INDUSTRIAL AND ENGINEERING CHEMISTRY
February, 1945
30 minutes. Hardness was determined with a Sward hardness rocker as follows:
Soybean
Oil
260° F. for 46 minutes 300” F. for 30 minutes
22 28
Milkweed Seed Oil 16 26
While the hardness of the milkweed alkyd enamels is less a t the lower baking temperature, this difference is minimized a t the higher temperature. However, a distinct advantage is shown by milkweed alkyd enamel in resistance t o dipcoloration, the difference being most marked a t the high-temperature bake. The results indicate t h a t milkweed seed oil is valuable for use in the preparation of alkyd resins, since the slow drying of the oil per se is overcome, while the valuable properties of the oil (flexibility and color retention) is imparted to the film.
181
counsel of Harry Lewis and the staff of that organization. They also wish t o express their appreciation to Arthur Cramer and J. P. Kass for o number of the analytical determinations, and to t h e Crown Oil Products Corporation for the use of their laboratory facilities during part of the investigation. LITERATURE CITED
Am. Oil Chem. SOL,Official and Tentative Methods, Jan., 1941. Gerhardt, F., IND. ENO.CHEM.,22, 160-3 (1930). Grace, N. H., et al., Chem. Industries, 54, 842-6 (1944). Jamieson, G. S., “Vegetable Fats and Oils”, New York, Reinhold Pub. Corp., 1943. (5) Kass, J. P., Loeb, H. B., Norris, F. A., and Burr, G. O., Oil & SOUP,17, 118-19 (1940).
(1) (2) (3) (4)
(6) Mitchell, J. H., Kraybill, H. R., and Zscheile, F. P., IND. ENG. CHEM.,ANAL.ED., 15, 1-3 (1943). (7) Rheineck, A. E., Phizrm. Arch., 10,69-80 (1939). (8) W e s t , Hoagland, and Curtis, J. B i d . Chem., 104, 627-34 (1934).
ACJCNOW LEDGMENT
The investigations here reported were carried out under the terms of a subcontract from the Institute of Paper Chemistry. The authors desire to express sincere appreciation of the aid and
PREBENTED before the Division of Paint, Varnish, a n d Plastics Chemistry a t the 108th Meeting of the AMERICAN CHEMICAL SOCIETY,New York, N. Y. Abstracted from Part I of the P h . D . thesis of H. J. Lanson, Polytechnic Institute of Brooklyn.
CHLORINATED KEROSENE Preparation and Physical Properties RAYMOND M. DEAN AND EUGENE LIEBER Standard Oil Company of New Jersey, Bayonne, N . J .
T
HE chlorination of petroleum hydrocarbons and their utilization are becoming increasingly important and have received considerable impetus in recent times. Both the physical and chemical properties of the chlorinated products of lower-molecular-weight fractions have been extensively studied and recorded in the literature, but not much can be found for the heavier fractions of petroleum. For the latter group the industrial applications have far oubtripped studies on fundamental physical and chemical properties. I n fact, for certain particular fractions data are lacking entirely. This is due t o the increased complexity of some of the lighter petroleum fractions extending beyond the gasoline range. Although lack of knowledge of the exact chemistry of chlorination of the higher petroleum fractions has not impeded their present industrial applications, i t is generally agreed that such data would materially broaden their scope. On the other hand, lack of physical data does markedly impede progress in this field, since such data are needed for plant design and control of operation for the chlorination procedure. Only fragmentary data have appeared in the literature on the physical properties of the chlorinated kerosene fractions of petroleum. Hartman (I) chlorinated kerosene from Pennsylvania petroleum by means of antimony pentachloride in the presence of iodine at 350 t o 360’ C. and reported the products t o be principally hexachloroethane and hexachlorobenzene together with
small quantities of tetrachloromethane and hexachlorobutsdiene. Schrauth (6) chlorinated kerosene t o monochloro derivatives for conversion to fatty acids. Thomas and Olin (6) studied the dehydrohalogenation of a chlorinated petroleum fraction to form olefins. Table I summarizes the Engler distillation of the kerosene used in the studies reported here. Table I1 presents elementary analysis, molecular weight, and other pertinent d a t a for this material. The elementary analysis and molecular weight determinations indicated the kerosene to have the average composition of ClaHzb. No further analysis of the composition of this material was a t tempted.
