Syftet med denna studie är att bidra med kunskapen om vilken innebörd läroplansbegreppet ”enkla kemiska processer” fått i förskolans naturvetenskapliga undervisning. Empirin samlades in genom kvalitativa semistrukturerade intervjuer av förskolepersonal, fördelat på sex förskollärare och fyra barnskötare. Resultatet visade att förskolepersonalen främst betonade undervisning om kemiska processer i syfte att förbereda barnen för framtida skolgång och ge positiva känslor för ämnet. Förskolepersonalen kopplade begreppet ”enkla kemiska processer” med undervisningsaktiviteter som är associerade med vatten, bakning, bakpulver, färg samt naturen som redskap. Resultatet visade även att kemiundervisning sker både planerat och spontant i verksamheten, samt att förskolepersonalen anser att kemiundervisningen ska genomföras utifrån barnens intresse och nyfikenhet, där det ska ske på ett lustfyllt sätt tillsammans med medforskande pedagoger.  En slutsats av studien är att förskolepersonalen har många tankar om vad ”en enkel kemisk process” är och hur det undervisas i förskolan, men att kemiämnet inte prioriteras i den dagliga verksamheten och att anledningen bland annat är att ämnet anses svårt. / The purpose of this study was to contribute knowledge about the meaning of the curriculum concept ”simple chemical processes” in preschool science teaching. The data was collected through qualitative semistructured interviews with preschool staff, consisting of six preschool teachers and four childminders. The study showed that the preschool staff mainly emphasized the importance of teaching chemical processes as preparation for the children's future schooling and encouragement of a positive attitude towards the subject chemistry. The preschool staff linked the concept of ”simple chemical processes” with teaching activities involving water, baking powder, baking and paint. They also linked the concept to changes in the natural world. The results also showed that chemistry teaching took place in both a planned and spontaneous way, and that the preschool staff believed that chemistry teaching should be based on the children's interest and curiosity. They believed that it should be undertaken in a fun way together with other involved educators present. One conclusion of the study is that the preschool staff varied in their interpretation of "simple chemical processes" and how they were taught in preschool. Chemistry teaching was not given high priority, according to the preschool staff, one of the reasons being that the subject was considered difficult.

Studiens syfte är att bidra med kunskap om lärares uppfattningar kring barns erfarenheter och lärande om kemiska processer och möjligheten till progression i övergången mellan förskola och förskoleklass, enligt lärare i dessa två skolformer. Studien utgår ifrån en kvalitativ metod med stöd av semistrukturerade intervjuer där nio informanter deltagit i studien.  Resultatet visar att lärarna uppfattar naturvetenskap på två olika vis, naturvetenskap som en helhet och naturvetenskap som biologi. Studien pekar även på att det till viss del finns en otydlig kommunikation vid samverkan kring övergångar mellan förskola och förskoleklass. Slutligen visar studien att de förmågor och kunskaper som lärarna beskriver prioriteras i informationsutbytet mellan förskola och förskoleklass är det sociala samspelet, språket och barns intressen.  Slutsatsen är att förskollärare och förskoleklasslärare behöver mer kunskap inom naturvetenskap med fokus på kemikaliska processer och fenomen, men också insyn och kunskap om varandras arbete. Det blir utmanade för lärare att skapa möjlighet till progression i barns lärande om kemikaliska processer och fenomen i ett övergångsarbete om det inte finns medveten undervisning eller samsyn kopplat till ämnesområdet. / The purpose of the study is to contribute knowledge about teachers' perceptions of children's experiences and learning about chemical processes and the possibility of progression in the transition between preschool and preschool class, according to teachers in these two school forms. The study is based on a qualitative method supported by semi-structured interviews where nine informants participated in the study.  The results of the study show that the teachers perceive science in two different ways, science as a whole and science as biology. The study also points out that there is to some extent an unclear communication when collaborating on transitions between preschool and preschool class. Finally, the study shows that the abilities and knowledge that the teachers describe prioritized in the exchange of information between preschool and preschool class is social interactions, language and children's interests.  The conclusion is that preschool teachers and preschool class teachers need more knowledge in science with a focus on chemical processes and phenomena, but also insight and knowledge about each other's work. It will be challenging for teachers to create the opportunity for progression in children's learning about chemical processes and phenomena in a transition work if there is no conscious teaching or consensus linked to the subject area.

