58 (21) (22) (23) (24)
INDUSTRIAL A N D ENGINEERING CHEMISTRY Flourney, R. W., Corrosion, 7, 129-33 (1951). Frenkel, AM.S., Eng. and Boiler House Rev.,66, 198-205 (1951). Furumi, T., Chem. Eng. ( J a w n ) , 15, 173-7 (1951). Gaddie, R. S., Proc. A m . SOC.Sugar Beet Technol. 6, 532-7
(1950). (25) Guastoni and Co., Ital. Patent 461,101 (Jan. 15, 1951). (26) Hedley, A. G. M., U.S. Patent 2,556,184 (June 12, 1951). (27) Honig, P., Proc. Intern. SOC. Sugai-Cane Technol., 7, 529-49 (1950). (28) Honig, P., Proc. Koninkl. Ned A k a d . Wetenschap., 54B, No. 2 110-19 (1951). (29) Langstroth, G . O., Diehl, C. H. H., and Winhold, E. J., Can. J . Research, 28A, 580-95 (1950). (30) Lauro, G., and Pellegatti, O., Ital. Patent 456,242 (March 29, 1950). (31) Leonard, J. D., Chem. Eng., 58, No. 9, 149-53 (1951). (32) Luchak, G., and Langstroth, G. O., Can. J . Research, 28A, 574-9 (1950). (33) Martynov, M. I., Sakharnaya Prom., 24, No. 11, 28-32 (1950). (34) Myers, J. E., and Jarzombek, R., Chem. Ew., 58, No. 11, 156-7 (1951). (35) Neuville, P.. I d s . ayr. et aliment (Paris), 67, 233-5 (1950). (36) Niewiadomsbi, S., and Wieczffifiski, K., Prremysl Chem., 29, NO. 6, 333-7 (1950). (37) Nikolaev, E. P., Sakharnaya Prom., 24, No. 11, 34-5 (1950). (38) Nyrop, J. E., U. S. Patent 2,585,825 (Feb. 12, 1952). (39) Partridge, S. M., J . Sci. Instr., 28, 28-9 (1951). ENG.CEEM.,43, 2926-31 (40) Peds, R. E., and Reddie, W. A., IND. (1951).
me$
Vol. 45, No. 1
Pichardo, G. M., and Romero, J . J . L., Sugar Abstr., 11, 178 (1949).
Praschan, V. C., Chem. Eny. Progr., 47, 325-30 (1951). Pujol, M. P., I o n , 11, 202-5 11951). Rabe, A . E., S. African Sugar J . , 35,461 (1951). Rani, W. E., and Marshall, W, R., Jr., Chern. Eng. Progr., 48, 141-6 (1952). Ibid., pp. 173-80. Rawlings, F. N., Proc. Am. SOC.Sugar Beet Technol., 6, 528-31 (1950). Regestad, S. O., Svensk Paperstidn., 54, 35-51 (1951). Saitzew, J., Brit. Patent 585,683 (Feb. 12, 1947). Samuelson, H. O., Swed. Patent 131,798 (May 29, 1951). Scott, D., Australian J . Dairy Tecknol., 5, 53-94 (1950). Sofronyuk, L. P., Sakharnaya Prom., 25, No. 8 , 26-8 (1951). Speyerer, H., Zucker, 4, 293-306 (1951). Teatini, D., Ital. Patent 457,279 ( M a y 12, 1950). Tegze, M.,Cukoripar, 3, 282-6 (1950). Tsuji, M., Geophys. Mag., 22, 11-20 (1950). Tverskaya, N. P., Izvest. A k a d . N a u k S.S.S.R., Ser. Geonraf. i Geojiz., 15, 74-81 (1951). Vere-Jones, N.W., -Vew Zealand J . Sci. Teciinol., 31B, S o . 3, 1 4 (1949). Walker, L. H., and Patterson, D. C., IND. ENQ.CHEW,43, 5346 (1951). Werner, E., Zucker, 4,467-70, 454-7 (1951). Yoder, R. J., and Dodge, B. F., Refrig. Eng., 60,156-9 (1952).
SOLVENT EXTRACTION
ROBERT E. TREYBAL
NEW YORK UNIVERSITY, NEW YORK 53, N. Y . The year's recorded progress in liquid extraction is considerable, with the work on the fluid dynamics of spray and packed towers, and on formation and behavior of liquid drops especially worthy of note. No innovations in equipment design were introduced, but minor variations were proposed for all major types. In the application to specific processes, sulfur removal and the separation of aromatic hydrocarbons from light distillates were given much attention in the petroleum industry, and many new solvents and techniques were proposed for the separation of oxygenated compounds from hydrocarbons in connection with the Fischer-Tropsch and related processes. In leaching relatively little fundamental work was reported, but there were many improvements proposed in techniques and equipment for the processing of oil seeds, sugar beets, and metal-bearing ores.
T
HE volume of the literature in both liquid and solvent
extraction has continued a t the high level of the past several years. This review is therefore not an exhaustive treatment of the year's developments, but is necessarily limited t o a consideration Qf the major contributions and to representative samples taken from among the remainder. LIQUID EXTRACTION
Several reviews of broad coverage have appeared. In addition t o the annual review of this series (a%), Von Berg and Wiegandt (180)have discussed briefly all phases of the subject, and Weisz (286)has reviewed the special problems of fractional countercurrent extraction. Maloney has summarized in chart form the principal considerations in choosing liquid extraction as a separation method (f78). EQUILIBRIA
Systems whose ternary liquid equilibria have been fairly thoroughly investigated, a t least to the extent of determination of several complete tie line compositions, are listed in Table I. Those systems for which only the distribution of a solute between immiscible phases has been determined are listed in Table 11. Table 111 lists the binary liquid systems fw which mutual solu-
bility data have been measured. In addition, thelimits of miscibilitywithin the ternary system castor oil-ethyl alcohol-water have been established (168), and the system succinonitrilewater-ethyl alcohol was used t o illustrate the effect of changing temperature on the appearance of new liquid phases (188). An extensive compilation of ternary systems which separate into two liquid layers has also been made (90). Bono and Brusset (26) have developed graphical methods of treating thermodynamic data to obtain binary nonelectrolytic liquid equilibria. The numerical calculation of tie lines and initial directions of binodal curves in 3- or &phase systems, including those containing solid components, are outlined by Meijering (186). Brancker (SO) has illustrated his method of computing quaternary equilibria from ternary data using the system acetone-water-vinyl acetate-acetaldehyde. Othmer and Thukar (606)have demonstrated that the effect of temperature on distribution coefficients can be shown by a linear pIot of the coefficients against the vapor pressure of water a t the corresponding temperature on logarithmic paper. METHODS OF CALCULATION
Klinkenberg (145) has presented simple derivations for the relation between number of stages, extraction factor, and the ratio of amounts of extracted solute in extract and raffinate, with and without reflux, for countercurrent, stagewise extraction with constant distribution coefficient. The results are also applied t o the separation of two components by a double-solvent system (fractional extraction) (146). Mathematical treatment of the data resulting from a Craig-
INDUSTRIAL AND ENGINEERING CHEMISTRY
January 1953 Table
1.
Ternary Liquid Equilibrla Temperature,
System Water-acetic acid-ethyl ether -methylene chloride -carbon tetrachloride -creosote -trichloroethylene -3-heptanol -heDtadecanol -aoetone-methyl ethyl ketone -benzene-trimethylamine -methanol-butyl alcohol -eth 1 alcohol-3-heptanol -furrural-n-butane -1-butene -isobutane -isobutene -nrouane - - - - ~-nicotineXEKe Oleic acid-triolein-methanol -95% methanol (as.) -907 methanol (aq.) 795% ethanql (as.) Methanol-fatty acids-grapeseed 011 -walnut oil -linseed oil Styrene-ethylbenzene-diethyleneglycal
c.
19
19 27
Table Literature Reference
(41)
(41) (899)
34
27 25 25. 50 25 25, 70 30 25 3 7 . 8 66 93 37'8 $6 37.8. 51:s: 66, 79.8 37.8 23.9. 3 7 . 8 23.9'37 8 64,
(606) (678) (204) (138) (1.98)
(109) 109) (109)
6?*70
20 20 20 20 25 25 25 25
type countercurrent distribution for analytical purposes has been considered by several authors (104, 107, 201, 285). Golumbic (104) and Gregory and Craig (107) have additionally discussed the general applicability of these techniques.
II.
