Effect of Uniform versus Intermittent Product Withdrawal from Distillation Columns D. M. OLDROYD AND L. A. GOLDBLATT Naval Stores Research Division, United States Department of Agriculture, N e w Orleans,
drawal rate as possible. . .However, in operating the high-efficiency column and packing here described, on closeboiling binary test mixtures a t high reflux ratios, very much better separations have been obtained by holding the column a t total reflux for periods of 30 minutes or more, and then withdrawing a quota of product almost instantaneously, again holding the column a t total reflux, and so on, than by withdrawing the product continuously at the same average rate as in the intermittent operation. .This unexpected advantage of intermittent product withdrawal, so outstanding as to merit the nickname “the free-wheeling effect” in the author’s laboratory, still is without theoretical explmation.
!t has long been tacitly assumed that the best way to operate highefficiency distillation columns is with as nearly continuous a productwithdrawal rate as possible. The relative effectiveness of intermittent VI. continuous product withdrawal for the separation of 01- and @pinene was tested with a heligrid-packed, a helices-packed, and a gauze-plate column. Especially with the heligrid-packed column distinctly better separation was obtained b y product withdrawal once every hour than once every 30 seconds.
F
.
R , ~ C T I O N A L distillation is one of the most important laboratory tools in the field of hydrocarbon research. It would be impossible t o enumerate here all the publications dealing with laboratory and commercial fractionating columns. Special mention should be made, however, of the excellent review of the literature on the construction, testing, and operation of laboratory fractionating columns made by Ward (9) and of two more recent papers on distillation practices and methods by Othmer (4) and Podbielniak (8). Despite these numerous publications and the real progress made, usually empirically, in the development of efficient laboratory fractionating columns, relatively little has been published on the practical operation of such columns. There remains t o be established a scientific basis for certain operational techniques no\y in common use, such as the preflooding technique, which have been developed through practical experience. That many differences of opinion exist concerning the preferred mode of operation, even for major elements, is revealed by the following excerpts from Ward’s review (9) :
I n the laboratory of the Kava1 Stores Research Division complex mixtures of terpene hydrocarbons are often carefully fractionated into individual pure components. For this purpose, three different types of columns are available: a vacuum-jacketed Podbielniak type, Figure 2. Reflux Controller and Top 1 inch (2.5 em.) in diameter, containing of Helices-Packed 4 feet of packing; an insulated, heatColumn compensated column, 1 inch in diameter, packed x i t h 3 / 1 6 inch Fenske-type glass hcliecs for 7 feet; and a Palkin type ( 5 ) , containing 45 individual gauze plates 1 inch in diameter, approximately 2 inches apart. Distillations are generally carried out a t reduced pressure (usually a t 20.0 mm. of mercury) to minimize thermal isomerization and at high reflux ratio to ensure maximum purity of product. Mixtures rich in a-pinene (boiling point at 20 mm. = 5 2 . 2 ” C.) and p-pinene (boiling point a! 20 mm. = 59.7” C.) are frequently distilled. I t was thought worth while, therefore, to investigate the utility of the “free-wheeling effect” in these distillations, especially since mixtures of pure cy- and P-pinene can be analyzed conveniently and accurately simply by measurement of the optical rotation, Biot’s relationship holding closely for these terpenes (3). hccordingly, two series of distillations were planned to test this free-wheeling effect.
The usual distillation practice is to keep the distillation rate constant. . .Some operators, however, increase the rate when collecting a pure component and decrrase the rate between components. .Most investigators use the term “reflux ratio” to designate the quantity of reflux per unit Tveight of product. . . 1Ic1lillan’s results show higher efficiency with medium rather than high or low reflux ratio. Calingaert and Huggins, ivith a coke-packed column, found the efficiency was proportional to the reflux ratio at constant vapor velocity. . .The usual practice is to maintain a constant reflux ratio: however, some investigators decrease the reflux x-hile collecting pure compounds and increase it at the critical points between compounds. . . Judging from thrir results, Hill and Ferris con. cluded the peak efficiency of a packed polumn was at a rate just below flooding. Podbielniak found maximum efficiency when the packing is barely wet. This is verified by Bruun and Schicktanz, whose results show efficiency decreased materially near the flooding point.
.
.
EXPERIMENTAL PROCEDURE
Figure 3. Reflux Controller and Top of HeligridColumn
I n the first series of distillations each of the three columns was operated so that the product withdrawal, or take-off, was “uniform”; in the second series, so that the withdrawal was “inter‘mittent”. It was planned that in so far as possible the operation of all the columns in a series would be alike, thus permitting evaluation of the response of the various columns both Lyith respect t o each other and with respect to the manner of product withdrawal.
