Carboxydothermus hydrogenoformans comme catalyseur biologique pour la conversion du monoxyde de carbone en hydrogène simultanément a la minéralisation de calcium et phosphate

La gazéification est aujourd'hui l'une des stratégies les plus prometteuses pour valoriser les déchets en énergie. Cette technologie thermo-chimique permet une réduction de 95 % de la masse des intrants et génère des cendres inertes ainsi que du gaz de synthèse (syngaz). Le syngaz est un combustible gazeux composé principalement de monoxyde de carbone (CO), d'hydrogène (H2) et de dioxyde de carbone (CO2). Le syngaz peut être utilisé pour produire de la chaleur et de l'électricité. Il est également la pierre angulaire d'un grand nombre de produits à haute valeur ajoutée, allant de l'éthanol à l'ammoniac et l'hydrogène pur. Les applications en aval de la production de syngaz sont dictées par son pouvoir calorifique, lui-même dépendant de la teneur du gaz en H2. L’augmentation du contenu du syngaz en H2 est rendu possible par la conversion catalytique à la vapeur d’eau, largement répandu dans le cadre du reformage du méthane pour la production d'hydrogène. Au cours de cette réaction, le CO est converti en H2 et CO2 selon : CO + H2O → CO2 + H2. Ce processus est possible grâce à des catalyseurs métalliques mis en contact avec le CO et de la vapeur. La conversion catalytique à la vapeur d’eau a jusqu'ici été réservé pour de grandes installations industrielles car elle nécessite un capital et des charges d’exploitations très importantes. Par conséquent, les installations de plus petite échelle et traitant des intrants de faible qualité (biomasse, déchets, boues ...), n'ont pas accès à cette technologie. Ainsi, la seule utilisation de leur syngaz à faible pouvoir calorifique, est limitée à la génération de chaleur ou, tout au plus, d'électricité. Afin de permettre à ces installations une gamme d’application plus vaste de leurs syngaz, une alternative économique à base de catalyseur biologique est proposée par l’utilisation de bactéries hyperthermophiles hydrogénogènes. L'objectif de cette thèse est d'utiliser Carboxydothermus hydrogenoformans, une bactérie thermophile carboxydotrophe hydrogénogène comme catalyseur biologique pour la conversion du monoxyde de carbone en hydrogène. Pour cela, l’impact d'un phénomène de biominéralisation sur la production d’H2 a été étudié. Ensuite, la faisabilité et les limites de l’utilisation de la souche dans un bioréacteur ont été évaluées. Tout d'abord, la caractérisation de la phase inorganique prédominante lorsque C. hydrogenoformans est inoculé dans le milieu DSMZ, a révélé une biominéralisation de phosphate de calcium (CaP) cristallin en deux phases. L’analyse par diffraction des rayons X et spectrométrie infrarouge à transformée de Fourier de ce matériau biphasique indique une signature caractéristique de la Mg-whitlockite, alors que les images obtenues par microscopie électronique à transmission ont montré l'existence de nanotiges cristallines s’apparentant à de l’hydroxyapatite. Dans les deux cas, le mode de biominéralisation semble être biologiquement induit plutôt que contrôlé. L'impact du précipité de CaP endogène sur le transfert de masse du CO et la production d’H2 a ensuite été étudié. Les résultats ont été comparés aux valeurs obtenues dans un milieu où aucune précipitation n'est observée. Dans le milieu DSMZ, le KLa apparent (0.22 ± 0.005 min-1) et le rendement de production d’H2 (89.11 ± 6.69 %) étaient plus élevés que ceux obtenus avec le milieu modifié (0.19 ± 0.015 min-1 et 82.60 ± 3.62% respectivement). La présence du précipité n'a eu aucune incidence sur l'activité microbienne. En somme, le précipité de CaP offre une nouvelle stratégie pour améliorer les performances de transfert de masse du CO en utilisant les propriétés hydrophobes de gaz. En second lieu, la conversion du CO en H2 par la souche Carboxydothermus hydrogenoformans fut étudiée et optimisée dans un réacteur gazosiphon de 35 L. Parmi toutes les conditions opérationnelles, le paramètre majeur fut le ratio du débit de recirculation du gaz sur le débit d'alimentation en CO (QR:Qin). Ce ratio impacte à la fois l'activité biologique et le taux de transfert de masse gaz-liquide. En effet, au dessus d’un ratio de 40, les performances de conversion du CO en H2 sont limitées par l’activité biologique alors qu’en dessous, elles sont limitées par le transfert de masse. Cela se concrétise par une efficacité de conversion maximale de 90.4 ± 0.3 % et une activité spécifique de 2.7 ± 0.4 molCO·g–1VSS·d–1. Malgré des résultats prometteurs, les performances du bioréacteur ont été limitées par une faible densité cellulaire, typique de la croissance planctonique de C. hydrogenoformans. Cette limite est le facteur le plus contraignant pour des taux de charge de CO plus élevés. Ces performances ont été comparées à celles obtenues dans un réacteur à fibres creuses (BRFC) inoculé par la souche. En dépit d’une densité cellulaire et d’une activité volumétrique plus élevées, les performances du BRFC à tout le moins cinétiquement limitées quand elles n’étaient pas impactées par le transfert de masse, l'encrassement et le vieillissement de la membrane. Afin de parer à la dégénérescence de C. hydrogenoformans en cas de pénurie de CO, la croissance de la bactérie sur pyruvate en tant que seule source de carbone a été également caractérisée. Fait intéressant, en présence simultanée de pyruvate et de CO, C. hydrogenoformans n’a amorcé la consommation de pyruvate qu’une fois le CO épuisé. Cela a été attribué à un mécanisme d'inhibition du métabolisme du pyruvate par le CO, faisant ainsi du pyruvate le candidat idéal pour un système in situ de secours.