Solute Fe(CNS)s LiI NaI KI, "41
UOi(N0;)r
Ca(NOs)z Co(NOa)l, Mg(rJ_ddi, WNOdn, Th++++ Acetic acid Aoetic acid Propionic acid Methanol
59
Distribution-Coefficient Data Literature Reference
Solvent System Water-ethyl ether Ethylene lycol-ethyl acetate Water-(et%yl ether isoprop 1 ether butyl ether, digthy1 Cetosolve: dibutyl Cellosolve, dibutyl Carbitol.isoamy1 acetate. methyl isobutyl ketone, cyclohexanone) Water-n-hexyl alcohol (Water-chloric acid-salts)-(benzene -thenoyltrifluoroacetone) (Water-aoety1acetone)-benzene Water-(hexane, benzene carbon tetrachloride, carbon 'disulfide. nitrobenzene) Water-many ' Water-( etroleum ether carbon tetrac8loride benzene: chloroform, chlordbenaene, nitrobensene) Water-(ethyl ether. ethyl acetate, butyl'ace2ate) Water-triolein Water-various carbonyl compounds Water-various carbonyl compounds Water-various carbon 1 compounds Water-n-bu+yraldehy$e
(1 73) (65) (108, 176)
(864) (996) (6866)
(69) 061) (60)
, (260)
'
Various alcohols 3-Butanediol Glycerol Gluoose, fructose Sugars glycols, and sugar alcohols Aniline and its methyl derivatives Organic acids, bases
(Water, water-oitrate-phosphate)cyclohexane Water:(isoamyl, octyl, oleyl aloohoh)
Quinol Estrone, 178-estradio1, estriol
Water-ethyl ether (Ethyl alcohol, methanol, water)(benzene, ethylaoetate, cyclohexane carbon tetrachloride, chlorofbrm)
(2so)
(76)
EQUIPMENT AND TECHNIQUES
Apparatus. A Dutch invention consists of a vertical tower, fitted with stationary annular baffles and rotating disks fixed to a vertical axial shaft; the disks are smaller in diameter than the openings of the baffles (202). Propellers or paddles agitate the counterflowing liquids in the unpacked tower of Callo and Hartvigsen (95), and perforated baffles affect redispersion of one of the phases. Steams' tower for countercurrent contact is a variant of the perforated-plate type (255). A new variation of the wetted-wall column contains vertical guides along which one of the liquids, that which preferentially wets the guides, flows (82). A gas or vapor is used to mix and propel the liquids through a new multistage mixer-settler apparatus (80). In another plant of this type, specifically adapted to separations with double-solvent systems, the mixer vessel is relatively large compared to the settler (136). Still another mixer-settler apparatus was developed specifically for production of quinine sulfate (159). A most interesting tower for the countercurrent contact of molten metals, or metals with extraction solvents such as molten slags, is constructed of refractory shapes (139); each stage of the multistage device consists essentially of small pools of the heavier liquid over which the light liquid flows. Techniques. Separation in double-solvent systems in a countercurrent, continuous contact tower is improved by maintaining a high ratio of heavy to light solvent above the feed point, and a low ratio below the feed (327); this is accomplished by appropriate withdrawals of solution from the column, solvent removal, and return of the remainder of the solution. By judicious use of extract reflux, the heat requirement for stripping the solvent from the extract is said to be greatly reduced (188). A portion of the extract phase is intermediately withdrawn, cooled, and subsequently returned to the tower used by Davis in the refining of lubricating oils (60). Repeated withdrawal and reintroduction of both extract and raffinate phases along the column are said t o increase the plate efficiency of a bubble-cap column used for extraction from 5 to 10% (110). Where phase contact is brought about by alternately forcing the immiscible phases through a perforated plate either by reciprocating motion of the plate or by action of a surge pump, equality of volume of the phases is ensured by recycling or temporary withdrawal of a portion of the liquids (203). Application of ultrasound t o a spray-tower extraction of
phenanthrene from methanol by gasoline increased the extraction by 76% in a small apparatus (117). Laboratory Apparatus. Craig and coworkers (56) have developed a glass extraction cascade which can be operated in completely automatic fashion to give as many as several thousand equilibrium contacts per 24 hours. Other multistage apparatus (84, 156) and special devices for easily emulsified mixtures (119, 125) and heat-sensitive compounds (68) were also described. A new laboratory column for countercurrent continuous contact;, with a central axial rotor, gave heights-equivalent-to-a-theoretical-stageof from 0.6 to 4 inches (239). Miscellaneous. The effects of physical properties of liquids and shape of tank on the efficiency of agitation of two insoluble liquids were studied in Japan (108); a critical speed above which separate layers were effectively dispersed was observed and correlated with system variables. Safety practices in propane refining of fats and oils were outlined (848). BUBBLES AND
DROPS
The velocity of rise of liquid and gaseous bubbles in liquid media was investigated thoroughly by Smirnov and Ruban (244), who were able to express their results in terms of dimensionless groups. Over the range of drop Reynolds numtrers 190 to 1000, it was unexpectedly found that the relative velocity of drop and continuum was independent of the viscosities of either phase. Internal circulation within liquid drops falling through water was studied visually by an ingenious technique (96): Diffusion of water into the drop caused a color change owing to the presence of cobalt chloride. Internal circulation depends upon the drop Table
111.
Liquid Solubilities
System Furfuryl alcohol-(rapeseed sunflower, tobacco, soybean, poppy seed, walnut, hemiseed, and olive oils) Water-n-butane Water-nitromethane Water-(Cd to Cia alcohols) Aniline-cyclohexane Aqueous salt solutions-(benzene, nitrobenzene, ethylene chloride)
Literature Reference
(5) (56) (63) (77)
{%;]
60
INDUSTRIAL AND ENGINEERING CHEMISTRY
Reynolds number, and is influenced by the viscosity of the drop and the interfacial tension. Keith and Hixson (142) studied drop formation and the breakup of liquid jets in a spray column, using glass nozzles. For each system and nozzle a minimum drop size was produced a t a particular flow rate. Rate of drop rise and coalescence was also studied. Some Japanese observations are also available (94). I n a very comprehensive work, Lewis, Jones, and Pratt ( 161 ) and Pratt and White (210) studied the formation and breakdown of drops flowing through packing in an extraction column, The average diameter of drops leaving a packing is independent of the size of those entering and there is a critical packing size above which the drop diameter is independent of size and type of packing, and of flow rate of dispersed phase up to flooding, although not independent of the flow rate of the continuous phase. Results are expressed mathematically. Steady-state and transient diffusion with chemical reaction into moving liquid drops was studied mathematically by Danckwerts (67). Kronig et al. (160)have continued their mathematical study of extraction rates from slowly moving drops. I n an experimental study, West and coworkers (287)found that extraction of acetic acid from benzene drops by water could be increased considerably by the presence of small amounts of the lower molecular weight alcohols. Special attention was given t o extraction during the period of free rise and to the presence of interfacial barriers to diffusion. E M U L S I O N S AND THEIR S E P A R A T I O N
I n the case of benzene-water emulsions formed in the presence of oleic or stearic acids, the formation of oil in water or water in oil emulsions depends upon the method of agitation and the temperature (133). Selective wetting of the vessel may also determine the type of emulsion formed ( 7 3 ) . Emulsions of water in mineral oil showed marked increase in viscosity beyond 50 volume % ' water, with a maximum a t from 72 to 82 volume % of the dispersed phase; beyond this concentration, phase inversion occurred (236). The performance of gravity oil-water separators of the type used for petroleum refinery wastes is discussed by Giles et al., who also present design data (101). Ingersoll (130) has presented a thorough literature review on settling of particles lighter than water, sedimentation, and design criteria for settling tanks. Barton (16) recommends passage of emulsions through a 2-inch bed of glass wool of small fiber diameter a t low velocities for emulsion separation. Copper or iron turnings and activated charcoal are recommended as coalescers ( I ) , and silicone-coated fibers are especially effective (120). Retention of gasolinesweetening agent dispersions for periods of a t least 7 minutes, a t low flow velocities, is effective in their separation (81). F L O W CAPACITIES OF TOWERS
A tower, 4.0 inches in internal diameter by 8 feet and of the Elgin type, was used by Minard and Johnson (193)t o determine the limiting flow characteristics of spray extraction towers. Rejection of drops from the entry cone, rather than flooding, was used as the criterion of flow capacity. Physical properties (viscosity of continuous phase 0.9 to 36 centipoises, specific gravity difference 0.1 to 0.595, interfacial tension 23 to 44 dynes per cm.) and orifice diameter (0.04 to 0.228 inch) and numbec (21 t o 97) were studied. The square roots of the limiting flow rates were linearly related as in previous packed tower studies, and the final correlation is given in terms of either drop diameter or nozzle characteristics, the latter presumably including the interfacial tension effect. Holdup data are also reported. Recent Japanese work (94)on smaller spray columns (1.15 to 2.22 inches in diameter) of the Elgin design provides additional holdup and flooding data. Nozzle diameters (0.0197 to 0.197 cm.), specific gravity difference (0.075 to 0.1 17), viscosities (0.8 to 300 centipoises),
Vol. 45, No. 1
and interfacial tension (34 to 52.7 dynes per cm.) were the major variables. Results are correlated in terms of dimensionless groups. Pratt and coworkers have measured holdup of dispersed phase and pressure drop ( 9 7 )and flooding rates ( 6 4 )in packed columns. The holdup cannot be calculated directly from pressure drop except in spray columns. Two, sometimes three, flow regimes were observed, and the holdup characteristics of each are described. Flooding data in 3-inch and 6-inch internal diameter columns of the Elgin type were measured for Raschig rings to 1 inch), Lessing rings ("8 t o '/z inch), and Berl saddles to 1 inch). The correlations of the data did not require inclusion of the viscosity, although this property was varied over the range 0.5 to 5.7 centipoises. A recent Russian work (140) developed experimentally the relation between the linear velocity of flon- of the continuous phase in a packed extraction column and the ratio of volumetric flow rates of the phases, interfacial tensions, viscosity and density of the liquids, and packing size. MASS TRANSFER RATES
