INDUSTRIAL A N D ENGINEERING CHEMISTRY
January 1950
perature difference was varied from 1 to 200" C. and the liquid velocity was varied from 0.1 to 1.5 meters per second. When the temperature difference was 20' C. and the pressure increased from 65 t o 74 kg. per square mm. the heat ffux density dropped from 113,000 t o 12,000 kcal. per square meter per hour. The critical temperature of change from bubble t o film boiling decreased from 20' C. at 0.9 of the critical pressure t o almost 0' C. at 0.97 of the critical pressure. Under conditions of bubble boiiing the heat transfer coefficient was independent of pressure; with film boiling the coefficient dropped as the pressure was increased. Liquid velocity apparently had no effect on the heat transfer coefficient with bubble boiling; with film boiling the coefficient increased as the velocity b a s raised. Kirschbaum (20)reports on boiling film coefficients with graphite. and porcelain tubes; the effect of velocity and temperature difference is reported. Seigel, Bryan, and Huppert (28)report data on the boiling of Freon 12 inside smooth horizontal copper tubes. The tubes used had internal diameters of 0.555 inch and length to diameter ratios of 123 to 432. They present the data in a graphical form with the heat flux and weight flow shown as a function of the temperature difference. The ratio of length t o diameter and the presence of oil has no apparent effect. Free evaporation into air streams is discussed by Chakravorty (9),and a method is described for estimating the evaporation within 20%. The effect of various phenomenon such as ripples, temperature variation, and edges is noted. O
.
LITERATURE CITED
(1) (2) (3) (4) (5)
Adelman, M., and Hall, R. H., Can. J . Research, 26F,57 (1948). Avramenko, G. D., Sakharnaya Prom., 22, No. 7,42 (1948). Bardoux, A. C., J . jabr. a c r e , 89, 126 (1948). Bartholmew, W. H., A n d . Chern., 21, 527 (1949). Birkett, L. S., Intern. Sugar J., 48, 189 (1946).
-=
47
( 6 ) Brown, A., Swiss Patent 227,579 (Oct. 1F1943). (7) Brown, H. F., Oil Gas J., 46,No. 52, 134, 149 (1948).
Casti, S., Italian Patent 413,511 (May 6,1946). Chakravorty, K. R., J.Imp. CoZZ. Chem. Eng. SOC.,3,46 (1947). Chivalibog, H., Frzeglad Chem., 5, 213 (1947). Chocquet, A. J., J . fabr. sucre, 88, 32, 52 (1947). Coates, J., Chem. Eng. Progress, 45,No. 1, 25 (1949). Coons, F. F., Proc. Am. SOC.Sugar Beet Technol., 5, 680 (1948). Dellicour, E., Belgian Patent 477,025 (November 1947). Griffiths, H , Trans.Inst. Chem. Engrs. (London),23, 113 (1945). Hedley, A. G. M., Joscelyne, F. M., McEntree, J. C . H., and Imperial -Chemical Industries Ltd., British Patent 612,603 (Nov. 15, 1948). (17) Hightower, J. V., Chem. Eng., 55, No. 12, 112, 136 (1948). ENO.CHEM.,41, (18) Hildebrandt, F. M., and Warren, K. H., IND.
(8) (9) (10) (11) (12) (13) (14) (16) (16)
754 (1949). (19) Holland, A. A,, Chem. Eng., 55, No. 12, 121 (1948). (20) Kirschbaum, E., Agnew Chem., ZOB, 235 (1948). (21) Loucks, C. M., and Groom, C. H., Paper Trade J., 127, No. 25, 26 (1948). (22) Lukomskii; 5. M., Izvest. Akad. Nauk. S.S.S.R. Otdel. Tekh. Nauk., 1947,967. (23) Mason, J . F., Corrosion, 4, No. 7, 305 (1948). (24) Planovskii, A. N., Rychkov. A. I., and Lekal, V. M,, Khim. Prom., 1947,No. 3, 11. (25) Porrvik, E. G., Swedish Patent 120,714 (Jan. 27, 1948). (26) Ross, S. D., Chem. Inds., 62,924 (1948). (27) Rufer, H., Lis& Cukrovar, 65,148 (1949). (28) Seigel, L. G., Bryan, W. L., and Huppert, N. C., Heating, Piping Air Cunditwning, 21, No. 1, 159 (1949). (29) Sofronyuk, L. P., Bakharnaya Prom ,22, No. 7 , 3 7 (1948). (30) Springer, H. P., Intern. Sugar J., 50,242 (1948). (31) Staub, S., Ibid., 50, 123 (1948). (32) Stofrow, J. A., Ind. Chemist, 24, 311 (1948). (33) Tromp, L. A., Proc. Assoc. Sugar Technol. Cuba, 21, 241 (1947). (34) Tyrer, H. G. P., and Richardson, A. R.,Intern. Sugar J.,50, 125 (1948). (35) Willaime, G., J.jabr. sucre, 89, 147 (1948). (36) Ibid., p. 175. RECEIVED November 26, 1949.
