ROBERT KUNIN RICHARD L. GUSTAFSON
ANNUAL REVIEW
Ion Continued development of systems and resins is hastening the penetration of ion exchange into hitherto “forbidden”areas of application
I.I A
1 1
n preparing this review, the authors have deviated
I from previous reviews and have attempted to develop a critical analysis of the current status of ion exchange technology. In doing so, they have focused their attention on the end result of the ion exchange operation as well as on the ion exchange phenomenon itself. The true value of an ion exchange operation cannot be appreciated unless it can be viewed in terms of the overall application and compared with other technologies that in many instances can accomplish the same result. The authors have also incorporated their assessment of trends based upon their personal experiences and their contact with various developments throughout the world that have not appeared as yet in the published literature. Td those unfamiliar with ion exchange technology, the full advantages of the basic technique are, of course, unknown. Ion exchange is a unique method for purifying, concentrating, and separating ionic species and various solvents. With the availability of the new ion exchange resins of high capacities and rates of exchange, it is possible to conduct these operations at high flow rates and with a minimum of equipment. It is often unappreciated that the ion exchange systems are unique in that they achieve steady state almost instantaneously and require no thermal energy. Availability of a host of ion exchange materials makes the technique quite versatile and flexible. Furthermore, the economics of ion exchange operations are quite favorable for small as well as large installations. Because of these unique features of ion exchange technology, it is quite understandable that there is scarcely an industry throughout the world that does not depend directly or indirectly upon some ion exchange operation. The past few years have seen marked progress in the adaptation of ion exchange to continuous, countercurrent, moving bed systems, thereby extending the VOL 5 9
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utility of ion exchange. Further, new ion exchange systems have been developed in which the concentration range of ion exchange has been increased and in which ion exchange has been linked to filtration with the availability of macroreticular ion exchange resin structures having porosities and surface areas enabling one to adsorb particulate matter. The macroreticular structures have also linked ion exchange to the field of adsorption. One now finds ion exchange resins being used for systems heretofore considered as “forbidden” areas. T o illustrate the extent to which ion exchange is being employed, a summary of the major areas of application is presented in Table I. These are applications that are now being practiced on a commercial scale. The list is a most impressive one and, if coupled with new areas of utility now under development, one can only conclude that ion exchange technology is not a stagnant development but one that is dynamic. Also ion exchange resins are being used more and more in nonpolar solvents and for solutions of higher concentrations. The former trend is a result of the development of the macroreticular ion exchange resins and the latter a development of continuous, countercurrent, moving bed systems. Of considerable interest is the extension of ion exchange technology to the treatment of brackish waters and to the renovation of sewage effluents. One might summarize the current status of ion exchange technology by simply stating that ion exchange is currently being gainfully employed for practically all applications formerly considered only as being theoretically possible. This has come with the development of new ion exchange resins and engineeriny designs that enable one to make fuller use of the ion exchange resins’ properties. I t must also be stated, however, that further improvements are indeed possible which will further extend the area of utility of ion exchange technology. As noted above, ion exchange must compete with other unit operations such as distillation, evaporation, extraction, and adsorption. As these unit operations improve, ion exchange must also improve to remain competitive; however, each of these has its specific advantages and there are many areas of application where there is no competition. I t is also of interest to note that great strides have been made in adapting and synthesizing ion exchange and related materials for applications essentially devoid of ion exchange reactions. The use of ion exchange resins as catalysts and the development of macroreticular nonionic adsorbents are examples of such applications.
TABLE I . S U M M A R Y O F MAJOR ION EXCHANGE RESIN A P P L I C A T I O N S I N C U R R E N T P R A C T I C E
1. Water Treatment
a. Water softening b. c. d. e. f. g. h. i. j.
k.
Dealkalization Deionization Desalination Color removal Oxygen removal Iron and manganese removal Nitrate removal Fluoride removal Colloid removal Waste treatment
2 . Purification
of Sugars a n d Polyhydric Alcohols
a. Cane, corn, and beet sugar b. Glycerin c. Sorbitol 3. Recovery a n d Purification of Biologicals a. b. c. d.
e. f. g. h.
Antibiotics Vitamins Amino acids Proteins Enzymes Plasma Blood Viruses
4. Recovery and Purification of Metals
a. b. c. d. e. f. g. h. i.
