Computer simulation of liquid flow patterns on distillation trays

This thesis describes work carried out to improve the fundamental modelling of liquid flows on distillation trays. A mathematical model is presented based on the principles of computerised fluid dynamics. It models the liquid flow in the horizontal directions allowing for the effects of the vapour through the use of an increased liquid turbulence, modelled by an eddy viscosity, and a resistance to liquid flow caused by the vapour being accelerated horizontally by the liquid. The resultant equations are similar to the Navier-Stokes equations with the addition of a resistance term.A mass-transfer model is used to calculate liquid concentration profiles and tray efficiencies. A heat and mass transfer analogy is used to compare theoretical concentration profiles to experimental water-cooling data obtained from a 2.44 metre diameter air-water distillation simulation rig. The ratios of air to water flow rates are varied in order to simulate three pressures: vacuum, atmospheric pressure and moderate pressure.For simulated atmospheric and moderate pressure distillation, the fluid mechanical model constantly over-predicts tray efficiencies with an accuracy of between +1.7% and +11.3%. This compares to -1.8% to -10.9% for the stagnant regions model (Porter et al. 1972) and +12.8% to +34.7% for the plug flow plus back-mixing model (Gerster et al. 1958). The model fails to predict the flow patterns and tray efficiencies for vacuum simulation due to the change in the mechanism of liquid transport, from a liquid continuous layer to a spray as the liquid flow-rate is reduced. This spray is not taken into account in the development of the fluid mechanical model. A sensitivity analysis carried out has shown that the fluid mechanical model is relatively insensitive to the prediction of the average height of clear liquid, and a reduction in the resistance term results in a slight loss of tray efficiency. But these effects are not great. The model is quite sensitive to the prediction of the eddy viscosity term. Variations can produce up to a 15% decrease in tray efficiency. The fluid mechanical model has been incorporated into a column model so that statistical optimisation techniques can be employed to fit a theoretical column concentration profile to experimental data. Through the use of this work mass-transfer data can be obtained.

Chloride resistance and durability of cement paste and concrete containing metakaolin

Metakaolin (MK), a calcined clay, was included as a partial cement replacement material, at up to 20% by weight of binder, in cement pastes and concrete, and its influence on the resistance to chloride ingress investigated. Reductions in effective chloride diffusion coefficients through hardened cement paste were obtained for binary blends and by combining OPC, MK and a second cement replacement material of pulverised fuel ash or ground granulated blast furnace slag. Steady state oxygen diffusion measurements through hardened cement pastes measured using an electrochemical cell showed that the interaction between charged species and the pore surfaces is a major factor in determining chloride diffusion rate. Rheology of the binder, particularly at high MK replacement levels, was found to have a dramatic influence on the diffusion performance of cement pastes. It was concluded that plasticising admixtures are essential for adequate dispersion of MK in cement pastes. Chloride concentration profile analysis of the concrete cylinders, exposed to sodium chloride solution for one year, was employed to obtain apparent chloride diffusion coefficients for concrete specimens. MK was found to reduce the depth of chloride penetration into concrete when compared with that of unblended mixes. Corrosion rate and corrosion potential measurements were taken on steel bars embedded in concrete exposed to a saline environment under conditions of cyclic wetting and drying. The initiation time for corrosion was found to be significantly longer for MK blended mixes than for plain OPC systems. The aggregate-paste interfacial zone of MK blended systems was investigated by steady state diffusion of chloride ions through mortar containing glass beads as model aggregate. For the model aggregate specimens tested the work confirmed the hypothesis that properties of the bulk paste are the controlling factors in ionic diffusion through mortar.

Hydrodynamics and mass transfer studies in a scheibel extractor

A 10 cm diameter four-stage Scheibel column with dispersed phase wetted packing sections has been constructed to study the hydrodynamics and mass transfer using the system toluene-acetone-water. The literature pertaining to the above extractor has been examined and the important phenomena such as droplet break-up and coalescence, mass transfer and backmixing have been reviewed. A critical analysis of the backmixing or axial mixing models and the corresponding techniques for parameter estimation was applied and an optimization technique based on Marquardt's algorithm was implemented. A single phase sampling technique was developed to estimate the acetone concentration profile in both phases along the column. Column flooding characteristics were investigated under various operating conditions and it was found that, when the impellers were located at about DI/5cm from the upper surface of the pads, the limiting flow rates increased with impeller speed. This unusual behaviour was explained in terms of the pumping effect created by the turbine impellers. Correlations were developed to predict Sauter mean drop diameters. A five-cell with backflow model was used to estimate the column performance (stage efficiency) and phases non-ideality (backflow parameters). Overall mass transfer coefficients were computed using the above model and compared with those calculated using the correlations based on single drop mechanism.

