Modeling reaction kinetics and mass transfer in ozonation in water solutions

This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

Kinetic aspects of ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: A combined electrical and mass transfer functions approach

The present paper quantifies and develops the kinetic aspects involved in the mechanism of interplay between electron and ions presented elsewhere(1) for KhFek[Fe(CN)(6)](l)center dot mH(2)O (Prussian Blue) host materials. Accordingly, there are three different electrochemical processes involved in the PB host materials: H3O+, K+, and H+ insertion/extraction mechanisms which here were fully kinetically studied by means of the use of combined electronic and mass transfer functions as a tool to separate all the processes. The use of combined electronic and mass transfer functions was very important to validate and confirm the proposed mechanism. This mechanism allows the electrochemical and chemical processes involved in the KhFek[Fe(CN)(6)](l)center dot mH(2)O host and Prussian Blue derivatives to be understood. In addition, a formalism was also developed to consider superficial oxygen reduction. From the analysis of the kinetic processes involved in the model, it was possible to demonstrate that the processes associated with K+ and H+ exchanges are reversible whereas the H3O+ insertion process was shown not to present a reversible pattern. This irreversible pattern is very peculiar and was shown to be related to the catalytic proton reduction reaction. Furthermore, from the model, it was possible to calculate the number density of available sites for each intercalation/deintercalation processes and infer that they are very similar for K+ and H+. Hence, the high prominence of the K+ exchange observed in the voltammetric responses has a kinetic origin and is not related to the amount of sites available for intercalation/deintercalation of the ions.

Hydrodynamics and mass transfer coefficient in activated sludge aerated stirred column reactor: Experimental analysis and modeling

The aerated stirred reactor (ASR) has been widely used in biochemical and wastewater treatment processes. The information describing how the activated sludge properties and operation conditions affect the hydrodynamics and mass transfer coefficient is missing in the literature. The aim of this study was to investigate the influence of flow regime, superficial gas velocity (U-G), power consumption unit (P/V-L), sludge loading, and apparent viscosity (pap) of activated sludge fluid on the mixing time (t(m)), gas hold-up (epsilon), and volumetric mass transfer coefficient (kLa) in an activated sludge aerated stirred column reactor (ASCR). The activated sludge fluid performed a non-Newtonian rheological behavior. The sludge loading significantly affected the fluid hydrodynamics and mass transfer. With an increase in the UG and P/V-L, the epsilon and k(L)a increased, and the t(m), decreased. The E, kLa, and tm,were influenced dramatically as the flow regime changed from homogeneous to heterogeneous patterns. The proposed mathematical models predicted the experimental results well under experimental conditions, indicating that the U-G, P/V-L, and mu(ap) had significant impact on the t(m) epsilon, and k(L)a. These models were able to give the tm, F, and kLa values with an error around +/- 8%, and always less than +/- 10%. (c) 2005 Wiley Periodicals, Inc.

Hydrodynamics and mass transfer coefficient in three-phase air-lift reactors containing activated sludge

This study was to investigate the impacts of operating conditions and liquid properties on the hydrodynamics and volumetric mass transfer coefficient in activated sludge air-lift reactors. Experiments were conducted in internal and external air-lift reactors. The activated sludge liquid displayed a non-Newtonian rheological behavior. With an increase in the superficial gas velocity, the liquid circulation velocity, gas holdup and mass transfer coefficient increased, and the gas residence time decreased. The liquid circulation velocity, gas holdup and the mass transfer coefficient decreased as the sludge loading increased. The flow regime in the activated sludge air-lift reactors had significant effect on the liquid circulation velocity and the gas holdup, but appeared to have little impact on the mass transfer coefficient. The experimental results in this study were best described by the empirical models, in which the reactor geometry, superficial gas velocity and/or power consumption unit, and solid and fluid properties were employed. (c) 2006 Elsevier B.V. All rights reserved.

