ANNUAL REVIEW
.
Liquid = Liquid Extraction
D. K. HARRIS P. N. VASHIST R. 6. BECKMANN
Obviously there are many situations that are not easily defined by this classification system-or the contribution fulfills both criteria-and in these cases the final decision may be justifiably questioned. The literature cited is not intended to be complete as such a task would be far too formidable but rather to present a reasonably comprehensive selection that will afford the interested practitioner a valuable background from which to develop a bibliography pertinent specifically to his interests. General Reviews
The foreign literature continues to dominate the field of liquid extraction reviews and from the standpoint of a n insight into the comparison of foreign and American practices, these general articles are invaluable. Zolotov and coworkers (IA, 144 75A) are particularly valuable in this regard. The earliest reference, that in 1962 by Alimarin and Zolotov (IA), is mentioned since it is primarily concerned with a comparison of terminologies used in English and Russian extraction works. The 15A) are concerned with a latter two works review of Russian theory and practice and the use of extraction as a n analytical tool. Ziolkowski (73A) has published a rather extensive treatise on liquid extraction in the chemical industry, with particular reference to Russian applications. T h e review by Kyrs, Konecny, and Jerabek (9A) is general, with a vocabulary of Czech extraction terminology. Another general review, of a n inconsequential nature, is that of Balt (ZA). An extremely valuable review, although limited to the period from January 1963 to June 1964, is that of Bischoff and Himmelblau (3A) which is a general survey of mass transfer literature during the aforementioned period but which contains many references pertinent to the application of liquid-liquid extraction. Other general review references of note are those of LeRoux ( I O A ) and Kamori and Tanaka ( 8 A ) . Rozen (72A) reviews the problem of evaluating the performance of large-scale industrial-type mass transfer equipment with particular reference to the development of a mass transfer theory and the evaluation of the effective interfacial area for transfer. Hanson (5A) derives an equipment classification for liquid-liquid extractors and offers a brief comparison of the general characteristics of each along with some general guidelines for the selection of a n extractor type best suited for a particular operation. Ingamells (6A) also discusses various devices used for liquid-liquid extraction, and Ipenburg (7A) offers yet another classification scheme for liquid-liquid extraction equipment based on the dominant feature of the mass transfer mechanism inherent to the particular unit. He also discusses the interrelating features of liquidliquid extraction, ion exchange, and adsorption. Markov and Korinfskaya (77A) also offer a review of various extractor types commonly used for liquid-liquid mass transfer operations. General Calculation Procedures
General calculational methods relating to the operation, design, or performance of an extraction column, 98
INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY
or relating to the selection of the optimum processing conditions are always of interest to those working in the field of liquid-liquid extraction. The necessity for the coupling of the mass transfer relationships and those of hydrodynamics under general conditions which are not easy to define-not to mention the complicating geometric equipment factors-creates the need for calculation and design procedures that afford a realistic approach to the actual physical phenomena taking place. Unfortunately, many of the calculational procedures proposed are not verified or tested in relation to a real situation and hence their applicability is limited, and in some cases they are unproved, even though their derivation is extremely interesting. These efforts often guide further experimentation. Graphical and/or analytical procedures relating to the calculation of the number of equilibrium stages for a variety of equilibrium relationships and contacting conditions are the subject of the works by Barreiro ( l B ) ,Davison and Harris (3B), Friday and Smith (4B), Mel’nikov (7B), Nikolaev and Kolesnikov ( I I B ) , and Pol’skii (73B). Brounshtein (ZB)develops the differential equations for multicomponent extraction systems with any type of equilibrium relationship and proposes numerical methods for the solution of the resultant equations. Oliver (7ZB)and Frolov and Stepanova (5B)discuss the distribution coefficient and its relation to design. Backmixing and fluid mixing in liquid-liquid extraction equipment continues to receive considerable attention. Wilburn (77B) discusses the mathematical determination of the concentration profiles in countercurrent extractors and Rod (75B)presents a graphical method based on a finite difference technique for evaluating the separation effect in extraction columns under conditions of longitudinal mixing. Prochazka and Landau (74B) present an analytical treatment of backmixing between stages, where the stage efficiency is not necessarily unity, for countercurrent stagewise extraction systems, and Takamatsu and Nakanishi (76B) d’ISCUSS fluid mixing in a cross-current contacting system. Optimal testing of liquid-liquid extraction columns and optimization of extraction separations processes are the subjects of works by Kiessling ( 6 B ) , Mitten and Nemhauser ( g B ) , and Moegli (70B). Also to be noted is the report of Mills (8B) who presents a review of the computer programs available for liquid-liquid extraction calculations. Other sections of this review pertaining to specific equipment types also report considerable activity relating to calculational procedures applicable to specific design or operational analysis problems. Extraction Systems and Processes
Most of the research and development work on extraction processes and systems has centered in specific systems and operating conditions necessary to accomplish a given purification and/or separation. Inorganic extractions, generally related to the removal of metal ions from solution or the recovery of rare earth and radioisotope metals, have continued to receive a major
share of the research interest (4C, SC, 73C, 77C-19CY 23C, 26C, 28C, 37C, 37C). Of more than passing interest are the works of Bobikov and Plaksin (8C), who attempt to explain the mass transfer exchange using the principles of chemical equilibria and reaction kinetics, and the report of Ishimori and coworkers (79C) who studied the extraction performance of more than 60 elements in a variety of extraction systems. Much of the early research that led to a better understanding of liquid-liquid extraction as a fundamental mass transfer operation was due to the pioneering works in the field of hydrocarbon processing for petroleum refining and petrochemical production and this area continues to receive active interest. References (3C, SC, 7C, 9C, 7OC, 72C, 76C, 24C, 30C, 34C-36C), all refer to extraction processes and operating conditions related to the production and/or purification of hydrocarbons. Ziolkowski (38C) and coworkers describe a four-column (pulse-type) extraction process for producing high purity caprolactam, using trichloroethylene as the solvent; Kagan (27C) and coworkers also present data on the extraction of caprolactam using trichloroethylene as the solvent. Plyashkevich (32‘2) and coworkers have reported on the extraction of caffeine using trichloroethane as the solvent in a sieve plate column. Matutano (27C) recovers mineral acids (0.05 to 10M) from aqueous solutions using Amberlite LA-2 (in kerosine) or trilaurylamine (in xylenes) as the extraction solvent; Kreevoy (25C) adds dodecylphenol, as a synergistic additive, to the amine solvents used for the recovery of inorganic mineral acids to improve the solute carrying power. Kahn and Wayman (2ZC) describe a multistage apparatus for the removal of organic contaminants, such as herbicides and pesticides, from natural waters using a liquid-liquid extraction process. Excellent recoveries and large throughputs were obtained. Baniel and Blumberg (2C) discuss the use of higher alcohols, particularly butyl alcohol, for concentrating aqueous solutions by solvent extraction. This idea has previously attracted interest for its possible adaptation to desalination processes. The use of solvent extraction for desalinating sea or brackish waters does not appear to be particularly promising at its present stage of development except for very special localized economic situations. Beckmann and Ellis (5C) have presented a review of the status of desalination extraction processes, and the annual research and process reports of the Office of Saline Water (29C) detail the latest information in this regard. Aarna and Urov (7C), and Goerz and Hoffman (74C) present information on the extraction of phenols from aqueous solutions. Aarna and Urov are primarily concerned with solvent selection, while Goerz and Hoffman present extensive data using a n RDC column and butyl acetate as the solvent.
