Simulation of an Integrated Gasification Combined Cycle with Chemical-Looping Combustion and CO2 sequestration

Chemical-looping combustion allows an integration of CO2 capture in a thermal power plant without energy penalty; secondly, a less exergy destruction in the combustion chemical transformation is achieved, leading to a greater overall thermal efficiency. This paper focus on the study of the energetic performance of this concept of combustion in an integrated gasification combined cycle power plant when synthesis gas is used as fuel for the gas turbines. After thermodynamic modelling and optimization of some cycle parameters, the power plant performance is evaluated under diverse working conditions and compared to a conventional integrated gasification combined cycle with precombustion capture. Energy savings in CO2 capture and storage has been quantified. The overall efficiency increase is found to be significant and even notable, reaching values of around 7%. In order to analyze the influence of syngas composition on the results, different H2-content fuels are considered.

Caracterización de parámetros petrofísicos relacionados con la capacidad de almacenamiento de CO2 en el acuífero salino profundo de Hontomín (Burgos)

La conciencia de la crisis de la modernidad -que comienza ya a finales del siglo XIX- ha cobrado más experiencia debido al conocimiento de los límites del desarrollo económico, ya que como parecía razonable pensar, también los recursos naturales son finitos. En 1972, el Club de Roma analizó las distintas opciones disponibles para conseguir armonizar el desarrollo sostenible y las limitaciones medioambientales. Fue en 1987 cuando la Comisión Mundial para el Medio Ambiente y el Desarrollo de la ONU definía por primera vez el concepto de desarrollo sostenible. Definición que posteriormente fue incorporada en todos los programas de la ONU y sirvió de eje, por ejemplo, a la Cumbre de la Tierra celebrada en Río de Janeiro en 1992. Parece evidente que satisfacer la demanda energética, fundamentalmente desde la Revolución Industrial en el s XIX, trajo consigo un creciente uso de los combustibles fósiles, con la consiguiente emisión de los gases de efecto invernadero (GEI) y el aumento de la temperatura global media terrestre. Esta temperatura se incrementó en los últimos cien años en una media de 0.74ºC. La mayor parte del incremento observado desde la mitad del siglo XX en esta temperatura media se debe, con una probabilidad de al menos el 90%, al aumento observado en los GEI antropogénicos, siendo uno de ellos el CO2 que proviene de la transformación del carbono de los combustibles fósiles durante su combustión. Ante el creciente uso de los combustibles fósiles, los proyectos CAC, proyectos de captura, transporte y almacenamiento, se presentan como una contribución al desarrollo sostenible ya que se trata de una tecnología que permite mitigar el cambio climático. Para valorar si la tecnología CAC es sostenible, habrá que comprobar si existe o no capacidad para almacenar el CO2 en una cantidad mayor a la de producción y durante el tiempo necesario que impone la evolución de la concentración de CO2 en la atmósfera para mantenerla por debajo de las 450ppmv (concentración de CO2 que propone el Panel Intergubernamental para el Cambio Climático). El desarrollo de los proyectos CAC completos pasa por la necesaria selección de adecuados almacenes de CO2 que sean capaces de soportar los efectos de las presiones de inyección, así como asegurar la capacidad de dichos almacenes y la estanqueidad del CO2 en los mismos. La caracterización geológica de un acuífero susceptible de ser almacén de CO2 debe conducir a determinar las propiedades que dicho almacén posee para asegurar un volumen adecuado de almacenamiento, una inyectabilidad del CO2 en el mismo a un ritmo adecuado y la estanqueidad del CO2 en dicho acuífero a largo plazo. El presente trabajo pretende estudiar los parámetros que tienen influencia en el cálculo de la capacidad del almacén, para lo que en primer lugar se ha desarrollado la tecnología necesaria para llevar a cabo la investigación mediante ensayos de laboratorio. Así, se ha desarrollado una patente, "ATAP, equipo para ensayos petrofísicos (P201231913)", con la que se ha llevado a cabo la parte experimental de este trabajo para la caracterización de los parámetros que tienen influencia en el cálculo de la capacidad del almacén. Una vez desarrollada la tecnología, se aborda el estudio de los distintos parámetros que tienen influencia en la capacidad del almacén realizando ensayos con ATAP. Estos ensayos definen el volumen del almacenamiento, llegándose a la conclusión de que en la determinación de este volumen, juegan un papel importante el alcance de los mecanismos trampa, físicos o químicos, del CO2 en el almacén. Ensayos que definen la capacidad del almacén de "aceptar" o "rechazar" el CO2 inyectado, la inyectabilidad, y por último, ensayos encaminados a determinar posibles fugas que se pueden dar a través de los pozos de inyección, definidos estos como caminos preferenciales de fugas en un almacén subterráneo de CO2. Queda de este modo caracterizada la estanqueidad del