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TRACTION
JOSEPH C. ELGIN
P R I N C E T O N UNIVERSITY, P R I N C E T O N , N. J.
. N -
UMEROUS publications dealing with solvent extraction during the past year indicate the continued interest and progress in this method of separating the components of mixtures. This is evident both in academic and industrial circles. Previous reviews (56) are continued herewith. Academic interest in solvent extraction operations stems a t least partly from their exemplification and embodiment, perhaps more comprehensively than other related opcrations, of the broadest application of basic design methods, the fundamental principles of phase equilibrium and interphase mass transfer, and the mechanical factors involved in the continuous countercurrent contacting of two phases. Equilibrium, mass transfer, and equipment performance data continue t o be accumulated, but the needs in these directions pointed out in previous reviews are far from being met. Improved methods of predicting quantitatively equilibrium data for liquid-liquid and liquid-solid phases and for more efficient contacting equipment for two liquids are particularly important. Principles and methods of liquid-liquid extraction were reviewed by Elgin (34), and the broad applications of extraction by Scheibel (109). Souders (99, 118) compared distillation, extraction, and extractive distillation, reviewed technical and economic factors involved in each, and gave a basis for choosing among the three methods for a given separation.
SOLUBILITY, P H A S E E Q U I L I B R I U M , S O L V E N T S
A review of recent literature on the thermodynamics of solutions and condensed systems has been supplied by Hougen and Hsu (65). Scatchard (107') reviewed equilibrium in mixtures of nonelectrolytes, and Parlin and Eyring (99) discussed briefly t h e properties of binary solutions of imperfect liquids. A comprehensive treatment of the solubility of nonelectrolytes has been provided by Hildebrand and Scott (56). T h e former has also given a critique on the solubility theory for nonelectrolytes (63). T h e measurement of solubility in the critical region was reviewed by Booth and Bidwell (14). Ternary solubilities, equilibrium distribution data, and phase diagrams have become available for the systems listed in Table I. It was also announced (117)t h a t INDUSTRIAL BND ENGINEERING CHEMISTRY would publish late in 1949 a n extensive review and bibliography of solubility diagrams and equilibriums in ternary systems. Arnoldand Coghlan (3) reported the determination of phase diagrams for water with toluene and other petroleum hydrocarbons a t high pressure and temperature-e.g., 1690 pounds per square inch and 300" C. Under these conditions toluene is soluble in water t o about 12%. Extending previous studies by one of the authors, Bogash and Hixson (11) measured temperature-composi-
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 I. PHASE EQUILIBRIUM DATA System
n-Hexane n-Heptane Allyl alcohol-water with Trichloroethylene Carbon tetrachloride A&ne-nitrobenzene-water Butanol-dibutyl ether-water Diisopropyl ether-isopropyl alcohol-water Dioxane-HC1-water Glycerol-water with aniline, benzyl alcohol, oyclohexanol, 1-butanol, acetone, methyl ethvl ketone. and twt-amyl alcohol Methyl ethyl ketone-water with n-Hexane n-Hentsne Methyl methacrylate Oleic acid-palmitic acid with Acetone n-Hexane
Temperature,
Reference
25
(117) ( 74)
c.
..