R. B. Beckmann is Dean of Engineering, University of Maryland. D. K. Harris and P. N . Vashist are Graduate Research Assistants in the Defartment of Chemical Engineering, University of Maryland.
AUTHORS
Scheibel (33C) describes a multitower solvent extraction scheme using a pair of mutually immiscible solvents; it is particularly attractive for lowering the heat requirements necessary for extraction processes. Jeffreys and Jensen (ZOC) present a n analysis of the complete process considerations for a batch extraction process, including solvent regeneration, and include simulation on a small analog computer; and Fillipov (77C) discusses the selection of the optimum operating conditions and the operating system for separation processes involving two-component systems-i.e., whether to use distillation, extraction, etc. Depending upon your view, once you specify and know the factors necessary to Fillipov’s analysis, the choice becomes relatively obvious. Goren (75C) improves a solvent extraction process by adding a solid that is preferentially wetted by the continuous phase. The principal advantage obtained from the use of such solids as activated charcoal, coal, foamed silicone, Teflon, Benton, PVC, PVCA, polyethylene, and sulfur was improved phase separation. Centrifugal Extractors
I n the centrifugal extractor field, Whatley and Woods ( 6 0 ) place cyclones tandem fashion to form what they term a “Stacked Clone” contactor. The cyclone cascade is such that the underflow from one unit communicates with the overflow from the preceding unit through a separating chamber and a pump. The unit was developed to minimize holdup, which is a critical feature when processing radioactive materials. Claimed stage efficiencies range from GO to 80%. Also for use in the field of radioisotope processing, Clark (30) has reported on a centrifugal type of extractor which utilizes air pressure to control the position of the dispersed phase settling in a centrifugal field and thus obtains improved mass transfer. A British patent ( 7 0 ) relating to the centrifugal extractor field improves the efficiency of extraction by design modifications permitting continuous solvent recirculation. Nadasy and Keraly ( 4 0 ) describe a unique arrangement of a rotating film extractor coupled with a supercentrifuge, which is particularly applicable to emulsion forming systems. Beskow and Palmquist ( 2 0 ) also report a new centrifugal type extractor. Todd and Podbielniak ( 5 D ) describe the various types of centrifugal extractors and present the general theory of centrifugal extraction. Centrally Agitated Columns (Rotating)
Rotating member columns have continued to receive a major share of interest in studies on performance, operating features, and analysis for special extraction problems or generalized studies hopefully leading to improved design and operation. Shtrobel and coworkers (77E, 7ZE) have published a series of papers on the hydrodynamics of RDC columns, both with and without mass transfer. Utilizing a variety of systems, they varied rotor speed between 200 and 2000 r.p.m. and the ratio of dispersed and continuous phase flow rates between 0.20 and 5.0 to develop correlating VOL. 5 8
NO.