CO2 en el acuífero a largo plazo y su influencia obvia en la determinación de la capacidad del almacén. Unido al propósito de la estimación de la capacidad del almacén, se encuentra el propósito de asegurar la estanqueidad de dichos almacenes en el tiempo, y adelantarse a la evolución de la pluma de CO2 en el interior de dichos almacenes. Para cumplir este propósito, se ha desarrollado un modelo dinámico a escala de laboratorio, mediante el programa ECLIPSE 300, con el fin de establecer una metodología para el cálculo de la capacidad estimada del almacén, así como el estudio de la evolución de la pluma de CO2 dentro del acuífero a lo largo del tiempo, partiendo de los resultados obtenidos en los ensayos realizados en ATAP y con la modelización de la probeta de roca almacén empleada en dichos ensayos. Presentamos por tanto un trabajo que establece las bases metodológicas para el estudio de la influencia de distintos parámetros petrofísicos en el cálculo de la capacidad del almacén unidos al desarrollo tecnológico de ATAP y su utilización para la determinación de dichos parámetros aplicables a cada acuífero concreto de estudio. ABSTRACT The crisis of modernity –which begins at the end of 19th Century- has been more important due to the knowledge of the limits of economic development, since it appeared to be thought reasonable, the natural resources are finite. In 1972, The Club of Rome analyzed the different options available in order to harmonize the sustainability and the environment development. It was in 1987 when The Global Commission on The Environment and the Development of UN, defined for the first time the concept of Sustainable Development. This definition that was fully incorporated in all the UN programs and it was useful as an axis, for example, in La Cumbre de la Tierra summit in Río de Janeiro in 1992. It seems obvious to satisfy energetic demand, basically after The Industrial Revolution in 19th Century, which represented an increasing use of fossil fuels, therefore greenhouse gases emission and the increasing of global average temperature. This temperature increased in the last 100 years up to 0.74ºC. The major part of the temperature increase is due to the increase observed in Greenhouse gases with human origin, at least with 90% of probability. The most important gas is the CO2 because of its quantity. In the face of the increasing use of fossil fuels, the CCS projects, Carbon Capture and Storage projects, appear as a contribution of sustainable development since it is a technology for avoiding the climate change. In order to evaluate if CCS technology is sustainable, it will be necessary to prove if the capacity for CO2 storage is available or not in a quantity greater than the production one and during the time necessary to keep the CO2 concentration in the atmosphere lower than 450ppmv (concentration imposed by IPCC). The development of full CCS projects goes through the selection of good CO2 storages that are able to support the effects of pressure injection, and assure the capacity of such storages and the watertightness of CO2. The geological characterization of the aquifer that could be potential CO2 storage should lead to determine the properties that such storage has in order to assure the adequate storage volume, the CO2 injectivity in a good rate, and the watertightness of the CO2 in the long term. The present work aims to study the parameters that have influence on the calculation of storage capacity, and for that purpose the appropriate technology has been developed for carrying out the research by mean of laboratory tests. Thus, a patent has been developed, "ATAP, equipo para ensayos petrofísicos (P201231913)", that has been used for developing the experimental part of this work. Once the technology has been developed, the study of different parameters, that have influence on the capacity of the storage, has been addressed developing different tests in ATAP. These tests define the storage volume which is related to the scope of different CO2 trap mechanisms, physical or chemical, in the storage. Tests that define the capacity of the storage to “accept” or “reject” the injected CO2, the injectivity, and tests led to determine possible leakages through injection wells. In this way we could talk about the watertightness in the aquifer in the long term and its influence on the storage capacity estimation. Together with the purpose of the storage capacity estimation, is the purpose of assuring the watertightness of such storages in the long term and anticipating the evolution of CO2 plume inside such aquifers. In order to fulfill this purpose, a dynamic model has been developed with ECLIPSE 300, for stablishing the methodology for the calculation of storage capacity estimation and the evolution of the CO2 plume, starting out with the tests carried out in ATAP. We present this work that establishes the methodology bases for the study of the influence of different petrophysics parameters in the calculation of the capacity of the storage together with the technological development of ATAP and its utilization for the determination of such parameters applicable to each aquifer.

