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l i ANNUAL REVIEW
Liquid-Liquid Extraction Fundamental contributions to knowledge of mass transfer, hydrodynamics and drop interactions are spurring advances in extraction processes
PARMA N. VASHIST ROBERT B. BECKMANN
c
ontinuing the format begun in 1965 (4F), this year's '.' review of the liquid-liquid extraction literature is concerned with the contributions to the more fundamental aspects of the liquid-liquid extraction mass transfer operation for the two years 1965 and 1966. Last year's 58 ( l l ) , 97-103 (1966)] disreview [IND. END. CHEM. cussed equipment and process developments that were reported during 1964 and 1965 and these developments will be reviewed again next year for 1966 and 1967. During 1965 and 1966, the primary research emphasis seemed to be on improving the correlation and prediction methods for the molecular diffusion coefficients in liquid systems, analyzing the transport problems in single drop systems, and further trying to evaluate the interfacial and coupling problems that exist in mass transfer and equilibrium situations. Considerable progress has been made in evaluating the concentration effect on the molecular diffusion coefficient for both ideal and nonideal systems, but no definitive solution has been put forth for associated systems. The hydrodynamic and mass transfer problems within single drops continue to get wide attention, and Russian authors have been particularly active in showing the interrelationships between such studies and the mathematical modeling of extraction units; similarly, foreign authors are most active in studying interfacial and coupled phenomena in extraction processes. Backmixing and the lure of generalized VOL. 5 9
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correlations seem to dominate the fundamental research on equipment types. Some excellent reviews have appeared during 1965 and 1966 and these should be quite valuable to anyone active in the liquid-liquid extraction field. Molecular Diffusion Coefficients
The measurement, correlation, and interpretation of molecular diffusion data in liquid systems continue to receive a significant amount of research attention, with association and concentration effects being of dominant importance. Specific references relating to measurement techniques are (76A, 26.4, 30A, 40.4, 45A, 47A). Duclaux et al. (76.4) describe a flow technique utilizing a solution in laminar flow along the axis of a long tube and measure the changing interface concentration rates. Related to this method is the work of Gruen and Walz (26.4) who discuss the theory of induction time methods for the determination of diffusion coefficients and thermal conductivities. Huber and Van Vught (30A) present an elution-chromatographic technique, applicable to liquid or gaseous systems, and offer procedures for determining optimum operating conditions. Related to these moving fluid techniques is the work of Golay (24A) which points out the difficulties of using a static diffusion constant concept to account for molecular diffusion in moving liquid systems. Marcinkowsky and co-workers (40A) report on a porous frit method for measuring selfdiffusion and tracer diffusion coefficients. Rastas and Kivalo (47.4) have analyzed the immersion and concentration difference effects inherent in the use of the openend capillary tube method for measuring diffusion coefficients and recommend certain experimental modifications for improved results. Experimental diffusion coefficients, of particular interest to liquid-liquid extraction operations, have been reported by several authors and Table I shows the systems reported. I t should be borne in mind that the table is not an exhaustive listing and that many of the other articles referred to in this review (particularly those presenting correlations) will also present new experimental data on diffusion coefficients. Astarita (3A) has reported briefly on the diffusivity effects in non-Newtonian liquids, and Wendt (67A) presents diffusion data for strong and weak electrolytes in ternary systems. The correlation of diffusion coefficients has received excellent attention during the past two years, particularly in reconciling the dependence of the diffusion coefficient upon concentration. Eyring and co-workers (51.4) have applied the structure theory of liquids to the calculation of the diffusion coefficients in simple liquid systems, and Yao (64A) has used a nonequilibrium thermodynamic approach to discuss the thermodynamic restrictions on 72
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diffusion coefficients in ternary systems and to compare the different definitions of diffusion coefficients. Cullinan (70A) has made a general analysis of the flux equations for multicomponent diffusion and combined these equations with fundamental information from the thermodynamics of irreversible processes to provide a uniform basis for the definition of the diffusion process. Mathur and Thodos (41.4) use dimensional analysis and experimental data to arrive at a generalized expression for the self-diffusion coefficient in liquids. Their correlating equation is:
where (3 is a self-diffusivity modulus [(mol. wt.)'12 x (T,)5/6(Pc)1js] and T , and P, are the reduced temperature and pressure. The correlation is only valid for simple liquids and the above equation for liquids (for which no experimental data were available) was developed by modifying a similar correlation for simple, dense gases. King and co-workers (36A) correlate the self-diffusion coefficients for nonelectrolytes at high dilution through the following equation :
2 = 4.4 T
x
lo-*
AH,
where the subscripts u and u refer to the solute and solvent, respectively, V is the molal volume at the normal boiling point (cc./g. mole), and AH is the latent heat of vaporization (cal./g. mole) at the normal boiling point. D is in sq. cm./sec., 1-1 in centipoises, and T in degrees Kelvin. The correlation is limited to those cases where ( D p / T ) is less than 1.5 X 10-7 cp. sq. cm./'K. sec. Many authors, past and present, have tried to correlate the concentration effect on mutual diffusion coefficients on the basis that the diffusion-viscosity product divided by an activity correction factor should be a linear function of the mole fractions and the infinitely- dilute diffusion coefficient. Bidlack and Anderson (4A) have pointed out the difficulties of this approach for both associated and nonassociated systems. Rathbun and Babb (48A) present an empirical, power function modification of this approach for mixtures of associated and nonpolar liquids as follows:
where s is an empirical parameter. Vignes (60A) has shown that excellent correlation may be obtained by
TABLE I.
