annual review
WILLIAM B. ELLIS ROBERT B. BECKMANN
Liquid-Liquid Extraction Rapid advancement of fundamental knowledge in thejeld of liquidliquid extraction is surveyed with reference to selected literature published oaer a two-year period starting at the beginning of 7963 dvances in the field of liquidA liquid extraction, ranging from the fundamental aspects of the process to the development and evaluation of new processes and equipment, have become a topic for review so formidable that a single article cannot cover adequately all aspects worthy of coverage. Accordingly, a program for review of this field is instituted, starting with this article, whereby basic and applied annual reviews will be published alternately. This review presents some of the contributions pertinent to the fundamental understanding of the liquidliquid extraction mass transfer operation that have been reported in the literature during 1963 and 1964. Next year's review will present the significant contributions in the process and equipment area for the years 1964 and 1965. The literature references cited are intended to be representative of the total contributions to the literature for the 19631964 period. The authors hope that the selection of literature presented offers the interested researcher a useful background from which to develop a bibliography pertinent to his immediate interests.
in their studies. The latter found the interfacial resistance to be less than 3y0 of the overall resistance. Kishinevskii and Kornienko (47, 57) found interfacial barriers significant and correlated the resistance with the distribution coefficient. Himmelblau (30) and Gibbs and Lazarraga (20)investigated the effect of concentration on the mass transfer coefficient. Using the Lewis equation, dC/dt = KA(C - C*)/V, they found that K varied directly with the diffusivity, thus continuing this controversy and bringing the divergent views full circle in the sense that we now have proponents stating that the mass transfer coefficient is independent of molecular diffusivity, D, that that it varies as it varies as and that it varies directly with D. Matthews and Hutchinson (68) studied mass transfer in a systern having a varying distribution coefficient and present two methods for determining the individual transfer COefficients from the concentration-time information. Ruckenstein (96) has presented an excellent review of the models for turbulent mass transfer in the vicinity of a fluid boundary which considers boundary layer models as well as the renewal models of Hanratty and Danckwerts.
Diffusivity Effect
The validity of the Whitman-Lewis two resistance theory continues to arouse considerable attention, pro and con. Ward and Quinn (726) and Brounshtein and Zheleznyak (9, 70) both verified the Whitman-Lewis concept and included an estimate of the interfacial resistance, if it exists,
Effects of Drop Motion
Several new quantitative relationships for the coefficients for mass transfer to and from drops moving in a continuous liquid media have emerged from research efforts of recent years. Resistance in the continuous phase was considered by
Grafton (24),by Kinard (41),and by Ruckenstein (94). Grafton analyzed diffusion from a solid sphere or cylinder in forced convection, but his consideration of the boundary layer and the subsequent variation of the continuous phase resistance can certainly shed light on a similar resistance for the case of a nonrigid interface. Kinard also considered rigid boundaries, but his study is restricted to the rear portion of the sphere. Ruckenstein's analysis includes all interfacial velocities and he concludes that the resistance in the continuous phase is reduced with increasing velocity at the interface. Skelland and Wellek (108)present a set of empirical equations, based on dimensional analysis and data from aqueous-organic systems, for the prediction of the resistance inside a single drop. One equation is for nonoscillating drops and two equations (each yielding the same standard deviation for the data correlated) are for oscillating drops. T h e drop Reynolds numbers ranged from 37 to 3114 and for all cases presented, the Skelland-Wellek correlations showed better prediction of the data than the Newman, Kronig, and Brink or the Handlos and Baron relationship. The only shortcoming is that the correlation method gives little or no information on the mechanism of transfer inside the drop. The overall resistance was considered by Kishinevskii and Kornienko (44) for drop Reynolds numbers greater than one and their resultant relationship agreed with Levich's analysis. Beek and Kramers ( 3 ) developed solutions to the diffusion equation for expanding gas bubbles ; however, their development should be of interest to those concerned with the liquid drop extraction case when the drop volume and interfacial area are changing.
