Dec., 1916
T H E J O C R N A L OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY THE
EFFECT
OF
TEMPERATURE
AND
1105 RATE
O F OIL
F L O W O N T H E P E R C E N T O F ORIGINAL OIL DECOMPOSED T O F O R M GAS A N D CARBON
Increase of temperature increased t h e decomposition of t h e starting oil which seems t o be t h e invariable rule in all hydrocarbon oils which have been subjected t o pressure a n d temperature treatment. When t h e r a t e of oil flow is increased t h e per cent of recovered oil increased, hence decreasing the decomposition of t h e starting oil used. This is in direct accord with theoretical considerations.l T h e differences between t h e per cent of recovered oil a n d I O O gives t h e per cent of starting oil going t o carbon a n d gas. T h e gas formed is usually scrubbed for its constituents which are soluble i n t h e scrubbing oil, leaving a gas which is usually utilized for heating t h e cracking tubes. T h e carbon formed is a small per cent of t h e original oil and is, in characteristics, similar t o ordinary lampblack. SUMMARY
\
)
3
I-The residue of a Pennsylvania crude oil after t h e gasoline h a d been removed was subjected t o t e m peratures of 600, 6 j o a n d 700' C. a t constant pressure of 150 lbs. a n d varying rates of oil flow of 17, 2 3 , 30, 36, 45 a n d 6; gal. per hr., for t h e purpose of gasoline formation from t h e residue. 11-The per cent of t h e recovered oil decreased with increase of temperature a n d increased with increase of t h e r a t e of oil flow. T h e specific gravity of t h e recovered oil increased with increase of temperat u r e b u t decreased with increase of t h e rate of oil flow. 111-Upon t h e basis of I O O gal. of oil'used t h e maxi m u m of 2 8 . 3 per cent of gasoline for every IOO used under conditions of 600' C. a n d 17 gal. per hr. was found. T h e best working conditions with this oil gave 2 2 . I per cent gasoline a t 6 j gal. per hr. a n d 650' C. IV-The minimum specific gravity of t h e gasoline formed was found t o be 0 . 7 4 5 a t 36 gal. per hr. a n d temperature of 600' C., under which conditions s g . j per cent gasoline was formed. V-The olefin formation in t h e gasoline cut ranged between 2 2 a n d 2 9 per cent in t h e recovered oil. Upon t h e basis of I O O gal. of oil used t h e minimum formation of 3 . 9 per cent a n d maximum of 7 . 9 per cent of olefins were recorded. VI-The per cent of oil going t o gas a n d carbon with t h e oil used gave a minimum of I O per cent a n d maxi m u m of 7 0 . 6 per cent. DEPARTMENT OF INORGANIC CHEMISTRY COLUMBIA UNIVERSITY, NEWYORKCITY
THE ESTERS OF OLEIC ACID AND THEIR HYDROGENATED PRODUCTS B y CARLETON ELLISAND LOUIS RABINOVITZ Received July 14, 1916
T h e hydrogenation of t h e glycerides of various unsaturated f a t t y acids in t h e presence of finely divided nickel has claimed t h e attention of numerous investigators. This problem, so important commercially, 1
Egloff and Twomey, Met. and Chem. E m . , 16 (1916), 245.
