The Cracking of Cottonseed Oil

GUSTAVEGLOFF AND J. C. MORRELL

Universal Oil Products Company, Chicago, Ill.

T
HE cracking of oils for motor fuels has been applied cooled condenser and a receiver. The still was equipped
almost exclusively to hydrocarbon oils, largely those with a pressure gage and wells for thermometers,
derived from petroleum. It is of considerable The pressure still was charged with 800 cc. cottonseed oil.
interest to study the behavior of cottonseed oil, as repre- The still was heated until a self-generated vapor pressure
sentative of the fatty or glyceride oils, when subjected to of 9.5 kg. per sq. cm. was reached, a t which point the gas
cracking conditions. While economic conditions forbid release valve was opened on the distillate receiver. The
the use of this oil for making gasoline at the present time, heat application was continued until 485" C. was reached.
future occasion, particularly a national emergency, might Above this temperature no further distillate appeared, and a
necessitate the production of motor fuel from such oils. residue of coke remained in the pressure still. The products
Its use as a source of motor fuel might also be practical in were gas, distillate oil, coke, and water.
such countries as Turkey and Egypt where large supplies of
cottonseed oil are available and the price of gasoline is high. PRODUCTS OF CRACKING
Mailhe (3) has produced materials within the boiling The summary of the cracking results is as follows:
range of motor fuel which he states are similar to American Pressure distillate:
gasoline by the catalytic pyrolysis of cottonseed oil, employ- % of charge 71.1
SD.ur. 0.772
ing fused zinc chloride as catalyst. He reports that the Wafer; % 5.3
products of such catalytic pyrolysis of vegetable oils are Coke, gas, and loss % of charge 23.6
Coke, Ib. 42 gal bdl of charge (grams/liter) 40 (116)
primarily ethylene hydrocarbons having a yellow color and Gas, cu. /t./bbl. bf charge (liters/liter) 916 (163)
strong odor. Upon further treatment with zinc chloride, Motor fuel:
&,o;;harge 58.7
the unpolymerized oils distilling between 240" and 280" C. Initial b. p. C
0.761
46
lose their yellow color and sharp odor, becoming colorless End b. _D.. . C. 225
and fluorescent. Water, acrolein, and a lean gas are formed Gas oil, Diesel, or furnace oil:
% of charge 10.6
in addition to the oil product. Sp. gr. 0.912
Gallo and Correlli (2) subjected vegetable oils to treat-
ment with superheated steam in the presence of alkaline PRESSURE DISTILLATE OIL. Analysis of the pressure dis-
earths and passed the vapors produced thereby over pumice tillate showed a saponification number of 40, an ester value
impregnated with ferrous oxide at a temperature of 550" C. of 7, and an acid value of 33; the acid and ester volume
The product thus produced was hydrogenated a t a tempera- were, respectively, 6 and 2 per cent of the pressure distillate.
ture of 200-250" C., employing a nickel catalyst. Sixty to This indicated that the glycerides were decomposed into
sixty-five per cent of a yellowish brown, volatile, fluorescent hydrocarbons, free and combined acids of relatively low
liquid, boiling from 45" to 350" C., leaving 5 per cent of a molecular weight, and water.
tarry residue, was produced. The pressure distillate containing the motor fuel and
Waterman and Perquin (4) studied the decomposition of Diesel or gas oil was fractionated, using an 800-cc. charge
cottonseed oil in a closed vessel a t a temperature of 450" C. and a Hempel column filled with glass beads:
They found that cottonseed oil loses its oxygen almost Sp. gr. 0.7749 Initial b. p , , a. C. 34
quantitatively as carbon monoxide, carbon dioxide, and DISTILLED DISTILLED DISTILLED
OVER TEMP. OYER TEMP. OVEB TBMP.
water, when heated with hydrogen in an autoclave a t 450" C. % c. % c. % O c.
The remaining product consists largely of a hydrocarbon 10 62 40 130 70 197
mixture with a high percentage within gasoline boiling range. 20 86 50 151 75 210
30 109 60 173 82.6 229
Cracking of cottonseed oil a t elevated temperature under
pressure yields over 54 per cent of refined gasoline. The yield of unrefined motor fuel of gasoline boiling range
The properties of the cottonseed used in this study are was 58.7 per cent of the cottonseed oil.
as follows: REFINING OF CRACKED DISTILLATE.The pressure dis-
tillate was treated with approximately 1 per cent by volume
Sp. gr. at 1 5 . V C. 0.823 Glycerides, % 96 of 93 per cent sulfuric acid. After settling, the sludge was
Acid va+e 2.0 Sulfur, Q
Polenski value % 1.0 water& 0:i withdrawn, and the oil was water-washed, neutralized with
Reichert-Meis&number 0.69 Coke, yweight 2.6
sodium hydroxide, and distilled with steam into motor fuel
A. 8. T, M. 1oO-CC. DISTILLATION
DISTILLED DISTILLED DISTILLED
and pressure distillate bottoms. For complete removal of
OVER TEMP. OVER TEMP. OVER TEMP. the esters and fatty acids, refluxing with strong sodium
% O c. % c. % c. hydroxide solutions, prior to acid treatment, is required ,
Initial 237 40 317 SO 363
although this is not necessary to refine the gasoline com-
10
20
30
302
314
31s
KO
60
70
328
336
351
90
95
End point
372
366
371
mer cially .
The sulfuric acid solution loss was 2 per cent of the pressure
distillate oil with a polymerization loss of 1.8 per cent.
The oil was cracked by the nonresiduum method of opera- Upon distillation of the refined pressure distillate into motor-
tion at a pressure of 9.5 kg. per sq. cm. (135 pounds per fuel pressure distillate bottoms there was a loss of 2 per cent.
square inch) and over a temperature range of 445' to 488 " C. CRACKED MOTORFUEL. The properties of the finished
The apparatus employed consisted of a still, 8 inches
(20.3 cm.) in diameter, made from a machined flanged drop motor fuel were as follows:
forging and companion flanged head with tongue and groove 0,761 Corrosion Negative
?%:'Saybolt 30+ Sulfur, % 0.01
closure; a vapor line with pressure control valve; a water- Doctor Sweet Gum, mg. per 100 cc. 33