<p>U okviru doktorske disertacije predstavljeni su postojeći i novi koncepti modeliranja<br />turbulentnog transporta ugljen-dioksida i azotnih oksida u povr&scaron;inskom sloju atmosfere<br />iznad ruralne oblasti. Cilj istraživanja je da se na osnovu postojećih saznanja o procesima<br />koji opisuju interakciju tlo-vegetacija-atmosfera i rezultata mikrometeorolo&scaron;kih<br />eksperimenata unapredi modeliranje procesa interakcije. Poseban akcenat stavljen je na<br />modeliranje turbulentnog transporta gasova iznad i unutar &scaron;umskog sklopa. Uticaj<br />vertikalne heterogenosti biljnog sklopa uveden je u predloženi postupak skaliranja<br />asimilacije ugljen-dioksida sa lista na biljni sklop i suve depozicije azotnih oksida.<br />Predloženi koncepti testirani su u okviru fizičke LAPS i hemijske MLC-Chem povr&scaron;inske<br />sheme. Za potrebe modeliranja turbulentnog transporta ugljen-dioksida razvijen je<br />modul za parametrizaciju intenziteta fotosinteze. Kvantitativna analiza rezultata izvedena<br />je poređenjem osmotrenih i simuliranih vrednosti turbulentnih flukseva ugljen-dioksida i<br />azotnih oksida na četiri karakteristična &scaron;umska sklopa. Unapređenje modeliranja<br />izvedeno je kaplovanjem testiranih povr&scaron;inskih shema u MLC-LAPS shemu. Kvalitet<br />simulacija MLC-LAPS sheme proveren je poređenjem izlaznih i osmotrenih<br />mikrometeorolo&scaron;kih veličina, koncentracije i turbulentnih flukseva gasova.</p> / <p>This PhD thesis deals with the current and new concepts of modeling turbulent<br />transport of carbon dioxide and nitrogen oxides in the surface layer of the atmosphere<br />above the rural areas. The aim of this research is to improve modeling of the interaction<br />between soil-vegetation-atmosphere based on existing knowledge about the processes<br />describing the interaction and results of micrometeorological experiments. Special<br />emphasis is placed on the modeling of turbulent transport of gases above and within<br />the forest canopy. Influence of vertical canopy heterogeneity was introduced in the<br />proposed method for scaling the assimilation of carbon dioxide from the leaf to canopy level and dry deposition of nitrogen oxides. The presented concepts are tested within the physical LAPS and chemical MLC-Chem surface schemes. For the purposes of modeling the turbulent transport of carbon dioxide the module for parameterization of photosynthesis was developed. Quantitative analysis of the results were made by comparing the observed and simulated values of turbulent fluxes of carbon dioxide and nitrogen oxides in four distinctive forest canopies. Modeling improvement was performed by coupling tested surface schemes into MLC-LAPS scheme. Quality of MLCLAPS scheme simulations is verified by comparing the output and observed micrometeorological elements and turbulent fluxes of energy and gases.</p>

A implantação de um projeto de utilização do biogás como fonte renovável de energia em pequena escala, requer a pesquisa de processos de limpeza do biogás e de captura de CO&#8322;, que contemplem os aspectos de sustentabilidade e de uma tecnologia que possa ser aplicada em pequenas instalações. Visando uma matéria-prima de baixo custo, o presente estudo utilizou cinzas de madeira como fonte de carbonatos para a absorção de CO&#8322;, buscando usar um resíduo como solvente, para melhorar a eficiência energética de um combustível de fonte renovável. As cinzas de madeira, geralmente possuem elevados valores de pH e são compostas, principalmente, por óxidos de potássio, magnésio e cálcio. O objetivo deste trabalho foi estudar a absorção do CO&#8322; por soluções de carbonatos totais e solúveis provenientes de suspensões de cinzas de madeira em água, através de experimentos realizados em escala laboratorial e de simulação empregando como base o carbonato de cálcio equivalente. A célula de absorção é uma ferramenta eficaz para estimar a capacidade de reter CO&#8322; em um solvente desconhecido, à temperatura e pressão ambientes. Os carbonatos solúveis extraídos das cinzas de madeira, com 5,33 % de CCE, têm a capacidade de absorver, em média, 0,77 g de CO&#8322; por 100g de cinzas de madeira, em condições ambientes. Já as cinzas com 89,74 % de CCE absorveram, em média, 12,6 g de CO&#8322; por 100 g de cinzas de madeira, em condições ambientes. Assim, podem-se caracterizar as cinzas de madeira como um potencial solvente para a absorção de CO&#8322;. A simulação de uma coluna de pratos perfurados, equivalente a uma coluna de pratos tipo chicana, através da tranferência da sua área de cortina, foi satisfatória. / The implementation of a project for the use of biogas as a renewable source of energy