Monitorización de emisiones de CO2 en un análogo natural mediante correlación con Índices de Vegetación

Entre las soluciones más satisfactorias al problema de las emisiones de CO2 está la captura y almacenamiento de este gas de efecto invernadero en reservorios profundos. Esta técnica implica la necesidad de monitorizar grandes extensiones de terreno. Utilizando una zona de vulcanismo residual, en la provincia de Ciudad Real, se han monitorizado las emisiones de CO2 utilizando imágenes de muy alta resolución espacial. Se han generado índices de vegetación, y estos se han correlacionado con medidas de contenido de CO2 del aire en los puntos de emisión. Los resultados han arrojado niveles de correlación significativos (p. ej.: SAVI = -0,93) y han llevado a descubrir un nuevo punto de emisión de CO2. Palabras clave: teledetección, CO2, vegetación, satélite Monitoring CO2 emissions in a natural analogue by correlating with vegetation indices Abstract: Among the most satisfactory solutions for the CO2 emissions problem is the capture and storage of this greenhouse gas in deep reservoirs. This technique involves the need to monitor large areas. Using a volcanic area with residual activity, in the province of Ciudad Real, CO2 emissions were monitored through very high spatial resolution imagery. Vegetation indexes were generated and correlated with measurements of the air?s CO2 content at the emission points. The results yielded significant correlation levels (e.g.: SAVI = -0.93) and led to the discovery of a new CO2 emission point. Keywords: remote sensing, CO2, vegetation, satellite.

Life cycle assessment of concentrated solar power (CSP) and the influence of hybridising with natural gas

Purpose Concentrating Solar Power (CSP) plants based on parabolic troughs utilize auxiliary fuels (usually natural gas) to facilitate start-up operations, avoid freezing of HTF and increase power output. This practice has a significant effect on the environmental performance of the technology. The aim of this paper is to quantify the sustainability of CSP and to analyse how this is affected by hybridisation with different natural gas (NG) inputs. Methods A complete Life Cycle (LC) inventory was gathered for a commercial wet-cooled 50 MWe CSP plant based on parabolic troughs. A sensitivity analysis was conducted to evaluate the environmental performance of the plant operating with different NG inputs (between 0 and 35% of gross electricity generation). ReCiPe Europe (H) was used as LCA methodology. CML 2 baseline 2000 World and ReCiPe Europe E were used for comparative purposes. Cumulative Energy Demands (CED) and Energy Payback Times (EPT) were also determined for each scenario. Results and discussion Operation of CSP using solar energy only produced the following environmental profile: climate change 26.6 kg CO2 eq/KWh, human toxicity 13.1 kg 1,4-DB eq/KWh, marine ecotoxicity 276 g 1,4-DB eq/KWh, natural land transformation 0.005 m2/KWh, eutrophication 10.1 g P eq/KWh, acidification 166 g SO2 eq/KWh. Most of these impacts are associated with extraction of raw materials and manufacturing of plant components. The utilization NG transformed the environmental profile of the technology, placing increasing weight on impacts related to its operation and maintenance. Significantly higher impacts were observed on categories like climate change (311 kg CO2 eq/MWh when using 35 % NG), natural land transformation, terrestrial acidification and fossil depletion. Despite its fossil nature, the use of NG had a beneficial effect on other impact categories (human and marine toxicity, freshwater eutrophication and natural land transformation) due to the higher electricity output achieved. The overall environmental performance of CSP significantly deteriorated with the use of NG (single score 3.52 pt in solar only operation compared to 36.1 pt when using 35 % NG). Other sustainability parameters like EPT and CED also increased substantially as a result of higher NG inputs. Quasilinear second-degree polynomial relationships were calculated between various environmental performance parameters and NG contributions. Conclusions Energy input from auxiliary NG determines the environmental profile of the CSP plant. Aggregated analysis shows a deleterious effect on the overall environmental performance of the technology as a result of NG utilization. This is due primarily to higher impacts on environmental categories like climate change, natural land transformation, fossil fuel depletion and terrestrial acidification. NG may be used in a more sustainable and cost-effective manner in combined cycle power plants, which achieve higher energy conversion efficiencies.