Prophylactic ranitidine treatment in critically ill children - a population pharmacokinetic study

Aims - To characterize the population pharmacokinetics of ranitidine in critically ill children and to determine the influence of various clinical and demographic factors on its disposition. Methods - Data were collected prospectively from 78 paediatric patients (n = 248 plasma samples) who received oral or intravenous ranitidine for prophylaxis against stress ulcers, gastrointestinal bleeding or the treatment of gastro-oesophageal reflux. Plasma samples were analysed using high-performance liquid chromatography, and the data were subjected to population pharmacokinetic analysis using nonlinear mixed-effects modelling. Results - A one-compartment model best described the plasma concentration profile, with an exponential structure for interindividual errors and a proportional structure for intra-individual error. After backward stepwise elimination, the final model showed a significant decrease in objective function value (−12.618; P < 0.001) compared with the weight-corrected base model. Final parameter estimates for the population were 32.1 l h−1 for total clearance and 285 l for volume of distribution, both allometrically modelled for a 70 kg adult. Final estimates for absorption rate constant and bioavailability were 1.31 h−1 and 27.5%, respectively. No significant relationship was found between age and weight-corrected ranitidine pharmacokinetic parameters in the final model, with the covariate for cardiac failure or surgery being shown to reduce clearance significantly by a factor of 0.46. Conclusions - Currently, ranitidine dose recommendations are based on children's weights. However, our findings suggest that a dosing scheme that takes into consideration both weight and cardiac failure/surgery would be more appropriate in order to avoid administration of higher or more frequent doses than necessary.

Aplicação do Na2S2O8, H2O2 e ferro na remediação de solos (latossolo e areia destrófica) contaminados com diesel

Environmental liabilities from accidents in the retail petroleum industry, especially in urban areas, have represented a serious problem whose impact reaches the underground, people's health and even economic losses with the remediation process. In U.S.A. are estimated hundreds of billions of dollars invested in soil remediation processes. The results of the reports and investigative reports of liabilities in fuel stations distributed in the urban area of Natal-RN were used to estimate the local scenario of contamination. This database has been possible to determine the main contaminants (BTEX, PAHs, TOC), affected neighborhoods and types of potentially more impacted soils. Experiments were carried out in order to reverse contamination of this scenario, where the soil type was a factor in the planning, because it influences directly on the effectiveness of remediation techniques studied: Oxidation by hydrogen peroxide and oxidation by sodium persulphate. These oxidants are activated forming free radicals (HO•-, SO4 •-, HO2 • , O2 •-, S2O8 -2, etc) responsible for to mineralize the hydrocarbons and other organic compounds (releasing O2 e CO2). In the activation process, the ferrous ions (II) and ferric (III) were studied as well as hydrogen peroxide activation technique with sodium persulfate, the latter being presented the best efficiency among all the study, when activated with Fe+3. In addition to defining the most efficient technique, the aim of this study was to evaluate the influence of different soils among oxidative techniques, characterizing the effect of the concentration of these oxidants and also the concentration of the catalysts. Exists in most scenarios evaluated the presence of intrinsic total iron soil matrix. The so-called latosols present microaggregates reddish indicating the presence of these reactive species like iron and clayey aspect. The kinetic study was conducted by experimental design and monitoring of the percentage of total carbon (SSM-5000A) in the solid and liquid phases, knowing that 82.4% of the diesel molecule is carbon. Yet organic carbon and pH of liquid samples were analyzed for technical, characterizing the influence of soil type and its operating condition. The Fenton-like technique H2O2 e Fe+2 presented satisfactory oxidation, including sandy soil, but well below the best result. The sodium persulphate only activated with temperature, even in the most favorable soil, did not provide good efficiency. The best technique in the study had the concentration profile with 2,2x10- 1mol.L-1 of Na2S2O8 activated with 6,53x10-1mol.L-1 of H2O2 and 2,5x10-2 Fe3+mol.L-1 which reduced in less than a day 96 contamination in red soil, initially with 66,667 mg of diesel per kg of clean soil

(Table 1) Stable nitrogen isotopes of ammonium in interstitial waters from ODP Site 164-997

