Sept., 1916
801
T H E JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
I n another case a sample of crude solvent naphtha, per cent of which boiled above 160’ C., was treated with I per cent of sulfuric acid of 98 per cent strength and t h e mixture was agitated for 2 hrs. It was t h e n freed from acid and distilled under ordinary atmospheric pressure a t 190’ C. The residue from this distillation was distilled t o 16j ’ C. under a vacuum of 29 in. a n d the residue from this second distillation was a thick, very viscous substance, dark in color a n d possessing a strong unpleasant odor which was quite different from t h e harder resin obtained from t h e solvent naphtha fraction (b. p . 160-180’ C.) used above. The yield of this viscous material amounted t o 1.9 per cent of t h e solvent naphtha taken. An interesting observation on t h e unsaponifiable nature of t h e coumarone resin was made with one of t h e harder samples obtained in this investigation. Solutions of t h e resin in benzol, etc., were applied t o glass t o form a thin film of t h e resin and when dry t h e plates were immersed in a liquid made by agitating Portland cement with water during t h e setting period. il t h i n paste of t h e cement and water was obtained in this way which was alkaline in refction. T h e effect of this alkaline extract on t h e coumarone resin film was compared with t h e results obtained b y similar treatment of films of drying oils and acid resins. I n t h e case of the saponifiable bodies, t h e destructive effect of the alkali was quickly observed, b u t with t h e films of coumarone resin no disintegrating action was noticed even after exposure t o t h e alkaline liquid for a period of several days. T h e films clouded a n d in some cases turned white, b u t t h e hardness a n d integrity of t h e coating did not appear t o be affected. This property of t h e resin is of interest in connection with t h e production of a coating for concrete and stucco which is entirely resistant t o t h e action of concrete alkali.’ 2;
92 GREENWOOD AVENUE kIONTCLAIR, XEW JERSEY
ON CALAMARY OIL By MITSLXARU TSUJIMOTO Received August 2 , 1915
This oil (Japanese: “Ika-abura”) is obtained from t h e internal organs, especially the livers, of various species of cuttle-fish, among others t h e calamaries (the genera Ommastrephus and Loligo), and is a byproduct of t h e manufacture of t h e so-called “dried cuttle-fish” (Japanese: ‘.‘Surum6”). Although the annual production of t h e latter in J a p a n amounts t o about 9,375,000 k g . , the oil has been brought into market rather lately. According t o a report of the Yokohama Fish Oil Company, t h e production of the oil in Hokkaido and other districts of J a p a n has annually increased, and it is stated t h a t t h e Iwat6 district (the northeastern coast of Honshiu) alone produced about 50,ooo kg. of t h e oil in 1913. If all t h e fish used for t h e drying purpose were utilized, t h e production of t h e oil would be increased very considerably. The oil is prepared b y boiling t h e organs of t h e fish with water. T h e process appears t o be rather primitive See U. S. Patents to Ellis, Nos. 999,439, 999,708 and 1,005,818.
and rough, judging from the quality of the commercial oil. T h e oil-content is recorded as about 2 t o 3 per cent of the wet raw material. J . Lewkowitsch, in his well-known work on oils, fats and waxes, has described t h e livers of decapods t o be very rich in oil, b u t hitherto any further information on such oils seems t o have been lacking. T h e sample of calamary oil examined b y t h e author was obtained from t h e Yokohama Fish Oil Company; i t was produced in Miyako-ch6 in the Iwat6 prefecture. T h e oil is a brownish red liquid of a very unpleasant odor; when spread on skin, a fishy smell peculiar t o fish oils was observed. T h e taste is also very disagreeable. Cooled b y ice, it solidified in a few hours. With concentrated sulfuric acid, a dark brown coloration with a slight purple tinge was formed. The chief properties of t h e oil were determined with the following results:
. .. . . 0.9316 3.88
Specificgravity (15°/40C.).. Acid value.. . . . . . . . . . . . Saponification value., , , , , . , Iodine value (Wijs). . . . . , , . , , Refractive index ( Z O O C.).. . . , Butyro refractometer ( Z O O C.)
..
189.64 177.02 1.4806 84.0
Tinsanonifiable matter.. 1.14% ,” GIyc&ine (extraction method). . . . . . . . . . . 10.24% Oxidized acids.. . . . . . , . 0.69% Melting point of the mixed f a t t y acids.. . . . 35-36OC. Polybromide of the mixed fatty acids.. , 57 .45yo
.
T h e polybromide was obtained b y dissolving t h e mixed f a t t y acids in ether, and dropping br’omine into t h e ice-cooled solution. I t is a white powder, turning brown at 200’ C. and decomposing at 2402 5 0 ’ C. without prexious melting. I t s bromine content was determined t o be 70.91 per cent by t h e Carius method. Calamary oil dries in t h e air when exposed in a thin layer, t h e drying property nearly corresponding t o t h a t of sardine oil. The oil is not refined b y Kambara earth with good results. I t is best refined b y alkali in the following way : T o I O O g . of the oil, j cc. of 2 0 per cent aqueous solution of caustic soda is added and stirred well. On gentle warming t o about 60-70” C. t h e brown emulsion “breaks,” with t h e separation of a dark viscous precipitate of coloring matters and impurities (the brown coloration is probably due t o the soaps of oxidized acids). A little further heating suffices, and t h e oil is then filtered from the precipitate. The refined calamary oil is pale yellow; its smell somewhat recalls t h a t of cod liver oil, the unpleasant odor being nearly removed. The Yokohama Fish Oil Company values the calamary oil as about equal t o herring oil. The refined calamary oil may be used as a substitute for cod liver oil, although its medicinal effects require some investigation. The oil may also be used for tanning, burning and soap-making purposes. T h e oil, especially t h e refined, is easily hydrogenated by nickel catalyzer, giving, according t o the author’s experiment, a white tallow-like fat of m. p. 43-44’ C. and iodine value 49.25. T h e chief use of t h e oil will, therefore, probably be as a raw material for hardened oils, as its price is below t h a t of other fish oils. INDUSTRIAL EXPERIMENT STATION TOKYO, JAPAN