Uranium Thorium Rare earths Transition metals Transuranic elements Gold Silver Platinum Chromium
b. Benzene c. Chlorinated hydrocarbons d. Acetone 6. Reagent Purification a. b. c. d. e.
Hydrochloric acid Formaldehyde Phenol LMonomers Alum
7. Preparation of Sols a. Silica b. Fe(OH)8 c. Alumina d. Thoria e. Zirconia 8. Catalysis a. b. c. d.
Sucrose inversion Esterification Acylation Condensation
9. Ion Exchange Resins as Medicines a. b. c. d. e. f. g.
h. i. j.
Antacids Sodium reduction Taste masking Sustained release Diagnostic Tablet disintegration pH control Potassium removal Skin disorders Toxin removal
10. Analysis (Control) a. Water b. Fertilizers c. Sugars d. Pharmaceuticals e. Hydrometallurgy
5. Solvent Purification a. Alcohols
Reviews
Several reviews and monographs have been written which cover many of the important areas of ion exchange. Marinsky (3A) has edited a book containing several contributed chapters on the fundamental aspects of ion exchange. Helfferich (7A) and Kunin ( 2 A ) have written two general reviews. Rickles (44) has written an extensive review of membrane technology and 96
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Robert Kunin and Richard L. Gustafson are with the Rohm and Haas Co., Philadelphia, Pa. The authors gratefully acknowledge the assistance in tfie preparation of this review from Dr. Erich Meitzner, M i s s D.Sosnowska, and the library staff of the Rohm and Haas Co. AUTHORS
economics. Weiner ( 5 A ) has reviewed the more recent technology of ion exchange associated with water treatment. Theory
The number of papers on studies relating to the theory of ion exchange are, by far, too numerous to mention individually in this review on ion exchange as a unit operation. Much effort has been expended relating various ion exchange phenomena to the physical and chemical structures of the ion exchangers involved and to the nature of the ionic species involved in the ion exchange reaction. More specifically, a vast effort has been directed toward achieving a better understanding of the equilibrium and kinetics of ion exchange and their relation to the columnar or chromatographic behavior of ion exchange systems. Ideally, one would like to be able to predict the columnar performance of an ion exchange column given the equilibrium and kinetic constants for an ion exchange system. With the vast amount of equilibrium and kinetic data available for the commonly used cation and anion exchange resins, our vast knowledge of electrolyte solutions, and the current status of column chromatographic theory, one would imagine that this would not be a difficult problem. For example, given the composition of a hard water supply, one would like to calculate the amount of water that could be softened by a column of a cation exchange resin before a fixed hardness leakage occurred. Unfortunately, this still cannot be done without prior experimentation. Further, given the experimental data for a particular water softening experiment, one still cannot calculate the performance of the same column for a water having a different composition, or for the same water but for the operation of the column at a greatly increased flow rate. Although some progress has been made, it has been limited to highly simplified systems remote from practical conditions. Fortunately, the required data for designing ion exchange resin plants for treating water and solutions of similar composition are now available in the form of technical bulletins published by the manufacturers of ion exchange resins. The huge effort in obtaining this information is not generally appreciated. From the viewpoint of the chemical engineer, many of the data on ion exchange equilibria and kinetics are of limited value except as a guide to predict trends and to assist the engineer and chemist to select the proper type of ion exchange resin and to select proper ranges of operating conditions. Of interest in this connection are the studies of Boyd and Bunzl (7B) and Attridge (2B) on the homogeneity of ion exchange resins and their absorption of electrolytes. I n spite of the careful measurements, confusion still reigns as to these aspects of ion exchange. Theory of ion exchange selectivities and the relationship between the structure of ion exchange resins and the nature of electrolyte solutions was the subject of several noteworthy papers by Marinsky (79B),Lindenbaum and Boyd (78B),Flett and Meares (7ZB),Heumann Vaslow and Boyd (29B, 30B), and and Patterson (76B),
Krylova, Soldatov, and Starobinets (17B). A systematic study of cation exchange in HBr solutions was reported by Nelson and Michelson (27B) and the anion exchange selectivity of 52 elements in H2S04 media was summarized by Strelow and Bothma (76B). Of timely interest are the anion selectivity studies of Ch’iu et al. (8B) on uranyl sulfate complexes, Barbier et al. (3B) on polyborates, and Starobinets and Gleim (25B)on fatty acids. I n view of the interest in the use of ion exchange resins in nonaqueous media. the studies of Novitskaya and Starobinets (22B) and Gorshkov et al. (73B) are most timely. Other significant equilibrium studies are those of Mathieson and Shet (2UB) on carboxylic cation exchangers, Hamann and McCay (74B) on the effect of pressure, and Dickel and Bunzl (77B) on the structure of water bound in ion exchange resins. Theoretical studies on ion exchange kinetics were reported by Turner et al. (27B) Vaisberg et al. (28B), Blickenstaff et al. (6B), Hanley et al. (75B), and Copeland et al. (7UB). Fundamental studies of columnar performance were described by Cooney ( 9 B ) , Beyer and James (4B,SB), Apostolache ( 7 B ) ,Persoz (23B),and Shulman et al. (24R).