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There are several references which offer data on single and aggregate drop extraction rates (8, 45,46,52, 727). Kishinevskii and Kornienko detected surface resistance at Reynolds numbers less than 300 and interfacial turbulence at Reynolds numbers greater than 400 ; Levich‘s equation for the continuous phase resistance seemed to predict the data for Reynolds numbers approximating 120, but Higbie’s equation seemed to prevail when the Reynolds number reached 500. Zheleznyak, Kishinevskii, Brounshtein, and Bezdel all found that the Kronig and Brink relationship held for small drops and all except Kishinevskii found Higbie‘s equation holding. Thornton (7 16) continues his excellent work on single droplet extraction rates and their use for predicting mass transfer in packed columns and mixer-settler extractors. Cell Configuration Coefficients
Olander (80)predicted theoretical coefficients for mass transfer in a stirred extraction cell similar to the Lewis cell and, despite the fact that his predicted coefficients were low by 35 to 40%, he concluded that the laminar flow model he used was sufficient to explain the transfer mechanism. Loosemoore and Prosser (62) objected to Olander’s analysis on the basis of data they collected on i! water-hydroxyquinolinekerosene system and Olander subsequently modified his previous model (87)by considering the transfer in the core of the cell (previously neglected) and this model shows better agreement with the data. Goncharenko, Gotlins’ka, and Akhtirs’ka (21, 23) developed an empirical relationship for an overall mass transfer coefficient in an impeller type mixer. Zheleznyak and Brounshtein (727) present an empirical relationship for the transfer resistance as a function of concentration, impeller speed, and phase densities in a Lewis type extraction cell. Howarth (32) has obtained mass transfer rates in an agitated extractor and compared his experimental results with those predicted by two limiting transfer mechanisms. Pechstein and Koennecke (86)measured the rate of mass transfer and the degree of dispersion in the mixing zone of a rotating disk extractor and give a graphical representation of their overall results. Fundamental studies on the transient character104
istics and on the effect of pulsations in columns have been presented by Staffin and Chu (110)and by Rozen (92). Stafin and Chu found it difficult to correlate their results on the basis of the linearized dynamic diffusion equations coupled with the familiar variables which determine the mass transfer coefficient. Role of Droplets
The mass transfer resulting during the period when a drop is being formed has continued to get extensive investigation although much controversy still surrounds the interpretation of the results. Popovich et al. (85)have developed a single equation which combines the effects of five different mechanisms and which relates the mass transferred to the driving force, diffusivity, the final drop diameter, the formation period, and time. The validity of the equation was evaluated for several systems and seemed to do a reasonably good job of representing the data available. Kroepelin et al. (55)and Koennecke and Swinscher (49)studied the effect of hydrodynamics on mass transfer during the period of drop formation. Kroepelin concluded that the transfer takes place during sudden explosive impulses rather than during a steady diffusion process. Atwood (2) used an interferometric technique to study mass transfer during the period of droplet formation. Some of the most extensive research of recent years has centered around the hydrodynamics of drop formation and coalescence, the oscillation and deformation of drops, interfacial motion, and drop holdup. Attempts to relate the fundamental mechanism of liquid-liquid mass transfer to convection, for a given system, has placed increased stress on the need for precise interpretation of the above factors as they relate to the hydrodynamic situation. The subject of droplet formation and coalescence, with or without mass transfer. has been treated rather extensively (36,37, 56, 57, 64,65,77,78,109, 132). MacKay and Mason (64,65)