25 25
(38)
Various 25 25 25 25 25 0, 25, 50
0, -10, -20, -30. -40
tion diagranw and critical solution temperatures for liquid propane with myristic and lauric acids and their triglyceride esters. They present a generalized correlation of critical solution temperature with molecular weight for such compounds. They also studied the solubilities and phase relationships of liquid propane with dioctadecylamine and a number of other high molecular weight aliphatic compounds. Temperature-composition and critical solution temperature data for binary systems of perfluoromethylcyclohexane with benzene, carbon tetrachloride, chlorobenzene, chloroform, and toluene were reported by Hildebrand and Cochran (64).Critical solution temperatures wcre found to be predictable from theoretical relations for regular solutions. Scott (111)reported the mutual solubilities of fluorocarbons with a series of liquids-e.g., ether, benzene, acetone, and aliphatic hydrocarbons. Davies and eo-workers ($1)reported the solubility and vapor pressure of methylene chloride and 1,2-dichloroethane in water. Solubility, critical solution temperature, and aniline point for eight mineral oils in typical extraction solvents were reported by Neyman-Pilat (86). McCay and co-workers (76) investigated the distribution of a gaseous solute, carbon dioxide, between a 5% aqueous sodium chloride solution and n-pentane, benzene, cyclohexane, dccahydronaphthalene, or hexadecane, at 40" C. I n each case the system was saturated with carbon dioxide. I n a related study Rorschach and Gardner (105) measured distribution coefficients for hydrogen sulfide between water and benzene, mid-continent straight-run gasoline, or kerosene a t temperatures from 15 O t o 35 C. They applied their data to the calculation of the solvent and ideal stage requirements for stripping hydrogen sulfide with water from each hydrocarbon between an initial 0.5% and a final 0.1 or 0.01% hydrogen sulfide content. Distribution of the alkaloid, anabasine, between water and organic solvents was studied by Bowen (15), who found ethylene dichloride t o be the most practical solvent for extracting this substance. Golumbic and eo-workers (46)studied the partition of a series of phenols between water and organic solvents such as cyclohexane. They report coefficients for 15 phenols and develop a t,heory for the selective extraction of these compounds in terms of their dissociation, association, and solubility in the two phases. Golunibic ( M ) applied the results t o the separation of isomeric phenols by countercurrent liquid distribution, and used the method to establish the purity of phenols. The distribution of hexadecylpyridoniuin chloride between water and nitrobenzene a t 25 C. was reported by Grieger and Kraus (46).
Vol. 42, No. 1
The solvent extraction of inorganic salts from aqueous solutiori is growing in interest. Keefer and Andrews (69) measured the solubility of cuprous chloride in aqueous allyl alcohol solutions at 25" C.. and concluded that two complexes with copper weic formed. The distribution of thorium nitrate between water and certain esters (1$5), of uranyl nitrato and nitric acid betweeu aqueous solutions and between aqueous solutions containing animonium nitrate and diethyl ether (&?), and oi pentavalent and trivalent antimony chloride between strong aqueous hydrochloric acid solutions and isopropyl ether ($3) has been determined. In the latter study a distribution coefficient of over 200 was found for pentavalent compared with 0.016 for trivalent antimony wit& 6.5 to 8.5 molar hydrochloric &id solutions. It was shown that antimonic could be separated from antimonious chloride by extractioli with isopropyl ether. Nachtrieb and Conway (84)and Nachtrieb and Fryxell (85) studied exhaustively the extraction of ferric chloride by isopropyl ether as a function of iron and hydrochlori( acid concentration and gave detailed data on the distribution coeficient. With the objective of developing the commercial separation of nickel and cobalt by solvent extraction from aqueoup solutions, Hixson and Garwin (S6) measured the solubility of nickel and cobalt chlorides in a variety of organic liquids. They found the alcohols t o be in general the best solvents and determined in detail the distribution coefficients of cobalt and nickel between capryl alcohol and water aqd water solutions of variow electrolytes. High concentrations of the latter markedly increased the coefficient in the organic phase. Hibshman (51) considered the separation of hydrocarbon\ b? distillation, solvent extraction, and extractive distillation from LI thermodynamic viewpoint. H e developed the thermodynamic relationships in terms of activity coefficients relating the selectivity and separation factors for the three methods. For the separation of components which follow approximately the perfect solution and gas laws, such as hydrocarbons, he showed that the product of the separation factors for extraction and for ordinarj distillation equals that for extractive distillation. For a typiua' selective solvent, dimethyl phthalate, he also calculatcd