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sugar boiler evaporation by using the condensate to drive a direct current generator by ... (3) Badger, W. L.. and Pye, D. J., Chem. E w . Progress, 4...
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INDUSTRIAL AND ENGINEERING CHEMISTRY

January 1952

Berger (7);the principle of vapor displacement is used in a sealed feed chamber. Tringer (49) describes a method of measuring sugar boiler evaporation by using the condensate to drive a direct current generator by means of a turbine. The voltage generated is proportional ‘to the evaporation rate and it is possible to integrate to obtain the total. Zahm (68) discloses a vacuum evaporator and condenser with special controls and discharge mechanism. The construction and operation of vacuum jets are explained and typical evaporator and dryer applications are worked out in detail by Tarasov (48). LITERATURE CITED

(I) Andersen, R., Dan. Patent 70,637(Feb. 20,1950). (2) Anderson, F. M., Repts. Hawaiian Sugar Teohnol., 5, 109-13 (1947). (3) Badger, W. L.. and Pye, D. J., Chem. E w . Progress, 46, 486-9

(1950). (4) Basu, K.L., Indian Patent 40,187 (June 7,1950). (5) Beau, Ch., and Nizery, M., Trans. 4th World Power Conf., &et. K, paper 3 (1950). ( 6 ) Bennett, A. N., U. S. Patent 2,535,117(Dee. 26, 1950). (7) Berger, F., C h m . Tech. (Berlin), Ver. Chem. Appa., 18, 12-13 (1945). ( 8 ) 3ergatrom, E.0. V., and Trobeek, K.G., Swed. Patent 129,903 (Oct. 24, 1950). (9) Bonnet, W. E., and Gerster, J. A., Chem. Eng. Progress, 47. 151-8 (1951). (10) Camp, A. C.,Sugar, 45, No. 6, 26-7 (1950). (11) Camp, A. C., and Slater, L. E., Chem. Eng., 57, No. 9, 108-11 (1950). (12) Chow, T. Y.,Chang, P. K., and Cheng, C. P., Taiwan Sugar J . Quart.,3,No. 1, 10-15 (1950). (13) Chow, T. Y.,Tseng, R. H., Chang, P. K., and Cheng, C. P., Ibid.. 3. NO.1. 1-9 (1950). (14) Craig, L.-C., Gregory; J. D., and Hausmann, W,, Anal. Chm., 22,1462 (1950). (15) Delgrado, S.V.,SugarZnd. Abstrao#s,11, 178 (1949). (16)Dornig, M., ahd Belloni, A., Ital. Patent 448,833 (May 27, 1949). (17)Douwes-Dekker, K.,S.African Sugar J., 34,297-305 (1960). (18)Essen, C.G., Svensk Papperstidn., 52,549-59 (1949). (19) Farber, E.A., Tram. A m . Soo. Mech. E w e . , 73,247-56 (1951). (20) Fritz, W.2. Ver. deut. Ing., Verfahrenstech,1, 1-1V (1943). U.S.Patent 2,535,730(Dee. 26,1950). (21) Gadret, R.H.,

m

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Hagglund, E., Tappi, 33,520-7 (1950). Henseey, R. O.,U. S.Patent 2,537,346(Jan. 9,1951 ). Holland, A. A., Chem. Eng., 58, No. 1, 106-7 (1951). Jackson, 8.B., Gas J., 262,395-7 (1950). Kermer, M.J., U. S. Patent 2,510,233(June 6,1950). Kirschbaum, E.,and Wachendorff, W.. 2. Ver. deut. Ing., Verfahrenstech, 3,61-71 (1942). Kuzub, N. A., Sakhornaya Prom., 23, No. 10,8-10 (1949). Lesesne. S. D.. U. 8.Patent 2.532.928(Dee. 5.1950). Lockman, C. J., Swed. Patent 128,820 (July 25, 1950). Zbid., 128,821 (July 25,1950). Lukyanov. N.,Myasnaya i Molochnaya Prom., 11, No. 4, 11-15 (1950). Zbid., No. 5,9-14 (1050). Matula, M.A., Sakhanucya Prom., 24, No. 2, 36-7 (1950). Muller, H., Swiss Patent 248,793(Feb. 16,1948). Zbid., 267,586 (June 16,1950). Nevstruev, I. I., SakharnuyaPrm., 24, No. 6,ll-14(1950). Pajares, J. A., Anales moc. Peruna technol. amcar, 1, 137-40 (1950). Phillips, M. A., Chem. Age (London),63, 681-2 (1950). Ramen, T.,Swed. Patent 129,221 (Aug. 22, 1950). Zbid., 130,277 (Dee. 5, 1950). Ibid.. 130,278 (Dee. 5, 1950). Rathje, C., and Schmitz, W., Ger. Patent 801,017 (Dee. 18, 1950). Rosenblad, C., Pulp & Paper Mag. Can., 51, No. 6 , 85-94 (1950). Rosenbloom. W. J., U. S.Patent 2,516,832(July 25, 1950). Schwob, Y.,French Patent 940,507(Dee. 15, 1948). Simmons, L. D., Chem. Eng., 57, No. 11,156-7 (1950). Tarasov, F., Myasnaya i Molochnaya Prom., 12, No. 1, 17-24 (1951). Tringer, F., Cukwipar, 3,9543 (1950). Troitskif, N.Y.,Sakharnaya Prom., 23, No. 2,21-4 (1949). Ulmer, R. C., Sugar, 45, No. 10,30-1 (1950). Van Heyningen, W.E., Brit. J . Exptl. Path., 30,302-5 (1949). Vogelbusch, W., 2. Ver. deut. Ing., Verfahremtech, 3,73 (1943). Weissberger, A., “Technique of Organic Chemistry,” New York, Intarscience Publishers, 1950. de Wijs, J. C., J . Phys. & Colloid Chem., 54,599-601 (1950). Wiseman, J. V., Blackmun, L. A., and Hellmers, H. D., U. S. Patent 2,528,481(Oct. 31,1950). Wolff, C. L.,and Leibson, I., Southern Power and Ind., 48, No. 8, 64-8 (1950). Zahm, G. G., U. S. Patent 2,512,513(June 20,1950). R E C E I V ~Octeber D 211, 1951.

SO WENT EXTRACTION ROBERT E. TREYBAL

NEW YORK UNIVERSITY, NEW YORK 53, N. Y .

In liquid extraction, noteworthy progress has been made in the gathering of equilibrium data and in the study of single liquid drops, mixing and settling characteristics of two-phase liquid mixtures, and methods of calculation particularly for double-solvent systems, as well as equipment design and operating characteristics. Metal separations, especially of the rarer metals, continued to occupy considerable attention. In the petroleum field activity was centered about the treatment of the lighter distillates, and a great many new applications of extraction to difficult separation problems were proposed. In leaching, the year’s progress is characterized by fundamental studies on rates of diffusion In relatively simple systems, and suggestions for new solvents for oilseed processes.

Scheibel and Frey (916)and Brown et al. (51)have summarized the subject briefly. An extended treatment in textbook tom has also become

(963). DIFFUSION AND EQUILIBRIA

T

HE tempo of reported activity in both the liquid and solid extraction fields has increased considerably during the past year. This review is not exhaustive, therefore, but is necessarily limited t o the major contributions and t o typical examples taken from among the remainder. LIQUID EXTRACTlON

Several reviews covering all aspects of the subject have appeared. In addition t o the annual review of this series (9&2),

A large number of measurements of diffusion coefficients have been reported which cannot be summarized here. Several new types of apparatus and techniques for this purpose are of interest, however ( 9 , 3 6 , 4 l ,61, 79,806, 966). The relationships between diffusivity and molecular dimensions have been investigated (IN), and an empirical method for estimating diffusivities from concentration, viscosity, and surface-tension data has been proposed (186). Bosworth discussed briefly (9.3) and at length (98)the mechanisms of various types of diffusion and mass trans-

