Tower Absorption Coefficients VI. Absorption of Ethylene Dichloride' H. B. OSBORN,JR., AND C. W. SIMMO;.;~, Lehigh University, Bethlehem, Pa.
R
An 85per cent recovery of ethylene dichloride is rectification, provides a n efficient means for the recovery various organic and inaccomplished by a countercurrent absorption of ethylene dichloride. Organic vaporsl system with kerosene, followed by rectification. from solvent treatments, have I n practical application, higher yields can be oblong been under consideration PROCEDURE tained by providing greater length of time of conand de\relopment. The cost of APPARATUS. An experimental the necessary equipment and the tact of carrier and extractor. set-up similar to that used by value Of the recovered product Absorption coeficients for a n ethylene dichloSimmons and Long ( 2 ) was ema r e t h e determining f e a t u r e s ride-kerosene system haz!e been determined and i;fpY$. 1~~~~~ of the feasibility of reclamavary with flow ratio, as shown in Figure 1. A side diameter was equipped for tion. countercurrent absorption. The logarithmic plot will yield a straight line. A rather simple solution of t o w e r w a s p a c k e d w i t h glass spheres having an average diamesuch a problem is found in a countercurrent absorption system followed by rectification ter of 1.85 cm. to a filled height of 68.5 cm. The drain-free ratio was determined and checked with previous work of the extractor.The success of such treatment is determined volume at 0.414, giving a gross volume of 2.83 liters and a drain-free by the properties of the solvent t o be recovered and it's rela- volume of 1.175 liters. The wash oil used was kerosene of the tionship to the extractor. Obviously, it is necessary to find following specifications: an extractor which will easily dissolve the solvent' under 0.808 Density a t 20' C., gram per cc. Molecular weight 168 consideration and at the same time have a low yapor pres34 Universal-Gaybolt viscosity (21' C.), seconds 'sure and a boiling point not too close t o that of the solvent. Air was supplied at constant' pressure through a wet test The use of eth;;lene dichloride as a solvent in various incarefully dried in a large calcium chloride tube, passed dustries results in waste gases containing as high as 10 per meter, through an electric furnace, and finally bubbled through ethylene cent dichloride. The solvent is a colorless liquid having a dichloride. The amount vaporized depended upon the sensible specific gravity of 1.265 and a molecular weight of 98.95; it heat of the air. Hence, careful control of the air temperature in is slightly soluble in water and quite soluble in various or- the heater made it possible to produce any desired concentration of ethylene dichloride. ganic liquids. T h e boiling point is 83.5" C. The air mixture was tested for ethylene dichloride before and A good extractor for such a substance is found in kerosene after scrubbing by means of a bleeding system running directly in which it is miscible in all proportions; the kerosene has a to a modified Orsat. The combustion of ethylene dichloride in excess oxygen is reprelow vapor pressure and a boiling point well over 100" C. It is desired t o show that a simple countercurrent absorption sented by the following equation: system of kerosene and ethylene dichloride-air, followed by 2CZHdClp 502 +4CO2 4HC1 2HzO A mixture of the ethylene dichloride with air was led intozthe 1 Previous articles i n this serles have appeared in IND. E N D . CHEM as usual measuring cvlinder and ignited in a combustion chamber ~ O ~ ~ O W 1S a : n d 11, 18, 989 and 991 (1927); 111. 22. 718 (19301: IV. 24. 301 with excess oxygen; the prodicts of combustion then passed (1932); V, 26, 529 (1934). ECOVERY systems for
p7fl;sc2wienf
+
T.4BLE
CZHICI?