1106
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
has been thoroughly studied from both t h e technical and scientific standpoint. Very little work was done on t h e hydrogenation of esters of oleic acid other t h a n t h e glycerine esters. In 1906 Bedfordl studied t h e esterification of linolic and linolenic acid and t h e hydrogenation of these esters in t h e presence of finely divided nickel. The ethyl and methyl esters of these acids were prepared b y him as follows: T h e free f a t t y acid was boiled under reflux with a n excess of t h e alcohol in t h e presence of a small amount of sulfuric acid. T h e product was t h e n treated with a n excess of sodium bicarbonate solution. T h e oil t h a t separated out was decanted off and dissolved in ether. T h e ether solution was washed with water, dried with anhydrous sodium sulfate and then distilled t o remove t h e ether. T h e oil left behind was purified b y vacuum distillation. T h e ethyl esters of linolic and linolenic acid were hydrogenated in t h e presence of finely divided nickel a t about 180' C. Ethyl stearate was obtained in both cases. T h e work done on the esterification of oleic and stearic acid is more extensive. Berthelot prepared t h e mono-glycerides b y heating t h e f a t t y acid with a n excess of glycerine in a sealed tube. This method generally gave a product contaminated with t h e diglyceride.2 Other methods for t h e preparation of t h e glycerides of f a t t y acids involve t h e use of halogen substituted glycerides and sodium salts of f a t t y acids.3 Mixtures of mono- and di-glycerides of t h e higher f a t t y acids may be prepared by heating their triglycerides with an excess of glycerine t o zoo t o z j o c C in t h e presence of such catalytic bodies as finely divided aluminum oxide, thorium oxide or titanium Di-glycerides are prepared similarly t o t h e monoglycerides with only t h e modification t h a t a larger proportion of f a t t y acid is employed, or t h a t the dihalogen substituted glycerides are employed instead of the mono as in t h e case of mono-glycerides. According t o Grun6 pure di-glycerides may be prepared b y treating 3 hrs. a t 70' C, a solution of I part f a t t y acid in I'/~ parts sulfuric acid (78.3 per cent acid strength) with glycero-di-sulfuric acid prepared from 4 par-ts sulfuric acid (98.3 per cent strength) and I p a r t glycerine. On heating I part of a-mono-stearin with three parts of stearic acid t o 2 8 0 ' C. for 3 hrs. Berthelot obtained a,a--distearin. Another method employed b y him for the preparation of this substance was t o heat stearin with an exceSs of glycerine t o 220' C. or t o heat equal parts of stearic acid and glycerine t o 160' C. for 1 4 hrs. It was also prepared b y Guth by heating I moleculc a,a-dichlorhydrin with z molecules cf sodium stearate in a sealed t u b e a t 13-0t o r j o " C . for 6 t o 8 hrs. The a.p-isomer was prepared from a,P-dibromohydrin and sodium stearate. a,a-Diolein was prepared b y Berthelot on heating I 1 " c b e r die Ungesittigten Saiiren des LeinBls," Dissertation. Erlangen, 1906; Ber., 42 (19091, 1324. 2 "Chimie organique fondee sur la spnthese, Paris," 1860, Vol. 11; A n n . d e chim. et d e p h y s . , [ 3 ] 4 1 (18541, 420. 3 K r a f t , B e y . , 86 (1903>, 4343; G u t h , Zeit. j Uiolog , 44 (1903), 7 8 ; R o m b u r g , K e c . d . Irav. chim. I'ays-Bas, 1882, 186. 4 Seifen. Zlg., 1914, 1092. German p a t e n t 277,641, 1914, t o A-aamlooze Vennootschap A n t . J u r g e n s Vereenigde Fabtieken. 5 Ber., 38 (19051, 2284.