Robert B. Beckmann is Head and William B. Ellis is Research Fellow at the Department of Chemical Engineering of The University of M a r y land. The authors acknowledge the assistance of their department staf in the preparation of this annual review. AUTHORS
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and Neumann (77)considered the breakup of the continuous phase liquid film which separates the drop from the coalesced phase at a point immediately preceding coalescence and found that an eruption, perhaps attributable to a Marangoni effect, could account for the observed break. Kaparthi and Light (40)have presented a photographic study of the deformation and oscillation of organic drops moving through a water phase. Taylor and Acrivos (114) have presented an interesting theoretical study of the deformation of moving drops and have concluded that the deformation Feometry is unaffected by the viscosity ratio of the continuous and dispersed phases. Davies (12),Akers (1). and Schechter and Farley (102) have presented comprehensive reviews on the role of interfacial activity in interphase mass transfer. Experimental studies of interfacial movement, usually accompanied by a theoretical or semitheoretical analysis have been reported (48,53. 60,81, 95, 100,101). Olander (81) found that interfacial turbulence can appear even at low concentration driving forces and that it need not be visually apparent to be prevailing in the transfer mechanism. Ruckenstein (95)has presented a theoretical argument to illustrate that the Marangoni effect has an influence on velocity and on mass transfer only for small drops, where the droplet Reynolds number is much less than one. Szekeley ( I 73) studied the convective fluxes caused by diffusion and concluded that the enhancement of the mass transfer rate is significant and cannot be ignored. The interfacial oscillations and movements of free drops have been experimentally measured and evaluated by Valentine and Heideger (721,723). Equipment Performance
Fundamental hydrodynamic studies related to the performance of extraction equipment continue to be prime topics for research and mathematical modeling. The hydrodynamics of breakup, coalescence, aiid holdup in liquid-liquid dispersions, particularly in packed or agitated extraction systems have been reported (15,25, 33, 38, 39, 66,7074,115, 117). Thornton (117)has developed a method for predicting the drop size distribution and the
holdup in impeller type mixer extraction units, and Misek (70-74) has developed a detailed treatment of the breakup and coalescence of dispersed droplets (in addition to the prediction of drop size distribution and holdup) in agitated systems. Madden and McCoy (66) have suggested a n interesting technique for measuring drop-size distribution, which involves freezing of dispersed droplets by polymerizing a surfactant. Misek (70) concluded that droplets of a dispersed liquid move in a n agitated system with an average vertical velocity equal to the terminal velocity for rigid spheres of the same density and size. The phenomenon of backmixing in continuous liquid-liquid