Kandi and Ghosh (199) extracted acetone and benzoic acid from water with benzene, and the former also with kerosene, in a 1.75-inch internal diameter perforated-plate column, Holdup and mass transfer coefficients, as well as heights of transfer units, are reported. Increasing the perforation area from 4.5 to 9% of the tower cross section did not influence the extraction rates, but inch reduced increase in the perforation diameter from '/'e t o them. Increased plate spacing reduced the column efficiency. Plate efficiencies were in the range 1.6 to 17.701, in the benzeneacetone-water system. Tink and Roxburgh ($68) extracted glycerol from water by n-butyraldehyde which reacts prith the glycerol to form a cyclic butyral. A 14-stage Scheibel column, 1 inch in diameter, was used, in which the efficiency of extraction was independent of rate of agitation, and increased with increase in temperature t o a maximum a t 30" to 35" C. The column, within limited conditions, extracted about 10% more glycerol than a single batch extraction allowed to reach equilibrium. Seltzer and Williams (234) transferred acetic acid between water and methyl isobutyl ketone in a spray column 3 inches in internal diameter by 14.5 feet in height. By photographic measurements of the drops, it was possible to establish the interfacial area of contact between phases and to separate the mass transfer coefficient and surface terms, which are customarily reported as a single quantity. The variation with flow changes in the combined term was due largely to variations in the interfacial area. Feick and Anderson ( 7 8 ) with a 1.44-inch by 36-inch extraction column packed with 1/2-inch lLlcMahon saddles and 3/s-inch Raschig rings extracted benzoic acid and acetic acid from water with toluene, with and v,-ithout a rapid pulsating agitation of the liquid contents of the tower. As much as 500% improvement in the extraction coefficient was obtained Kith agitation. Rubin and Lehman (224) have derived relationships between over-all HTU's for extraction in relatively dilute solution which permit linear correlations of experimental data. Thus, for any system, straight lines are obtained when HTUoc is plotted against C with l / D SLS parameter, or against l / D with C as parameter. Alternatively, a three-dimensional plot of HTUoc against C and 1/D yields a surface. I-ITUoc is the over-all height of a transfer unit, and C and D are the rates of flow of the continuous and dispersed phases, respectively. ANALYSIS
KOresume will be given here of the very extensive applications of liquid extraction to analysis. Attention is called instead t o the series of thorough reviews by Craig (65), and t o that of Irving (131) which deals specifically with applications to inorganic analysis.
January 1953
INDUSTRIAL AND ENGINEERING CHEMISTRY PROCESS APPLICATIONS
Petroleum Processing. A general review wm prepared by Gester (99). Desulfurization was the subject of many patents. Aqueous hydrogen fluoride ( 1 4 3 3 , 100,124, 162), boron trifluoride (164), and fluosulfonic acid ( 4 7 ) comprise the fluorine compounds suggested as extraction agents. Aqueous mercuric acetate preferentially extracts cyclic sulfides ( 2 1 ) ,although mercaptans may also be removed. Polyolefin glycols are effective particularly when used a t moderately high temperatures (86). Saturated solutions of cuprous chloride in a glycol ether remove mercaptans, and the reagent may be regenerated by air oxidation, extraction, and reduction (172). Amine sulfonates extract both sulfur com-
4
*
i
,
pounds and aromatic hydrocarbons (136). The use of aqueous sodium hydroxide of progressively increasing strength in a series of extractions (268) is effective for hydrogen sulfide and mercaptans. Bolt ( 2 3 ) suggests a scheme for caustic extraction of mercaptans without destruction of desirable phenols. Caustic soda is also used with wetting agents to reduce emulsification (88). Many substances have been suggested for use with caustic solutions to improve desulfurization: aromatic mercaptans (115), lignin (I%’), polyhydroxybenzenes (42), sulfonated wood tar (9), alkali metal sulfonates (43, naphthenic acids (611), pyridine with an oxidizing agent (W), and many others (26, 616, 169). Details and improvements in the use of caustic methanol solutions have also been revealed ( 2 4 , 3 7 , 149, ,270). Alkanolamines alone (221) and with glycol ethers (184) have also been suggested as solvents for the caustic. Disulfides are first converted t o sulfenyl halides, and these extracted with caustic (123). Regeneration of spent caustic solution by extraction of the sulfur has also been proposed (34, 269). Yahnke et al. (292) have successfully removed mercaptans from light distillate fuels by a two-stage extraction with a solvent containing aqueous potassium hydroxide, methanol, and potassium cresylates. Aromatic hydrocarbons are separated from the products of platforming operations by a glycol-water solution in the new Udex process. Operating and design data for recovering 500 ’barrels per day of aromatics by this process a t the Eastern States Petroleum Co.’s Houston plant have been made available (44, 914) and another plant t o recover some 400 barrels per day is being built at the Roosevelt Oil and Refinery Corp. in Michigan (45). Improvements in the sulfur dioxide process have been suggested ( M I ) , and oxydipropionitrile (189), the azeotropic mixture of hydrocarbons with methyl cyanide (66),and the complex of boron trifluoride with certain oxygenated compounds (163) were suggested as new solvents for aromatic recovery. The last also decolprizes hydrocarbon oils and other natural products 1166). Kerosenes, gas oils, and Diesel fuels may be refined with furfural (6, 6, 17, 179, 180, %@?),liquid sulfur dioxide ( S I ) , and hydrogen fluoride (89, 168). In the field of lubricating-oil refining, an experimental demonstration of the inability of conventional phase diagrams to permit reliable prediction of extraction results was made (93). Hydrogen fluoride, alone (18, 166) and with sulfur dioxide (ZOO), and fluosulfonic acid (40) were suggested as selective solvents for lubricant refining. Improvements in the furfural refining process were proposed by Stone (267), and Davis has described methods for the simultaneous extraction of different charge oils in a single system (61). Petroleum residues may be treated either with furfural or with a 90% solution of cresol in water t o give substantially identical results with respect to yield and properties of the raffinate (98). A long list of double-solvent combinations has been proposed (197). In propane deasphalting, higher yields result if the asphaltic phase, rather than the precipitant phase, is made continuous (688); separate stages rather than continuous contact are suggested by Kiersted (1.48) and other improvements by DeVault (66). Liquefied hydrogen fluoride (11) and di-(p-cyanoethyl) amine ( 4 ) were proposed as asphalt pre-
61
cipitants. Kuhn (151) has prepared a list of all United States refineries producing lubricating oils, together with their capacities and the nature of their refining processes. The annual solvent consumption is also given. Clarke (60)has proposed the use of a variety of solvents in the solvent fractionation of wax-containing mixtures, a t temperatures sufficiently high t o ensure the presence of two liquid phases. Fat and Oil Processes. General reviews are provided by Sakurai (228) and Schwitzer (233). Fatty acids may be extracted from olive oil ( d i g ) , sunflowerseed oil (133), and rice oil (226) by aqueous alcohol. Addition of a polypropylene glycol to aqueous alkali improves this reagent as an acid extractant (86). Soybean oil may be extracted with aqueous methanol followed by aqueous caustic to remove acids (8). The highly unsaturated fatty acids may be separately recovered from propane extracts by first crystallizing the saturated acids (267). The soap stock obtained by alkali refining of vegetable oils may be fractionated after acidification with a double-solvent system of furfural and naphtha (48); the naphtha retains the sterols. The fatty acids from linseed oil have been fractionated by two double-solvent systems, petroleum naphtha-furfuraldehyde and petroleum-aqueous methanol (68). Linseed oil phosphatides were fractionated between hexane and aqueous ethyl alcohol (176). Many improvements in the furfural extraction process for vegetable oils have been described by Freeman (91); these generally involve the simultaneous use of petroleum naphtha. Furfural is also useful in removal of high iodine-number fractions from fish oils (164). Liquefied propane is used simultaneously to decolorize fats and to provide chilling for crystallization of saturated materials (162),and to fractionate menhaden oil (67). Recycling part of the residue from a propane extraction can improve the flow characteristics within the extraction towers (29). Harris and Hayward (114) have given extensive details and analyses of a process involving leaching of cottonseed flakes with 2-propanol followed by liquid-liquid extraction with hexane. The combined process produces a greater yield of uniform quality oil than either pressing or hexane leaching alone. Refuse palm oil alone or in naphtha solution yields a*bleachableproduct when extracted with dilute aqueous mineral acids (10). Sesamin is precipitated from sesame oil by petroleum ether ( 7 9 ) . Olive oil (231) and colza oil (106) can be fractionated by solvents. Cox (64)has examined the Twitchell process of fat splitting, and has given consideration to the possibilities of using this process in a continuous countercurrent multistage fashion. Tall oil may be refined by acidification of the crude soaps in the presence of hydrocarbons as solvents (116), whence the refined oil accumulates in the solvent. The rosin and fatty acid components may be separated by preferential esterification and extraction of the fatty acids ( 4 9 ) or by fractionation with the double-solvent system hydrocarbon-aqueous alkali (6%’). Alternatively, the saturated fatty acids may be extracted after air oxidation of the tall oil (72). Manufactured Gas Processes. General reviews of methods of removing phenols from gas works effluents were prepared by Smid ( 2 @ ) and Marsden (181). European practice is described by Le Paslier (160). Practical experiences with the use of butyl acetate as an extraction solvent for phenols, including a discussion of solvent losses and corrosion problems, are provided by Munderloh (196). T h a t solvent (butyl acetate) and also benzene were tried in India (266); benzene will be economical provided steam costs are low. Phenol has been successfully removed from petroleum refinery accumulator waste by extraction with a mixed solvent containing 66% benzene and 34% fluid catalytic cracker gasoline in a York-Scheibel column (20,46,693). A 99.9% reduction in phenol content of waste containing 200 p.p.m. phenol is said to be feasible. The phenol is subsequently removed from the solvent as sodium phenolate. A description of a phenol recovery
62
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
'
Table Separation or Process Conidendrin from sulfite liquor Oat oil from oat fermentation slops Hydroxy fatty acids from wood tar Color. bodies from wood rosin Vanillin from solutions Glycerol, sugars, from water Carbonyl sulfide from hydrocarbons m- from p-xylene Fatty acids from water Detergents from water Butanolones from water Satd. from unsatd. fatty acids Nicotine from water Aliuhatic acids from water Amines from each other Methyl formate from propylene oxide Organic acids from water Methyl butyl ketone from butyl alcohol Dicyanodialkyl ethers, sulfides or amines from hydrocarbons Guaiacol and cresols from wood oil Copper from dicyanobutene Ethyl alcohol from water Organic acids from water Tars from shale oil More-from less-satd. compounds Aldehydes from ketones Secondary from primary alkylamines Nitrated kerosenefrom kerosene
IV.