11
NOVEMBER 1 9 6 6
99
equations for describing the flooding characteristics of R D C columns. For their mass transfer studies they found the following dimensionless equation to represent the mass transfer performance for aqueous systems: (HTU)od dD
=
CI~II (Fr)a(Ga)-1.27(K,)1.19(Ap/pc)o.71 X
where, M is the distribution coefficient, and L = ( V I ) / VC), the flow rate ratio. K, = We2 Re2/Fr = u 2 / ,u:gdD and G a = p ~ ~ g d = ~ Re2/Fr; ~ / p ~ where ~ we is the Weber number, Re is the Reynolds number, Fr is the Froude number, and Ga is the Galileo number, d D is the diameter of the rotor, and u is the interfacial tension. (For hydrodynamic region I, CI = 1.94 X 1O1O and a = -0.27; for region 11, CII = 1.68 X 1010 and a is 1.85.) The existence of operation in hydrodynamic region I or I1 is defined by the system and the operating variables. The authors claim the above equation reproduces the experimental results to about =!= 23%. Ponikarov and coworkers ( 9 E ) have similarly suggested dimensionless equations for limiting loads and the number of transfer units in RDC extractors. King and Rhodes (7E) give a general review of the field of application for the R D C column and also describe a high efficiency, high volume throughput unit. Stemerding, Lumb, and Lips (75E)have reported axial and backmixing studies in RDC columns and report that mixing behavior can be correlated with geometric and operating variables. Stainthorp and Sudall (74E) used a dye-pulse response technique to evaluate backmixing between stages of an RDC column and found that performance could be effectively predicted on the basis of a n assumed stage efficiency, their developed backmixing factors, and the holdup data or correlations of previous investigators. The expressions proposed refer only to the continuous phase, and definitive work is still lacking to evaluate backmixing of the dispersed phase. Pechstein and Koennecke (8E) studied the “concentration” effect on the degree of dispersion and mass transfer in the mixing zones of an R D C column using a diethylene system. Bock, glycol (2y0 water)-benzene-hexane Hesse, and Reich ( 7 E ) describe a n R D C unit of Jena glass for experimental scale extraction investigations and give relatively complete performance characteristic information for the unit. Kagan and coworkers (6E) have performed a comprehensive evaluation of the hydrodynamics existing within an RDC column. Goerz and Hoffman (3E) have devised a specially constructed RDC unit to permit comparison evaluations with other types of column extractors, and Brink and Gericke (2E) discuss the design problems, concerning a n R D C unit, for those systems in which the phase properties change markedly between stages and for which conventional correlations do not hold. They specifically discuss the design for a contactor to separate oxy compounds from Fischer-Tropsch synthesis oil. 100
INDUSTRIAL A N D ENGINEERING CHEMISTRY
Gutoff (4E) has measured the interstage mixing in a n Oldshue-Rushton column and found it to be low a t low agitator speeds but increasing very rapidly with speed once the turbulence region is reached. The extent of interstage mixing reported by him is similar to that reported in literature for RDC columns. Hartley and coworkers (5E) describe a 10-vessel cascade apparatus where agitation is obtained by using sheathed magnetizable rods within the vessel and moving permanent magnets on the outside. Spence and Streeton (73E) studied the rotary extractor from the point of view of mechanism of operation and utility for the extraction of uranium, and Shell Internationale Research (70E) has patented a modified type of centralIy agitated column. Mixer-Settler Extractors
There have been relatively few really new significant equipment developments during the 1964-65 period. Most of the ideas and innovations have been modifications of the older, more conventional types of mixersettler extractors to overcome a particular operational difficulty and/or improve the performance characteristics necessary for a particular system. The mixersettler-type units, however, continue to receive considerable development interest, because of their versatility and the ease with which operational modifications can be made. Treybal (72F) has incorporated mixersettler units in a vertical extractor tower with a novel design to increase throughputs and improve efficiency. The design permits control of the dispersed phase holdup independent of flow rates and agitator speeds and utilizes recycle to improve performance characteristics. The idea of stacking mixer-settler units in a vertical array within a column is popular for the obvious reasons of conserving spacq and minimizing interconnecting piping. Hazen and Cline ( 5 F ) , Galeev, Gur’yanov, and Mikhailov (3F, 4 F ) , Mehner (IOF),Leisibach (7F),and Entoleter, Inc. ( 2 F ) all describe mixer-settler extractor modifications in a column array to accomplish (hopefully) improved performance. Webster ( 73F) has reported tests on a high intensity mixer which would be suitable for application to mixer-settler extraction units or columns, and Tettamanti and coworkers ( 7 I F ) have designed a vertical mixer for extractor application. Korovin, Reznik, and Apraksin (6F) discuss the application of a mixer-settler extraction column to the recovery of zirconium and hafnium; Borbat and coworkers (IF)describe a unit particularly adapted for slow extraction processes and those difficult to separate which uses vertical barriers and a screw-propeller mixer. Lukhakooder and Surde (8F,9 F ) discuss the design of extractors using propeller mixers and also present a n analytical calculation scheme for conditions of a linear equilibrium dependence. Packed, Spray, and Plate-Type Columns
A staff article in Chemical and Engineering News (7G) recently reported that packed columns for mass transfer
operations, including liquid-liquid extraction, were riding a renewed surge of interest. This optimistic viewpoint was related to improved design techniques which lessened the need for overdesign and resulted in a more competitive position for this simple and fundamental contactor. Despite this reportorial zest, there have been no startling innovations in the field of packed, spray, and plate-type columns that have suddenly enlarged their sphere of applicability; to be sure, improved knowledge of the fundamental behavior of these units is enabling the engineer to design or operate such extractors more efficiently, but their basic limitations remain. Jeffreys and Ellis (78G) have presented a good state-ofthe-art review (for data up to 1962, although published in 1964) on the methods and correlations available for predicting mass transfer rates in spray, packed, and agitated sieve plate columns. Rogen and coworkers (38G) suggest that the scaleup from laboratory or pilot plant extractors be done on the basis of hydrodynamic modeling, disregarding mass transfer effects. This suggestion is based on the premise that hydrodynamic effects dominate such scaleup problems. Unfortunately, the authors do not offer any criteria for determining when such an analogy is applicable, and an unrestrained application could be disastrous. Chandrasekaran and Ladha (5G) have devised yet another generalized correlation for estimating the dispersed phase holdup at flooding for packed columns and relate this holdup to the prediction of mass transfer performance. Since the design or operation of packed, spray, and plate-type extraction columns is intimately related to the magnitude of the dispersed phase holdup, backmixing of either or both phases, and general hydrodynamic behavior, most of the current works have been related to these problem areas. Moon, Hennico, and Vermeulen (34G) have continued Vermeulen’s excellent works on longitudinal dispersion in packed extraction columns-both with and without pulsations. A one-dimensional diffusion model permits an accurate design of the dispersion effect in packed columns. Justice (20G) reports on the use of frequency response methods for the analysis of packed extraction columns. Dunn, Lapidus, and Elgin (73G) present the effect of mass transfer on the dispersed phase holdup and droplet coalescence in countercurrent fluidized systems. Ustraikh, Brounshtein, and Pokorskii (44G) offer comparative extraction performance data on packed and sieve plate columns using multicomponent hydrocarbondiethylene glycol systems. Kroepelin (30G) and Subbaraya (47G) both attempt to improve the performance of packed liquid extraction columns by using an inert gas stream to improve droplet agitation and lessen backmixing. The improvement, as indicated by the HETS, was quite significant in many cases. This method has also been used on spray columns and spray columns containing a variety of dispersion baffles. Rigg and Churchill (37G) have reported on the hydrodynamic behavior of immiscible liquids in cocurrent flow through packed beds. The dispersed phase consisted of spherical droplets with a Gaussian diameter distribution and the
