Kinetic modeling of mechanisms of industrially important organic reactions in gas and liquid phase

This dissertation is based on 5 articles which deal with reaction mechanisms of the following selected industrially important organic reactions: 1. dehydrocyclization of n-butylbenzene to produce naphthalene 2. dehydrocyclization of 1-(p-tolyl)-2-methylbutane (MB) to produce 2,6-dimethylnaphthalene 3. esterification of neopentyl glycol (NPG) with different carboxylic acids to produce monoesters 4. skeletal isomerization of 1-pentene to produce 2-methyl-1-butene and 2-methyl-2-butene The results of initial- and integral-rate experiments of n-butylbenzene dehydrocyclization over selfmade chromia/alumina catalyst were applied when investigating reaction 2. Reaction 2 was performed using commercial chromia/alumina of different acidity, platina on silica and vanadium/calcium/alumina as catalysts. On all catalysts used for the dehydrocyclization, major reactions were fragmentation of MB and 1-(p-tolyl)-2-methylbutenes (MBes), dehydrogenation of MB, double bond transfer, hydrogenation and 1,6-cyclization of MBes. Minor reactions were 1,5-cyclization of MBes and methyl group fragmentation of 1,6- cyclization products. Esterification reactions of NPG were performed using three different carboxylic acids: propionic, isobutyric and 2-ethylhexanoic acid. Commercial heterogeneous gellular (Dowex 50WX2), macroreticular (Amberlyst 15) type resins and homogeneous para-toluene sulfonic acid were used as catalysts. At first NPG reacted with carboxylic acids to form corresponding monoester and water. Then monoester esterified with carboxylic acid to form corresponding diester. In disproportionation reaction two monoester molecules formed NPG and corresponding diester. All these three reactions can attain equilibrium. Concerning esterification, water was removed from the reactor in order to prevent backward reaction. Skeletal isomerization experiments of 1-pentene were performed over HZSM-22 catalyst. Isomerization reactions of three different kind were detected: double bond, cis-trans and skeletal isomerization. Minor side reaction were dimerization and fragmentation. Monomolecular and bimolecular reaction mechanisms for skeletal isomerization explained experimental results almost equally well. Pseudohomogeneous kinetic parameters of reactions 1 and 2 were estimated by usual least squares fitting. Concerning reactions 3 and 4 kinetic parameters were estimated by the leastsquares method, but also the possible cross-correlation and identifiability of parameters were determined using Markov chain Monte Carlo (MCMC) method. Finally using MCMC method, the estimation of model parameters and predictions were performed according to the Bayesian paradigm. According to the fitting results suggested reaction mechanisms explained experimental results rather well. When the possible cross-correlation and identifiability of parameters (Reactions 3 and 4) were determined using MCMC method, the parameters identified well, and no pathological cross-correlation could be seen between any parameter pair.

Determinação de amônia no ar utilizando um sensor piezelétrico de quartzo

Neste estudo, procurou-se desenvolver e avaliar filmes para a captação e quantificação de vapores de amônia no ar, através de um sensor piezelétrico de quartzo. Muitas substâncias e suas misturas, em diferentes proporções, foram investigadas como possíveis filmes captores. Em etapas seguintes, verificaram-se alguns parâmetros importantes como o efeito da vazão do poluente, da temperatura de trabalho e da massa da película, otimizando-se as condições experimentais para a montagem do método. Concluiu-se que o filme mais promissor, sob as condições ajustadas, seria uma mistura 2:1 (v/v) de solução comercial (A) de ácido glicólico (70 % m/m) em água, adicionada a tetrakis(hidroxietil)etilenodiamina - THEED (3:4 v/v), com uma solução saturada (B) de ácido tânico em acetona. Estudos de repetibilidade, do tempo de contacto (poluente-sensor) e de alguns possíveis interferentes completaram os trabalhos. As curvas analíticas resultantes mostraram faixas lineares na região de trabalho (2,0 a 11 ppm v ou 1,4 a 7,7 mg/m³ de NH3), para quatro diferentes tempos de exposição (0,5; 1; 2 e 3 min), com coeficientes de correlação (r) variando entre 0,9994 e 0,9980, e respectivas sensibilidades de 13,5 a 42,0 Hz / ppm v.