on a small scale, requires research into cleaning the biogas and CO&#8322; capture processes, with sustainability and technology that can be applied in small installations. The present study uses wood ash as a source of carbonate for CO&#8322; absorption, seeking to use waste as a solvent, to improve the energy efficiency of a renewable fuel source. Wood ash is a solid waste with organic and inorganic components, obtained from combustion of wood. Its chemical composition may vary according the tree species, soil type, climate and combustion characteristics. The resulting suspension of ash in water has typical properties of high pH values and high concentrations of carbonates. The aim of this work is to study the absorption of CO&#8322; by solutions of total carbonates and soluble carbonates from suspensions of wood ashes in water, through experiments conducted in laboratory scale and employing simulation based on the calcium carbonate equivalent. A simple device was successfully developed that could predict the absorption potential for CO&#8322; of a solvent with unknown composition in ambient conditions of temperature and pressure. The soluble carbonates had 5.33% of calcium carbonate equivalence absorbed 0.77g CO&#8322; / 100g ashes, at approx. 700 mmHg and 20°C. Ashes with 89.74% of calcium carbonate equivalence absorbed 12.6g CO&#8322; / 100g ashes, at approx. 700 mmHg and 20°C. This study suggests that wood fuel ashes are a potential solvent for CO&#8322; absorption. The simulation of an equivalent column of perforated plates to a column of baffle plates, through the transfer of its area curtain was satisfactory.

Medidas eletroquímicas, incluindo voltametria cíclica com e sem rotação do eletrodo, cronoamperometria, deconvolução experimental, aplicação de procedimentos eletroquímicos de envelhecimento e programas de perturbação de potencial foram empregadas no estudo eletroquímico da interface estanho/solução de bicarbonato de sódio 0,5 mol L-1. Os estudos preliminares evidenciaram a natureza complexa dos processos que ocorrem no sistema e várias séries de ensaios foram propostos a partir desses resultados. Observou-se o deslocamento do principal pico catódico, devido à mudanças das configurações de energia do filme, que foram analisadas mediante a aplicação de procedimentos de envelhecimento potenciostático e potenciodinâmico. A ocorrência de reativação em condições de baixa velocidade de varredura e a razão entre as cargas anódica e catódica sempre superior à unidade foram atribuídas à dissolução. O emprego de eletrodo de disco rotativo permitiu acompanhar a presença de espécies solúveis de Sn(II) envolvidas nos primeiros estágios de formação de filme. Foi observado que há contribuição difusional no controle da cinética dos dois primeiros processos anódicos. A variação da corrente com a rotação deve-se à difusão de uma mesma espécie nos dois processos anódicos. A presença de óxidos formados em diferentes condições experimentais com características e propriedades elétricas diferentes, evidenciada nos ensaios preliminares, foi analisada sob uma abordagem modelística. A ocorrência de processos de nucleação na redução, sugerida pela presença de histerese de corrente e pela dependência da corrente do pico de redução com a velocidade de varredura, foi confirmada com o emprego de medidas cronoamperométricas. Programas de perturbação de potencial, com o objetivo de eletromodificar a superfície do estanho, foram aplicados. A influência das variáveis de interesse (velocidade da perturbação, tempo de duração, limites de potencial, catodização e número de catodizações) no aparecimento de mudanças no perfil padrão foi estudada. A cinética de desprendimento de oxigênio foi analisada mediante curvas de Tafel, para avaliar as mudanças das propriedades eletrocatalíticas das superfícies resultantes da aplicação dos programas de perturbação. / Electrochemical measurements including cyclic voltammetry with and without electrode rotation, chronoamperometry, experimental deconvolution, electrochemical ageing procedures, and perturbing potential programmes, were carried out in order to study the tin/0,5 mol L-1 sodium bicarbonate solution interface. Preliminary studies evidence the complex nature of the processes and enable the proposal of various series of experiments. The potential shift of the main cathodic current peak was assigned to changes in the energetic configuration of the species formed during the positive scan. That effect was studied by means of potenciostatic and potentiodynamic ageing procedures. Reactivation occurrence at low sweep rates and the anodic to cathodic charges ratio always higher than one, were attributed to dissolution. Rotating