foram amostras de papada e barriga com concentração de índices de 330NMP/g que posteriormente zeraram. O tratamento com banho de água quente nas carcaças foi eficiente, com diferença significativa de positividade antes e após a intervenção. Houveram casos de contaminação cruzada após a intervenção em animais que permaneceram positivos e animais negativos. As tipificações de todos os positivos foram Salmonella Typhimurium

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
Neste trabalho são estudados dois processos que utilizam biogás para obtenção do biohidrogênio. Inicialmente é analisado o processo de eletrólise da água, com o uso de energia elétrica gerada em conjunto motor de combustão interna/gerador (MCI) operando com biogás de aterro sanitário. Visando aproveitamento de calor dos gases de escape do MCI estuda-se o potencial de geração de energia térmica útil pela aplicação da técnica de cogeração. Considera-se dois casos: o primeiro para a produção de água quente em um trocador de calor, e o segundo, para a produção de água gelada em um sistema de refrigeração por absorção. Posteriormente é estudada a reforma a vapor de biogás para a produção de biohidrogênio, que utiliza também esse biocombustível para a geração de vapor superaquecido necessário ao processo de reforma. O objetivo é efetuar a análise energética de modo a determinar as eficiências dos processos, o potencial de produção de biohidrogênio, água quente ou água gelada, nos aterros sanitários da cidade de São Paulo. Também é efetuada análise de engenharia econômica para a determinação do custos da produção de biohidrogênio, água quente e água gelada, em US$/kWh. Esse estudo baseia-se em parâmetros tais como, investimento capital, custos de manutenção e operação dos equipamentos, período equivalente de utilização e período de amortização de capital. Em fase final, foram realizados estudos de impactos ambientais para a determinação das eficiências ecológicas dos processos de produção de biohidrogênio (reforma a vapor e eletrólise), considerando as emissões de poluentes, o dióxido de carbono equivalente e os indicadores de poluição. Como conclusões, tem-se que considerando a disponibilidade de biogás da cidade de São Paulo, existe potencial para a produção de biohidrogênio, e que o processo de reforma a vapor do biogás apresenta maior nível de eficiência sob o ponto de vista termodinâmico. Quando se considera a eletrólise incorporando a técnica da cogeração com a produção simultânea de eletricidade e água quente ou água gelada, observa-se aumento da eficiência energética do processo. A reforma a vapor do biogás, também se mostra mais atrativa economicamente de acordo com os parâmetros considerados. Sobre o ponto de vista ambiental, o processo de eletrólise com produção de água gelada apresenta maior eficiência ecológica, seguidos do processo de produção de água quente, reforma a vapor e somente eletrólise.
In this work is studied two processes to obtain hydrogen using biogas. Initially is analyzed the process of electrolysis of water, with the use of electricity generated in conjunction with an internal combustion engine / generator (ICE) operating with landfill biogas. generated by an internal combustion engine/generator operating with landfill biogas, is analyzed. In order to take advantage of the exhaust gases from the combustion of biogas, the potential of cogeneration is studied, another two cases are considered. The first one studies the production of hot water in the heat exchanger and the second analyzes the use of absorption refrigeration system to produce cold water. Subsequently it is studied the steam reform of biogas for the production of hydrogen, which is constituted of biogas burning for the generation of superheated steam used in the conversion of the fuel input. The objective is to make the energy analysis in order to determine the efficiency of the processes and the potential of producing hydrogen, hot water or ice water in the landfills of the city of São Paulo using the biogas generated. An economic engineering analysis to determine the production hydrogen cost, hot water and ice water, in US$/kWh, based on capital investment, maintenance and operation costs, equivalent period of use and payback. In the final phase, environmental study method is applied to determine the ecological efficiencies of the hydrogen production processes using biogas, considering the emissions of pollutants, carbon dioxide equivalent and pollution indicator. As a conclusion, considering the hydrogen production capacity and the biogas availability of the city of São Paulo, the process of steam reforming of the biogas is more thermodynamically efficient. When considering the electrolysis incorporating the cogeneration technique with the simultaneous production of electricity and hot water or cold water, it is observed an increase in the energy efficiency of the process. The steam reform of the biogas is more attractive economically according to the considered parameters. From the environmental point of view, the process of electrolysis with the production of cold water presents greater ecological efficiency, followed by the process of hot water production, steam reforming and only electrolysis.

L'agriculture est à l'interface de plusieurs éléments du milieu naturel (eau, sol, climat,...) mais aussi de la société (économie, politique, démographie,...). Si durant des siècles elle a surtout été soumise au milieu naturel et à ses fluctuations (notamment climatiques), l'évolution des sociétés et surtout des techniques l'en ont en partie détachée, rendant les éléments sociaux et économiques premiers. Cette évolution est nette depuis le lendemain de la seconde guerre mondiale. Cependant, à l'heure où l'on parle de changement climatique, de réchauffement global, le climat et l'agriculture sont-ils déconnectés l'un de l'autre ? L'originalité de notre étude tient à sa localisation, un bassin versant déficitaire, au type d'agriculture présente (polyculture et forte part des cultures irriguées) et à la démarche scientifique qui l'accompagne. Celle-ci fait appel à différentes techniques : enquêtes, entretiens, analyses de données climatologiques, hydrologiques) qui seront étudiées à travers leur mise en relation à travers l'approche systémique. L'approche systémique nous permet de mettre en évidence les rapports existant entre les différents éléments concernés mais aussi de nous situer dans le temps. Notre étude prend en compte la place de la sécheresse dans l'évolution des pratiques agricoles ; l'inscription des modifications des pratiques agricoles peuvent inscrire des modifications dans le milieu support de leurs activités ; la modification de la relation à la ressource en fonction de l'adaptation des pratiques agricoles , et l'inscription des relations de pouvoir dans l'espace et le temps.