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coefficients for various solute-solvent systems were determined as follows: acetic acid between water and ethyl acetate, butyl Components acetate, ethyl propionate, and ethyl butyrate ( 2 4 3 ) ; acetic and butyric acids between water and isophorone or o-cresol (124); System Tem%eE+ture* ~~~~~~E~ Water-uranyl nitrate-ethyl ether 25 (187) penicillin between water and butyl acetate, ethyl acetate, and -diethyl Cellosolve 25 trichloroethylene as a function of p H (267); acetylacetone be-dihexyl ether 25 (1~71 tween benzene and water (110);acetic, citric, tartaric, and gly-methyl isobutyl ketone 25 -isobutyl alcohol 25 (187) colic acids between water and tributyl phosphate as a function of -aluminum nitrate-hexyl alcohol 25 (846) -pyridine-benzenea 15, 45, 60 (%SO) temperature (188); a number of methyl-substituted pyridines -methyl ethyl ketone-naphtha 26.7 (18) and quinolines between cyclohexane or chloroform and water or -furfural-kthylene glycol 25 (68) Propane-methane-stearic acid 85.4.71.2 (18) citrate-phosphate buffer (90); uranyl nitrate between water and -trimyristin 69.6,61 (18) ethyl, butyl, amyl, and isopropyl acetates, methyl ethyl and Benzene-heptane-furfural ca. 25 (21.2) methyl isobutyl ketones, and n-butyl, isobutyl, and isoamyl alco-@,@I-irmnodipropionitrile ea. 25 (812) -8, @'-oxydipropiomtrile ca 25 hols and isobutyl methyl carbinol ( 1 2 9 ) ; iodine between carbon -@,@'-thodipropionitrile ca 25 -(methylimino) diacetonitrile ca: 25 {$I$)tetrachloride and aqueous potassium iodide (136); some 150 -8- [(cyanomethyl)ethylaminoI organic compounds of various types between water and isobutyl1 propionitnle ca. 25 (818) -8-(cyanomethoxy)propionitrile ca. 25 (82.9) alcohol (46); and nicotine between water and a variety of solvents -2-cyanoethyl acetate ca. 25 (BIB) -a,8'-oxydipropionitrile ea. 25 (81%) as a function of temperature (9). Equilibrium distribution meas-N,N-bis(2-cyanoethyI)scetamide ca. 25 ($18) urements served as a means of studying other phenomena: the -cyclohexane-@, 8'-iminodipropionitrile ea. 25 -@, 0'-oxydipropionitrile ca. 25 exchange of CN beheen h'i(CN)4'- and C N - ( 1 4 7 ) ; the hy-@, @'-thiodipropionitrile ca. 25 b21B) drolysis and polymerization of zirconium in perchloric acid 8-Methylnaphthalene-dodecane- @,@'-iminodi(61); the formation of complex ions of thorium (60); and protein propionitrile ca. 25 (81.9) - 8 ,B'-oxydipropionitrile cs. 25 ()lB) binding (116). Golumbic and Weller described a new technique -Tetralin-8, 8'-oxydipropiofor measuring unusually large distribution coefficients (91). 25 Application of the Gibbs-Duhem equation t o the prediction of a Solutropic. liquid-liquid equilibria (28), and empirical treatment of the total vapor pressures of binary systems to obtain activity coefficientc in ternary systems (32) were reviewed. Various rare-earth chlorides and nitrates were distributed between water and l-pentanol containing ammonium thiocyanate fer: molecular and eddy, ordinary and activated, steady- and ( 5 ) . Data for the systems methyl isobutyl ketone and aqueous unsteady-state. Treatments of the phase rule and heterogeneous equilibria, inhydrochloric acid with sodium dichromate, vanadic acid, and cluding those portions of the subject of particular interest here, sodium dichromatevanadic acid mixtures were reported (267). are available in the comprehensive treatise by Ricci (203) and in Methods of predicting quaternary equilibria from termary data were reviewed by Brancker ( 1 4 , 2 6 ) ,and graphical representations the less extensive work of Wetmore and LeRoy (269). Zernike (278)considered a modification of the phase rule in applications t o of quaternary (25, 199, 246), quinary (131 ), and polycomponent critical phenomena. ( 1 9 2 ) equilibria were described. A system containing eight The miscibilities of l,l'-dichlorodimethyl ether with alcohols liquid phases in equilibrium was discovered ( 1 3 7 ) . and hydrocarbons were found generally t o be greater than those of chlorex ( 1 5 4 ) . The two-liquid system uranyl sulfate-water DROPS, INTERFACIAL TENSION, AND E M U L S I O N S was studied in detail from its critical solution temperature, 295' to 374" C. where the water-rich layer becomes identical Smirnov and Polyuta (229), investigating the size of liquid drops issuing from a capillary immersed in a second immiscible with thd vapor phase (121). Binary liquid equilibria for bromine with 1-trifluoro-2-dichloro-3-difluorochloropropane (236) and for liquid, concluded that the governing factors were capillary perfluoro-n-heptane with various hydrocarbons and chlorinated diameter, interfacial tension, and the densities of the liquids, but hydrocarbons (108) were studied in detail, and the critical sohthe influence of flow rate was not found. The instability of small tion temperatures for sulfur-butyl phthalate (30) and carbon wavelike disturbances, imposed on the upper surface of a small tetrachloride-perfluoromethylcyclohexane( 2 7 9 ) were measured. quantity of a liquid accelerated rapidly downward through a n Both upper and lower consolute temperatures were found in the immiscible liquid, was studied by Lewis ( 1 4 4 ) : The instability system water-4,6-dimethyl-1,2-pyrone( 3 7 0 ) . The immiscibility follows a first-order theory except when a considerable amplitude has been attained, Martynov explained the nonsphericity of of liquid metals was considered by Mayer (165). The effect of various acid concentrations on the critical solution temperature of drops in certain emulsions through the lower energy of the nonspherical surfaces (161). Rates of extraction from single drops hexane with castor oil (160) and of lecithin, aucrose, and water on were measured by West et al. (268), who also found that benzene that of soybean oil with ethanol (116)were reported. Hildebrand reviewed the factors determining the solubility among drops rising through water attained a velocity equal t o that calculated for rigid spheres, provided their volume was below 0.04 nonelectrolytes ( 1 0 7 ) ; the reproducibility of liquid-liquid supersaturation (93) and the thermodynamic explanation of lower ml. Kronig (139) continued theoretical studies on rates of mass critical solution temperatures were considered (186). The use of transfer from spherical drops. electrical conductivity in determining liquid miscibility was Interfacial tensions were reported for a variety of liquid-liquid systems: decahydronaphthalene, cyclohexane, decane, and ocproposed ( 4 ) and micromethods for determining critical solution tane with water from 20" to 70" C. (906);benzene and decane temperatures were described ( 7 8 ) . Ternary systems were studied fairly extensively. Various with water from 1 to 700 atmospheres, and from 20" to 132" C. (171); esters of chloroacetic acid with water from 26" to 70" C. methods for determining the solubilities and tie lines, and applica( 1 1 7 ) ; mineral oil, cottonseed oil, and amyl acetate with water iu tions of phase separations to analysis, were explained by Haase the presence of various monoglycerides ( 9 4 ) ; paraffin oil and un(95). The geometry of the triangular phase-diagram configurations was related to the distribution coefficients thermodynamidecyl alcohol with water in the presence of dextrose, sucrose, and lactose a t 25" C. (66). Methods of measuring interfacial tension of cally (207). I n addition, a large number of data were reported. Those systems for which substantially complete ternary equilibmetals in molten slags (196), and the application of contracting liquid-jet t,echniques for freshly formed surfaces ( 1 ) were deria were obtained are listed in Table I. Additional distribution Table 1.

Liquid Equilibrium Data for Systems of Three or More

8%)

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January 1952

INDUSTRIAL A N D ENGINEERING CHEMISTRY

COURTESY. MAX 6 . MILLER

Largest Duo-Sol Refining Plant Ever Built, Operating at a 13,000-Barrel-per-Day

scribed. Applications of Antonoff’s rule were considered (178); near the critical solution temperature it is inapplicable (197). Spontaneous emulsification in certain systems was studied (163,869); the phenomenon was ascribed t o negative interfacial tension (837). A systematic study of size distribution within emulsions and related quantities wm made (118), and inversion phenomena were reviewed (909). Many addition agents for breaking petroleum-water (68,133) and petroleum-furfural (33) emulsions were proposed. Petroleum-water emulsions may also be broken by a high-voltage coalescing field (166),or by adjusting the phase ratio, pH, and temperature, followed by contact with fibrous glass (139). Forcing an emulsion against a porous diaphragm with sufficient pressure to cause the flow of at least one of the phases is also effective (130). In a study, the report for pihich was prepared in 1943 but which has just recently become publicly available, Tepe and Woods (948)investigated the settling of isobutyl alcohol-water emulsions. Cyclone-type separators were unsatisfactory, as were coiled tubes fitted with an internal vane near the outlet for splitting the phases at the interface. The poor results obtained by causing the emulsion t o flow through a closed channel were ascribed to the disturbing influence of entrained air, but open channels permitted a separating efficiency of 75% for contact times of 7.5 seconds. Oldshue and Rushton (184) investigated the mixing and settling characteristics of methyl isobutyl ketone-water emulsions in 6- and 12-inch vessels. A critical speed of the impeller during mixing, above which the break time of the emulsion dropped drastically, was found. Break time was decreased by increasing temperature and by the addition of very small amounts of acetic acid. METHODS OF CALCULATION

General reviews of fundamental methods of calculation of numbers of stages, etc., were provided by Jodra (119),Hamer (98),and, for multicomponent separations, by van Dorsser (66). Several new methods of dealing with multicomponent systems have been devised. Cruickshank et al. (66)advanced a simple method of dealing with the separation of binary mixtures with mixed solvents graphically on Cartesian coordinates, limited to those quaternary systems whose tetrahedral representation shows a straight-line profile for the heterogeneous volume. Countercurrent extraction calculations for such systems are discussed by Brancker (86). Compere apd Rylaad (@) have described a

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INC.

Capacity, Cit-Con Oil Corp., Lake Charles, La.

simple cyclic scheme of conducting batch extractions whichin relatively few cycles yields results similar to a continuous countercurrent process, for cases of immiscible solvents but where distribution coefficients are not necessarily constant. Their methods were confirmed experimentally by separating phenol and picric acid using benzene and aqueous salt solutions as solvents. For cases where the distribution coefficients are constant, Scheibel (814) developed an approximate algebraic computation of the approach to steady-state conditions for each cycle of such a batchwise process, thus permitting estimates of the number of cycles required t o simulate the steady-state conditions to any desired degree. Sandell (811) derived expressions for calculating recovery and extent of separations in such systems with particular emphasis on analytical applications. Berg et al. (IS)have Suggested the use of the “overlap coefficient,” a concept originalIy proposed for multicomponent distillation, as a correlating device for extraction of such complex mixtures as petroleum. The device permits generalization of the interdependence of reflux ratio, number of stages and product specification, and assists in establishing the optimum design conditions. Weber (966)suggested using the “degree of exchange” as a standard for evaluating extraction performance. A number of reviews of the methods of Craig and mathematical analyses of the results obtained by his device have appeared (17,184, 186,116,188). Probability-function tables are used by Nichols to assist in the calculation of the degree of such separations ( H i ) ,and the theory of least squares by Backer (8). Johnson (181) has continued his studies on the stepwise separation of a batch of a mixture by considering the case where the solutes are introduced into a cascade in which one solvent flows continuously through the system while the second remains static in each stage. A solute thus introduced into the first stage passes through the system in a concentration wave closely allied t o that appearing in a partition chromatographic column. Mason and Piret (188)discussed the prediction of performance of continuous agitated vessels during nonsteady-state operation. Procedures for minimizing below-at andard product during starting-up periods were presented. Jones (188) offered graphical treatment of the continuous operation. EQUIPMENT AND FLOWSHEETS

Several improvements in design of countercurrent extraction columns have been suggested. The column of Davis and Krautl (69),especially adapted for solvent refining of lubricating oils,

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INDUSTRIAL AND ENGINEERING CHEMISTRY

features improved separation of extract and r a h t e through use of a combination of perforated plates for dispersion and horizontal baffle plates for collection and coalescence of the dispersed phase. Findlay ( 7 7 ) suggests the use of a tray column with bubble eaps for air agitation t o create additional turbulence. Tepe and Woods (248), who were looking for devices which would incur a minimum'of holding time per stage, investigated perforated-plate columns experimentally. Isobutyl alcohol and water were brought in contact in a 9-inch diameter column, and when the free area of the plates was 15% of the total cross section, at 1.5-inch plate spacing, a contact time of less than 4.25 seconds per actual stage was possible; the stage efficiency was not measured. The system kerosene-water could not be successfully handled under the same conditions. The flow characteristics of spray towers fed with transformer oil and water, with both liquids dispersed a t different times, were studied abroad (69). It was concluded that a rate of flow for the dispersed liquid such that drops, rather than jets, result is the most favorable. Oldshue and Rushton (184)proposed a countercurrent extraction column separated into a number of compartments by horizontal plates and internally agitated by impellers on a vertical shaft. A general description of the agitated, packed towers of Scheibel's design was given (40). Eisenlohr (68) described a n important new centrifugal extractor (Luwesta extractor) containing three actual stages and permitting countertlow of the contacted liquids. Data are presented on the efficiency of extraction of acetic acid from water and of penicillin. New Podbielniak centrifugal extractors can handle up t o 30,000 gallons per hour of combined liquid flow, with as many as 12 stages per unit, and other machines for handling liquids with suspended solids are also available (194). Where distributors for the dispersed phase are in the form of perforated spiders, Ayres (6) uses constricted openings in order to minimize clogging of the perforations by increasing the velocity of flow through the opening. The distributor is installed in a settling tank, the entire assembly thus constituting a stage, Nagata and coworkers (176, 177) studied agitation of liquidliquid mixtures in a cylindrical vessel; they concluded that intensity of agitation can best be measured in terms of power input per unit volume of liquid, and that baffle plates should be placed l/*-paddle length from the axis of the vessel, submerged paddle length, their width should be 10% of the vessel diameter, and their length 40%. Insertion of the agitator in such vessels should be oft-center deliberately t o produce a vortex if foams are t o be avoided, according to Paterno and Paladin0 (191). Mixing of water with a variety of liquids was studied by Fragoso (80). A description of the Kellogg Co. design of an alkylator, a device which may be generally useful for contact of immiscible liquids, was published (39). The use of a membrane t o separate the phases between which extraction is t o take place has been suggested (240). For immiscible liquids, a semipermeable membrane may be used, provided a pressure is maintained t o prevent the flow of the liquid for which the membrane is permeable. If the membrane is impermeable t o both, even two miscible liquids may be used as the extracting phases. For separating ternary mixtures, such as an aqueous solution of two solutes, a suggested flowsheet involves extraction with one solvent, extraction of the extract with water, and further extraction of the second extract with a second solvent ( 2 5 8 ) . For the laboratory, Craig ( 6 3 )described a completely automatic 220-stage cascade constructed of glass. Another laboratory apparatus provides continuous, countercurrent operation by virtue of a rotating impeller placed between the liquid feed reservoirs (239). Flooding. Crawford and Wilke ( 5 5 ) studied the flooding characteristics of Oh-,1-, and 1.5-inch carbon Raschig rings in a lZinch diameter tower. Wide ranges of viscosity, density, density difference, and interfacial tension for the liquid phases