disc measurements evidence the presence of soluble species, probably Sn(II) species, involved in the first steps of film formation. It was observed that a diffusional contribution has to be taken into account into the global control that involves the first two anodic processes. The same current-rotation dependence observed suggests the diffusion of the same species for both the anodic processes. The films formed under different experimental conditions, which exhibit differences in nature and electric properties, were studied under a modelistic approach. Current hysteresis presence as well as the dependence of peak current with sweep rate observed at the preliminary studies, suggest cathodic nucleation processes. Nucleation was confirmed by means of chronoamperometric measurements. In order to electromodify tin surface, the electrode was subjected to perturbing potential programmes. The influence of experimental variables (as perturbation sweep rate, perturbation time, potential limits, cathodic polarization and number of cathodic polarization applied) on the cathodic profile was studied. Oxygen evolution reaction, in terms of Tafel plots, was used in order to evaluate changes in the electrocatalytic properties of the modified surfaces.

A implantação de um projeto de utilização do biogás como fonte renovável de energia em pequena escala, requer a pesquisa de processos de limpeza do biogás e de captura de CO&#8322;, que contemplem os aspectos de sustentabilidade e de uma tecnologia que possa ser aplicada em pequenas instalações. Visando uma matéria-prima de baixo custo, o presente estudo utilizou cinzas de madeira como fonte de carbonatos para a absorção de CO&#8322;, buscando usar um resíduo como solvente, para melhorar a eficiência energética de um combustível de fonte renovável. As cinzas de madeira, geralmente possuem elevados valores de pH e são compostas, principalmente, por óxidos de potássio, magnésio e cálcio. O objetivo deste trabalho foi estudar a absorção do CO&#8322; por soluções de carbonatos totais e solúveis provenientes de suspensões de cinzas de madeira em água, através de experimentos realizados em escala laboratorial e de simulação empregando como base o carbonato de cálcio equivalente. A célula de absorção é uma ferramenta eficaz para estimar a capacidade de reter CO&#8322; em um solvente desconhecido, à temperatura e pressão ambientes. Os carbonatos solúveis extraídos das cinzas de madeira, com 5,33 % de CCE, têm a capacidade de absorver, em média, 0,77 g de CO&#8322; por 100g de cinzas de madeira, em condições ambientes. Já as cinzas com 89,74 % de CCE absorveram, em média, 12,6 g de CO&#8322; por 100 g de cinzas de madeira, em condições ambientes. Assim, podem-se caracterizar as cinzas de madeira como um potencial solvente para a absorção de CO&#8322;. A simulação de uma coluna de pratos perfurados, equivalente a uma coluna de pratos tipo chicana, através da tranferência da sua área de cortina, foi satisfatória. / The implementation of a project for the use of biogas as a renewable source of energy on a small scale, requires research into cleaning the biogas and CO&#8322; capture processes, with sustainability and technology that can be applied in small installations. The present study uses wood ash as a source of carbonate for CO&#8322; absorption, seeking to use waste as a solvent, to improve the energy efficiency of a renewable fuel source. Wood ash is a solid waste with organic and inorganic components, obtained from combustion of wood. Its chemical composition may vary according the tree species, soil type, climate and combustion characteristics. The resulting suspension of ash in water has typical properties of high pH values and high concentrations of carbonates. The aim of this work is to study the absorption of CO&#8322; by solutions of total carbonates and soluble carbonates from suspensions of wood ashes in water, through experiments conducted in laboratory scale and employing simulation based on the calcium carbonate equivalent. A simple device was successfully developed that could predict the absorption potential for CO&#8322; of a solvent with unknown composition in ambient conditions of temperature and pressure. The soluble carbonates had 5.33% of calcium carbonate equivalence absorbed 0.77g CO&#8322; / 100g ashes, at approx. 700 mmHg and 20°C. Ashes with 89.74% of calcium carbonate equivalence absorbed 12.6g CO&#8322; / 100g ashes, at approx. 700 mmHg and 20°C. This study suggests that wood fuel ashes are a potential solvent for CO&#8322; absorption. The simulation of an equivalent column of perforated plates to a column of baffle plates, through the transfer of its area curtain was satisfactory.