EXPERIMENTAL DIFFUSION M EASU R E M ENTS Binary Systems I. Solute Diffusion in Water: Acetic acid (29A), atmospheric gas components (62A), benzene and naphthalene derivatives (49A),carbon dioxide ( 5 7 4 59A), chloroacetic acid (ZZA), ethanol ( 97A), ethylene glycol ( 8 A ) , inorganic salts (73A, 78A, 29A, 28A, 39A), light hydrocarbons (62A, 6 3 A ) , mannitol ( 79A), methanol (39A), nitrous oxide (59A), N,N-dimethyl acetamide ( 7 A ) , sucrose ( 7 3 A , 7 4 A ) , urea ( Z A , 73A),and water (33A). 11. Solute Diffusion i n Aqueous Solutions: Antibiotics in saline solutions (23A), carbon dioxide in monoethanolamine solutions (58A), hydrogen or methane in electrolyte solutions ( 2 7 A ) , L-a-alanine or p-alanine in water solutions ( 7 A ) , phosphoric acid in phosphate solutions (ZOA), silver nitrate in silver nitrate solutions (3ZA), sucrose and mannitol in solution ( 4 4 A ) , and water in inorganic salt and ionic solutions ( 3 3 A , 424). 111. Solute Diffusion i n Paraffin, Naphthene, and Aromatic Hydrocarbon Solvents: Acetone in benzene ( 72A), benzene, cyclohexane, isooctane, and n-heptane self-diffusion ( 5 A ) , benzene in cyclohexane (34A),carbon tetrachloride and cyclohexane in cyclohexane ( 3 8 A ) , cyclohexane in benzene (54A), cyclohexane and polystyrene in toluene and cyclohexane (74A, 75A), noctane, methylcyclohexane, or 1-heptanol in methylcyclohexane, cyclohexanone, and 1-heptanol (53A), and npropanol in toluene (56A), paraffin hydrocarbon systems (4A, 25A, 5OA). IV. Solute Diffusion i n Miscellaneous Organic Solvents: Acetone ( 9 A ) , hexane ( 4 A ) , hydrogen, neon, and argon (&A), and trichloromethane ( 9 A ) ,all in carbon tetrachloride. Acetone-benzene-carbon tetrachloride binary pairs ( 12A). Trichloromethane in acetone ( 9 A ) , and helium, hydrogen, deuterium, neon, nitrogen and argon in perfluorotributylamine (46A). Benzene and naphthalene derivatives in dioxane, also benzene and phenylmethane in diethylene glycol (49A); naphthalene, biphenyl, and anthracene in dioxane-water, dimethylformamide, and anthracene ( 4 3 A ) . Polyacrylonitrile in dimethylformamide (55.4) and the binary pairs of the water-sucrose-glycerin system ( 79A). Atomic mercury in isooctane (37A) and silver nitrate in acetonitrile and benzonitrile ( 3 7 A ) .
which raises the infinitely dilute coefficients to a molefraction power before multiplying the product by the activity correction factor. The equation is for nonassociated solutions, ideal or nonideal. Although Vignes presents his development on a n empirical basis, Cullinan ( ? ? A ) has subsequently shown that a modification of Eyring’s “hole” model and absolute rate theory will lead to Vignes’ type of expression. I n general, this approach looks quite promising for interrelating diffusion and vapor-liquid equilibrium processes for nonassociated systems. Graue and Sage ( 2 5 A ) present two expressions suitable for calculating the Chapman-Cowling diffusion coefficients for liquid phase, binary, saturated hydrocarbon systems from methane through n-decane. Rhodes (52%) and King (35A) also discuss the concentration influence on mass transfer and the diffusion coefficient. T h e Annual Mass Transfer Reviews of Bischoff and Himmelblau (6A) for 1965 and 1966 also present some additional valuable references for recent work in this area. Droplet Behavior
The role of drops, singly or as assemblages in liquidliquid extraction has continued to receive increased research emphasis.