contactors has been given theoretical consideration by Vermuelen and coworkers (29,75, 76), and by Sehmel and Babb (706); Vermuelen (29) also presents experimental data in support of his mathematical model. Experimental studies of axial dispersion have been reported by Hazelbeck and Geankoplis (28)for a spray type extraction column; by Stemerding and Lumb (777) for a rotating disk extraction column; and by Gel’perin and Neustroev (78) for a perforated plate extraction column. All report some type of correlation for predicting the axial mixing coefficients. Konopik and Burkhart (50) evaluated, experimentally, the the effect of surface tension on the mass transfer coefficient in a pulsed extraction column and reported a n inverse relationship between the mass transfer coefficient and surface tension.
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Surfactants’ Role
T h e role of surface active agents in liquid-liquid interphase mass transfer, particularly concerning their influence on interfacial phenomena, droplet hydrodynamics, and mass transfer, has continued to receive increased research emphasis. The effect of surfactants on the terminal velocity of rising or falling drops has been reported (26,59,98,99, 702). In all cases it was noted that the Stokesian settling rate was decreased by the presence of surfactants. Santt (99)reported the existence of a critical diameter; a drop having a diameter less than the critical diameter exhibits no internal circulation. T h e validity of this was investigated by altering the surface tension with
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surfactants and noting internal circulation behavior. Griffith (26) observed the development of a nearly immobile cap on the rear of the drop ; the formation of the cap was attributed to the net result of the continuous phase drag piling up the surfactant at the rear of the droplet. Mass transfer across interfaces in the presence of surfactants was studied by Boyadjiev (5, 6), by Kretzschmar (54,and by Liiide and Winkler (67). Linde found that the surfactant stabilized the interfacial hydrodynamics and decreased the mass transfer coefficient. Boyadjiev, noting that a surfactant exhibits a minimum of mobility as its concentration is increased and the mobility of the interface goes through a minimum, described the phenomenon in which the rate of mass transfer goes through a minimum as does the surfactant mobility. Coupled Phenomena
There are several references in which the authors have reported on theoretical or experimental considerations in coupled mass transferchemical reaction systems, and which should be of interest as such systems might apply to liquid-liquid extraction behavior (7, 34, 84, 85, 97, 718, 724). Huang and Kuo (34) presented a mass transfer model based on the film-penetration model coupled with a first-order chemical reaction at the interface. Ruckenstein (97) noted the possible unstable conditions that might arise through the effect of a chemical reaction on interfacial activity. Reviews, Treatises, and Texts
Some of the most welcome additions to the liquid-liquid extraction literature have appeared in the form of new or revised books and review articles. One of the most valuable of these is the book by .4.W. Francis ( 7 6 ) on liquid-liquid equilibriums. The compilation includes ternary data for both aqueous and nonaqueous systems as well as critical solution temperatures supplementary to those previously published by Francis. The field has long needed a comprehensive book of this character. I n this same vein, Treybal (720) has brought out the second edition of his long recognized and excellent text in this field. A Russian book in this field has 106