Vol. 44, No. I

were covered. The resulting correlation is based on the observation that for each liquid pair the sum of the square roots of the superficial linear velocities of flow is a constant a t flooding. M A S S TRANSFER

Sherwood (9.86)has skillfully outlined the present status of the theoretical and experimental approaches t o the transfer of heat and mass between phasee, and fluid friction. The nature of the flow process, molecular and eddy diffusion, and combined effects are considered, and the fundamental similarity among the processes is pointed out. I n a fundamental study of the rate of extraction from individuah drops, West el al. (368)extracted acetic acid from drops of benzene by a continuous water phase. From 14 t o 20% of the acid was extracted during drop formation, fractions that are considerably smaller than those reported earlier elsewhere. The extraction rates occurring during the period of drop rise could be correlated on the assumption that the drops were rigid spheres, although observation of the drops indicated that actually they were neither spherical nor rigid. Berg e l al. (13)extracted methyl ethyl ketone from naphtha by water in a 37-foot column, 2 and 3 inches in diameter, packed with &mm. Raschig rings. Heights equivalent to a theoreticai stage varied from 1.3 t o 6.9 feet. Best results were obtained when water was the dispersed phase, irrespective of which phase preferentially wet the packing. The same tower was used to extract a dewaxed lubrieating oil with furfural. The separation of cobalt and nickel was successfully demonstrated by Kylander and Garwin (140). Cobaltous chloride waa preferentially extracted from a n aqueous solution containing nickelous chloride and hydrochloric acid by capryl alcohol in a spray tower 68 inches long and 1.24 inches in diameter, alcohol dispersed, The ratio of cobalt t o nickel could be increased from 1.3 t o 1 in the feed t o 200 to 1 in the extract. Heights of transfer units and mass transfer coefficients are reported: (HTU)oal,,h,i for the cobalt extraction is in the range 4 to 6 feet. Oldshue and Rushton (184) investigated the extraction of acetic acid between methyl isobutyl ketone and water in a 6-inch diameter column fitted with internal agitators, horizontal compartmenting plates, and vertical baaes. High throughputs were possible. Superior results were obtained when the mixing impellers were placed between the horizontal plates, with higher acid concentrations, and when the acid was extracted into the water. The effects of distance between horizontal plates, size of openings in the plates, impeller diameter, and impeller speed were also studied; heights equivalent t o a theoretical stage varied from 3 t o 34 inches. New data on the extraction of acetic acid between toluene and water in a laboratory spray tower were reported ( 8 6 ) . Particular attention was paid t o end effects, which were determined by an internal sampling technique. The rate of extraction of phenol from water into benzene was measured in a batch-agitated vessel 4.1 inches in diameter, and also in a continuous flow apparatus where the dispersion was obtained by a high velocity gas stream (276). The latter proved more effective. The rate of heat transfer to water-mineral oil mixtures in an agitated kettle 30 inches in diameter was reported ( 5 7 ) . LIQUID EXTRACTION PROCESSES

Petroleum Refining. I n the field of conventional refining the developments have been rather meager. Engel and Palmquist (70) suggested preliminary extraction of mineral oils with concentrated sulfuric acid for removal of the most unstable portions prior t o subsequent multistage acid treatment, for better quality and yield of raffinate. Furfural used in solvent refining operations is recovered by steam distillation in the presence of acidneutralizing substances t o prevent decomposition and polymerization of the solvent (925). A new Ohio lubricating-oil re-

January 1952

INDUSTRIAL AND ENGINEERING CHEMISTRY

finery featuring propane deasphalting and furfural solvent refining was briefly described (164), as well as a Canary Island installation using the same processes (76,106). A general discussion of lubricant refining was provided by Blauhut (14). Considerable attention has been given to separations of the lower boiling hydrocarbons. Sulfuric acid was found t o be selective in extracting isobutylene from a mixture of olefins and paraffins (208). Sulfuric acid-alkyl sulfonic acid solutions are selective in separating certain hexenes from other six-carbon hydrocarbons (113). Aqueous silver salt solutions containing an amine salt such as silver nitrate and butylamine nitrate (YZ), or containing phenol (&), selectively extract unsaturated hydrocarbons from mixtures. Olefins may be separated from paraffins, or diolefins from mono-olefins, by a cuprous salt solution containing 0-anisidine (201). The bischloroformate esters are also selective solvents (166). A blend of a polar solvent such as ethanolamine with a substance having compound-forming tendencies for olefins and diolefinns, such as paraldehyde or sulfur dioxide, is similarly useful (167). Close-boiling hydrocarbons, such as heptanes and cyclohexane, may be separated by extraction with a solvent such as furfural followed by extraction of the cyclohexane from the furfural with octane, in a process proposed by Hachmuth (96). Multiple extraction with a double-solvent system can separate p a r a f i s , olefins, and diolefins (168). Furfural used for recovery of butene from light-hydrocarbon fractions and which has become contaminated with foam-producing substances may be freed of the latter by extraction with low-boiling aliphatic hydrocarbons (16). Low-temperature extraction with SUIfur dioxide, particularly with a supplementary low-boiling paraftin solvent, is effective in extraction of a concentrated aromatic fraction from heavy gasolines (249). Fluorine compounds as selective solvents have had particular attention. Arsenic trifluoride selectively extracts aromatics and precipitates asphalts (182). Liquid anhydrous hydrogen fluoride causes condensation of rraphthalenes and their extraction from paraffinic mixtures (146). A mixed solvent containing hydrogen fluoride and boron trifluoride selectively extracts m-xylene from mixtures with the ortho- and para- isomers (29),and also in the presence of other hydrocarbons (146,166), through formation of a complex with the m-xylene. The same mixture effectively desulfurizes and removes aromatics from high-sulfur crudes (114). Removal of hydrogen sulfide from three- and four-carbon hydrocarbons with the regenerative potassium phosphate process in the liquid phase is successfully carried out in a large plant (277). Mercaptan(thio1)sulfur may be extracted from gasolines in an oxygen-free system by aqueous alkali solution containing tannin, and the treating solution may be regenerated by air blowing (99). High-boiling tar acids (198) and a wide variety of other substances (20) have also been suggested as “solutizers.” Caustic extract, if acidified to p H 9, will permit extraction of aromatic mercaptans by ether (166)or by low-boiling p a r a f f i (817). General descriptions of modern sweetening processes are provided by Walther (2629,and Kalichevsky (123) has given detailed accounts. Fat and Oil Processes. A general review of the furfural and propane fractionation of drying oils was given by Gloyer (87) and by Schwitzer (221). Farr (78) has given a general description of the solvent fractionation of the vegetable oils for obtaining fractions of high iodine number, with particular attention t o soybean and linseed oils. For fractionation into products of various degrees of unsaturation, Freeman and Gloyer (81)proposed countercurrent extraction of glyceride oils with furfural a t temperatures sufficiently low to ensure incomplete miscibility. Gloyer (88) suggested extraction with furfural, followed by extraction of the raffinate with water saturated with furfural, with a brge reflux return t o the first extractor. If such extractions are canied out under a blanket of inert gas, an improved product results (193).

57

The flavor stability of furfural-refined soybean oil has been evaluated (920). By extraction of a vegetable oil such as soybean oil with propane a t high solvent ratios and at successively higher temperstures and pressures, fractions rich in sterols and tocopherols, vitamins, fatty acids, and a nonreverting neutral oil for edible purposes can be obtained (149). Propane extraction of cottonseed or,corn oils provides vitamin E concentrates (109). Propane extraction of wool-grease emulsion, with successively increasing solvent ratios, temperatures, and pressures yields fractions containing water, odoriferous impurities, sterols and sterol esters, and alcohols, esters, and glycerides (976). An improvement of the Solexol process involves refluxing portions of the r a m a t e phase, resulting in better yields of phosphatides from soybean oil, and vitamin fractions from palm oil (190). Data for winterizing cottonseed and peanut oils with acetone were reported (927). Antioxidants for oils and fats may be 1p covered from crude vegetable oils by treatment with aqueous ammonia and acetone, followed by extraction with any of a number of common, oxygenated, organic solvents (34). Unsaponih b l e matter separates from the remainder of a fat by addition of a finely divided inert solid prior t o solvent extraction (82). Oils, fats, and waxes may be freed of acids by extraction with solvents containing neutralizing substances, such as methanol containing potassium hydroxide (183). Alcohols, acids, and ketones of low molecular weight are selective solvents for separating fatty acids from unsaponifiable material (176). Crude fatty acids are refined in high yield with liquefied petroleum gases (244). A study of the uncatalyzed, continuous hydrolysis of fats with water indicated that higher pressures and water-fat ratios result in higher fatty acid yields. A two-stage process, using 15 and 35% water, respectively, was recommended (189). Batch hydrolysis of several fatg at a variety of conditions was studied by Sturzenegger and Sturm (949). Manufactured-Gas Processes. Phenols, particularly polyhydric phenols, are more oompletely extracted from aqueous ammoniacal liquors with butyl acetate than with benzene (169). Other suggested solvents include certain six-carbon ketones (160), dibutyl or diisopropyl ether (MO),a dephenolated straw-oil fraction ( I @ ) , or a mixture of esters and ethers (phenosalvan) (30.4). The phenol-recovery plant of the Allied Chemical and Dye Corp., Ironton, Ohio, uses benzene in a two-stage centrifugal pump mixer and decanter extractor, followed by water and caustic wash of the extract, t o give a 95 to 98% phenol removal (97). The plant of the National Tube Co.,Lorain, Ohio, uses bensene in a 65-foot countercurrent tower with a 95.5% phenol removal

(961). Tar acids may be removed from ~ i l and s tam by extraction with aqueous caustic (161); with aqueous methanol, which is superior to other alcohols (83,100); with liquid ammonia a t low temperaturfs (164);or with aqueous methanol and heptane in a doublesolvent process (179). Pyridine may be removed from crude benzene with aqueous sulfuric acid (60). Nitrogen bases generally can be removed from tars by extraction with aqueous solutions of acids or acid salt solutions containing methanol (19). Golumbic et al. (92)analyzed various fractions from the distillstion of coal hydrogenation oil using a Craig instrument. Pharmaceuticals. There has been continued active application of liquid extraution to the antibiotic manufacturing processes. Improvements in the concentration of penicillin from culture liquors {68,128, 167),and in the isolation of penicillin salts (81, 47, 111, 112, 14.9, 170, 909,9.28)involve extraction. The operation is also useful in the manufacture and separation of such antibiotics m terramycin (981),aflvin and bacitracin (116, 180), streptomycin ( I @ ) , biotin (89),subtilin (27), and tyrothricin (10). A general review of extraction techniques in this field was offered (86). The separation and recovery of natural (71,966) and synthetia (4.9) estrogens, the cortex hormones 97), and digitalis from

(a,

$8

INDUSTRIAL AND E N G I N E E R I N G CHEMISTRY Table II.