The aim of the research study was to evaluate the levels of 14C and 3H radionuclides in Hartbeespoort Dam water and to determine if these radionuclides are within regulatory concerns. Water samples from Hartbeespoort Dam were prepared using the Sample Oxidiser Method and measurements of selected radionuclides were done using Liquid Scintillation Counter Quantulus 1220. The results evaluated suggest that water from Hartbeespoort Dam contains levels of 14C and 3H radionuclides that are within regulatory limits. The highest average concentration for 14C measured was 3.77E+01 (+/-2.47E-01) Bq/L, whereas the highest average concentration measured for 3H was 2.74E+01 (+/- 2.30E-01) Bq/L. The observations made regarding the impacts of climate on the 14C radionuclide were that, the concentration levels were higher during winter season when there was a rain than during rainy seasons. Tritium results showed that the climate conditions did not have any significant impacts on the concentration levels. When the concentrations of these radionuclides are above regulatory levels (14C is 100 Bq/L and 3H is10000 Bq/L), their impacts may cause harm to public`s health and the environment. Therefore, Necsa as a nuclear facility owner and National Nuclear Regulator (NNR) as a regulator are responsible for ensuring the public protection from radioactive effluents that contain not just 3H and 14C, but any radionuclide which may cause harm to public`s health.
Environmental Sciences
M. Sc. (Environmental Science)

The aim of the research study was to evaluate the levels of 14C and 3H radionuclides in Hartbeespoort Dam water and to determine if these radionuclides are within regulatory concerns. Water samples from Hartbeespoort Dam were prepared using the Sample Oxidiser Method and measurements of selected radionuclides were done using Liquid Scintillation Counter Quantulus 1220. The results evaluated suggest that water from Hartbeespoort Dam contains levels of 14C and 3H radionuclides that are within regulatory limits. The highest average concentration for 14C measured was 3.77E+01 (+/-2.47E-01) Bq/L, whereas the highest average concentration measured for 3H was 2.74E+01 (+/- 2.30E-01) Bq/L. The observations made regarding the impacts of climate on the 14C radionuclide were that, the concentration levels were higher during winter season when there was a rain than during rainy seasons. Tritium results showed that the climate conditions did not have any significant impacts on the concentration levels. When the concentrations of these radionuclides are above regulatory levels (14C is 100 Bq/L and 3H is10000 Bq/L), their impacts may cause harm to public`s health and the environment. Therefore, Necsa as a nuclear facility owner and National Nuclear Regulator (NNR) as a regulator are responsible for ensuring the public protection from radioactive effluents that contain not just 3H and 14C, but any radionuclide which may cause harm to public`s health.
Environmental Sciences
M. Sc. (Environmental Science)

Trace component analysis in gasification processes are important part of elemental component balances in order to understand the fate of these participating compounds in the feedstock. Residual traces in the raw synthesis gas after quench could bring about the poisoning of catalysts and corrosion effects on plant facilities. The objective of this work is to investigate the effects of quenching operation on the trace components during test campaigns of the autothermal non-catalytic reforming of natural gas (Gas-POX) mode in the HP POX (high pressure partial oxidation) test plant. In order to achieve this, Aspen Plus simulation model of the quench chamber of the HP POX test plant was developed to re-calculate the quench chamber input amount of different trace compounds from their output amount measured during test points of the Gas-POX campaigns. Variation in quench water temperatures from 130 °C to 220 °C and pH value of quench water as well as the resulting variation in Henry´s and Dissociation constant of the traces (CO2, H2S, NH3 and HCN) changed the distribution of traces calculated in the quench water. The formation of traces of organic acid (formic acid and acetic acid) and traces of BTEX, PAHs and soot in the quench water effluent were discussed. The discrepancies between equilibrium constant and reaction quotient (non-equilibrium or real) for the formation of NH3 and HCN at the exit of the gasifier were discussed. The assessment of the results in this work should lead to the improvement in the understanding of trace components and concepts that could be employed to influence their formation and reduction.:List of Figures vii List of Tables xii List of Abbreviations and Symbols xiii 1 Introduction 1 1.1 Background 1 1.2 Objective of the Work 4 1.3 Overview of the Work 5 2 Process and test conditions 6 2.1 HP POX test plant 6 2.2 Test campaign procedure 8 2.2.1 Gas-POX operating parameter range 8 2.2.2 Gas-POX experiments 9 2.2.3 Net reactions of partial oxidation 9 2.3 Gaseous feedstock characterization 11 2.3.1 Natural gas feedstock composition 11 2.4 Analytical methods for gaseous products 12 2.4.1 Hot gas sampling 12 2.4.2 Raw synthesis gas analysis after quench 13 2.5 Aqueous phase product analysis 14 2.5.1 Molecularly dissolved trace compounds and their ions trace analysis 14 2.5.2 Other trace analysis 15 2.6 Limit of accuracy