Ion Exchange By Robert Kunnin-2

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Ion Exchange Robert Kunin Ind. Eng. Chem., 1949, 41 (1), 55-59 • DOI: 10.1021/ie50469a016 Downloaded from http://pubs.acs.org on January 23, 2009

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Industrial & Engineering Chemistry is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036

INDUSTRIAL AND ENGINEERING CHEMISTRY

January 1949

water vapor and the consequent effect on conductivity were not discussed. The utility of an apparatus using hydraulic analog was described by Leopold (30) for problems relating t o spacc cooling. A review of dimensionless groups and the relations between them for momentum, heat, and mass transfer was presented by Xlinkenberg and Mooy (2%) and the analogies between these three unit operations were pointed out. LITERATURE CITED

(1) Beatty, K. O., and Katz, D. L., Chzrn. Eng. Progrese, 44, 55 (1948). (2) Bonilla, C. F., IND. ENG.CHEM.,40, 1098 (1948). (3) Bonilla, C. F., and Eisenberg, A. A., Ibid., p. 1113. (4) Bradley, C. B., and Stone, J. F., Chem. Eng. Progress, 44, 723 (1948). (5) Brinn, M. S., Friedman, S. J., Gluckert, F. A,, and Pigford, R. L., IND. ENG.CHEM.,40, 1050 (1948). ( 6 ) Butterworth, A. V., Chem. Eng. Progress, 43, 597 (1947). (7) Carslaw, H. S., and Jaeger, J. C., “Conduction of Heat in Solids,” London and New York, Oxford Univ. Press, 1947. (8) Cholette, A., Chcm. Eng, Progress, 44, 81 (1948). (9) Cichelli, M. T., IND.ENG.CHEM.,40, 1032 (1948). (10) Comings, E. W., Clapp, J. T., and Taylor, J. F., Ibid., p. 1076. (11) Davis, D. S., Chem. Inds., 63, No. 8, 286 (1948). ENG.CHEM.,40, 1070 (12) Deitz, V. R., and Robinson, H. E., IND. (1948). (13) Dunn, W. E., Jr., and Bonilla, C. F., Ibid., p. 1101. (14) Eckert, E. R. G., Dept. of Commerce, OTS, PB 19899. (15) Edson, K. C., and Powell, J. S., Oil Gas J., 47, No. 5, 71 (1948). (16) Edwards, D. A., Bonilla, C. F., and Cichelli, M. T., IND.ENG. CHEM.,40, 1105 (1948). (17) Farber, E. A., and Scorah, R. L., Trans. Am. SOC.Mech. Engrs., 70,369 (1948). (18) Gunderson, L. O., and Denman, W. L., IND. ENG.CHEM.,40, 1363 (1948). (19) Hall, T. A., and Tsao, P. H., PTOC. Roy. Soc. (London) A191, 6 ( 1947). (20) Hawkins, G. A., and Warner, C. F., IND. ENG.CHEM.,40, 517 (1948). (21) Huebler, Jack, Ibid., p. 1094. (22) Ingersoll, L. R., and Pless, H.J., Heating, Piping, A i r Conditioning, 20, No. 7, 119 (1948). (23) Ingersoll, L. R., Zobel, 0. J., and Ingersoll, A. C., “Heat Con-

duction with Engineering and Geological Applications,” New York, McGraw-Hill Book Co., 1948. (24) Jaooby, A. L., and Bischmann, L. C., IND. ENQ.CHEM.,40, 1360 (1948). (25) Jakob, M., Trans. Am. SOC.Mech. Engrs., 70, 25 (1948). (26) Johnson, H. A., Heating, Piping, A i r Conditioning, 20, No. 5 , 121 (1948).