Direct numerical simulation of turbulent flow and mass transfer around a rotating circular cylinder

Turbulent flow around a rotating circular cylinder has numerous applications including wall shear stress and mass-transfer measurement related to the corrosion studies. It is also of interest in the context of flow over convex surfaces where standard turbulence models perform poorly. The main purpose of this paper is to elucidate the basic turbulence mechanism around a rotating cylinder at low Reynolds numbers to provide a better understanding of flow fundamentals. Direct numerical simulation (DNS) has been performed in a reference frame rotating at constant angular velocity with the cylinder. The governing equations are discretized by using a finite-volume method. As for fully developed channel, pipe, and boundary layer flows, a laminar sublayer, buffer layer, and logarithmic outer region were observed. The level of mean velocity is lower in the buffer and outer regions but the logarithmic region still has a slope equal to the inverse of the von Karman constant. Instantaneous flow visualization revealed that the turbulence length scale typically decreases as the Reynolds number increases. Wavelet analysis provided some insight into the dependence of structural characteristics on wave number. The budget of the turbulent kinetic energy was computed and found to be similar to that in plane channel flow as well as in pipe and zero pressure gradient boundary layer flows. Coriolis effects show as an equivalent production for the azimuthal and radial velocity fluctuations leading to their ratio being lowered relative to similar nonrotating boundary layer flows.

The hydrodynamic behaviour and mass transfer characteristics of single droplets in a pulsed sieve plate column

The literature relating to the performance of pulsed sieve plate liquid-liquid extraction columns and the relevant hydrodynamic phenomenon have been surveyed. Hydrodynamic behaviour and mass transfer characteristics of droplets in turbulent and non-turbulent conditions have also been reviewed. Hydrodynamic behaviour, i.e. terminal and characteristic velocity of droplets, droplet size and droplet breakup processes, and mass transfer characteristics of single droplets (d≤0.6 cm) were investigated under pulsed (mixer-settler & transitional regimes) and non-pulsed conditions in a 5.0 cm diameter, 100 cm high, pulsed sieve plate column with three different sieve plate types and variable plate spacing. The system used was toluene (displaced) - acetone - distilled water. Existing photographic techniques for following and recording the droplet behaviour, and for observing the parameters of the pulse and the pulse shape were further developed and improved. A unique illumination technique was developed by which a moving droplet could be photographed using cine or video photography with good contrast without using any dye. Droplet size from a given nozzle and droplet velocity for a given droplet diameter are reduced under pulsing condition, and it was noted that this effect is enhanced in the presence of sieve plate. The droplet breakup processes are well explained by reference to an impact-breakup mechanism. New correlations to predict droplet diameter based on this mechanism are given below.vskip 1.0cm or in dimensionless groups as follows:- (We)crit= 3.12 - 1.79 (Eo)crit A correlation based on the isotropic turbulence theory was developed to calculate droplet diameter in the emulsion regime.vskip 1.0cm Experimental results show that in the mixer-settler and transitional regimes, pulsing parameters had little effect on the overall dispersed phase mass transfer coefficient during the droplet formation and unhindered travel periods.

Mass transfer in fluidized bed drying of moist particulate

Bubbling fluidized bed technology is one of the most effective mean for interaction between solid and gas flow, mainly due to its good mixing and high heat and mass transfer rate. It has been widely used at a commercial scale for drying of grains such as in pharmaceutical, fertilizers and food industries. When applied to drying of non-pours moist solid particles, the water is drawn-off driven by the difference in water concentration between the solid phase and the fluidizing gas. In most cases, the fluidizing gas or drying agent is air. Despite of the simplicity of its operation, the design of a bubbling fluidized bed dryer requires an understanding of the combined complexity in hydrodynamics and the mass transfer mechanism. On the other hand, reliable mass transfer coefficient equations are also required to satisfy the growing interest in mathematical modelling and simulation, for accurate prediction of the process kinetics. This chapter presents an overview of the various mechanisms contributing to particulate drying in a bubbling fluidized bed and the mass transfer coefficient corresponding to each mechanism. In addition, a case study on measuring the overall mass transfer coefficient is discussed. These measurements are then used for the validation of mass transfer coefficient correlations and for assessing the various assumptions used in developing these correlations.

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.

Unsteady buoyancy driven flows and heat transfer through coupled thermal boundary layers in a partitioned triangular enclosure

A numerical investigation has been carried out for the coupled thermal boundary layers on both sides of a partition placed in an isosceles triangular enclosure along its middle symmetric line. The working fluid is considered as air which is initially quiescent. A sudden temperature difference between two zones of the enclosure has been imposed to trigger the natural convection. It is anticipated from the numerical simulations that the coupled thermal boundary layers development adjacent to the partition undergoes three distinct stages; namely an initial stage, a transitional stage and a steady state stage. Time dependent features of the coupled thermal boundary layers as well as the overall natural convection flow in the partitioned enclosure have been discussed and compared with the non-partitioned enclosure. Moreover, heat transfer as a form of local and overall average Nusselt number through the coupled thermal boundary layers and the inclined walls is also examined.