Wellek, Agrawal, and Skelland (4OB) present a relationship to predict the shape of nonoscillating liquid drops moving in liquid media from a knowledge of the physical properties of the Newtonian dispersed and continuous liquid phases, the droplet size, and relative droplet velocity. They found the deformation or eccentricity, E, a ratio of horizontal and vertical diameters of the drop, to be a function only of the Weber number and the viscosity ratio over the entire range of NRe (6.0 to 1345) and wide range of physical parameters. Princen and Mason (37B) have extended the theory governing the shape of a liquid drop floating in equilibrium at a horizontal fluid interface to some special cases and included the effect of the variation of physical properties. Matsunobu (24B) studied the motion of a deformed drop in Stokes flow to characterize the departure of the drop surface from a sphere by determining the flow fields, both external and internal to the drop. Raghavendra and Rao (32B)analyzed the momentum transfer for the case of assemblages of liquid drops falling through a stagnant column of an immiscible liquid. They correlated the motion of the drops (when falling in form of isolated assemblages in the same horizontal plane, or one behind the other a t a regular frequency in a single stream) in terms of the drag coefficient, the Reynolds number, the Weber number, a physical property group, and interference groups for the horizontal and the vertical planes. Valentas et al. (38B) have developed a mathematical model to relate the droplet breakup in a two-phase system to the distribution of droplet sizes. They found that the conservation equation leads to a n integral equation involving the influent distribution function, the vessel distribution function, and a Kernel describing the breakup mechanism. Olney (28B) used a photographic study of a rotating disk contactor to find the drop size distribution for different systems under varying flow conditions. H e confirms the existence of a fairly wide distribution of drop sizes in the flow contactor. Glinkin and Tyabin (?OB) have similarly reported on the arithmetic mean, the mean surface, and the mean volume of drop diameters resulting from a nozzle flow impinging on a rotating disk. Paul and Sleicher (29B) report a n experimental investigation of the maximum drop size in the flow of two immiscible liquids in turbulent pipe flow. Vivdenko and Shabalin (39B) used high speed photographic studies to find the flow conditions necessary for the formation of uniform 0.5- to 1-mm. drops. Drops can be made uniform by maintaining the nozzle discharge velocity in the laminar flow region, decreasing the viscosity of the solution or reaction mixture, and constructing the nozzle of a nonwettable material to sharpen the profile of the spray. VOL. 5 9
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Mass transfer to or from single or multiple drops remains a c ha1lenging field for research Surface tension has little effect on the homogeneity of the drops. Ayen and Westwater (2B) measured the growth of liquid drops suspended in supersaturated binary liquid mixture using cinephotomicrography, and present it as a new method for obtaining liquid-liquid diffusivities for systems with negligible free convection. Wolfe (42B) used the high speed photographic technique to find the mechanism of breakup of liquid drops. Several authors (5B, 73B, 77B, 78B, 25B, 36B, 39B) have reported experimental investigations relating to coalescence phenomena for dispersed liquid droplets. Belk (3B) and Jeffreys and Hawksley (72B) present the effects of physical property parameters on the rate of coalescence of liquid drops in hydrocarbon systems; Jeffreys (72B) also discusses the effect of the specific mass transfer rate on the coalescence phenomenon. The mass transfer rate to or from a single drop or swarms of drops remains a challenging field of research in liquid-liquid extraction. Several new mass transfer models have been proposed during the past two years and the earlier models have been tested for their accuracy, resulting in modifications for some cases. Olander (27B) considered the accuracy of the mathematical development of the Handlos-Baron drop extraction model for the constant velocity regime. He observed that the fraction extracted predicted by the HandlosBaron solution underestimates the consequence of the Haadlos-Baron model by substantial amounts at small values of the dimensionless time; this has also been observed experimentally by Skelland and Wellek [A.Z.Ch. E. J . 10, 491 (1964)l. Wellek and Skelland (47B) have modified the Hand10s-Baron turbulence model for circulating and/or oscillating drops by considering the effect of a finite continuous phase resistance in the boundary conditions of the original equation. Rose and Kintner (34B), using the concepts of interfacial stretch and internal droplet mixing, develop a mass transfer model for vigorously oscillating single liquid drops moving in a liquid field. The fractional extraction, E, is related to the effective diffusivity, the drop volume, the initial drop radius, the amplitude, and the frequency of oscillation and time. This concept results in a much more rapid transfer rate for highly oscillating drops where the circulatory patterns of the Hadamard type are nearly eliminated and there is a very high degree of turbulent mixing. Kadenskaya, Zheleznyak, and Brounshtein (75B) found the coefficients of mass transfer for single drops using ethyl acetate to extract acetic acid from aqueous solutions of varying concentrations. These values agree 74