55

(27) Kayan, C. F., IND. ENQ.CHEM.,40, 1044 (1948). (28) Klinkenberg, A., and H. H. Mooy, Chem. Eng. Progrers, 44, 17 (1948). (29) Leigh, R. S., and Vanderweil, R. G., Heating, Piping, A i r Conditioning, 20, No. 2, 107 (1948). (30) Leopold, C. S., Ibid., No. 7, 105 (1948). (31) Leva, M., and Grummer, M., IND.ENG.CHEM.,40, 415 (1948). (32) Leva, M., Weintraub, M., Grummer, M., and Clark, E. L., Ibid., p. 747. (33) Lof, G. 0. G., and Hawley, R. W., Ibid., p. 1061. (34) Lund, G., and Dodge, B. F., Ibid., 40, 1019 (1948). (35) McAdams, W. H., Addoms, J. N., Rinaldo, P. M., and Day, R. S., Chem. Eng. Progress, 44, 639 (1948). * (36) Mclntire, 0. R., and Kennedy, R. N., Ibid., 44, 727 (1948). (37) Martinelli, R. C., Trans. Am. Soe., Mech. Engrs., 69, 947 (1947). (38) Martinelli, R. C., and Nelson, D. B., Ibid., 70, 695 (1948). (39) Palmer, B. M., and Taylor, R. B., Chem. Eng. Progress, 44, 652 (1948). (40) Palmer, G., IND.ENG.CHEM.,40, 89 (1948). (41) Parmelee, G. V., and Aubele, W. W., Heating, Piping, A i r Conditioning, 20, No. 6, 116 (1948). (42) Parmelee, G. V., Aubele, W. W., and Huebscher, R. G., Ibid., 20, No. 1, 158 (1948). (43) Paschkis, V., “Industrial Electric Furnaces and Appliances,” Vol. 2, New York, Interscience Pub. Co., 1948. (44) Pratt, N. H., Trans. Inst. Chem. Engrs. (London), advance copy, Dee. 9, 1947. (45) Rosenthal, D., and Cameron, R. H., Trans. Am. SOC.Mech. Engrs., 69, 961 (1947). (46) Rumford, F., J . Soc. Chem. I n d . (London),66, 309 (1947). (47) Rushton, J. H., Lichtmann, R. S., and Mahony, L. H., IND. ENG.CHEM.,40, 1082 (1948). (48) Sanders, V., Chem. Eng. Progress, 44, 804 (1948). (49) Sinnott, M. J., and Siebert, C. A., IND.ENG.CHEM.,40, 1039 (1948). (50) Stewart, J. P., Heating, Piping, A i r Conditioning, 20, No. 8, 121 (1948). (51) Touloukian, Y. S., Hawkins, G. A., and Jakob, M., Trans, Am. SOC.Mech. Engrs., 70, 13 (1948). (52) Van Buskirk, E. C., and Surland, C. C., Chem. Eng. Prograss, 44, 803 (1948). (53) Watzinger, A., and Lorentzen, G., Ing. Vetenskaps Akad., Handl. No. 166, 3-22 (1942). (54) White, J. F., Chem. Eng. Progrem, 44, 647 (1948). (55) White, R. E., Refrig. Engr., 55, 375 (1948). (56) Wilhelm, R. H., Johnson, W. C., Wynkoop, R.. and Collier, D. W., Chem. Eng. Progress, 44, 105 (1948). (57) Winding, C. C., and Cheney, A. J., Jr., IND,EXG.CHEM.,40, 1087 (1948). (58) Witzig, W. F.’, Penney, G. W., and Cyphers, J. A., Refrig. Eng., 56, 153 (1948). RECEIVED October IS, 1948.

ION EXCHANGE @$

ROBERT Kl”,

RESINOUS PRODUCTS DIVISION,

R O H M AND H A A S C O M P A N Y , PHILADELPHIA, P A .

T

HE advances made in the field of ion exchange during the past year have been considerable and have widened the scope of this unit operation. However, the increased importance of this operation is due not, solely to recent technological advances but t o the increased effort of many states and the Federal Government t o reduce stream and river pollution by legal means and t o a large extent to the dwindling supply of important resources at a critical period of increased production. The technological advances in ion exchange during 1948 centered chiefly about three major points: (1) advances in the synthesis of new exchangers, (2) newer approaches in the engineering principles involved, and (3) large scale studies of processes involving ion exchange equilibria. However, although these advances may be the major ones, significant advances have also heen realized along theoretical lines and new applications.

Several leading chemical journals (21-23, 45) have reviewed the uses of ion exchange substances and have presented reviews including both theory and application. Hopkins (6‘4) reviewed the use of ion exchange resins for water softening and Baroni ( 5 ) , Davies (Sd), and Winters (128) reviewed the more general uses for these ion exchange resins, including possible large scale uses. A recent review covered the history, terminology, properties, and applications of several ion exchange resins (104). THEORY

OF ION E X C H A N G E

During 1948, several contributions were made to the theory of ion exchange occurring in both organic and inorganic exchange substances. Glueckauf (48)presented a mathematical treatment relating the concentration history (C/Co) with the Freundlich and

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I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY

Vol. 41, No. 1

for determining the exchange capacity of soils. Although these methods have been used for siliceous materials, the findings of these investigators are of interest in the investigations of other exchangers. The effects of the exchangeable ions on thp ceramic properties of clays have been btudied by Francis (45). The exchange equilibria involving the acidic groups of fatty acid crystals and humic acid has been described by Trapesnikov and Lipets (123) and Barbier and Trocm6 (4). The anion exchanger properties of dumina have been studied by Graham ~ n FIorning d (59). WATER SOFTENING