Solvent Halogenated hydrocarbons, etc. Dichloroethane Pyroligneous acid Naphtha-diethylene glycol monoethyl ether Acetoacetic ester Butyraldehyde Aqueous ethanolamine
VoI. 45, No. I
Miscellaneous Liquid Extraction Processes Literature Reierence (163)
(894)
(273) (147, 148)
Pentane-sulfur dioxide Tributvl - uhosuhate-ben. . zene n-Butyl alcohol Butyl acetate Hydrocarbon-polar solvent Kerosene Isophorone Buffer solution-organic solvent Aqueous sodium hydroxide Fatty acids Water Water Benzene Aqueous hydrogen cyanide Aqueous potassium carbonate Methyl ethyl ketone with isopropyl ether Liquid ammonia Perfluorinated hydrocarbons Sodium bisulfite with hydrocarbons Hydrocarbon-water Nitromethane
process using butyl acetate on water streams and aqueous caustic on oils is given (170). Phenols and other tar acids can be recovered from light oils by extraction with aqueous alkali-metal phenolates and extracting the resulting extract with diisopropyl ether or other solvents (71). T h e resinous phenols in tars were isolated by a series of extractions with benzene (279), and a discussion of the sulfur dioxide extraction of such tars is given b y Terres (265). The nitrogen bases are removed by extraction with solutions of certain acid ammonium salts (177). Pharmaceutical Products. As in previous years, liquid extraction has been used considerably in the isolation and manufacture of antibiotics. Many improvements in the concentration of penicillin and penicillin derivatives have been suggested (52, 69, 85,103,118,141, 169, 212, 215, 946, 247, 277,289). Other antibiotics, such as the familiar streptomycin (199, 263, 276) and bacitracin (,%?IS), as well as t h e newer reticulin (126),rhodomycin (S2, 2S8), fumagillin (74),griseolutein (276),polymyxin (964), and quadrifidins ( 7 0 ) are all isolated by extraction operations. Estrogens (16) and vasopressin preparations (974) are isolated in highly potent form by liquid extraction. Vitamin A is extracted from fish-liver oils with furfural as solvent (92). Countercurrent distribution analysis of insulin with sec-butyl alcohol and aqueous dichloroacetic acid revealed t h e presence of two major constituents when 900 stages were employed (119). Miscellaneous Processes. A large number of processes using liquid extraction as the major separation method have been proposed, and Table IV lists a representative selection from these. As in previous years, a large number of these pertain t o the removal of oxygenated compounds from the oily product of hydrocarbon syntheses of t h e Fischer-Tropsch type. I n addition t o these, Souders et al. (208,661) have proposed interesting methods for the continuous double-solvent separation of organic acids or bases involving repeated adjustment of pH.
Separation or Process Impurities from furfural Sulfuric acid from sulfonic acids Hydroquinone from tars Fluoroalkanes from perfluoro. alkanes Organic acids from hydrocarbons Oxygenated compounds from hydrocarbona Oxygenated compounds from hydrocarbons Oxygenated compounds from hydrocarbons Oxveenated comDounds from hydrocarbons Oxygenated compounds from hydrocarbons Oxygenated compounds from hydrocarbons Oxygenated compounds from hydrocarbons Oxygenated compounds from hydrocarbons Aldehydes and ketones from hydrocarbons Alcohols from hydrocarbons Iron oxide from hydrocarbons Thorium from rare earth solutions Rhenium from water Cerium from rare earth solutions Ceric nitrate from aq. nitric acid Zirconium from hafnium solutions Gallium trichloride from water Various metals from aq. nitric acid Water from aq. hydrogen fluoride
Solvent Hydrocarbons Concd. hydrochloric acid Water-dimethoxybenzene Hydrogen fluoride Aqueous ethanolamine
+
Saponification aq. methanol Ethylene glycol Water, alcohol -4q.inorganic salts
.41cohols Methanol Sodium bisulfite
+ soaps
Aqueous acetic acid Sodium bisulfite solution Aqueous alcohols Aqueous sodium sulfite Water-amyl or butyl alcohol Chloroform tetraphenylarsonium chloride Tributyl phosphate
+
Ethyl ether
+
chelating Benzene agents Ethyl ether Ethyl ether Anhydrous liquid hydrogen chloride
Some of the processes listed in Table I V pertain t o the separation of metals from aqueous solution. I n this connection, a description of the ether-extraction process for purification of uranium, as used by the French Commissariat of Atomic Energy, has become available (75). LEACHING
Theoretical and Design Methods. Piret and his coworkers (555) have continued their studies of the leaching of soluble materials from porous solids. Equations for unsteady-state diffusion from solids of various shapes were developed and tested. The pore-shape factor was again successfully used in these systems. Mass transfer rates between water and cylindrical tablets of benzoic acid in a fixed bed were studied in Japan (532). A general correlation which included new as well as previously published data was developed t o relate heights of transfer units, Reynolds numbers, particle diameters, and fractional voids. I n a series of theoretical papers (561), additional Japanese work on methods of calculation for countercurrent multistage leaching is reported. Systems in which adsorption of solutes on the solids may not be neglected and where equilibrium in each stage is not reached are considered, and equations and charts developed. Equipment. Reviews of continuous equipment were provided by Christiansen (SI@ and Depmer (316). In t h e countercurrent equipment of Fitts and Lorn (32'3) solid and solvent both pass through successive containers, with drainage of the solids in each. Means for retaining the solid a t intervals in such devices is provided by Mueller (847). Alternatively, the solids may be scraped from one troughlike container t o another by rotating paddles, while contacted with counterflowing solvent (SgO). Urff (371 ) describes a battery of rotating drums fitted with screens for solidsolvent separation. In the leaching of pine wood chips, the hot spent wood can be completely discharged without handling in the device suggested by Jones (536). I n the special field of oil seed
January 1953
4
-
INDUSTRIAL AND ENGINEERING CHEMISTRY
leaching, Bonotto’s improvements include a conveyor conduit equipped with a settler t o free the miscella of fines (303),and a device for drying the spent seed by contact with hot solvent vapors from the miscella and steam (309). Variants of the latter are suggested also by Leslie (343). A solvent leg in which a bucket conveyor lifts the leached meal avoids the necessity of unusual valve mechanisms for discharge of solids (996). The Bottaro device (356) consists of relatively small pipes each containing a spiral, and as spiral and pipe rotate the solid and solvent are moved countercurrently. Separation of fines from miscella on a continuous basis is accomplished by passing the mixture upwards slowly through a series of pipes in parallel, each equipped with a small orifice a t the top (367), Improved diffusers for sugar beet leaching are described by Ruth (361) and Diedrichs (317). The most important development in this field appears to be the Oliver-Morton diffuser, consisting of multiple U-shaped cells containing a mechanical device for transporting the cossettes from cell to cell ($11). Wet grinding of solids and solvent followed by continuous filtration was proposed as a possible technique for leaching generally (330). Simple laboratory apparatus is described by Napoli and Sch.mall(348). Oilseed Processes. A review was prepared by Paquot (363) and the practical aspects of plant operation are