Extraction processes mass transfer

The critical temperature of pure CO2 is 31°C [7]. For the subcritical range of 31-50°C, the fluid entering the extraction cell will consist of two phases - a liquid methanol phase and a supercritical phase. It has been reported that the diffusivity of liquid is about 10-100 times smaller than that of the supercritical fluid [6] and this implies that the difficulty of mass transfer associated with the former is also magnified by the same factor. In an extraction process, mass transfer occurs during 1) the fluid s penetration of the matrix s pores and 2) the subsequent transport of the analyte (solute) from the matrix into the bulk fluid [6]. The presence of entrained liquid methanol droplets will thus greatly increases the amount of mass transfer resistance present in the system. Such resistance is reduced upon an increase in temperature and this accounts for the rise in extraction efficiency observed in the temperature range of 45-50°C. 

With increasing density, the extraction rate increases at constant temperature. Density is responsible for the capacity and solvent power of a solvent, as the solubility of a compound rises wiA increasing density. In the extraction process, mass transfer is also of importance. Therefore, the extraction results will be different for the sanie density at different temperatures. 

The third fundamental transfer process, mass transfer, occurs in distillation, absorption, drying, liquid-liquid extraction, adsorption, and membrane processes. When mass is being transferred from one distinct phase to aiiother or through a single phase, the basic mechanisms are the same whether the phase is a gas, liquid, or solid. This was also shown in heat transfer, where the transfer of heat by conduction followed Fourier s law in a gas, solid, or liquid. 

In addition to extractive reaction, mass transfer is another important influence factor in the extraction process. When the mass transfer reached a stable state, the whole systems can keep a dynamic balance. The mass transfer happened between the aqueous phase and ILs, and the extraction kinetics interface of RE"" (n = 3 or 4) in ILs was shown in Fig. 5.6. Because the mass transfer rate also affects the extraction rate, the rate of RE " extraction is determined both by the chemical reaction rate and the mass transfer rate. Which one is more important in the two main factors is up to the experimental conditions. 

Diffusion and Mass Transfer During Leaching. Rates of extraction from individual particles are difficult to assess because it is impossible to define the shapes of the pores or channels through which mass transfer (qv) has to take place. However, the nature of the diffusional process in a porous soHd could be illustrated by considering the diffusion of solute through a pore. This is described mathematically by the diffusion equation, the solutions of which indicate that the concentration in the pore would be expected to decrease according to an exponential decay function. 

Chemistry. Chemical separation is achieved by countercurrent Hquid— Hquid extraction and involves the mass transfer of solutes between an aqueous phase and an immiscible organic phase. In the PUREX process, the organic phase is typically a mixture of 30% by volume tri- -butyl phosphate (solvent) and a normal paraffin hydrocarbon (diluent). The latter is typically dodecane or a high grade kerosene (20). A number of other solvent or diluent systems have been investigated, but none has proved to be a substantial improvement (21). 

The separation of components by liquid-liquid extraction depends primarily on the thermodynamic equilibrium partition of those components between the two liquid phases. Knowledge of these partition relationships is essential for selecting the ratio or extraction solvent to feed that enters an extraction process and for evaluating the mass-transfer rates or theoretical stage efficiencies achieved in process equipment. Since two liquid phases that are immiscible are used, the thermodynamic equilibrium involves considerable evaluation of nonideal solutions. In the simplest case a feed solvent F contains a solute that is to be transferred into an extraction solvent S. 

The main objective for calculating the number of theoretical stages (or mass-transfer units) in the design of a hquid-liquid extraction process is to evaluate the compromise between the size of the equipment, or number of contactors required, and the ratio of extraction solvent to feed flow rates required to achieve the desired transfer of mass from one phase to the other. In any mass-transfer process there can be an infinite number of combinations of flow rates, number of stages, and degrees of solute transfer. The optimum is governed by economic considerations. 

In processing, it is frequently necessary to separate a mixture into its components and, in a physical process, differences in a particular property are exploited as the basis for the separation process. Thus, fractional distillation depends on differences in volatility. gas absorption on differences in solubility of the gases in a selective absorbent and, similarly, liquid-liquid extraction is based on on the selectivity of an immiscible liquid solvent for one of the constituents. The rate at which the process takes place is dependent both on the driving force (concentration difference) and on the mass transfer resistance. In most of these applications, mass transfer takes place across a phase boundary where the concentrations on either side of the interface are related by the phase equilibrium relationship. Where a chemical reaction takes place during the course of the mass transfer process, the overall transfer rate depends on both the chemical kinetics of the reaction and on the mass transfer resistance, and it is important to understand the relative significance of these two factors in any practical application. 