Typical Ion Exhange Water Softening Units

Langmuir isotherms for the column adsorptions of cupric ions and the separation of copper and manganese on a sulfonic acid exchanger. Gregor (83,54) derived thermodynamically the swelling and contraction of cation exchangers upon exchanging one cation for another. The adsorpt'ion of methylene blue by clay surfaces was described by Plesch and Robertson (100) as being composcd of two processes, the first an irreversible exchange adsorption and the second a reversible Freundlich adsorption. Along similar lines, Mongar and Wasserman (87) and Ingersoll and Johnson (66)attributed t o some extent the contraction and elongation of alginate fibers to the exchange of ions at the various ionic groups. The equilibria and column behavior of the weakly acidic carboxylic exchanger and a strong base anion exchanger were reported by Kunin and Barry (67) and Kunin and McGarvey (68). Tendeloo ( f 9 0 ) and Marshall and his students (79-82) have continued their electrochemical studies of ion exchange systems. The membrane electrodes of Marshall should be of interest in a study of systems other than those involving clay. The ion exchange behavior of cotton and oxycellulose has been studied extensively by Davidson (BT-WS), Davidson and Neve11 (50, 31), and Church (24). The exchange properties of the succinate, glutaric, and phthalic acid esters of cotton have been studied by McIntire and Scherick (76). Extending his ion exchange studies to the soil-plant system, Mattson (83) found the Donnan equilibrium to apply to the exchange of ions between the ionic components of both the soil and the plant. The ion exchange studies on clays and soils st,ill occupy a major portion of the total contributions. Mitra (86) concludes that if the exchange capacity of kaolinite is due to brolten ionic bonds a t the crystal surface, an increase in the cation exchange capacity on grinding should be accompanied by an increase in anion exchange capacity. The exchange properties of various clays and clay minerals have been examined by Rost (106), Vend1 (124), Teichner (fl9), Dittler (S6), and Sieling (111). Gorbunov and Tsyurupa (50)have investigated the influence of pressure (1 to 200 kg. per sq. em.) on the ion exchange equilibria in clays and soils. Mukherjee and Nandi (92) have compared the various methods

Hlight ( I d ) , Harding arid Trclbler p%), bIiedendorp (&), Spaulding i f I B ) , Morris and Carritt (88),~ i n d lIamer (57) have compared the v u i ous methods for softening water fox industrial purposes, citing the circunitances where the ion exchang~ method may be employed advantagrously. T h t use aid operation of home u ater softening units have been reviewed by Olson (Ob),Maffitt (77), cDuff (75). A study of the use of organic exchangers for \of iening R aters that have hcen chlorinated has rrsulted in tlic conclusion that nuclear sulfonlc acld cation escliaugers are much mort stable than the phenol sulfonic acid exchangers ( 2 6 ) Cruiclrshank and Braithxaite (B6) have studied the use of variouk sterilizing agents for use with phenol-formaldehyde exchangcw The softening propel ties of several synthetic gel zeolites have been compared by Kagai and Xurakami (94)and a m&od fox ascertaining their efficiency has been described by lckerman ( I ) The various aspects of the microbial fouling of zeolite watei softeners have been revieii pd by Williams (127). Breitcnsteiri and Rergei ( 1 7 ) suggest the USB of certain cation exchangers foi deoiling boiler feed water. Webb and Yoder (185) recommend the use of a hydrogen zeolite effluent for dissolving boiler scale. DEIONIZATION

Thc tieiouization operation has been extended to systems that arc sensitive t o pH changes by virtue of the availability of a strong base anion exchange resin (83). The strong base anion exchange regin permits one to operate in a manlier that excludes the intermediate acid formation encountered in the conventional methods. This is achieved either by passing the erectrolyte through the strong base anion exchanger and then through the sulfonic or carboxylic acid cation exchanger or by means of a mixed bed operation in which the mixture of the strong base anion exchanger and strong acid cation exchanger is employed in a batchnise operation. HydrauIic separation of the two exchanger phases for regeneration purposes has been demonstrated (39).

Riley and Day (105) have reviewed the engineering aspects of deionization of solutions by ion exchange resins. The importance of using water of a deionized quality in porcelain enamel has been emphasized by Pavlisch (98). The use of fluorides for the conversion of silicic acid to the strong acid, fluosilicic acid, for silica removal purposes has been reviewed and studied by Bauman, Eichorn, and Wirth (8),MeBrian (74), and C a k e and Lane (19). Calise and Lane prefer the use of a