No systematic study has been reported correlating the
tive index, surface tension, furfural point, kinematic viscosity, solid point, specific gravity, flash and fire points, and molecular weight. These data are correlated with the degree of chlorination and the average molecular compositions obtained. A number of derived values are presented comprising molecular refraction, mnolecdar volume, and parachlor. These are correlated again& atomic chlorine contents of the chlorinated products.
physical properties of chlorinated kerosene with degree of chlorination. The object of this paper is to present such a study for a kerosene fraction boiling between 348” and 525’ F. and having a low aromatic content (high ‘furfural miscibility temperature”) and chlorinated from 5 to 60% chlorine content in steps of approximately 5%. The measurements comprise elementary analysis, refrac-
METHOD OF CHLORINATION
Figure 1 shows the chlorination apparatus. A 72,000-gram portion of kerosene was placed in the 12-liter Pyrex balloon flask, equipped with a n alundum thimble for dispersing the chlorine, a thermometer, and a safety tube dipping into the liquid. T h e safety tube also served as a means of withdrawing samples from the chlorination mixture. The chlorination was conducted at 200’ F., using the water bath as a heating and cooling medium. The degree of chlorination was determined approximately from time to time by weighing the flask and its contents. At the desired degrees of chlorination, samples of about one liter were with-
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
182
Vol. 37, No. 2
TABLE I. ENGLERDISTILLATION O F ORIGINAL K E R O ~ E N E
J CHLORINE CYLINDER
SAFETY FLASK
Initial 10% aver
iig 30% R
Figure 1. Apparatus Used for Chlorination
drawn. After a sample was withdrawn it was immediately cooled and blown with a gentle current of dry air, at room temperature, until the exit gases were free of gaseous hydrogen chloride. EFFICIENCY OF CHLORINATION. The relation between efficiency of chlorination and chlorine content was determined for a sample of chlorokerosene which varied from 0 to approximately 55% chlorine by weight. The amount of chlorine lost was calculated, assuming that the only reaction was substitution of a chlorine atom for a hydrogen atom as follows:
+ Clz
--f
R-Cl
+ HCl
where R represents a molecule of kerosene or chlorinated kerosene. The data obtained are summarized below: 7 Lost of Total % Chlorine Lost Since yo Chlorine in
a
b
F.'
B.P.,
80%
456 464 478
B.P.,
Final Residue
O
F.
497 525 525 1.5%
ON
ALUNDU THIMBLE
R-H
B.P., F. 348 390 400 406 418
C1 Kerosene
dhlorine Useda
Last Readingb
12.2 19.5 31.4 38.5 43.0 48.6 51.9 54.3
-8.3
-8.3 2.0 0 -2.8 7.0 11.5 14.3 35.2
0.9
0.5 -0.4 0.6
3.5 4.8 8.8
chlorine content was above 40%, the loss of chlorine increa.;ed with chlorine content up to a loss of 35% for chlorinated kerosene containing approximately 55% chlorine. The chlorination for the determination of efficiency of chlorination w&s run in the following manner: 2.5 gallons of kerosene were placed in a 12-liter Pyrex flask fitted with an alundum thimble, a thermometer, a gas exit line, and a safety tube. A water bath fitted with an immersion heater was used for heating arid cooling. The temperature of the kerosene was raised to 175" F., and chlorine was blown in. The chlorine dissolved until the kerosene had picked up about 2% by weight of chlorine. This induction period was followed by a fairly violent reaction during which the temperature rose 10-15" F. From this point on, the reaction ran smoothly, the chlorinated kerosene gaining about 2% chlorine per hour with the temperature held a t 185-205' F. From time to time the flask holding the chlorinated kerosene and the cylinder containing the chlorine were weighed and the weight changes noted. The amount of chlorine in the chlorinated kerosene n'as calculated on the basis of the substitution reaction only. Double this value was conyidered to be utilized chlorine, and this value for utilized chlorine was subtracted from the chlorine which had come out of the cylinder to give the loss figure. ANALYTICAL PROCEDURES
Estimated error *2%: Minus sign indicates gain. 100 minus the figures in this column gives the efficiency of chlorination.
