Gas liquid equilibria at high pressures

Este trabalho tem como objectivo a medição da solubilidade de gases em líquidos a altas pressões. Para a realização experimental foi usada uma célula de altas pressões de volume variável e um método de observação directa para a detecção das transições de fase. As condições usadas neste trabalho experimental foram temperaturas entre 276.00 e 373.15 K e pressões ate 100 MPa. Numa primeira fase foram efectuadas medições de solubilidade de metano em anilina pura e para uma solução aquosa de composição mássica igual a 5% em anilina. A anilina é fundamentalmente usada em processos como a produção de borracha, de poliuretanos, pigmentos e tintas, fármacos, herbicidas e fungicidas. É usualmente produzida através de processos de redução do nitrobenzeno por reacção com o HCl. De facto, esta síntese é um processo químico complexo onde um grande número de processos compete entre si. Alterações nas condições do processo com a possível formação de produtos intermediários podem afectar a eficiência do processo. Para a sua melhoria foi sugerido que o hidrogénio usado fosse simultaneamente produzido e gasto no reactor principal. Neste caso e para a produção do mesmo, era necessário adicionar metano e água ao reactor. Tendo por base a ideia de que as reacções onde o hidrogénio é reagente e produto ocorrem em simultâneo, torna-se clara a importância do estudo da solubilidade do metano em anilina pura e em soluções aquosas desta. Numa segunda fase foi estudada a solubilidade do dióxido de carbono em soluções aquosas de tri-iso-butil(metil)fosfónio tosilato, com composições molares são de 4, 8 e 12% em líquido iónico. Este pertencente à família dos fosfónios. Possui uma viscosidade e densidade elevadas, é térmica e quimicamente estável e ainda possui uma elevada polaridade. Apresenta uma miscibilidade completa em água e nos solventes mais usuais, como o diclorometano e tolueno, não sendo no entanto míscivel em hexano. O tri-isobutil( metil)fosfónium tosilato é usado como solvente nos processos de hidroformilação de olefinas e ainda em processos de captura e conversão de dióxido de carbono. Neste trabalho experimental, a temperatura e a pressão foram inicialmente aumentadas até o sistema atingir o equilíbrio. A pressão é diminuída lentamente até se verificar o aparecimento/desaparecimento da última bolha de gás. A pressão à qual a última bolha de gás desaparece representa a pressão de equilíbrio para aquela temperatura. Este procedimento foi efectuado para vários sistemas e várias temperaturas.

Alternativas Processuais e Valorização de Correntes da Refinaria de Matosinhos.

Evolução, ato ou efeito de evoluir, sequência de transformações, desenvolvimento progressivo. Se tudo à nossa volta se transforma, a indústria tem de acompanhar esse sistema evolutivo, tornando assim imprescindível alterar ou melhorar processos de produção quando estes não se enquadram com a realidade, ou porque o mercado se altera, ou porque as necessidades mudam, ou por simplesmente ser mais rentável. Sendo a Galp Energia uma empresa que se encontra sempre na vanguarda da evolução tecnológica, encontra no Departamento de Engenharia Química do Instituto Superior de Engenharia do Porto um aliado na procura do melhor modo de valorizar os seus produtos. A Refinaria de Matosinhos tem atualmente duas correntes de gasolina leve e uma de refinado que apresentam grande potencialidade de valorização. Parte destas correntes incorporam atualmente a pool de nafta química da refinaria que é vendida à Repsol Polímeros. O desafio que é proposto baseia-se em valorizar essas correntes através da sua isomerização aumentando o seu RON podendo então ter como fim a pool de gasolinas. Tirando partido da tecnologia disponível para este efeito são apresentados quatro cenários de possíveis soluções. Sendo os dois primeiros excluídos por violarem restrições impostas, o terceiro e quarto cenários foram analisados de um ponto de vista económico. O terceiro cenário conduz a gasolina leve da Fábrica de Aromáticos para a pool de gasolinas sem qualquer tratamento e a gasolina leve da Fábrica de Combustíveis continua a integrar a pool de nafta química. O refinado da Fábrica de Aromáticos será enviado para um splitter, sendo a corrente de topo destinada à pool de nafta química e a corrente de fundo enviada a um reator de isomerização, Isomalk-4SM, passando previamente por uma torre de argila de forma a assegurar que a restrição em teor de olefinas no reator não é violada. O efluente, com RON maior, integrará igualmente a pool de gasolinas. No quarto cenário a corrente de refinado da Fábrica de Aromáticos não sofre qualquer tratamento, continuando a alimentar a unidade de solventes, a gasolina leve da Fábrica de Aromáticos irá diretamente para a pool de gasolinas e a gasolina leve da Fábrica de Combustíveis passará pelo Isomalk-2SM para aumentar o índice de octanos garantido assim ter condições de integrar a pool de gasolinas. Dissertação de Mestrado em Engenharia Química Isomerização de Gasolina Leve O terceiro cenário apresenta um aumento de 4 576 773 € anuais nas receitas e o quarto alcança 11 333 982 € anuais. O investimento inicial total do terceiro cenário é de 28 821 608 € quando o quarto cenário carece de um investimento inicial de apenas 18 028 349 €. Quanto aos custos associados à implementação da unidade estes demonstram-se elevados, o terceiro cenário apresenta um custo de 23 133 429 € enquanto o do quarto cenário é de 13 998 797 €. O quarto cenário apresenta-se assim como a solução mais rentável para o objetivo desta dissertação.