addition of surfactant had a negligible effect on droplet formation. Dil’man (8G) and Chekhov and Planovskii (6G) have reported results on tray type of mass transfer equipment, with particular concern for liquid mixing problems. Pulse column performance (packed, plate, and/or spray) results have been reported by Karpecheva and coworkers (23G, 24G), Lindstrom (3ZG), Kaebisch and Sauer (27G), Kagan (ZZG), Doronin et al. (9G--72G), Konopik and Burkhart (27G), Roshchin et al. (39G), and Kiessling (25G, 26G). Bril and Costa (4G) present flooding data to show increased column capacity with increasing temperature. Dimensionless, generalized expressions for the flooding rates in packed pulsed columns are derived by Konovalov and Romankov (28G). Doronin and Nikolaev (TOG) give a mathematical relationship for determining the combined phase flow rates, and Bolotnikov and Romankov (3G) determine the system dependent constants for a dimensionless, but not generalized, relation for several systems. Theoretical and experimental studies of dispersed phase and longitudinal mixing in sieve plate columns are reported by Bell (7G) and by Sehmel and Babb (40G), respectively. Gel’perin and Neustroev (74G) provide equations and graphs, taking account of longitudinal mixing, for use in the design of pulsed tray-type columns. Misek (33G) applies a theory of turbulence to the flow within the plate holes to obtain a relationship for the drop size resulting from droplet breakup. Still considering pulsed columns, Doronin et al. ( 7 7G) obtain helical flow by drilling holes a t 40’ angles with respect to the plate surface. They find the effect best when alternate plates are perforated in opposite directions with the heavy phase dispersed. With the light phase dispersed Doronin and Nikolaev (9G) had previously used the “best” arrangement and, finding no improvement, attributed the discrepancy to centrifuging of the light dispersed phase. General discussions of pulsed column design are given by Thwaites (43G) and Jones (79G). Vibrating column performance results have been presented by Bolotnikov and Romankov (ZG), and Gel’perin et. a l ( 7 4 G 7 6 G ) . Double perforated plates were used by Gel’perin ( 75G) to achieve greater efficiency. Prochazka et al, (36G) determine empirically an expression for throughput in terms of system and equipment parameters. Grigor’ev et al. (77G) find lower mechanical energy input for a vibrating plate column than for the same size pulsed column. They also give suggested starting design data. Szabo and coworkers (42G) present the advantages of controlled cycling operation when using a sieve plate column, and Perovskii (35G) treats the effect of piston-induced pulsations on extraction column performance using a theory of harmonic oscillations. The agreement between measured and calculated values is quite good. There were three significant modifications to pulsed and vibrating types of extraction columns apart from minor modifications, on existing types, to improve perVOL. 5 8
NO. 1 1
NOVEMBER 1 9 6 6
101
formance characteristics. Koski (29G) pulses a column containing spaced plates which are “wet” only by one of the phases in such a manner that the continuous phase alternates and emulsion conditions are obtainedthe column may also be operated as a mixer-settler unit. Landau et al. (37G) modify a vibrating plate column to permit the passage of the continuous phase around the perforated vibrating plates rather than through them. The column is analogous to a vibrating sieve plate column. Wagner (45G) also modifies the vibrating plate principle by using tapered vibrating passages which assist with a pumping action and superimposing fixed baffles between the vibrating plates. laboratory Equipment
While laboratory equipment, per se, was not considered a primary objective of this review since almost anything from buckets to milk bottles may be effectively used in this regard, there were, however, a few significant articles of interest to the practitioner or researcher in the field of liquid-liquid extraction. Palacek and Skala (8H)describe a continuous, universal extractor which may be used under reduced-pressure conditions, and Meltzer, Buchler, and Frank ( 6 H ) describe a completely automated laboratory extractor which may be operated unattended. Bergot ( 7 H ) similarly describes an automatic apparatus which uses a pulsed gas stream to entrain dispersed droplets and afford automatic control. Sarma ( 7 0 H ) describes an all-glass continuous laboratory extraction apparatus developed for evaluating extraction processes relating to rare metals recoveries. Other laboratory extraction apparatus of glass are described by Doering and Tarver ( 3 H ) , Ferrari (H), Oriton (7H), and Sandoval (9H). A laboratory mixer-settler type of apparatus having 10 or 20 stages is described by Sraier (72H), and Josephson ( 5 H ) and Butler (2H)relate to the use of the Soxhlet type of extractor, the latter showing the modifications necessary to enable the “dry type’’ to be used as a liquidliquid extractor. Wasicky (74H) describes an improvement to the Clevenger apparatus, and Schoenenberger (77H) modifies the Craig apparatus to permit a variable heavy phase layer volume. Finally, Stage ( 7 3 H ) has reviewed the procedures and apparatus available for laboratory liquid-liquid extractions. Miscellaneous Equipment
There are always a few equipment innovations which are dictated by specific and unusual processing conditions but nonetheless do represent equipment ideas although they do not fit the normal scheme of classification. The period 1964-65 was no exception. Watt (41) utilizes two counterrotating drums, with interconnecting tubes for interphase movement, for particular application in the vitamin industry. Holt and Desborough ( 7 1 ) use perforated plates in a horizontal array ; the perforated plates being grouped in clusters with a larger spacing between “clusters” for coalescence and separation. The unit is reported to offer an improvement over similar horizontal extractors because 102
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
of the variable spacing and the fine dispersions produced. Schaub, Hibbel, and Schleper (21) modify the conventional spray-type extraction column with an internal spiral and the use of a recirculating inert gas stream to provide additional agitation and temperature control. This latter scheme of utilizing a gas stream to improve droplet dispersion and turbulence and to modify the normal holdup relationships has also been used with conventional types of spray or packed columns. A British patent of the U. S. Atomic Energy Commission (31) describes the use of a series of annular columns surrounding the central extraction column to improve the radiation hazard conditions attendant with the extractive processing of spent uranium fuel rod solutions.