Podbielniak (8) pointed out the possibility that intermittent product withdrawal might be superior t o uniform product withdrawal: The measurement and control of reflux ratio for high efficiency columns are most important in obtaining best possible separation with a column in a given time of distillation. . . It has long been tacitly assumed that the best way. to operate any column is with as nearly continuous a product-with-
La:
Figure 1. Reflux Controller and Top of Gauze Plate Column
All three columns were operated simultaneously from a single control panel and “column line” manifold maintained at 20.0
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762
Vol. 18, No. 12
described by Carter arid Johnson (2) (Figures 1 and 2 ) , “uniform” withdraival was arranged for by use of an electric time switch operating on a 30-second cycle and sct at 170. I n the case of the Podbielniak column (Figure 3) since the smallest portion of product that could he withdrawn reliably was about 0.2 cc., the “uniform” withdrawal was arranged for by use of an electric time switch operating on a 5-minute cycle and set a t 0.13%. This gave a takeoff of 3.0 cc. per hour when the reflux was 300 cc. per hour. I n the case of the ‘Linterrnittent” withdrawal, all the columns had a product withdrawal period of 36 seconds followed by a shut-in period of 69 minutes and 24 seconds. This could be arranged for by use of a time switch operating on a 1-hour cycle and set at 1%. The optical rotation of each fraction (about 20 cc.) was measured and then plotted against grams of product withdrawal from each column. RESULTS AND DISCUSSION
Figure 4.
Uniform Product Withdrawal
Figure 4 shows such plots for some of the intermediate fractions obtained by uniform product withdrawal for all three columns operated simultaneously. Figure 6 illustrates similar plots obtained usingintermittent product withdrawal. These plots permit a direct comparison of the effectiveness of all three columns, as well as an evaluation of the effect of uniform versus intermittent product Jvithdrawal. [The performance of a column measured in theoretical plates at atmospheric pressure cannot be interpreted as the plateage of that column operating under vacuum. Thus Byron, Bowman, and Coull (1) point out that “a 50-plate column (at atmospheric pressure) would realize only half a plate a t 7.6 mm. of mercury”.] The fractions Jyith the higheetrotation, for both 01- and 0-pinene, were obtained from thr Podbielniak column. Table I shows for all six distillations the size in grams of the intermediate portions
through constant-voltage transform& and the Variacs were adjusted manually from time to time to maintain the desired throughput. hctive ebullition was maintained by means of an electrically heated boiling promoter ( 7 ) . Product take-off was maintained at 3 cc. per hour by suitable electrically operated timing devices. Each still pot was charged with 500 grams of a stock mixture of 50% or-pinene and 50% 8-pinene (by weight), and distillation was continued \yithout interruption until the 0-pinene plateau had been reached or until reflux a t the head ceased. Each distillation lasted about a week, and fractions were cut at 6- or 8-hour intervals. Although it was desired to condition and operate all three columns as similarly as possible, certain dissimilarities could not be avoided, owing to the differences in construction of the three columns. For example, the Podbielniak column, being vacuum-jacketed, required no heat compensation for the jacket, whereas the heat loss from both the helices-packed and the gauze-plate columns was partially compensated by four thermostatically controlled, electrically heated resistance units in each column. I n order to minimize possible differences arising from different manipulation of the thermostats, they were preset, so that each column would be losing a slight amount of heat a t the boiling point of or-pinene and were left unchanged throughout the distillations. To obviate the possibility of differences in efficiency arising from any difference in degree of thoroughness of preflooding none of the columns was flooded. Each column was allowed to reflux for approximately 5 hours before product withdrawal was begun. I n the case of the helices-packed column and the gauze-plate column, each fitted with a modified head of the type
Figure 5.
Intermittent Product Withdrawal
December, 1946 Table
ANALYTICAL EDITION
I. Comparison of Uniform and Intermittent Product Withdrawal Grams of Product between a- and p-Pinene of Indicated Purity 99.570 99% 98% 95(>
Podbielniak column Uniform Intermittent Decrease Helices-packed column Uniform Intermittent Decrease Gauze-plate column Uniform Intermittent Decrease
138
97
74
58
121 -
95 -
73 1
56 2
184 1 2 13
138 130 -
105 103 2
87 72 __ 1.5
17
2
8
quantity of material of intermediate purity obtained when operating under uniform as against intermittent withdrawal. Of the three columns tested the Podbielniak column, when operated under the conditions of this test, made the best showing; the gauze-plate column, the poorest. Furthermore, for the Podbielniak column, when intermittent rather than u'niform product viithdrawal was used, the improvement was very marked anti
163
consistent, showing a decrease in size of intermediate fractions of approximate 35% a t all levels of purity. Although some improvement was also apparent in the operation of the other two columns, this improvement in several cases was within the limits of possible experimental error. It may, therefore, be concluded that when operating highefficiency columns a t high reflux ratios it is not necessary to use as nearly continuous product withdrawal as possible. I n fact, n-hen a reflux ratio of 100 to 1 is used, better separations are obtained by product withdrawal once every hour than once every 30 seconds. LITERATURE CITED
(1) Byron, E. S., Bowman, J. R., and Coull, J., Reprint, Symposium on Bench Scale Techniques, Division of Petroleum Chemistry, SOCIETY(Sept. p. 16 108th Meeting, AMERICANCHEMICAL 11 to 15, 1944). (2) Carter, A . S., and Johnson, F. W., U. S.Patent 2,251,185 (July 29, 1941). (3) Fuguitt, R. E.. Stallcup, W. D., and Hawkins, J. E., J . A m . Chem. Soc., 64, 2978 (1942). (4) Othmer, D. F., Chem. Met. Eng., 49, 84 (May, 1942). ( 5 ) Palkin, S., IND. ENG.CHEM.,ANAL.ED.,3,377 (1931). (6) Ibid.,7, 436 (1935). (7) Palkin, S., and Chadwick, T. C., Ibid., 11, 509 (1939). (8) Podbielniak, W.J., Ibid.,13,639 (19411. (9) TYard, C. C., U.9. Bur. Mines. Tech. Paper 600 (1939).