January 1949

INDUSTRIAL AND ENGINEERING CHEMISTRY

basic anion exchanger rather than the fluoride method. Gilwood (47) has reviewed the five methods for removing silica, two of which involve the principles of ion exchange. Thompson and McGarvey (121) have studied the variables for both the anion and cation exchange resins t h a t affect the quality of the deionized water produced by the passage of the raw water through a series of both beds. Such factors as flow rates, regeneration level, regenerants, and water composition were included. Cristy and Lembcke (25) have made a thorough study on both a laboratory and plant scale of a unit for the deionization of formalin. Even though some degradation was apparent in the anion resin, the loss did not indicate the operation to be economically unsound. However, Lampitt, Money, and Judge (69) found the deionization of pectin by ion exchange t o be unsatisfactory. The removal of Raney nickel in sorbitol has been achieved with ion exchangers by Porter (102). Treatment of organic nitriles with ion exchange resins is suggested in a patent of Blann (13). Heavy metal salts of silicate exchangers have been used by Nachod (93) for the desulfuration of hydrocarbons. Ham and Barnes (56) apply a unique method for removing bacteria from water, consisting of impressing a high voltage (100 to 2000 volts) across an anion exchange resin bed. The use of the deionization operation for the treatment of sugar juices, sirups, and wastes has been tried on both pilot plant and plant units with varying degrees of success and conclusions. Mindler (86) and Bloch and Ritchie (15) have reported on pilot plant and plant scale runs on the deionization of cane sirups, molasses, and juices. Although considerable success was achieved during the study, such factors as water requirements, sucrose inversion, and resin deterioration diminished the attractiveness of the process. Porter (101), Ellison and Porter (41), and Dickinson (33, 34) have described plant runs on the deionization of beet juices at several western beet sugar refineries. Although considerable enthusiasm has been expressed, the economics has not proved as attractive as was originally expected; i t is still of considerable interest. In a recent review of new developments in sugar techniques, Wilcox (126) concludes t h a t although ion exchange is of interest in the beet sugar industry, it is impractical in the field of cane sugar because of marketing conditions. Morrison (89) and Mandry (78) have reported successful ion exchange operations for beet sugar, the latter claiming ion exchange will replace the Steffens house. Other contributions t o the application of ion exchange to sugar solutions have been made by Handelman and Rogge (68),Gustafson (66),Smirnov and Goncharenko (lid), and MacAdam (78). Of considerable interest is the report of Felton (44) on the plant ion exchange operation in Hawaii for treating wastes containing sugar and recovering these sugars as a n edible packing sirup. Challinor, Kieser, and Pollard (20)have found that the removal of nutrients (calcium, magnesium, zinc, phosphorus, and nitrogen) from apple juice by ion exchange markedly improves the stability of the juice towards microbiological spoilage. The application of ion exchange t o the sugar industries still is open t o considerable question, although technically the operation has achieved the goal. The failings of the ion exchange operation for sugar applications have been purely economic: increasing costs of regenerant solutions and a variable price for molasses. Should the cost of regenerants and the price of molasses drop t o prcwar levels, the ion exchange method for treating sugar solutions would be much more attractive.

57

exchanger in particular, for the recovery and purification of complex bases of pharmaceutical importance. The separation of amino acids and the adsorption and recovery of alkaloids and vitamins were investigated. The chief advantage of a carboxylic exchanger is that it readily adsorbs the complex organic nitrogen bases on the salt form of the exchanger and readily permits the elution of these bases with a stoichiometric quantity of dilute acid. I n comparison with the extreme difficulty with which nitrogen bases are removed from sulfonic exchangers, carboxylic exchangers represent an advance in the recovery of these bases. Hems, Page, and Waller (62) have studied the use of sulfonic and carboxylic cation exchange resins for separating basic amino acids. Elmore (42) and Harris and Thomas (60) have separated cytidine from uridine with the aid of a sulfonic acid exchanger. Using the same exchange resin, Bendall, Partridge, and Westall (10) have used the Tiselius displacement technique for separating amino acids. Use has been made of siliceous exchangers for the concentration and purification of the paralytic poison present in certain shellfish (115). Alderton and Fevold (2) have suggested the use of clays for the isolation of the enzyme lysoaime, present in eggwhite. Kingsbury, Mindler, and Gilwood (66) have recovered nicotine in cigaret tobrtcco dryer gases, using a sulfonic acid cation exchanger. Gore (61)and Mottern and Buck (90) adsorb and recover organic acids in fruit juices using a n anion exchange

resin. A problem that is becoming of increasing importance is the recovery of metal wastes that are polluting streams. Distelhorst (36) and Wise (130) are investigating the use of ion exchange for the recovery of wastes containing zinc, chromium, and copper. The use of ion exchange has been suggested as a means for overcoming the problem of disposing large volumes of radioactive wastes (88). Hiester, McCarthy, and Benson (65) propose the use of cation exchange resins in the separation of lignosulfonic acids from sulfite waste liquors. The separation of radium from barium using a cation exchanger in a cascade arrangement has been investigated by Reid (103). Spedding and his group (117) have proposed a change in their ion exchange method for the separation of rare earths. L A B O R A T O R Y APPLICATIONS

