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of ion exchange technology in the milling and refining of beet ... ion exchange tech- nology have ..... (70B) Vasil'ev, V. P., and Parkhomenko, N. V.,...
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ROBERT KUNIN RICHARD L. GUSTAFSON

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I I

ion txcnange Major developments center in areas of pollution, equipment improvement, atomic energy, and agriculture.

rogress made by a particular technology can be assessed in one P ofseveral ways such as tons of chemicals produced, dollar investment, or numbers of installations. I n the Annual Review on Ion Exchange for 1951, the author attempted to assess progress made by the development in terms of the amount of interest generated using, as a n index, the number of ion exchange publications appearing annually. Although there are many faults with this approach, the method is simple and has proved to be of some value. Figure 1 of that article illustrated the results of such an analysis. The numbers are impressive, indicating the wholesome dynamics of ion exchange technology. This progress has been a result of several factors: Availability of a wide array of ion exchange materials of high capacity and excellent durability Ease in which ion exchange materials can be “housed” or engineered Ion exchange systems reach steady state quickly Availability of good theoretical background enabling one to predict performance A review of the literature and events of the past year indicates that the major developments center around the increased demand for high-quality water, the development of countercurrent and continuously operated equipment, the increased demand for highpurity uranium concentrates by the atomic energy industry, the increased concern over pollution abatement, and the increased interest and use of ion exchange technology in the milling and refining of beet, cane, and corn sugar. Reviews

Several comprehensive general reviews on ion exchange technology have been written by Mikes (3OA), Kuehne ( 2 4 A ) , and Chandrasekharan ( Q A ) . Marinsky (28A) has edited a book on the applications of ion exchange. Extensive reviews on the synthesis and properties of ion exchange materials were written by Chmutov ( 7 0 A ) , Martinola and Naumann (ZQA), Wheaton and Hatch (42A), Manecke (27A),and Hering (79A). With respect to the fundamentals of ion exchange, the review by Boyd ( 6 A ) on thermodynamics is outstanding. I n the area of water treatment, the books by Arden ( 3 A ) and Applebaum ( 7 A ) are long-overdue contributions. Other reviews in the field of water treatment include those of Itoh ( 2 7 A ) ,D’Elia (77A), Applebaum ( Z A ) , Bogatyrev ( 4 A ) , Zak ( 4 3 A ) Burley et al. ( 7 A ) , Tamura ( 4 0 A ) , Koehler ( 2 3 A ) , Homer (ZOA), Eliassen ( 7 5 A ) , and Schiffers ( 3 6 A ) . Reviews pertaining to various aspects of chromatography were 38

INDUSTRIAL A N D ENGINEERING CHEMISTRY

prepared by Tremillon ( 4 7 A ) , Boross ( 5 A ) , Egashira et al. ( 7 4 A ) , Rogozhin and Davankov (34A),Senyavin (37A), and Haynes( 78A). I n the area of ion exchange as applied to organic systems, two reviews by Presting and Kreuter (33A) and Moody and Thomas ( 3 7 A ) are of considerable interest. The reviews by Sherry (38A) and Doremus (73A) on ion exchange in silicates are noteworthy. Noteworthy reviews on ion exchange membranes and their properties were written by Carter ( 8 A ) , Savenko et al. (35A)), Gregor (76A),Laeuger ( 2 5 A ) ,Sollner ( 3 Q A ) ,Diamond and Wright (7ZA), McRae et al. ( 2 6 A ) , Haklits (77A), Kepinski and Chlubek ( Z Z A ) , and Nishiwaki (32A). Theory

Most of the publications on the theoretical aspects of ion exchange can best be summarized in tabular form (Table I). A review of this mass of fundamental information still leaves one in a quandary concerning anomalies pertaining to the heterogeneity or homogeneity of ion exchange resins, application of the Donnan distribution of electrolytes, or rates of diffusion in weak electrolyte ion exchange resins. Water and Waste Treatment

As noted in the introduction, the role of ion exchange is steadily increasing in all facets of water and waste treatment. D’Elia (7C, 8C) has critically analyzed the various aspects of the role of ion exchange in the softening of water. The use of carboxylic acid cation exchange resins for the dealkalization of water supplies has been described by Downing et al. (7ZC). Studies on the removal by ion exchange of specific troublesome agents from water supplies include those of Kas’yanenko et al. ( 7 9 C ) on organics, Vlasak et d.(4OC) on nitrates, Deson and Rosset (70C) on boron, and Hau (77C) on arsenic. Several noteworthy studies on the use of ion exchange for the production of “ultra-pure” water include those of Arden (7C, ZC), Michalson (26C), Sono et al. (38C), and Ryan et al. (34C). Perrin (37C) and Budziszewski (6C) have described the use of ion exchange‘resins for producing sterile and pyrogen-free water. Studies on the desalination of saline waters by means of ion exchange resins have been described by Breg-