Rubisco activase constrains the photosynthetic potential of leaves at high temperature and CO2

Net photosynthesis (Pn) is inhibited by moderate heat stress. To elucidate the mechanism of inhibition, we examined the effects of temperature on gas exchange and ribulose 1,5-bisphosphate carboxylase/oxygenase (Rubisco) activation in cotton and tobacco leaves and compared the responses to those of the isolated enzymes. Depending on the CO2 concentration, Pn decreased when temperatures exceeded 35–40°C. This response was inconsistent with the response predicted from the properties of fully activated Rubisco. Rubisco deactivated in leaves when temperature was increased and also in response to high CO2 or low O2. The decrease in Rubisco activation occurred when leaf temperatures exceeded 35°C, whereas the activities of isolated activase and Rubisco were highest at 42°C and >50°C, respectively. In the absence of activase, isolated Rubisco deactivated under catalytic conditions and the rate of deactivation increased with temperature but not with CO2. The ability of activase to maintain or promote Rubisco activation in vitro also decreased with temperature but was not affected by CO2. Increasing the activase/Rubisco ratio reduced Rubisco deactivation at higher temperatures. The results indicate that, as temperature increases, the rate of Rubisco deactivation exceeds the capacity of activase to promote activation. The decrease in Rubisco activation that occurred in leaves at high CO2 was not caused by a faster rate of deactivation, but by reduced activase activity possibly in response to unfavorable ATP/ADP ratios. When adjustments were made for changes in activation state, the kinetic properties of Rubisco predicted the response of Pn at high temperature and CO2.

On strategies for reducing greenhouse gas emissions

Equity is of fundamental concern in the quest for international cooperation to stabilize greenhouse gas concentrations by the reduction of emissions. By modeling the carbon cycle, we estimate the global CO2 emissions that would be required to stabilize the atmospheric concentration of CO2 at levels ranging from 450 to 1,000 ppm. These are compared, on both an absolute and a per-capita basis, to scenarios for emissions from the developed and developing worlds generated by socio-economic models under the assumption that actions to mitigate greenhouse gas emissions are not taken. Need and equity have provided strong arguments for developing countries to request that the developed world takes the lead in controlling its emissions, while permitting the developing countries in the meantime to use primarily fossil fuels for their development. Even with major and early control of CO2 emissions by the developed world, limiting concentration to 450 ppm implies that the developing world also would need to control its emissions within decades, given that we expect developing world emissions would otherwise double over this time. Scenarios leading to CO2 concentrations of 550 ppm exhibit a reduction of the developed world's per-capita emission by about 50% over the next 50 years. Even for the higher stabilization levels considered, the developing world would not be able to use fossil fuels for their development in the manner that the developed world has used them.

Global air-sea flux of CO2: An estimate based on measurements of sea–air pCO2 difference

Approximately 250,000 measurements made for the pCO2 difference between surface water and the marine atmosphere, ΔpCO2, have been assembled for the global oceans. Observations made in the equatorial Pacific during El Nino events have been excluded from the data set. These observations are mapped on the global 4° × 5° grid for a single virtual calendar year (chosen arbitrarily to be 1990) representing a non-El Nino year. Monthly global distributions of ΔpCO2 have been constructed using an interpolation method based on a lateral advection–diffusion transport equation. The net flux of CO2 across the sea surface has been computed using ΔpCO2 distributions and CO2 gas transfer coefficients across sea surface. The annual net uptake flux of CO2 by the global oceans thus estimated ranges from 0.60 to 1.34 Gt-C⋅yr−1 depending on different formulations used for wind speed dependence on the gas transfer coefficient. These estimates are subject to an error of up to 75% resulting from the numerical interpolation method used to estimate the distribution of ΔpCO2 over the global oceans. Temperate and polar oceans of the both hemispheres are the major sinks for atmospheric CO2, whereas the equatorial oceans are the major sources for CO2. The Atlantic Ocean is the most important CO2 sink, providing about 60% of the global ocean uptake, while the Pacific Ocean is neutral because of its equatorial source flux being balanced by the sink flux of the temperate oceans. The Indian and Southern Oceans take up about 20% each.