Insulation System in an Integrated Motor Compressor

A high-speed and high-voltage solid-rotor induction machine provides beneficial features for natural gas compressor technology. The mechanical robustness of the machine enables its use in an integrated motor-compressor. The technology uses a centrifugal compressor, which is mounted on the same shaft with the high-speed electrical machine driving it. No gearbox is needed as the speed is determined by the frequency converter. The cooling is provided by the process gas, which flows through the motor and is capable of transferring the heat away from the motor. The technology has been used in the compressors in the natural gas supply chain in the central Europe. New areas of application include natural gas compressors working at the wellheads of the subsea gas reservoir. A key challenge for the design of such a motor is the resistance of the stator insulation to the raw natural gas from the well. The gas contains water and heavy hydrocarbon compounds and it is far harsher than the sales gas in the natural gas supply network. The objective of this doctoral thesis is to discuss the resistance of the insulation to the raw natural gas and the phenomena degrading the insulation. The presence of partial discharges is analyzed in this doctoral dissertation. The breakdown voltage of the gas is measured as a function of pressure and gap distance. The partial discharge activity is measured on small samples representing the windings of the machine. The electrical field behavior is also modeled by finite element methods. Based on the measurements it has been concluded that the discharges are expected to disappear at gas pressures above 4 – 5 bar. The disappearance of discharges is caused by the breakdown strength of the gas, which increases as the pressure increases. Based on the finite element analysis, the physical length of a discharge seen in the PD measurements at atmospheric pressure was approximated to be 40 – 120 m. The chemical aging of the insulation when exposed to raw natural gas is discussed based on a vast set of experimental tests with the gas mixture representing the real gas mixture at the wellhead. The mixture was created by mixing dry hydrocarbon gas, heavy hydrocarbon compounds, monoethylene glycol, and water. The mixture was chosen to be more aggressive by increasing the amount of liquid substances. Furthermore, the temperature and pressure were increased, which resulted in accelerated test conditions. The time required to detect severe degradation was thus decreased. The test program included a comparison of materials, an analysis of the e ects of di erent compounds in the gas mixture, namely water and heavy hydrocarbons, on the aging, an analysis of the e ects of temperature and exposure duration, and also an analysis on the e ect of sudden pressure changes on the degradation of the insulating materials. It was found in the tests that an insulation consisting of mica, glass, and epoxy resin can tolerate the raw natural gas, but it experiences some degradation. The key material in the composite insulation is the resin, which largely defines the performance of the insulation system. The degradation of the insulation is mostly determined by the amount of gas mixture di used into it. The di usion was seen to follow Fick’s second law, but the coe cients were not accurately defined. The di usion was not sensitive to temperature, but it was dependent upon the thermodynamic state of the gas mixture, in other words, the amounts of liquid components in the gas. The weight increase observed was mostly related to heavy hydrocarbon compounds, which act as plasticizers in the epoxy resin. The di usion of these compounds is determined by the crosslink density of the resin. Water causes slight changes in the chemical structure, but these changes do not significantly contribute to the aging phenomena. Sudden changes in pressure can lead to severe damages in the insulation, because the motion of the di used gas is able to create internal cracks in the insulation. Therefore, the di usion only reduces the mechanical strength of the insulation, but the ultimate breakdown can potentially be caused by a sudden drop in the pressure of the process gas.