in measurement systems 15 2.7 Summary 17 3 Simulation and methods 18 3.1 Test points calculation of the HP POX test campaign 18 3.1.1 Aspen Plus model for HP POX quench water system 19 3.2 Gas-POX 201 VP1 quench water system model simulation by Aspen Plus 23 3.2.1 Measured and calculated input parameters 23 3.2.2 Calculated sensitivity studies of species and their distribution for test point (VP1) 24 3.3 Used calculation tools related to the work 25 3.3.1 VBA in Excel 25 3.3.2 Python as interface between Aspen Plus and Microsoft Excel 26 3.3.3 Aspen Simulation Workbook 27 3.4 Summary 29 4 Trace components in quench water system 30 4.1 Physico-chemical parameters of quench water 31 4.1.1 Quench water pH adjustment 32 4.1.2 Henry constant 34 4.1.3 Dissociation constant 35 4.1.4 Organic acids in quench water 38 4.2 Carbon dioxide (CO2) 39 4.2.1 Results of sensitivity study: quench water temperature variation effects on CO2 41 4.2.2 Results of sensitivity study: quench water pH variation influence on CO2 42 4.3 Nitrogen compounds 43 4.3.1 Ammonia (NH3) 44 4.3.2 Results of sensitivity study: quench water temperature variation effects on NH3 46 4.3.3 Results of sensitivity study: quench water pH variation influence on NH3 47 4.3.4 Hydrogen Cyanide (HCN) 48 4.3.5 Results of sensitivity study: quench water temperature variation effects on HCN 50 4.3.6 Results of sensitivity study: quench water pH variation influence on HCN 50 4.4 Sulphur compounds: H2S 51 4.4.1 Results of sensitivity study: quench water temperature variation effects on H2S 53 4.4.2 Results of sensitivity study: quench water pH variation influence on H2S 54 4.5 Summary 55 5 Organic acids trace studies in quench water 57 5.1 Organic acids interaction with ammonia compounds in the quench water 57 5.2 Formic acid 62 5.2.1 Trace of formic acid in quench water 64 5.3 Acetic acid 67 5.3.1 Trace of acetic acid in quench water 69 5.4 Summary 72 6 Temperature approach studies for NH3 and HCN formation in gasifier 74 6.1 Nitrogen compounds: NH3 and HCN 74 6.2 Ammonia (NH3) formation in the gasifer 77 6.3 Hydrogen cyanide (HCN) formation in the gasifier 79 6.4 Discrepancies between back-calculated reaction quotients and equilibrium constants of the NH3 formation 81 6.4.1 Case 1: calculated equilibrium distribution between N2, NH3 and HCN 81 6.4.2 Case 2: calculated equilibrium distribution between NH3 and HCN 83 6.5 Summary 84 7 Traces of BTEX, PAHs and soot in quench water 86 7.1 Quench water behaviour 87 7.2 BTEX compounds 88 7.2.1 BTEX in quench water effluent 90 7.3 PAH compounds 93 7.3.1 PAHs in quench water effluent 95 7.4 Soot formation 99 7.4.1 Soots in quench water effluent 101 7.5 Summary 102 8 Summary and outlook 103 Bibliography 106 9 Appendix 135 List of Figures Figure 2.1: HP POX test plant main facility components and material flow courtesy of [Lurgi GmbH, 2008] 6 Figure 2.2: Simplified scheme of HP POX plant (including quench system) [Lurgi GmbH, 2008] 7 Figure 2.3: Overview of reactions of methane 10 Figure 3.1: Simplified scheme for HP POX quench water system 18 Figure 3.2: Aspen Plus flow diagrams of simulated HP POX quench water system 19 Figure 3.3: Integration of information and functions in VBA via Microsoft Excel to Aspen Plus model 25 Figure 3.4: Integration of information and functions in Python via Microsoft Excel to Aspen Plus model 26 Figure 3.5: ASW enables Excel users to rapidly run scenarios using the underlying rigorous models to analyze plant data, monitor performance, and make better decisions. 27 Figure 4.1: Vapour-liquid equilibria system of CO2, H2S, NH3, HCN and organic acids in the quench water and extended mechanisms according to [Kamps et al., 2001], [Alvaro et al., 2000], [Kuranov et al., 1996], [Xia et al., 1999] and [Edwards et al., 1978]. 30 Figure 4.2: HP POX quench water system with pH regulator for sensitivity studies 34 Figure 4.3: Henry´s constant for CO2, H2S, NH3 and HCN derived from [Edwards et al., 1978] for CO2, [Alvaro et al., 2000] for NH3, [Kamps et al., 2001] for H2S, and [Rumpf et al., 1992] for HCN 35 Figure 4.4: Dissociation constants for CO2, H2S, NH3, HCN and H2O derived from [Alvaro et al., 2000], [Kamps et al., 2001], and [Edwards et al., 1978] 37 Figure 4.5: The flow of CO2 in the quench water cycle (test point VP1). 40 Figure 4.6: Calculated quench water temperature variation and effects on CO2 distribution 42 Figure 4.7: Calculated influence of pH regulation and effects on CO2 distribution 43 Figure 4.8: The flow of NH3 in the quench water cycle (test point VP1). 46 Figure 4.9: Calculated quench water temperature variation and effects on NH3 distribution 47 Figure 4.10: Calculated influence of pH regulation and effects on NH3 distribution 48 Figure 4.11: The flow of HCN in the quench water cycle (test point VP1). 49 Figure 4.12: Calculated quench water temperature variation and effects on HCN distribution 50 Figure 4.13: Calculated influence of pH regulation and effects on HCN distribution 51 Figure 4.14: The flow of H2S in the quench water cycle (test point VP1) 53 Figure 4.15: Calculated quench water temperature variation and effects on H2S distribution 54 Figure 4.16: Calculated influence of pH regulation and effects on H2S distribution 55 Figure 5.1: Aspen Plus back-calculated (real) formic acid concentration, quench water temperature and the calculated equilibrium formic acid concentration against back-calculated (real) ammonia concentration for the 47 test points (using amongst others sampled HCOO- and NH4+ values according to Table 2.6). 