REFERENCES General Reviews (1A) Alimarin, I. P., Zolotov, Yu. A., J . Anal. Chem. USSR (Engl.) 17 (2), 263 (1962). (2A) Balt, S., Chem. Weekblad 60 (121, 161 (1964). (3A) Bischoff, K . B., Himmelblau, D. ?VI., ISD. ENO.CHEM.56 (12), 61 (1964). (4A) Ellis, IV. B., Beckmann, R.B., Ibid., 57 (111, 103 (1965). (5A) Hanson, C., Brit. Chem. Eng. 10 (l),34 (1965). (6A) Ingamells, C. O., Chemirt-Analyt 53 (Z), 55 (1964). (7A) Ipenburg, K . Van, Chem. Weekblnd 59 (40), 540 (1963). (8A) Kamori, S., Tanaka, M., Buseki Kagaku, Shinpo Sosetsu 1964, p. llOR. (9A) Kyrs, M.:Konecny, C., Jerabek, V., Chem. Listy 59 (Z), 193 (1965). (10A) LeRoux, L. J., Tydskr. Natuur. iuetenrkappe 3 (l), 25 (1963). (11A) Markov, V. K., Korinfskaya, M. F., Zauodsk. Lab. 28 ( l l ) , 1376 (1962). (12A) Rozen, A. M . , Khim. Prom. 2,85 (1965). (13A) Ziolkowski, Z., Zhidkostnaya Ekstroktisya u Khimcheskoi Promyshlennasti, Leningrad, Gas. Nnuchn. Tekhn. I z d . Khim. Lit. 1963, 478 pp. (14A) Zolotov Yu A. T r . Komis. Po Analit. Khim. Akad. Nauk SSSR, Inst. Geokhim. Analit. Khim.’15, 3 ! (1’965). (15A) Zolotov Yu. A. Petrukhin, 0. M., Z h . Vses. Khim. Obschchestva im. D. Z. Mendeleeuo 9’(2), 145 ’(1964). General Calculation Procedures (1B) Barreiro, G . T., Quim. In:. (Bilbno) 9, 50 (1962). (2B) Brounshtein, B. I., ProLsessy Zhidkostnoi Ekstraktsii, Tr. Nauchn.-Tekhn. Soveshch., Leningrad 1961, 76. (3B) Davison, R. R.,Harris, 1%’. D., A.I.Ch.E. J . 11 (31, 555 (1965). (4B) Friday, J. R., Smith, B. D., Ibid., 10 (5), 698 (1964). (5B) Frolov, A. F., Stepanova, V. A,, Uch. Zap. Yaroslavsk. Tekhnol. Inst. 8 , 347 (1 962). (6B) Kiessling, R., Kernenergie 6 (IO), 540 (1963). (7B) Mel’nikov, B. G., Z h . Prikl. Khim. 37 (21, 317 (1964). (8B) Mills A . L., U.K. At. Energy Authority, Reactor Group, T R G Rept. No. 902(D) 10 pp. d965). (9B) Mitten, L. G., Nemhauser, G. L., Can. J.Chem. Eng. 41 (5), 187 (1963). (10B) Moegli, A , , Chem. Ingr. Tech. 37 (3), 210 (1965). (11B) Nikolaev, A. V., Kolesnikov, A. A., Dokl. Aknd. Nauk SSSR 163 ( 3 ) , 681 (1 965). (12B) Oliver, E. D., Hydrocarbon Process. Petrol. Rejner 42 ( 1 2 ) , 107 (1963). (13B) Pol’skii, G. V., Izv. Vysshikh Uchebn. Zauedenii, Pihchevaya Tekhnol. 6 , 125 (1963). (14B) Prochazka, J., Landau, J., Collection Czech. Chem. Commun. 28, 1927 (1963). (15B) Rod, V., Brit. Chem. En!. 9,300 (1964). (16B) Takamatsu, T., Nakanishi, E., Kugaku Kogoku 27 (12), 932 (1963). (17B) Wilburn, N. P., IND. ESG. CHEM.FUNDAMEXTAU 3 ( 3 ) , 189 (1964). Extraction Systems a n d Processes (1C) Aarna, A , , Urov, K. E., T r . Tallinsk. Politekhn. Inst., Ser. A . 210,109,1964. (2C) Baniel, A,, Blumberg, R., Ind. Chemist 39, 9, 460 (1963). ( 3 C ) Barton, Paul, Ph.D. thesis, Pennsylvania State University, University Microfilms (Ann Arbor, Mich.) 64-5339,329 pp., 1964. (4C) Beccu, K. D., Kerntechnik 6 (l), 5 (1964). (5C) Beckmann, R. B., Ellis, W. B., First Znt. Sym. on Water Desalinalion SWD-19, Washington, D. C., Oct. 3-7, 1965. (6C) Bikkulov, A. Z . , Popov, V. A., Groschev, B. M., Khim. i Tekhnol. Topliud i M a s e l 10 (6), 13 (1965). (7C) Bikkulov, A. Z . , Popov, V. A , , Groschev, B. M., Ne,ftepererabotka i A’eftikhim Nauchn,-Tekhn. Sb. 1965 (6), p. 33. (8C) Bobikov, P. I., Plaksin, I. N., Izu. Akad. Nauk SSSR Met. i Gorn. Delo. 1964 (3), p. 107. (9C) Coltington, G. I. (toTexaco, Inc.), U. S . Patent 3,200,065 (Aug. 10, 1965). (1OC) Fierce, M‘. L., Millikan, A. F. (to Pure Oil Co.), Ibid., 3,197,400 (July 27, 1965). (11C) Fillipov, G. G., T r . Mosk. Khim. Tekhnol. Inst. 40, 113 (1963). (1ZC) Gere, D. R., Ph.D. thesis, Kansas State University, University LMicrofilms (Ann Arbor, Mich.) 65-6856, 142 pp., 1965. (13C) Gerisch, S., Ziegenbolg, S., Neue Huette 9 (l), 39 (1964). (14C) Goerz, R., Hoffman, G., Chem. Tech. (Berltn) 16 (2), 80 (1964).
