## Dynamic Modelling and Simulation of (Pulsed and Stirred) Liquid-Liquid Extraction Columns using the Population Balance Equation

• The discrete nature of the dispersed phase (swarm of droplet) in stirred and pulsed liquid-liquid extraction columns makes its mathematical modelling of such complex system a tedious task. The dispersed phase is considered as a population of droplets distributed randomly with respect to their internal properties (such as: droplet size and solute concentration) at a specific location in space. Hence, the population balance equation has been emerged as a mathematical tool to model and describe such complex behaviour. However, the resulting model is too complicated. Accordingly, the analytical solution of such a mathematical model does not exist except for particular cases. Therefore, numerical solutions are resorted to in general. This is due to the inherent nonlinearities in the convective and diffusive terms as well as the appearance of many integrals in the source term. However, modelling and simulation of liquid extraction columns is not an easy task because of the discrete nature of the dispersed phase, which consist of population of droplets. The natural frame work for taking this into account is the population balance approach. In part of this doctoral thesis work, a rigours mathematical model based on the bivariate population balance frame work (the base of LLECMOD ‘‘Liquid-Liquid Extraction Column Module’’) for the steady state and dynamic simulation of pulsed (sieve plate and packed) liquid-liquid extraction columns is developed. The model simulates the coupled hydrodynamic and mass transfer for pulsed (packed and sieve plate) extraction columns. The model is programmed using visual digital FORTRAN and then integrated into the LLECMOD program. Within LLECMOD the user can simulate different types of extraction columns including stirred and pulsed ones. The basis of LLECMOD depends on stable robust numerical algorithms based on an extended version of a fixed pivot technique after Attarakih et al., 2003 (to take into account interphase solute transfer) and advanced computational fluid dynamics numerical methods. Experimental validated correlations are used for the estimation of the droplet terminal velocity in extraction columns based on single and swarm droplet experiments in laboratory scale devices. Additionally, recent published correlations for turbulent energy dissipation, droplet breakage and coalescence frequencies are discussed as been used in this version of LLECMOD. Moreover, coalescence model from literature derived from a stochastical description have been modified to fit the deterministic population model. As a case study, LLECMOD is used here to simulate the steady state performance of pulsed extraction columns under different operating conditions, which include pulsation intensity and volumetric flow rates are simulated. The effect of pulsation intensity (on the holdup, mean droplet diameter and solute concentration) is found to have more profound effect on systems of high interfacial tension. On the hand, the variation of volumetric flow rates have substantial effect on the holdup, mean droplet diameter and solute concentration profiles for chemical systems with low interfacial tension. Two chemical test systems recommended by the European Federation of Chemical Engineering (water-acetone (solute)-n-butyl acetate and water-acetone (solute)-toluene) and an industrial test system are used in the simulation. Model predictions are successfully validated against steady state and transient experimental data, where good agreements are achieved. The simulated results (holdup, mean droplet diameter and mass transfer profiles) compared to the experimental data show that LLECMOD is a powerful simulation tool, which can efficiently predict the dynamic and steady state performance of pulsed extraction columns. In other part of this doctoral thesis work, the steady state performance of extraction columns is studied taking into account the effect of dispersed phase inlet condition (light or heavy phase is dispersed) and the direction of mass transfer (from continuous to dispersed phase and vice versa) using the population balance framework. LLECMOD, a program that uses multivariate population balance models, is extended to take into account the direction of mass transfer and the dispersed phase inlet. As a case study, LLECMOD is used to simulate pilot plant RDC columns where the steady state mean flow properties (dispersed phase hold up and droplet mean diameter) and the solute concentration profiles are compared to the available experimental data. Three chemical systems were used: sulpholane–benzene–n-heptane, water–acetone–toluene and water–acetone–n-butyl acetate. The dispersed phase inlet and the direction of mass transfer as well as the chemical system physical properties are found to have profound effect on the steady state performance of the RDC column. For example, the mean droplet diameter is found to persist invariant when the heavy phase is dispersed and the extractor efficiency is higher when the direction of mass transfer is from the continuous to the dispersed phase. For the purpose of experimental validation, it is found that LLECMOD predictions are in good agreement with the available experimental data concerning the dispersed phase hold up, mean droplet diameter and solute concentration profiles in both phases. In a further part of this doctoral thesis, a mathematical model is developed for liquid extraction columns based on the multivariate population balance equation (PBE) and the primary secondary particle method (PSPM) introduced by Attarakih, 2010 (US Patent Application: 0100106467). It is extended to include the momentum balance for the dispersed phase. The advantage of momentum balance is to eliminate the need for often conflicting correlations used in estimating the terminal velocity of single and swarm of droplets. The resulting mathematical model is complex due to the integral nature of the population balance equation. To reduce the complexity of this model, while maintaining most of the information drawn from the continuous population balance equation, the concept of the PSPM is used. Based on the multivariate population balance equation and the PSPM a mathematical model is developed for any liquid extraction column. The secondary particle could be envisaged as a fluid particle carrying information about the distribution as it is evolved in space and time, in the meanwhile the primary particles carry the mean properties of the population such as total droplet concentration; mean droplet diameter dispersed phase hold up and so on. This information reflects the particle-particle interactions (breakage and coalescence) and transport (convection and diffusion). The developed model is discretized in space using a first-order upwind method, while semi-implicit first-order scheme in time is used to simulate a pilot plant RDC extraction column. Here the effect of the number of primary particles (classes) on the final predicted solution is investigated. Numerical results show that the solution converge fast even as the number of primary particle is increased. The terminal droplet velocity of the individual primary particle is found the most sensitive to the number of primary particles. Other mean population properties like the droplet mean diameter, mean hold up and the concentration profiles are also found to converge along the column height by increasing the number of primary particles. The predicted steady state profiles (droplet diameter, holdup and the concentration profiles) along a pilot RDC extraction column are compared to the experimental data where good agreement is achieved. In addition to this a robust rigorous mathematical model based on the bivariate population balance equation is developed to predict the steady state and dynamic behaviour of the interacting hydrodynamics and mass transfer in Kühni extraction columns. The developed model is extended to include the momentum balance for the calculation of the droplet velocity. The effects of step changes in the important input variables (such as volumetric flow rates, rotational speed, inlet solute concentrations etc.) on the output variables (dispersed phase holdup, mean droplet diameter and the concentration profiles) are investigated. The last topic of this doctoral thesis is developed to transient problems. The unsteady state analysis reveals the fact that the largest time constant (slowest response) is due to the mass transfer. On the contrary, the hydrodynamic response of the dispersed phase holdup is very fast when compared to the mass transfer due to the relative fast motion of the dispersed droplets with respect to the continuous phase. The dynamic behaviour of the dispersed and continuous phases shows a lag time that increases away from the feed points of both phases. Moreover, the solute concentration response shows a highly nonlinear behaviour due to both positive and negative step changes in the input variables. The simulation results are in good agreement with the experimental ones and show the usefulness of the model.

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Author: Moutasem Jaradat urn:nbn:de:hbz:386-kluedo-32685 Han-Jörg Bart Doctoral Thesis English 2012/09/20 2012 Technische Universität Kaiserslautern Technische Universität Kaiserslautern 2012/09/14 2012/09/25 106 Fachbereich Maschinenbau und Verfahrenstechnik 6 Technik, Medizin, angewandte Wissenschaften / 66 Chemische Verfahrenstechnik / 660 Chemische Verfahrenstechnik Standard gemäß KLUEDO-Leitlinien vom 10.09.2012

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