Ammonium (NH4+) concentration profiles in piston-core sediments of the Carolina Rise and Blake Ridge generally have linear concentration profiles within the sulfate reduction zone (Borowski, 1998). Deep Sea Drilling Project (DSDP) Site 533, located on the Blake Ridge, also displayed a linear ammonium concentration profile through the sulfate reduction zone and the profile linearity continues into the upper methanogenic zone to a depth of ~200 meters below seafloor (mbsf), where the first methane gas hydrates probably occur (Jenden and Gieskes, 1983, doi:10.2973/dsdp.proc.76.114.1983; Kvenvolden and Barnard, 1983, doi:10.2973/dsdp.proc.76.106.1983). Sediments from the Ocean Drilling Program (ODP) Leg 164 deep holes (Sites 994, 995, and 997) also exhibit linear ammonium profiles above the top of the gas hydrate zone (~200 mbsf) (Paull, Matsumoto, Wallace, et al., 1996, doi:10.2973/odp.proc.ir.164.1996). We hypothesized that a possible cause of linear ammonium profiles was diffusion of ammonium from a concentrated ammonium source at depth. We further reasoned that if this ammonium were produced by microbial fermentation reactions at depth, that a comparison of the nitrogen isotopic composition of sedimentary organic nitrogen and the nitrogen with pore-water ammonium would test this hypothesis. Convergence with depth of d15N values of the nitrogen source (sedimentary organic matter) and the nitrogen product (dissolved NH4+) would strongly suggest that ammonium was produced within a particular depth zone by microbial fermentation reactions. Here, we report d15N values of pore-water ammonium from selected interstitial water (IW) samples from Site 997, sampled during ODP Leg 164.

Propriedades tribomecânicas de superfícies de titânio carbonitretadas por plasma

Interstitial compounds of titanium have been mainly studied due to the large range of properties acquired when C, N, O and H atoms are added. In this work, surfaces of TiCxNy were produced by thermochemical treatments assisted by plasma with different proportions of Ar + N2 + CH4 gas mixture. The Ar gas flow was fixed in 4 sccm, varying only N2 and CH4 gas flows. During the thermochemical treatment, the plasma was monitored by Optical Emission Spectroscopy (OES) for the investigation of the influence of active species. After treatments, C and N concentration profile, crystalline and amorphous phases were analyzed by Nuclear Reaction (NRA). Besides tribomechanical properties of the Ti surface were studied through the nanohardness measurements and friction coefficient determination. The worn areas were evaluated by profilometry and Scanning Electronic Microscope (SEM) in order to verify the wear mechanism present in each material. It has been seen which the properties like nanohardness and friction coefficient have strong relation with luminous intensity of species of the plasma, suggesting a using of this characteristic as a parameter of process

Impacts of limestone and nitrogen top dressing application on the potassium content in the soil profile and marandu-grass leaf concentration

Objetivou-se avaliar os efeitos de nitrogênio (0, 100, 200, 300 e 400 kg/ha.ano), com ou sem aplicação de calcário dolomítico em cobertura, sobre o teor de potássio (K) do solo nas profundidades de 0 a 5; 5 a 10; e 10 a 20 cm e a concentração de potássio na planta. O experimento foi realizado em Latossolo Vermelho distroférrico de relevo suavemente ondulado, disposto em esquema fatorial 5 × 2, em blocos casualizados, com quatro repetições. A adubação nitrogenada promoveu aumento linear na concentração de potássio na planta e no teor desse mineral na camada de 0 a 5 cm do solo. Ocorreu efeito de inibição competitiva entre a absorção de potássio e cálcio e entre potássio e magnésio. Embora uma fração significativa de potássio retorne à camada superficial do solo pelo resíduo de forragem, em decorrência da maior produção de massa, o aumento da concentração de potássio na planta nas mais altas doses de nitrogênio comprova a importância do suprimento de potássio para a planta, por intensificar a massa de forragem.

Follicle profile and plasma gonadotropin concentration in pubertal female ponies

Twelve female ponies were examined daily for 30 days and classified as ovulating (OV; N = 6; 197 ± 6 kg) or prepubertal (PP; N = 6; 196 ± 9 kg). Follicles were detected by ultrasound and gonadotropins quantified by radioimmunoassay. The mean diameter of the largest follicles was significantly larger in OV (38 ± 1 mm) than in PP (26 ± 2 mm) but there was no difference between groups in the size of the second largest follicle. There were more small follicles (<24 mm) in the PP than in the OV group, but PP fillies had a smaller number of follicles >29 mm than the OV fillies. Follicle-stimulating hormone (FSH) levels did not differ between groups but PP fillies had lower luteinizing hormone (LH) peak (8 ± 1 ng/ml) and basal (4 ± 0.5 ng/ml) levels, lower peak magnitude (2 ± 0.2 ng/ml) and period average (5 ± 0.6 ng/ml) than OV fillies (32 ± 4.5, 8 ± 1.2, 17.1 ± 6, and 15 ± 2.3 ng/ml, respectively). The PP group, in contrast to the OV group, showed no relationship between FSH surge and follicle wave emergence. We conclude that an LH concentration higher than 8 ng/ml is needed for follicle growth to a preovulatory size. Wave emergence and FSH secretion seem to be independent events, probably due to an inhibitory neural system in these PP animals. PP fillies may provide a physiological model for the study of follicle wave emergence which apparently does not depend on gonadotropin levels.