Desenvolvimento de material BaCexPr1-xO3 (0 ≤ X ≤ 1) com estrutura perovskita para oxidação catalítica do CO a CO2 em reator de leito fixo

Barium Cerate (BaCeO3) is perovskite type structure of ABO3, wherein A and B are metal cations. These materials, or doped, have been studied by having characteristics that make them promising for the application in fuel cells solid oxide, hydrogen and oxygen permeation, as catalysts, etc .. However, as the ceramic materials mixed conductivity have been produced by different synthesis methods, some conditions directly influence the final properties, one of the most important doping Site B, which may have direct influence on the crystallite size, which in turn directly influences their catalytic activity. In this study, perovskite-type (BaCexO3) had cerium gradually replaced by praseodymium to obtain ternary type materials BaCexPr1-xO3 and BaPrO3 binaries. These materials were synthesized by EDTA/Citrate complexing method and the material characterized via XRD, SEM and BET for the identification of their structure, morphology and surface area. Moreover were performed on all materials, catalytic test in a fixed bed reactor for the identification of that person responsible for complete conversion of CO to CO2 at low operating temperature, which step can be used as the subsequent production of synthesis gas (CO + H2) from methane oxidation. In the present work the crystalline phase having the orthorhombic structure was obtained for all compositions, with a morphology consisting of agglomerated particles being more pronounced with increasing praseodymium in the crystal structure. The average crystal size was between 100 nm and 142,2 nm. The surface areas were 2,62 m²g-1 for the BaCeO3 composition, 3,03 m²g-1 to BaCe0,5Pr0,5O3 composition and 2,37 m²g-1 to BaPrO3 composition. Regarding the catalytic tests, we can conclude that the optimal flow reactor operation was 50 ml / min and the composition regarding the maximum rate of conversion to the lowest temperature was BaCeO3 to 400° C. Meanwhile, there was found that the partially replaced by praseodymium, cerium, there was a decrease in the catalytic activity of the material.

Efeitos dos exercícios aeróbio contínuo e intervalado na variabilidade da frequência cardíaca em adultos jovens saudáveis. Ensaio clínico aleatório

The high-intensity interval exercise has been described as an option for increasing physical activity and its use also being suggested in the therapeutic management of many conditions such as diabetes mellitus and heart failure. However, the knowledge of its physiological effects and parameters that can assure greater safety for interval exercise prescription; especially its effect on short- and medium-term (24 hours after exercise) exercise recovery, need to be clarified. This study objective was to evaluate the effect of continuous and interval aerobic exercise on the cardiac autonomic control immediate and medium term (24 hours), by assessing heart rate variability (HRV). The present study is a randomized crossover clinical trial in which healthy young individuals with low level of physical activity had the VFC 24 hours measured by a heart rate sensor and portable accelerometer (3D eMotion HRV, Kuopio, Finland) before and after continuous aerobic exercise (60-70% HR max, 21 min.) and interval exercise (cycle 1 min. 80-90% HR max, 2 min. at 50-60% HR max, duration 21 min.). HRV was measured in the time and frequency domain and the sympathovagal balance determined by the ratio LF / HF. Nonlinear evaluation was calculated by Shannon entropy. The data demonstrated delayed heart rate recovery immediate after exercise and lower HR after 24 hours compared to pre intervention values, especially in the interval exercise group. There was a tendency to higher predominance and representatives index values of sympathetic stimulation during the day in interval exercise group; however, without statistical significance. The study results help to clarify the effects of interval exercise on the 24 hours following interval exercise, setting parameters for prescription and for further evaluation of groups with metabolic and cardiovascular diseases.