been published by Ziolkowski ( 129). The general subject of extraction theory and practice has been reviewed recently in several articles (14, 79, 83, 730, 7 3 7 ) . Of these, the work by Olney and Miller (83)seems to be the most comprehensive. Kintner (42) has reviewed the many references, many of them his own, on drop phenomena pertaining to liquid-liquid extraction. T h e review is extensive and discusses the important developments pertaining to drop motion, oscillation, circulation, and deformation. Methods of predicting liquid-liquid ternary equilibrium information from binary data have been reported by Chen and Kyle ( 7 7 ) and by Pesko (87). The technique of Chen and Kyle is specifically oriented to computers. The physical chemistry of the extraction process and the equilibrium relationships involved are given extensive theoretical treatment by McGlashan (63),Schuberth (104, 705), Susanov (772). Rowlinson ( g o ) , and Rozen (97). The work by Rozen includes an extensive review of the subject. BIBLIOGRAPHY (1) Akers. J. B., Birrnintham L’niu., Chem. Engr. 14 (2), 36 (1953). (2) Atwood, G. A , , Unix Microjlms (Ann .4rbor, Mich.) Order .Vo. 64-402, 171 p p , ; Disserinlion Abs!r. 24. 2824 (1964). (3) Brek, W. J., Kramers, H . , Chem. Eng. Sci. 17, 909 (1962). (4) Bezdel, L. S., Zheleanyak, A. S., Brounshtein, B. I., Protsesry Zhidkorlnoi Ekstrnkfsii, T r . .%-such.Tekhn. Sooeshch., Leniiierad 1961, 148 (1963). (5) Boyadjiev, L.: Compt. Rend. Acad. Bulgare Sci. 1 6 (2), 145 (1963). (6) Boyadjiev, L., Izu. I R I t . Otshla ??cor$. Khim. B!il,for. Aced. ‘Vauk 1, 41 (1963). (7) Brounshtein, B. I., Tr. Gos. Inst. Prikl. Khim. 49, 162-9 (1962). (8) Brounshtein, B. I., Gutman, I. R., Prolsessy Zhtdkorlnoi Ekslraktsii, Tr. A‘auchn.-Tekhn. Soueshch., Leningrad 1961, 17 (1963). (9) Brounshtein B. I. Zheleznyak A. S., Dokl. h o d . Nauk S.k’R 153 ’(4), 889 (196;). (10) Rrounshtein, B. I., Zheleznyak, 4.S., Protsessy Zhidkostnoi Ekstraklrii, Tr. Nnuchn.- Tekhn. Sooeshch., Leningrad 1961, 39 (1963). (11) Chen, T. C.: Kyle, G. B , Kansas State Univ. Eng. Expt. Sta. Spec. Rep:. N o . 40, 16 pp. (1963). (12) Davies, J. T., Adoan. Chem. Eng. 4, 1 (1963). (13) Davies J T. Rideal E. K., “Interfacial Phenomena,”’Acaddmic Press, New York, 1963. (14) deNie, L. H., Chem. Process E n l . 44, 20 (1063). 15) Dunn, Irving J., Uniu. Micro.fi!ms (Ann Arbor, Mich.), 0rd.r N o . 64-6261, 104 pp.; Dizrertation Atstr. 25 (l), 337 (1964). (1 6) Francis, A. LV., “Liquid-Liquid Equilibrium,” Interscience, New York, 1963. (17) Frolov A . F. Loqinova M. A. Ustavshchikov, B.F., Zh.’Fir. K k m . 38 (7),’1837 (lb64). (18) Gel’perin. T.I,, Keustroev, S. A , , Khim. Prom. 1964 ( 5 ) , p. 360. (19) Gel’perin, N. I., Pebalk, V. L., Zh. Vstr. Khim. Obshchesioa im.D. I . Msndeleeua 8 (5), 595 (1963). (20) Gibbs, R. K., Lazarraga, I., Himmelblau, D. M., Brit.Chem. En:. 8 , 538 (1963). (21) Goncharenko, G. K., Gotlins’ka, A. P., Protsessy Zhidkostnoi Ekrhktr2i. Tr. .Vauchn.-Tekhn. Soveshch., Leningrad 1961, 222 (1963). (22) Gosse, J. Vigliecca L. Rev. Inrt. Franc. Pelrole Ann. Combus;. Lipides li, 1;28 (1962). (23) Gotlins’ka. A . P., Akhtirs’ka, 4. A,, Khim. Prom. .Vmk.-Tehhn. Z6.1962 (3), p. 15. (24) Grafton, R . I\’., Ciiem Eng. Sri. 18, 457 (1963).