(15C) Goren, M. B. (to Kerr McGce Oil Ind., Inc.), U. S. Patent 3,154,390 (Oct. 27, 1964). (16C) Groll, H . P. A., Ibid., 3,186,938 (June 1, 1965). (17C) Guenzler G., Moehl, P., Reinstst@ Wiss. Tech., Intern. Symp. 7, Dresden, 1961, p. 193 (Publ. 1963). (18C) Hauighorst, C. R., Chem. Eng. 70 (231, 228 (1963). (19C) Ishimori, T., Akatsu, E., Wen-Pin Cheng, Tsukuechi, K., Osakabe, T., U. S. At. Energy Comm. Accession No. 4245, Rept. JAERI-1062,32pp. (1964). (2OC) Jeffreys, G. V., Jensen, V. G., Brit. Chem. Eng. 10, 304 (1965). (21C) Kagan, S. Z., Trukhanov, V. G., Kostin, P. A,, Krudryavtsev, E. N., Khim. Prom. 2, 94 (1964). (22C) Kahn, L., Wayman, C. H., Anal. Chem. 36 (7), 1340 (1964). (23C) Khapkar, S. M., Sb. Cult. (Culcutta) 30 (4), 191 (1964). (24C) Knowles W D Nelson B A (to Shell Internationale Res. Maatschappij) Ger. Patent 1:19i,5!$ (June io, i9i5). (25C) Kreevoy, M. M., Ditsch, L. T. (to General Mills), U. S . Patent 3,186,809 (June 1, 1965). (26C) Lyle, S. J., Shendrikar, A. D., Anal. Chim. Acto. 32 (6), 575 (1965). (27C) Matutano, L., Comm. Energie At. (Rr.) Rappt. C. E. A-R 2760,55 pp. (1965). (28C) Moore, F. L., Mullins, W. T., Anal. Chem. 37 (6), 687 (1965). (29C) Office of Saline Water, U. S. Dept. of Interior, Saline Water Conversion Report, published January each year. (30C) Penisten, J. R. (to Univ. Oil Prod. Co.), U. S. Patent 3,179,708 (April 20, 1965). (31C) Peppard, D. F., Mason, G. W., Argonne Nutl. Lub. Rev. 1 (3), 11 (1964). (32C) Plyashkevich A. M., Bulatov, S. N., Ryabinin, V. A., Zelinskaya, L. G., Med. Prom. SSSR i 9 (5), 37 (1965). (33C) Scheibel, E. G. (to York Process Equipment Corp.), U.S. Patent 3,177,196 (April 6, 1965). (34C) Sheely, H. R., Wilkinson, W. F. (to Badger Mfg. Co.), Brit. Patent 945,245 (Dec. 23, 1963). (35C) Sherk, F. T. (to Phillips Petroleum Co.), U. S. Patent 3,201,492 (Aug. 17, 1965). (36C) Sidorchuk, I. I., Indyukov, N. M., Mardzhanov, G. M., Arerb. Khim. Zh. 5 , 11 (1964). (37C) Sraier, V., Judernu Energie 11, 336 (1965). (38C) Ziolkowski, Z., Respondek, J., Przondo, J., Przemysl. Chem. 43.(4), 224 (1964)’ Centrifugal Extractors (ID) Aktiebolag Separator, Brit. Patent 992,858 (May 26, 1765). (2D) Beskow, S., Palmquist, T. E. (to Aktiebolag Separator), Ibid., 941,937 (Nov’ 20, 1963). (3D) Clark, A. T., Jr., Nucl. Sci. Abstr. 19 (9), 1922 (1965). (4D) Nadasy, M.,Keraly, R., Nehervegyip Kut Inst. Kozlemen 2, 315 (1963). (5D) Todd, D. B., Podbielniak, W. J., Chem. Eng. Prog. 61 (5), 69 (1965). (6D) Whatley, M. E., Woods, W. M., U. S . At. Energy Comm. ORNL-3533, 51 pp., 1964. Centrally Agitated Columns (Rotating) (1E) Bock, L., Hesse, A., Reich, G., Chem. Tech. (Berlin) 16 (21, 85 (1964). (2E) Brink, A,, Gericke, J. J., S.African Ind. Chemist 18 (II), 152 (1964). (3E) Goerz, R., Hoffman, G., Freibergrer Forschungsh 295A, 11 (1 964). (4E) Gutoff, E.B., A.I.Ch.E. J . 11 (4), 712 (1965). (5E) Hartley, G. S., Howes, R., McLauchlan, J. W. G., Lab. Pruct. 14 ( S ) , 578 (1965). (6E) Kagan, S Z Aerov M . E Volkova T. S Protsess Zhidkustnoi Ekstruktsii, Tr.Nauchn.