Qualitative air flow modelling and analysis of data centre air conditioning as multiple jet array

This work identifies the importance of plenum pressure on the performance of the data centre. The present methodology followed in the industry considers the pressure drop across the tile as a dependant variable, but it is shown in this work that this is the only one independent variable that is responsible for the entire flow dynamics in the data centre, and any design or assessment procedure must consider the pressure difference across the tile as the primary independent variable. This concept is further explained by the studies on the effect of dampers on the flow characteristics. The dampers have found to introduce an additional pressure drop there by reducing the effective pressure drop across the tile. The effect of damper is to change the flow both in quantitative and qualitative aspects. But the effect of damper on the flow in the quantitative aspect is only considered while using the damper as an aid for capacity control. Results from the present study suggest that the use of dampers must be avoided in data centre and well designed tiles which give required flow rates must be used in the appropriate locations. In the present study the effect of hot air recirculation is studied with suitable assumptions. It identifies that, the pressure drop across the tile is a dominant parameter which governs the recirculation. The rack suction pressure of the hardware along with the pressure drop across the tile determines the point of recirculation in the cold aisle. The positioning of hardware in the racks play an important role in controlling the recirculation point. The present study is thus helpful in the design of data centre air flow, based on the theory of jets. The air flow can be modelled both quantitatively and qualitatively based on the results.

Efecto de ajuste del flujo dializante (Qd) sobre la eficacia en hemodialisis a pacientes de bajo peso

Introducción: Las guías KDOQI del 2006 utilizan patrón de adecuación de diálisis el Kt/V, donde V es volumen de distribución de la úrea, pacientes de bajo peso tienen menor agua corporal total, menor V, que podrían reducir el requerimiento de Qd sin afectar la eficiencia de la diálisis. Objetivo: Evaluar el efecto sobre la adecuación de hemodiálisis que produce la reducción del Qd en pacientes con peso menor o igual a 60 kg . Metodología: Se incluyeron pacientes con Enfermedad Renal crónica en hemodiálisis de forma regular con peso menor o igual a 60 Kg de la unidad renal, para evaluar dos períodos I y II, se continuaron los parámetros de la terapia, con descenso del Qd para el segundo período . Las variables fueron recolectadas de forma directa por los investigadores de la historia clínica . Los valores así obtenidos serían comparados mediante prueba t para variables relacionadas o pareadas, y significancia estadística de la prueba inferior a 0,05. Resultados: Se incluyeron 61 pacientes, el 60.7% sexo femenino, promedio de edad 57,3 años (DE 14,8). Edad promedio de los hombres 60,1 (DE 13,9) y de las mujeres fue de 55,9 (DE 15,4). No se encontraron diferencias estadísticamente significativas para las variables Kt/V y Hb, con descenso significativo del P. (p 0.015) Conclusiones: Este estudio demuestra que se logra una adecuada terapia con Qd inferiores a los estándares tradicionales, con 400ml /min en pacientes de bajo peso, siempre y cuando se mantengan los demás parámetros de suplencia renal.