The Cellular Oxygen Sensor PHD2 in Cancer Growth

Adequate supply of oxygen is essential for the survival of multicellular organisms. However, in several conditions the supply of oxygen can be disturbed and the tissue oxygenation is compromised. This condition is termed hypoxia. Oxygen homeostasis is maintained by the regulation of both the use and delivery of oxygen through complex, sensitive and cell-type specific transcriptional responses to hypoxia. This is mainly achieved by one master regulator, a transcription factor called hypoxiainducible factor 1 (HIF-1). The amount of HIF-1 is under tight oxygen-dependent control by a family of oxygen-dependent prolyl hydroxylase domain proteins (PHDs) that function as the cellular oxygen sensors. Three family members (PHD1-3) are known to regulate HIF of which the PHD2 isoform is thought to be the main regulator of HIF-1. The supply of oxygen can be disturbed in pathophysiological conditions, such as ischemic disorders and cancer. Cancer cells in the hypoxic parts of the tumors exploit the ability of HIF-1 to turn on the mechanisms for their survival, resistance to treatment, and escape from the oxygen- and nutrient-deprived environment. In this study, the expression and regulation of PHD2 were studied in normal and cancerous tissues, and its significance in tumor growth. The results show that the expression of PHD2 is induced in hypoxic cells. It is overexpressed in head and neck squamous cell carcinomas and colon adenocarcinomas. Although PHD2 normally resides in the cytoplasm, nuclear translocation of PHD2 was also seen in a subset of tumor cells. Together with the overexpression, the nuclear localization correlated with the aggressiveness of the tumors. The nuclear localization of PHD2 caused an increase in the anchorage-independent growth of cancer cells. This study provides information on the role of PHD2, the main regulator of HIF expression, in cancer progression. This knowledge may prove to be valuable in targeting the HIF pathway in cancer treatment.

Implementing gateway monitoring service for infrastructure sensor networks

Wireless sensor networks and its applications have been widely researched and implemented in both commercial and non commercial areas. The usage of wireless sensor network has developed its market from military usage to daily use of human livings. Wireless sensor network applications from monitoring prospect are used in home monitoring, farm fields and habitant monitoring to buildings structural monitoring. As the usage boundaries of wireless sensor networks and its applications are emerging there are definite ongoing research, such as lifetime for wireless sensor network, security of sensor nodes and expanding the applications with modern day scenarios of applications as web services. The main focus in this thesis work is to study and implement monitoring application for infrastructure based sensor network and expand its usability as web service to facilitate mobile clients. The developed application is implemented for wireless sensor nodes information collection and monitoring purpose enabling home or office environment remote monitoring for a user.

Tratamento de ruídos e caracterização de fisionomias do Cerrado utilizando séries temporais do sensor MODIS

O Cerrado é formado por um mosaico de fisionomias campestres, savânicas e florestais que possuem um típico ciclo fenológico. Nesse contexto, os dados do MODIS fornecem medidas diárias que permitem monitorar a sazonal fenologia da vegetação. O objetivo deste trabalho foi caracterizar formações savânicas, formações florestais e áreas de cerrado convertido pela ação antrópica, utilizando séries temporais de NDVI e EVI do sensor MODIS, após a suavização de ruídos. A metodologia adotada pode ser subdividida nos seguintes passos: (a) confecção do cubo temporal com NDVI e EVI, onde o perfil em z corresponde à assinatura temporal, (b) tratamento do ruído e (c) detecção das assinaturas temporais. A Transformação pela Fração Mínima de Ruído (MNF) foi aplicada para suavizar ruídos contidos nas séries temporais. Os resultados indicaram que os valores de NDVI foram maiores que os valores de EVI e existiu relação com as estações do ano. As formações florestais foram as que apresentaram maiores valores de NDVI e EVI, possuindo ainda as menores variações entre as estações. As áreas convertidas apresentaram os menores valores dos dois índices, tendo grande queda em seus valores no início da estação seca, provavelmente por se tratar do período de colheita. O estudo concluiu que as séries temporais NDVI e EVI são úteis na diferenciação dos tipos de vegetação.

Uso do produto MOD13Q1 do sensor Modis para análise temporal e mapeamento das florestas nas Serras do Sudeste e Campanha Meridional do Rio Grande do Sul

Imagens NDVI (Índice de Vegetação por Diferença Normalizada) do sensor Modis foram utilizadas para mapear as classes de uso e cobertura da terra nas Serras do Sudeste e Campanha Meridional do Rio Grande do Sul. A metodologia compreendeu a elaboração de um banco de dados espaciais e a aplicação de técnicas de processamento digital (contraste linear, classificação digital e operações aritméticas) sobre imagens dos satélites Landsat e Terra de diversas datas. Os resultados indicaram que a cobertura florestal passou de 8,6% para 11,6% e 14,3% da área total da microrregião Serras do Sudeste, entre os anos 2000, 2004 e 2008. Na Campanha Meridional, a expansão da cobertura florestal passou de 11,1% para 11,2% e 11,5% da área total no mesmo período. Conclui-se que imagens MOD13Q1, de baixa resolução espacial (250 m), podem ser usadas em grandes áreas para mapear florestas e os demais temas adequadamente.