Advanced Nuclear Energy Systems: Heat Transfer Issues and Trends

Almost 450 nuclear power plants are currently operating throughout the world and supplying about 17% of the world’s electricity. These plants perform safely, reliably, and have no free-release of byproducts to the environment. Given the current rate of growth in electricity demand and the ever growing concerns for the environment, the US consumer will favor energy sources that can satisfy the need for electricity and other energy-intensive products (1) on a sustainable basis with minimal environmental impact, (2) with enhanced reliability and safety and (3) competitive economics. Given that advances are made to fully apply the potential benefits of nuclear energy systems, the next generation of nuclear systems can provide a vital part of a long-term, diversified energy supply. The Department of Energy has begun research on such a new generation of nuclear energy systems that can be made available to the market by 2030 or earlier, and that can offer significant advances toward these challenging goals [1]. These future nuclear power systems will require advances in materials, reactor physics as well as heat transfer to realize their full potential. In this paper, a summary of these advanced nuclear power systems is presented along with a short synopsis of the important heat transfer issues. Given the nature of research and the dynamics of these conceptual designs, key aspects of the physics will be provided, with details left for the presentation.

Degradação do PMMA através da reação despolimerização uitlizando catalisadores de óxidos mistos

In this work, mixed oxides were synthesized by two methods: polymeric precursor and gel-combustion. The oxides, Niquelate of Lanthanum, Cobaltate of Lanthanum and Cuprate of Lanthanum were synthesized by the polymeric precursor method, and treated at 300 º C for 2 hours, calcined at 800 º C for 6h in air atmosphere. In gel-combustion method were produced and oxides using urea and citric acid as fuel, forming for each fuel the following oxides Ferrate of Lanthanum, Cobaltato of Lanthanum and Ferrato of Cobalt and Lanthanum, which were submitted to the combustion process assisted by microwave power maximum of 10min. The samples were characterized by: thermogravimetric analysis, X-ray diffraction; fisisorção of N2 (BET method) and scanning electron microscopy. The reactions catalytic of depolymerization of poly (methyl methacrylate), were performed in a reactor of silica, with catalytic and heating system equipped with a data acquisition system and the gas chromatograph. For the catalysts synthesized using the polymeric precursor method, the cuprate of lanthanum was best for the depolymerization of the recycled polymer, obtaining 100% conversion in less time 554 (min), and the pure polymer, was the Niquelate of Lanthanum, with 100% conversion in less time 314 (min). By gel-combustion method using urea as fuel which was the best result obtained Ferrate of Lanthanum for the pure polymer with 100% conversion in less time 657 (min), and the recycled polymer was Cobaltate of Lanthanum with 100 % conversion in less time 779 (min). And using citric acid to obtain the best result for the pure polymer, was Ferrate of Lanthanum with 100% conversion in less time 821 (min and) for the recycled polymer, was Ferrate of Lanthanum with 98.28% conversion in less time 635 (min)