D et e rminat ion oF I-TrichIo ro - 2,2 - bis( p -c hIoropheny l)et ha ne in DDT Dusts and ,Oil Solutions J. B. LACLAIR California State Department of Agriculture, Bureau of Chemistry, Sacramento, Calif.
A method is described for the determination of l-trichloro-P,2bis(p-chloropheny1)ethane (p,p'-DDT) in commercial dusts and oil solutions. The method i s based upon the dehydrochlorination of the sample at 25.0" * 0.1 C. in 95% ethyl alcohol solution for dust mixtures, and in kerosene solution for oil solutions, for 1 5 minutes, using 20 ml. o f N ethanolic sodium hydroxide. Comparative results are given for the crystallization method and the method described. Possible sources of error are discussed.
T
HE insecticidal value of a n ecoiioniic poison containing D D T is believed primarily due to its content of the pnrapara' isomer, l-trichloro-2,2-bis(p-chlorophenyl)ethane ( p , p ' D D T ) ; and in enforcement of the Agricultural Code of the State of California pertaining to labeling and sale of agricultural chemicals, it is necessary to determine the percentage of this compound in commercial dusts and sprays. Several useful methods have been developed (6, 7 , 8, 15, 15) for determining or detecting total DDT, but they are not applicable to the quantitative estimation of the individual principal isomers occurring in commercial DDT. The crystallization method of Cristol, Hayes, and Haller ( 5 ) has proved most valuable for the determination of p,p'-DDT in the 'technical product and straight D D T dust formulations, but i t is not applicable to oil solutions, such as fly spra~rs,or dusts containing pyrethrum powder or concentrates and is timejonsuming when applied to low percentage dust mixtures. The complex mixtures making up modern commercia! insecticides cause serious interference in most colorimetric. methods (1, S. 10). Cristol (4) has suggested that the difference in reaction rates of p,p'-DDT and o,p'-DDT to dehydrochlorination might be used for determination of the para-para' isomer in technical
D D T . This reaction was investigated by the author, arid procedures were developed applicable to most commercial D D T dusts and sprays. [Since the submission of this paper an article on the determination of p,p'-DDT in technical DD'T has been published ( 2 2 ) .] EXPERIMENTAL
A number of commercially available technical a r i d purified grade D D T samples of known p,p'-DDT content, as determined by the Cristol, Hayes, and Haller crystallization method (4), were dehydrochlorinated undcr strict conditions of temperature and concentration. A 1.000-gram sample was dissolved in 75.0 ml. of 95% ethyl ethanolic alcohol, and reacted 15 5inutes with 20.00 nil. of sodium hydroxide at 25.0 * 0.1" C. A graph of the per cent chloride ion formed, as ordinate, and per cent p,p'-DDT of the samples as abscissa, gave a straight line, which could be expie-sed by the formula:
(yochloride
X 11) - 9.30 =
% p,p'-DDT
A 0.500-gram sample was dissolved in kerosene, made u p to 100.0 ml. with kerosene, and reacted 15 minutes with 20.00 ml. of S ethanolic sodium hydroxide a t 25.0" * 0.1" C., while being stirred a t 700 t o 800 r.p.m. A graph of the per cent chloride ion formed and per cent p,p'-DDT of the samples gave a straight line, expressible by the formula:
( % chloride X 23) - 16.90%
=
% p,p'-DDT
REAGENTS AND APPARATUS
Ethyl alcohol, commercial 190-proof, 95% by volume. Ethanolic sodium hydroxide, 1.000 IV. Dissolve 41 to 12 grams of C.P. sodium hydroxide pellets in about 350 ml. of ethxl alcohol with the aid of heat, cool, and filter into a 1-liter vulumetric flask. Add alcohol almost to mark, and mix. Ytandttrd-