Electrical Equivalent Circuit for Dry Bacteriorhodopsin Sensor

Bacteriorhodopsin (BR) is a photosensitive protein which functions as a light-driven proton pump. Due to its photoactivity, BR could be used in photosensing and information processing which has inspired researchers to study the photoelectric response and the appropriate measurement instrumentation for BR. In this thesis, the measurement instrumentation connected to a dry BR sensor was confirmed to affect the photovoltage response measured by using voltage amplifiers. Changing of the input impedance of the measurement instrumentation was shown to alter a part of the measured photovoltage response. The photocurrent measurements using transimpedance amplifier and the presented electrical equivalent circuit were used to show that the photocurrent measurements have no significant effect on the photoelectric response. The photocurrent was shown to be a derivate of the photovoltage response measured from the dry BR sensor when it was compared to the response measured with a voltage amplifier. This confirmed that another part of the photovoltage response was not affected by the measurement instrumentation. The time-variant behavior of the dry BR sensor was confirmed in both the photocurrent and the photovoltage measurements. This was caused by the fact that the capacitance of the dry BR sensor changes with the excitation light intensity.

Modelo para estimativa do potencial produtivo em trigo e cevada por meio do sensor GreenSeeker

Áreas com diferentes potenciais de rendimento dentro de uma lavoura necessitam ser manejadas separadamente, para fins de aplicação da adubação nitrogenada em cobertura. O equipamento baseado em sensoriamento remoto terrestre (GreenSeeker) é um dos instrumentos utilizados para separar diferentes zonas de manejo. Para fazer isso, o sensor permite a definição de classes para estimar o potencial produtivo de forma ágil, precisa e em tempo real. Com o instrumento, foi desenvolvido um modelo para estimativa do potencial produtivo em trigo e cevada, correlacionando o Índice de Vegetação por Diferença Normalizada (NDVI) com a biomassa seca acumulada na parte aérea, por ocasião da emissão da sexta folha do colmo principal. A base do modelo foi a formação de classes de potencial produtivo correspondentes a zonas específicas de manejo da lavoura. Essas classes não necessitam ser específicas para diferentes cultivares e/ou espécies, visto que não se detectaram diferenças que justificassem a formação de grupos para elas. As superfícies de fundo (resíduos de restevas de soja e milho) tiveram efeitos significativos nas leituras do sensor. O modelo continua válido mesmo se as leituras de NDVI forem feitas antes ou após o período recomendado para tal, podendo ser ajustado com sub ou superestimação. As análises de variabilidade espacial, futuramente, podem avaliar se, as zonas de potencial produtivo estimadas pelas classes de NDVI propostas pelo modelo, correspondem à flutuação espacial da biomassa, doses de N aplicadas e rendimento de grãos.

Avaliação de sensor capacitivo para o monitoramento do teor de água do solo

Este trabalho teve como objetivo avaliar sensores capacitivos desenvolvidos para monitorar o teor de água do solo. Os sensores foram submetidos a testes para avaliar o efeito da temperatura, o tempo de resposta, obter a equação de calibração e determinar a sua sensibilidade. Foram analisados em diferentes situações (solo, água e ar) e temperaturas (25 ºC; 20 ºC; 15 ºC; 10 ºC; 5º C e 0 ºC). A calibração foi efetuada com um dos sensores capacitivos instalado em uma coluna de solo (indeformada) contida em um tubo de PVC (0,015066 m³) e suspensa em um dos lados de uma balança de braços. Na outra extremidade da balança, havia uma célula de carga conectada a um sistema de aquisição de dados. Os resultados indicaram redução na frequência do sensor capacitivo com o aumento da temperatura. O sensor capacitivo apresentou alta velocidade de resposta (menos de um segundo) ao imergi-lo na água e às variações da quantidade de água na amostra de solo e detectou as mudanças de perda de água pela coluna de solo no decorrer deste experimento, apresentando maior sensibilidade à medida que se diminui o conteúdo de água no solo. Portanto, o sensor capacitivo pode ser utilizado para determinar o teor de água do solo de forma adequada.