Síntese e caracterização de catalisadores de LaNiO3 não suportados e suportados em Al2O3 e ZrO2 para a reforma a vapor do metano

Ionic oxides with ABO3 structure, where A represents a rare earth element or an alkaline metal and B is a transition metal from group VIII of the periodic table are potential catalysts for oxidation and good candidates for steam reforming reaction. Different methods have been considered for the synthesis of the oxide materials with perovskite structure to produce a high homogeneous material with low amount of impurities and low calcination temperatures. In the current work, oxides with the LaNiO3 formula had been synthesized using the method of the polymeric precursors. The thermal treatment of the materials took place at 300 ºC for 2h. The material supported in alumina and/or zirconia was calcined at 800 ºC temperature for 4h. The samples had been characterized by the following techniques: thermogravimetry; infrared spectroscopy; X-ray diffraction; specific surface area; distribution of particle size; scanning electron microscopy and thermo-programmed reduction. The steam reforming reaction was carried out in a pilot plant using reducing atmosphere in the reactor with a mixture of 10% H2-Argon, a mass about 5g of catalyst, flowing at 50 mL.min-1. The temperature range used was 50 - 1000 oC with a heating rate of 10 oC.min-1. A thermal conductivity detector was used to analyze the gas after the water trapping, in order to permit to quantify the consumption of hydrogen for the lanthanum nickelates (LaNiO3). The results showed that lanthanum nickelate were more efficient when supported in alumina than when supported in zirconia. It was observed that the methane conversion was approximately 100% and the selectivity to hydrogen was about 70%. In all cases were verified low selectivity to CO and CO2

Produção de biodiesel a partir de óleo de coco (Cocos nucifera L

The production of biodiesel has become an important and attractive process for the production of alternative fuels. This work presents a study of the biodiesel production from coconut oil (Cocos nucifera L.), by two routes: direct transesterification using NaOH as catalyst and esterification (with H2SO4) followed by basic transesterification. The reactor was built in pirex with 1L of capacity and was equipped with a jacket coupled with a thermostatic bath to temperature control, a mecanical stirring is also present in the reactor. The analysis of oil composition was carried out by gas chromatography and esters compounds were identified. The parameters of molar ratio oil/alcohol, reaction time and temperature were studied and their influence on the conversion products was evaluated using experimental planning (23). The molar ratio was the most significant variable by the statistical planning analysis. Conversions up to 85.3% where achived in the esterification/transesterification, with molar ratio 1:6 at 60ºC and 90 minutes of reaction. For the direct transesterification, route conversions up 87.4% eas obtained using 1:6.5 molar ratio at 80ºC and 60 minutes of reaction. The Coconut oil was characterized by their physic chemical properties and key constituents of the oil. The lauric acid was the main constituint and the oil showed high acidity. The biodiesel produced was characterized by its main physicochemical properties, indicating satisfactory results when compared to standard values of National Petroleum Agency. The work was supplemented with a preliminary assessment of the reaction kinetic

Implementação de um modelo computacional para estudo do processo Fischer-Tropsch em reator de leito de lama

This work aims at the implementation and adaptation of a computational model for the study of the Fischer-Tropsch reaction in a slurry bed reactor from synthesis gas (CO+H2) for the selective production of hydrocarbons (CnHm), with emphasis on evaluation of the influence of operating conditions on the distribution of products formed during the reaction.The present model takes into account effects of rigorous phase equilibrium in a reactive flash drum, a detailed kinetic model able of predicting the formation of each chemical species of the reaction system, as well as control loops of the process variables for pressure and level of slurry phase. As a result, a system of Differential Algebraic Equations was solved using the computational code DASSL (Petzold, 1982). The consistent initialization for the problem was based on phase equilibrium formed by the existing components in the reactor. In addition, the index of the system was reduced to 1 by the introduction of control laws that govern the output of the reactor products. The results were compared qualitatively with experimental data collected in the Fischer-Tropsch Synthesis plant installed at Laboratório de Processamento de Gás - CTGÁS-ER-Natal/RN