Efeitos da terapia laser de baixa intensidade associada ao exercício aeróbio no reparo de tenotomia do tendão de aquiles de ratos diabéticos

Diabetes Mellitus (DM ) is a complex disease that requires continuous medical care for the reduction of risk factors in addition to glycemic control. The typical hyperglycemia of this disease produces glycosylation of proteins and so the consequence is the accumulation of glycosylation final products in various human tissues, among them, the tendon. The aerobic exercise (AE) and the low level laser therapy (LLLT) have been used to treat tendinopathies in individuals with or without DM. Objective: The aim of this study was to watch the effect of the LLLT and the AE, in association, in partial tenotomy of the tissue repair of the Achilles tendon (AT) of diabetic rats. Methods: 91 animals were utilized and divided in to the following groups: control group (GC), injured control group (GCL), diabetic group (GD), diabetic group LLLT (GD – TLBI), diabetic group trained (GD - EX) and diabetic group trained laser (GD-EX+TLBI). The animals were submitted to intervention with AE, using a protocol with a progressive increase of time (12 to 60 min) and speed of (4 to 9 m/min), and the LLLT (660 nm laser, 10mW, 4 J/cm², single point for 16 seconds, three times for week). It was analyzed morphological, biomechanical and molecular characteristics. For data showing normal distribution was used one-way ANOVA test and post hoc Tukey and data without normal distribution was used Mann Whitney test and post hoc Dunn's. It was accepted p <0.05 for statistical significance Results: The biomechanical tests indicated major improvement in the GC and GD-EX+TLBI groups when compared with the diabetic groups in the following variables: maximum load, strain, absorbed energy, stress, cross section area, elastic modulus and energy density (p<0.05). The analysis through molecular biology indicated that the association of aerobic exercise and LLLT generated an increase of the collagen I gene expression and modulated the expression of the MMP2 and MMP9 (p<0.05). No observed any major improvement in the morphological variable studied. Conclusion: the LLLT associated with aerobic exercise promotes and increase of the mechanical properties, in the control of collagen I gene expression and of the MMP2 and MMP9 of the diabetic rats.

Análise da disponibilidade da instrumentação nuclear de um reator de pesquisa

The maintenance of systems and equipment is a central question related to Production Engineering. Although systems are not fully reliable, it is often necessary to minimize the failure occurrence likelihood. The failures occurrences can have disastrous consequences during a plane flight or operation of a nuclear power plant. The elaboration of a maintenance plan has as objective the prevention and recovery from system failures, increasing reliability and reducing the cost of unplanned shutdowns. It is also important to consider the issues related to organizations safety, especially those dealing with dangerous technologies. The objective of this thesis is to propose a method for maintenance analysis of a nuclear research reactor, using a socio-technical approach, and focused on existing conditions in Brazil. The research reactor studied belongs to the federal government and it is located in the city of Rio de Janeiro. The specific objective of this thesis is to develop the availability analysis of one of the principal systems of the research reactor, the nuclear instrumentation system. In this analysis, were taken into account not only the technical aspects of the modules related to nuclear instrumentation system, but also the human and organizational factors that could affect the availability of the nuclear instrumentation system. The results showed the influence of these factors on the availability of the nuclear instrumentation system.

Reator de leito estruturado com recirculação submetido à aeração intermitente no tratamento de esgoto sanitário

The release of nitrogen compounds in water bodies can result in many environmental problems, so treat wastewater, such as sewage in order to remove not only organic matter but also nitrogen has been studied a few decades. From the above, the objective of this study was to evaluate the performance of a structured bed reactor, continuous flow, with recirculation, in removing organic matter and nitrogen present in wastewater under different cycles of intermittent aeration (AI) and to evaluate the influence of these cycles in the development of nitrifying bacteria (Oxidizing Bacteria Ammonia - BOA and Bacteria Oxidizing Nitrite - BON) and denitrifying (DESN) adhered (Support Material - MS) and suspension (Effluent - EF and sludge - LD). The reactor used has usable volume of 9.4 L. As support materials (MS) polyurethane foam was used, cut and fixed in PVC rods. 3 were worked aeration phases (AE) and non-aeration (AN) at different stage: Stage 1 (4 h EA / AN 2H); Stage 2 (2H EA / AN 1 h) and Phase 3 (2H EA / AN 2 h). During all hydraulic detention time phases was kept at 16 h and the effluent recirculated at a rate of 3 times the inflow. Were analyzed: pH, total alkalinity, temperature, chemical oxygen demand (COD), Biochemical Oxygen Demand (BOD), nitrogen Kjeldhl Total (NKT), ammonia-N-N-NH4+, nitrito-N-NO2+andnitrato-NO3-. The concentration of BOA, BON and DESN was determined using the number More Provável.gSSV-1 (NMP.gSSV-1). In phase 1 the percentage removal NTK N-NH4+ and NT was 76±10%, 70±21% and 67±10% respectively. In Phase 2 80±15% of removel NKT, 86±15% of N-NH4+ e 68±9% of removel NT e na Fase 3 de 58±20%, 72±28% and 41±6% of NKT, N-NH4+ of NT, respectively. The denitrification efficiency in stage 3 was over 70%, indicating that occurred in the reactor the process of simultaneous nitrification and denitrification (NDS). DQOT the removal percentages were 88 ± 4% in Phase 1, 94 ± 7 in Phase 2 and 90± 11% in Phase 3. The multivariate ANOVA applied to NMP.gSSV-1, it indicated that there was significant (F: 20,2, p <0,01) between the analyzed concentration of organisms AI in different cycles, but the differences between NMP.gSSV-1 depends not only isolated factors but of which means, and phase groups being analysis. From the results it is concluded that the working system is efficient in terms of nitrogen removal and organic matter, and that the stage with the highest availability of Dissolved Oxygen (DO) and C/N ratio (Step 2), was the one obtained the lower concentrations of organic matter effluents and N-NH4+. Hinted that there was a significant difference between the concentration (NMP.100mL-1) of the analyzed organizations (BOA, BON and DESN), but this difference does not depend on factors alone but of which means (MS, EF or LD), stages (1, 2 or 3) and groups (BOA, BON and DESN) is being considered.