out
In
%
%
1 2
3.5 4.4 6.3 7.4 5.3 4.9 5.7 0.45 5.5 2.6 3.0 4.1 4.7 5.7 5.2 3.4 4.3 2.3 1.0 3.1 3.7 4.1 3.9 1.8 2.0 2.6 4.8 2.01 2.3 1.0
0.448 0.512 0.913 0.991 0.600 0.519 0.991 0.073 0.871 0.532 0.621 0.639 0.721 0.834 0.761 0.763 0.781 0.932 0.416 0.713 0.762 0.931 0.876 0.312 0.300 0.410 0.760 0.310 0.425 0.210
4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
A4BSORPTIOX O F
EXTRhCTOR
CARRIER
Gram-moles per min. 0.930 8.58 9.62 0.975 7.54 0.933 6.92 0.930 0.931 6.71 9.11 0.930 0.931 6.51 6.72 0.931 0.930 7.28 6.62 1.012 1,000 6.27 9.01 1,000 7.56 0.931 7.67 0.935 0.951 8.31 5.74 0.956 5.55 0.971 0.952 1.13 0.987 1.10 0.930 1.87 5.2s 0.971 0.971 4.05 0.971 3.41 0.930 5.72 0.999 7.57 7.41 1.012 9.24 1,012 9.46 1.012 11.90 1.252 12.05 1.252
TEMPERATURE
R4TI0, .I'
PRESSURE
Gas In
Extractor out
9.23 9.87 $08 ,.45 7.21 9.7s 7.00 7.22 I .83 6 53 6 27 9.01 8.13 8.21 8.75 6.00 5.72 1.19 1.11 2.01 5.44 4.17 3.51 6.15 7.58 7.31 9.12 9.36 9.50 9.63
Mm. Hg 760,15 760.15 760.3 760.4 760.7 760.0 760.0 760.0 760.0 759.1 759.1 759.1 759.8 759.8 758.3 761.1 758.3 75s. 3 761.1 761.1 758.1 758.5 758.5 761.1 761.3 761.3 761.3 761.3 760,O 760.0
23.7 23.7 23.7 23.6 23.7 23.5 23.5 23.7 23.6 23.7 23.6 23.7 23.8 23.8 23.8 23.6 23.6 23.6 23.7 23.6 23.8 23.6 23.8 23.7 23.6 23.8 23.6 23.7 23.7 23.7
29.1 29.0 29.1 29.1 29.1 29.0 29.0 29.2 29.2 29.2 29.2 29.1 29.1 29.1 29.1 29.0 29.0 29.0 29.0 29.1 29.1 29.2 29.0 29.2 29.1 29.1 29.1 29.1 29.0 29.0
856
+
ETHE-LETE DICHLORIDE
MOLE FLOW
TEST
3
I.
+
AV.
c.
c.
OPERATINQ ABSORPTION COEFFICIENT, FREE K VOL. Liters 0.967 0.941 0,992 1,008 1.012 0.953 1,017 1.007 1.003 1.014 1,022 0.957 0.992 0.984 0.973 0.936 1.040 0.900 0.907 1.060 1.047 1.076 1.092 1.047 1.090 1.094 0.950 0.939 1.009 0.931
47.1 52.2 43.4 41.6 41.2 47.2 39.1 40.1 41.8 38.3 37.3 46.0 42.2 43.1 25.0 37.1 36.9 30.7 30.4 31.5 35.7 34.2 33.4 27.1 41.1 40.3 46.2 27.5 48.9 49.2
August, 1934
I N D U S T R I A L AIVD E N G I I V E E R I K G C H E M I S T R Y
857
through water to remove the r6c values and absorption co”” hydrochloric acid and water efficients obtainable from vapor, and the r e m a i n i n g 2 carbon dioxide was absorbed 2’’ the equation of Bennetch in potassium hydroxide. ga5 and Simmons ( I ) , are listed This provided a quick method in Table I. The coeffifor determining the ethylene S4O dichloride concent,ration in 3 cients have been p l o t t e d against mole flow ratio in the air, as it is easily calcuj Z1C5 lated directly from the carbon 1 4 5 6 7 8 io Figure 1. dioxide formed. I ~ L LFLOW F A T I O .r Rectification of the exIn Order to determine the FIGURE 1. -4BSORPTION COEFFICIENTS FOR ETHI-LESE DItractor containing various accuracy of this method, a CHLORIDE amounts of ethylene dichlomeasured quantity of air was bubbled through the dichloride produced d i s t i l l a t e s ride in the bubble tower for one hour. The arnount vaporized .with a maxinlum concentration of 0.02 per cent kerosene >.,-.as determined by replacement method and the composition of the air mixture J.,-:Lscalculated from these determinations. The in the Orsnt analyses run on this mixture during the hour remained ACKNOWLEDGMENT substantially constant and checked the determination by the method just described to two decimals in percentage composiThis investigatioll JTas carried out under the Henry Marition. son Byllesby Memorial Research Fellowship in Engineering. The air supplied through the wet test meter had a n averLITERSTCRE C I T E D age humidity of 26 per cent a t 20” C. and corrections were lllade for this ia deternlining the dry roluntes used in the (1) Bennetch and Simmons, ISD. EXG.C H E x . , 24, 301 (1932). Long’ Ibid” 22’ 718 (1930). calculations. Each run was in operation for 30 minutes before (2) XIas 16, 1934. any data \.,-ere taken. These data, together with calculated RECEIYED ;=c
0
3.
