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.

Reactive dissolution of sedimentary rocks in flue gas desulfurization : modeling and experimental investigation

Svavel förekommer i kol och olja och oxideras vid förbränning till svaveldioxid (SO2). Årligen utsläpps stora mängder svaveldioxid som åstadkommer sura regn, minskning av stratosfäriskt ozon och sjukdomar. Av dessa orsaker är det nödvändigt att minska utsläppen av svaveldioxid. Den teknologi som rör planering av reaktorer och processer för rökgasavsvavling (FGD) har utvecklats kraftigt och idag använder man olika typer av lösningar. De vanligaste alternativen för FGD är våtskrubber- och semitorra skrubbersystem (Spray Dry Scrubbers, SDS) och injektionsprocesser för absorbenter. SDS-processer har studerats bland annat av Ahlbeck [4] och Klingspor [5] och injektionsprocesser av Alvfors [6]. Kalksten, som i huvusak består av kalciumkarbonat, används i rökgasavsvavling på grund av sin förmåga att binda svavel i form av sulfatsalter. Den vanligaste rökgasavsvavlingsmetoden är våtskrubbning, där det sedimentära stenmaterialets upplösningshastighet är en av de faktorer som påverkar resultatet mest. Utvärdering av kalkstensreaktivitet är därför speciellt viktig vid planering och drift av anläggningar för rökgasavsvavling. Målsättningen med detta arbete var att modellera upplösningen av olika typers kalksten för att få en kvantitativ utvärdering av kvaliteten på de analyserade proverna. Därtill testades även karbonatbiprodukter från stålindustrin för att utvärdera möjligheter att använda andra råmaterial. Det transienta förloppet har analyserats, varvid upplösningshastigheten modellerades bl.a. i avseende på tid och pH. Under arbetets gång har antalet empiriska korrelationer minskats till fördel för fysikaliska modeller av diffusiva och konvektiva masstransportfenomen. En målsättning var att skapa en effektiv och snabb metod för att testa olika absorbenter för rökgasavsvavling under transienta förlopp. I arbetet användes PSD-analys, gjordes pH-mätningar och andra utvärderingar av de fysikaliska parametrar som ingår i beräkningarna. On-line mätningar för de icke-stationära variablerna tid och pH ger möjlighet att eliminera osäkerheter. Vissa modeller kan vara komplicerade. En modell för upplösningshastigheten med mer detaljerad utvärdering av parametrar och färre approximationer är därför nödvändig då man vill utvärdera reaktionshastigheten för fasta partiklar i sur miljö. Arbetet utfördes under fyra år och fem peer review-artiklar ingår i avhandlingen.

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.

Advanced orbital pipe welding

Since the introduction of automatic orbital welding in pipeline application in 1961, significant improvements have been obtained in orbital pipe welding systems. Requirement of more productive welding systems for pipeline application forces manufacturers to innovate new advanced systems and welding processes for orbital welding method. Various methods have been used to make welding process adaptive, such as visual sensing, passive visual sensing, real-time intelligent control, scan welding technique, multi laser vision sensor, thermal scanning, adaptive image processing, neural network model, machine vision, and optical sensing. Numerous studies are reviewed and discussed in this Master’s thesis and based on a wide range of experiments which already have been accomplished by different researches the vision sensor are reported to be the best choice for adaptive orbital pipe welding system. Also, in this study the most welding processes as well as the most pipe variations welded by orbital welding systems mainly for oil and gas pipeline applications are explained. The welding results show that Gas Metal Arc Welding (GMAW) and its variants like Surface Tension Transfer (STT) and modified short circuit are the most preferred processes in the welding of root pass and can be replaced to the Gas Tungsten Arc Welding (GTAW) in many applications. Furthermore, dual-tandem gas metal arc welding technique is currently considered the most efficient method in the welding of fill pass. Orbital GTAW process mostly is applied for applications ranging from single run welding of thin walled stainless tubes to multi run welding of thick walled pipes. Flux cored arc welding process is faster process with higher deposition rate and recently this process is getting more popular in pipe welding applications. Also, combination of gas metal arc welding and Nd:YAG laser has shown acceptable results in girth welding of land pipelines for oil and gas industry. This Master’s thesis can be implemented as a guideline in welding of pipes and tubes to achieve higher quality and efficiency. Also, this research can be used as a base material for future investigations to supplement present finding.

Initial development and gas exchange of Talisia subalbens (Mart.) Radlk. under different shading conditions

Ecophysiological studies under semi-controlled conditions in nurseries and greenhouses are essential to enable the use of native species to recover degraded areas and for commercial planting. Talisia subalbens (Mart) Radlk, 'cascudo', is a native fruiting species of the Cerrado on the verge of extinction. The ecophysiological performance of this species was evaluated in nursery conditions under different levels of shading (full sunshine, 30%, 50% and 70%). Initial growth, biomass allocation, gas exchange and chlorophyll content of the plants were analyzed. Full sunshine cultivated plants showed a higher accumulation of total, shoot, and root dry biomass. There was no significant difference in the root/shoot ratio among the treatments. Seedlings cultivated under full sunshine and 30% shading showed higher values for height, basal diameter, and leaf area. Differences in stomata conductance and photosynthesis rate were not observed among the different shading levels. Plants cultivated under 70% of shading had higher contents of chlorophyll a, b, and total. During the initial phase with higher levels of radiation were fundamental for the development of T. subalbens seedlings.

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.

GAS EXCHANGE IN YOUNG PLANTS OF Tabebuia aurea(Bignoniaceae Juss.) SUBJECTED TO FLOODING STRESS1

ABSTRACT The Paratudo (Tabebuia aurea) is a species occurring in the Pantanal of Miranda, Mato Grosso do Sul, Brazil, an area characterized by seasonal flooding. To evaluate the tolerance of this plant to flooding, plants aged four months were grown in flooded soil and in non-flooded soil (control group). Stomatal conductance, transpiration and CO2 assimilation were measured during the stress (48 days) and recovery (11 days) period, totalling 59 days. The values of stomatal conductance of the control group and stressed plants at the beginning of the flooded were 0.33 mol m-2s-1 and reached 0.02 mol m-2 s-1 (46th day) at the end of this event. For the transpiration parameter, the initial rate was 3.1 mol m s-1, and the final rate reached 0.2 or 0.3 mol m-2 s-1 (47/48 th day). The initial photosynthesis rate was 8.9 mmol m-2s-1 and oscillated after the sixth day, and the rate reached zero on the 48th day. When the photosynthesis rate reached zero, the potted plants were dried, and the rate was analyzed (11th day). The following values were obtained for dried plants: stomatal conductance = 0.26 mol m-2 s-1, transpiration rate = 2.5 mol m-2 s-1 and photosynthesis rate = 7.8 mmol m-2 s-1. Flooded soil reduced photosynthesis and stomatal conductance, leading to the hypertrophy of the lenticels. These parameters recovered and after this period, and plants exhibited tolerance to flooding stress by reducing their physiological activities.

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.