With increasing environmental awareness and natural resource limitations, researchers must begin to incorporate sustainability into their process and product designs. One target for green engineering is in reaction and separation design. This is typically done in a wasteful and often toxic manner with organic solvents and lack of recycle. The following thesis discusses alternatives to these costly separations by means of ionic liquids, benign extraction, separation with carbon dioxide, and near critical water. Ionic liquids are combined with carbon dioxide to induce melting point depressions of up to 124 degrees Celsius. Using this system as a reaction medium will offer control over the reaction phases while utilizing green solvents. Benign extractions are performed on both ferulic acid and on proteins from biomass by replacing alkaline solvents and costly protein separation techniques with simple liquid-liquid extraction. This means simpler systems and less waste than from previous methods. This thesis also discusses an opportunity for more efficient separation and recycle of a pharmaceutical catalyst, Mn-Salen. Using carbon dioxide with the organic aqueous tunable solvent system, the reaction can be run homogeneously and the product and catalyst separated heterogeneously, thus creating an extremely efficient process. Lastly, near critical water is used as an extraction and reaction medium by extracting ferulic acid from Brewers Spent Grain and then catalyzing its transformation to 4-vinylguaiacol. In this manner a simple, benign process is used to turn waste into valuable chemicals. Although somewhat different, each of the studied processes strives to eliminate waste and toxicity of many commonly used reaction and separation techniques, thus creating safe and sustainable processes.

The motivations for the research issues addressed in this thesis are based on the needs of the aerospace structural analysis and the design community. The specific focus is related to the characterization and shock induced chemical reactions of multi-functional structural-energetic materials that are also know as the reactive structural materials and their reaction capabilities. Usually motivation for selection of aerospace structural materials is to realize required strength characteristics and favorable strength to weight ratios. The term strength implies resistance to loads experienced during the service life of the structure, including resistance to fatigue loads, corrosion and other extreme conditions. Thus, basically the structural materials are single function materials that resist loads experienced during the service life of the structure. However, it is desirable to select materials that are capable of offering more than one basic function of strength. Very often, the second function is the capability to provide functions of sensing and actuation. In this thesis, the second function is different. The second function is the energetic characteristics. Thus, the choice of dual functions of the material are the structural characteristics and energetic characteristics. These materials are also known by other names such as the reactive material structures or dual functional structural energetic materials. Specifically the selected reactive materials include mixtures of selected metals and metal oxides that are also known as thermite mixtures, reacting intermetallic combinations and oxidizing materials. There are several techniques that are available to synthesize these structural energetic materials or reactive material structures and new synthesis techniques constitute an open research area. The focus of this thesis, however, is the characterization of chemical reactions of reactive material structures that involve two or more solids (or condensed matter). The subject of studies of the shock or thermally induced chemical reactions of the two solids comprising these reactive materials, from first principles, is a relatively new field of study. The published literature on ab initio principles or quantum mechanics based approach contains the ab initio or ab initio-molecular dynamics studies in related fields of a solid and a gas. One such study in the literature involves a gas and a solid. This is an investigation of the adsorption of gasses such as carbon monoxide (CO) on Tungsten. The motivation for these studies is to synthesize alternate or synthetic fuel technology by Fischer-Tropsch process. In this thesis these studies are first to establish the procedure for solid-solid reaction and then to extend that to consider