Gasificação de biomassa num reator de leito fluidizado à escala piloto

A gasificação de biomassa permite a produção de um gás combustível com capacidade para reduzir o consumo de combustíveis fósseis. Contudo, para promover a utilização deste processo a nível industrial é necessário ultrapassar diversas limitações e elaborar tecnologias de gasificação que sejam mais rentáveis e eficientes. No presente trabalho efetuou-se a gasificação direta com ar, num reator auto-térmico com um leito fluidizado borbulhante, de diferentes tipos de biomassa provenientes da floresta portuguesa, nomeadamente pellets de madeira e diferentes tipos de biomassa florestal residual derivada de eucalipto. A investigação foi realizada numa instalação à escala piloto localizada no Departamento de Ambiente e Ordenamento da Universidade de Aveiro. A infraestrutura foi desenvolvida de modo a permitir o estudo do processo de gasificação de biomassa. O reator utilizado apresenta 3 metros de altura, consistindo a câmara de gasificação em 2.25 metros, 0.25 metros de diâmetro interno e uma potência entre 40 e 70 kWth. O leito é composto por areia (partículas com granulometria entre os 355 e 1000 µm) e tem uma altura de 0.23 m. A infraestrutura experimental oferece condições para efetuar a gasificação de biomassa, determinar a composição do gás produzido em termos de CO, CO2, H2, N2, CH4 e C2H4 e efetuar a sua combustão num queimador localizado a jusante do reator. O leito fluidizado operou com temperaturas médias entre os 700 e 850ºC. Para as razões de equivalência estabelecidas, entre 0.17 e 0.36, o gás seco apresentou uma composição que, em termos volumétricos e em função das condições operatórias, variou entre 14.0 a 21.4% CO, 14.2 a 17.5% CO2, 3.6 a 5.8% CH4, 1.3 a 2.4% C2H4, 2.0 a 10.2% H2 e 48.9 a 61.1% N2. A maior concentração de CO, CH4 e C2H4 foi observada durante a gasificação de biomassa residual florestal derivada de eucalipto com razão de equivalência de 0.17, contudo, a maior concentração de H2 foi obtida na gasificação de pellets de madeira com razão de equivalência de 0.25. Tendo em conta a composição gasosa, o poder calorífico inferior do gás seco encontrou-se entre 4.4 e 6.9 MJ/Nm3 e os valores mais elevados foram observados durante os processos de gasificação efetuados com menor razão de equivalência. A produção específica de gás variou entre 1.2 e 2.2 Nm3/kg biomassa bs, a eficiência do gás arrefecido entre 41.1 e 62.6% e a eficiência de conversão de carbono entre 60.0 e 87.5%, encontrando-se na gama dos valores reportados na literatura. A melhor condição, em termos da eficiência de gás arrefecido, consistiu na gasificação de biomassa residual florestal derivada de eucalipto com razão de equivalência de 0.25, e em termos da produção específica de gás seco e eficiência de conversão de carbono, na gasificação de biomassa residual florestal derivada de eucalipto com razão de equivalência de 0.35. Contudo, o gás com maior poder calorífico inferior foi obtido durante a gasificação de biomassa residual florestal derivada de eucalipto com razão de equivalência de 0.17. O reator demonstrou adequabilidade na gasificação de diferentes tipos de biomassa e foram observadas condições estáveis de operação, tanto em termos de temperatura como da composição do gás produzido. Geralmente, o gás apresentou propriedades combustíveis apropriadas para ser comburido de forma contínua e estável pelo queimador de gás, sem ser necessária uma fonte de ignição permanente ou a utilização de um combustível auxiliar.