Water Treatment
I n the area of water treatment, several notable trends in the field are evident. Of particular interest is the dependence of the power and electronics industries upon ion exchanqe technology to produce water of extraordinarily high purity at high flow rates using water sources of constantly decreasing quality. This trend has required improved pretreatment practices, new engineering innovations, and new ion exchange resins. The concern over waste regenerant disposal and capital investment costs has resulted in the use of countercurrent regeneration techniques and the increased use of carboxylic cation exchange resins for the dealkalization and deionization of waters containing a significant proportion of alkalinity. A significant interest in the use of ion exchange technology for the desalination of brackish waters and the renovation of domestic and industrial sewage effluents is apparent. The development of new ion exchangers and techniques for employing them has expanded the use of ion exchange for treating water high in C O D (organic matter) and turbidity. Because of pollution and increased usage of fertilizers, steps have been taken to devise anion exchange techniques for removing phosphates, nitrates, and even borates. Fresenius et al. (2C) have reported on their large scale studies on the removal of nitrates from drinking water using the chloride form of an anion exchange resin. I n connection with the treatment of condensate in a high pressure power plant or the primary loop of a nuclear power plant, McGarvey (5C) has calculated the optimum temperature to operate a deionization system. Kun and Kunin (4C)have described their laboratory and field studies on the development of a macroreticular VOL. 5 9
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anion exchange resin capable of removing colloidal and nonreactive silica as well as other colloids from deionized water. Interest in the use of ion exchange resin techniques for the desalination of brackish water and sewage effluents is illustrated by the studies of Apfel and Kingsbury ( I C ) and Weiss et al. (8C-77C). The expanded potential of ion exchange technology for reclaiming water from industrial waste effluents is illustrated by the studies of Krasnov and Ovchinnikova (3C) and Pollio and Kunin (6C) on pyridine and phenol wastes and Pollio and Kunin (7C) on reclaiming water from acid mine drainage waste waters. Hydrometallurgy
Applications, such as the use of rare earths for the phosphors of colored TV, the expanded use of atomic energy for power generation, and the continued emphasis on the prevention of stream pollution emanating from the metal processing and plating industries, continue to stimulate studies on the use of ion exchange for the recovery and purification of metals. Stamberg and Prochazka (730) and Reynolds et al. (700) have reviewed many of the important applications in ion exchange hydrometallurgy. Goldblatt ( 7 0 ) and Faure et al. (60)have described recent developments in the use of anion exchangers for the recovery and purification of uranium in South Africa. Other studies include that of Bodiu and Sprinceana ( I D ) on gold recovery, Selezneva ( 7 7 0 ) on selenium, and Dean et al. (40)on cesium. Various studies on plating wastes and metal processing wastes include those of Davankov et al. ( 3 0 ) , Poliskin ( Q D ) ,Borgclte (ZD), Dembeck ( 5 0 ) , Oliver0 (80), Sloan and Nitti ( 7 2 0 ) , and Swanton ( 7 4 0 ) . Pharmaceutical Chemistry and Biochemistry
Of the various industries, the pharmaceutical industry has found ion exchange to be a most valuable processing technique. I t would be fair to state that ion exchange has played a most important role in the production of several antibiotics, vitamins, and other important biologicals at low cost. Several studies have been conipleted recently attempting to improve on these techniques and to develop ion exchange techniques for new biologicals. Kotula (4E), Libinson and Slugina (5E), Savitskaya et al. (9E), Shirato et al. (70E), and Klyueva (3E) have reported their work on the use of ion exchange for antibiotic recovery and purification. Similar studies have been presented by Gordienko and Belikov (2E) on amino acids, Pirogov et al. 17E) on nucleotides, Surinov et al. (77E) and Takei et al. (7.23) on enzymes, Ezhov (7E) on gibberellin, and hloretti et 01. (6E) and Plager (8E)on blood and plasma. Food Technology