1'01. 8, NO. 1 2
part of a-mono-olein with j parts oleic acid t o 250' C. for several hours, or on heating olein with glycerol t o 2 0 0 ' C. for z z hrs. G u t h prepared t h e a,a-diolein from a,a-dichlorhydrin and sodium oleate. a,P-Diolein was prepared from a,P,dichlorhydrin and sodium oleate. Bethelot prepared pure triglycerides b y heating glycerine and f a t t y acids.' Scheij* heated glycerol with an excess of f a t t y acid in a slow current of air with t h e object of obtaining complete esterification b y removing t h e water as i t was formed. Tri-stearin can also be prepared b y heating mono-stearin or distearin with a n excess of stearic acid or tri-hydrin with sodium stearate. T h e method of preparation of tri-olein is similar in all respects t o the preparation of tri-stearin. Esters of f a t t y acids other t h a n glycerides are prepared b y dissolving t h e f a t t y acid in methyl, ethyl, amyl, etc., alcohols, then passing a current of hydrochloric acid through t h e solution and washing t h e product with water.3 Ethyl stearate was prepared with a yield of 80 per cent by heating stearic acid in a 3 per cent solution of dry hydrochloric acid in ethyl alcoh01.~ Pottevin5 prepared esters of oleic acid b y adding t o t h e mixture of t h e f a t t y acid and alcohol I per cent of finely divided hog's pancreas which had been exhausted with ether and alcohol.6 EXPERIlIENTAL
I n an investigation pertaining t o the hydrogenation of oils which has been in progress in this laboratory for some time, information was desired on t h e behavior of various esters of t h e f a t t y acids in the hydrogenation process and in connection with this work t h e oleic esters of methyl! ethyl. propyl, butyl, amyl and benzyl alcohols were prepared, also t h e glycerides of oleic acid. These products in t u r n were hydrogenated and t h e behavior of each during the hydrogenation operation nras noted. T h e following d a t a briefly indicate some of t h e results obtained during t h e investigation. M E T H Y L OLEATE
U.S. P. oleic acid
( j 6 . 4 g . ) was dissolved i n 2 j . 6 g. acetone-free methyl alcohol. The solution was treated with 0 . 7 g. sulfuric acid and then boiled for ,j1/2 hrs. The product, which separated into two layers on standing, 17-as washed a number of times with distilled water until free from sulfuric acid. The emulsion t h a t was obtained was broken b y heating for a short while on a hot :-cater bath. T h e oily layer was carefully decanted from t h e aqueous layer and dried. T h e oil did not possess any characteristic odor. I t was homogeneous and almost colorless. I t had an acid number of I j . 6 . The oil was treated with a I O per cent aqueous solution of sodium hydroxide in t h e cold. After intimate mixing t h e caustic soda vias drawn off and A n n . d e chim. e1 de p h s s . , [ 3 ] 41 (1854)> 420. Rec. d . tyaz'. chim. Pays-Bas., 18, 160. 8 I,ewkoiritsch, "Oils, Fats and Waxes," 1 (1913), 148. 4 Holzrnan, Arch. der Pharm., 236 (189Si, 409; Chenr. Cenl., 11, 69 (1898), 755, 5 Comyl. rend., 138 (1904), 3 7 8 ; Chem. Cent., I, 7 1 (19041, 787 6 Lewkowitsch, "Oils, Fats and Waxes," 1 (1913), 6-37. 1
3
Dec., 1916
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
t h e oil was washed with a s a t u r a t e d solution of sodium chloride until t h e wash waters ceased t o react alkaline. This t r e a t m e n t removed all of t h e free caustic soda leaving t h e oil a n d t h e saponified oleic acid intimately mixed with one another. T h e mixture of soap a n d methyl oleate was shaken with I j t o 2 0 times its volume of water a n d allowed t o s t a n d until t h e emulsion separated into t w o layers. The lower t u r b i d layer, containing most of t h e soap in solution, was drawn off a n d t h e operation repeated until t h e wash waters were free from turbidity. T h e dried ester was a liquid a n d was milky in appearance. On standing for several hours t h e turbidity disappeared from t h e upper portion of t h e ester. T h e acid number of t h e oil fell t o 1.3. The iodine number was found t o be 87.0. T h e theoretical iodine number of methyl oleate is 8j.8. T h e experiment was repeated with t h e object of preparing methyl oleate free from turbidity a n d gave t h e same results as obtained above. H Y D R O G E N A T I O K O F M E T H Y L OLEATE-A portion of methyl oleate containing I per cent of finely divided metallic nickel (reduced for I 5 t o 2 0 min. i n a s t r e a m of hydrogen a t 320 t o 3 j o o C.) was treated for about 2 hrs. a t about 180 t o 2 0 0 ' C. with hydrogen which was simply allowed t o bubble through t h e liquid as a brisk stream, thereby maintaining t h e catalyzer i n suspension. The mixture of oil a n d catalyzer was filtered in t h e hot oven. T h e filtered solid product obtained was white a n d crystalline. I t h a d a n iodine number of 0 . 