-?ekik. Suveslkh. LeniAggrud 1961: 156 (Gub. 1961). (7E) King, P. J., Rhodes, E., M f g . Chemist 35 (61, 51 (1 964). (8E) Fechstein, G., Koennecke, H. G., Z. Physik. Chem. (Leiprig) 225 (5/6), 418 (1964). (BE! Ponikarov, I. I., Nikolaev, A. M., Zhavoronkov, N. M., T r . K U Z Q WKhim. ~, Technol. Inst. 1962 (30), p. 352. (10E) Shell Internationale Research Maatschappij, N. V., Belg. Patent 632,926 (Nov. 28, 1963). (11E) Shtrobel, V., Romankov, P. G., Konovalov, V. I., Lyutaya, N. S., Z h . Prikl. Khtm. 36 (12), 2672 (1963). (12E) Ibid., 37 (l), 50 (1964). (13E) Spence, R., Streeton, R. J. W., Chem. Process Eng. 44 (lo), 597 (1763). (14E) Stainthorp, F. P., Sudall, N., Trans. Inst. Chem. Eng. (London) 42 (5), T198 (1964). (15E) Stemerding, S., Lumb, E. C., Lips, J., Chem. Zngr. Tech. 35 (121, 844 (1963). Mixer-Settler Extractors (1F) Borbat, V. F., Baranov, M. N., Borisovskii, V. F., Bobikov, P. I., U.S.S.R. Patent 167,819 (Feb. 5, 1965). (2F) Entoleter, Inc., Neth. Patent 6,409,249 (Feb. 15, 1965). (3F) Galeev, A. F., Gur’yanov, A. T., Mikhailov, G. M., U.S.S.R. Patent 159,491 (Dec. 28, 1963). (4F) Ibid., 167,824 (Feb. 5, 1965). (5F) Haaen, W. C., Cline, R. L. (to Kerr-McGee Oil Ind., Inc.), U. S. Patent 3,206,288 (Sepr. 14, 1965). (6F) Korovin, S. S., Reznik, A. M., Apraksin, I. A., Blirkikh p o Suoistuam Redkikh Metal. 1962, p. 42. (7F) Leisibach, J., Chem. Zngr. Tech. 37 (31, 205 (1965). (8F) Lukhakooder, E. T., Surde, E. K., Tr. Tullinrk. Politekhn, Inst. Ser. A 210, 193 (1964). (9F) Ibid., p. 179. (10F) Mehner, W. (to Metallgesellschaft A. G.), Ger. Patent 1,184,322 (Dec. 31’ 1964). (11F) Tettamanti, K., Migra E., Nagy, S., Nogradi, M., Sawinsky, J., Hung. Patent 151,614 (Sept. 25, 1&4). (12F) Treybal, R. E., Chem. Eng. Prog. 60 (5), 77 (1964). (13F) Webster, D. S., U. S. At. Energy Comm. DP-847,35 pp. (1763). Packed, Spray, a n d Plate Type Columns (1G) Bell, R. L., University of Washington, Seattle, University Microfilms (Ann Arbor, Mich.), Order No. 64-11, 156, 517 pp.; Dissertation Abstr. 25 (5), 2895 (1964) (Eng.).
(2G) Bolotnikov, F. S., Romankov, P. G., Zh. Prikl.Khim. 3 7 (l), 46 (1964). (3G) Ibid., (Z), 310 (1964). (4G) Bril K. J. Costa, E. C., Publ. IEA No. 77, Inst. Energia At., Brazil, 47 pp. (1 964) IEng.).’ (5G) ,Chandrasekaran, P., Ladha, G. S., Chem. Process Design Symp., Banguloru. Indtu 1961, 129 (Publ. 1963). (6G) Chekhov, 0.S., Planovskii, A. N., Sokolinskii, Yu. A,, Khim. Orom. 10, 768 (1964). (7G) Chem. Eng. News 43 (38), 64 (1965). (8G) Dil’man, V. V., Zh. Prikl. Khim. 37 (ll), 2456 (1964). (9G) Doronin, V. N., Nikolaev, A. M., Izvest. Vysshikh Uchebn. Zuuedenii, Khim. Khim. Tekhnol. 7 (41, 665 (1964) (Russ.). (10G) Ibid., (3), 497 (1964). (11G) Doronin, V.N.,Nikolaev, A.M., Khim.i Ne/t.Mushinostr.2,5 (1965). (12G) Doronin V N Zhavoronkov N. M Nikolaev A. M. Protsesry Zhidkostnoi Ekstraktsii, T:.iuucxn.-Tekhn. Suwesh)ch., Len&grud 1961: 132 (&b. 1963). (13G) Dunn, I., Lapidus, L.,Elgin, J. C., A.I.Ch.E. J. 11 (l), !58 (1965). (14G) Gel’perin, N. I., Neustroev, S. A., Khim. Prom. 5,360 (1964). (15G) Gel’ erin, N. I., Pebalk, V. L., Chekhomov, Yu. K., Khim. Prom. 41 (l), 37 (1 965p (Russ.). (16G) Gel’perin N.I., Pebalk, V. L., Chekhomov, Yu. K.,U.S.S.R.Patent 166,649 (Dec. 1, 1964f. (17G) Grigor’ev, S. M.,Neimand, N. V., Miroedova E. V. Burtseva, V. N., Anikeev, L. S., Protsessy Zhidkostnoi Ekstruktsii, Tr.’ Nauchb.- Tekhn. Soucshch., Leningrad 1961, 204 (Pub. 1963). (18G) Jeffreys, G. V., Ellis, S. R. M., Congr. Chem. Eng. Equip. Design 1962, 65 (Publ. 1964). (19G) Jones S. C. University of Michigan, Ann Arbor, University Microfilms (Ann Arbbr, Miih,), Order No, 63-6911, 190 pp.; Dissertation Abstr. 24, 1519 (1963). (20G) Justice, R. G., U. S . At. Energy Comm. T.1.D.-21986,159 pp. (1963). (21G) Kaebisch, G., Sauer, H., Ger. Patent 1,168,392 (April 23, 1964). (22G) Kagan, S. Z . , Aerov, M. E., Lonik, V., Volkova, T. S., Iruest. Vysshikh Uchebn. Zauedenii, Khim. i Khim. Tekhnol. 