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with the Kroning and Brink model to show that the dispersed phase is the controlling factor, at least for this case. Marsh and Heideger (23B) employed a photographic technique for a dispersed phase controlled extraction study of the transfer of methylcarbitol from individual drops of a benzene-carbon tetrachloride mixture dispersed in water. They observed a 14-fold decrease in transfer rate during the first second after formation, which may be due to the decay of internal circulation induced by the formation process. Drops were internally stagnant after several seconds of life. Levich et al. (20B, 21B) have analyzed the theory of unsteady diffusion from a moving drop conforming to the rule of Hadamard and Rybezinski. They derive the equations for continuous phase controlled mass transfer cases. Johns and Beckmann ( 74B) extended the theory of solute extraction in a viscous single drop system to show the dependence of: (1) asymptotic Nusselt number on the Peclet number (iVpe = 0 to m ) ; ( 2 ) diffusion entry region Nusselt number on the Peclet number and the initial concentration profile. They cite some experimental evidence that flow fields similar to the Hadamard stream function may exist a t continuous phase Reynolds numbers up to 10, although this is theoretically limited to Reynolds numbers below 1.0. Angelo et al. (7B) applied a generalization of the penetration theory for surface stretch to the forming of oscillating drops for predicting rates of mass or heat transfer. They refined the Rose-Kintner analysis (343) of mass transfer for the dispersed phase controlled case. Analyzing the drop formation at submerged nozzles, they found that the growth of surface during this process is essentially linear. Predictions from this surface stretch model agree well with predictions based on the assumption of continual formation of fresh surface by Groothuis and Kramers [Chem. Eng. Sci. 4, 17 (1955)l and Beek and Kraniers [Zbid., 16, 909 (1962)l. ?his model indicates that the mass transfer behavior during the rise period is approximately 14 times as important as during the formation period for the equipment used in their study. They also developed an expression for the more general situation of appreciable resistance in each phase by assuming the surface stretch model to describe the transfer process in both phases, Brounshtein et al. ( 4 B ) also took into account the resistance in both phases of different systems to compare experimental and calculated values of the coefficients of mass transfer into spherical drops. Rozen and co-workers (35B) have presented a study on the use of hydrodynamic and mass transfer calculations on single drop models to evaluate extraction apparatus performance.
Nitsch (26B) suggests that the transfer of material between liquid phases (occurring with falling or rising droplets) can be regarded as either a transport problem or a reaction problem and that the systematic application of principles of reaction kinetics can actually identify the rate determining process. Levich et al. (ZOB, 27B) indicate the nonapplicability of the relation derived by Kronig and Brink for mass transfer in extraction from drops falling freely through a liquid at large Peclet numbers and with the principal resistance to mass transfer in the diffusion boundary layer. They suggest the equation for the flow of a substance from a drop under such conditions to be a function of the ratio of dynamic viscosities inside and outside of the drop, the coefficients of diffusion inside and outside of the drop, the concentrations of the substance being extracted inside and outside of the drop, and a coefficient from a n expression for the equilibrium concentration based on Henry’s Law. Kimla (76B) has derived a general equation for the diffusion flux to the surface of a liquid sphere in a liquid solution flowing at a constant velocity. Tang et al. (37B) have presented a simplified model for the mass transfer rate and the size distribution of the droplets of the dispersed phase in a perforated plate (pulsed) type system. Gal-Or and Hoelscher (8B) propose a mathematical model to account for the interaction between drops or bubbles in a swarm, as well as the effect of particle size distribution. They solved the equations for unsteadystate mass transfer with and without chemical reaction when the drops or bubbles are suspended in an agitated fluid, and also the steady state diffusion to a family of moving drops with clean interface and without interaction and/or chemical reaction. Coughlin and Von Berg ( 6 B ) studied mass and heat transfer in a mixer settler and found that virtually all transfer takes place to drops moving through a continuous phase of essentially uniform concentration and temperature; end effects were apparently negligible. I n general, their experimental results agree better with the models based on eddy diffusion in a vibrating drop than those models which postulate a stagnant or circulating drop. Letan and Kehat (79B) have described a method for the measurement of the temperature and concentration of organic drops flowing in a continuous aqueous medium; the method uses the preferential wetting property of many plastics for organic liquids. Linde and Sehrt (22B) studied the Marangoni instability effect on the hydrodynamic resistance of drops for mass transfer in both exchange directions. For mass transfer in the direction of the hydrodynamic instability of the plane phase boundary, the hydrodynamic resist-
N . Vashist is a Graduate Research Assistant in the Chemical Engineering Department, University of Maryland. Robert B. Beckmann is Dean of Engineering at the University of Maryland.
