68
INDUSTRIAL AND ENGINEERING CHEMISTRY
(97) Shiraa, R. N., Hanson, D. K , , and Gibson, C. H., IND.EZTG. CHEM.,42, 871 (1950). (98) Simons, J. H., and Dunlap, R. D., J . Chem. Phgs., 18, 335 (1950). (99) Smith, K. A., and Smith, R . B., Petroleum Processing, 4, 1355 (1949). (100) Smith, T. E., and Bonnex, R. F., IND.ENG.& E x , 41, 2567 f 1949). (101) Starr, E’., Jr., Anderson, J. P., and Davidson, V. &I., Anal Chem., 21, 1197 (1949). (102) Steinhauser, H. H., and White, R. E , IND.ENG.CHEM.,41, 2912 (1949). (103) Struck, R. T., and Kinney, C . R . , Ibid.,42,77 (1950). (104) Thomas, G . R., O’Konski, C. T., and Hurd, C . D., 9 7 m l . Ciiem., 22, 1221 (1950), (105) Thomas, J. W., Shinn, L. A , , Wiaenian, H. G., and Moore, I,. ‘4.. Ibid., 22, 726 (1950). (108) Trevoy, D. J., and Drickamer, H. G., J . Chem. Phys.. 17, t 117 (1949). (107) Uitti, K . D . , Petroleum Processing. 5 , 41 (1950). (10s) Underwood, A. J. V., Chem. Eng. Progress, 45, fi09 (1949).
(109) (110) (111) (112) (113) (114) (115) (116) (117) (118) (119) (120) (121) (122) (123) (124)
Vol. 43, No. 1
Underwood, -4. J V., IND.ENG.CHEM.,41, 2844 (1949). Wall, F. T., and Stent, G. S., J . Chem. Phus., 17, 1112 (1949). Watson, H. E., Ind. Chemzst, 25, 503 (1949). Weil, B. H., PetroZellnzProcessing,5 , 13 (1950). Weisman, J., and Bonilla, C . F.. IND.ENG.CHem. 42, 1099 (1950). White, B. C., U.S. Patent 2,488,249 (Nov. 15,1949). White, G. E., Chern. Eng. Progiess, 46, 363 (1950). Wilke, C. R., Ibid., 46, 95 (1950). Williams, G. C., Stigger, 1;. K., and Sichoia, J. H., Ibid., 46, 7 (1950). Williams, R. K . , and Kaugle. J. &I., Gil Gas .I., 48,S o . 46, 241 (1950). Woerner, R. C., U. S.Patent 2,494.274 (Jan. 10, 1950). Wood, S.E., IND.E m . CHEX, 42, 660 (1950). Yamada, S.,Oganai, S., and Chuno, T.. J . SOC.Brewin47 Japan, 43, 37 (1948). Yu, K. T., and C o d , J., Clteni. Eng. Progress, 46, 89 (1950). Yu, K. T., and Coull, J., J . Inst. Petroleum, 35,770 (1949). Zenz, F. A,, PetToZezim Refiner,29, No. 6, 103 (1960).
RECEII. X D Ortober 17, 1950.
HIGH VACUUM ISTILLATlON -
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KENNETH C. D. HICKMAN 56 THACKERAY ROAD, ROCHESTER 10,
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(this still and the previous one use grooved evaporating sutfaces, fruit juice dehydration b y removal of water vapor at low temperatures. A pilot plant single strikitlglg reminiscent of the reviewer’s own early labors) is operstage and a research multistage falling Rlm still were also described. ated with residual pressures in thP micron range. Both papers present a wealth of authentic operating data. ONOGLYCERIDES, custom-tailored by molecular disAssigned to the Socony Vacuum Oil Company, a patent issued tillation to fit special requirements, have emerged from to Schlesman and Fawcett (42)describes a short-path still in which Embree’s laboratory a t Distillation Products Industries the evaporating surlace is heated by radiation selectively ahinto large supply during 1950. Glycerol, reacted with unsorbed by the “wanted” molecule. Schlesman offers an intersaturated fatty acids ( 2 2 ) has found favor in the baking indusesting modification (4f)wherein energy of radio frequency is used try, where the purified monoesters are said to possess “lightto prevent condensation of a constituent of a mixture. Examples ening” qualities unexpectedly enhanced by the absence of diof compounds which can be separated in this manner range from esters (41). Produced as a heart cut from the crude reaction phenyl nitrite to tryptane. Although not strictly in the provmiuture, the monoesters are one of the few main products (in ince of this review, the effect of sound waves on attainment contrast with stripping cuts and vitamins) obtained in quantity of equilibrium in packed columns (9) may be compared with by molecular distillation. the above. A variant of the hot-cold still should also receive Vacuum dehydration has continued its phenomenal expansion. notice ( 1 3 ) . In 1950, upwards of 120,000,000 gallons of fruit juices are said Laboratory high vacuum distillation has advanced more in by Morse to have been concentrated, four to one, for freeze techniques and application than in design A complete fallingcanning, This evaporation (If, 29, SI, @), which is done a t film installation (36) for drug research is generically a descendant 8 t o 12 mm. of mercury. involved the total removal of some 180 of the Quackenbush and Stembock design with stirred evaporator. billion cubic feet of vapor. Steam ejection, single and multiple Stills for small samples, milligrams (8) t o a few grams ( 3 7 ) have effect, heat pump cycles employing ammonia compressors (30) made their long-awaited