Estudo da gasificação do glicerol em reator de leito fixo

As metas da União Europeia para 2020 em termos de biocombustíveis e biolíquidos traduziram-se, na última década, num destaque da indústria de biodiesel em Portugal. Inerente ao processo de produção biodiesel está um subproduto, o glicerol bruto, cujo estudo tem vindo a ser alvo de interesse na comunidade científica. O objetivo principal deste trabalho consistiu no estudo da gasificação do glicerol técnico e do glicerol bruto, usando vapor como agente oxidante. Pretendeu-se avaliar a composição do gás de produção obtido e os parâmetros de gasificação, como a percentagem de conversão de carbono e de hidrogénio, o rendimento de gás seco, a eficiência de gás frio e o poder calorífico do gás produzido. No estudo da gasificação do glicerol técnico avaliou-se o efeito da temperatura na performance do processo, entre 750 – 1000 ºC, e estudou-se ainda o efeito do caudal de alimentação ao reator (3,8 mL/min, 6,5 mL/min e 10,0 mL/min). Para o caudal mais baixo, estudou-se o efeito da razão de mistura glicerol/água (25/75, 40/60, 60/40 e 75/25) e para a razão de mistura 60/40 foi avaliada a influência da adição de ar como agente gasificante. O estudo da gasificação do glicerol bruto foi feito realizando ensaios de gasificação numa gama de temperaturas de 750 ºC a 1000 ºC, para uma razão de mistura glicerol/água (60/40) com o caudal de 3,8 mL/min e usando apenas vapor de água como agente de gasificação. Os ensaios foram realizados num reator de leito fixo de 500 mm de comprimento e 90 mm de diâmetro interno, composto por um leito de alumina com partículas de 5 mm de diâmetro. O aquecimento foi realizado com um forno elétrico de 4 kW. A amostra de gás de produção recolhida foi analisada por cromatografia gasosa com detector de termocondutividade. Os resultados obtidos na gasificação do glicerol técnico, revelaram que a temperatura é uma variável preponderante no desempenho do processo de gasificação. À exceção do poder calorífico superior, para o qual se obteve uma ligeira diminuição de valores com o aumento da temperatura, os valores mais elevados dos parâmetros de gasificação foram obtidos para temperaturas superiores a 900 ºC. Esta temperatura parece ser determinante no modelo cinético de gasificação do glicerol, condicionando a composição do gás de produção obtido. Concluiu-se ainda que, na gama de caudais testada, o caudal de alimentação ao reator não teve influência no processo de gasificação. Os ensaios realizados para avaliar o efeito da razão de mistura permitiram verificar que, o aumento da adição de água à alimentação se traduz na redução do teor de CO e de CH4 e no aumento do teor de H2 e CO2, no gás de produção. Para a razão de mistura 25/75 foram obtidos valores de 1,3 para o rácio H2/CO para temperaturas superiores a 900 ºC. A influência da adição de água tornou-se mais evidente nos ensaios de gasificação realizados a temperaturas superiores a 900 ºC. Verificou-se um aumento da conversão de carbono, do rendimento de gás seco e da eficiência do gás frio e uma ligeira diminuição do poder calorífico e da potência disponível, no gás de produção. Para as razões de misturas 60/40 e 40/60 obtiveram-se resultados, para os parâmetros de gasificação, da mesma ordem de grandeza e com valores intermédios entre os obtidos para as razões de mistura 25/75 e 75/25. Porém, quanto maior o teor de água alimentado maior o consumo de energia associado à vaporização da água. Assim, o aumento do teor de água na mistura só apresentará interesse industrial se o objetivo passar pela produção de hidrogénio. Quanto ao efeito da adição de ar como agente de gasificação, os resultados obtidos dão indicação que se poderão potenciar algumas reações exotérmicas que contribuirão para a redução do consumo energético global do processo. Por outro lado, o gás de produção apresentou um rácio H2/CO interessante do ponto de vista da sua aplicação industrial, superior em 35 % ao verificado para a gasificação efetuada apenas na presença de vapor. À exceção do decréscimo no valor do poder calorífico superior do gás de produção, os restantes parâmetros estudados apresentaram a mesma ordem de grandeza, dos obtidos para o estudo da mesma razão de mistura na ausência de ar. Relativamente ao estudo da gasificação do glicerol bruto, obtiveram-se valores de rácio H2/CO e eficiência de gás frio mais elevados que os valores obtidos para a mesma razão de mistura usando glicerol técnico. Os demais parâmetros de gasificação avaliados mostraram-se semelhantes entre as duas matérias-primas, verificando-se apenas uma ligeira diminuição no valor do poder calorífico superior do gás produzido com glicerol bruto. Os resultados obtidos demonstram a possibilidade de valorização energética do glicerol bruto resultante da produção de biodiesel.