4 a n d melted at 37' C. T h e melting point of this product as well as t h e melting point of t h e esters described below were determined as follows: A glass capillary about 2 in. long a n d open a t both ends was filled about I/6th full with molten oil. After t h e oil h a d solidified t h e capillary was attached in t h e usual way t o a thermometer a n d immersed i n a water b a t h having t h e upper part of t h e capillary above t h e surface of t h e liquid. T h e melting point noted was t h a t temperature a t which t h e oil became sufficiently molten t o be moved upwardly in t h e capillary b y t h e pressure of t h e water. ETHYL OLEATE
Oleic acid ( 5 0 g . ) , 5 0 g. of ethyl alcohol (sp. gr. 0.816 a t I j' C.) and I g. concentrated sulfuric acid were boiled for 4l/2 hrs. T h e product on standing separated out a heavy oil. Separation of oil in this manner was also observed in t h e oi her esterification experiments. The product was washed with distilled water until i t was free from alcohol a n d sulfuric acid. T h e emulsion of water a n d oil was treated i n t h e same way as t h e emulsion obtained in t h e case of methyl oleate. T h e dried oil had a straw-yellow color a n d possessed a n agreeable odor. T h e acid number was 19.8. T h e free oleic acid was removed with I O per cent aqueous sodium hydroxide according t o t h e method described under methyl oleate. The acid number of t h e ethyl oleate was reduced b y this t r e a t m e n t from 19.8 t o 0.6. I t s iodine number was 83.3. T h e iodine number of pure ethyl oleate is 81.9. H Y D R O G E N A T I O K O F E T H Y L OLEATE-A portion of t h e ethyl oleate containing I per cent of metallic nickel
1107
(reduced for 15 min. i n a stream of hydrogen a t 320 t o 3 j o " C.) was exposed t o a rapid current of hydrogen for about 2 hrs. T h e oil was filtered through a n ordinary filter paper in t h e hot oven. T h e product melted a t 31' C. I t s iodine. number was 5.3. PROPYL OLEATE
Oleic acid (56.4 g.), 24 g. propyl alcohol (Kahlbaum) a n d 0.4 g. concentrated sulfuric acid were boiled for 4l/* hrs. T h e mixture was washed free from sulfuric acid a n d alcohol a n d t h e oil was dried in t h e usual way. T h e acid number of t h e product was 1 1 . 2 . I t was t h e n treated with alkali according t o t h e method described above. The acid number was reduced b y this t r e a t m e n t t o 0.5. T h e product was practically colorless a n d without odor. Like methyl oleate i t possessed a marked turbidity, b u t on standing t h e upper portion of t h e product became clear. The iodine value of t h e product was found t o be 77.9. T h e iodine value of pure propyl oleate is 78.4. H Y D R O G E N A T I O N O F P R O P Y L OLEATE-The hydrogenation in this case was carried out under conditions practically identical t o those employed in t h e hydrogenation of methyl a n d ethyl oleate. The hardened oil had a n iodine number of 1.3. I t melted a t 2 7 ' C. ISO-BUTYL
OLEATE
T h e amounts of material employed in t h e preparation of butyl oleate were 56.4 g. oleic acid, 29.6 g. isobutyl alcohol ( C . P.)a n d 0 . j g. concentrated sulfuric acid. T h e mixture was boiled for s1/4 hrs. a n d t h e n washed free from sulfuric acid a n d steam-distilled until t h e distillate came over odorless. T h e oil had a n acid number of 9.3. Treatment with alkali reduced t h e acid number t o 0.4. T h e ester was of a strawyellow color a n d practically odorless. I t h a d a n iodine number of 75.7. T h e iodine number of pure iso-butyl oleate is 75.1. H Y D R O G E N A T I O S O F ISO-BUTYL OLEATE-The ester was hydrogenated for about 2 hrs. in t h e presence of I per cent metallic nickel (reduced for I j min. a t 320 t o 350' C.). T h e temperature of hydrogenation was 180 t o 2 0 0 ' C. The hydrogenated product was soft a n d translucent a n d distinctly crystalline. It somewhat resembles crude paraffin. I t had an iodine va!ue of 0 . 2 a n d melted a t 2 j ' C. AbIYL OLEATE