Does Leaf Position within a Canopy Affect Acclimation of Photosynthesis to Elevated CO2?1 : Analysis of a Wheat Crop under Free-Air CO2 Enrichment

Previous studies of photosynthetic acclimation to elevated CO2 have focused on the most recently expanded, sunlit leaves in the canopy. We examined acclimation in a vertical profile of leaves through a canopy of wheat (Triticum aestivum L.). The crop was grown at an elevated CO2 partial pressure of 55 Pa within a replicated field experiment using free-air CO2 enrichment. Gas exchange was used to estimate in vivo carboxylation capacity and the maximum rate of ribulose-1,5-bisphosphate-limited photosynthesis. Net photosynthetic CO2 uptake was measured for leaves in situ within the canopy. Leaf contents of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco), light-harvesting-complex (LHC) proteins, and total N were determined. Elevated CO2 did not affect carboxylation capacity in the most recently expanded leaves but led to a decrease in lower, shaded leaves during grain development. Despite this acclimation, in situ photosynthetic CO2 uptake remained higher under elevated CO2. Acclimation at elevated CO2 was accompanied by decreases in both Rubisco and total leaf N contents and an increase in LHC content. Elevated CO2 led to a larger increase in LHC/Rubisco in lower canopy leaves than in the uppermost leaf. Acclimation of leaf photosynthesis to elevated CO2 therefore depended on both vertical position within the canopy and the developmental stage.

Relationship between CO2 Assimilation, Photosynthetic Electron Transport, and Active O2 Metabolism in Leaves of Maize in the Field during Periods of Low Temperature1

Measurements of the quantum efficiencies of photosynthetic electron transport through photosystem II (φPSII) and CO2 assimilation (φCO2) were made simultaneously on leaves of maize (Zea mays) crops in the United Kingdom during the early growing season, when chilling conditions were experienced. The activities of a range of enzymes involved with scavenging active O2 species and the levels of key antioxidants were also measured. When leaves were exposed to low temperatures during development, the ratio of φPSII/φCO2 was elevated, indicating the operation of an alternative sink to CO2 for photosynthetic reducing equivalents. The activities of ascorbate peroxidase, monodehydroascorbate reductase, dehydroascorbate reductase, glutathione reductase, and superoxide dismutase and the levels of ascorbate and α-tocopherol were also elevated during chilling periods. This supports the hypothesis that the relative flux of photosynthetic reducing equivalents to O2 via the Mehler reaction is higher when leaves develop under chilling conditions. Lipoxygenase activity and lipid peroxidation were also increased during low temperatures, suggesting that lipoxygenase-mediated peroxidation of membrane lipids contributes to the oxidative damage occurring in chill-stressed leaves.

Uptake of HCO3− and CO2 in Cells and Chloroplasts from the Microalgae Chlamydomonas reinhardtii and Dunaliella tertiolecta1

Mass-spectrometric disequilibrium analysis was applied to investigate CO2 uptake and HCO3− transport in cells and chloroplasts of the microalgae Dunaliella tertiolecta and Chlamydomonas reinhardtii, which were grown in air enriched with 5% (v/v) CO2 (high-Ci cells) or in ambient air (low-Ci cells). High- and low-Ci cells of both species had the capacity to transport CO2 and HCO3−, with maximum rates being largely unaffected by the growth conditions. In high- and low-Ci cells of D. tertiolecta, HCO3− was the dominant inorganic C species taken up, whereas HCO3− and CO2 were used at similar rates by C. reinhardtii. The apparent affinities of HCO3− transport and CO2 uptake increased 3- to 9-fold in both species upon acclimation to air. Photosynthetically active chloroplasts isolated from both species were able to transport CO2 and HCO3−. For chloroplasts from C. reinhardtii, the concentrations of HCO3− and CO2 required for half-maximal activity declined from 446 to 33 μm and 6.8 to 0.6 μm, respectively, after acclimation of the parent cells to air; the corresponding values for chloroplasts from D. tertiolecta decreased from 203 to 58 μm and 5.8 to 0.5 μm, respectively. These results indicate the presence of inducible high-affinity HCO3− and CO2 transporters at the chloroplast envelope membrane.