Desenvolvimento de uma Metodologia para a Seletividade cinética aplicada ao processo de hidroconversão do petróleo, ocorrendo em reator gás-líquido

Este trabalho tem como objetivo desenvolver uma metodologia de seletividade cinética, para os pseudocomponentes do petróleo em escoamento gás-liquido em colunas de bolhas usando a Fluidodinâmica Computacional (CFD). Uma geometria cilíndrica de 2,5m de altura e 0,162m de diâmetro foi usada tanto na validação fluidodinâmica com base em dados experimentais da literatura, como na análise cinética do reator operando em dois modos distintos em relação a fase líquida: batelada e contínuo. Todos os casos de estudo operam em regime heterogêneo de escoamento, com velocidade superficial do gás igual a 8 cm/s e diâmetro médio de bolhas de 6 mm. O modelo fluidodinâmico validado apresentou boa concordância com os dados experimentais, sendo empregado como base para a implementação do modelo cinético de rede de Krishna e Saxena (1989). A análise da hidroconversão foi realizada a 371ºC, e os resultados mostraram o comportamento esperado para o processo reativo estudado, definindo-se os tempos (batelada) e posições axiais (contínuo) de coleta ideal para os pseudocomponentes leves. Em síntese, ressaltase o uso da ferramenta CFD no entendimento, desenvolvimento e otimização de processos.

Aplicação de modelo matemático em sistema de lamas ativadas na estação de tratamento de águas residuais de Albufeira Poente

Dissertação de Mestrado, Engenharia do Ambiente, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2015

Pirólise termoquímica de pós da fibra de coco seco em um reator de cilindro rotativo para produção de bio-óleo

This master thesis aims at developing a new methodology for thermochemical degradation of dry coconut fiber (dp = 0.25mm) using laboratory rotating cylinder reactor with the goal of producing bio-oil. The biomass was characterized by infrared spectroscopy with Fourier transform FTIR, thermogravimetric analysis TG, with evaluation of activation energy the in non-isothermal regime with heating rates of 5 and 10 °C/min, differential themogravimetric analysis DTG, sweeping electron microscopy SEM, higher heating value - HHV, immediate analysis such as evaluated all the amounts of its main constituents, i.e., lignin, cellulose and hemicelluloses. In the process, it was evaluated: reaction temperature (450, 500 and 550oC), carrier gas flow rate (50 and 100 cm³/min) and spin speed (20 and 25 Hz) to condensate the bio-oil. The feed rate of biomass (540 g/h), the rotation of the rotating cylinder (33.7 rpm) and reaction time (30 33 min) were constant. The phases obtained from the process of pyrolysis of dry coconut fiber were bio-oil, char and the gas phase non-condensed. A macroscopic mass balance was applied based on the weight of each phase to evaluate their yield. The highest yield of 20% was obtained from the following conditions: temperature of 500oC, inert gas flow of 100 cm³/min and spin speed of 20 Hz. In that condition, the yield in char was 24.3%, non-condensable gas phase was 37.6% and losses of approximately 22.6%. The following physicochemical properties: density, viscosity, pH, higher heating value, char content, FTIR and CHN analysis were evaluated. The sample obtained in the best operational condition was subjected to a qualitative chromatographic analysis aiming to know the constituents of the produced bio-oil, which were: phenol followed by sirigol, acetovanilona and vinyl guaiacol. The solid phase (char) was characterized through an immediate analysis (evaluation of moisture, volatiles, ashes and fixed carbon), higher heating value and FTIR. The non-condensing gas phase presented as main constituents CO2, CO and H2. The results were compared to the ones mentioned by the literature.