Estudo da remoção de Ba2+, Ni2+, Cd2+, Cu3+, Cr3+, Sr2+, Zn2+ por eletrocoagulação em água associada à produção de petróleo

Among the waste generated in the petrochemical industry water associated with oil production is the most important. It is considered one of the great challenges due to the presence of considered toxic chemicals present in this composition. The presence of these substances difficult to reuse the water associated with the enhanced recovery processes, so that prior to their reuse or disposal, treatment is necessary. This paper aimed to study the removal efficiency of chemical species: Ba2+, Ni2+, Cd2+, Cu2+, Cr3+, Sr2+ and Zn2+, present in the composition of the water associated with oil production by electrocoagulation. The evaluation of removal of these chemical species was performed by laboratory tests using electrochemical batch reactors and continuous flow. Initial tests were performed with electrocoagulation of synthetic wastewater in batch reactor using iron electrode. Results of removal of Zn2+ and Ni2+ were 78 % and 59 % respectively. While the percentage of removed Ba2+ was 19 % by 30 minutes of treatment and by applying current of 1.10 A. The tests were performed on effluent batch reactor applying the electrochemical technique with stainless steel electrodes 304, the objective was to remove part of the dispersed oil and also of organic compounds in the effluent. Under the experimental conditions used, the maximum result was obtained TOG was 60 % and TOC was approximately 50 % compared to the initial concentration. In the experiments carried out in continuous reactor, with effluent semisynthetic, have been used electrodes of iron and aluminum and the results were 100 % removal of Cd2+, Cu2+, Cr3+ and Zn2+ and 77 % of Sr2+. These percentages were only attainable through the use of the iron electrode. However, when the electrode was replaced by aluminum, there was a reduction in the percentage of removal to 65 %, using the same flow rate and current. Therefore according to the results obtained using the iron electrode was more effective in removing these metals and the conditions of lower current and lower flow rate was satisfactory, as observed in the experimental design adopted

Concepção e estudo de um biofiltro para tratamento de compostos orgânicos voláteis COVs

In the last decade, biological purification of gaseous waste has become an important alternative to many conventional methods of exhaust air treatment. More recently, biofiltration has proved to be an effective and inexpensive method for the treatment of air contaminated with volatile organic compounds (VOCs). A biofilter consists in a reactor packed with a porous solid bed material, where the microorganisms are fixed. During the biofiltration process, polluted air is transported through the biofilter medium where the contaminant is degraded. Within the biofilm, the pollutants in the waste gases are energy and carbon sources for microbial metabolism and are transformed into CO2, water and biomass. The bed material should be characterized by satisfactory mechanical and physical properties as structure, void fraction, specific area and flow resistance. The aim of this research was the biofilter construction and study of the biological degradation of ethanol and toluene, as well as the modeling of the process. Luffa cylindrica is a brazilian fiber that was used as the filtering material of the present work. The parameters and conditions studied were: composition of nutrients solution; effect of microflorae strains, namely Pseudomanas putida and Rhodococcus rhodochrous; waste gas composition; air flow rate; and inlet load of VOCs. The biofilter operated in diffusion regime and the best results for remotion capacity were obtained when a microorganisms consortion of Pseudomanas putida and Rhodococcus rhodochrous,were used, with a gas flow rate of 1 m3.h-1 and molar ratio nitrogene/phosphore N/P=2 in the nutrients solution. The maximum remotion capacity for ethanol was around 90 g.m-3.h-1 and 50 g.m-3.h-1 to toluene. It was proved that toluene has inhibitory effect on the ethanol remotion When the two VOCs were present in the same waste gas, there was a decrease of 40% in ethanol remotion capacity. Luffa cylindrica does not present considerable pressure drop. Ottengraf and van Lith models were used to represent the results obtained for ethanol and toluene, respectively. The application of the transient model indicated a satisfactory approximation between the experimental results obtained for ethanol and toluene vapors biofiltration and the ones predicted it