vaporliquid and liquid-liquid separation factois from partial pressuiv data for the pure components. This led t o the conclusion that t h e boiling range of a mixture separable hp a liquid-liquid process ib roughly three times that by a vapor-liquid process, and that the selectivities toward hydrocarbons with equal boiling points but different chemical structures increase with the boiling point, arid places the classes of hydrocarbons in definite order with respect tc' their separation." Kalichevsky (68) discussed the more important factors involved in evaluating the selectivity and solvent power of solvents and the conduct of oil extraction in laboratory and plant. Reviewing the principles of extractive distillation, Scheibel (108) outlined metliods of choosing a suitable solvent and of predicting the relative effectiveness of solvents and the existence of azeotropes. Certaiii theoretical equations were found by Shukla and Bhsgwat (113) i(, agree well with the data for several ternary systems. An exteusive compilation of azeotropic and nonazeotropic binary and ternary systems by I-Iorsley (61) will be useful in considering extraction processes. MacGee (78) outlined the properties of eleven commercial hexane-type extraction naphthas, and Hightower (68) discussea three new petroleum solvents and their applications. Solv+wi production arid consumption have been reviewed (19). LABORATORY EXTRACTION
An excellent review of extraction :is an anslytical procedure \w* published by Craig (68). The analysis of fatty acids--e.g., acetic, propionic, and butyric-in binary and ternary mixtures in the presence and absence of formic acid by extraction with bilch solvents as isopropyl ether and isoamyl alcohol waq dencrihd by Tsai and F u (138
January 1950
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I N D U S T R I A L A N D ENG3fNEERING C H l M I S T R Y
The theory and pertinent algebraic equations were also given. Baaed on the solubility properties of the system, Siggia and Hanna (114) showed how one-phase ternary systems can b e analyzed without separate determination of each component. The method is applicable when two of the three component&are mutually immiscible. Patschky and Kiermeier ( 9 7 ) concluded that extraction is better than distillation for separating acetic acid from pentane. Kirschman and Pomeroy (71 ) discussed the determination of oil in oil-field waste waters by solvent extraction methods. Booth (13)‘reported results of the extraction of carotene from green leaves with light petroleum, and Ayres and Dooley ( 4 ) report of cottonseed with various petroleum hydrocarbons. Leviton (76) extracted lactose and soluble proteins from skim milk with methanol on a laboratory scale ‘at low ‘temperatu novel laboratory method for extracting solid hubstance easily decompose on heating was proposed example, phenoplastic resins were dissolved and depusited in layers 1p thick on quartz or glass pebbles from which they could be extracted. An apparatug wlts described. Various forms of laboratory extraction and countercurrent disb ystems and apparatus were described by Chut ),Raymond (101), Nolan (87),Urdgand Post (%9
49.
was reported by Fuqua (40).Results were stated to be superior to sed t o remove mercaptans from gasoline by treatment with tannin solutions, and operating results and costs en. Data for solvent extracting three’ oil distillates with in a countercurrent tower packed with‘Raschi fitted with an agitator were also given (131:). Economics of extraction and brief accounts of extraction tech-’ niques and of horizontal and vertical extractors h&ve been given (110),and apparatus and automatic control methods have been proposed (W, 1%). Smith (116) reviewed extensively agitator& I,
CALCULATION AND DESIGN
Mathematical relationships and calculation methods for vari-
Several studies of mass solid phases were reported sired. Laddha and Smith values for each liquid film
relatively low. Studies of. m a y transfer t o flowing fluids fluidized beds of solid particles such as those o helm (77) and Hobson and Thodos (68)are d
their estimation such as those developed by basic interest. Hixson and Smith (67) developed a procedure usbful for predicting the quantitative perfo liquid-liquid extraction systems. They the weight of solute transferred from one and verified i t experimentally for the almost ideal system carbon tetrachloride-iodine-water in a series of geometrically similar vessels. The numerical effect of agitation speed on the rate of solute transfer was given. Mack and Marriner (80) correlated agitator performance with mass transfer for the solid-liquid system benzoic acid-dilute sodium hydroxide and various operating variabl e.g., types of radial flow agitators, tank size, liquid level, baffling. Flooding data for a 2.6-inch Raschig rings and l/g-inch por pairs were reported by Breckenf tained two alternate general coir erature data. Successful applica previously used for vapor-liquid
distillation, concluding that the latter on factor relative t o distillation t o be economic unless special considerations are involved. ?’ !