59 Figure 5.2: Aspen plus back-calculated (real) formic acid concentration, back-calculated (real) ammonia concentration and the calculated equilibrium formic acid concentration against quench water temperature for the 47 test points (using amongst others sampled HCOO- and NH4+ values according to Table 2.6). 60 Figure 5.3: Aspen plus back-calculated (real) acetic acid concentration, quench water temperature and the calculated equilibrium acetic acid concentration against back-calculated (real) ammonia concentration for the 47 test points. 61 Figure 5.4: Aspen plus back-calculated (real) acetic acid concentration, back-calculated (real) ammonia concentration and the calculated equilibrium acetic acid concentration against quench water temperature for the 47 test points. 62 Figure 5.5: Concentration of formic acid (Aspen plus calculated m_eq and back-calculted m_real) formation in the quench and quench water temperature for the 47 test points. 64 Figure 5.6: Concentration of formic acid (Aspen plus calculated m_eq and back-calculted m_real) in the quench against quench water temperature for the 47 test points (as in Fig.5.2). 65 Figure 5.7: Comparison between formic acid equilibrium constant (Keq), reaction quotient (Kreal) and the quench water temperature for the 47 test points. 66 Figure 5.8: Comparison between formic acid equilibrium constant (Keq) and reaction quotient (Kreal) against quench water temperatures for the 47 test points. 67 Figure 5.9: Concentration of acetic acid (Aspen plus calculated m_eq and back-calculted m_real) in the quench and quench water temperature for the 47 test points. 69 Figure 5.10: Concentration of acetic acid (Aspen plus calculated m_eq and back-calculted m_real) in the quench against quench water temperature for the 47 test points (as in Fig.5.4). 70 Figure 5.11: Comparison between acetic acid equilibrium constant (Keq), reaction quotient (Kreal) and the quench water temperature for the 47 test points. 71 Figure 5.12: Comparison between acetic acid equilibrium constant (Keq) and reaction quotient (Kreal) against quench water temperatures for the 47 test points. 72 Figure 6.1: Mole fraction of gas compoents in the hot gas outlet out of gasifier against hot gas temperature for the 47 test points 76 Figure 6.2: Calculated reaction quotient (Q) and equlibrium constant (Keq) for NH3 against hot gas temperature for the 47 test points (see Fig. 9.10 in Appendix) 77 Figure 6.3: NH3 temperature approach against hot gas temperature for the 47 test points (see Fig. 9.11 in Appendix) 78 Figure 6.4: Calculated reaction quotient (Q) and equlibrium constant (Keq) for HCN against hot gas temperature for the 47 test points (see Fig. 9.13 in Appendix) 79 Figure 6.5: HCN temperature approach against hot gas temperature for the 47 test points (see Fig. 9.14 in Appendix) 80 Figure 6.6: Comparison between calculated real and equilibrium hot gas N2, NH3 and HCN mol fractions against their respective hot gas temperature (case 1). 82 Figure 6.7: Relations between back-calculated real and equilibrium hot gas N2, NH3 and HCN mol fractions (for chemical equilibrium according to equations (6.1) and (6.4)) against their respective hot gas temperature (see Case 1, Section 6.4.1, and Fig. 6.6) 82 Figure 6.8: Comparison between calculated real and equilibrium hot gas HCN mol fraction against their respective hot gas temperature (case 2). 83 Figure 6.9: Relations between back-calculated real and equilibrium hot gas HCN mol fractions, and change in NH3 mol fractions (for chemical equilibrium according to equation (6.4)), against their respective hot gas temperature (see. Case 2, Section 6.4.2 and Fig. 6.7) 84 Figure 6.10 Comparison between NH3 and HCN formation (mole fraction) calculated equilibrium constant (Keq) and calculated reaction quotient (Q), N2 consumption and hot gas temperatures for the 47 test points (case 1 and case 2). 85 Figure 7.1: HP POX test plant quench water system 88 Figure 7.2: Traces of BTEX measured in the Gas-POX 203 – 207 quench water effluent sample. 91 Figure 7.3: Individual component of BTEX measured in the Gas-POX 203 – 207 quench water effluent sample. 92 Figure 7.4: (a) Alkyl radical decomposition and (b) C1 and C2 hydrocarbons oxidation mechanism [Warnatz et al., 2000] 93 Figure 7.5: Recombination of C3H3 to form benzene 94 Figure 7.6: The Diels - Alder reaction for the formation of PAHs 95 Figure 7.7: Amount of PAHs that were detected in Gas-POX 203 – 207 test points quench water effluent samples. 97 Figure 7.8: Distribution of PAH compounds in Gas-POX 203 – 207 quench water effluent samples. 98 Figure 7.9: Some steps in soot formation [McEnally et al., 2006]. 99 Figure 7.10: Illustration of soot formation path in homogenous mixture [Bockhorn et al., 1994] 100 Figure 9.1: Aspen flow sheet set up for HP POX quench system GasPOX 201 VP1 (simplified and extension of Fig. 3.2, organic acids not taken into account). Tabulated values are given in Table 9.11. 