As in the pharmaceutical industry, ion exchange has become a routine unit operation in the processing of various food products and supplements such as sugar, fruit juices, milk, gelatin, and glutamic acid. Most of 98
INDUSTRIAL AND ENGINEERING CHEMISTRY
the commercial ion exchange resins now have approval of the U. S. Food and Drug Administration (FDA) for food processing. The use of ion exchange for processing corn, beet, and cane sugar is rapidly expanding as a result of the availability of ion exchange resins possessing improved properties and the requirement of higher sugar recoveries and purities. Improvements relating to the decolorization and softening of various sugar juices and liquors have been described by Andrus ( I F ) , Pucherna (70F), Zsigmond et al. (75F),and Gryllus et al. (5F). Engineering analyses of sugar purification by means of ion exclusion have been made by Schultz et al. (7ZF), and Lowe et al. ( 9 F ) . The recovery of sugar from pineapple juices has been investigated by Su and Wu (73F). Purification of xylose has been described by Leikin (8F). A process for the purification of pure glucose for medical purposes has been presented by Ionescu et al. (6F). The use of ion exchange for the treatment of grape juice and wine has been studied by Vibhakar et al. (74F) and Esau and Amerine (ZF). A process for producing a low-sodium milk has been developed by Ionescu et al. (7F). The development and evaluation of an ion exchange process for removing radioactive strontium present in milk were reported in detail by Fooks et al. (3F) and Sadler et al. (77F). Several full scale plant tests demonstrated that over 90y0of the radioactive strontium could be removed from whole milk without detracting from the flavor or quality. Frolova et al. ( 4 F ) have shown that sunflower seed oil can be refined by means of an anion exchange resin. Catalysis
Although the fact that ion exchange materials have catalytic properties has been known for over 50 years and although inorganic exchangers such as the silicates have long been used as catalysts throughout the petroleum industry, the widespread utility of ion exchange resins as catalysts has been slow in development until recently. Development of the macroreticular ion exchange resins having surface areas and pore structures similar to those of the inorganic adsorbents and catalysts has sparked this advancement. Although many publications on this topic appear annually, it is difficult to assess the degree to which ion exchange resins are employed as catalysts. It is, however, safe to speculate that a modest number of successful commercial applications of ion exchange catalysis are now in use and new7 ones can be expected to appear. The hydrolysis of esters using ion exchange resins of the sulfonic acid type is still being actively studied, and the results of Ordyan et al. (QG),Tartarelli et al. (74G), and Spes (72G) are of interest to note. Esterification reactions were reported by Isagulyants and Trofimov (5G), Polyanskii et al. ( I I G ) , Karpov et al. (6G), and Sultanov et al. (73G). Alkylation reactions were investigated by Isagulyants and Safarov (4G) and Tsvetkov et a l . (75G). Other studies include those of Mekhtiev et al. (8G) on cyanoethylation, Aoki et al. (7G) on vinyl polymerization, Bogatskii et al. (3G) on phosphite syn-
thesis, Ozaki and Tsuchiya (70G) on isomerization, Beal et al. (ZG) on acetal formation, and Lesek and Lisi (7G) on the removal of monomer catalyst inhibitors.
ration of the lanthanides. Haeupke and Wolf ( 6 J ) have measured the phenol extraction coefficients for a series of liquid amine anion and phosphate cation exchangers.