discussed by Brady (306). The Exsolex process, a combined expeller and leachingprocedure, is described in detail (319), and a full description of the Rotod, an 18-cell percolation leaching device, has been given (379). The use of liquid propane in a continuous countercurrent seed leaching process is proposed by Rubin (360). By heating the propane miscella, fines are carried down by a precipitated liquid phase (316). Mixtures of certain chlorinated hydrocarbons are claimed to be noncorrosive and nonpoisonous solvents (376). Hexane, benzene, ether, acetone, and butanone were compared for the leaching of cottonseed (320) in a series of pilot plant tests, and while each solvent offered certain advantages, hexane seemed best from the over-all point of view. Hexane and hexane-alcohol mixtures were also compared (698): With alcohol present, more extractable material is removed from the cottonseed. Ethyl alcohol as a solvent is the principal feature of a proposed process, and it provides an oil requiring no further refining (999). The problem of solvent losses, with a discussion of a variety of possible causes, was considered in detail by Helme (35’8). A prepilot plant investigation of cottonseed leaching with hexane, involving slurrying the seeds, vacuum filtration, and countercurrent leaching, provides data on filtration rates, concentrations, and extractabilities (368). The process is designed especially for small plants. Attempts were also made to leach the comminuted whole seed, but the process is satisfactory only if the first-cut linters have been removed (313). Prewetting of the cottonseed meats prior to leaching with a hydrocarbon-containing solvent permits reduction in flake thickness and consequent rapid percolation and more effective oil removal (380). Rice polishings may be leached with aqueous alcohol to remove free fat acids prior to the principal leaching (331). This aolvent also yields a satisfactory oil from peanuts, but not from colza seed (346). Methanol or acetone satisfactorily leach egonol from ego seed (344). Soybean meal from trichloroethylene leaching is a raw material for the manufacture of soybean protein, which is, in turn, leached from the seed with naphtha (339). Gelling temperatures of the water leach of such soybean meals were studied by Arnold and Chen (997). A plant designed t o leach oil from peanuts in such fashion as to permit the protein of the meal to be used for manufacture of a woollike fiber has been described (349). Sugar Processes. The physical and chemical properties of the raw material which led to the different methods of processing sugar cane and sugar beets are discussed by Willcox (379), who suggests that milling, together with leaching of canes, can increase leaching efficiencies nearly 100%. Fick’s law has been ap-
63
plied to leaching of sugar from beet cossettes (361) and the results have been confirmed by application t o experimental data. By prescalding the beet cossettes in raw juice, practically no colloids are later pressed from the leached residues (377). Lowtemperature leaching of the beets saves steam and yields a harder pulp of light color and an improved juice (374). Introduction of aqueous sulfur dioxide into a low-temperature diffusion battery also improved the juice (304). Incidental improvements in the diffusion battery which can lead to increased efficiency are discussed by several authors (318,360, 366). Experiences with the Hildebrand continuous diffuser in Germany are described (366). Benzene (376) and paraffin hydrocarbons or chlorinated hydrocarbons (346) are recommended for leaching of cane wax from sugar cane residues. Miscellaneous Organic Processes. The material precipitated by alcohol from the extract produced during spruce-bark tannin leaching has been studied as a function of the tannin content of the extract (327). Tanning extracts from dried, shredded, and ground canaigre roots are produced by continuous countercurrent leaching in a Kennedy apparatus with water (367) or with aqueous organic solvents in a stationary vat system (368). Liquefied propane serves as a solvent for leaching of flower petals, and the solvent is readily removed and recovered (309). Pyrethrin solutions are obtained by leaching the dried and ground residue following an initial leach of pyrethrum flowers (334). Alcoholic solvents are effective in leaching fatty acids from starches (369). Mannitol and laminarin have been leached on a laboratory scale from brown marine algae with acidified methanol (301). Sulfuric acid leaching of seaweed removes iodine, which is released from the solution by treatment with sodium nitrite (399). Alcoholic leaching of Japanese buckwheat removes rutin, which is then readily recovered (310). Gelatin and glue are leached from skin shreds in a countercurrent system with hot water (326),or by alternate leaching with water and a grease solvent (370). Yeast may be defatted in a continuous countercurrent horizontal apparatus with Skellysolve-B (806). Other processes reported upon include the leaching of cananthrol from Cascara sagrada bark with methanol (349), an antioxidant for vitamin A from rice germ with benzene and ethyl alcohol (337),pectic substances from vegetable matter with aqueous ammonium salts (373), antibiotic substances from a variety of fruits and natural products (333),soluble coffee from ground, roasted coffee (314, 396), and caffeine from tea leaves (369). Methylene chloride at pressures of 100 to 1500 pounds per square inch and moderate temperatures will leach waxes and oils from ground oil-bearing shales, coals, and lignites J364). Inorganic Processes. Alumina is leached from compressed pellets of kaolin by acids, thereby reducing filter loads; the acid is readily leached from the pellet residues (35’9). Alternatively, the alumina may be leached first by sulfur dioxide, followed by sulfuric acid (366). Vanadium is leached from precipitates of lead vanadate produced by lead treatment of the leach liquors from soda-ash roasting of chrome ores (364). Tungsten is leached from ores in a ball mill with aqueous caustic, thus simultaneously releasing the tungsten by pulverization (363). Nickel is leached directly from pulverized sulfide ores with strong aqueous ammonia in the presence of air ( S I C ) , or from nepouite with inorganic acids saturated with an iron salt (338). The optimum conditions for leaching rare earth metals from monazite sands with sulfuric acid were established (341). Extensive fundamental studies on the techniques of leaching gold from its ores with cyanide solutions have been reported upon (308,336). Ozone and a high-frequency electromagnetic field assist the cyanide-gold leaching (378). Alternatively, activated carbon loaded with gold, but little silver, may be leached with caustic cyanide solutions, according t o the results of extensive pilot plant studies (381). Sulfur may be leached from finely powdered ores with carbon disulfide (300)or with gas oil (361). Hot toluene will leach sulfur from spent gas works oxide (307),and the sulfur can be separated
I N D U S T R I A L AND E N G I NEE R I N G CHEMISTRY
64
from the simultaneously removed tar by fractional crystallization
of the sulfur. LITERATURE CITED
(1) Aktivkohle-Union Verwaltungs-Ges., French Patent 956,149
(Jan. 25, 1950).
(2) ilmagasa, M., Iimori, S., Takahashi, N., and Sakakibara, H., J . Chem. SOC.J a p a n , 2nd. Chem. Sect., 52, 319, 321 (1949). (3) Angelescu, E., and Esanu, F., Acad. Rep. Populare Romdne, Bul. Stiint. Ser. Mat., Fiz., Chim., 2, 387 (1950).