Aplicação de argila branca comercial pura e modificada para adsorção de sulfeto de hidrogênio

In this work were synthesized matrix-based commercial white clay in its composition having large amounts of kaolinite and quartz, with a certain percentage of iron oxide for use as an adsorbent for hydrogen sulfide (H2S). To characterize the effect of initial matrix techniques were used to characterize XRD, FTIR, XRF and TG. The initial clay mineral matrix was placed in contact with 0.1 molar solutions of the salts of Co2+, Ni2+, Cr3+ and a solution 0.1 g / 100ml rhodamine B. During the synthesis process, the solutions were placed in contact with the initial matrix for a period of 48 hours in order to have ion exchange with the clay mineral. To check the amount of exchanged metals, we used the technique of X-ray Fluorescence (XRF). After synthesis was initiated the process of adsorption of H2S, where the arrays were placed in the reactor, then by passing a stream of hydrogen sulfide. The matrix along with the reactor was weighed before and after to measure the amount of gas adsorbed. Based on the gravimetric data the matrix which had the highest performance of the adsorption matrix was exchanged with Ni2+ ions, obtaining a result of 11.13 mg H2S / g matrix, then the matrix coated with rhodamine B which was reached 10.13 mg H2S / g matrix

Teste tuberculínico em indivíduos com infecção pelo vírus da imunodeficiência humana: relação com número de linfócitos T periféricos e atividade tuberculosa

OBJETIVO: Avaliar os resultados do teste tuberculínico e relacioná-los com a presença ou não de tuberculose em atividade e com a contagem de linfócitos T CD4+/CD8+. MÉTODOS: Foram revisados 802 prontuários de pacientes com síndrome da imunodeficiência adquirida atendidos no período de agosto de 1985 a março de 2003. Cento e oitenta e cinco pacientes realizaram o teste tuberculínico (23,1%) e, destes, 107 eram do sexo masculino (57,8%). A média de idade no grupo de reatores ao teste tuberculínico foi de 30,6 anos, com desvio-padrão de 6,62 anos, e entre os não reatores de 34,45 anos com desvio-padrão de 10,32 anos. Foram constituídos dois grupos de estudo: reatores ao teste tuberculínico, com 28 pacientes, e não reatores ao teste tuberculínico, com 157 pacientes. RESULTADOS: Grande parte dos indivíduos foi pouco responsiva ao teste tuberculínico. Constatou-se, no grupo de reatores, maior porcentagem de indivíduos com tuberculose ativa à época da realização do teste, quando se comparou com os não reatores. Dez pacientes entre os reatores e onze entre os não reatores apresentavam alguma forma clínica de tuberculose em atividade à época da realização do teste, sendo que seis do primeiro grupo e oito do segundo tinham contagem de linfócitos T CD4+ menor que 200 células/mm³. CONCLUSÃO: Indurações maiores do que 5 mm não se relacionaram com contagens absolutas mais altas de células T CD4+.

Studies on the electrochemical disinfection of water containing Escherichia coli using a Dimensionally Stable Anode

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Improvement of L(+)-lactic acid production from cassava wastewater by Lactobacillus rhamnosus B 103

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Samarium(III) and praseodymium(III) biosorption on Sargassum sp.: Batch study

This work evaluates the potential of a Sargassum biomass for the biosorption of Sm(III) and Pr(III) using synthetic solutions. Under selected experimental conditions (excess of sorbent), the biosorption kinetics were fast: 30-40 min were sufficient for the complete recovery of the metals. The kinetic profiles were modeled using the pseudo-second order rate equation. The second objective of this study was to evaluate the possibility to separate these metals. Biosorption isotherms and uptake kinetics for the two metals (in binary component solutions) were almost overlapped. The biomass did not show significant selectivity for any of these two metals, in batch reactor. (C) 2010 Elsevier Ltd. All rights reserved.

Desempenho de reatores anaeróbios de fluxo ascendente com manta de lodo em dois estágios tratando águas residuárias de suinocultura

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)