The usefulness of ion exchange substances in the laboratory has progressed t o a stage where exchange substances are becoming common laboratory reagents for analytical and preparative purposes. Applezwieg ($) has presented a comprehensive review of the use of ion exchange adsorbents as laboratory tools. Lur’e (71)and Lur’e and Filippova (72)have reviewed the use of organic exchangers in analytical chemistry. Ernsberger and France (43) have utilized sulfonic acid cation exchangers for converting lignosulfonates t o the free acid. Schubert (107) and Schubert and Richter (108)describe a method for determining equilibrium constants of complexes, utilizing a sulfonic acid exchanger. Papageorge and Lamar (97) utilize a n exchanger in the analysis of thiamine. Duglish (39) suggests the adsorption of aneurine on a siliceous exchanger prior t o its estimation. Serfass, Theis, Thorstensen, and Aganval (110) have continued the study of the composition of chromium complexes utilizing ion exchange resins. Drake (38) has devised a microapparatus for automatically recording the chromatographic separation of amino acids on an anion exchange resin. Eidinoff (40) has suggested a method for studying the ion exchange separations of isotopes. CATALYSIS

SEPARATIONS AND CONCENTRATIONS

The usefulness of ion exchange principles for the separation of various ionic species and the recovery of these constituents in a purer and more concentrated form have been further emphasized by several studies during the past year. Winters and Kunin (129) have explored the use of ion exchangers, the carboxylic type of ion

The utilization of the ion exchange complex as a catalyst offers many interesting possibilities. Levesque and Craig (70) have studied the esterification of oleic acid and butanol using a sulfonic acid exchanger. Haskell (61) has studied the fundamental aspects of this catalytic action and has found the mechanism t o be analogous t o the homogeneous reaction. The relationship be-

58

INDUSTRIAL AND ENGINEERING CHEMISTRY

tween the cracking activity of a silicate catalyst and its base exchange properties has been extensively studied by Bitepazh (1%). BIOLOGICAL APPLICATIONS

Bersin (11) has critically reviewed the significance of ion exchange for various biological and biochemical processes. The use of ion exchange resins for the removal of sodium from the intestinal tract in the treatment of heart ailments is under investigation ($7, 109). The use of anion exchange units as an artificial kidney for a dog has also received considerable attention (91). NEW EXCHANGERS

The availability of carboxylic cation exchange resins fi hose cation exchange activity is associated with carboxylic groups and high capacity nuclear sulfonic acid cation exchangers has been announced (7, 8, 9, 18, I i , $3). A bead type of phenol sulfonic acid cation exchanger and a strong base anion exchanger havealso been announced ($8). Several patents (49,96, 99,214, 118, ‘199)have been issued revealing new ion exchange resin compositions. Synthetic crystals having the gas adsorptive and ion exchange properties of the natural zeolite, chabazite, have been prepared by Barrer (6, 6) by autoclaving natural and synthetic hydrous silicates with barium and potassium chlorides. Smith and Page (113) describe the use of insoluble, liquid amines as liquid anion exchangers. Tertiary amines such as methyldioctylamine, methyldinonylamine, and trioctylamine were found to be efficient. Although significant advances have been achieved in the realm of this new unit operation, from a chemical engineering viewpoint, much remains to be done. The treatment of equilibria and rate data for design purposes (in particular, column operation) is incomplete and demands further study. Economic studies of various ion exchange applications are practically nonexistent outside of the applications of water softening and deionization and in these cases the information is incomplete. As the usefulness of the ion exchange unit operation increases, the above studies become of increased importance. LITERATURE CITED

(1) Ackerman, A., Bull. soc. c h i n . France, 1947, 619. (2) Alderton, G., and Fevold, H. L., U. 6 . Patent 2,443,452 (June 1, 1948). (3) Applezwieg, N., Ann. N . Y . Acad. Sci., 49, 295 (1948). (4) Barbier, G., and Trocm6, S., Compt. rend., 224, 1582 (1947). (6) Baroni, A., Materie plastiche, 14, 16 (1948). (6) Barrer, R. M., J . Chem. SOC.,1948, 127. (7) Barrer, R. M., and Riley, D. W., Ibid., 1948, 133. (8) Bauman, W. C., Eichorn, J.. and Wirth, L. F., IND. ENG. CHEM.,39, 1453 (1947). (9) Bauman, W. L., Skidmore, J. R., and Camum, R. H., Ibid.. 40, 1350 (1948). (10)Bendall, J. R., Partridge. S. M., and Westall, R. G., Nature, 160. 374 (1947). (11) Bersin, T., Naturwissennschaftc, 33, 108 (1946). (12) Bitepazh, Yu. A., J . Gen. Chem. (U.S.S.R.), 17, 199 (1947). (13) Blann, W. A., U. S. Patent 2,444,589 (July 6 , 1948). (14) Blight, F. C., Mech. World, 122, 179 (1947). (15) Bloch, E., and Ritchie, R. J., IND. ENQ.CHZM., 39, 1581 (1948). (16) Braithwaite, D. C., D’Amico, J. S., and Thompson, M. T., Division of Water, Sewage, and Sanitation Chemistry, 114th Meeting, AM. CHEM.Soo.. September 1948. (17) Breitenstein, G. von, and Berger, H., Bull. Brit. Coal Utilization Research Assoc., 9, 349 (1943). (18) Brown, W. E., Chem. Eng. News, 26, 1480 (1948). (19) Cslise, V. J., and Lane, M., Chem. Eng. Progress, 44, 269 (1948). (20) Challinor, S. W., Kieser, M. E., and Pollard, A,, Nature, 161, 1023 (1948). (21) Chem. Eng., 55,119 (1948). (22) Chem. Brig., 55, 164 (1948) (23) Chent. Eng. Progress, 44, 18 (1948). (24) Church, H. F., J . SOC.Chem. Ind.. 66, 223 (1V47). (26) Cristy, G. A,, and Lembcke, R. E., Chem. Eng. Progress, 44, 417 (1948). I