the effects of mechanical strain and temperature on the binding energy and chemisorptions of CO on tungsten. Then in this thesis, similar studies are also conducted on the effect of mechanical strain and temperature on the binding energies of Titanium and hydrogen. The motivations are again to understand the method and extend the method to such solid-solid reactions. A second motivation is to seek strained conditions that favor hydrogen storage and strain conditions that release hydrogen easily when needed. Following the establishment of ab initio and ab initio studies of chemical reactions between a solid and a gas, the next step of research is to study thermally induced chemical reaction between two solids (Ni+Al). Thus, specific new studies of the thesis are as follows: 1. Ab initio Studies of Binding energies associated with chemisorption of (a) CO on W surfaces (111, and 100) at elevated temperatures and strains and (b) adsorption of hydrogen in titanium base. 2. Equations of state of mixtures of reactive material structures from ab initio methods 3. Ab initio studies of the reaction initiation, transition states and reaction products of intermetallic mixtures of (Ni+Al) at elevated temperatures and strains. 4. Press-cure synthesis of Nano-nickel and nano-aluminum based reactive material structures and DTA tests to study experimentally initiation of chemical reactions, due to thermal energy input.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Environmental contamination by drugs of antibiotic action can bring as a consequence the development of more resistant bacteria, altering the microbial community structure in nature. Due to its widespread use, ciprofloxacin has been identified in trace concentrations in sewage treatment plants (STPs) and surface waters, since the conventional processes of wastewater treatment does not remove the usual drugs completely, these substances have been detected in drinking water, which represents a direct risk to humans, since the constant contamination of water may be associated with the continuous process and reuse of the water increasing worldwide. In this study, a method of electrochemical oxidation of ciprofloxacin, since the transfer of electrons, drugs can be processed, biodegraded or mineralized. The electrochemical oxidation of the drugs can occur in a satisfactory manner, the surface of some anode metal oxide, capable of generating oxygen and simultaneously with the formation of higher oxides or superoxide. This mechanism is at the surface of ADE ® coated and immobilized metal oxides. To identify and monitor the change in concentration of ciprofloxacin was analyzed their absorption spectra in the ultraviolet and visible (200-800 nm). Ciprofloxacin in aqueous solution shows two absorption peaks in completely different bands and with maximum at 270 nm and 315 nm. The nature of the electrolyte and the pH had great influence on the speed of the degradation process. In the midst of Cl- was a more efficient degradation. In studies with HCl, NaCl and KCl was observed 100% removal of the yellow color characteristic of the presence of Cl-anion and subsequent formation of hypochlorite (ClO-). In turn, the pH was a limiting factor in this process, where it was observed that the reaction proceeds in most satisfactorily at pH values below 4.0. The current that showed the best result was 80 mA. The method of supplying water to said acid chloride in ciprofloxacin can be completely degraded within 5 min. / A contaminação ambiental por fármacos de ação antibiótica pode trazer como consequência o desenvolvimento de bactérias mais resistentes, alterando a estrutura da comunidade microbiana na natureza. Devido a sua ampla utilização, a ciprofloxacina vem sendo identificada em concentrações-traço em estações de tratamento de esgotos (ETEs) e águas superficiais, uma vez que os processos convencionais de tratamento de efluentes usuais não removem os fármacos completamente, essas substâncias têm sido detectadas em águas potáveis, o que caracteriza um risco direto para os seres humanos, visto que a constante contaminação das fontes de água pode ser associada ao processo contínuo e crescente de reutilização da água em todo o mundo. Neste estudo foi desenvolvido um método de oxidação eletroquímica da ciprofloxacina, uma vez que na transferência de elétrons, os fármacos podem ser transformados, biodegradados ou mineralizados. A oxidação eletroquímica dos fármacos pode ocorrer de forma satisfatória, na superfície de alguns ânodos de óxidos metálicos, em condições de geração simultânea