8 ( l ) , 142 (1965) (Russ.). (23G) Karpecheva, S. M., Chemarin, N.,G., Bychkov, A. E., Zakharov, E. I., Devyatkin, V. I., Zhadanov, B. V., Khim. t Nejt. Mushinostr. 1,24 (1965). (24G) Karpecheva, S. M., Zakharov, E. I., Kiseleva, L. F., Zh. Prikl. Khim. 37 (12), 2668 (1964). (25G) Kiessling, R., East Ger. Patent 37,145 (April 26, 1965). (26G) Kiessling, R., Kernenergie 6 (4), 168 (1963) (Ger.). (27G) Konopik, A. G., Burkhart, L., U. S. At. Energy Comm. IS-334, 66 pp. (1960). (28G) Konovalov, V. I., Romankov, P. G., Protsessy Zhidkoslnoi Ekstruktsii, Tr. Nauchn.-Tekhn. Soueshch., Leningrud 1961, 138 (Publ. 1963). (29G) Koski, 0. H., (to the U. S. At. Energy Comm.), U. S. Patent 3,108,859 (Oct. 29, 1963). (30G) Kroepelin, H.,Brit. Patent 3,110,568 (Nov. 12, 1963). (31G) Landau J Prochazka J., Souhrada, F., Nekovar, P., Cull. Czech. Chem. Commun. 29 (12j,’3003 (19645. (32G) Lindstrom, 0. (to Allmanna Svenska Elektriska Aktiebolag), S . Patent 3,110,568 (Nov. 12, 1963). (33G) Misek, T . ,Collection Czech. Chem. Commun. 29 (I), 755 (1964). (34G) Moon J, S. Hennico, A., Vermeulen, T., U. S. At. Energy Comm. UCRL10928,114pp. (i963). (35G) Perovskii, A. P., Khim. i Ne/t. Mashinostr. 3, 23 (1965). (36G) Prochazka, J., Landau, J., Nekovar, P., Souhrada, F., Collection Cxech. Chem. Cummun. 30, 158 (1965) (Eng.). (37G) Rigg,R. C.,Churchill, S. W., A.Z.Ch.E. J . 10 (6), 810 (1964). (38G) Rogen, A. M., Lapavok, L. I., Elatomtsev, B. V., Khim. i Neft. Mushinostr. 4, 14 (1964). (39G) Roshchin, A. N., Baranov, G. P., Chemezov, V. A., T r . Vses. Nauchn.-Zssled. I Konslrukt. Inst. Khim. Mashinostr. 35, 61 (1960). (40G) Sehmel, G. A., Babb, A. L., IND.END.CHEM.,PROCESS D E s I o N DEVELOP. 3 (31, 210 (1964). (41G) Subbaraya, K., Indian Chem. Eng. 5 (3), 65 (1963). (42G) Szabo T. T Lloyd, W. Q., Cannon, M. R., Speaker, S. S., Chem. Eng. Progr. 60 (i),66 (i964). (43G) Thwaites, J. M., Dechemn Monograph. 55 (955-975), 241 (1965) (Eng.). (44G) Ustraikh, M. A , , Brounshtein, B. J., Pokorskii, V. N., T r . Nauch. Tek. Sou., Leningrad 1960, 74 (Pub. 1963). (45G) Wagner, R. C. (to Societe Saint-Gobain Nucleaire), Fr. Patent 1,388,767 (Feb. 12, 1965).
u.
Laboratory Equipment (1H) Bergot, J., Annr. Fuls. Expert Chim. 57 (664), 157 (1964). (2H) Butler, T. J., Am. J. Clin. Path. 41 (6), 663 (1964). (3H) Doering, C. H., Tarver, G. H., Anal. Biachem. 9 (4), 489 (1964). (4H) Ferrari, A. (to Technion Instruments), Belg. Patent 638,262 (April 6, 1964). (5H) Josephson, B., Clin. Chim. Actu 10 (3), 290 (1964). (6H) Meltzer, H. L.,Buchler, J., Frank, Z., Anal. Chem. 37 (6), 721 (1965). (7H) Oriton, L., Ion 24 (2741, 269 (1964). (8H) Palacek, J., Skala, V., Chem. Listy 5 8 (9), 1095 (1964). (9H) Sandoval, A., Bol. Inst. Quim. Univ. Nul. Anton. M e x . l5,25 (1963). (10H) Sarma, B., L A B D E V (Kanpur, India) 3 (I), 50 (1965). (11H) Schoenenberger, H., Eder, M., Bamann, E., Z. Anal. Cham. 202 (l), 1 (1964). (12H) Sraier, V., Judernu Energie 11, 52 (1965). (13H) Stage, H.,Chem. Z. 88,13, 517 (1964). (14H) Wasicky, R., REU.Fuc. Farm. Bioguim. Uniu. Suo Puulo 1 (l), 77 (1963). Miscellaneous Equipment (11) Holt, N. A. H., Desborough, D. (to A. P. Y. Ltd.), Brit. Patent 995,766 (Jan. 23, 1965). (21) Schaub, F Hibbel, J Schleper, B. (to Ruhrchemie, A. G.), Ger. Patent 1,183,890 ( ~ 2 23, . 1964j.’ (31) U. S.At. Energy Comm.,Brit. Patent 1,003,965 (Sept. 8, 1965). (41) Watt, P. R. (to Vitamins Ltd.), Zbid., 988,646 (July 21, 1965).
VOL. 5 8
NO. 1 1
NOVEMBER 1 9 6 6
103