Vol. 41, No. 1

(26) Cruickshank, G. A., and Braithwaite, D. G., Division of Water, Sewage, and Sanitation Chemistry, 114th Meeting, AM. CHEM.SOC., September 1948. (27) Davidson, C. F., J . Teztile Inst., 39, T59 (1948). (28) Ibid., 39, T66 (1948). (29) Ibid.. 39. T87 (1948). (30j Davidson, C. F., an‘d NeveIl, T. P., I b g . , 39, T93 (1948). (31) Ibid., 39, T102 (1948). (32) Davies, c. W., Chemistry & Industry, 51 (1948). (33) Dickinson, B. N., Chem. Eng., 55, 114 (1948). (34) Dickinson, B. N., Eighth Annual Conf. Food Technol., June 1948. (35) Distelhorst, 5. D., Southern Power and Ind., 66, 58 (1948). (36) Dittler. K.. Ceram. Abstracts. 24. 80 (1946). (37) Deck, W., Trans. Assoc. Am. P h y s i c & ? ,59, 282 (1946). (38) Drake, B., Nature, 160 (1947). (39) DugIish, C., Q w T ~ .J . Pharm. Pharmacal., 20, 257 (1947). (40) Eidinoff, M. L., J . Chem. Phys., 15, 527 (1947). (41) Ellison, H. E., and Porter, L. D., Sugar, 43, 30 (March 1948). (42) Elmore, D. T., Nature, 161, 931 (1948). (43) Ernsberger, F. M., and France, W. G., J . Phys. Colloid Chem., 52,267 (1948). (44) Felton, G., Eighbh Annual Conf. Food Technol., June 1948. (45) Forecast, 10,243 (1948). (46) Francis, M., Chimie & Industrie, 58, 163 (1947). (47) Gilwood, M. E., Power, 91, 86 (1947). (48) Glueckhauf, E., J . Chem. SOC.,1947, 1302. (49) Goetz, A., U. S. Patent 2,445,669 (July 20, 1948). (60) Gorbunov, N. I., and Tsyurupa, Pedoiogy (U.S.S.R.), 1947, No. 3,167. (51) Gore, H. C., Fruit Products J . , 27, 75 (1947). (52) Graham, R. P., and Homing, A. E., J . Am. Chem. Soc., 69,1214 (1947). (53) Gregor, H. P., Ibid., 70, 1293 (1948). (64) Gregor, H. P., and Bregman, J. I., Ibid., 70, 2370 (1948). (55) Gustafson, H. B., and Faley, L. 9., U. S. Patent 2,402,960 (July 2, 1948). (56) Ham, G. P., and Barnes, It. B., Ibid., 2,428,329 (8ept. 30, 1947). (57) Hamer, P., Ind. Chemist, 24, 362 (June 1948). (58) Handelman, M., and Rogge, R. H., Chem. Eng. Progress, 44,683 ( 1948). (59) Harding, H. G., and Trebler, H. h., Food Technol., 1, 478 (1947). (60) Harris, R. J. C., and Thomas, J. F., Nature, 161, 931 (1948) (61) Haskell, V. C., Ph. D. dissertation, Columbia University, 1948. (62) Hems, B. A., Page, J. E., and Waller, J. C., J . SOC.Chem. Ind., 67, 77 (1948). (63) Hiester, N. K., McCarthy, J. L., and Benson, H. K., Paper Trade J . , 126, 58 (1948). (64) Hopkins, S. J., Affg. Chemist, 17, 285 (1946). (65) Ingersoll, H. G., and Johnson, A. A., Nature, 162, 225 (1948). (66) Kingsbury, A. D., Mindler, A. B., and Gilwood, M. B,., Chem. Eng. Progress, 44, 497 (1948). (67) Kunin, R., and Barry, R. E., Division of Industrial & Engineering Chemistry, 114th Meeting, AM. CHEWSOC.,September 1948. (68) Kunin, R., and McGarvey, F. X., Ibid., Sopteinber 1948. (69) Lanipitt, L. H., Money, R. M., Judge, B. E., and Uric, A , J. SOC.Chem. Ind., 66, 121 (1947). (70) Levesque, C. L., arid Craig, A. M.,IND.END.CIIEM.,40, 96 (1948). (71) Lur’e, Yu. Yu., Zuuodslcuva Lah., 13, 332 (1947). (72) Lur’o, Yu. Yu., itnd Filippovn, N . A., Ibid., 13, 589 (1947). (73) Machdam, W. T., Food Packer, 28, 34 (1947). (74) McBrian, R., Am. Ry. Eng. Assoc. Bull., 469, 74 (1047). (75) RifacDuff, H. W., J . A m . Water Works Assoc., 40, 309 (1948). (76) McIntire, F. C . , and Schenok, J. R., J . A n . Chem. Soc., 70, 1193 (1948). (77) Maffitt, D. L., J . Am. Water W o r k s Assoc., 40, 293 (1948). (78) Mandry, E., Sugar, 43, 5 (August 1948). (79) Marshall, C. E., Soil Sci., 65, 57 (1948). (80) Marshall, C. E., and Ayres, A. P., J . Am. Chem. Soc., 70, 1297 (1948). (81) Marshall, C. E., and Ayres, A. P., Soil Sci. SOC.Am. Proc., 11, 171 (1946). (82) Marshall, C. E., and Eime, L. O., ,J, Am. Chem. Soc., 70, 1302 (1948). (83) Mattson, S., Kgl. Laiatbrwks-HBuskoZ, Ann., 15, 308 (1948). (84) Miedondorp, XI., Rayon, 29, 85 (1948). (85) Mindlcr. A . I.%.,INU. ENG. CHEM.,40, 1211 (1948). (86) Mitra, R. P., J. Indian Chcm. Soc., 23, 386 (1947). (87) Mongar, J. L., and Wassertnan, h., Nature, 159, 740 (1947). (88) Morris, J. C., and Carritt, J. B., J . New Engl. Water TOorks A880C., 62, la(l948)