cemA homologue essential to CO2 transport in the cyanobacterium Synechocystis PCC6803.

We have isolated mutants of Synechocystis PCC6803 that grew very slowly in a low-sodium medium, which is unfavorable for HCO3(-) transport, and examined two of these mutants (SC1 and SC2) for their ability to take up CO2 and HCO3(-) in the light. The CO2 transport activity of SC1 and SC2 was much lower than that of the wild type (WT), whereas there was no difference between the mutants and the WT in their activity of HCO3(-) transport. A clone containing a 3.9-kilobase-pair insert DNA that transforms both mutants to the WT phenotype was isolated from a genomic library of WT Synechocystis. Sequencing of the insert DNA in the region of mutations in SC1 and SC2 revealed an open reading frame (designated cotA), which showed significant amino-acid sequence homology to cemA encoding a protein found in the inner envelope membrane of chloroplasts. The cotA gene is present in a single copy and was not cotranscribed with any other gene(s). cotA encodes a protein of 247 amino acids containing four transmembrane domains. There was substitution of a single base in SC1 and two bases in SC2 in their cotA genes. A possible role of the cotA gene product in CO2 transport is discussed.

Relationship between photosynthetic electron transport and pH gradient across the thylakoid membrane in intact leaves.

Under conditions (0.2% CO2; 1% O2) that allow high rates of photosynthesis, chlorophyll fluorescence was measured simultaneously with carbon assimilation at various light intensities in spinach (Spinacia oleracea) leaves. Using a stoichiometry of 3 ATP/CO2 and the known relationship between ATP synthesis rate and driving force (Delta pH), we calculated the light-dependent pH gradient (Delta pH) across the thylakoid membrane in intact leaves. These Delta pH values were correlated with the photochemical (qP) and nonphotochemical (qN) quenching of chlorophyll fluorescence and with the quantum yield of photosystem II (phiPSII). At Delta pH > 2.1 all three parameters (qP, qN, and phiPSII) changed very steeply with increasing DeltapH (decreasing pH in the thylakoid). The observed pH dependences followed hexacooperative titration curves with slightly different pKa values. The significance of the steep pH dependences with slightly different pKa values is discussed in relation to the regulation of photosynthetic electron transport in intact leaves.

Síntese, caracterização e modificação de superfícies de sílicas mesoporosas ordenadas para captura de CO2