New Ion Exchange Materials
Ion Exchange Membrane Technology
As the limits of ion exchange resin technology are being extended, the need for ion exchange materials of greater physical and chemical stability becomes apparent, and the quest for ion exchangers of greater specificity expands. Higher selectivity, however, is at times a detriment since it is often accompanied by poor kinetics and regeneration or elution efficiency. Of the many publications on ion exchange resin synthesis, few refer to the detailed study of synthesis variables. Exceptions to this are the papers of Wiley and Venkatachalam (ZOH, 27H), Pokrovskaya and Soldatov (72H), and Kolesnikov et al. (5H) on the sulfonation reaction. As examples of the interest in phosphorus based cation exchange resins are the studies of Marhol and Chmelicek (IOH), Leikin et al. (8H), and Bebikh and Sakodynskaya ( Z H ) . The interest in chelating structures is exemplified by the work of Koster and Schmuckler (7H), Gustrow ( 3 H ) , and Tazuke and Nakamura (76H). Also of interest are the efforts of Vasil’eva and Gavurina (79H) on amphoteric ion exchangers, Winnicki (22H) and Manecke and Bourwieg (9H) on redox resins, and Trochimczuk (77H) and Korshak et al. ( 6 H ) on optically active ion exchangers. An emphasis on the stability of ion exchange resins, particularly the anion exchange resins, is illustrated by the thermal stability studies of Peryshkina et al. (77H) and Shaburov and Saldadze (74H) and the radiation stability studies of Kolditz and Wendt (4H),Skorokhod and Ousyanko (75H), Rauzen and Solov’eva (73H), Tulupov tt al. (78H),and Ahmed et al. ( 7 H ) .
Although the use of ion exchange membranes has been slow in development, considerable progress has been made in the synthesis of such ion exchange materials and in the design of electrochemical cells for their use. At the present time, there must be at least 200 such cells, electrodialysis units, operating throughout the world desalting a daily aggregate volume of 5 million gal. of brackish water. Other applications currently in operation include the treatment of whey and the electrolytic conversion of acrylonitrile to adiponitrile. DeLong (7K) has studied the use of electrodialysis for the treatment of home water supplies. Indusekhar and Krishnaswamy (3K) and Grebenyuk and Gnusin (2K) have described water electrodialysis studies both for the treatment of seawater and for producing high quality water. Mintz et al. ( 4 K ) and Shubin et al. ( 6 K ) demonstrated the use of ion exchange membranes for the treatment of cryolite and sulfite waste liquors. The purification of sugar liquors by ion exchange electrodialysis has been reported by Suzuki and Mochizuki (7K) and Mishchuk and Litvak (5K).
Liquid I o n Exchange Technology
The simplicity of liquid-liquid extraction, particularly as applied to continuous countercurrent systems, has stimulated considerable interest in the use of liquid anion exchangers, the number of potential applications for liquid exchangers has been limited to a few hydrometallurgical, pharmaceutical, and waste treatment applications. Although both liquid anion and cation exchangers are available, only the weak base anion exchangers have been particularly attractive except in a few cases. The extraction coefficients for several liquid amine exchangers for 63 metals in HC1 and LiCl