AUTHORS Parma
ance increased by a maximum of 100% compared with the same system and the diffusing substance in phase equilibrium; while for the opposite direction, a maximum increase of 33y0 was measured. This large increase in hydrodynamic resistance, caused by the presence of soluble surface-active substances, is attributed to partial or complete inhibition of the inner circulation of the drops and by the change of their resistance. Horton and Fritsch ( 7 7B) measured the circulation velocities inside large drops suspended in a fluid flowing upward and observed a slow decay of internal velocity and a change in circulatory pattern with the accumulation of minute amounts of colloidal impurities a t the interface. Ramanadham (33B) has developed a simple harmonic equation for the surface vibrations of liquids, resulting from a drop falling on the surface of the same liquid species. Deryagin and Dukhin (7B) have expanded the theory of diffusive thermophoretic interaction between growing droplets of a pure liquid to include droplet interactions. Gieseke and Mitchell ( Q B )investigated different methods of sizing drops collected on slides or in cells, and Price (30B) has described an electronic drop counter. Coupled and Interfacial Phenomena
Interest in interfacial phenomena and the coupled phenomenon of simultaneous mass transfer and chemical reaction in liquid extraction type systems continues to receive considerable attention by United States and foreign researchers. Rideal (77C) has presented a brief review of the different mechanisms by which material may transfer from one liquid phase to another through a liquid-liquid interface. Shimbashi and Shiba (79C-27C) have used the layer adsorption technique to measure the activation energy for adsorption and desorption a t the interface, in the transfer of butyric acid from an aqueous phase to either carbon tetrachloride or benzene; they also discuss the general diffusion equations and the determining boundary conditions at the interface. Brounshtein and Zheleznyak (7C) and Ward and Quinn (24C) have reported experimental investigations of the interfacial resistance question and both researches found interfacial resistance to be negligibly small, in contrast to previous investigators. Berg and Baldwin (5C), Hoshino and Sato (IOC), and Maroudes and Sawistowski (73C) all report experimental investigation3 of the interfacial turbulence spontaneously arising when two liquid phases are brought in contact in the presence of a transferring solute. Hoshina and Sat0 (70C) also report on the effect of surface active agents on interfacial turbulence. Astarita (4C) has described the asymptotic solution of the differential equations for the coupled mass transferchemical reaction situation considering various dominant regimes, and although the article does not specifically apply to liquid-liquid systems, the results obtained can readily be translated to such systems. Experimental investigations of the coupled phenomena are reported by Sharma (78C), Nitsch (74C), Johnson and R a a l ( 7 I C ) , Artyukin and co-workers (3C), Bobikov (6C), Pinajian VOL. 5 9 NO. 1 1 N O V E M B E R 1 9 6 7
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(75C),Gupta (9C), Rao (76C) and by Brounshtein and Zheleznyak (7C). Abranizon, Kremnev, and co-workers (IC, 2C, 72C, 22C, 23C) report a comprehensive series of investigations directed toward the delineation of the effects of chemical reaction, interfacial resistance, and simple chemical bonding on the mass transfer rate in liquid-liquid extraction type systems. Cell Configuration Coefficients
The mass transfer occurring in the different types of extraction equipment has received added fundamental attention, although much controversy still exists in the interpretation of the results since one piece of equipment differs from another in many respects. Mixer-Settler Extractors. Berestovoi and Romankov ( I D ) ,Lukin et al. ( 2 7 0 ) , and Berestovoj et al. (20)have studied mass transfer in mixer-settler extractors with a centrifugal separator. They define a volumetric mass transfer coefficient and derive a dimensionless equation for correlation. The final correlation indicates a dependence of the mass transfer coefficient on the volume flow rate of both phases, the agitator speed, the density of the continuous phase, the viscosities of both phases, and on the interfacial tension. The influence of the flow rate of the solvent phase and of the coefficient of distribution may, however, be regarded as negligible compared with the mean deviation of *15% which they found for the proposed correlation in their observations. In a cascade of three mixer-settler extractors with a centrifugal phase distributor, the general correlation reproduces the data with an average deviation of +177'. Halligan (700, 7 I D ) proposes four mathematical models, based on assumed flow characteristic in the settling chamber of a mixer-settler extractor, to predict the composition of the effluent streams. The model that assumed perfect mixing and 100% stage efficiency in the mixing chambers, homogeneity of the aqueous phase in the settling chamber (HNOp-HaO-Bu3Po4 in varsol system), and plug flow of the organic phase in the settling chamber predicted the effluent concentrations most accurately. Increasing the number of stages in the cascade improved the predictions by all the four models. Kagan and Kovalev (760,7 7 0 ) have reported an extensive study of the average droplet diameter in continuous flow, agitated vessels. They found the dependence of the average drop diameter to be more complex than predicted by the usual correlations using the power input per unit volume and the interfacial tension-density ratio as power function parameters. Continuous Countercurrent Flow Equipment. King (780) obtained numerical solutions for mass transfer behavior during countercurrent flow of two fluid phases across a short contact interval fixed in space. The two simplified models-(1) a simple penetration behavior for both phases and (2) laminar boundary layer behavior for one phase and a simple penetration model for the +20% and 14%, respectively, other phase-gave higher values of the over-all rate of mass transfer than that predicted by using the classical two-film addition of resistances. Rod (260) proposes a graphical method