Separation or Process Tannin from aoueous Dercolates of sumac etc. Tree-tbbacco alkaloid from ethylene dichloride solution Concentration of hydrocarbon sulfates and sulfonates Monohydric alcohols from oily impuritiea Unsaponifiable matter from tall-oil soaps Sulfur-containing liquids from tars Sugar-cane wax from color bodies and fatty materials Halogenated alkaryl compounds from alkaryl hydrocarbons Carotene from chlorophyll concentrate Chlorinated hydrocarbons from paraffins Lactic acid from aqueous fermentation liquor

Miscellaneous Liquid Extraction Processes

Solvent Ethvl acetate Aqu"eous aluminum sulfate Sodium chloride with cyclohexanol Water with diisopropyl ether Aqueous isopropyl alcohol with naDhtha Meth 1 butyl ketond w i d water Methyl cyanide, etc.

Literature Reference

Tetraethyl pyrophosphate from reaction nuxture Poly lycerides from reaction mixture Polyfydroxy compounda (humectants) from reaction mixture Polypentaerythritol and formic acid from pentaerythritol Organic oxygenated compounds from hydrocarbons

(49)

16:03

Propane Water with furfuryl alcohol, etc. Propane

Ketones from hydrocarbons Hydrocarbons from aqueous oxygenated compounds Oxygenated compounds from water

Tin, arsenic, molybdenum from hydrofluoric acid solutions of fluorides Antimony, mercury, cadmium, gold, and tin iodides from aqueous hydriodic acid Thorium nitrate from water containing mixed rare-earth nitrates Thorium nitrate from aqueous neodymium nitrate

Carboxylic acids Tertiary amines with chloroform or alco-

$r

Iodine from oil-well waters

bons

Chlorobenzene, etc. Methanol

t%

Ethanol

(879)

Tributyl hosphate Aqueous apk+i salts of carboxylicacida Acetonitrile Aqueous sulfuric or phosphoric acid Low-boiling hydrocarbons Aliphatic hydrocarbons

Separation or Process F a t t y acids from water Organic oxygenated compounds from sodium salts of organic acids Neutral organic oxygenated compounds from each other Oxygenated compounds from water and organic acids Tars from spent sulfuric acid

ueous alkali yl acetate or butanol Purification of pine-wood ketonic oils Aqueous ferric chloride Paraffin hydrocarNitrocarboxylic from fatty acids Fractionation of hydro1 lignin Cyanamide and polymers from water

Vol. 44, No. 1

(874)

(180, 881)

aqueous extracts (86) and other alkaloids ( 7 4 ) also use extraction techniguea. Miscellaneous Processes. A large number of diverse extraction processes have been suggested and reported upon, a representative selection from which is listed in Table 11. As the table indicates, much attention has been paid t o the separation of oxygenated organic compounds from the aqueous and oily layers of the hydrocarbon-synthesis processes, and t o the separation of metals. I n connection with the latter processes, Bock (16)has reviewed recent progress in the separation gf the rare-earth metals, including developments in extraction, and Calvin (S6) has considered the use of chelating reagents in extraction. More generally, Belck (11)has reviewed and compared the methods of separating binary azeotropes, including extraction, and a new edition of Mellan's compilation of data on industrial solvents has appeared (169). ANALYSIS

No attempt is made to record here the many publications having t o do with the use of extraction in analytical chemistry, a8 the subject is thoroughly reviewed annually elsewhere. See, for example, t h e reviews of Craig (&$), Morrison (l74),Hellberg (106),and Babko (7). LEACHING

A general review was prepared by Lerman (389). Theoretical and Design Methods. Fitch (305) has presented a general treatment for calculating steady-state transfer processes particularly useful in leaching problems. The theory of countercurrent decantation was studied in detail by Ore1 (a@), and stepwise countercurrent leaching of dodder seed with trichloroethylene was investigated (S18). Rates of flow of water through starch in a perforated basket centrifuge ( 2 9 4 ) , and of hexane miscella through beds of soybean flakes ( a g o ) , have been recorded.

Solvent Cyclic hydrocarbons Isophorone or cresols Aqueous ethanol with pentane Triethylamine ethyl sulfonate Naphtha Inert hydrocarbon oil Ethyl ether Ethyl ether n-Hexyl alcohol, methyl - n - hexyl ketone, etc. 1-Pentanol with ammonium thiocyanate (Chlorination) refined petroleum Propyl or butyl ethere Water

+

Gallium from aqueous hydrochloric acid Lithium chloride from 2-ethylhexanol Ferric chloride from aqueous uranyl chloride Ethyl ether Nitromethane Ceric nitrate from water Ceric nitrate from water Butyl phosphate Protoactinium chloride from zinc, etc., @,@' - Dichlorodiethyl ether solutions Protoactinium from aqueous acid solu- Amyl acetate with tion cupferron Radioberyllium from solutions of other Benzene with thenelements oyltrifluoroacetone Neodymium from erbium solutions Chloroform with 5.7dichloro-8-quinolinol Zirconium from hafnium i n aqueous hy- Benzene with trirfluoracetyl acetone drochloric acid Sodium dichromate from aqueous vana- Methyl isobutyl kedic acid and hydrochloric acid tone Gallium from crude aqueous sodium Chloroform with 8aluminate quinolinol

The rate of leaching in batchwise operations, for cases where the diffusional resistance of the solid may be neglected, was developed and the results were verified with data on leaching of ground chaulmoogra seeds (3S4). A fundamental study of leaching rates was reported upon by Piret et al. (345). In t.his work, various aqueous solutions were leached from carrier solids of diverse complexity: capillary tubes, beds of glass beads, and porous alumina spheres. Theoretical equations were developed for leaching of a solute from spheres in batch, parallel, and countercurrent operation, and the case for batch leaching WM verified by experiments with porous spheres. To assist in the interpretation of the data, the concept of an idealized equivalent sphere of no internal diffusional resistance, whose time for extraction differs from that for the real sphere by a porosity factor, was successfully introduced, New Equipment. Smith (559) has described a new machine for the continuous leaching of oilseeds based on percolation of the solvent through the solids, while the solids are conveyed on a horizontally moving porous belt. Several designs for equipment best suited for special applications have been suggested: asphalts and bituminous rocks ( 9 8 5 ) , oil shales and t a r sands (SS4), and oil-bearing seeds (986, 189, 313, 561, S65, 371, 376). Rotary-type leaching equipment (336, 548) and outlet-valve mechanisms for withdrawal of solids from towers (280, S77) have been described. Several laboratory designs, generally of the Soxhlet type, were suggested (SlO,S21, S 2 9 , 3 S l ) Oilseed Leaching. Several general reviews have appeared (297, 332, SS6, 3 4 4 ) . That by Cofield ( 9 9 7 ) is particularly thorough and includes an excellent description of modern equipment. The effect of temperature on the leaching rate for soybeans, cottonseeds, and flaxseeds was investigated thoroughly for several solvents (375). Darkly colored cottonseed and peanut oils leached from fairly dry seeds are the result of factors other than the-drying temperature (333); for most satisfactory leaching of

January 1952

I N D U S T R I A L A N D - E N0 I N E E R I N 0 C H E M I S T R Y

these seeds, a moisture content of 9 to 10% is recommended (347). Hydraulically pressed okraseed oil is inferior in color and stability t o solvent-leached oil (30). Several modifications of conventional processes were described: drying and grinding of seeds between repeated leachings (282); a program of drying, pressing, grinding, heating, and flaking, followed by leaching (302); and pre-expelling. of the oil prior t o leaching (Exsolex process) (939). A salad oil may be leached from rice bran with hexane, leaving a good cattle-feed residue (928). Cooling the castor oil-heptane solution resulting fiom the leaching of castor beans produces two insoluble liquid phases, one oil-rich (367). A similar process was proposed using ethanol on soybeans (287). Distillers’ dried grains may be leached in a soybean plant to yield a product similar t o corn oil (379). The methylpentanes are desirable substitutes for hexane as a leaching solvent for cottonseeds (283). Isopropyl alcohol or acetone gives good oil recovery and reduces free gossypol in the meal (916). Phosphatides in the ethylene dichloride extract of cottonseed meal are responsible for its antioxidant properties (330). Trichloroethylene is an effective leaching solvent for such materials as wheat germ flakes, milkweed seed, sorghum germ, etc. (3.69). The residue from cottonseed leaching with the combined solvent hexane-water is fit for stock feed (288). The use of the hot oil from the same seed as a leaching solvent was proposed

($96). Sugar Beets. The leaching of sugar beets (diffusion process) has been reviewed generally (333,340, 368). Detailed data on rates of leaching, material balances, concentmtions of solutions t o be expected, etc., have also appeared (302,317,8.42, 366). The silver-diffusion process (319)and installations in Europe (368) have been described in detail; capacities, methods of operation, and efficiencies for various processes were compared (374). Heat-resistant microorganisms may cause loss of sucrose and increased acidity of the product of the diffusion battery (991). High operating temperatures cause the appearance of colloidal material in the product (386). Preliminary soaking of the cosettes (370)and the use of sulfur dioxide and relatively low temperatures (290) favor improved operation and product. Miscellaneous Processes.. Leaching of alumina from Caribbean bauxites (869),calcium aluminates (366),aluminous shales (326),and alunite (3M) has been described. Anpnonium carbonate solutions ardused for leaching roasted copper ores (299), sulfuric acid for lithium (803)and :obalt (314) ores, ferric sulfate solution for leaching zinc from zinc sulfide concentrates (327), and higher ketones and alcohols for leaching thorium nitrate from mixed rare-earth nitrates (367). Radium-barium (307)and hafnium-zirconium (308) mixtures may be separated by a fusionleaching process. Descriptions of Canadian (364)and American (296)leaching practice for uranium ores were made available. Sulfur may be leached continuously from its ores with carbon disulfide (362),and from spent gas-works oxide by a fluidized-bed technique (32.9). Other articles and patents described such processes as leaching of tannin from woods and barks (281,360,360),sugar-cane wax from cachaza (337,366), mannitol (362)and alkali-metal salts (300)from seaweed, pectin from citrus fruit peel (312),vitamin A from fish livers (293, 316,363),aconitine from tubers (348).morphine from poppy capsules in a diffusion battery (a@),ennymes from animal pancreas (306),alkaloids from plants (sod),perfumes from floral material with butane (338),and soluble coffee extract from ground, roasted coffee (284,898, 311, 364, 361). Weiler (37.3) has reviewed patents on leaching of brown coal. LITERATURE CITED

(1) Addison. C.C., and Elliot, T. A., J . Chem. SOC.,1950, 3090. (2) Anderson, J. S.,and Saddington, K., Ibid., 1949 (Suppl. issue 2), S381. (3) Arnold, G. B., Hees, H. V., and Stewart, M. M. (to Texas Co.), U.S.Patent 2,516,940(Aug. 1, 1950).