solutions were determined by Seeley and Crouse ( 9 J ) . Extraction of the transition elements by liquid anion exchangers from HC1 solutions was studied in detail by Yanagisawa et al. ( 7 7 J ) , Agers et al. ( I J ) , and Egawa (5J). Other extraction studies employing weak base liquid anion exchangers include those of Kamiya ( 7 J ) for vanadium, Murray et al. ( 8 J ) for uranium in sulfuric acid liquors, Deptula ( 4 J ) for chloroplatinates, Churchward and Bridges ( 3 4 for tungsten recovery, Sinegribova and Yagodin (7UJ) for the separation of zirconium and hafnium, and Bauer (21)for the extraction and sepa-
Apparatus
Of the various developments that have occurred recently in ion exchange engineering, the “coming of age” of continuously operated countercurrent, moving bed systems is the most significant. A number of these are now in operation throughout the world for the treatment of water, sugar, and waste liquors, including mixed bed systems. Recent studies of such systems have been described by Shulman et al. (3.L). Basic hydraulic data for mixed bed systems have been presented by Bogatyrev ( 7 L ) . A report on the use of powdered mixed bed systems combining filtration and deionization has been given by Sailer and Meuli (ZL). A review of countercurrent regeneration has been reported by Thompson and Reents ( 4 L ) . REFERENCES Reviews (1A) Helfferich, F. G., Aduan. Chromatog. 1, 3-60 (1965). (2A) Kunin, R., Encycl. Ind. Chem. Anal. 2, 346-69 (1966). (3A) Marinsky, J. A., “Ion Exchange,” Marcel Dekker, New York, 1966. (4A) Rickles, R. N., “Membranes; Technology and Economics,” Noyes Development Corp., Park Ridge, N. J. (SA) Weiner, R., Galvanotcchnik 57 (a), 518-27 (1 966). Theory (1B) Apostolache, S., Reu. Cham. (Bucharest) 17 ( l l ) , 676-8 (1966). (2B) Artridge, C. J., Nature 211, 1293 (1966). (3B) Barbier, Y., Rosset, R., Tremillon, B., Bull. Soc. C h m . France (10),-.3352-6 (1966). (4B) Beyer, W. A., James, D. B., IND.ENG.CHEM.FUNDAMENTALS 5,433-4 (August 1966). (SB) Zbzd., 6 ( l ) , 160 (1967). (6B) Blickenstaff, R. A., Wagner, J. D., Dranofl, J. S., J . Phyr. Chem. 71, 1665-9, 1670-4 (1967). (7B) Boyd, G. E., Bunzl, K., J . Am. Chem. Soc. 89, 1776-80 (1967). (BB) Ch’iu,L., Ling, T.-J., Wu, F-Y.,P’ei,K.-W., Yuan Tzu Neng (3), 215-32 (1965). (9B) Cooney, D. O., IND.ENG.CHEM.FUNDAMENTALS 6 ( I ) , 159 (1967). (10B) Copeland, J. P., e t o l . , A.I.Ch.E. J . 13, 449-52 (1967). (11B) Dickel, G., Bunzl, K., Z . Phyrik. Chcm. 51, 13-26 (1966). (12B) Flctt, D. S., Meares, P., Trans. Faraday Soc. 62,1469-81 (1966). (13B) Gorshkov, V. I., Korolev, Yu. Z., Shabanov, A. A,, Zh. F i r . K h m . 40 (R), 1878-87 (1966).
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(14B) Hamann, S . D . , McCay, I. W., A . Z . C h . E . J . 12 (3), 495-8 (1966). (15B) Hanley, M. B., Churms, S. C., Leiaegang, E. C., Chem. Cornmiin. 1967, (Z), pp. 78-79. (16B) Heumann, h-.R., Patterson, D . , Cannd. J . Chem. 44, 2139 (1966). (17B) Kryiova, A. A , , Soldatov, V. S., Srarobinets, G. L., Zh. Fir. Khim. 40 (6), 1203-6 (1966). (18B) Lindenbaum, S., Boyd, G. E., J . Phjr. Chtm. 71, 581-9 (February 1967). (19B) Marinsky, J. A,, Ibid., pp. 1572-8. (20B) Mathieson, A. R., Sher, R . T.?J.Pol~me,Sci., Pt. A-1 4 (12), 2945-62 (1966). (21B) Nelson, F., hiichelson, D. C., J. Ch,oniatog. 