PROCESS METHODS AND DATA
Process and data for the commercial countercurrent solvent exon of soybean oil using nonflammable solvents were given by well (60). Work of the Northern Regional Research Labo-: ratory on the solveht extraction of soybeans was reported (7, 17,471. The effect of variables such as temperature and moisture ., content on the solvent extraction of oil from rice polishes was described ( I n , l%?). &elective solvent fractionation data for linseed oil together with possible applications were reported (106). Bishop arid co-workers (IO) described the pilot plant ektraction
50
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
and separation of some chemical constituents of white spruce bark with methanol. Process and results for producing 75 and 95% aromatic concentrates for aviation fuels by extracting a light naphtha sidestream crude oil distillate with liquid sulfur dioxide at -20" t o -60' F. were described by Moy (81). T h e refining of residual stocks for lubricating oils by a double solvent extraction with propane to precipitate asphalt and a mixture of phenol and cresol t o improve viscosity index and color was described by Cobb (25). Processes for extracting phenol from coal t a r mixtures with various solvents were described by Murdoch and Cuckney (82) and the effect of variables, pilot plant, and process for extracting sucrose, invert sugars, and nonsugars from molasses with ethanol and isopropyl alcohol by Reich (108). APPLICATIONS
Large scale commercial solvent extraction applications previously reviewed have continued and in many cases expanded. Some potential large scale applications t o the separation of a variety of types of complex mixtures and numerous minor applications in many fields have recently been proposed and many patented. There appear t o have been few basically new commercial applications introduced during the year. I n particular, the application of solvent extraction methods t o recovering oils from vegetable beans and seeds is expanding. It is reported (18) t h a t 37.6% of the 1 9 4 7 4 8 soybean crop was treated by solvent extraction fer oil recovery compared with 28.2% for 1 9 4 5 4 6 . T h e first continuous solvent plant in this country for the production of rice bran oil went into production (20). It employs an Allis-Chalmers unit with hexane solvent similar t o those of other vegetable oil processes and is capable of handling 5.0 tons of rice bran, yielding approximately 10 tons of raw crude oil per day. T h e liquid propane extraction of animal, vegetable, and marine oils is understood t o be incyeasing. I t s techniques and principlw together with flow sheets and variables for various applications were reviewed by Passino (95). Paleni (91) reviewed the technology of solvent-extracting seed oils; Gloyer (43), the refining and fractionating of soybean oil by countercurrent extraction with furfural; while Gastrock and D'Aquin (41) summarized the work and results of the Southern Regional Research Laboratory in pilot plant studies of solvent-extracting cottonseed and peanuts. New methods of extending solvent extraction to the production of castor oil, and the Sherwin-Williams process and plant were described (93). Kalichevsky discussed the procedures and variables involved in the several lubricating oil solvent dewaxing processes (67) and the modern solvent refining and deasphalting of lubricating oils (66). The sulfur dioxide extraction process for oils was reviewed by Obergfell (89), who also summarized pilot and commercial plant data. A new sugar refining process based on the solvent extraction of raw sugar with methanol has been developed (61)and is now in pilot plant stage. Hixson and Garwin (56) concluded t h a t t h e separation of nickel and cobalt by solvent extraction has commercial possibilities. Elgin (36) described methods and solvents for the concentration, recovery, and purification of aqueous glycerol by liquid-liquid extraction. An interesting large scale application t o the desalting of crude oil was described by Hayes and eo-workers (49). T h e crude oil is washed with water, heated above 200" F., and passed through a bed of glass fibers t o coalesce and break the resulting water emulsion, and the desalted oil is then separated from the water. Operating full scale, the salt content of 10,000 barrels per day of a West Texas crude carrying 100 t o 200 pounds of salt per 1000 barrels is reduced 80 t o 94%. A process for preparing rutin from buckwheat leaf meal and green buckwheat (27) and a process for extracting alumina from clay which involves leaching with hot aqueous ammonium bisulfate (118)have been described. Scheibel (109) reviewed commercial applications and processes and