59

(4) Askevold, R. J. (to Pure Oil Co.), Ibid., 2,548,763 (April 10, 1951). (5) Asselin, G. F.,Audrieth, L.F., and Comings, E. W., J . Phgs. c& Colloid Chem., 54, 640 (1950). (6) Ayres, C. E. (to Phillips Petroleum Co.), U. S. Patent 2,531, 647 (Nov. 28, 1950). (7) Babko, A. K., Zavodskaya Lab., 16, 527 (1950). (8) Backer, J. E., J. Am. Chem. Soc., 73, 1023 (1951). ENQ.CHEM.,42, 2530 (1950). (9) Badgett, C. O.,IND. (10) Baron, A. L. (to S. B. Penick & Co.), U. S. Patent 2,534,541 (Dec. 19, 1950). (11) Belck. L.. Chem.-lno.-Te&.. 23. 90 11951). Berg,C. H. 0. (to Union Oil Co. of Calif& U. 5. Patent 2,541,468 (Feb. 13, 1951). Berg, C., Manders, M., and Switzer, R., Chem. Eng. Progress, 47, 11 (1951). Blauhut, W.,Chem. Tech., 2, 247 (1950). Boatright, R. G.,Kilpatrick, M. O., and Derrick, W. S. (to Phillips Petroleum Co.), U. 8. Patent 2,523,554(Sept. 26, 1950). Bock, R., Angew. Cham., 62A, 375 (1950). Bock, R. M., J . Am. Chem. SOC.,72, 4269 (1950). Bogash, R.,and Hixson, A. N., Chem. Eng. Progress, 47, 347 (1961). Bolomey, R. A., and Wish, L., J . A m . Chem. Soo., 72, 4483 (1960). (20) Bok, J.‘A., and Tom, T.B. (to Standard Oil Co. of Indiana), U. 8. Patent 2,550,905(May 1, 1951). (21) Boots Pure Drug Co., Ltd., Martin, A. J. P., and Stroud, S. W., Brit. Patent 639,432(June 28, 1950). (22) Bosworth, R. C. L., “Physics in Chemical Industry,” New York. Macmillan Co.. 1951. (23) Bosworth, R. C. L., Rob. Australian Chem. Inst. J . and Proc., 16, 460 (1949). (24) Brancker, A. V., Ind. Chemist, 27, 243 (1951). (25) Branoker. A. V.. Petrcleum (London). 14. 123 (1951). (26) Brazhnikova, M. G., Uspekhi S&rem&nol’Biol:, 29, 360 (1960). (27) Brjnck,-N. G.,Mayfield, J., and Folkers, K., J . Am. Chem. SOC.,73,330 (1951). (28) Brodin, J . , Compt. rend., 227, 1080 (1948). (29) Brooke, L. F., Langlois, G. E.. and Strickland. A. E. (to California ResearchCorp.), U. 8. Patent 2,521,444 (Sept. 6, 1950). (30) Brooke, M.,J. A m . Chem. SOC.,72, 5748 (1950). (31) Brown, G. G., and Associates, “Unit Operations,” New York, John Wiley & Sons, 1950. and Kortum, G., Angew. Chem.. (32) Buchholz-Meisenheimer, H., 63, 163 (1951). (33) Buis, M. (to Shell Development Co.), U. S. Patent 2,516,614 (July 25, 1950). (34) Buxton, L. 0. (to Nopoo Chemical Co.), U. S. Patents 2,515,858-80 (July 18, 1950). (35) Cdvet, E., Rev.optique, 29, 35 (1950). (36) Calvin, M.,Experientia, 6, 135 (1950). (37) Carbone, W. E.,Sewage and I d . Wastes, 22,200 (1950). (38) Carrara, G.,U. S. Patents 2,537,510(Jan, 9, 1951), 2,548,588 (April 10, 1951). (39) Chem. Eng., 58, No.4, 142 (1951). (40) Chem. Eng. Progress, 47, No. 7, 20 (1951). (41) Chmutov, K. V., and Slonim, I. Y., Zhur. Fiz. Khim., 24, 1383 (1950). (42) Christenson, R. M., and Gloyer, 8. W. (to Pittsburgh Plate Glass Co.), U. S. Patent 2,530,809(Nov. 21, 1950). (43) CIBA, Ltd., Swiss Patent 268,510 (July 1, 1950). (44)Ibid.,268,324 (Aug. 16, 1950). (45) Cole, R.M.(to Shell Development Co.), U. 5. Patent 2,523,681 (Sept. 26, 1950). (46) Collander, R., Acta Chem. Scad., 4, 1085 (1950). (47) Commercial Solvents Corp., Brit. Patents 642,369-72(1950). (48) Compagnie de produits chimiques et electrom6tallurgiques Alais, Froges, et Camargue, French Patent 952,976(Nov. 28, 1949). (49) Compere, E. L., and Ryland, A., IND.ENG.CHEM.,43, 239 (1951). (50) Concordia Bergbau, A.-G., Ger. Patent 800,665 (Nov. 27, 1950). (51) Connick, R. E., and Reas, W. H., J. Am. Chem. SOC.,73, 1171 (1951). (52) Conway, J. B.,and Norton, J. J., IND.ENG.CHEM.,43, 1433 (1951). (53) Craig, L. C., AnaE. Chem., 22, 1346 (1950). (54) Ibid., 23, 38 (1951). (55) Crawford, J. W.,and Wilke, C. R., Chem. Eng. Progress, 47, 423 (1951).

INDUSTRIAL A N D ENGINEERING CHEMISTRY Cruickshank, A. J. B., Haertsch, N., and Hunter, T. G., IND. ENO.CHEM.,42, 2154 (1950). Cummings, G. H., and West, A. S., Ibid., 42,2303 (1950). Dammers, H. F., U. S.Patent 2,522.212 (Sept. 12, 1950). Davis, H. R., and Kraus, F. (to Lummus Co.), Ibid., 2,528,426 (Oct. 31, 1950). Day, R. A., Jr., and Stoughton. R. W., J. A m . Chem. SOC.,72, 5662 (1950). Dean, R. B., Ibid., 71, 3127 (1949). De Groote, M., and Keiser, B. (to Petrolite Corp., Ltd.), U. S.Patents 2,518,668 (Aug. 15, 1950), 2,524,889-92 (Oct. 12, 1950), 2,541,990-2,013 (Feb. 20, 1951). 2,543,489 (Feb. 27,1951). Dolliver, M. A., and Glaser, C. (to E. R. Squibb & Sons), U. S. Patent 2,509,055 (May 23, 1950). Dornte, R. W. (to Standard Oil Development Co.), Ibid., 2,537,658 (Jan. 9, 1951). Dormer, A. H. de Haas van, r?v&deur (Holland), 62, 59 (1950). Douglas, H. W., Trans. Faraday Soc., 46, 1082, 1090 (1950). Egberts, R. W,, and Hooton, J. (to Standard Oil Development Co.), U. S. Patent 2,510,806 (June 6, 1950). Eisenlohr, H., I n d . Chemist, 27, 271 (1951); Chem.-Ing.-Tech., 23,12 (1951); Prospectus, Lurgi Gesellschaft fiir Warmetechnik M.B.H. Ekel, E. S., and Shabalin, K. N., J . Applied Chem. U.S.S.R., 23, 161 (1950). Engel. B. K.. and Palmauist, F. T. E. (to Aktiebolaget Separa&-Nobel). Brit. Patent 645.826 (Nov. 8. 1950). Engel, L. L.;'Slaunwhite, W. R., Carter, P.;and Nathanson, I. T.,J. Biol. Chem.,185,255 (1950). English, A. C., and Dole, M., J. Am. Chem. Soc., 72, 3261 (1950). Fitrr, H., Oil Cotour Trade J., 114, 729 (1948). Feinstein, L., and Hannan, P. J., U. S. Patent 2,525,785 (Oct. 17, 1950). Feinstein, L., Hannan, P. J., and McCabe, E. T., IND.ENG. CHEM,,43, 1402 (1951). Ferrer, A. P., and Mor& F. C., Ion,11, 3 (1951). Findlay, R. A. (to Phillips Petroleum Co.), U. S. Patent 2,520,391 (Aug. 29, 1950). Fischer, R., Mikrochemie ver. Mikrochim. Acta, 36/37, 296 (1951). Fischer, W., Ger. Patent 801,986 (Jan. 29, 1951). Fragoso, J. H., Bol. wlegw quim. Puerto Rico, 7, 18 (1950). Freeman, S. E., and Gloyer, S.W. (to Pittsburgh Plate Glass Co.), U. S. Patent 2,539,661 (Jan. 30, 1951). Freiman, M. (to Vitamins, Inc.), Ibid., 2,516,112 (July 25, 1950). Funasaha, W., Yohogawa, C., and Suga, S., J. Chem. SOC. Japan, Ind. Chem. Sect., 51, 27 (1948). Gavrilescu, G., Rev. Teh. A G I R , 3, 165 (1949). Geankoplis, C. J., Wells, P. L., and Hawk, E. L., IND.ENG. CHEM.,43, 1848 (1951). Gisvold, O., U. S. Patent 2,534,260 (Dec. 19, 1950). Gloyer, S. W., J . Am. Oil Chemist-s' SOC.,27, 462 (1950). Gloyer, 8. W. (to Pittsburgh Plate Glaas Co.), U. S. Patent 2,524,103 (Oct. 3, 1950). Goldberg, M. W., and Sternberg, L. H. (to Hoffmann-La Roche, Inc.), Ibid., 2,489,232-8 (Feb. 22, 1949); Brit. Patent 628,902 (Sept. 7, 1949). Golumbic, C., and Orchin, M., J . Am. Chem. Soc., 72, 4145 (1950). Golumbic, C., and Weller, S., Anal. Chem., 22, 1418 (1950). Golumbic, C., Woolfolk, E. O., Friedell, R. A., and Orchin, M., J . Am. Chem. SOC.,72, 1939 (1950). Gopal, R., and Rastogi, R. P., J . Indian Chem. SOC.,27, 401 (1950). Gros, T. A., and Feuge, R. O., J . Am. Oil Chemists' SOC.,28, 1 (1951). Haase, R., Angew. C h a . , A60, 4 (1948). Hachmuth, K. H. (to Phillips Petroleum Co.), U. S . Patent 2.515.217 (Julv 18. 1950). Haines,' W. J., and 'Johnson, R. H. (to Upjohn Co.), Ibid., 2,528,880 (Nov. 7, 1950). Hamer, A. W., Roy. Australian Chem. Inst. J. and Proc., 17, 88 (1950). Happel, J., and Cauley, S. P. (to Socony-Vacuum Oil Co.), U. S. Patent 2,516,837 (Aug. 1, 1950). Hara, N., Osawa, M.. and Azuma, H., J . Chem. SOC.Japan, Ind. Eng. Sest., 51, 150 (1948). Harban, A. A., and Johnson, C. E. (to Standard Oil Co. of Indiana), U. S. Patent 2,522,619 (Sept. 19, 1950). Hasselstrom, T., and Stoll, M. (to U. S. Industrial Chemicals, Inc.), Ibid., 2,547,208 (April 3, 1951). Hawes, T. P.,, and Giraitis, A. P. (to Standard Oil Development Co.). Ibid.. 2,612,327 (June 20, 1950).