Processos como a purificação do metano (CH4) e a produção de hidrogênio gasoso (H2) envolvem etapas de separação de CO2. Atualmente, etanolaminas como monoetanolamina (MEA), dietanolamina (DEA), metildietanolamina (MDEA) e trietanolamina (TEA) são as substâncias mais utilizadas no processo de separação/captura de CO2 em processos industriais. Entretanto, o uso destas substâncias apresenta alguns inconvenientes devido à alta volatilidade, dificuldade de se trabalhar com material líquido, também ao alto gasto energético envolvido das etapas de regeneração e à baixa estabilidade térmica e química. Com base nessa problemática, esse trabalho teve por objetivo a síntese de um tipo de sílica mesoporosa altamente ordenada (SBA-15) de modo a utilizá-la no processo de captura de CO2. O trabalho foi dividido em quatro etapas experimentais que envolveram a síntese da SBA-15, o estudo do comportamento térmico de algumas etanolaminas livres, síntese e caracterização de materiais adsorventes preparados a partir de incorporação de etanolaminas à SBA-15 e estudo da eficiência de captura de CO2 por esses materiais. Novas alternativas de síntese da SBA-15 foram estudadas neste trabalho, visando aperfeiçoar as propriedades texturais do material produzido. Tais alternativas são baseadas na remoção do surfatante, utilizado como molde na síntese da sílica mesoporosa, por meio da extração por Soxhlet, utilizando diferentes solventes. O processo contribuiu para melhorar as propriedades do material obtido, evitando o encolhimento da estrutura que pode ser ocasionado durante a etapa de calcinação. Por meio de técnicas como TG/DTG, DSC, FTIR e Análise Elementar de C, H e N foi realizada a caracterização físico-química e termoanalítica da MEA, DEA, MDEA e TEA, visando melhor conhecer as características destas substâncias. Estudos cinéticos baseados nos métodos termogravimétricos isotérmicos e não isotérmicos (Método de Ozawa) foram realizados, permitindo a determinação de parâmetros cinéticos envolvidos nas etapas de volatilização/decomposição térmica das etanolaminas. Além das técnicas acima mencionadas, MEV, MET, SAXS e Medidas de Adsorção de N2 foram utilizadas na caraterização da SBA-15 antes e após a incorporação das etanolaminas. Dentre as etanolaminas estudadas, a TEA apresentou maior estabilidade térmica, entretanto, devido ao seu maior impedimento estérico, é a etanolamina que apresenta menor afinidade com o CO2. Diferentemente das demais etanolaminas estudadas, a decomposição térmica da DEA envolve uma reação intramolecular, levando a formação de MEA e óxido de etileno. A incorporação destes materiais à SBA-15 aumentou a estabilidade térmica das etanolaminas, uma vez que parte do material permanece dentro dos poros da sílica. Os ensaios de adsorção de CO2 mostraram que a incorporação da MEA à SBA-15 catalisou o processo de decomposição térmica da mesma. A MDEA foi a etanolamina que apresentou maior poder de captura de CO2 e sua estabilidade térmica foi consideravelmente aumentada quando a mesma foi incorporada à SBA-15, aumentando também seu potencial de captura de CO2.

Injetor intravascular de CO2: estudo in vivo de viabilidade inicial do dispositivo e de qualidade de imagem

INTRODUÇÃO: Durante procedimentos endovasculares, estão presentes os riscos relacionados ao uso dos contrastes iodados, tais como a nefropatia por contraste, uma vez que é fundamental o emprego de um meio de contraste para a obtenção das imagens radiológicas vasculares. A injeção intravascular de gás CO2 purificado é reconhecidamente uma alternativa relativamente mais segura ao contraste iodado, contudo, seu manuseio artesanal pode também trazer dificuldades técnicas e riscos aos pacientes. Para contemplar estas questões, foi desenvolvido o protótipo de um injetor intravascular de CO2 medicinal, microprocessado, dedicado à obtenção de imagens angiográficas. OBJETIVOS: Realizar os testes de viabilidade técnica inicial do protótipo em modelo in vivo. MÉTODOS: Realizar a angioplastia da artéria renal esquerda de 10 porcos, divididos em 2 grupos: Grupo 1 (n=5) injeção de contraste iodado, Grupo 2 (n=5) injeção de CO2 através do protótipo. Monitorização clínica e laboratorial dos animais no pré, intra e pós-operatório, com exames de função renal na véspera e 48h após os procedimentos e 3 gasometrias arteriais seriadas no intra-operatório. Observação clínica foi mantida por 48h no pós- operatório. RESULTADOS: Os procedimentos de angioplastia com CO2 foram realizados com sucesso técnico de 100%, sem necessidade de complementação com injeção de contraste iodado no Grupo 2. Não foram identificadas falhas no protótipo em funcionamento. Não foram identificadas alterações clínicas ou radiológicas sugestivas de contaminação por ar ambiente do sistema de CO2 e nem alterações laboratoriais nos animais. As imagens angiográficas obtidas no Grupo 2 foram consideradas, numa avaliação subjetiva, relativamente inferiores às imagens obtidas no Grupo 1. DISCUSSÃO: A qualidade inferior de imagem no Grupo 2 pode ser atribuída ao equipamento de fluoroscopia utilizado, com software desatualizado em relação aos equipamentos atuais, que incluem pré-configurações para angiografia com CO2; no entanto, ainda assim todos os procedimentos propostos no Grupo 2 foram realizados com sucesso técnico, o que nos leva a classificar as imagens deste grupo 2 como satisfatórias. O manuseio do aparelho mostrou-se ágil e eficiente, com a programação dos parâmetros sendo realizada com facilidade através do visor \"touch screen\", comparativamente superior ao método artesanal de injeção de CO2 com seringas em selo d\'água. CONCLUSÕES: O protótipo do aparelho injetor intravascular de CO2 funcionou de forma adequada durante os testes e as imagens obtidas permitiram a compleição com sucesso dos procedimentos. Portanto, os resultados positivos obtidos sugerem que o equipamento é tecnicamente viável