135 Figure 9.2: Comparison between the Henry´s constant profiles: Aspen Plus (markers) and Literatures (solid lines) ([Edwards et al., 1978] for CO2, [Alvaro et al., 2000] for NH3, [Kamps et al., 2001] for H2S, and [Rumpf et al., 1992] for HCN as it can be seen in Fig. 4.3) 137 Figure 9.3: Henry´s constant profiles derived from literatures ([Edwards et al., 1978] for CO2, [Alvaro Pérez-Salado et al., 2000] for NH3, [Kamps et al., 2001] for H2S, and [Rumpf et al., 1992] for HCN as it can be seen in Fig. 4.3) 137 Figure 9.4: Comparison between the dissociation constant profiles: Aspen Plus (markers) and Literatures (solid or dashed lines) [Alvaro et al., 2000], [Kamps et al., 2001], and [Edwards et al., 1978] as in Fig.4.4. 138 Figure 9.5: Dissociation constant profiles derived from literatures [Kamps et al., 2001], and [Edwards et al., 1978] as in Fig.4.4. 138 Figure 9.6: Calculated pH values, temperature range and species 139 Figure 9.7: Aspen Plus flow sheet setup for organic acid compounds calculations (GasPOX 201 VP1, see also Table 9.12) 142 Figure 9.8: Aspen Plus flow sheet setup for nitrogen compounds calculations (GasPOX 201 VP1, see also Table 9.12, organic acids are taken into account in the aqueous streams of the quench system) 145 Figure 9.9: Yield of ammonia in gasifier (calculated real) and hot gas temperature against the 47 test points 146 Figure 9.10: Kreal or reaction quotient for ammonia formation in the gasifier against the 47 test points. 146 Figure 9.11: Temperature approach studies for ammonia and the 47 test points 147 Figure 9.12: Yield of HCN from the gasifier (calculated real and equilibrium) and hot gas temperature and the 47 test points 147 Figure 9.13: Comparison between equilibrium constant and reaction quotient for HCN and 47 test points 148 Figure 9.14: Temperature approach studies for HCN and the 47 test points 148 Figure 9.15: Comparison among equilibrium constants of reactions against temperature, T [°C] 149 Figure 9.16: Comparison among equilibrium constants of reactions against temperature, 1/T [1/K] 150 List of Tables Table 2.1: Outline of Gas-POX mode operating parameter range 8 Table 2.2: Outline of test runs operating mode and parameters of chosen test campaigns 9 Table 2.3: Natural gas feedstock compositions 12 Table 2.4: Product synthesis gas analysis method (hot gas before quench) [Brüggemann, 2010] 12 Table 2.5: Analysis methods for raw synthesis gas [Brüggemann, 2010] 13 Table 2.6: Analysis methods for aqueous phase products [Brüggemann, 2010] 14 Table 2.7: Relative accuracy for the measured value for temperature, pressure and flow of each feed and product stream [Meyer, 2007] and [Brüggemann, 2010] 17 Table 3.1: Description of blocks used in Aspen Plus simulation. 20 Table 3.2: HP POX test plant quench water cycle parameters Gas-POX 201 VP1* 23 Table 3.3: pH regulator parameters 24 Table 4.1: Organic acids distribution in streams for VP1 based on calculation from Aspen Plus. 38 Table 4.2: The distribution of CO2 and its ions in all the streams 40 Table 4.3: The distribution of NH3 and its ions in all the streams 45 Table 4.4: The distribution of HCN and its ions in all the streams 49 Table 4.5: The distribution of H2S and its ions in all the streams 52 Table 7.1: Relative sooting tendency [Tesner et al., 2010] 101 Table 9.1: Natural gas feed analysis method [Brüggemann, 2010] 135 Table 9.2: pH scale with examples of solution [NALCO 2008] 136 Table 9.3: Gas-POX test campaigns and with designated serial numbers 140 Table 9.4: Summary of correlation coefficient (r) from Figures in Chapter 5 144 Table 9.5: Comparison among reactions temperatures and heat of reactions 149 Table 9.6: Content of BTEX compounds in Gas-POX quench water samples 151 Table 9.7: BTEX in quench water effluent samples results 152 Table 9.8: Content of PAH compounds in Gas-POX quench water samples 157 Table 9.9: PAHs in quench water effluent samples results 160 Table 9.10: Soot in quench water effluent samples results 169 Table 9.11: Aspen Plus flow sheet setup stream details (GasPOX 201 VP1, according to Fig.3.2 and Fig.9.1, organic acids not taken into account) 170 Table 9.12: Aspen Plus flow sheet setup for organic acid and nitrogen compounds calculations for GasPOX 201 VP1 (according to Figures 9.7 and 9.8, organic acids are taken into account) 174

1 Abstract Faculty of Pharmacy in Hradec Králové, Charles University in Prague Department of Pharmaceutical Chemistry and Drug Control Ljiljana Subara Synthesis of Model Water-Soluble Azaphthalocyanine Fluorescence Quencher Azaphthalocyanine (AzaPc) or tetrapyrazinoporphyrazine as they are often termed in literature, and its substituted derivatives have been investigated extensively for applications as photodynamic therapeutics, dyes, catalysts, liquid crystals, non-linear optical materials and as a red fluorophore. Quenching in general is a process that decreases the fluorescence of another compound. Azaphthalocyanine quenchers are synthetic dyes that decrease fluorescence by absorbing energy over a wide range of wavelengths to dissipate their absorbed energy as non fluorescence. However, in order to do so they must remain in close contact with the fluorescent compound. In this work, we describe the approaches used for the synthesis of azaphthalocyanines (AzaPc) and ways to increasing quenching properties while attaining water solubility. We synthesized a compound which had water solubility as a hydrochloride and no aggregation, however it lacked sufficient quenching properties, and remained difficult to purify on TLC. For improvement of quenching an alternative precursor substituted with a tertiary amine...