Vol. 44, No. 1

(104) Hayes, E. T., Williams, F. P., and Sternberg, W., Ibid., 2,533,246 (Dec. 12. 1950). (105) Heat Enaineerina. 101 .-5-1, \. ~, 26: _ -( ,-19 . (106) Hellberg H., Farm. Revy, 50, 301 (1951). (107) Hildebrand, J. H., Proc. Natl. Acad. Sci. U.S., 36, 7 (1950). (108) Hildebrand, J. H., Fisher, B. B., and Benesi, H. A., J . A m . Chem. SOC.,72, 4348 (1950). (109) Hixson, A. W., and Miller, R., U. S. Patent 2,508,387 ( M a y 23, 1950). (110) Hixsoni A. W., and Miller, R. (to Chemical Foundation, Inc.), Ibid., 2,548,885 (April 17, 1951). (111) Hodge, E. B. (to Commercial Solvents Corp.). Zbid.. 2.520.098 (Aug. 22, 1950). (112) Ibid., 2,520,099 (Aug. 22, 1950). (113) Hudson, B. E. (to Standard Oil Development Co.), Ibid., 2,530,332 (Kov. 14, 1950). (114) Hughes, E. C., Scoville, W. E., Whitacre, C. H., Faris, R. B., Bartleson,'J. D., and Darling, S. M., IND. ENG.CHEM.,43, 750 (1951). (115) Iguchi, M., and Sato, M., J . SOC.Chem. Ind. Japan, Suppl. Binding, 46, 222 (1947). (116) Inskeep, G. C., Bennett, R. E., Dudley, J. F., and Shepard, M. W., IND.ENG.CHEM.,43, 1488 (1951). (117) Jasper, J. J., and Mayer, W. J., J . Am. Chem, Soc., 72, 4767 (1950). (118) Jellinek, H. H. G., J. SOC.Chem. I d . , 69, 225 (1950). (119) Jodra, L. G., Rev. cienc. aplicada (Madrid),4, 137 (1950). (120) Johnson, E. A. (to Standard Oil Co. of Indiana), U. S.Patent 2,535,069 (Dec. 26, 1950). (121) Johnsoh, J. D. A., J . Chem. SOC.,1950, 1743. (122) Jonea, R. W., Chem. Eng. Progress, 47, 46 (1951). (123) Kalichevsky, V. A., Petroleum Refiner, 30, 95, 111, 122 (1951). (124) Kalopissis, G., Chimie et industrie, 64, 563 (1950). (125) Karlson, P., and Hecker, E., 2. Naturforsch., 56, 227 (1950). (126) Karush, F., J. A m . Chem. SOC.,73, 1246 (1951). (127) Katzin, L. I., and Sullivan, J. C., J . Phys. & Colloid Chem., 55, 346 (1951). (128) Keto, W. L., and Martin, J. L. (to Commercial Solvents Corp.), U. S. Patent 2,530,883 (Nov. 21, 1950). (129) Keyser, W. L. de, Cypres, R., and Herrmann, M., Bull. centre phys. nucleaire univ. libre Bruselles, No. 17 (1950). (130) Kilpatrick, M. (to United States of America, c / o U S.A.E.C.), U. S. Patent 2,521,121 (Sept. 5, 1950). (131) Kimura, R., Rept. Inst. Scz. Tech. (Tokyo Univ.), 1, 31, 41 (1947). (132) Kirkbride, C. G. (to Owens-Corning Fiberglas Corp. and Standard Oil Co. of Indiana), U. s. Patent 2,522,378 (Sept. 12, 1950). (133) Kirkoatrick. W. H.. and Wilson. D. L. fto Visco Products Co.). Ibik,-2,514,399 (July 11, 1950). (134) Kitahara, S., Repts. Sci. Research Inst. ( T o k y o ) , 24, 454 (1948). (135) Ibid., 25, 165 (1949). (136) Ibid., 26, 218 (1950). (137) Kittsley, S. L., and Goeden, H. A , , J. Am. Chem. SOC.,72, 4841 (1950). (138) Kozacik, A. P., and Sachanen, A. Tu'., U. S. Patent 2,522,678 (Sept. 19, 1950). (139) Kronig, R., and Bruijsten, J., Applied Sci. Research, A2, 439 (1951). (140) Kylander, R. L., and Garwin, L., Chem. Eng. Progress, 47, 186 (1951). (141) Lauer,'G. G., and Passino, H. J. (to M. W. Kellogg Co.), U. S. Patent 2,516,127 (July 25, 1950). (142) Leaders, W. M., and Norris, F. A. (to Swift and Co.), Ibid., 2,521,234 (Sept. 5, 1950). (143) Leigh, T., Pryce, J. M., and Imperial Chemical Industries, Ltd., Brit. Patent 645,037 (Oct. 25, 1950). (144) Lewis, D. J., Proc. Roy. SOC.(London),A202, 81 (1950). (145) Lien, A. P. (to Standard Oil Co. of Indiana), U. S. Patent 2,525,809-10 (Oct. 17, 1950). (146) Lien, A. P., and McCauley, D. A. (to Standard Oil Co. of Indiana), Ibid., 2,528,892 (Nov. 7, 1950). (147) Long, F. A., J . Am. Chem. SOC.,73,537 (1951). (148) Lott, W. A., Bernstein, J., and Heuser, L. J. (to E. R. Squibb and Sons), U. S. Patent 2,537,933 (Jan. 9, 1951). (149) Lowenstein-Lom, V., Petroleum (London),14,33 (1951). (150) Lowenstein-Lom, V.,Schnabel, B., and Kejla, V., Gaz, Woda i Tech. Sanit., 24, 94 (1950). (151) Low Temperature Carbonisation, Ltd., Horne, D., Marshall, R. P., and Boudy, H. F., Brit. Patent 647,487 (Dec. 12, 1950). (152) Low TemDerature Carbonisation. Ltd., and Pound, G. 8.. Ibid., 648,752 (Jan. 10, 1951). (153) Lukasiewicz. S. J., and Denton, W. I. (to Socony-Vacuum Oil Co., Inc.), U. S.Patent 2,515,928 (July 18, 1950). (154) Lupfer, G. L., Petroleum Processing, 6, 34 (1951). I . -

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(155) McCauley, D. A,, Shoemaker, B. H., and Lien, A. P., IND. ENQ.CHEM.,42, 2103 (1950). (156) . . McClennan. J. K.. and Strickland, B. R. (to Standard Oil Development Co.), U. S. Patent 2,525,153 (Oct. 10,1950). (157) McMillan, G. W. (to Commercial Solvents Corp.), Ibid., 2,509,010 (May 23, 1950). (158) Maddock, A. G., and Miles, G. L., J. Chem. Soc., 1949 (Suppl. Issue 2), 5253. (159) Maddock, A. G., and Stein, L. H., Ibid., 1949 (Suppl. Issue 2), 8258. (160) Martinenghi, G. B., Olearia, 5 , 5 (1951). (161) Martynov, V. M., Kolloid Zhur., 12, 359 (1950). (162) Mason, D. R.. and Piret, E. L., IND.ENG. CHEM.,43, 1210 (1951). (163) Matalon, R., Trans. Faraday Soc., 46, 674 (1950). (164) Matsumoto, Y., and Ishida, K., J . Chem. SOC.Japan, Ind. Chem. Sect., 52, 92 (1949). (165) Mayer, A,, Atti ist. veneto sci., 106, Pt. 2,47 (1948). (166) Mayland, B. J., Ruehlen, F. N., and White, E. E. (to Phillips Petroleum Co.), U. S. Patent 2,508,723 (May 23, 1950). (167) Mayland, B. J., and White, E. E. (to Phillips Petroleum Co.), Ibid., 2,527,951 (Oct. 31, 1950). (168) Ibid., 2,552,198 (May 8, 1951). (169) Mellan, I., “Industrial Solvents,” 2nd ed., New York, Reinhold Publishing Corp., 1950. (170) Merck and Co., Ino., Brit. Patent 637,184 (May 17, 1950). (171) Michaels, A. S., and Hauser, A. E., J. Phys. & Colloid Chem., 55, 408 (1951). (172) Miller, R., U. S. Patent 2,511,824 (June 13, 1950). (173) Moeller. T., and Jackson, D. E., Anal. Chem., 22, 1393 (1950). (174) Morrison, G. H., Ibid., 22, 1388 (1950). (175) Myers, L.D. (to Emery Industries, Inc.), U. 8. Patent 2,520,470 (Aue. 29. 1950). (176) NagaG, S, Kitamurr, K., Fujinaga, G., and Tanii, Y., Chem. Eng. (Japan), 15,59 (1951). (177) Nagata, S., Yokoyama, T., and Honjyo, M., Ibid., 15, 49 (1951). (178) Nellensteyn, F. J., CoEloid Chenz., 7 , 513 (1950). (179) Neuworth, M. B., Hofmann, V., and Kelly, T. E., IND.ENQ. CHEM.,43, 1689 (1951). (180) Newton, G. G. F., and Abraham, E. P., Biochenz. J . , 47, 257 (1950). (181) Nichols, P. Lo, Anal. Chem., 22, 915 (1950). (182) N. V. de Bataafsche Petroleum Maatschappij, French Patent 952,262 (Nov. 14, 1949). (183) Ofner, A., Hungarian Patent 135,577 (April 25, 1949). (184) Oldshue, J. Y., and Rushton, J. H., paper presented before Am. Inst. Chem. Engrs., Kansas City, Mo., May 14, 1951. (185) Olson, R. L., and Walton, J. S., IND.ENG.CHEM.,43, 703 (1951). (186) Ono, S., Mem. Faculty Eng., Kyushu Uniu., 12, 201 (1950). (187) Padgett, F. L. (to Ethyl Corp.), U. S. Patent 2,531,361 (Nov. 21, 1950). (188) Pagel, H. A., and Schwab, K. D., Anal. Chem., 22,1207 (1950). (189) Pequot, C., and Ricket, H., J. recherches centre natl. recherches sci., 1950,70; Bull. mens. ITERG, 4,332 (1950). (190) Passino, H. J. (to M. W. Kellogg Co.), U. S. Patent 2,523,630 (Sept. 26, 1950). (191) Paterno. F.. and Paladino, S., Ital. Patent 454,664 (Jan. 28. 1950). (192) Perel’man, F. M., and Zvorykin, A. Ya., Izvest. Sektora Fiz.Khim. Anal.. Inst. Obshchei i Neoro. Khim.. Akad. Nauk S.S.S.R.,19,’.144 (1949). (193) Pittsburgh Plate Glass Co., Brit. Patent 644,917 (Oct. 18, 1950). (194) Podbielniak, Inc., prospectus. (195) Polson, A,, and van der Reyden, D., Biochim. et Biophys. Acta, 5, 358 (1959). (196) Popel, S. I., Esin, 0. A., and Gel’d, P. V., Doklady Akad. Nauk S.S.S.R.,74, 1097 (1950). (197) Prigogine, I., and Defay, R., Bull. SOC.chim. Belges, 59, 255 (1950). (198) Pure Oil Co., Brit. Patent 651,513 (April 4, 1951). (199) Radischchev, V. P., Izvest. Sektora Fiz.-Khim. Anal., Inst. Obshchei i Neorg. Khim., Akad. Nauk S.S.S.R., 15, 5 (1947). (200) Ratchford, W. P., Harris, E. H., Fisher, C. H., and Willits, C. 0.. IND. ENC.CHEM.,43, 778 (1951). (201) Ray, G. C. (to Phillips Petroleum Co.), U. S. Patent 2,526,971 (Oct. 24, 1950). (202) Rhodehamel, H. W. (to Eli Lilly and Co.), Ibid., 2,547,782 (April 3, 1951). (203) Ricci, J. E., “Phase Rule and Heterogeneous Equilibrium,” New York, D. Van Nostrand Co., 1951. (204) Riediger, B., Z . ‘Ver. deut. Ing. Verfahrenstech., No. 4, 119 (1943). (205) Rogener. H., Kolloid-Z., 118, 10 (1950).