Estudo do processo de absorção e dessorção de CO2 na solução aquosa de metildietanolamina e piperazina.

Estudou-se o processo de absorção e dessorção de CO2 em solução aquosa da mistura de metildietanolamina (MDEA) e piperazina (PZ). Os ensaios de absorção foram realizados numa coluna de parede molhada com promotor de película, e, os ensaios de dessorção num sistema de semibatelada, ambos em escala de laboratório. Os testes experimentais de absorção foram realizados a 298 K e pressão atmosférica, com vazão de gás (CO2 e ar atmosférico) de 2,2.10-4 m3 s-1 e as seguintes vazões de líquido: 1,0.10-6; 1,3.10-6 e 1,7.10-6 m3 s-1. O sistema de absorção foi caracterizado através da determinação da área interfacial, a, o coeficiente volumétrico de transferência de massa, kGa, e o coeficiente volumétrico global médio de transferência de massa, KGa. No caso dos ensaios de dessorção, estes foram realizados nas temperaturas de 353, 363 e 368 K, onde empregou-se uma solução carbonatada de 10% PZ-20% MDEA e uma corrente de ar atmosférico nas vazões de 1,1.10-5 m3 s-1 e 2,7.10-5 m3 s-1. Este sistema foi caracterizado através da determinação do coeficiente volumétrico global de transferência de massa, KLa. Os resultados experimentais da área interfacial mostram que este é função da vazão do líquido, sugerindo uma maior área de irrigação como o aumento desta, onde teve-se uma maior área de transferência de massa. O resultado do parâmetro, KGa, indica uma dependência da vazão de líquido, a qual está associada à variação da área interfacial e à dependência do parâmetro KG com o perfil das concentrações da MDEA e PZ ao longo da coluna. A partir da teoria do duplo filme e pelo conhecimento dos parâmetros KGa, a e kGa, estimou-se um parâmetro cinético-difusivo associado à fase líquida, (( ) ) . Os resultados experimentais mostram que esse parâmetro varia pouco com a vazão de líquido, indicando tratar-se de um processo independente da hidrodinâmica do líquido, característico de sistemas com reação rápida. A concentração das aminas e carbamatos, nos ensaios de absorção e dessorção, foi determinada através dos modelos de calibração obtidas pela técnica de espectroscopia no infravermelho. Nos ensaios de absorção, foram observados que a concentração de PZ teve uma variação considerável (4 a 5% massa massa-1), entanto que a de MDEA variou pouco (0,3 a 0,5% massa massa-1), sugerindo que o processo de absorção de CO2 na mistura MDEA-PZ é controlado principalmente pela PZ, e supõe-se que a MDEA tem um papel de receptor de prótons procedentes da reação entre a PZ e o CO2. Nos ensaios de dessorção, observou-se que esse processo é afetado pela temperatura, sendo que, em temperaturas perto da ebulição (372 K), a taxa de dessorção de CO2 é maior do que em temperaturas menores, em certa forma é devido à dependência da velocidade de reação química com a temperatura. Os resultados do parâmetro KLa indicam que este diminui em função da concentração de carbamato de PZ (por exemplo, na temperatura de 368 K, de 7,5.10-4 a 1,0.10-4 s-1), devido a que este componente é decomposto em altas temperaturas gerando o CO2 e as aminas, sugerindo uma diminuição na velocidade de dessorção de CO2. Assim também, os resultados experimentais do parâmetro KLa indicam que este aumenta ligeiramente com a vazão do gás.