January 1949

INDUSTRIAL AND ENGINEERING CHEMISTaY

(89) Morrkon, W.S., Sugar, 43,48 (August 1948). (90) Mottern, H. H,, and Buck, R. E., U. 5. Patent 2,445,583 (1948). (91) Mu-irhead. E.E., and Reid, A. F., J . Lab. Clin. Med., 33, 841 (July 1948). (92) Mukherjee, 9. K.,and Nandi, S. K., Indian J . AUT.Sci., 14,74 (1944). (93) Nachod, F. C., U. 9. Patent 2,422,982(June 8, 1948). (94) Nagai, S., and Murakami, K., J . SOC.Chem. Ind. Japan, 44,709 (1941). (95) Olson, H, M.,J. A m . Water Works Assoc., 40,301 (1948). (96) Oxford, W. E”., Jr., U. S. Patent 2,437,475(March 9, 1945). (97) Papageorge, E., and Lamar, M. V., Arch. Biochem., 14, 310 (1945). (98) Pavlisch, L. A.,Enamlist, 25, 21 (1948). (99) Pemberton, R. T., and Holmes, E. L., Brit. Patent 601,321 (1948). (100) Plesch, P. H.,and Robertson, Nature, 161,1020 (1948). (101) Porter, L. B.,Sugar, 42,22 (1947). (102) Porter, R.W., Chem. Eng., 54, 115 (1947). (103) Reid, A. I?., IND.ENC.CHEM.,40, 76 (1948). (104) Resinous ReporteT, 9,3 (1948). (105) Riley, F. R., and Day, H. M., Chem. Eng. Progress, 44, 353 (1948). (106) Rost, R., Vhtnik Stat. Geol. ostuvu Rep. Ceskoslov, 22, 334 (1947). (107) Schubert, J., J. Phys. Colloid Chem., 52, 340 (1948). (108) Schubert, J., and Richter, J. W., Ibid., 52,350 (1948).