25 414-41 (1966). (22R) Kovitskaya, L. V., Srarobiners, G. L., Dokl. . A n d . .l'ook Bdoruss. S S R 10 ( l o ) , 755-8 (1966). (23B) Persoz, J., Bull. Soc. Chim. F m m , 1967, pp. 523-30 (February). (24B) Shulman, H. L., et a!., IND. LO. CHEM.PROCESSDESIGNDEVEL. 5 , 257-60 (July 1966). (25B) Starobinets, G. L., Gleim, I. F., Russ. J.P/z))s. Chem. 39 ( O ) , 1166-9 (1966). (26Bj Strelow, F. \V. E., Bothma, C. J. C.. Arid. Chem. 39. 595-9 (1967). (27B) Turner, J. C. R . , Church, M. R., Johnson, .4, S. TV., Snowdon, C. B., Chem. E n g . Sci. 21 (4), 317-25 (1966). (28B) Vaisberg, E. S., Yakhonrova, L. F., Bruns, B. P.. Zip. Fir. Khim. 40, (81, 1884-8 (1966). (29B) Vaslow, F., Boyd, G. E., J . Phjs. Ciirm. 70 ( 7 ) ,2295-9 (1966). (30B) Ibid., (8),pp. 7507-1 1. Water Treatment (1C) Apfel, G., Kingsbury, A. \V., Ind. Ib'nter Eng. 4,30-4 (March 1967). (PC) Fresenius, W., Bibo, F. J., Schneidw, TV., Gns Wnrsetfoch 107 (12), 306-9 (1966). (3C) Krasnov, B. P., Ovchinnikova, I. V.. Koks i Khim. 1966 (a), pp. 47-50. (4C) Kun, K . A,, Kunin, R., Ind. Iliutir Eng. 3, 16 (November 1966). (5C) McGarvey, F. X., EJiuent FVater Trentnienf J . 6, 421 A. (September 1966). (6C) Pollio, F. X., Kunin, R., E n u r o n . Scr. Tech. 1, 160 (1967). (7'2) Ibid., pp. 235-41. (8C) ,Weiss, D . E., Bolto, B. A . , McSeill, R.. Macpherson. A. S., Siudnk, R., Swinton, E. A., Willis, D., Aiisttalinn J.Chem. 19 (4), 561-87 (1966). (9C) Ibid. pp. 589-608. (10'2) Ibid., (51, pp. 765-89. (11C) Ibid., pp. 791-9. Hydrometallurgy ( I D ) Bodiu, D., Sprinceana, U . , Reu. A-iinelor (Bucharest) 16 (12), 526-31 (1965). (2D) Borgolre, T., Wasser Luft Betrieb 10 ( 9 ) , 607-9 (1966). (3D) Davankov, A . B., Laufer, V. M . , Zubakova, L. R . , Aptova, T. A,, Mironov, A . A., Z h . Prikl. Khim. 39 (O), 2067-74 (1966). (4D) Dean, K . C., h-ichols, I. L., Clemmons, B. H., J . M e t a l s 18 (11), 1198-202 (1966). (5D) Dembeck, H., Wnsser, Luft Belrieb 1 0 (Z), 93-7 (1966). (6D) Faure, A.: Finney, S., Hart, H. P., Jordaan, C . L., Lloyd, P. J., Robinson, R. E., van Heerden, D., Viljoen, E. B., J . S. Africnn Inst. M m i n g A4et. 66 (a), 319-41 (1966). (7D) Goldblatt, E. L., Ibid., pp. 342-56 (1966). (8D) Olivero, L., Gaivanoterlinira 17 (41, 75-85 (1966). (9D) Poliskin, J., Ind. Water Eng. 2, 20-2 (September 1165). (IOD) Reynolds, D . H., Long, \V. V., Bhappu, R . B., T m n r . Soc. 'Mining Eng. A I M E 235 (4), 355-60 (1966). (11D) Selezneva, K. A,, Izu. Axad. .Tot& Knr. SSR, Ser. Khan. 16 (4), 31-4 (1966) (12D) Sloan, L., Nitti,N. J.,Ili. State TYaterSzm., Circ. 91, 101-11 (1966). (13D) Stamberg, K., Prochazka, J. J., Ciiem. L i s ! ~GO (6),770-82 (1966). ( 1 4 0 ) Swanton, \V. F., Chem. Engr. 74 (4) 128 (1967). Pharmaceutical Chemistry a n d Biochemistry (1E) Ezhov, V. A.. Uch. Zap., itfordoask. Goi. L h s u . , No. 46, 81-5 (1965). (2E) Gordienko, S . V.,Belikov, V. >I., Z h . Prik!. Khim. 39 (lo), 2382 (1966). (3E) Klyueva, L. M., Gel'perin, K. I., Ainshtein, V. G., Bylinkina, E. S., '\fed. Prom. SSSR 20 (12), 6-10 (1966). (4E) Kotula, Z.: Acta Polon. Piiotm. 23 (I), 29-34 (1966). (5E) Libinson, G. S., Slugina, M. D., Russ. J.Piys. Chem. 39 (11), 1502-5 (1965) (6E) Moretti, G., Staeffen, J., Ballan, P., Catanzano, G., Faivre, J., Reu. F m t i c . Etudes Ciin. Bioi. 11 (9), 938 -43 (1966). (7E) Pirogov, V. S., Dmitrenko, L. V., Samsonov, G. 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