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(25) Graham, G. P., Saint James, R., SOL.Hydrotech. France Compt. Rend. Journees Hydrauiigue, 7emes, Paris,’79621, 166 (1963). (26) Griffith, R . A?., Chem. Eng. Sci. 17, 1057 (1962). (27) Groothuis, H . , Zuiderileg, F. J., Ibid., 19, 63 (1964). (28) Hazelbeck, D. E. Geankoplis C J., I N D . Eso. CHEU.FVNDAME&ALS 2, 310 (196;). (29) Hennico, Alphonse, Gabriel, Jacques Vermeulen Theodore U. S. Atomic Eneriy Comm. UC’RL-10636, 1’90 pp. (1963). (30) Himmelblau, D. hl., Ibid., TID-19451, 36 pp. (1 963). (31) Holland, F. A,, Brit. Chern. Eng. 9 , 96 (1964). (32) Howarth, W. J., Chem. En,?. Sci. 18, 47 (1963). (33) Ibid., 19, 33 (1964). (34) Huang Chen-Jung Kuo, Chaiang-Hai, A . I.Ch.E. J.’9, 161 (1963j. (35) Izard J. A. TV.? Cavers S. D., Forsyth, J. S.. Chem. E&. Sci. 18, 467 (1965). (36) Jackson R., Trans. Imt. Chem. Engrs. (London) 42 (4), (19k4). (37L J e f f r e p , G. V., Kawksley, J. L., J . AppC. Chem. IL, 329 (1962). (38) Kagan, S. Z.? Aerov, M. E.,Volko\a, T. S . ProtsPss Zhidkostnoi Ekrtraktsii Tr iVnuchn.- Tekhn. Soueshd., Leninprad 1961, 156 (i903j. (39) Kagan S. V. 4rrov M E. Volkova T. S. Trukhandv, V. Gi, Z h . P r h . Khirn: 37 ( l ) , 5s’ (1964): (40) Kaparthi Ramalingam, Light Wiiliam, J. Sci. Ind. Res.’(India) 21B, 565 (1962): (41) Kinard, G. E., Manning? F. S., Manning W.P., Brit.Chem. Ene. ,. 8.. 326 (19631. , ( 4 2 ) Kintner, R . C., Adoan. Chem. Eng. 4, 51 (1963). (43) Kishinevskii hl. Kh., Kornienko, T. S., Zh. Priki. Khim. 36 ‘(51, 1008 (1963). (44) Ibid., (X), p. 1869. (45) Ibid., (12), p. 2681. (46) Itid., 37 (4), 844 (1964). (47) Ibid., (9). P. 2071. (48) Kishinevskii. XI. Kh., Mochalova, L. A,, Tr. p o Khim. i Khim Tethnol.4, 885 (1961). (49) Koennecke, H. G., Swinscher, R., 2. Physik. Ciiem. (Leipzig) 222, 173 (1963). (50) Konopik, 4. E.. Burkhart, L. U. S . Atomic Energy Comm. I.S.-334, 66 pp. (19i0). (51) Kornienko 7 . S., Kishinevskii, M. K., Zh. Prik!. Khim 38 (6), 1238 (1963). (52) Ibid., (lo), p. 2224. (53) Kremnev, L. Ya., Ahramzon A. A. Kiyanovskaya, Yu. L., D o k l . Akad. N&k SSSR’ 150 (3), 836 (1963). (54) Krerzrchmar, G., Voriraege Originalfassung, Intern. Kongr. Grenzjaechenaktiue Stof/, 3, Cologne 1960 2, 344 (1961). (55) Kroepelin, H., Neumann, H. J. Proett, E., 5th TVorld Petrol, Congr. Proc. 1959, 3i1 (1960). (56) Lang, S. B., Univ. Microjilrnr (Ann Arbor, Mich.) Order ,Vo. 63-6256, 156 pp.; Disseriation Abstr. 24, 1208 (1963). (57) Lang S. B. U S . Atomic Energy Comm. UCRL-i0097, 259 pp, (1962). (58) Levich. V. G., “Physicochemical Hydrodynamics,” Prenhce Hall, Englewood Cliffs, h-,J., 1962. (59) Levich, V. G., Kuznetsov, A. XI., Dokl. Akad. ‘Vauk S S S R 146, 145 (1962). (60) Linde, H., ThieFsen, D., 2. Physik. Chem. (Leipzig) 221, 97 (1962). (61) Linde, H., M‘inkler, K., I6id., 225, 223 (1964). oosemoore M. J., Prosser, A. P., Chem. En,?. (6?ci.L18, 555 (166;). (63) McGlashan, hl. L., Ann. Repl. Progr. Chem. (Cham. Soc. London) 59, 73 (1963). (64) ILfacKay, G. D. Xi., Mason, S. G., Can. J . Chem. Eng. 41 (5), 203 (1963). (65) MacKay, G. D. M., Mason, S. G., J . Colloid Sci. 18 (71, 674 (1963). (66) Madden, A. J., McCoy, B. J., Chem. Eng. Sci. 19 (7), 506 (1964). (67) hlarchello, J. M., Toor, H. L., IND. E N G . CHEWFUSDAMESTAI.~ 2, 8 (1963). (68) Matthews T., Hutchinson, H. P., Intern. J . Heat .Mass T k s f e r 5 , 1139 (1962). (69) Meyer, A , , Koennecke, H . G , Z. Phjrik. Chem. (Leifizig) 222, 111 (1963). (70) Misek, Tomas, Collection Czech. Chem. Commun. 28, 570 (1963). (71) Ibid., 29,1755 (1964). (72) Ibid., p. 2086. (73) Misek, Tamas, Kralovo~olska Strojirna N o . 1, 37 (1961). (74) Ibid., No. 1-2, 1 3 (1962). (75) Miyauchi, Terukatsu, Vermeulen, Theodore, IND.ENG.CHEM.FUNDAMENTALS 2, 304 (1963). (76) M o o n J. S. Hennico Alphonse, Vermeulen, Theodord, U. s‘. Atomic hnergy Comm. URCL10928, 119 pp. (1963). (77) Neumann, H. J., i~rflturwissetrschaften 50 (1 6), 544 (1963). ~
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