de oxigênio e com a formação de óxidos superiores ou superóxidos. Este mecanismo é observado na superfície dos ADE® revestidos e imobilizados por óxidos metálicos. Para identificar e acompanhar a mudança de concentração da ciprofloxacina foi analisado o seu espectro de absorção na região do ultravioleta e visível (200-800 nm). A ciprofloxacina em solução aquosa apresenta dois picos de absorção em bandas completamente distintas e com máximos em 270 nm e 315 nm. A natureza do eletrólito e o pH apresentou grande influência na velocidade do processo de degradação. Em meio a Cl- ocorreu uma maior eficiência na degradação. Nos estudos com HCl, NaCl e KCl foi observado 100% de remoção da cor amarelada, característica da presença do ânion Cl- e da posterior formação de hipoclorito (ClO-). Por sua vez, o pH foi um dos fatores limitantes deste processo, onde foi possível observar que a reação acontece de maneira mais satisfatória em valores de pH abaixo de 4,0. A corrente que apresentou o melhor resultado foi de 80mA. A aplicação do método em água de abastecimento indicou que em meio ácido contendo cloreto a ciprofloxacina pode ser completamente degradada em apenas 5 min.

Orientador: Rubens Maciel Filho / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-16T11:19:21Z (GMT). No. of bitstreams: 1 MartinezArias_EdgarLeonardo_M.pdf: 60155872 bytes, checksum: 6edb8dbfd65cb71ea0a617a741e58925 (MD5) Previous issue date: 2010 / Resumo: A tecnologia da microreação é um importante método de intensificação de processos que oferece numerosos benefícios para a indústria de processos químicos. A elevada razão área superficial-volume aumenta as taxas de transferência de massa e energia, melhorando a eficiência e o desempenho dos reatores, e permitindo um aumento na segurança resultante do baixo hold-up em comparação com o reator convencional. O fluxo de líquidos imiscíveis nos microreatores tem mostrado uma intensificação da transferência de massa através da aplicação de estruturas internas que servem como misturadores passivos, o que aumenta a difusão e, conseqüentemente, aumenta a taxa de reação observada. Nesta dissertação, destaca-se o estudo da hidrodinâmica e da influência dos parâmetros de reação na intensificação da produção contínua de biodiesel em três microreatores com configurações diferentes, através de técnicas experimentais e computacionais. Experimentos foram realizados para caracterizar o óleo de mamona como potencial matéria prima para a produção de biodiesel. Testes reológicos, calorimetria diferencial de varredura (DSC), termogravimetria (TG/DTG) e cromatografia gasosa foram utilizados para determinar as propriedades físicas e químicas do óleo vegetal. Cromatografia de exclusão de tamanho (HPLC/SEC) foi utilizada para avaliar as diferentes variáveis que afetam a reação de transesterificação de óleo de mamona com etanol anidro tendo o hidróxido de sódio como catalisador em um reator em batelada. O efeito da temperatura, razão molar álcool/óleo, concentração de catalisador e tempo de reação foram analisados, observando a variação da composição do meio de reação. Um modelo matemático foi aplicado para descrever a cinética química de transesterificação. Tecnologias de microfabricação convencionais, tais como fotolitografia e litografia macia foram aplicadas na fabricação de microreatores utilizando fotorresiste SU-8 e polidimetilsiloxano (PDMS). Várias dificuldades no processamento do fotorresiste SU-8 para obter estruturas complexas através do processo de fotolitografia foram discutidas. No processo de litografia macia o molde foi fabricado com base em técnicas de fotolitografia, onde o fotorresiste SU-8 foi usado para construir a estrutura dos moldes dos microreatores. Experimentos foram realizados para a análise da influência da geometria do microreator. Três diferentes estruturas foram construídas: T, Omega e Tesla. A mistura dentro dos microreatores para baixos números de Reynolds foi avaliada mediante procedimentos experimentais e simulações de dinâmica de fluidos (CFD). A caracterização qualitativa da mistura foi realizada através da observação da evolução da mistura do óleo de mamona/etanol para diferentes razões de fluxo com base na taxa de transferência de um corante solvatocrômico entre os dois líquidos imiscíveis. Além disso, mediante simulações CFD foi possível caracterizar as circulações internas e capturar o mecanismo de geração de mistura, melhorando a compreensão dos resultados obtidos experimentalmente. Finalmente, a produção contínua de biodiesel foi estudada nos microreatores, a fim de