碩士
朝陽科技大學
營建工程系碩士班
95
Taiwan area along with the industry and commerce fast prosperity simultaneously grows many waste processing questions. It is estimated approximately has eight thousand fifty hundred thousand tons general trash productions every year. Therefore, the government starts to impel "the garbage disposal plan", devotes to construct the large-scale trash cremation factory, and solves the garbage disposal problem. According to EPA regulations, bottom ash and fly ash produced from MSW incinerators should be properly treated before disposal. Reclamation of incinerated ash by plasma high temperature molten technology is available method to recycle the MSW ashes. Water-quenched slag from plasma vitrification of ash residues was used as eco-cement in this study. This research first by Pozzolanic activity index test for water-quenched slag from plasma was used as water-quenched slag concrete basis of the mechanical properties. The experimental project includes: basic mechanical properties experiment, optics microscopy examination, X-ray diffraction, and freeze-thaw test. This water-quenched slag concrete research was appraised by substitution performance result in different substitution quantity of cement. The findings showed both the 20% water-quenched slag concrete and plain concrete have close mechanics characteristics. In the freeze-thaw cycle endurance test, its strength declines slightly. The 20% substitution of cement with water-quenched slag from plasma might be used as eco-cement.

碩士
國立交通大學
土木工程研究所
83
During the steel-refining process, the dregs are produced in Basic Oxygen Furance. The dregs quenched by water are called Water Quenched Basic Oxygen Furance (WQBOF) slag. About 80% of WQBOF slag will pass the NO.4 sieve. This research are separt- ed to two part: 1.Using the WQBOF slag to substitute part of the fine aggre- gate of concrete. 2.Using the fine powder of WQBOF slag to substitute cement. In part 1 of this study; there are three kinds of mix design The design strengths of concrete are 175, 210, and 280 kg/cm2. Because WQBOF slag has larger specific gravity and contain le- ss fine power, therefore, WQBOF slag, river sand, and fly ash are used as fine aggregate of concrete to improve its conesio- n. Superplasticizers are also added to improve the workability concrete. When 60% of WQBOF slag and 20% of fly ash are used to substitute fine aggregate, the concrete will get better wo- rkability and higher strength. Moreover, WQBOF slag aggregate concrete will not crack under long-time exposure condition. In the second part of this study; the fine powder of WQBOF slag passed #100 sieve substituted part of the cement of the standard-mortar with a water-cement ratio of 0.6. The specim- en''s compressive, flexural, and tensile strength will reduce with increasing WQBOF slag content.

碩士
朝陽科技大學
營建工程系碩士班
96
In recent years, there will be estimated 8.5 million tons of wastes each year in Taiwan, that is, such wastes will produce 1.5 to 2.0 million tons of ashes after being burned up in the incinerator. However, because these ashes contain a lot of pernicious materials including heavy metals and dioxins, the government promotes the “Waste Disposal Project” to building up large-scale incineration plants to solve the serious impact of wastes and ashes on the ecological environment. This research adopts the plasma melting technology to treat the incinerator ashes in high temperature in order to effectively reach the recycling and reutilization of resources derived from incinerator ashes. Through plasma melting technology, the ashes will be vitrified into microcrystalline materials that are called as water quenched slag. In terms of the characteristics of water quenched slag, this article will study the feasibility of resource reutilization for the ingredient of artificial stones. This research will add coloring agents in the production to make the artificial stone have different colors in order to apply to the product made of artificial stones. Furthermore, this article will use the artificial stones made of water quenched slag by replacing stone powder. The testing items include such physical and chemical tests as hardness, specific gravity, water absorption rate, compressive resistance, tensile strength, heat resistance and toxicity leaching. This research also uses different quality of the artificial stone made of water quenched slag and the proportion of resins to substitute for the effect analysis. The result shows that the physical property of test specimen without the case is more similar to that of the generally artificial stone if the proportion of coarse water quenched slag is high. For the tensile strength test, it is found that the strength will be stronger if the content of water quenched slag is less and the resin content is more. Besides, the compressive strength will not be changed regularly in compliance with the quantity of resins or water quenched slag. For the heat resistance test, it is shown that its softening point and break point is similar to those of artificial stones. For such testing result, we can know that the artificial stone powders made of water quenched slag can substitute for the artificial stone powders and can be used as ecological and environment-friendly materials.

碩士
國立交通大學
土木工程學系
84
To conform usability of water-quenched BF slag substitution offshore sand,the effect on concrete by water-quenched BF slag, which produced by China Steel Corp.,in different percentage of substitute was inve-stigate. Under the conditions of 3 different fineness modulous of offshore sand,5 different slag substitutes,1 slump and 4 different water-cement ratios, properties such as workability,compressive strength,tensile strength,durability,diffusibility,elapsing time,agg-regation, etc., of concrete composed of different substitutes of water- quenched BF slag were compared.The particles of water-quenched BF slag are mostly in globular shape and with good flowability. The workability then can be enhanced and the consumption of water can be reduced as the ratio of substitution increased. However,the bleeding and segregation also become more prominent when the ratio of substitution increased due to its high specific gravity. Therefore,the best ratio of substitution is around 40% to 55%. The substitution may be reasonably reduced if the fineness modulous of offshore sand can be enhanced.The results of this study showed that the compressive strength of all concrete composed of water-quenched BF slag in different substitution were better than that of concrete composed of offshore sand. The change of tensile strength and water tightness are similar to that of compressive strength.As the substitution increased,the durability was enhanc-ed,the shrinkage lessened,and the time of aggregation delayed.