(4) Antle, H. R., U. S.Patent 2,572,583 (Oct. 23, 1950). (5) Arnold, G., and Kovach, L., Ibid., 2,529,274 (Nov. 7, 1960). (6) Arnold, G. B., and Skelton, W. E. (to Texas Co.), Ibid., 2,567,172 (Sept. 11, 1951). (7) Asselin, G., and Audrieth, L. F. (to U. 9. A., c/o Secy. of the Navy), Ibid., 2,578,623 (Dec. 11, 1951). (8) Ayers, A. L., Ibid.,2,561,330 (July 24, 1951). (9) Ayers, G. W., and Harton, E. E. (to Pure Oil Co.), Ibid., 2,529,670 (Nov. 14, 1950). (10) Babayan, V. K., Ibid., 2,587,954 (March 4, 1952). (11) Badertscher, D. E., and King, W. H. (to Socony-Vacuum 011 Co.), Ibid., 2,546,916 [March 27, 1951). (12) Badgett, C. O., IND. ENG.CHEW,43, 2370 (1951). (13) Badisohe Anilin und Soda-Fabrik, French Patent 953,774 (Dee. 13. 1949). (14) Barieau, R. E. (to California Research Corp.), U. S. Patent 2,584,248 (Feb. 5, 1952). (15) Barton, P.D. (to Sun Oil Co.), Ibid., 2,588,794 (March 11, 1952). (16) Bates, R. W., and Cohen, H. (to E. R. Squibb and Sons), Ibid., 2,565,115 (Aug. 21, 1951). (17) Beavon, D. K. (to Texas Co.), Ibid., 2,526,722 (Oct. 24, 1950). (18) Benedict, B. C. (to Phillips Petroleum Co.), Ibid., 2,590,490 (March 25, 1952). (19) Bergmann, E. D. (to Polymerisable Products, Ltd.), Ibid., 2,560,921 (July 17, 1951). (20) BieN, J. A., paper presented a t Purdue Industrial Waste Conference, May 7, 1952. (21) Birch, S.F., and Mc.4llan, D. T., J . Inst. Petroleum, 37, 443 (1951). (22) Bock, R., and Bock, E., 2. anorg. u. allgent. Chem., 263, 146 (1960). (23) Bolt, J. A. (to Standard Oil Co. of Indiana), U. S. Patent 2.457.975 [Jan. 4. 1949). (24) Bond, D. C. ito Pure Oil Co.), Ibid., 2,535,833 (Dec. 26, 1950). (25) Ibid., 2,589,663 (March 18, 1952). (26) Bono, D., and Brusset, H., Bull. soc. chim.France, 1951, 568. (27) Boobar. M. G., Kerschner, P. M., Struck, R. T.. Herbert, S. A., Gruver, IT.L., and Kinney. C. R.. IND.ENG.CHEW..43. 2922 11951). (28) Braae, B. (to Aktiebolaget Separator), Swed. Patent 132,138 (July 3, 1951). (29) Brabets, R. I. (to Swift and Co.), U. S.Patent 2,596,066 (May 6, 1952). (30) Brancker, A. V., Ind. Chemist, 27, 243 (1951). (31) Brandon, R. C. (to Standard Oil Development Co.), U. S . Patent 2,560,330 (July 10, 1951). (32) Brockman, H., Bauer, K., and Borchers, I., Chem. Ber., 84, 700 (1951). (33) Brooke, L. F., Holm, M. M., and Elliott, L. P. (to California Research Corp.), U. S. Patent 2,465,964 (March 29, 1949). (34) Brooks, J. A., Krause, J. H., Tom, T. B., and Fragen, N. (to Standard Oil Co. of Indiana). Ibid.. 2.556.414 (June 12.1951). (35) Brooks, W. B., Gibbs, G. B., and McKetta, J. J.; Petroleum Refiner,30, No. 10, 118 (1951). (36) Browder, J. G., and Smith, A. R. (to Standard Oil Development Co.), U. S.Patent 2,565,349 (Aug. 21, 1951). (37) . , Brown. K. M.. and Johnstone, W. W. (to Ziniversal Oil Products Co.), Ibid., 2,549,052 (April 17, 1951). (38) Burton, W. P., and McGrath, H. G. (to M. IV. Kellogg Co.), Ib;d., 2,568,717 (Sept. 25, 1951). (39) Calkins, W. H. (to E. I. du Pont de Nemours & Co.), Ibid., 2,557,258 (June 19, 1951). (40) Carnell, P. H. (to Phillips Petroleum Co.), Ihid., 2,538,293 (Jan. 16, 1951). (41) Casarico, A., Ann. chim. (Rome), 41, 199 (1951). (42) Cauley, S. P. (to Socony-Vacuum Oil Co.), U. S.Patent 2,468,701 (April 26, 1949). (43) Champagnat, A. (to Soc. g8n. des huiles de p8trole), Ibid., 2,481,570 (Sept. 13, 1949). (44) Chem. Eng., 59, No. 5, 242 (1952). (45) Chem. Eng. News, 29, 4817 (1951). (46) Ibid., 30, 2060 (1952). (47) Chenicek, J. A. (to Universal Oil Products Co.), U. S.Patent 2,486,519 (Nov. 1, 1949).
Vol. 45, No. 1
Christenson, R. M. (to Pittsburgh Plate Glass Co.), Ibid., 2,573,891 (Nov. 6, 1951). Christenson, R. M.,and Harpt, R. E. (to Pittsburgh Plate Glass Co.), Ibid., 2,573,890 (Nov. 6 , 1951). CIarke, E. W. (to Atlantic Refining Co.), Ibid., 2,541,338-40 (Feb. 13, 1951), 2,578,510-12 (Dec. 11, 1951). Collander, R., Acta Chem. Scand., 5, 774 (1951). Commercial Solvents Corp., Brit. Patent 653,375 (May 16, 1951). Corelli, R. M., Aerotecnica, 30, 32 (1950). Cox, C. B., T r a m . Inst. Chem. Engrs. (London),27, 123 (1949). Craig, L. C . , Anal. Chem., 24, 66 (1952). Craig, L. C., Hausmann, W., Ahrens, E. H., and Harfenist, E. J., Ibid., 23, 1236 (1951). Danckwerts, P. V., Trans. Faraday Soc.. 47, 1014 (1951). Davies, L. S., and Edwards, IT.G. H., J . Sci. Food Agr., 2, 429, 431 (1951). Davies; M.,-Jones, P., Patnaik, D., and Moelwyn-Hughes, E. A., J . Chem. SOC.,1951, 1249. Davis, H. R. (to Lummus Co.), U. S. Patent 2,468,044 (April 26, 1949). Ibid., 2,492,787 (Dee. 27, 1949). Davis, J. W..and Suurlin. H. hI. (to Hercules Powder Co.). Ibid.. 2.558.543 i J k e 2s. 19511. Dawson, L. R., and Griffith, E. J:, Trans. Kentucky Acad. Sci., 13, 137 (1951). Dell, F. R., and Pratt. H. R. C., Trans. Inst. Chem. Engrs. (London), 29, 89 (1951). Denton, W. I., and Bishop, R. B. (to Socony-Vacuum Oil Co.), U. S. Patent 2.463.479 (March 1. 1949). DeVault, A. N. ’(to Phillips Petroleum C o . ) , Ibid., 2,527,404 (Oct. 24,1950). Dickinson, N. L., and Meyers, J. M., J . Am. Oil Chemists’ SOC., 29, 235 (1952). Dobson, F., and Randall, S. S.,Biochem ,J., 49, 399 (1951). Dobson, J., Gudgeon, H., and Leigh, T. (toImperial Chemical Industries, Ltd.), Brit. Patent 654,255 (June 13, 1951). Doery, H. M . , Gardner, J. F., Burton, H. S., and Abraham, E. P., Antibiotics & Chemotherapy, 1, 409 (1951). Doughty, E. W.,Murray, J. V., and Fales, J. D. (to Union Carbide and Carbon Corp.), U. S. Patent 2,595,516 (May 6, 1952). Dunlap, L. H., and Sievert, C. F. (to Armstrong Cork Co.), Ibid., 2,565,484 (Aug. 28, 1951). Dvoretskaya, R. M., Kolloid Zhur., 13, 432 (1951). Eble, T. E., and Hanson, F. R., Antibiotics & Chemotherapy, 1, 54 (1951). Eichner, C., Goldschmidt, B., and Vertes, P., Bull. soc. chim. France, 1951, 140. Engel, L. L., Slaunwhite, W. R., Carter, P., and Olmsted, P. C., J . Biol. Chem., 191, 621 (1951). Erichsen, L., Brennstof-Chem., 33, 166 (1952). Feick, G . , and Anderson, H. AI., IND.ENC.CHEM.,44, 404 (1952). Feinstein, L., and Rengel, S.J., U. S.Patent 2,557,956 (June 6, 1951). Fenske, M. R., and Tegge, B. R. (to Standard Oil Development Co.), Ibid., 2,580,010 (Dec. 25, 1951). Ferguson, L. L. (to Socony-Vacuum Oil Co.), Ibid., 2,462,810 (Feb. 22, 1949). Ferris, S. W., Lamson, E. R., and Smith, D. M. (to Atlantic Refining Co.), Ibid., 2,472,578 (June 7, 1949). Finn, R. K. (to Merck & Co., Inc.), Ibid., 2,563,779 (dug. 7, 1951). Fischer, W., and Jubermann, O., Chem. Ing. Tech., 23, 298 (1951). Floyd, C. M. (to Standard Oil Development Co.), U. S.Patent 2,514,997 (July 11, 1950). Folzenlogen, R. G . (to Buckeye Cotton Oil Co.), Ibid., 2,563,327-8 (Aug. 7, 1951). Fortess, F., Rosenthal, -4.J., and White, B. B. (to Celanese Corp. of America), Ibid., 2,572,128 (Oct. 23. 1951). Foster Wheeler, Ltd., Brit. Patent 659,740 (Oct. 24, 1951). Fragen, N. (to Standard Oil Co. of Indiana), U. S. Patent 2,525,813 (Oct. 17, 1950). Francis, A. W , in “Solubilities of Inorganic and Organic Compounds,” A. Siedell and W. F. Linke, eds., Suppl. to 3rd ed., New York, D. Van Nostrand Co., 1952. Freeman, S. E. (to Pittsburgh Plate Glass Co.), U. S.Patents 2,573,896, 2,573,898-900 (Nov. 6, 1951). Freeman, S. E., and Gloyer, S.W. (to Pittsburgh Plate Glass Go.), Ibid., 2,573,897, 2,573,902 (Nov. 6, 1951). Freund, M., and Vamos, A,, Erdol u. KohZe, 5, 283 (1952). Fujita, S., Todokoro, X., and Tanizawa, E., Chem. E ~ Q . ( J a p a n ) , 15, 164 (1951).
January 1953
e
.