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(206) Rose, W. E., and Seyer, W. F., J. Phys. & Colloid Chem., 55, 439 (1951). (207) Rotinyants, L. A., Izvest. Sektora Fiz.-Khim. Anal., Inst. Obshchei i Neorg. Khim., Akad. Nauk S.S.S.R.,17,64 (1949). (208) Rupp, W. H., and Packie, J. W. (to Standard Oil Development Co.), U. S. Patent 2,509,885 (May 30, 1950). 76, 305 (1950). (209) Ruse, A., Seij~-~le-Fette-W~7achse, (210) Rydberg, J., S v m k Kern. Tid., 62, 179 (1950). (211) Sandell, E. B., Anal. Chim. Acta, 4,504 (1950). (212) Saunders, K. W., IND.ENQ.CHEM.,43, 121 (1951). (213) Schaeffer, B. B. (to Mathieson Chemical Corp.), U. S. Patent 2,540,915 (Feb. 6, 1951). (214) Scheibel, E. G., IND. ENQ.CHEM.,43, 242 (1951). (215) Scheibel. E. 0..and Freu. A. J., in “Encvclowdia of Chemical Tech‘ology,” Vol. 6,-R. E. Kirk and D.‘F. Othmer eds., New York, Interscience Encyclopedia, 1951. (216) Schlockauer, H., Qqimicu (Rio de Janeiro), 5 , No. 3, 49 (1949). (217) Schmidt, A. J. (to Standard Oil Development Co.), U. 5. Patent 2,523,154 (Sept. 19, 1950). (218) Schuerch, C., Jr., J. Am. Chem. SOC.,72,3838 (1950). (219) Schultz, B. G., and Larsen, E. M., Ibid., 72,3610 (1950). (220) Schwab, A. W., Moser, H. A., Cooney, P. M., and Evans, C. D., J . Am. Oil Chemists’ Soc., 27, 314 (1950). (221) Schwitzer. M. K., “Continuous Processing of Fats,” London, Leonard Hill, 1951. (222) Secoy, C. H., J . Am. C h . Soc., 72, 3343 (1950). (223) Sheehan, J. C.. and Tishler, M. (to Merck and Co., Inc.), U. S. Patent 2,492,243 (Dec. 27, 1949). (224) Sheeline, H. W., Etherington, L. D., and Morgan, J. P. (to Standard Oil Development Go.), Ibid., 2,526,508 (Oct. 17, 1950). (225) Shell Refining and Marketing Co., Ltd., Berriman, J. A., and Selbie, J. C., Brit. Patent 649,666 (Jan. 31, 1951). (2261 Sherwood. T. K.. IND.ENG.CHEM..42. 2077 (1950). (227j Skau, E. L., Dopp, W. N., Burleigh, E. G., and Banowite, L. F., J . Am. Oil Chemists’ SOL, 27, 556 (1950). (228) Slaunwhite, W. R., Anal. Chem., 23,687 (1951). (229) Smirnov, N. I., and Polyuta, S. E., Zhur. Priklad. Khim. ( J . Applied Chem.), 21, 1137 (1948). (230) Smith, J. C., Stibolt, V. D., and Day, R. W., IND.ENQ.CHEM., 43, 190 (1951). (231) Sobin, B. A., Finlay, A. C., and Kane, J. H. (to Chas. Pfizer & Co.), U. 5. Patent 2,516,080 (July 18, 1950). (232) Soci6t6 anon. des manufactures des glace8 et produits chimiques de Saint-Gobain, Chauny and Cirey, Brit. Patent 636,600 (May 3, 1950). (233) Soci6t6 pyrenbenne de carburants et solvsnts, French Patent 940,549 (Dec. 15, 1948). (234) Ibid., 940,550 (Dec. 15, 1948). (235) Solomon, E. (to M. W. Kellogg Co.), U. 5. Patent 2,540,143 (Feb. 6, 1951). (236) Spicer, W. M., and Meyer, L. H., J . Am. Chem. SOC.,73, 934 (1961). ,- - - - ,. (237) Stachelberg, M. V., Klochner, E., and Mohrhauer, P., Kolr l~id-Z.,115,53 (1949). (238) Steinkohlenbergwerke Rheinpreussen, Chemische Werke. Ger. Patent 800,407 (Nov. 6, 1950). (239) Stepanov, R. N., Vul’fson, N. S., and Mikova, I. A., Zavodskaya Lab.,16, 1131 (1950). (240) Stockdale, R. A. G., and Wm. Ranson and Son, Ltd., Brit. Patent 645,876 (Nov. 8, 1950). (241) Strand, C. P. (to- Shell Development Co.), U. S. Patent 2,515,140 (July 11, 1950). ENQ.CEEM., 43, 510 (242) Sturaenegger, A., and Sturm, H., IND. (1951). (243) Sumarokov, V. P., and Klinskitch, E. V., Zhur. Priklad. Khim., 23, 641 (1950). (244) Synergic Foundation, Inc., Brit. Patent 639,941 (July 12, 1950). (245) Tanaka, Y., BUZZ.Chem. SOC.Japan, 23, No. 1, 11 (1950). (246) Templeton, C. C., .J. Phys. & Colloid Chem., 54, 1255 (1950). (247) Templeton, C. C., and Hall, N. R., I b i d , 54,958 (1950). (248) Tepe, J. B., and Woods, W. K., “Design of Ether-Water Contacting System,” AECD-2864 (Jan. 18, 1943). (249) Terres, E., Brennsfaff-Chem., 32, 134 (1951). (250) Texas Development Corp., Brit. Patent 646,925 (Nov. 29, 1950). (251) Thompson, N. B., Sewage and Ind. Wastes, 22,205 (1950). (252) Treybal, R. E., IND.ENC.CHEM.,43, 79 (1951). (253) Treybal, R. E., “Liquid Extraction,” New York, McGrawHill Book Co., 1951. (254) Tschamler, H., and Krischai, H., Monatsh., 81, 612 (1950). (255) Turner, D. W. (to Petrolite Corp., Ltd.), U. S. Patent 2,527,690 (Oct. 31, 1950). (256) Turner, W., Elliott, E. C., and Richlin, I. (to Borden Co.), Ibid., 2,519,516 (Aug. 22, 1950).

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INDUSTRIAL A N D ENGINEERING CHEMISTRY

(257) Umezawa, S.,Suomi, T., and Nakada, S., J . Chem. SOC.Japan, Ind. Chem. Sect., 52, 72 (1949). (258) Uainee de Melle, French Patent 942,096(Jan. 28, 1949). (259) Vandor, J., Magyar Kem. Lapja, 4,592 (1949). (260) Vlasak, F.,and Kosinova, L., Chem. Listy, 42, 32 (1948). (261) Walker, S.W., and Latta, J. E. (to Stanolind Oil and Gas Co.), U. S. Patents 2,535,700-1(Jan. 26,1950). (262) Walther, C., Erddl u. Kohle, 3,327 (1950). (263)Warf, J. C., J . Am. Chem. SOC.,71,3257 (1949). (264) Warf, J. C. (to United States of America, c/o AEC), U. S. Patent 2,623,892(Sept. 26, 1950). (265) Washburn, E.R., and Dunning, H. N., J . Am. Chem. Soc., 73, 1311 (1951). (266)Weber, U. v., Chem. Tech., 2, 241 (1950). (267) Weinhardt, A. E.,and Hixson, A. N., IND.ENQ.CHEM.,43, 1676 (1951). (268) West, F.B., Robinson, P. A., Morgenthaler, A. C., Beck, T. R., and McGregor, D.K., Ibid., 43,234 (1951). (269) Wetmore, F. E., and LeRoy, D. J., “Principles of Phase Equilibria,” New York, McGraw-Hill Book Co., 1950. (270) Wiley, R. H., and Smith, N. R., J. Am. Chem. Soc., 73, 1383 (1951). (271) Willis, N. E. (to Monsanto Chemical Co.), U. S. Patent 2,523.243 (Sept. 19. 1950). (272) Wittkff, H., and Roach,~J.R. (to General Mills, Inc.), Ibid., 2,520,670(Aug. 29, 1950). (273)Ibid., 2,520,671 (Aug. 29,1950). (274) WyIer, J. A. (to Trojan Powder Co.), Ibid., 2,532,253(Nov. 28, 1950). (275) Yagi, S.,Miyauchi, T., and Kogure, K., Chem. Eng. ( J a p a n ) , 15, 65 (1951). (276) Young, H. H., and Christopher, E. F. (to Swift and Co.), U. S. Patent 2,528,482(Oct. 31, 1950). (277) Zahnstecher, L. W.,Petroleum Refiner, 29, No. 7, 107 (1950); Heat Engineering, 25, 61 (1950). (278) Zernike, J., Rec. trav. chim., 68,585 (1949). J . Phys. & Colloid Chem., 54, 1306 (1950). (279) Zimm, B. H., LEACHING

(280) Anderson, R. T. (to V. D. Anderson Co.), U. S. Patent 2,548,333 (April 10, 1951). (281) Apunaev, 0.S.,Legkaya Prom., 10,No. 10,24 (1950). (282) Arnaud, G., Ital. Patent 454,621 (Jan. 28, 1950). (283) AQers, A. L., and Scott, C. R., J . Am. Oil Chemists’ SOC.,28, 348 (1951). (284) Bacot, P. A. (to Soci6t6 immobilibre et financeire du Parc), U.S. Patent 2,522,014(Sept. 12,1950). (285) Baj, E., Ital. Patent 450,938 (Aug. 19, 1949). (286) Bartoiini, A.,Ibid., 444,418 (Jan. 21, 1949). (287) Beckel, A. C., Cowan, J. C., and Belter, P. A. (to United States of America, c / o Sec. of Agriculture), U. S. Patent 2,524,037 (Oct. 3, 1950). (288) Bendler, A. J., and McNeil, D., J. Am. Oil Chemists’ SOC.,28, 164 (1951). (289) Bilbe, C. W. (to Allis-Chalmers Manufacturing Co.), U. S. Patent 2,545,938(March 20, 1951). (290) Brammeyer, J. J., Deeg, J. F., Verhaart, M. L. A., Vlies, G. S. vander, and Waterman, H. I., Chimie et industrie, 63, 369, 612 (1950). (291) Breveglieri, V., I d . saccar. ital., 43, 199 (1950). (292) . . Brunner. L., and Krassa, P., Bot. minwo soc. nacl. mineria (Chile),59, 34 (1947). (293) Buffa. A., Chimica e industria ( M i l a n ) ,32,429 (1950). (294) Burak, N.,and Storrow, J. A., J . SOC.Chem. I d . , 69,8 (1950). (295) Butler, J. A., Eng. Mining J., 152, No. 3,56 (1951). (296) Chaudary, M. A,, Indian Patent 39,493(June 7, 1950). (297) Cofield, E. P., Chem. Eng., 58, No. 1, 127 (1951). (298) Cole, H. M. (to General Foods Corp.), U. S. Patent 2,542,119 (Feb. 20, 1951). (299) Cornell, D., and Katz, D. L., IND. ENG.CHEM.,43,992 (1951). (300) Desparmet, E.,French Patent 940,731 (Dec. 21, 1948). (301) Dronov, C. F.,Sakharnaya Prom., 23, No. 10,15; No. 11, 24 (1949). (302) Dunning, J. W.(to V. D. Anderson Co.), U. S. Patent 2,551,254 (May 1, 1951). (303) Ellestad, R. B., and Leute, K. M. (to Metalloy Corp.), Ibid., 2,616,109(July 25, 1950). (304) Feinstein, L., and Hannan, P. J. (to United States of America), Ibid., 2,525,784(Oct. 17,1950). (305) Fitch, E. B:, C h m . Eng. Progress, 47, 83 (1951). (306) Frederiksen. S. E. (to Novo Terapeutisk Laboratorium A/S), U. S. Patent 2,524,658(Oct. 3,1950). (307) Fujiwara, S.,J. Chem. SOC.Japan, Pure Chem. Sect., 71, 386 (1950). (308) Ibid., p. 387.