碩士
國立屏東科技大學
機械工程系所
95
This paper studies the optimal processes of making water-quenched slag powder using the Taguchi method. This research work includes two phases: (1) to obtain the optimal gas flow rate in the pneumatic system; and (2) to obtain the optimal conditions of milling water-quenched slag powder. In the first part of research, the control factors include: (i) the recycle damper opening (%), (ii) the primary wind turbine damper opening (%), (iii) the second wind turbine damper opening (%), and (iv) the rotation speed of the separator (rpm). The temperature at exit of mill increased 7%, when the optimal operating conditions (i.e., the separator with a rotation speed of 710 rpm, the recycle damper with an opening of 85%, the second wind turbine damper with an opening of 40%, and primary wind turbine damper with an opening of 47.5%), were applied. In the second part of research, the control factors include: (i) the amount of water-quenched slag (ton/hr), (ii) the primary wind turbine damper opening,(%), (iii) the mill-roller tension (kg/cm2), and (iv) the rotation speed of the separator (rpm). The amount of water-quenched slag powder at exit of mill increased by 35%, when the optimal operating conditions (i.e., the separator with a rotation speed of 710 rpm, the mill-roller with a tension of 95kg/cm2, the primary wind turbine damper with an opening of 43.5%, and the amount water-quenched slag of 58.5ton/hr), were applied. The third part of the research is a discussion on preventing steel plate corrosion, with an optimization experiment which selects the rainbow sign ready mixed paint (yellow)/the artificial turpentine, China Hi-ment Corporation’s slag powder (＜25 m ), as well as Taiwan Electric Power Company’s Big Lin cinders powder (35um); Center Steel Carbon Company’s artificial graphite (＜25 m ) was the control factor. The theory confirmation experiment result showed that with the ready mixed paint (yellow) 20 grams /4 gram artificial turpentine, China Hi-ment Corporation’s slag powder 4 grams (＜25 m ), Taiwan Electric Power Company’s Big Lin cinders powder 2 grams (35um) as well as Center Steel Carbon Company’s artificial graphite 4 grams (＜25 m ), the steel plate weight was enhanced approximately 2.2%. The steel plate corrosion prevention effect is obvious.

碩士
國立成功大學
環境工程學系
84
THE FEASIBILITY OF WASTEWATER SLUDGE STABILIZATION WITH FLY ASH AND WATER QUENCHED SLAGJuu-En Chang and Yi-Kuo ChangDepartment of Environmental EngineeringNational Cheng Kung UniversityABSTRACTWastewater sludges contain nutrients and organic matters which make them suitable for reclaiming and improving marginal soils. But when the quantities used are not properly controlled, the sludge can be harmful to the lands and plants both. Fly ash and slag contain a predominant fraction of pozzolanic materials (Si, Ca, and Al oxides) which have the pollutant stabilization ability and they benefit soil. Therefore, the fly ash and slag can be useful for stabilization of organic matters in the wastewater sludge, and the mixture can be applied to land with a minimal environmental impact. In this study, fly ash and slag were used as additives to stabilize the organic matters, ammonia and phosphate in wastewater sludge. The sludge was obtained from an industrial park wastewater treatment plant, the fly ash was from a power plant, and the water quenched slag was from a steel plant. To determine the optimal operating conditions, parameters such as curing time, curing temperature, additive dosages, water content and pH value were varied. Leaching tests were performed to evaluate the stabilization efficacy of the additives at designed dosages, water content and curing conditions. Experimental results show that both fly ash and slag could effectively reduce the leaching-out rates of DOC and NH3-N of the wastewater sludge, and the leached out DOC decreased with increased additive dosages. The adsorption capacity for DOC and NH3-N of the fly ash was higher than slag, because the fly ash had a larger specific surface area. The optimal operating conditions for the stabilization of wastewater sludge by fly ash and slag are : leaching out ratio (Lr) of DOC was 0.43 with slag as additive only for 7-day curing; Lr of NH3-N was 0.17 with slag as additive only for 14-day curing; while Lr of PO43- was 0.50 with slag or fly ash as additive for 3-hour curing. SEM-EDX and XRD microanalysis show that the adsorption performance was better than encapsulation at the beginning of curing, but the stabilization mechanism turned into fixation/stabilization as a result from Pozzolanic reaction when curing time increased. Also, curing at low temperature could inhibit sludge biodegradation and resulted in a decrease in leaching-out rates of DOC, NH3-N and ortho-P.Key words : wastewater sludge, stabilization, fly ash, slag

碩士
國立成功大學
環境工程學系
105
In recent years, fossil fuel has been widely used by human thus booming the economy. A great amount of carbon dioxide releasing from fossil fuel combustion causes the global warming. As a result, carbon dioxide capture and storage techniques are needed to solve this issue. Oxy-fuel combustion system is a carbon dioxide capture technology, contributing to higher capture efficiency due to concentrated CO2, decreasing processing cost, and easy alterations. This study used the water-quenched slag and the desulfurization slag as the sorbents. It not only reduces the cost of sorbent but also has a high calcium content that can highly absorb CO2 of the flue gas in a fluidized bed reactor system and increases the reutilization of the waste. Therefore, this study simulated oxy-fuel combustion condition to capture carbon dioxide with De-S and GGBS slags in a fluidized bed reactor system at high temperature. Results of this study are summarized as follows： 1.With the increasing temperature both for empirical model prediction and experimental results, the minimum fluidized velocity of De-S and GGBS slags at various particle sizes have a decrease trend. However, the particle size and particle density of slags can influence the values of the minimum fluidized velocity at various temperatures. 2.According to the results of TGA analysis, De-S and GGBS slags react with carbon dioxide at various temperatures, weight change of the De-S slag is much higher than the GGBS slag. 3.Regarding to the various operating parameters such as temperature, water vapor, flow velocity and CO2 concentration, it can be found that an increase of the carbon dioxide concentration can significant impact the slags sorption utilization. When the gas velocity reaches minimum fluidized velocity, the sorption utilization sorption of the slags at various particle sizes will be the best. As the velocity becomes higher than minimum fluidized velocity, the slag sorption utilization decreases. The little water vapor for 5% can promote CO2 capture of slag at various particle sizes and excessive water vapor for 10% at various particle sizes affect pore structure. 4.The best operating temperature is about 600oC for the CO2 capture with De-S slag at various particle sizes; the best operating temperature is about 500oC for the CO2 capture with GGBS slag at various particle sizes. It can be found that De-S slags at various particle sizes for the CO2 capture are superior to the GGBS slags . 5.The pilot plant is 10 times the size of the laboratory set, conducting the capture of carbon dioxide from air and oxy-fuel combustion conditions. It can be found that the utilization of 150-300μm De-S slag at 600 oC is better than other temperature. The utilization of 150-300μm De-S slags for the capture of carbon dioxide from oxy-fuel combustion is higher than air combustion due to the increase in carbon dioxide partial pressure of the flue gas from oxy-fuel combustion.