AUTHORS Robert Kunin and Richard L . Gustafson are with the Rohm and Haas Go. in Philadelphia, Pa. The authors gratefully acknowledge assistance in the preparation of this review from Dr. Erich Meitzner, Miss Dolores Sosnowska, and the librav staff of the Rohm and Haas Co.

man and Shackelford (5C), Vassiliou and Sturla (3QC), Kunin (23C), Osaka (30C), Glueck (76C), Ennis et al. (73C), Murray (27C),and Klein et al. (27C). Studies on the use of ion exchange for the treatment of domestic and industrial wastes were presented by Housiau (18C), Pollio et al. (32C), Fineman (15C), Bosholm and Richter (4C), DeLora Soria and Yu (QC),Kemmer (ZOC), and Nozaki (29C). The use of countercurrent and related techniques in ion exchange systems has been described by Nichols (28C), Downing et al. (77C), Wuenscher et al. (42C), Baeva et al. (3C), Schiffers (35C), Wieland (36C, 47C), Prokhorova (33C), Laskorin et al. (25C), Shasherin and Verteshev (37C),Laentzsch (24C),Klein et al. (22C), Yurkin and Redozubova (43C),and Evans et al. (74C).

TABLE I.

REFERENCES PERTAINING TO ION EXCHANGE THEORY

Equilibria Thermodynamics Cation exchange (sulfonic acid) Alkalies Alkaline earths Organic cations Carboxylic cation exchangers Chelating resins P hosphonic exchangers Zeolite minerals Nonaqueous solvents

Hydrometallurgy

Areas of the field of hydrometallurgy that are of considerable interest are those pertaining to uranium production, noble metal recovery, and the recovery of metal values from the plating industry and coolant tower waters. With respect to the recovery and purification of uranium for atomic energy purposes, the studies of Tataru et al. (20, 30, 18D), Marcu and Sacelean (?TO), and Kunin et al. ( 1 0 0 ) are of considerable interest. Studies pertaining to the recovery of gold and other noble metals have been presented by Demidov ( d o ) , Zdorova (220), Marcus et al. ( 7 2 0 ) , and Strel’nikova et al. ( 1 7 0 ) . I t is now common practice to recover traces of gold from plating rinses using strong base anion exchange resins and ashing the anion exchanger for its gold values. Studies related to the recovery of less valuable metals from plating operations were conducted by Vucurovic (79D), Ionescu et al. ( 8 0 ) , Demidov (5D), Yatsuk et al. (ZOO), and Marquardt (130). Other areas involving the use of ion exchange in hydrometallurgy are summarized in Table 11. Biochemistry and Pharmaceutical Chemistry

Most of the important contributions to the use of ion exchange for the recovery of biologically active and related compounds are reported in Table 111. Food Processing

The Federal Drug Administration has issued regulations concerning the use of several new ion exchange resin formulations (IF). Ion exchange continues to grow in importance in the refining of sugar throughout the world. Fundamental data obtained by Saunders ( 2 4 F ) , Sutherland and Montfort (32F), and Pieck et al. (27F) will be of value to all those considering the use of ion exchange for sugar refining. Studies on the use of ion exchange resins for sugar decolorization were presented by Schneider et al. (25F) and Ionescu et al. (IOF). Studies on the decalcification and deionization of sugar juices and syrups were reported by Gupta et al. (8F), Perschak (ZOF), Sano and Yamaha (23F), Mukherjee et al. (78F), Assalini (3F), Meleshko et al. (77F), and Kauczor (73F). Sugawara et al. (31F), Hitzel ( 9 F ) , Ivanyuk and Kartashov ( 7 IF), and Kauczor (73F) have described results on the use of continuous and countercurrent ion exchange resin systems for sugar refining. Concern over the contamination of milk by radionuclides ,has stimulated the ion exchange studies of Walker and Edmondson (33F), Glascock et al. (6F, 7F), Marshall et al. (16F), Murphy et al. (7QF,30F), Dickerson et al. ( 5 F ) ,and Koga et al. (75F, 22F). Studies on the use of ion exchange for the treatment of wines were reported by Berg et al. (4F), Arjun (ZF),and Kagami (72F). Related to the food industries are the studies of Skogley (26F), Kim et al. (74F), Soukup (ZQF),and Soldatov et al. (27F, 28F) on the use of ion exchange resins as artificial soil media for the growth of plants. Catalysis

Ion exchange and catalysis have been as closely associated over the years as have ion exchange and adsorption. As in previous years, much of the published literature in this area has centered about cation exchangers. Of considerable interest is the fact that most of these publications originated in the U.S.S.R. Fatkulina (2G) has correlated the catalytic activity of sulfonic acid cation exchangers with the hydrogen ion activity of the ion exchanger. Other similar studies include those of Tursin and Chebotareva (73G) and Sevcik ( 7 7G) on esterification, Ap’ok et al. (7G) and Kallo and Preszler (8G) on olefins, reactions, Starkov et al. (72G), Gauvreau and Lattes (3G), and Kolesnikov et al. (QG)on alkyla-