appearance. The well known (preand combinations thereof have performed the transfer of water 1939) glass falling-film installation offered by Schott and Genosfrom juice to condensate. I n addition to orange, lemon, pinesen has been redesigned (39) to permit recirculation of residue. apple, grape, and apple juices (5-7, f b , 49) an important newcomparable to the operation of a cyclic-batch still. comer is a soluble coffee (6, 6, 11, 19,43, 45), which is being proMadorskg and associates have continued their noteworthy duced at a water-vapor pressure of about 1 mm. and a residual researches in high vacuum chemistry, pyrolysis, and distillation. air atmosphere of less than 30 microns. Here indeed is an exOf particular interest is a 10-column falling-film still (25)with the tension of megavacuums into the true high vacuum field. columns arranged side by side on the bench and interconnected Items of news in industrial short-path distillation are few, by magnetic pumps which combine and recirculate residues and but they show two significant trends: on the one hand to dedistillates in appropriate directions. That such an assembly can glamorize and on the other to explore new fundamental phebe operated a t all, in mutual balance, is a tribute to operative nomena. Spence (47) describes a falling-film still of pilot plant skill, but the cost has been high: capacity, to be operated a t relatively high saturation pressures and without benefit of condensation pump. Dioctyl phthalate To keep the system in balance it is necessary to have the same pumping rate for all columns and to evaporate exactly half the can be distilled with a feed rate of 370 pounds per hour to yield liquids. The evaporating rate is more difficult to control: in a water-white distillate, 85 to 60 A.Ph.A. color; a still with a order to blanket any deviation from conditions of balance the rapacity of 1. ton an hour is projected. A falling-film evaporator evaporating rates were adjusted to a little over 5OVo of the amount of liquid pumped into the crown of each column. I n experiby Benner and DiNardo (2) with tubular, remote condense1 T h e two outstanding events of the year in high vacuum distillation were the introduction of molecularly distilled monoglycerides of fatty acids and the continued industrial expansion of
January 1951
INDUSTRIAL AND ENGINEERING CHEMISTRY
mental tests with a binary mixture, the ten-column molecular still gave at e uilibrium a se aration of the two constituents equivalent to %out thirteen tteoretical plates. The operation was continuous lasting several weeks at a time and requiring very little attention.
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Madorsky (86) and Wsterman et al. (60) have severally described spring balance evaporative stills for microanalysis. Madorsky’s experiments (84) with the fission of hydrocarbon chains by heat show that macromolecules break a t random until a fragment can escape by evaporation. Turning now t o studies with the molecular still, a complete account of distillation of tocopherol-bearing oils is offered by Green and Watt (16). Using the cyclic-batch still of Hickman, the elimination techniques of Embree and Hickman, and much of the data of Baxter, Rawlings, and associates, they succeed in pointing to the disturbing fact that the elimination maximum of the mixed tocopherols occurs at quite different temperatures according to the oil of origin. Your reviewer accepts this as a fact with which future research must cope. It is curious, however, that the authors, who are so well informed in the field, should advance the statement that such work involves chemical concentration of tocopherols either before or after molecular distillation and that there has been little or no reference t o the practical aspects of large scale tocopherol concentration. To correct the record, it should be pointed out that hundreds of tons of raw vegetable oils have been stripped in commercial routine and the strippings redistilled in molecular vacuums to 20 to 50% tocopherols without chemical intervention, Together with the concentration of deodorizer sludge, these operations constitute a sizable industry. A patent issued this year (go), assigned to Distillation Products Industries, describes the conversion of 7- t o a-tocopherol, a process which should not be without influence on the natural resources of “potent” vitamin E. The sum total of knowledge of vapor pressures of phlegmatic liquids, including phthalate esters, plasticizers and glycerides, has been increased by two excellent papers by Perry et al. (34, 36). The pendulum tensimeter, redesigned for use with an air box instead of the previously used oversized and dangerous oil bath, has