+
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for the determination of mass transfer coefficient as well as the coefficients of axial dispersion in countercurrent extraction equipment-differential contact or stagewise. The method is not limited to the case of a linear equilibrium relation. Prochazka and Landau (240)have derived relations between the stage efficiency and the mass transfer coefficient for various arrangements of the phase flows in multistage systems. The stage efficiency has the advantage over the Murphree efficiency, in that the numerical value is the same for both phases. Souhrada et al. (300) also report on the interrelated effects of backmixing. Wilburn and Nicholson (320) have given a nonlinear model determination method for concentration profiles in a two-phase continuous countercurrent extractor. Spray Columns. Zheleznyak and Brounshtein (340, 350) and Kadenskaya et al. (720) have continued their work on spray columns. I n a study of the end effect at the dispersed phase inlet (340) for single drops, they found that the mass transfer coefficient is independent of the column height when the limiting factor is the resistance of the continuous phase. But the end effect at the dispersed phase inlet is large when the limiting factor is the resistance of the dispersed phase and the transfer coefficient increases with a decrease in the column height. Studying the end effect at the continuous phase entrance to the column, they found that the important variables were the flow ratio of the two phases and the height of the column. The end effects are primarily caused by linear mixing in the column. Subba Rao and Venkata Rao (370) also report experimental studies of the mass transfer coefficient in spray columns. Mixing effects in spray columns may also be deduced from the heat transfer studies of Letan and Kehart (200). Packed Columns. Rajagopalan and Ladha ( 2 5 0 ) offer a mathematical model for the estimation of the effective diffusivities for mass and heat transfer in packed beds. Degaleesan and Ladha (50)present a generalized dimensionless correlation for mass transfer of acetone from a continuous aqueous phase to dispersed organic phases, and vice versa, to compare the developed relationship with the experimental data. Dispersion and liquid distribution effects in packed columns have been reported by Olbrich and co-workers (230) and Kolar and Stanek (79D). Sieve Plate Columns. Setterwall (270) studied the formation of drops and the influence of various parameters on the mass transfer coefficient in a sieve plate column. For the case of droplet formation, the mass transfer coefficient is independent of time while for longer time of contact it is inversely proportional to the square root of the droplet residence time in the continuous phase. Guseinov et al. (80)had shown in their earlier work that jet conditions are more effective for mass transfer than either the dropwise or the transition hydrodynamic conditions. I n the work they considered the effect of the physicochemical properties of the systems on the mass transfer coefficient at jet conditions in
a sieve plate column. Expressing the Nusselt number as Nu = (B,do)D,, where B, is the mass transfer coefficient in the dispersed phase, do is the diameter of sieve plate aperture, and 0,is the coefficient of the solute diffusion in dispersed phase, and similarly defining the Reynolds number and Prandtl number, they offer various relationships for the different cases, which agree with the experimental values within 15y0. Smith (280) has studied the application of the penetration theory to mass transfer on a sieve-tray type of contactor.
Equipment
Coupled
with
Other
Phenomena.
Sokolov and Reshanov ( 2 9 0 ) studied the mass transfer in extractors with gas bubbling to increase the dispersion of the liquid phase. I n a three-stage contactor (each formed by a mixing chamber and a calming chamber), the efficiency of the first stage varied between 70 and 94y0, and the mass transfer coefficient, related to the unit interphase area, did not depend upon the apparent gas velocity which meant that the increase of the stage efficiency resulted from the increased interfacial area. Pulsed columns continue to receive widespread attention. Brounshtein and Shapiro ( 3 0 ) compare calculated with experimental results to evaluate backmixing and turbulent diffusion effects. Meyer and Koennecke (220) used a motion picture technique to investigate pulsing effects on the phase separation boundaries in pulsed packed and spray columns. Ziolkowski and Kubica ( 3 6 0 ) used a packed, pulsed column to investigate acetic acid extraction from organic liquids by a n aqueous phase, and they offer a generalized correlation in terms of the transfer unit height. Zheleznyak ( 3 3 0 ) also offers a general correlation for the mass transfer coefficient in pulsed, perforated plate columns, and Gel'perin and co-workers ( 6 0 ) have reported experimental studies of drop size distribution. Other experimental studies on pulsation effects are reported (30, 70, 220, 3 3 0 , and 3 6 0 ) . Guseinov and co-workers ( 9 0 ) discuss the use of statistical dynamics to evaluate extractor performance and Burova and Planovskii ( 4 0 ) combine hydrodynamical considerations with dimensional analysis to correlate physicochemical characteristics and extraction performance. Kagan and his co-workers (730-750) have continued their extensive work on calculation methods, axial mixing, and the interrelationships of the mass transfer coefficient and the mixing coefficient. liquid-liquid Equilibria and Extraction Processes