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
(95) Gallo, S. G., and Hartvigsen (to Standard Oil Development Co.), U. S. Patent 2,562,783 (July 31, 1951). (96) Garner, F. H., and Skelland, A. H. P., Inst. Chem. Engrs. (London), Conf. on Mixing and Agitation in Liquid Media, p. 37, July 17, 1951. (97) Gayler, R., and Pratt, H. R. C., Trans. Inst. Chem. Engrs. (London), 29, 110 (1951). (98) Geschwind, O,, Naftu, 6, 20 (1950). (99) Gester, G. C., Advances in Chem. Ser., No. 5 , 177 (1951). (100) Giachetto, J. J., Snuggs, J. F., and Bock, J. A. (to Standard Oil Co. of Indiana), U. S. Patent 2,532,492 (Dec. 5, 1950). (101) Giles, R. N., Scheineman, F. W., Nicholson, C. T., and Austin, R. J., Sewage and I n d . Wastes, 23, 281 (1951). (102) Glueckhauf, E., McKay, H. A. C., and Mathieson, A. R., Trans. Faraday SOC.,47, 437 (1951). (103) Goldman, L. (to American Cyanamid Co.), U. S. Patent 2,547,640 (April 3, 19513. (104) Golumbic, C., Anal. Chem., 23, 1210 (1951). (105) Golumbic, C., and Goldbach, G., J . Am. Chem. Soc., 73, 3966 (1951). (106) Gordon,. E., Congr. tech. intern. ind. peintures et inds. ussoc., 1, 465 (1947). (107) Gregory, J. D., and Craig, L. C., Ann. N. Y . Acad. Sci., 53, 1015 (1951). (108) Griffin, E. L., Phillips, G., Claffey, J. B., Skalamera, J. J., and Strolle, E. O., IND. ENG.CHEM.,44, 274 (1952). (109) Griswold, J., West, R. V., and McMillin, K. K., Chem. Eng. Progress, Symposium Ser., 48, No. 2, 62 (1952). (110) Hanson, G. H. (to Phillips Petroleum CO.), U. S. Patent 2,564,970 (Aug. 21, 1951). (111) Hanson, 0. M., and Linn, C. B. (to Universal OiI Products Co.), Ibid., 2,594, 554 (April 29, 1952). (112) Harfenist, E. J., and Craig, L. C., J . Am. Chem. SOC.,73, 877 11951). -, (113) Harner, H. R., paper presented to Electrochemical Society, Philadelphia, May 4, 1952. (114) Harris, W. D., and Hayward, J. W., Bull. Am. Mech. ColE. T a u s , 6, No. 9 (1950). (115) Hart, J. A., Hollis, L. N., and Randolph, J. W. (to SoconyVacuum Oil Co.). U. 5. Patent 2.460.227 (Jan. 25. 1949). (116) Hasselstrom, T., and Stoll, M. (to National Distillers Products Corp.), I b g . , 2,575,013 (Nov. 13, 1951). (117) Haul, R., Rust, H. H., and Lutzow, J., Naturwissenschaften, 37, 523 (1950). (118) Heathcote, C. W., and Rettew, G. R. (to Wyeth, Inc.), U. S. Patent 2,562,715 (July 31, 1951). (119) Henry, R., and Sorba, R., Bull. soc. chim. biol., 33, 1612 (1951). (120) Hersberger, A. B. (to Atlantic Refining Co.), U. S. Patent 2,556,722 (June 12, 1951). (121) Heas, H. V., and Arnold, G. B. (to Texas Co.), Ibid., 2,558,557 (June 26, 1951). 1122) . , Hibbard. R. R.. and Veatch. F. (to Standard Oil Co. of Ohio). I W . , 2,464,576 (Maroh 15, 1949). (123) Himel, C. M. (to Phillips Petroleum Co.), Ibid., 2,503,486 (April 11, 1950). (124) Holm, M. M., Brooke, L. F., and Berlenbach, B. E. (to California Research Corp.), Ibid., 2,479,238 (Aug. 16, 1949). (125) Holmes. F. E.. Anal. Chem.. 23, 935 (1951). (126) Hosoya, S., Solda, M., Komatsu, N:, Fujimoto, H., Sonoda, Y., and Arai, R., J . Antihiotics ( J a p a n ) , 4, 222 (1951). (127) Huffman, E. H., and Beaufait, L. J. (to U.S.A., c/o Atomic Energy Commission), U. S. Patent 2,566,665 (Sept. 4, 1951). (128) Hughes, H. E., and Maloney, J. O., C h m . Eng. Progress, 48, 192 (1952). (129) Ikeda, H., and Ikeda, H., J . Sci. ResearchInst. ( T o k y o ) ,45, 161 (1951). (130) Ingersoll, A. C., Petroleum Refiner, 30, No. 6, 106 (1951). (131) Irving, H. M., Quart. Revs. (London), 5, 200 (1951). (132) Isemura, T., and Tachibana, R., M e m . Inst. Sci. Ind. Research Osaka Univ., 6 , 54 (1948); 7, 97, 104 (1950); Chem. Researches ( J a p a n ) , 9, 159, 198 (1951). (133) Jaky, M., Mezdgazdasdg 0 Ipar, 3, No. 11/12, 8 (1949). (134) Johnson, A. B., and Condit, D. H. (to California Research Corp.), U. S. Patent 2,594,311 (April 29, 1952). (135) Johnson, C. E., and Harban, A. A. (to Standard Oil Co. of Indiana), Ibid., 2,522,618 (Sept. 19, 1950). (136) Johnson, J. D. A. (to Beecham Research Labs., Ltd.), Brit. Patent 663,876 (Dec. 27,1951); U. S. Patent 2,599,836 (June 10, 1952). (137) Johnson, K. C. (to U.S.A., c / o Atomic Energy Commission), U. 9. Patent 2,549,609 (April 17, 1951). (138) Jones, H. E., and Grigsby, W. E., IND.ENG. CHEM.,44, 378 (1952). (139) Jordan, J. F., U. S. Patent 2,572,489 (Oct. 23, 1951). (140) Kafarov, V. V., and Planovskaya, M. A., Zhur. Priklad. Khim., 24, 624 (1951).
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I .
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65
(141) Kanzawa, T., Kawai, H., and Ho, T., Ann. Repts. Takeda Research Lab., 9, 57 (1950). (142) Keith, F. W., and Hixson, A. N., paper presented to AM. CHEM. SOC., Buffalo, N, Y., March 23, 1952. (143) Kiersted, W. (to Texaco Development Co.), U. S. Patent 2,500,757 (March 14, 1950). (144) King, C. C., and Dickinson, N. L. D. (to M. W. Kellogg Co.), Ibid., 2,552,564 (May 15, 1951). (145) Klinkenberg, A,, Chem. Eng. Sci., 1, 86 (1951). (146) Klinkenberg, A., Lauwerier, H. A., and Reman, G. H., Ibid., 1, 93 (1951). (147) Knox. W. G.. and Cunninsham. G. L.. U. S. Patent 2.573.454 (Oct. 30, 1951). (148) Knor, W. G., and Deniston, G. L., Ibid., 2,560,876 (July 17, 1951). (149) Krause, J. H., and Tom, T. B. (to Standard Oil Co. of Indiana), Ibid., 2,560,178 (July 10, 1951). (150) Kronig, R., van der Veen, B., and Ijzerman, P., Appl. Sci. Research, A3, 103 (1951). (151) Kuhn, W. E., Chem. Eng. News, 30, 979 (1952). (152) Lacey, F. E., and Leaders, W. M. (to Swift & Co.), U. S. Patent 2,552,797 (May 15, 1951). (153) Lackey, H. B. (to Crown Zellerbach Corp.), Ibid., 2,577,470 (Dec. 4, 1951). (154) Lamo, M. A. de, Montequi, R., and Doadrio, A., Pubs. inst. qu‘int. “Alonao Barba” (Madrid), 4, 295 (1950). (155) Lathe, G. H., and Ruthven, C. R. J., Biochem. J., 49, 540 (1951). (156) Lauer, G. G., and Pratt, R. S. (to M. W. Kellogg Co.), U. S. Patent 2,540,129 (Feb. 6, 1951). (157) Leaders, W. M., and Lacey, F. E., Ibid., 2,576,841 (Nov. 27, 1951). (158) Lee, R.‘J., and Drennan, P. S. (to Pan American Refining Co.), Ibid., 2,575,718 (Nov. 20, 1951). (159) Leighton, N. G., Univ. Pontificia Bolivar, 16, 68 (1951). (160) Le Paslier, R., Compt. rend. congr. ind. gaz, L y o n , 66, 219 (1949). (161) Lewis, J. B., Jones, I., and Pratt, H. R. C., Trans. Inst. Chem. Engrs. (London), 29, 126 (1951). (162) Lien, A. P., and Evering, B. L., IND.ENG.CHEM.,44, 874 (1952). (163) Lien, A. P., and Evering, B. L. (to Standard Oil Co. of Indiana), U. S. Patent 2,495,850 (Jan. 31,.1950). (164) Ibid., 2,495,851. (165) Lien, A. P., Evering, B. L., and Haecki, F. W. (to Standard Oil Co. of Indiana), Ibid., 2,564,071 (Aug. 14, 1951). (166) Lien, A. P., Evering, B. L., and Shoemaker, B. H. (to Standard Oil Co. of Indiana), Ibid., 2,495,852 (Jan. 31, 1950). (167) Lindenberg, B. A., J. chim. phys., 48, 350 (1951). (168) Loran, M. R., and Guth, E. P., J . Am. Pharm. Assoc., 40,465 (1951). (169) Lovens Kemiske Fabrik Ved A. Kongsted, Danish Patent 72,434 (April 23, 1951). (170) Lowenstein-Lom, V., Petroleum, 15, 154,160 (1952). (171) Luten, D. B., and Benedictis, A. (to Shell Development Co.), U. S. Patent 2,527.017 (Oct. 24, 1950). (172) McBride, J. A,, and Carney, S. C. (to Phillips Petroleum Co.), Ibid., 2,503,627 (April 11, 1950). (173) Macdonald, J. Y.. Mitchell. K. M.. and Mitchell, A. T. S.. J . Chem. Soc., 1951, 1574. (174) McGrath, H. G., Passino, H. J., and Rubin, L. C. (to M. W. Kellogg Co.), U. S. Patent 2,571,151 (Oct. 16, 1951). (175) McGuire, T. A., and Earle, F. R., J . Am. Oil Chemists’ SOC.,28, 328 (1951). (176) McKay, H. A. C., and Mathieson, A. R., Trans. Faraday SOC., 47, 428 (1951). (177) McKinnis, A. C. (to Union Oil Co. of California), U. S. Patent 2,518,353 (Aug. 8, 1950). (178) Maloney, J. O., Dept. Chem. Eng., Univ. of Kansas. publ. by author, September 1951. (179) Manley, R. E. (to Texas Co.), U. S. Patent 2,475,147 (July 6, 1949). . (180) Ibid., 2,507,861 (May 16, 1950). (181) Marsden, A., Gas World, 133, 524, 653, 672 (1951). (182) Mavity, J. M. (to Universal Oil Products Co.), U. S.Patent 2,564,911 (Aug. 21, 1951). (183) Mayland, B. J., and White, E. E. (to Phillips Petroleum Co.), Ibid., 2,484,305 (Oct. 11, 1949). (184) Meadows, J. L., and Martin, J. N. (to Texas Co.), Ibid., 2,546,345 (March 27, 1951). (185) Medcalf, E. C., and Sisco, W. E. (to American Cyanamid Co.), Ibid., 2,568,159-60 (Sept. 18, 1951). (186) Meijering, J. L., Philips Research Repts., 6, 183 (1951). (187) Mercer, K. K., and Catterall, W. E., U. S. Patent 2,588,268 (March 4, 1952). I
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(188) Mertslin, R. V., and Parkacheva, V. V.. Zhur. Obschel Khim., 20, 1929 (1950).