Vol. 44, No. 1

(309) Funaki, K.,Bull. Tokyo Inst. Technol., Ser. B , 1950, No. 1, 165 pp. (310) Gerard, R.,Chim. anal., 32, 155,278 (1950). (311) Germinal, S.A.,Swiss Patent 264,898(Feb. 1, 1950). (312) Graham, R. P., and Shepherd, A. D. (to United States of America, c/o Sec. of Agriculture), U. S. Patent 2,548,895 (April 17, 1951). (313) Hamacher, J. D.,and Barns, R. W. (to Detrex Corp.), Ibid., 2,547,577(April 3,1951). (314) Hamasumi, M.,Isawa, M., Suiuki, R., Kameda, M., and Hosoda, K., Bull. Research Inst. Mineral Dressing Metall., 1, 3 (1942). (315) Harris, W. D., and Hoyward, J. W., J . Am. Oil Chemists’ So@., 27, 273 (1950). (316) Hartman, L., Ibid., 27, 409 (1950). (317) Henglein, F. A.,Zucker, 4, 139 (1951). (318) Henglein, F.A., and Sohns, G., Chem.-Ztg., 74, 348 (1950). (319) Hrudka, G. E., Sugar, 46, No. 4,40 (1951). (320) Hussain, S. A., and Dollear, F. G., J . Am. Oil Chemists’ SOC., 27, 295 (1950). (321) Huste, R. L., and Iacobucci, A n d e s asoc. qutm. argentina, 38, 203 (1950). (322) Jann, P. E., and Zimmerman, H. K., Chemist-AnaZust, 39, 72 (1950). (323) Johnson, E., Inst. Gas Engrs., Commun. 378(a) (1950);Gas J . , 265, 108 (1951). (324) Kelly, T. B. (to Universal Oil Products Co.). U. S. Patent 2.536.373 (Jan. 2. 1951). (325) Kitagawa, J:, Oyama, F:, and Kiyomiya, S., Japan, Patent 177,206(Dec. 20, 1948). (326) Kokhan, M. A.,and Simakova, E. I., Sakharnaya Prom., 24, No. 2,23 (1950). (327) Kuz’minykh, I. N.,and Yakhontova. E. L.. Zhur. Priklad. Khim.; 23, 1121 (1950). (328) Lee, J. A., Chem. Eng., 57,No. 9,123 (1950). (329) Lerman, F.,in “Encyclopedia of Chemical Technology,” Vol. 6,R. E.Kirk and D. F. Othmer, eds., New York, Interscience Encyclopedia, 1951. (330) Lipa, H. J., Can. J. Research, 28F, 451 (1950). (331) Luberoff, B. F., Chemist-Analyst, 39,40 (1950). (332) McCubbin. K..J . Am. Oil Chemists’ SOC..28.310 (1951). - - -, (333j McGinnis, R. A.,“Beet-Sugar Technology,’; New York, Reinhold Publishing Corp., 1951. (334) Machline, C., and Bethencourt, P. G . W., &$mica (Rio de Janeiro), 5, No. 3, 58 (1949). (335) McInnis. C. C.,Paint, Oil.Chem. Rev.. 113. No, 9.20 (1950). (336) Martinenghi, G.B., Olearia, 4, 285 (1950): (337) Merz, V., Intern. Sugar J., 53, 11 (1951). (338) Meunier, E.P., I d . parfum., 5, 26 (1950). (339) Moore, N. H., Chem. Eng., 57, No. 6,106 (1950). (340) Nowakowski, B., Gaz. Cukrownicza, 88,291 (1948); Sugar I d . Abstracts, 11, 17 (1949). (341) Oplatka, G., Magyar Kem. Lap& 4, 573,645 (1949). (342) Oplatka, G., and Szoke, S., Cukoripar, 3, 56 (1950). (343) Orel, R.,Chimie et i n d w t r i e , 64, 37 (1950). (344)Parkin, F. P., J . Am. Oil Chemists’ Soc., 27,451 (1950). (345) Piret, E.L., Ebel, R. A., Kiang, C . T., and Armstrong, W. P., Chem. Eng. Progress, 47, 405 (1951). (346) Raffieries Nord-Ocean, French Patent 943,064(Feb. 25,1949). (347) Reuther, C. G.,Westbrook, R. D., Hoffman,W. H., Vis, H. L. E., and Gastrock, E. A., J . Am. Oil Chemists’ SOC.,28, 146 (1951). (348) Rogers, E. F. (to Merck & Co., Inc.), U. 5. Patent 2,521,805 (Sept. 12, 1950). (349) Russell, R. F., Iowa State Coll. J . Sci., 25, 348 (1951). (350) Sagoschen, J. A,, Osterr. Leder-Ztg., 6,45 (1951). (351) Salino, A,, and Monti, M., Ital. Patent 444,223 (Jan. 17, 1949). (352) Sanderson, W.,and Sons, Ibid., 454,612(Jan. 28, 1950). (353) Sanford, F. B., and Karsick, N. L., C m . Fisheries Rev., 12. No. 6,4 (1950). (354) Schaeppi, J. H., and Mosimann, W., U. S. Patent 2,518,441 (Aug. 15, 1950). (355) Schneider, F., Zucker-Beihefte, No. 1, 1 (1950). (356) Seailles, J. C.,Brit. Patents 637,578 (May 24, 1950), 640,145 (July 12, 1950). (357) Sly, G.,Australian Patent 137,130 (May 25,1950). (358) Smet, Andre, Sum-.belge., 69,241 (1950). (359) Smith, C. T., J . Am. Oil Chemists’ SOC.,28,274 (1951). (360) Societh Capuana per lo xilon, Ital. Patent 445,084 (Feb. 5, 1949). (361) Solca, D,, Swiss Patent 266,358 (April 17, 1950). (382) Sorenson, N., and Kristensen, K., U. S. Patent 2,516,350 (July 25, 1950). (363) Spadaro, J. J., McCourtney, E. J., andVix, H. L. E., J. A m Oil Chemists’ SOC.,27, 394 (1950).

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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

January 1952

(364)Staff of Dept. of Mines and Tech. Surveys, Ottawa, Canada, Trans. Can. I n s t . M i n i n ~Met., 53,454 (1950). (365) Straight, H.R.,U. 5. Patents 2,517,143 (Aug. 1, 1950), 2,550,947 (May 1, 1951). (366) Swenson, 0. J. (to Cuban-American Sugar Co. and S. C. Johnson and Son. Inc.). Ibid.. 2.554.073 (Mav 22. 1951). (367) Templeton, C.‘C.,and HRl1,’N. F., J; P&s. ?&’ Colloid Chem., 54, 954 (1950). (308) Thielepape, E.,Zucker, 3,444 (1950). (369) Tiemann, T.D.,J . Metals, 3, 389 (1951). (370) Vasseux, J., and Vasseux, P., French Patent 940,871 (Dec. 27, 1948).

63

(371) Viarengo, M., Ital. Patent 446,760(March 25,1949). 28,195 (1951). (372) Walker, D.D., J . Am. OiZChemists’ SOC., (373) Weiler, W., Chem.-Zlg., 74, 731 (1950). (3741 Werner, W., Zucker,2 , 182 (1949). (375) Wingard, M. R.,and Phillips, R. C., J . Am. Oil Chemists’ SOC. 28, 149 (1951). (376) Woody, G.V., and Bilbe, C. W. (to Allis-Chalmers Manufae turing Co.), U. S. Patent 2,551,820(May 8, 1951). (377) Zies, C.W., and Weigel, F. W. (to V. D. Anderson Co.), Ibid., 2,549,997(April 24, 1951). R ~ C E I V EOctober ~D 10,1951.

FILTRATIO N DS

S. A. MILLER

UNIVERSITY OF K A N S A S , LAWRENCE, K A N .

The principal recent contributions to filtration theory consist of further investigation of the flow of fluids through a packed bed and the experimental confirmation of the ability to predict filtration resistance from cake permeability. Interesting scale-up data for vacuum filters have been reported, and filtration theory has been used successfully to interpret the operations of petroleum dewaxing and sugar filtration. Continued study of viscose has shed additional light on filter-medium filtration. The most spectacular examples of equipment advance are a new continuous-pressure filter and a continuous-belt vacuum filter, but many smaller but valuable improvements to existing designs have been developed. Dyne1 filter fabrics continue to earn praise for their performance, and Orlon has now joined the Family of commercially available synthetics. Resin-impregnated fibrous clarifying cartridges are another major development. Filtration has been the subject of two symposia and of a number of interesting reviews.

T

H E year ending October 1951,like the one preceding, produced an extraordinary number of publications on filtration. This review attempts to cite those of particular value to the chemical industry. It includes uncritical coverage of many of the relevant patents that have appeared and mentions some of the newest issues of industrial brochures on filters. As in previous annual reviewe of this series, the scope excludes gas clarification, centrifugal and sedimentary separation, adsorptive percolation, and biofltration. G E N E R A L REVIEWS

Two brief summaries of the principles of filtration and of the most frequently used filters have appeared. Wilson’s treatment (166) is directed principally toward liquid clarification, while Rumford (136)gives the usual undetailed coverage of an elementary unit operations text. Industrial filtration equipment, including filter media and accessories, has also been discussed in a series of papers by Darner (46)and in a review by Waeser (160). The latter listed a large number of German patents on filters, from the earliest ones to the latest, cited selected foreign patents of recent issue, and gave a brief review of recent papers on filtrsr tion theory and practice. Rietema (134)is the author of a good survey of filtration theory, which is thorough and somewhat critical. It covers cake filtration to about 1947and filter-medium filtration to date. A summary of the applications of filtration to analytical chemistry, with 109 references, has been prepared by Villanova (166). Ultrafiltration, of great laboratory importance to the bio sciences, has been discussed historically by Amat (6). Filtration was the subject of two symposia: a general program of four papers (31) presented to a group of chemical engineers, and a series of five topics on wine processing (7)sponsored by the

American Society of E n o l o g i s t s . Some of the latter papers (67,67, 161) are mentioned subsequently in this review, but because the forme] are to be published in their: entirety in the near future, a report of them will be deferred until they have appeared. Nelson (116) h a s r e p u b l i s h e d filter investment costs which were originally issued in 1947 and 1948, and Leonard (106) has suggested some maintenance charges for several types of vacuum and pressure filters. Leonard’s data are most welcome, for they represent a variety seldom offered. THEORY, EXPERIMENTAL D A T A , AND D E S I G N

Four publications have appeared which do not deal directly with filtration but are closely related to the flow phenomena encountered in a filter. Brownell and coworkers (21)revised the original Brownell correlation on flow through packed beds to provide a general plot which is easier to use and, according to the authors, more accurate. It differs from the prototype principally in the method of inclusion of sphericity, porosity, and roughness. Martin, McCabe, and Monrad (108)studied the pressure drop experienced by a liquid paSeing through a bed of carefully oriented spheres, but failed to correlate the data for the several orientations-@sted. They pointed out that orientation as well ae porosity importantly influences pressure drops. Ishkin and Kazaner (92) investigated the flow of a gasliquid mixture through a porous medium, and Crosier (30)has published his complete data on two-phsse liquid flow through porous masses. Several attempts have been made to confirm filtration theory for specific constant-pressure cake filtrations. Winning (168) found that his filter-press data on calcium carbonate did not obey the expected parabolic law, and offered an unconvincing treatc ment of the data. H o h g and Lockhart (84)conducted an excellent study of filter-cake resistance and achieved the first clear demonstration that permeability data and filtration data are consistent. This is a significant contribution, for it confirms the validity of using permeability tests as a design basis for fitere, recommended some time ago by Ruth and by Carman. It is unfortunate that Hofling and Lockhart investigated only a single low pressure (10 pounds per square inch) and a substantially in-