Iodine Reducing Value of Orange Juice Effect of Sodium Benzoate and Heat 11.A. JOSLY?;
AKD
G. L. MARSH,Fruit Products Laboratory, University of California, Berkeley, Calif.
vitamin is novel and, if true,[of great concern to the industry. biological assay, that sodium benzoate and various other The results of the above investigators, howeVer, are contrary substances which had a preservative action against gross to those obtained by Morgan et al. (4) which indicated that fermentation of lemon juice exerted a destructive effect on sodium benzoate in concentration of 0.10 per cent was without vitamin C, two additional papers in which practically the effect on the vitamin C potency of sweetened orange juice. same conclusion is reached have appeared Bennett and Certain results obtained in the course of this study of the Tarbert ( I ) claim as a result of very limited investigations changes occurring during the deterioration of orange juice seem t h a t the use of any preservative which is efficient in prevent- to indicate that the destruction of reducing value and vitamin ing fermentation is followed by a decrease and eventually a C content observed in preserved juices is due tooxidation rather of the indophenol reducing power of lemon than to some little-understood effect of the preservative. Prodisappearance __ longed storage studies made to juice. They conclude th’at in determine the factors involved in untreated juice t h e r e d u c i n g Data reported here show that the iodine rethe darkening of bottled orange factor is protected from atmosducing power of orange juices does not diminish juice indicated that the iodine repheric oxidation by the action a great deal in storage in the absence or presence ducing power of the juice was of a n enzyme which, if inhibited of preservatives andlor heat treatment, provided more rapidly lost under certain or destroyed by t h e usual storage conditions than under oxidation is retarded or prevented f r o m occurring means, results in rapid loss of others. Some of the early data reducing power. Cultrera (2) by such procedures as vacuum-sealing or canning. obtained on the rate of loss of presents data based on 2,6-diI n samples exposed to air the reducing factor is iodine reducing power of the juice chlorophenol-indophenol t i t r a rapidly oxidized. The amount of loss of reducing has some bearing on this particution and on biological assay invalue occurring is conditioned by the amount of lar problem, and i t is therefore dicating t h a t lemon juice prepresented a t this time. Although available oxygen. served with 350 p. p. m. of sulfur the iodine reducing value may dioxide rapidly loses i t s a n t i The writers believe that a n enzyme protecting not be as specific a measure of scorbutic power, thus confirmthe reducing factor f r o m atmospheric oxidation ascorbic acid content of orange ing in part the findings of Bendoes not exist in fresh orange juice but that such juice as 2,6-dichlorophenol-indonett and Tarbert. Although it a protective agency m a y be elaborated in fermented phenol titration, it has recently was early shown t h a t vitamin juice by the causative organisms. been shown that it is fairly reliC is readily destroyed by oxiable in indicatingrelative changes dation, especially a t high temI t is concluded that the loss in reducing value of i n a s c o r b i c a c i d c o n t e n t of peratures and high p H values, orange juice is due to oxidation and that preservathe idea that commonly used orange juice exposed to air (3) tives of the benzoate type or heat treatment in the food preservatives, such a s as in the present investigation. absence of air have no destructizqe action on fhP sodium benzoate and s u l f i t e s , If this is true, the results rereducing power. actually destroy a n t i s c o r b u t i c ported here indicate that destruc-
S
INCE the report of Williams and Corran ( 5 ) , based on