In this process, the two streams flow countercurrently through the column and undergo a continuous change in composition. At any location are in dynamic rather than thermodynamic equilibium. Such processes are frequently carried out in packed columns, in which the liquid (or one of the two liquids in the case of a liquid-liquid extraction process) wets die surface of the packing, thus increasing the interfacial area available for mass transfer and, in addition, promoting high film mass transfer coefficients within each phase. 

Micro reactors permit high-throughput screening of process chemistries imder controlled conditions, unlike most conventional macroscopic systems [2], In addition, extraction of kinetic parameters from sensor data is possible, as heat and mass transfer can be fully characterized due to the laminar-flow condihons applied. More uniform thermal condihons can also be utilized. Further, reactor designs can be developed in this way that have specific research and development funchons. 

Extraction can be performed in stirred tanks if the process proceeds fast and separation of phases is ea.sy, but column extractors are most commonly used. The column can be filled with a particulate material. The liquids flow countercurrently whereby the flow can be uniform or pulsed. Reciprocated and rotary agitators are often used to enhance mass transfer. An example of the latter type is shown in Fig. 7.2-13 (asymmetric rotating disk (ARD) extractor). 

A countercurrent extraction cascade with reaction A + B C was considered by Ingham and Dunn (1974), as shown in Fig. 3.40. The reaction takes place between a solute A in the L-phase, which is transferred to the G-phase by the process of mass transfer, where it then reacts with a second component, B, also in the G-phase, to form an inert product, C. 

The problems relating to mass transfer may be elucidated out by two clear-cut yet different methods one using the concept of equilibrium stages, and the other built on diffusional rate processes. The selection of a method depends on the type of device in which the operation is performed. Distillation (and sometimes also liquid extraction) are carried out in equipment such as mixer settler trains, diffusion batteries, or plate towers which contain a series of discrete processing units, and problems in these spheres are usually solved by equilibrium-stage calculation. Gas absorption and other operations which are performed in packed towers and similar devices are usually dealt with utilizing the concept of a diffusional process. All mass transfer calculations, however, involve a knowledge of the equilibrium relationships between phases. 

In the simplest cases, the solvent may consist of one specified component, although in fact in a steady-state cyclic process it is highly unlikely that the solvent will ever come back to the initial composition at time zero. Rather, perhaps, one can say that make-up will entail addition of one material only. Again, clearly this need not be a pure compound, but its composition should be consistent. The single solvent offers limited scope for manipulating the system since it alone must meet all process and operational requirements. In other words, it must satisfy all aspects that will lead to an overall viable system. These aspects include selectivity, capacity, solubility, mass transfer, phase separation, costs, among others. The solvent is, therefore, a mixture components. The solvent components are extractant, (ii) diluent, (iii) modifier, and (iv) synergist. 

Various models of SFE have been published, which aim at understanding the kinetics of the processes. For many dynamic extractions of compounds from solid matrices, e.g. for additives in polymers, the analytes are present in small amounts in the matrix and during extraction their concentration in the SCF is well below the solubility limit. The rate of extraction is then not determined principally by solubility, but by the rate of mass transfer out of the matrix. Supercritical gas extraction usually falls very clearly into the class of purely diffusional operations. Gere et al. [285] have reported the physico-chemical principles that are the foundation of theory and practice of SCF analytical techniques. The authors stress in particular the use of intrinsic solubility parameters (such as the Hildebrand solubility parameter 5), in relation to the solubility of analytes in SCFs and optimisation of SFE conditions. 

In order to increase the overall extraction efficiency during SFE sonication has been applied [352]. Ultrasound creates intense sinusoidal variations in density and pressure, which improve solute mass transfer. Development of an SFE method is a time-consuming process. For new methods, analysts should refer the results to a traditional sample preparation method such as Soxhlet or LLE. 

The efficiency of extraction is mainly dependent on temperature as it influences physical properties of the sample and its interaction with the liquid phase. The extraction is influenced by the surface tension of the solvent and its penetration into the sample (i.e. its viscosity) and by the diffusion rate and solubility of the analytes all parameters that are normally improved by a temperature increase. High temperature increases the rate of extraction. Lou et al. [122] studied the kinetics of mass transfer in PFE of polymeric samples considering that the extraction process in PFE consists of three steps ... 

Diffusion coefficients are needed in the design of mass transfer processes such as gas absorption, distillation and liquid-liquid extraction. 

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