Mass transfer liquid extraction

The aim of extraction is to promote mass transfer or extraction reaction between two phases (a mutually insoluble liquid-liquid system) by dispersing one liquid phase in another. In principle, creating a larger interface area in this operation is advantageous. However, it is necessary to consider that interface phenomena depend on the type of system. Extractors are classified into three types ... 

The properties of supercritical fluids that make them useful chromatographic mobile phases also make their use as extraction solvents an attractive option for polymer analysis. The low viscosities and high solute diffusivities allow efficient mass transfer during extraction, and the relatively low extraction temperatures reduce the risk of analyte degradation. Thus, the extraction of polymer additives from polymer matrices by using supercritical fluids has many advantages over conventional liquid solvent extraction, with the potential of higher recoveries and shorter analysis times. The further combination... 

Liquid 2 is introduced through the bore of the porous hollow fibers from one end and flows out to the other side, in effective countercurrent flow to liquid However, locally on both sides of the baffle, liquid ti is in crossflow around each hollow fiber and therefore around liquid 4-Since crossflow introduces very efficient liquid-phase mass transfer at a low Reynolds number in such systems, it is preferable to introduce that liquid phase to the shell side whose resistance is likely to control the mass-transfer/ solvent extraction rate. Further, the liquid phase wetting the pores of the membrane should prefereably be the lower resistance phase. These considerations are described in detail in Prasad and Sirkar (2001) for both porous hydro-phobic as well as porous hydrophilic membranes. 

Sedimentation is also used for other purposes. For example, relative motion of particles and Hquid iacreases the mass-transfer coefficient. This motion is particularly useful ia solvent extraction ia immiscible Hquid—Hquid systems (see Extraction, liquid-liquid). An important commercial use of sedimentation is ia continuous countercurrent washing, where a series of continuous thickeners is used ia a countercurrent mode ia conjunction with reslurrying to remove mother liquor or to wash soluble substances from the soHds. Most appHcations of sedimentation are, however, ia straight sohd—Hquid separation. 

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. 

The other common objective for calculating the number of countercurrent theoretical stages (or mass-transfer units) is to evaluate the performance of hquid-liquid extraction test equipment in a pilot plant or to evaluate production equipment in an industrial plant. Most liq-uid-hquid extraction equipment in common use can oe designed to achieve the equivalent of 1 to 8 theoretical countercurrent stages, with some designed to achieve 10 to 12 stages. 

For liquid/liquid extraction, data on mass transfer rate of the system at typical operating conditions are required. Also required are an applicable liquid/liquid equilibrium curve and data on chemical reactions occurring after mass transfer in the mixer. 

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. 

The theoretical treatment which has been developed in Sections 10.2-10.4 relates to mass transfer within a single phase in which no discontinuities exist. In many important applications of mass transfer, however, material is transferred across a phase boundary. Thus, in distillation a vapour and liquid are brought into contact in the fractionating column and the more volatile material is transferred from the liquid to the vapour while the less volatile constituent is transferred in the opposite direction this is an example of equimolecular counterdiffusion. In gas absorption, the soluble gas diffuses to the surface, dissolves in the liquid, and then passes into the bulk of the liquid, and the carrier gas is not transferred. In both of these examples, one phase is a liquid and the other a gas. In liquid -liquid extraction however, a solute is transferred from one liquid solvent to another across a phase boundary, and in the dissolution of a crystal the solute is transferred from a solid to a liquid. 

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. 

In a liquid-liquid extraction unit, spherical drops of solvent of uniform size are continuously fed to a continuous phase of lower density which is flowing vertically upwards, and hence countercurrently with respect to the droplets. The resistance to mass transfer may be regarded as lying wholly within the drops and the penetration theory may be applied. The upward velocity of the liquid, which may be taken as uniform over the cross-section of the vessel, is one-half of the terminal falling velocity of the droplets in the still liquid. 

Liquid-gas-solids mixing 275 Liquid-liquid extraction, mass transfer 599 Liquid metals, heat transfer 523 meters 269... 

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). 

Experimental gas-solid mass-transfer data have been obtained for naphthalene in CO2 to develop correlations for mass-transfer coefficients [Lim, Holder, and Shah, Am. Chem. Soc. Symp. Ser, 406, 379 (1989)]. The mass-transfer coefficient increases dramatically near the critical point, goes through a maximum, and then decreases gradually. The strong natural convection at SCF conditions leads to higher mass-transfer rates than in liquid solvents. A comprehensive mass-transfer model has been developed for SCF extraction from an aqueous phase to CO2 in countercurrent columns [Seibert and Moosberg, Sep. Sci. Techrwl, 23, 2049 (1988) Brunner, op. cit.]. 

The archetypal, stagewise extraction device is the mixer-settler. This consists essentially of a well-mixed agitated vessel, in which the two liquid phases are mixed and brought into intimate contact to form a two phase dispersion, which then flows into the settler for the mechanical separation of the two liquid phases by continuous decantation. The settler, in its most basic form, consists of a large empty tank, provided with weirs to allow the separated phases to discharge. The dispersion entering the settler from the mixer forms an emulsion band, from which the dispersed phase droplets coalesce into the two separate liquid phases. The mixer must adequately disperse the two phases, and the hydrodynamic conditions within the mixer are usually such that a close approach to equilibrium is obtained within the mixer. The settler therefore contributes little mass transfer function to the overall extraction device. 

This section concerns the modelling of countercurrent flow, differential mass transfer applications, for both steady-state and non-steady-state design or simulation purposes. For simplicity, the treatment is restricted to the case of a single solute, transferring between two inert phases, as in the standard treatments of liquid-liquid extraction or gas absorption column design. 

Chapter 3 concerns the dynamic characteristics of stagewise types of equipment, based on the concept of the well-stirred tank. In this, the various types of stirred-tank chemical reactor operation are considered, together with allowance for heat effects, non-ideal flow, control and safety. Also included is the modelling of stagewise mass transfer applications, based on liquid-liquid extraction, gas absorption and distillation. 

Although the Lewis cell was introduced over 50 years ago, and has several drawbacks, it is still used widely to study liquid-liquid interfacial kinetics, due to its simplicity and the adaptable nature of the experimental setup. For example, it was used recently to study the hydrolysis kinetics of -butyl acetate in the presence of a phase transfer catalyst [21]. Modeling of the system involved solving mass balance equations for coupled mass transfer and reactions for all of the species involved. Further recent applications of modified Lewis cells have focused on stripping-extraction kinetics [22-24], uncatalyzed hydrolysis [25,26], and partitioning kinetics [27]. 

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. 

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