Development of capacitive sensor for measuring soil water content

The irrigation management based on the monitoring of the soil water content allows for the minimization of the amount of water applied, making its use more efficient. Taking into account these aspects, in this work, a sensor for measuring the soil water content was developed to allow real time automation of irrigation systems. This way, problems affecting crop yielding such as irregularities in the time to turn on or turn off the pump, and excess or deficit of water can be solved. To develop the sensors were used stainless steel rods, resin, and insulating varnish. The sensors measuring circuit was based on a microcontroller, which gives its output signal in the digital format. The sensors were calibrated using soil of the type “Quartzarenic Neosoil”. A third order polynomial model was fitted to the experimental data between the values of water content corresponding to the field capacity and the wilting point to correlate the soil water content obtained by the oven standard method with those measured by the electronic circuit, with a coefficient of determination of 93.17%, and an accuracy in the measures of ±0.010 kg kg-1. Based on the results, it was concluded that the sensor and its implemented measuring circuit can be used in the automation process of irrigation systems.

Experimental evaluation of the performance of a wireless sensor network in agricultural environments

The aim of this study was to perform an experimental study to evaluate the proper operation distance between the nodes of a wireless sensor network available on the market for different agricultural crops (maize, physic nut, eucalyptus). The experimental data of the network performance offers to farmers and researchers information that might be useful to the sizing and project of the wireless sensor networks in similar situations to those studied. The evaluation showed that the separation of the nodes depends on the type of culture and it is a critical factor to ensure the feasibility of using WSN. In the configuration used, sending packets every 2 seconds, the battery life was about four days. Therefore, the autonomy may be increased with a longer interval of time between sending packets.

Seasonality of net radiation in two sub-basins of Paracatu by the use of modis sensor products

The net radiation (Rn) represents the main source of energy for physical and chemical processes that occur in the surface-atmosphere interface, and it is used for air and soil heating, water transfer, in the form of vapor from the surface to the atmosphere, and for the metabolism of plants, especially photosynthesis. If there is no record of net radiation in certain areas, the use of information is important to help determine it. Among them we can highlight those provided by remote sensing. In this context, this work aims to estimate the net radiation, with the use of products of MODIS sensor, in the sub-basins of Entre Ribeiros creek and Preto River, located between the Brazilian states of Goiás and Minas Gerais. The SEBAL (Surface Energy Balance Algorithm for Land) was used to obtain the Rn in four different days in the period of July to October, 2007. The Rn results obtained were consistent with others cited in the literature and are important because the orbital information can help determine the Rn in areas where there are not automatic weather stations to record the net radiation.

Uso de imagens do sensor orbital modis na estimação de datas do ciclo de desenvolvimento da cultura da soja para o estado do Paraná – Brasil

RESUMO O Estado do Paraná caracteriza-se por uma grande variabilidade de épocas de semeadura (DS) e, consequentemente, pelo desenvolvimento máximo vegetativo (DMDV), colheita (DC) e ciclo (CI) para a cultura da soja. O objetivo deste trabalho foi estimar essas datas para o período de primavera-verão do ano-safra de 2011/2012, por meio de séries temporais de imagens do Índice de Vegetação Realçado (do inglês Enhanced Vegetation Index - EVI) do sensor Modis (Moderate Resolution Imaging Spectroradiometer). Gerou-se um perfil espectrotemporal médio de EVI, considerando todos os pixels mapeados como soja dentro de cada município. Estes dados serviram de entrada no software Timesat para estimar os decêndios do ciclo da cultura (DS, DMDV, DC e CI) por municípios. Os resultados mostraram que existe grande variabilidade de datas de plantio em diferentes mesorregiões do Estado. Verificaram-se também divergências entre os resultados encontrados e os dados oficiais de DS e DC. A maior parte da semeadura (65,16%) esteve entre o terceiro decêndio de outubro e o primeiro decêndio de novembro. A maior parte da área de soja do Estado do Paraná (65,46%) teve seu DMDV em janeiro e colheita em março (53,92%).