The first column gives the calculated chlorine content of the chlorinated kerosene, The second column gives the percentage chlorine lost of the total used, and the third column gives the percentage chlorine lost for each increment of chlorine content of the chlorinated kerosene. Up to a chlorine content of approximately 12% the efficiency appears to be greater than 100%. This may be due in part to addition of chlorine t o double bonds. Also, there were errors in weighing the large quantities of chlorinated kerosene and chlorine which were often of the same order of magnitude as the differences between the weights. When the chlorine content of the chlorokerosene was between 12 and 40% by weight the loss of chlorine was approximately 0%. When the
Carbon and hydrogen were determined by the conventional combustion procedure. Chlorine was determined by combustion with sodium peroxide in a Parr bomb followed by a Mohr titration; the data for chlorine as presented in Table I1 are the mean of three independent determinations. Refractive indices were determined by an Abbe refractometer. For surface tensions at 25" C., a du Noiiy precision surface tensiometer was used. Furfural miscibility temperatures were obtained by the method of Rice and Lieber (3). Rlolecular weights were determined ebullioscopically. Viscosities were found kinematically a t three temperatures by the method of Ruh, Walker, and Dean (3). Specific gravities were determined over a range of temperatures by means of both precision hydrometers and pycnometers under thermostatically controlled conditions. The mean of three or more independent determinations were taken on all specific gravities. Solid points and open-cup flash and fire points were obtained by conventional A.S.T.M. procedures (Designations D97-39 and D92-33).
TABLE 11. SUMMARY O F EXPERlMENTAL DATA Elementary Cl C 107-47 0 86.06 5.9 81.46 107-20 107-14 11.1 77.12 107-19 16.0 73.14 107-26 20.5 68.84 107-27 25.5 64.72 107-28 30.9 60.59 107-29 35.8 56.65 107-8 39.6 52.84 io7-12 45.3 48.68 52.1 42.33 107-9 107-13 54.1 40.26 .. 107-15 58.4 0 Extrapolated value.
No.
Analysis, % H Total
13.99 13.09 12,36 11.34 10.68 9.89 9.04 8.29 7.76 6.80 5.50 5.09
..
100.05 100.45 100.58 100.48 100.02 100.11 100.53 100,74 100.20 100.78 99.93 99.45
..
Surface Tension
Refractive Index at 25OC.
(25' C.),
1.4476 1.4530 1.4595 1.4657 1.4724 1.4788 1.4870 1.4959 1.5030 1.5141 1.5289 1,5352 1.5490
27.0 28.0 29.1 29.7 30.6 31.7 33.2 35.0 36.4 38.6 41.9 43.7
Dynes/
Cm.
..
Furfural Point,
C. +98.1 184.0 +66.5 149.6 +30.9 t11.2 -15.5
.... .. ** . . ..
Mol.
Wt. 176.8
292
.. .. .. ..
Viscosity at
Centistokes
1.71 1.96 2.33 2.79 3.50 4.55 6.80 11.17 18.77 48,39 321.9 941.7 12.500a
looo F. Saybolt see.
33.8 35.3 37.6 40.9 48.1 62.9 92.4 224.0 1487.0 4350.0 57,750
A.S.T.M. Specific Solid Gravity, Point, ' F. 60/60° F.
-35 -45 - 55 - 60 - 75