avaliar a influência de parâmetros tais como: geometria, massa de catalisador, temperatura de reação, razão molar etanol/óleo e tempo de residência no rendimento da reação. Os resultados obtidos mostraram que o microreator Tesla exibiu maior mistura e alta conversão para baixos números de Reynolds em comparação com os microreatores T e Omega. Uma conversão de etil ésteres de aproximadamente 98,9% foi obtida no microreator Tesla, enquanto, para os microreatores T e Omega a conversão foi ao redor de 79,1% e 96,2%, respectivamente. Além disso, uma fibra óptica conectada ao espectrômetro portátil no infravermelho próximo foi utilizada para avaliar a possibilidade do monitoramento on-line da reação de transesterificação. / Abstract: Microreactor technology is an important method of process intensification which offers potential benefits to the chemical process industries due to the well-defined high specific interfacial area available for heat and mass transfer, which increases transfer rates, improves efficiency and reactor performance, and enhances safety resulting from low holdups when compared to the conventional reactors. The immiscible liquid-liquid two-phase flow has shown a better intensifying of mass transfer through application of internal structures that serve as passive mixers in microreactors, which enhances diffusive penetration and consequently increases the reaction rates observed. The present work highlights the hydrodynamics and the influence of process parameters in the intensification of the continuous biodiesel production using an alkaline catalyst in three different microreactors through complementary experimental and computational techniques. Initially, experiments were carried out to characterize the castor oil as potential feedstock for biodiesel production. Rheological test, differential scanning calorimetry (DSC), thermogravimetric analysis (TG/DTG) and gas chromatography were performed. Size-exclusion chromatography (SEC) was used to evaluate the different variables that affect the transesterification reaction of castor oil with anhydrous ethanol and sodium hydroxide as catalyst in a jacketed glass batch reactor. The effects of temperature, ethanol/castor oil molar ratio, catalyst concentration, and reaction time were analyzed by observing the variation of the reaction medium composition. A mathematical model was applied to describe chemical kinetic of transesterification based on the reversible mechanism of the reactions. Traditional micromanufacturing technology such as photolithography and soft lithography using SU-8 photoresist and polydimethylsiloxane (PDMS) respectively were employed for fabrication of microreactors. Several difficulties of SU-8 processing to obtain complex structures through the photolithography process have been discussed. In the soft lithography process the mold was fabricated based on photolithography techniques, and SU-8 photoresist was used to construct microreactor structure templates. Experiments were carried out to allow an examination of the influence of reactor path geometry. Three different templates were applied for evaluation: T-, Omega, and Tesla-shaped microreactors. The mixing inside of microreactors at low Reynolds number was evaluated with experimental procedures and computational fluid dynamics simulations (CFD). A qualitative characterization of the mixing was firstly carried out by observing the mixture evolution of castor oil/ethanol at different rate flow ratios on basis of the transfer of a solvatochromatic dye between the two immiscible fluids. In addition, CFD methodologies were developed to characterize internal circulations and to capture the generation mixing mechanism without chemical reaction, improved the understanding of immiscible ethanol/castor oil system. Finally, continuous biodiesel production was studied in the microreactors in order to evaluate the influence of the geometrical parameters, catalyst amount, reaction temperature, molar ratio ethanol to oil, and residence time on performance of the reaction. The Tesla-Shaped microreactor exhibited higher conversions at low Reynolds number when compared with T- and Omega-shaped microreactors. Ethyl ester conversion was about 98.9% in Tesla-shaped microreactor, whereas for T- and Omega-shaped microreactor it was only about 79.1% and 96.2% respectively. On the other hand, fiber-optic near infrared spectroscopy was used to evaluate the possibility of monitoring quantitatively the transesterification reaction on-line. / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química