Some excellent researches were reported in the 196566 period dealing with liquid-liquid phase equilibria and related effects that should be of considerable interest to those working in the field of solvent extraction. Abe and Flory ( I E ) have developed a semitheoretical basis for treating critical solution temperatures and phase equilibria in binary systems. Experimental verification and justification of their method and theory are based on data for four hydrocarbon-perfluorocarbon systems. Heric and co-workers (9E) have reported data on the furfural-waterybutyric acid system (25" and 30" C.), and they compared the results with previous studies using
acetic and propionic acids in furfural-water systems. Kawamura et al. (IOE)have reported an interesting study on the effects of temperature and additives in a paraffin hydrocarbon-amine-inorganic (HzS04) acid type of system and have related these parameters to phase separation problems. Kemula and co-workers ( I 7E) tried without success to correlate the distribution coefficients for organic acids-water-organic solvent-type systems with dielectric constants or interfacial tension parameters; some success was achieved by using the HildebrandScatchard solubility parameters. Steib (76E, 77E) reports a n extensive investigation of the liquid-liquid phase equilibria for quaternary systems involved in separating aromatic-nonaromatic hydrocarbons by aqueous alkylformamide solvents. Shamsal Huq and Lodhi (75E) have reported excellent equilibria data, over a temperature range of 5' to 35" C.,for the benzoic acid-benzenewater system and include the problem of acid dimerization in their considerations. Takashima et al. (78E)have reported on the carbon tetrachloride extraction of halogen and inorganic species from aqueous acid solutions, and Lesteva and co-workers ( I Z E ) have reported on the methanol-water-isoprene system. Anyone concerned with liquid-liquid phase equilibria should also refer to the excellent reviews of Gerster (7F) and Davies (3F). Although not concerned with experimental phase equilibria per se, the mathematical works of Chen and Ceaglske (6E) and Almin (ZE) should be considered by anyone using cross- or countercurrent extraction apparatus to achieve equilibrium distribution. These developments can assist in optimizing or minimizing solvent ratios and/or stages to reach equilibrium conditions. Several interesting researches have been reported which relate primarily to specific extraction processes, although the results may also be of concern to other similar extraction systems. Mueller (74E) has reported on the dilution effect in extracting trivalent metals by acid solutions of trilaurylamine hydrochloride, and Lloyd and Oertel (73E) have used a theoretical mechanism approach to evaluate the solvent possibilities of long chain amine extractants as an aid in solvent selection and design. Frolov and Sergievskii (8E) have studied the chemical interactions caused by various organic phase additives upon the amine extraction of aqueous sulfuric acid solutions. The amines used were of the type R 3 N and the additives used were benzene, nitrobenzene, chloroform, octyl alcohol, methanol, acetic acid, and acetone. Balashov and Serafimov (3E) have reported on the mono- and dibutyrate chlorohydrin esters of pentaerythritol in butyric acid-water systems such as occur during the production of 3,3-bis(chloromethyl)oxacyclobutane monomer. Coward and Smith (7E) have reported on the use of seven solvents and four aldehyde additives for the extraction of metanephrines from aqueous solution. The solvent extraction of complex petroleum hydrocarbon systems has been reviewed from the standpoints of solvent selection, solvent requirements, and processing requirements by Woodle ( 79E), Bikkulov (5E), and Bijur (4E). VOL. 5 9
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Reviews, Treatises, and Texts
The literature on liquid-liquid extraction continues to increase at a phenomenal rate; an example of this literature volume is the review of Freiser (SF) who collated 796 references, covering the period from 1963-65, on survey reviews, books, equilibrium studies, kinetic and coupled phenomena, mass transfer, processes, apparatus, and techniques and procedures pertaining to solvent extraction. Gerster (7F) has presented a review on extraction equilibria, including the latest theoretical and empirical procedures for correlating and extending equilibrium data. Included in Gerster’s review are recommended approaches for screening and selecting possible solvents for a proposed extraction separation process. Davies ( 3 F ) also has reviewed the principles of solvent selection. Diffusion in liquid systems, particularly applicable to extraction type systems, have been reviewed by Nienow (73F), Lightfoot and Cussler (IOF), Von Halle et al. (ZOF), Lightfoot et al. ( I I F ) , and by Solc (78F). A considerable number of review papers have appeared treating the mass transfer aspects of solvent extraction. A comprehensive review of the recent literature on mass transfer in liquid-liquid systems has been prepared by Brown ( I F ) ; special emphasis was devoted to the role of surface active agents. Some more general reviews have been presented by Soejima (77F), Marcus ( I Z F ) , Kalbagh (9F),Johns et al. (8F), and Ellis and Beckmann (47).