provided the data. The accuracy of individual points has suffered slightly but unimportantly, considering that many of the substances measured could not be of pedigree purity. As an orienting gesture, the work will prove invaluable. Concerning the theory of molecular distillation and computations necessary as a base for advance in devices for self-managed multiple stills (molecular fractionation), the reviewer cannot but be impressed with the analogy between the distribution curves for multiple series solvent extractions and the molecular elimination curves. Papers by Nichols (SS),Tipson (48),and Golumbic ( 1 4 ) will repay study, together with one by Bradley and Shellard ( 4 ) which bears more directly on unit distillations. Some prominence was given to vacuum coating of metals and glasses in the last review, but this year a statement that progrem (10, 18) is toward bigger and better rather than novelty will suffice. Instrumentation includes two minor modifications of the McLeod gage (1,16) and an improved Knudsen (88, &). Considerable activity is noted in setups for measuring the gases evolved from vacuum fusion (17,83), and vacuum fusion itself finds expanded application. The device of the year in vacuum aids which, if not new is certainly not well enough known, is a valve for placing two mechanical vacuum pumps 6rst in parallel and then in series as high vacuum is attained (3). Reviews are less in evidence (H); exceptions are two lengthy illustrated accounts (@, 4 4 ) of molecular distillation (38,40)in foreign jour-
69
nals. Descriptions of advanced vacuum engineering (38) continue to be released by government agencies. LITERATURE CITED
(1) Azelband. M. A.. Reu. Sci. Inst.. 21, 511-13 (1950). Benner, F. C., and DiNardo, A., IND.ENQ. CHEM.,42, 1930-4 (1950). Blasco, E., and Miranda, L., Anales real SOC. espair. fis y quim, 46A,69-75 (1950). Bradley, R. S., and Shellard, A. D., Trans. Faraday SOC.,45, 501-7 (1949). Business Week, 62 (Feb. 4,1950). Ibid.., 37 - (Ami1 29. 1950). Chem. Eng. News, 27,3880 (1948). Chin, H. S.,J . Chem. Eng. China, 15,28-33 (1948). Coffin, C. C.,and Funt, B. L., J . Phys. & Colloid Chem., 53, 891-4 (1949). Diminick, Glen L. (to Radio Corp. of America), U. S. Patent 2,482,329(Sept. 20, 1949). Fortune, 40, 121 (September 1949). Food I d . , 68-70 (July 1949). Goldsbarry, A. W. (to Pure Oil Co. of Ohio), U. S. Patent 2,477,595(Mar. 10, 1948). Golumbic, Calvin, Anal. Chem., 22, 579-85(1950). Green, J., and Watt, P. R., J . Sci. Food and Agri., 1, 157-62 (1950). Groszkowski, Janusz, Nature, 164,886-7 (1949). Gulbrauser, E. A., and Andrew, K. F., IND.ENG.CHEM.,41, 2762 (1949). Guldner, W. G., and Beach, A. L., Anal. Chem., 22, 366-7 (1850). Hellier, E.G.,Food I d a . , 21, 1191-3 (1949). Hickman. K. C. D., and Weissler, L. (to Distillation Products, Inc.), U. S. Patent 2,486,540(Nov. 1, 1949). Khurt, N. H., and Welch, E. A,, J . Am. Oil Chemists SOC.,27, 344-6 (1950). Khurt, N. H.,Welch, E. A., and Kovarik, F. J., Ibid., 27,31013 (1950). McGeary, R. K.,Stanley, J. X., and Yensen, T. D., Trans. Am. Soo. Metals, Preprint No. 10 (1949). Madorsky, 6. L., J . Research Natl. Bur. Standards, 40, 41725 (1948). Ibid., 44, 135-9 (1950). Madorsky, S. L., Rev. Sci. Instruments, 21,393-4 (1950). Masch, L. W., Chem. Eng. Tech., 22, 141-6 (1950). Meers, J. T.,and Parduo, L. A., Phys. Rev., 74,119 (1948). Morse, R.S.,Chemistry & Industry, 1948,13-19. Ibid., p, 14. Morse, R. S.,IND.ENG.CHEM.,39,1064 (September 1947). Natl. Nuclear Energy Ser., Div. I, 1, “Vacuum Equipment and Techniques” (1949). Nichols, Peter L., Anal. Chem., 22,915-18 (1950). Perry, E. H., and Weber, W. H., J . Am. Chem. SOC.,71, 372630 (1949). Perry, E. H., Weber, W. H., and Danbert, B. F., Ibid., 71, 3720-6 (1949). Prignar, M., Wilt, W. A., and Nachod, F. C., Anal. Chem., 22, 1065-6 (1950). Roper, J. N., Jr., Ibid., 21, 1575 (1949). Sakurai, Toshio, J . J a p a n Chem., extra edition No. 1, 83-98 (May 1949); No. 2,98 (July 1949). Santiago, E. B., and Gonyales-Montes, L. M., I o n , 9,273-82 (1949). Ibid., pp. 338-51. Schlesman, Charleton H. (to Socony Vacuum Oil Co.), U. 5. Patent 2,455,812(Dec. 7, 1948). Ibid., 2,486,684(Nov. 1, 1949). Schroeder, A. L., and Schwarz, H. W., Chem. Eng. Progress, 45, No. 6,370-6 (June 1949). Schwartz, C. M., and Lavender, R., Rev. Sci. Instruments, 19, 814 (1948). Schwarz, H. W., IND. ENQ.CEEM.,40,2028 (1948). Schwarz, H. W., and Penn, F. E., Ibid., 40, 938-44 (1948). Spenoe, LeRoy U.,Ibid., 42,1926-9 (1950). Tipson, R. Stewart, Anal. Chem., 22,628-36 (1950). W a l l St. Journal (Nov. 29, 1949). Waterman, H.I., Rec. trao. chim., 68,939-44 (1949).
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REC~;IVED October 28, 1950.