Desenvolvimento de uma unidade pirolítica com reator de cilindro rotativo: obtenção de bio-óleo

The demand for alternative sources of energy drives the technological development so that many fuels and energy conversion processes before judged as inadequate or even non-viable, are now competing fuels and so-called traditional processes. Thus, biomass plays an important role and is considered one of the sources of renewable energy most important of our planet. Biomass accounts for 29.2% of all renewable energy sources. The share of biomass energy from Brazil in the OIE is 13.6%, well above the world average of participation. Various types of pyrolysis processes have been studied in recent years, highlighting the process of fast pyrolysis of biomass to obtain bio-oil. The continuous fast pyrolysis, the most investigated and improved are the fluidized bed and ablative, but is being studied and developed other types in order to obtain Bio-oil a better quality, higher productivity, lower energy consumption, increased stability and process reliability and lower production cost. The stability of the product bio-oil is fundamental to designing consumer devices such as burners, engines and turbines. This study was motivated to produce Bio-oil, through the conversion of plant biomass or the use of its industrial and agricultural waste, presenting an alternative proposal for thermochemical pyrolysis process, taking advantage of particle dynamics in the rotating bed that favors the right gas-solid contact and heat transfer and mass. The pyrolyser designed to operate in a continuous process, a feeder containing two stages, a divisive system of biomass integrated with a tab of coal fines and a system of condensing steam pyrolytic. The prototype has been tested with sawdust, using a complete experimental design on two levels to investigate the sensitivity of factors: the process temperature, gas flow drag and spin speed compared to the mass yield of bio-oil. The best result was obtained in the condition of 570 oC, 25 Hz and 200 cm3/min, temperature being the parameter of greatest significance. The mass balance of the elementary stages presented in the order of 20% and 37% liquid pyrolytic carbon. We determined the properties of liquid and solid products of pyrolysis as density, viscosity, pH, PCI, and the composition characterized by chemical analysis, revealing the composition and properties of a Bio-oil.

Avaliação da biodegradabilidade anaeróbia de resíduos da bovinocultura e da suinocultura

The biodegradability of animal wastes production was evaluated through a simplified methodology that allowed the verification of the applicability of anaerobic processes. The experiments were performed in bath reactors, with granular sludge of three origins: UASB reactor treating dairy effluent, UASB reactor treating swine effluent and UASB reactor treating effluent of slaughterhouse of poultry. The experiments (1) - dairy effluent and poultry slaughterhouse non-adapted sludge; (2) -swine effluent and poultry slaughterhouse non-adapted sludge; (3) - dairy effluent and poultry slaughterhouse adapted sludge; (4) - swine effluent and poultry slaughterhouse adapted sludge; (5) - dairy effluent and dairy sludge, and (6) - swine effluent and swine sludge were performed in Incubator Shaker, at a temperature of 35 °C, under agitation at a 150 rpm, for 5 minutes, every 1 hour. A substrat:biomass relationship of 0.5 was used. Kinetic models of Monod, Zero Order, First and Second Order were tested and it was verified that the First Order model provided the best adjustment. The apparent First Order kinetic parameter (k1) was estimated for the experiments 1; 2; 3; 4; 5, and 6, as 2.51 x 10-2; 2.49 x 10-2; 1.90 x 10-2; 3.09 x 10-2; 2.54 x 10-2; 4.09 x 10-2 h-1, respectively.