1426
 ," ,"
9% 0 c. 9% " c. *l<,iJt,*re 0.16 liixed oaibon 90.18
S 83 60 128 Voiatiies 8.48 Ash 1.20
10 76 8n 187
m s9 khd b. p 201
CRACKED GAS. ' h e eas uroduced bv cracking cottonseed
A hydrocarbon annlysis ( 1 ) of tho refined motor fuel oil wits analyzed by t& ljurrell and "I'odbieinLk methods
dhomed the following percentages: and tlie results combined showed the following percentages
of components:
H r o a u c ~ a a o nG ~ o u r Y' G*e 70 GAS %
P&r*(F"* :17., Metiism s s . 2 1'r"irYlene 8.8
UnshtilrsLer 27.1 Etilsrla 12.2 1 3 Uutsdiene 2.3
Naphtheuee
Arornst,lcs
R.!1
25.9
Propane
Butane
5.2 riydroaen 8.0
1 . g Carbon munorids 5.8
Isubutane 2 . 9 Carbon dioxide 6.7
IsopBntnne 0 . 8 Nitrogen (by diaerenoei 8.4
PHESBUHC: S . residue left after
L)ISrILLATE U O P ~ P ~ M The Pentme + Iwzbei paraifi~a 2.1
the motor fuel was distilled from the refined pressure d i e
tillate was suitable for Diesel or gas oil, or could be cracked W-nTEn. The water produced by converdion of the cotton-
in % second operation to increase the +d of motor fuel. seed oil showed a relatively high acidity of 3.6 normality.
This oil had the following properties: Aldehydes were also present in sinall quantities.

..
do. IF. 0.912 Initial b. 0.. * C. 236 CITED
LITERATUBE
UlrnlrEo DIBT'LLD" niiifllrsEo (1) Egluff andMorrell. IND. ENQ.CHBaa., 1 8 , 3 5 4 (19'26).
OYER 'r*MP. OVEB TtihlP. oYBB TEMP,
% 0C. % 0 c. % c, (2) Gallo and Carrelli. Atli mngl. MC. chin. pura appli&, 1923,
10 239 so 263 80 300 257.
20 247 80 269 90 351 (3) Mailhe, Compt. rend., 173, 358, 658 (1921);
176, 36, and 177,
80 261 70 282 95 883 202. a20 (1923).
ti) 257 (4) Waterman and Pcrqnin. Proe. Acad. Sn'. Amsterdam, 27. 83-92

No. 23 of the historical

reproductions is from a
oeintinn in the R O V d l Art
~alleryofDresdek, hav-
ing been reproduced from
an engrnving made from
the original by Hoermam.
The painting was a t
one time owned by, Dr.
Richard Meed, physlcxan
to the King of England.
This is the fifth Teniem
painting to be reproduced
in this series.

(Pbutagrapbia copiea of thla

regroduotion oan be obtsinad
from D. D. Beroisbeima.. 50
E m I l s t S t . , New Yark. N.Y
See page Il73,October. 1032,
issue.)