An HMV mapping study of a pulsating jet system

A new system for the generation of hydrodynamic modulated voltammetry (HMV) is presented. This system consists of an oscillating jet produced through the mechanical vibration of a large diaphragm. The structure of the cell is such that a relatively small vibration is transferred to a large fluid flow at the jet outlet. Positioning of an electrode (Pt, 0.5 mm or 25 mu m diameter) over the exit of this jet enables the detection of the modulated flow of liquid. While this flow creates modest mass transfer rates (time averaged similar to 0.015 cm s(-1)) it can also be used to create a HMV system where a 'lock-in' approach is adopted to investigate the redox chemistry in question. This is demonstrated for the Fe(CN)(6)(3-/4-) redox system. Here 'lock-in' to the modulated hydrodynamic signal is achieved through the deployment of bespoke software. The apparatus and procedure is shown to produce a simple and efficient way to obtain the desired signal. In addition the spatial variation of the HMV signal, phase correction and time averaged current with respect to the jet orifice is presented. (C) 2008 Elsevier B.V. All rights reserved.

Small-angle x-ray scattering study of flow alignment of a thermotropic liquid crystal in the nematic and smectic phases

WThe capillary flow alignment of the thermotropic liquid crystal 4-n-octyl-4′-cyanobiphenyl in the nematic and smectic phases is investigated using time-resolved synchrotron small-angle x-ray scattering. Samples were cooled from the isotropic phase to erase prior orientation. Upon cooling through the nematic phase under Poiseuille flow in a circular capillary, a transition from the alignment of mesogens along the flow direction to the alignment of layers along the flow direction (mesogens perpendicular to flow) appears to occur continuously at the cooling rate applied. The transition is centered on a temperature at which the Leslie viscosity coefficient α3 changes sign. The configuration with layers aligned along the flow direction is also observed in the smectic phase. The transition in the nematic phase on cooling has previously been ascribed to an aligning-nonaligning or tumbling transition. At high flow rates there is evidence for tumbling around an average alignment of layers along the flow direction. At lower flow rates this orientation is more clearly defined. The layer alignment is ascribed to surface-induced ordering propagating into the bulk of the capillary, an observation supported by the parallel alignment of layers observed for a static sample at low temperatures in the nematic phase.

Influence of water flow rate on shear bond strength of resin composite to Er : YAG cavity preparation

Purpose: To evaluate in vitro the influence of water flow rate on shear bond strength of a resin composite to enamel and dentin after Er:YAG cavity preparation. Methods: Ten bovine incisors were selected and roots removed. Crowns were sectioned in four pieces, resulting in 40 samples that were individually embedded in polyester resin (n=10), and ground to plane the enamel and expose the dentin. The bonding site was delimited and samples were randomly assigned according to cavity preparation: (1) Er:YAG/1.0 mL/minute; (2) Er:YAG/1.5 mL/minute; (3) Er:YAG/2.0 mL/minute and (4) High speed handpiece/bur (control group). Samples were fixed to a metallic device, where composite resin cylinders were prepared. Subsequently, they were stored for 24 hours and subjected to a shear bond strength test (500N at 0.5 mm/minute). Results: Means (MPa) were: enamel: 1: 12.8; 2: 16.8; 3: 17.5; 4: 36.0 and Dentin: 1: 13.6; 2: 18.7; 3: 12.1; 4: 21.3. Data were submitted to ANOVA and Tukey`s test. Adhesion to enamel was more efficient than for dentin. The cavities prepared with conventional bur (control) presented higher statistically significant bond strength values (P<0.05) than for Er:YAG laser for both enamel and dentin. No significant differences were observed between water flow rates employed during enamel ablation. For dentin, the shear bond strength of 2.0 mL/minute water flow rate was lower than for 1.5 mL/minute and 1.0 mL/minute rates. The Er:YAG laser adversely affected shear bond strength of resin composite to both enamel and dentin, regardless of the water flow rate used.