Dissertação de Mestrado Integrado em Engenharia Electrotécnica e de Computadores apresentada à Faculdade de Ciências e Tecnologia
O sistema solar térmico para aquecimento de água é utilizado principalmente em ambiente doméstico para as Águas Quentes Sanitárias, sendo nos dias de hoje um serviço indispensável para o bem-estar de todos nós. De modo a garantir a estabilidade dos sistemas de energia elétrica, tendo em conta a descentralização da geração elétrica e a produção a nível local, a gestão da procura tem ganho cada vez mais importância. A gestão da procura permite desviar e diminuir consumos de energia eléctrica, pelo que pode ser usada para evitar picos da procura, no entanto, para o consumidor final, a gestão da procura torna-se mais interessante se utilizada com a finalidade de desviar consumos para reduzir a fatura da eletricidade. É neste âmbito que no presente trabalho serão utilizados softwares de simulação de gestão da procura, de modo a tornar os sistemas de aquecimento de águas sanitárias mais eficientes e mais apelativos em termos económicos.O presente trabalho foi desenvolvido no âmbito da Dissertação de Mestrado Integrado em Engenharia Eletrotécnica e de Computadores, lecionada no Departamento de Engenharia Eletrotécnica e de Computadores da Faculdade de Ciências e Tecnologia da Universidade de Coimbra, no ano letivo 2015/2016, tendo como objetivo a criação e modelação de sistemas de aquecimento de água quente com painéis térmicos e apoio elétrico.Neste trabalho é apresentada a simulação e comparação de vários modelos de sistema solar térmico, entre os quais, o sistema termossifão, o sistema de circulação forçada com aquecimento direto e indireto.É também apresentado um algoritmo desenvolvido em MATLAB, validado através do TRNSYS, que dada a previsão da temperatura, da radiação solar e do consumo diário é capaz de conseguir reproduzir o funcionamento de um sistema de águas quentes sanitárias com painéis solares e apoio elétrico de circulação forçada e aquecimento indireto. Com esta ferramenta é possível simular e analisar cenários alternativos de funcionamento dos sistemas de aquecimento solar de água com apoio elétrico. As ações submetidas no funcionamento normal do algoritmo são a variação da temperatura máxima do depósito e a introdução de interrupções definidas pelo utilizador.Com a introdução das chamadas redes inteligentes (Smart grids), surgiu a oportunidade de entregar energia de uma forma controlada e inteligente desde o ponto de geração até ao consumidor, devido à evolução das tecnologias de informação e comunicação (TIC). Para observar as ações de gestão do lado da procura que podem ser avaliadas, foi desenvolvida uma ferramenta de simulação que permite alterar o funcionamento normal do algoritmo que tinha sido criado para simular o sistema de aquecimento de água quente com painéis térmicos e apoio elétrico em Matlab.
The solar thermal energy system for water heating is used mainly for domestic consumption for the Sanitary Hot Waters, being nowadays an essential good for the wellbeing of everyone.With the purpose of granting Electric Energy Systems stability, taking into account the decentralized electricity generation and local production, demand side management has gained increasing importance.The demand management divert and reduce electrical energy consumption, therefore can be used to prevent peak demand, however, for the end consumer, demand management becomes more interesting if used for the purpose of diverting consumption to reduce the invoice of electricity. It is in this context that the present work will make use of simulation software for demand management, in order to make the sanitary water heating systems more efficient and more attractive in economic terms. This work was developed within the framework of the Masters dissertation of the Master’s degree in Electrical and Computer Engineering, taught in the Department of Electrical and Computer Engineering of the Faculty of Sciences and Technology of the University of Coimbra, in the academic year of 2015/2016 with the purpose of modeling the sanitary hot water systems with thermal panels and electrical support.In this work, a simulation and comparison of various solar thermal energy systems is presented, among which are: the thermosiphon system and the forced-circulation system with direct and indirect heating.It is also presented a MATLAB developed algorithm is validated through TRNSYS, which when given the temperature prediction of the solar radiation and daily consumption is capable of reproducing a system of sanitary hot water systems with solar panels and electrical support and forced-circulation and indirect heating. With this tool it is possible to simulate and analyze alternative scenarios of operation of solar water heating systems with electrical support. The actions subjected to the normal operation of the algorithm are the maximum variation in temperature of the tank and the insertion of interruptions defined by the user.With the introduction of so-called intelligent networks (smart grids), the opportunity arose to deliver energy in a controlled and intelligent manner from the point of generation to the consumer, due to the evolution of information and communication technologies (ICT). To observe the demand side management actions that can be evaluated, a simulation tool that allows the change of normal operation of the algorithm that had been created to simulate the hot water heating system with thermal panels and electrical support in Matlab was developed.