Amyl oleate was prepared as follows: 56.4 g. and oleic acid, 33.2 g. amyl alcohol (B. P. 13-132) 0.9 g. concentrated sulfuric acid were boiled under a reflux condenser f o r s1,J4 hrs. T h e product was washed free from acid a n d steam-distilled until t h e distillate came over odorless. The dried ester h a d a n acid number of 4.5. After t r e a t m e n t with alkali solution t h e acid number fell t o 0.7. T h e ester was brownish yellow in color and possessed a n odor characteristic of fats a n d oils. I t s iodine value was 71.3. T h e iodine value of pure amyl oleate is 7 2 . 1 . H Y D R O G E N A T I O N O F A M Y L OLEATE-The product was hydrogenated in t h e usual manner under conditions similar t o those employed in t h e previous experiments. The hydrogenated product mas soft a n d non-homo-
I
108
T H E JOrRLXAL OF I N D l - S T R I A L A N D ENGINEERING C H E M I S T R Y
geneous, consisting of a liquid oil and a crystalline body. It resembled crude paraffin. I t had an iodine value of 1.7 and melted a t 2 2 ' C. G L Y C E R I N E 0 LE AT E
Oleic acid (56.4 g.) a n d 18.4 g. glycerine were heated for 5 hrs. a t 240' C. with continuous stirring. The oily product was washed several times with warm water a n d dried. I t s acid number was 0.6. It was dark in color, very viscous and not uniform in appearance. I n cool weather a crystalline body formed which rendered t h e ester opaque. T h e iodine number of t h e product was 69.4. Pure glycerol mono-oleate has an iodine number of 71.3. H Y D R O G E S A T I O N O F G L Y C E R Y L OI,EATE-The ester was hydrogenated in t h e usual way. Treatment with hydrogen for about 2 hrs. a t 180 t o zoo' C. gave a product which melted a t 59' C. and possessing an iodine number of 6.5. T h e hydrogenated product was similar in appearance t o a good grade of hardened cottonseed oil, except t h a t it was somewhat darker in color. BENZYL OLEATE
Oleic acid ( j 6 g.), 49 g. benzyl alcohol a n d I g. concentrated sulfuric acid were boiled under reflux for 6 hrs. T h e product was steam-distilled until the distillate came over odorless. T h e oil was then treated with alkali t o remove t h e free oleic acid, dried and distilled a t 2 5 t o 40 mm. pressure. The oil came over largely a t 2 7 5 l o 2 8 5 " C. I t was light yellow in color and practically odorless. I t s acid value was 0.7, and t h e iodine value was 62.3. The iodine value of pure benzyl oleate is 68.2. I n another case, the same amounts of benzyl alcohol and oleic acid were used b u t t h e amount of sulfuric acid was reduced t o 0.j g. T h e mixture was heated for jl/, hrs. a t 14 j t o I j o o C. T h e product was steam-distilled, washed free from acid and dried. I t had a n acid number of 8.7. Treatment with sodium hydroxide solution reduced t h e acid number t o 0.4. The ester was of a dark brown color, almost odorless and had a n iodine value of 54.5. H Y D R O G E K A T I O N O F B E K Z Y L OLEATE-Hydrogenation i n t h e presence of finely divided reduced nickel gave a product which had a n iodine value of 6.3 and a melting point of 28' C. B E H A I I O R O F O L E I C A C I D WITH P H E K O L , R E S O R C I K A N D
BETA-NAPHTHOL Oleic acid (28.2 9.) and 37.6 g. phenol were boiled f o r 4 hrs. under reflux. The product was then washed with boiling water until it was free from phenol. T h e acid number of t h e dried oil was 201. Oleic acid (28 g.) a n d 2 2 g. resorcin were treated for 4 hrs. at 180 t o zoo" C. A considerable amount of t h e resorcin was lost b y sublimation, T h e product darkened considerably. I t was purified b y washing with h o t water a n d drying. I t s acid value was 197. Betanaphthol when heated with oleic acid for several hours t o 200' C. failed t o combine with it. OLEIC A C I D AND A K I L I N E
Aniline (24.4 g.) and 37 g. oleic acid were heated a n d e r a reflux condenser for 4 hrs. a t 170 t o 190' C.