(189) Metcalf, E . C., Hill, A. G., and Vriens, G. N., Petroleum Refiner,30, No. 7, 97 (1951). (190) Michael, V. F. (to Stanolind Oil and Gas Co.), U. S. Patent 2,544,562 (March 6, 1951). (191) Ibid., 2,555,553 (June 5, 1951). (192) Miller, S. A., Bann, B., and Ponsford, A. P., J. Applied Chem., 1, 523 (1951). (193) Minard, G. W., and Johnson, A. I., Chem. Eng. Progress, 48, 62 (1952). (194) Mitchell, R. L., and McNair, TV. T. (to Celanese Corp. of America), U. S. Patent 2,550,847 (May 1, 1951). (195) Morrell, C. E., and McAteer, J. H. (to Standard Oil Development Co.), Ibid., 2,569,384-5 (Sept. 25, 1951). (196) Munderloh. H.. Erdol u . Kohle. 4. 177 (1951). (197j Myers, H. C. (to Socony-Vacuum Oil Co:), U.‘S. Patent 2,582,883 (Jan. 15, 1952). (198) Nagata, S., Yoshioka, N., Yokayama, T., and Teramoto, D., Trans. Soc. Chem. Engrs. ( J a p a n ) , 8 , 43 (1950). (199) Nandi. S. K.. and Ghosh, S. K.. J . I n d i a n Chem. Soc.. I n d . & News Ed., 13, 93, 103, 108 (1950). (200) Nash, M. E. (to Phillips Petroleum Co.), U.S. Patent 2,538,321 (Jan. 16, 1951). (201) Newton, G. G. F., and Abraham, E. P., Nature, 169,69 (1952). (202) N. V. de Bataafsche Petroleum Maatschappij, Dutch Patent 67,932 (May 15, 1951). (203) Ibid.. 68.805 (Oot. 15. 1951). (204j Oth&r,’D. F., Chudgar, &I. XI., and Levy, S. L., IND. ENG. CHEM.,44, 1872 (1952). (205) Othmer, D. F., and Thukar, M. S., Ibid., 44, 1654 (1952). (206) Oualline, C. M., and Van V’inkle, A., Ibid., 44, 1668 (1952). (207) Palm. J. W.. and Kina. J. A. (to Cities Service Oil Co.). ,. U. S. Patent 2,563,739 (Lug. 7, 1951). (208) Pierotti, G. J., French, F. A., and Souders, M. (to Shell Development Co.), Ibid., 2,556,213 (June 12, 1951). (209) Pittsburgh Plate Glass Co., Brit. Patent 658,967 (Oct. 17, 1951). (210) Pratt, H. R. C., and White, A. S., Chemistry & Industry, 1952, 358. (211) Pure Oil Co., Brit. Patent 656,837 (Sept. 5, 1951). (212) Rawlins, A. L., and Crooks, H. M. (to Parke, Davis BS Co.), C. S.Patent 2,577,762 (June 19, 1951). (213) Regna, P. P., and Solomons, I. A. (to Chas. Pfiaer & Co., Inc.), Ibid., 2,556,375 (dune 12, 1951). (214) Resen, F. L.,OiZGasJ., 50, No. 43, 55 (1952). (215) Rhodehamel, H. W. (to Eli Lilly & Co.), U. S. Patent 2,567,679 (Sept. 11, 1951). (216) Ricards, H. A., and Ryder, J. W. (to Standard Oil Development Co.),Ibid., 2,570,277 (Oct. 9, 1951). (217) Rigamonti, R., Vaccarino, C., and Duzzi, A., Chimica e i n d m tria (XMiZan).33. 619 (1951). (218) Rius, A., and’crespi, M.‘ A., Anales realsoc. espafi. fds. qul‘m., 47B, 243 (1951). (219) Rizzuti, P., Olii minerali, grassi e saponi, colori e uernici, 24, 78 (1947). (220) Robinson, R. A., J . Chem. SOC.,1952, 263. (221) Rosenstein, I,. (to Texaco Development Corp.), U. S. Patent 2,575,602 (Dee. 11, 1951). (222) Rottig, W. (to Ruhrchemie -4.-G.), Ibid., 2,581,712 (Jan. 8 , 1952). (223) Rowden, R. W., and Rice, 0. K., J . Chem. Phys., 19, 1423 (1951). (224) Rubin, B., and Lehman, H. R., Atomic Energy Commission, AECD-3030 (Sept. 12, 1950). (225) Rydberg, J., Acta Chem. Scand., 4, 1503 (1950). (226) Sagawa, K., Japan. Patent 179,842 (Aug. 9, 1949). (227) Sagenkahn, M. L. (to Shell Development Co.), U. S. Patent 2,579,867 (Dee. 25, 1951). (228) Sakurai, T., Y u s h i R a g a h Kuokaishi, 1, No. 1, 33 (1952). (229) Saletore, S. A., RIene, P. S.,and Warhadpande, U. R., Trans. I n d i a n Inst. Chem. Engrs., 2, 1948-49, 16. (230) Sandborn, L. T. (to Crossett Lumber Co.), U. S. Patent 2,573,990 (Nov. 6, 1951). (231) Santelli, E., Olearia, 5, 165 (1951). (232) Saylor, J. H., Whitten, A. I., Claiborne, I., and Gross, P. M., J . Am. Chem. Soc., 74, 1778 (1952). (233) Schwitaer, M. K., “Continuous Processing of Fats,” London, Leonard Hill, 1951. (234) Seltzer, S., and Williams, C. B., paper presented to Am. Inst. Chem. Engrs., Atlanta, Ga., March 19, 1952. (235) Sharp, L. G., and Carmody, D. R. (to Stanolind Oil & Gas Co.), U. S. Patent 2,568,517 (Sept. 18, 1951). (236) Sherman, P., J. SOC. Chem. Ind., 69, Suppl. No. 2, 570 (1950). (237) Sherwin, D. S. (to Phillips Petroleum Co.), U. 5. Patent 2,558,587 (June 26, 1951).
Vol. 45, No. 1
(238) Shockman, G., and Waksman, S. A., Antibiotics & Chemotherapy, 1, 68 (1951). (239) Short, J. F., and Twigg, G. H., IND.ENQ. CHEY.,43, 2932 (1951). (240) Shurter, R. A. (to Commercial Solvents Corp.), U. S. Patent 2,597,755 (May 20, 1952.) (241) S.I.F.E.M., French Patent 965,206 (Sept. 6, 1950). (242) Skelton, W. E., and Arnold, G. B. (to Texas Co.), U. e. Patents 2,534,382-3 (Dee. 19, 1950). (243) Smid, J., Paliva, 31, 35 (1951). (244) Smirnov, N. I., and Ruban, V. L., Zhur. Priklad. I