Vol. 42, No. 1
outlined with flow diagrams proposed commercial methods for separating the components of complex coal tar distillates and the aqueous products from synthetic fuel processes b y solvent extraction. Numerous applications t o the separation and recovery of hydrocarbons from their mixtures, the recovery of olefins, the separation of fatty oils, especially mixtures of palmitic, stearic, oleic, and linolenic acids into components by a combination of filtration and liquid phase extraction a t low temperature, and various proposed solvent extraction methods for veg~tableoils and fatty acids are exemplified (5,8,39,43,60,93,94,Q6,119,160, 166,126). Various procedures and solvent combinations are employed. Solvent extraction has been applied t o the removal of aldehydes from hydrocarbon mixture3 with aqueous ammonia (130); t o the separation and iecovery of mixtures of hydrocarbons and oxygenated compounds produced from the catalytic hydrogenation of carbon monoxide and dioxide (YO, 7 s ) ; t o the removal and recovery of high concentrations of mercaptans from hydrocarbon oils (36); and to the separation nf coal tar distillates into aromatic hydrocarbons containing only a nonarornatic double bond and a fraction containing only aromatic unsaturates --e.g., styrene from a light coal tar distillate (66). IIodges and Cashman (69) improved pour point depressant additives of the Friedel-Crafts condensation type by extraction a t 150' to 250' F. with a solvent such as ethyl acetate, while Almquist and Davis ( 1 ) obtained amino acids from protein hydrolyxates by extraction with water-immiscible solveiitr suitable for the acids. There seems little doubt but that both liquid-liquid and liquid-solid extraction are destined for still more evtensive development and application in the future. LITERATURE CITED
(1) Alniquist, H. J., and Davis, J. G. (to F. E. Booth Co.), U. S. Patent 2.471.053 (Mav 24. 1949). (2) Anderson, J. A., Jr. (to Standard Oil Development Go.), Zbid., 2,459,404 (Jan. 18, 1949). (3) Arnold, G . B., and Coghlan, G. A., Division of Petroleum Chemistry, 115th Meeting, AM. CHEIM. SOC.,San Francisco, Calif., 1949. (4) Ayres, A. I,., and Dooley, J. J., J. Am. Oil Chemists' SOC., 25, 372 (1948). ( 5 ) Bain, F. A., and Emmerson, H. R. (to Standard Oil Development Co.), U. s. Patent 2,463,846 (March 8, 1949). (6) Bartels, C. R., and Kleiman, G., Chem. Eng. Progrtm, 45, 589 (1949). (7) Beckel, A. C., U. S. Dept. Bgr., Bur. dp..Ind. Chem., AIC 196 (1948). (8) Beckel, A. C., and Belter, P. A. (to U. S. A,), U. S. Patent 2,469,147 (May 3, 1949). (9) Berg, C., Mrtnders, M., and Switzer, R., paper presented at LOB
Angeles, Calif., regional meeting, Am. Inst. Chem. Engrs., March 1949. 10) Bishop, C. I., Harwood, V. D., and Purves, C. B., paper presented at Montreal Regional Meeting, Am. Inst. Chem. Engrs., September 1949. 11) Boaash, R., and Hixson, A. N.. Chem. Ena. Pyoaress, 45, 597 (1949).
Bogdanov, N. F., U.S.S.R. Patent 68,362 (April 30, 1947). Booth, V. H., AnaE. Chem., 21,957 (1949). Booth and Bidwell, Chem. Revs., 44, 477 (1949). Bomen, C. V., IND. ENQ.CHEW,41, 1295 (1949). Breckenfeld, R. R., and Wilke, C. R., paper presented at Los Angeles, Calif., Regional Meeting, Am. Inst. Chem. Engrs., March 1949. (17) Brekke, 0. L., U. S. Dept. Agr., Bur. Agr. h d . Chem., AXC 194 (1948). (18) Chem. Eng., 56, No. 7, 74 (July 1949). (19) Ibid., 56, No. 11, 367 (1948). (20) Chem. Eng. News, 27, 1658 (1949). (21) Chem. Inds., 63,No.6, 935 (December 1948). (22) Ibid., 64,No.5, 740 (1949). (23) Ibid., 64,No. 6, 926 (1949). (24) Chute, W. J., and Wright, G. F., Anal. Chem., 21, 193 (1949). (25) Cobb, M. L., Petroleum Engr., 21'2, No. 5, 47 (1949). (26) Colborne, R. S. (to B.X. Plastics, Ltd.), Brit. Patent 573,111 (12) (13) (14) (15) (16)
(Nov. 7, 1945). (27) Couch, J. F., and co-workers, U. S. Dept. Agr., Bur. Agr. Ind. Chem., AIC 202 (1949).
January 1950
INDUSTRIAL AND ENG INEERING CHEMISTRY l(1949). 56 (1948). H. K., J . SOC.Chem.
1
4
,
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