YO^. 8. NO. 1 2
The mixture darkened considerably. It was steamdistilled until t h e distillate was free from aniline. The acid number of t h e steam-distilled product was 30.5. It became solid on standing. The substance was treated with a solution of sodium hydroxide and washed free from alltali and sodium oleate. T h e acid number of t h e product was reduced t o 3.6. T h e product melted a t 3 4 " C. It was dark brown in color and had a greasy feel. H Y D R O G E N A T I O N O F T H E PRODUCT-The material was hydrogenated for z hrs. a t 190 t o 200" C. in t h e presence of I per cent finely divided reduced metallic nickel. The hydrogenated product was filtered in t h e hot oven. I t had a n iodine number of 3 0 . 3 . T h e iodine value of the unhydrogenated substance was 69.5. T h e iodine value of oleic anilide is 71.6. T h e product melted a t 76" C. and was very hard and brittle. This and other allied bodies are being made t h e subject of further investigation in this laboratory. S U $1 M A R Y
I-The esters of oleic acid with methyl, ethyl, propyl, iso-butyl. amyl and benzyl alcohols and also glycerine were prepared. These bodies were of oily consistency a n d liquid a t room temperature. 11-These esters were hydrogenated in a liquid state in the presence of finely divided reduced nickel and products were obtained t h a t were practically saturated. 111-The nature of t h e alcohol did not seem t o affect t o a n y great extent t h e rate or degree of hydrogenation of t h e oil. IT'--A product derived b y heating oleic acid and aniline was found t o hydrogenate readily t o form relatively a very hard product. 92 GREEA-~COOD AVBPI'UE ~IONTCLA XEIV I R , JERSEY ~
-_
WATER ABSORPTION BY VULCANIZED FIBER By ROLLING. MYERS Received August 3, 1916
The writer conceived t h e idea of using vulcanized fiber for a golf ball covering, i. e., as a substitute for t h e more expensive g u t t a percha or rubber. T h e TABLEI
Expt. NO.
.. z..... 1.. .
Color and
Texture Hard Red
3..... 4..... 5.."..
GRAMS WEIGHT Time After Per cent Immersed ImWater Inches Hours Original mersion Absorbed 0.591 0.866 46.53 4 1 X 1 X l/32 0.890 48.58 0.599 0.558 0.810 46.16 0.569 0.846 48.66 2.5 X 2.5 X 1/18 5.5 6.700 9.490 41.64 45.07 9.72 1,222 1.704 39.44 4 1 x 1 X :/Le 1.254 1.751 39.63 1.275 1.742 36.62 1.285 1 ,766 37.46 1 X 1 X liis 4 1.341 1.785 33.10 1.208 1.610 33.27 1.327 1.764 32.93 1.300 1.725 36.69 3.7 X 1 . 1 X ~ / I 7.360 9.790 33.08 2 X 2 X1/n 4 6.995 51 06 1 x 1 X'/1e 1.721 2:3jl 37:76 1.254 1.772 41.30 1.829 2.599 42.09 1.546 2.178 40.87
Size in
.
6.....
7... . 8.....
9
., .. . . .. . ... IS..... 19... . . 10.
11..
Flexible
12.... 13. " . . 14,.~. . 15 . . . ~ .Hardgray 16.... 17.. .
I
.
AVERAGEABSORPTIOH(PSRCENTAGBS) FOR 4 HOURSIMMERSION Dimensions Hard Red Flexible Red Hard Grav 1 X 1 X'/sn in. 47.98 51.06 1 X 1 X l j in. ~ 38.25 3i:j4 40,50