Flow injection analysis of ethyl xanthate by gas diffusion and UV detection as CS(2) for process monitoring of sulfide ore flotation

A sensitive and robust analytical method for spectrophotometric determination of ethyl xanthate, CH(3)CH(2)OCS(2)(-) at trace concentrations in pulp solutions from froth flotation process is proposed. The analytical method is based on the decomposition of ethyl xanthate. EtX(-), with 2.0 mol L(-1) HCl generating ethanol and carbon disulfide. CS(2). A gas diffusion cell assures that only the volatile compounds diffuse through a PTFE membrane towards an acceptor stream of deionized water, thus avoiding the interferences of non-volatile compounds and suspended particles. The CS(2) is selectively detected by UV absorbance at 206 nm (epsilon = 65,000 L mol(-1) cm(-1)). The measured absorbance is directly proportional to EtX(-) concentration present in the sample solutions. The Beer`s law is obeyed in a 1 x 10(-6) to 2 x 10(-4) mol L(-1) concentration range of ethyl xanthate in the pulp with an excellent correlation coefficient (r = 0.999) and a detection limit of 3.1 x 10(-7) mol L(-1), corresponding to 38 mu g L. At flow rates of 200 mu L min(-1) of the donor stream and 100 mu L min(-1) of the acceptor channel a sampling rate of 15 injections per hour could be achieved with RSD < 2.3% (n = 10, 300 mu L injections of 1 x 10(-5) mol L(-1) EtX(-)). Two practical applications demonstrate the versatility of the FIA method: (i) evaluation the free EtX(-) concentration during a laboratory study of the EtX(-) adsorption capacity on pulverized sulfide ore (pyrite) and (ii) monitoring of EtX(-) at different stages (from starting load to washing effluents) of a flotation pilot plant processing a Cu-Zn sulfide ore. (C) 2010 Elsevier By. All rights reserved.

Characterization of residential chimney conditions for flue gas flow measurements

A literature survey and a theoretical study were performed to characterize residential chimney conditions for flue gas flow measurements. The focus is on Pitot-static probes to give sufficient basis for the development and calibration of a velocity pressure averaging probe suitable for the continuous dynamic (i.e. non steady state) measurement of the low flow velocities present in residential chimneys. The flow conditions do not meet the requirements set in ISO 10780 and ISO 3966 for Pitot-static probe measurements, and the methods and their uncertainties are not valid. The flow velocities in residential chimneys from a heating boiler under normal operating condi-tions are shown to be so low that they in some conditions result in voiding the assumptions of non-viscous fluid justifying the use of the quadratic Bernoulli equation. A non-linear Reynolds number dependent calibration coefficient that is correcting for the viscous effects is needed to avoid significant measurement errors. The wide range of flow velocity during normal boiler operation also results in the flow type changing from laminar, across the laminar to turbulent transition region, to fully turbulent flow, resulting in significant changes of the velocity profile during dynamic measurements. In addition, the short duct lengths (and changes of flow direction and duct shape) used in practice are shown to result in that the measurements are done in the hydrodynamic entrance region where the flow velocity profiles most likely are neither symmetrical nor fully developed. A measurement method insensitive to velocity profile changes is thus needed, if the flow velocity profile cannot otherwise be determined or predicted with reasonable accuracy for the whole measurement range. Because of particulate matter and condensing fluids in the flue gas it is beneficial if the probe can be constructed so that it can easily be taken out for cleaning, and equipped with a locking mechanism to always ensure the same alignment in the duct without affecting the calibration. The literature implies that there may be a significant time lag in the measurements of low flow rates due to viscous effects in the internal impact pressure passages of Pitot probes, and the significance in the discussed application should be studied experimentally. The measured differential pressures from Pitot-static probes in residential chimney flows are so low that the calibration and given uncertainties of commercially available pressure transducers are not adequate. The pressure transducers should be calibrated specifically for the application, preferably in combination with the probe, and the significance of all different error sources should be investigated carefully. Care should be taken also with the temperature measurement, e.g. with averaging of several sensors, as significant temperature gradients may be present in flue gas ducts.