Reviews related to fluid dynamic factors of concern to dispersed liquid-liquid systems are also to be noted. Fleetwood (5F) has reviewed the recent developments related to countercurrent distribution phenomena; Vignes (79F)and Salami et al. (76F) offer excellent reviews of the hydrodynamics of dispersed liquid-liquid systems. Coalescence mechanisms, mechanical settling aids, electrical field effects, and the effect of impurities on mass transfer-particularly pertaining to industrial type separation problems-have been briefly reviewed by Brown and Hanson ( 2 F ) . Williams (27F)has discussed the status of the use of dynamics to study the fundamentals of mass transfer, and Patient (74F) has described the most recent advances in automatic sampling and analytical devices as aids to fundamental extraction studies. Two Russian works are particularly noteworthy: Zhavoronkov and Romankov (22F) have reviewed the main trends of the USSR Academy of Sciences relating to mass transfer research, and Plaksin (75F)has published a book on ion exchange and solvent extraction methods in various chemical separation processes of the U.S.S.R. REFERENCES Molecular Diffusion Coefficients (1A) Albrighr, J. G., J. Phjs. Chem. 70 (71,2299 (1966). (2A) Albright, J. G., Mills, R., Ibid., 69 (9), 3120 (1965). 4 (Z), 236-7 (1965). (3A) Astarita, G., IND.E h c . CHEM.FUNDAMENTALS (4A) Bidlack, D. L., Anderson, D. K., J. Phjs. Chem. 6 8 (Z), 3790-4 (1964). (5A) Birkett, J. D ,Lyons, P. A , , Ibid., 69 ( 8 ) , 2782 (1965). (6A) Bischoff, K . B., Himmelblau, D. M.,I h D . ENG.CHEW57 (12), 54-62 (1965) and 5 8 (12), 32-41 (1966). (7.4) Board, Mr. J., Spalding, S. C., Jr., A.I.Ch.E J. 12 (Z), 349 (1966). (SA) Byers, C. H., King, C. J., J. Phys. Chem. 70 (a), 2499 (1966).
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Droplet Behavior (1B) Angelo, J. B., Lightfoot, E . S., Howard, D. W., A.I.Ch.E. J. 12 (4), 751-60 (1966). (2B) Ayen, R . J., Westwater, J. W., Ibid., 10 (6), 885-9 (1964). (3B) Belk, T. E., Chem. Eng. Progr. 6 1 (lo), 72 (1965). (4B) Brounshtein, B. I., Gitman, I. R., Zhalenznyak, A. S., Doki. Akad. Nauk. S.S.S.R. 162 (6), 1336-8 (1965). (5B) Brown, A . H., Hanson, C., Trunr. Farudoy SOC. 61 (512), 1754 (1965). VonBerg, R. L., Chem. Eng. Sci. 21 ( l ) , 3-18 (1966). (6B) Coughlin, R . W., (7B) Deryagin, B. V., Dukhin, S. S., Kolloidn. Zh. 24 (4), 424-30 (1962). (8B) Gal-Or, B., Hoelscher, H . E., A.2.Ch.E. J . 12 (3), 499-508 (1966). (9B) Gieseke, J. A., Mitchell, R . I., J . Chem. Eng. Data 10 (4), 350-3 (1965). (10B) Glinkin, A . D., Tyabin, N. V., T r . Karnnsk. Khim.-Tekhnol. Znnst. No. 32, 173 (1965). (11B) Horton, T. J., Frirsch, T. R., Kintner, R . C., Can. J . Chem. Eng. 43 (3), 143-6 (1965). (12B) Jeffreys, G.V., Hawksley, J. L., A.I.Ch.E.J. 11 (3), 413 (1965). (13B) Jeffreys, G. V., Lawson, G. B., Trans. Inst. Chem. Engrs. (London) 43 ( 9 ) , T294 (1965).
(14B) Johns, Jr., L. E., Beckmann, R. B., A.I.Ch.E.J. 12 ( l ) , 10-16 (1966). (15B) Kadenskaya, N. I., Zhalenznyak, A. S., Brounshtein, B. I., Zh. Prtkl. Khim. 38 (5), 1156-9 (1965). (16B) Kimla, A., Collectton Czech. Chem. Commun. 30 (5), 1416-26 (1965). (17B) Kochletov, V. I., Klepikov, E. S., Garaishin, R. M., Kollotdn. Zh. 27 (Z), 203 (1965). (18B) Komasawa, Y., Hisatani, S., Kunigita, E., Otake, T., Kagaku Kogaku 30 (5), 450 (1966). (19B) Letan, R., Kehat, E., Chem. Eng,Sci. 20 (9), 856 (1965). (2OB) Levich, V. G., K r lor, V. S., Vozotilin, V. P., Dokl. Akad. Nauk. S.S.S.R. 160 (6), 1358-60 (1965y. (21B) Levich, V. G., Krylor, V. S., Vorotihn, V. P., Ibtd., 161 (31,648-51 (1965). (22B) Linde, H., Sehrt, B., Z . Phystk. Chem. (Letpztg) 231 (3-4), 151-72 (1966). 4 0 (Z), (23B) Marsh, B. D., Heideger, W. J., IND. ENC. CHEM.FUNDAMENTALS 129-33 (1965). (24B) Matsunobu, Y., J . Phys. Soc. Japan 21 (e), 1596-1602 (1966). (258) Nichols, F. A., J. &PI. Phys. 37 (7), 2805 (1966). 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