Anion exchange Metal complexes Organic acids Borates

38, QB, IOB, 25B, 446, 468, 708

lB, 13B, 408, 58B, 63B, 73B 35B, 74B 16B 4B, 31B, 4 7 8 , 5 7 8 , 6ZB 22B, 54B, 60B 278 6B-8B, 368, 428, 50B,55B 26B, 28B, 33B, 368, 37B,45B, 49B, 57B, 64B

15B, 358, 39B, 43B, 64B, 65B, 7 7 8 24B, 298, 308, 7ZB 17B,52B

Kinetics

IIB, 12B, 78-27B, 23B, 3ZB, 41B, 488, 68B-70B, 75B

Column dynamics

ZB,5B, 14B,538,56B, 66B, 6 7 8

TABLE I I. H Y DROM ETALLU RGl CAL APPLICATIONS Chromium Selenium A1u m in u m Cesium Lithium Plutonium Germanium

9D, 7 6 0 270 6D

750 70 10

14D

TABLE 111. BIOCHEMICAL A N D , PHARMACEUTICAL CHEMISTRY Applications

Rejerences

Antibiotics Vitamins Amino acids Enzymes Proteins Alkaloids Organic bases Organic acids

2-4E, 15E 13E 17E

8E 5E, 7E QE l E , 6E, IOE, lZE, 16E 1 IE, 14E

TABLE IV. NEW ION EXCHANGE MATERIALS, SYNTHESIS PROCEDURES, AND EVALUATIONS Subjects

References

Copolymerization Sulfonation Chloromethylation Macroreticular polymers Ultrafine particles Phosphonic acid cation exchangers Chelating polymers Anion exchange resins Optically active polymers Redox polymers Inorganic exchangers Stability of ion exchange resins Test methods

TABLE V.

28H, 42H, 64-66H 12H, 77H, 43H, 60H, 67H, 68H 14H 7H, 9H, ?OH, 75H, 23H, 26H, 35H 47H 32H, 47H, 54H 5H, 6H, 46H, 52H 22H, 24H, 34H, 40H, 44H, 69H 78H, 55H 27H, 30H, 37H, 36H, 37H, 59H, 61H, 62H 1-4H, 8H, 17H, 7QH, 38H 73H, 16H, 33H, 39H, 45H, 4851H, 53H, 57H, 58H, 70H, 77H 20H,27H, 25H, 29H, 56H, 63H

ION EXCHANGE MEMBRANES

Subjects

References

Preparation Basic properties Desalination

VOL. 6 1

3K, 12K, 23K 2 K , 5K, 6K, QK, 13K, 14K, 16K, 77K, 22K, 25-27K 7K, 4K, 7K, 8K, IOK, 77K, 15K, 78-21K, 24K, 28K

NO.

12

DECEMBER 1969

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tion, Matyschok and Ropuszynski ( 7 0 G ) and Isagulyants et al. (6G, 7G) on condensation, Gauvreau et al. (4G) on hydrogenation, a n d Herlihy (5G) on dehydration. Studies on catalysis with anion exchange resins were described by Vollmert and Saatweher (74G). N e w Ion Exchange Materials

The virile nature of ion exchange technology has been a result of the commercial availability of high-capacity, selective, and durable ion exchange materials. The wide array of studies on the development of new ion exchange materials and methods for their preparation summarized in Table IV is further evidence of the continued growth of ion exchange technology. liquid Ion Exchangers

Many of the liquid cation exchange studies have been devoted to the use of organophosphorus extractants for the purification of rare earths and related materials. Included in these studies are those of Sistkova et al. ( Z J ) ,Navratil (7QJ-Z7J), Hala ( I O J ) , Goto ( S J ) , Owens and Smutz ( Z Z J ) , and Sebenik (23J). Other studies include those of Ioffe ( 7 3 J ) and Kojima b t QL. ( 7 6 3 ) on copper, Golinski (8J)on indium, Logomerac and NovoseI (17J) on aluminum, Hila1 and Kiwan ( 7 7 J ) , Jickling et al. ( 7 5 J ) , Funaki et al. ( 5 4 , Cross ( 7 J )on uranium, Marchenko and Voronina (785) on antimony, Gerisch and Ziegenbalg ( 6 J ) on vanadium, molybdenum, tungsten, and rhenium, Hofer ( 7 2 J )on tin, Ishimori et al. (74J)on rhodium, Fedorov et al. ( 3 J )and Deptula ( 2 J ) on chromium, Fritz and Gillette ( 4 J ) on sulfonic acids, and Gil’bert et al. ( 7 J )on a series of metal chloride complexes. Ion Exchange Membrane Processes

The electrodialysis of saline waters and fuel cells still represent the major applications for ion exchange membranes. Table V summarizes the major developments that occurred during the pas1 year in the field of ion exchange membranes.

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