Morfologia radicular e suprimento de potássio às raízes de milheto de acordo com a disponibilidade de água e potássio

O milheto (Pennisetum glaucum) é cultivado em épocas com deficiência hídrica, o que pode afetar a absorção de K. Este trabalho visou quantificar a importância de potenciais de água do solo (-0,03; -0,05; -0,10 e -0,50 MPa), associados a doses de potássio (15 e 120 mg dm-3 de K) na morfologia radicular e nos processos de transporte de K às raízes de milheto. O experimento foi realizado em Botucatu (SP), em casa de vegetação. O milheto foi cultivado até 28 dias após a emergência, quando foram avaliados a fitomassa produzida e os teores de K, assim como a morfologia radicular. Foi estimada a contribuição do fluxo de massa e da difusão para o transporte de K no solo. Independentemente da dose de potássio e do teor de água no solo, a difusão foi o principal mecanismo de transporte de K até as raízes do milheto. Houve maior contribuição relativa do fluxo de massa, que correspondeu a 12 % do absorvido, na menor dose de potássio, contra 4 % na maior dose. Não houve efeito da disponibilidade hídrica nos mecanismos de transporte de K até as raízes do milheto.

Importância do fluxo de massa e difusão no suprimento de potássio ao algodoeiro como variável de água e potássio no solo

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estudo de uma coluna de absorção recheada para desidratação do gás natural utilizando microemulsão como absorvente

During natural gas processing, water removal is considered as a fundamental step in that combination of hydrocarbons and water favors the formation of hydrates. The gas produced in the Potiguar Basin (Brazil) presents high water content (approximately 15000 ppm) and its dehydration is achieved via absorption and adsorption operations. This process is carried out at the Gas Treatment Unit (GTU) in Guamaré (GMR), in the State of Rio Grande do Norte. However, it is a costly process, which does not provide satisfactory results when water contents as low as 0.5 ppm are required as the exit of the GTU. In view of this, microemulsions research is regarded as an alternative to natural gas dehydration activities. Microemulsions can be used as desiccant fluids because of their unique proprieties, namely solubilization enhancement, reduction in interfacial tensions and large interfacial area between continuous and dispersed phases. These are actually important parameters to ensure the efficiency of an absorption column. In this work, the formulation of the desiccant fluid was determined via phases diagram construction, employing there nonionic surfactants (RDG 60, UNTL L60 and AMD 60) and a nonpolar fluid provided by Petrobras GMR (Brazil) typically comprising low-molecular weight liquid hydrocarbons ( a solvent commonly know as aguarrás ). From the array of phases diagrams built, four representative formulations have been selected for providing better results: 30% RDG 60-70% aguarrás; 15% RDG 60-15% AMD 60-70% aguarrás, 30% UNTL L60-70% aguarrás, 15% UNTL L60-15% AMD 60-70% aguarrás. Since commercial natural gas is already processed, and therefore dehydrated, it was necessary to moister some sample prior to all assays. It was then allowed to cool down to 13ºC and interacted with wet 8-12 mesh 4A molecular sieve, thus enabling the generation of gas samples with water content (approximately 15000 ppm). The determination of the equilibrium curves was performed based on the dynamic method, which stagnated liquid phase and gas phase at a flow rate of 200 mL min-1. The hydrodynamic study was done with the aim of established the pressure drop and dynamic liquid hold-up. This investigation allowed are to set the working flow rates at 840 mL min-1 for the gas phase and 600 mLmin-1 for the liquid phase. The mass transfer study indicated that the system formed by UNTL L60- turpentine-natural gas the highest value of NUT

Ecological impacts from syngas burning in internal combustion engine: Technical and economic aspects

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A model to predict R134a refrigerant leakage through the radial clearance of rolling piston compressors

In this paper a non-isothermal two-phase model for oil-R134a refrigerant mixture flow is presented to predict the R134a leakage through the radial clearance of rolling piston compressors. The flow is divided in a liquid single-phase region and in a two-phase region, in which the homogeneous model is used to simulate the flow. The refrigerant leakage is determined using the mixture mass flow rate and the refrigerant mass fraction variation along the flow. The results are obtained for inlet pressures varying from 200 to 700 kPa, inlet temperatures ranging from 40 to 60 degrees C, and minimal clearances between 10 and 60 mu m. The results are firstly compared to existing isothermal model data, showing that there is a significant difference between the leakage flow rates predicted by isothermal and non-isothermal models. Finally, a useful general equation for compressor designers is proposed to calculate the refrigerant leakage for a large range of operation conditions. (C) 2012 Elsevier Ltd and IIR. All rights reserved.

Mathematical modeling of the ester oil-refrigerant R134A mixture two-phase flow with foam formation through a small diameter tube

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Numerical analysis of refrigerant flow along non-adiabatic capillary tubes using a two-fluid model

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