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(109) Science Navs Letter, 28 (May 1948). (110) Serfaas, R. J., Theis, E. R., Thorstenaen, T. C., and Aganval, R. E., J . Am. Leather Chem. Assoc., 43,132 (1948). (111) Siding, D. H., Soil Sei. SOC.Am. Proc., 11, 161 (1946). (112) Smirnov, V. A., and Goncharenko, 8. E., J . Applied Chem. (U.S.S.R.), 20, 449 (1947). (113) Smith, E.L.,and Page, J. E., J . SOC.Chem. Ind., 67,48 (1948). (114) Smith, G.W., U. 8.Patent, 2,433,167(1948). et al., J . A m . Chem. SOC.,70, 1016 (1948). (115) Sommer, H., (116)Spaulding, C. H.,PubEic Works. 77, 27, (1946). (117) Spedding, I?. H.,et al., J . Ant. Chem. SOC.,70, 1671 (1948). (118) Sussman, S.,U. 9. Patent 2,442,989(June 8, 1948). (119) Teichner, S.,Compt. rend., 225, 1337 (1947). (120) Tendeloo, H.J. C., Diecussion8 Faraday Society, 1, 293 (1947). (121) Thompson, J., and McGarvey, E”. X., Chem. Ind., 62, 55 (1948). (122) Thurston, J. T.,U. S. Patent 2,440,669(April 27,1948). (123) Trapeznikov, A. A., and Lipets, M. E., J . Phys. Chem. (U.S.S.R.),21,109 (1947). (124) Vend, M., Roy. Hung. Palatina-Joseph Univ., Tech. Econ. Sci. Pubs. Dept. Mining Met., 15,344 (1943). (125) Webb, T. L.B., and Yoder, J. D.,Power, 92,99 (1948). (126) Wilcox, 0 . W., Sugar, 43,21 (August 1948). (127) Williams, W. L.,J . Am. Water Works, Assoc., 39, 779 (1947). (128) Winters, J. C., C h m . Ind., 62, 764 (1948). (129) Winters, J. C.,and Kunin, R., IND.ENG.CHEM.,in press. (130) Wise, W. S.,Sewage Works J . , 20, 96 (1498). R E C ~ I V EOctober D 16, 1948.

MATERIALS HANDLING &!!! ROBERT E. WRIGHT, MONSANTO CHEMICAL COMPANY, ST. LOUIS 4,

MO.

NLIKE some other unit operations, very few articles on materials handling appear in the literature. However, this does not indicate a lack of progress, because the advances in this field are reflected in new equipment. This review describes recent developments in materials handling equipment and covers some of the items believed to be of most interest. LIQUID AND GAS HANDLING

Pumps. A proportioning pump, called the Constametric ( I d ) , is based on a new principle which permits a constant controllable rate of flow without pulsation. Pulsation is eliminated by driving the plungers through cams which are so arranged that as one plunger nears the end of its stroke, its speed is slowed a rate equal to the starting forward speed of the second plunger. The capacity of the pump is fully adjustable by manual or automatic methods while the pump is in operation. There is no variation in capacity delivered, owing t o change of discharge pressure. Models are available with capacities from a minimum of 75 ml. per hour to a maximum of 35 gallons per hour. This pump is available in a variety of construction materials. Another new proportioning pump known as Airometric (1.9)can be operated on compressed air or natural gas where electricity is not available. I n a new vertical booster and transfer pump (19) the suction and discharge nozzles are of the same size and on the same center lines, so that the pump can be used in a pipe line like a fitting. This pump would be especially useful for the acceleration of the flow of liquids in existing pipe lines. It is available in capacities from 400 to 1400 gallons per minute. Although such huge pumps are not of probable use in the chemical process industriea, i t is nevertheless interesting to note the giant irrigation pumps (720,000 gallons per minute) now under construction. These pumps are being built for the Grand Coulee area and are a t least eight times larger than

any comparable pump in the world. Each pump will operate against a normal head of 270 feet and will be driven by a 65,000h.p. synchronous motor. The initial installation of six pumps will be completed before the end of 1949; by 1951 six more will be installed (1-4). A new portable pump (14) can fill a 100-pound butane or propane cylinder in 6 minutes. The pump has a rated capacity of 4 gallons per minute at 3500 r.p.m. and develops differential pressures up to 40 pounds per square inch. A new line of self-priming pumps for corrosive services is being introduced ( 9 ) . These pumps are considered to be a marked advance because of their much larger air pumping capacity, and their ability to prime rapidly against higher heads (up to 15 feet), and because they are available in a complete range of corrosionresisting alloys. A handy pump weighing only 11 pounds has been introduced for unloading acid carboys (6). The pumping unit consists of a small electric centrifugal air compressor mounted on a self-sealing connection which is slipped into the carboy neck. When the pump is operating, air pressure builds up in the carboy and forces the acid out through a tube which extends from the bottom of the carboy through the sealing connection. Compressors. Last year’s review mentioned the motor-driven centrifugal compressors being installed on Tennessee Gas Transmission Company’s 24-inch line. Three of these cornpressors are now in service at a station at Moorehead, Ky., and their performance is being carefully studied to determine operating chsracteristics and economics (B). Six centrifugal compressor stations are now operating on the Big Inch and the Little Big Inch natural gas lines of Texas Eastern Transmission Corporation. Eventually there will be sixteen of these centrifugal compressor stations on these lines, requiring 177,500 h.p. The discussion leading to the decision to