888
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 C H E M I S T R Y
1701. 8,
NO.IO
T h e oil was hydrogenated a t 190 t o 200' C. for 5 hrs. It hardened t o a melting point of 4 j t o 46' C. DOGFISH OIL--A number of samples of this oil have been examined in this laboratory and have proved somewhat difficult t o hydrogenate. I n one case, a sample of the oil was agitated with copper hydrate for I hr. and then treated with hydrogen, using a
of the presence of phosphates or chlorides was obtained. A blank test on t h e original copper hydrate showed no sulfates or sulfur present, indicating t h a t sulfur compounds are removed from f a t t y oils containing them, by treatment with copper hydrate in the manner stated.
EFFECT O F HALOGENS, HALOGEBCOMPOCBDS, SCI,FUR,ETC.,O N HYDROGENATION OF COTTONSEED OIL Catalyzer: Xickel Oxide (5 per cent of the weight of t h e oil) reduced in oil a t 250' C. for 112 hr. Expt. Substance Per cent Temp. Time Effect on NO. Added Added C. Hrs. Oil 1.0 Bromine 200 2 No hardening 1 .o 200 2 1 . 0 200 Iodine 1 . 0 200 0.5 200 0.5 200 200 Antimony Bromide 1 . 0 1.0 200 2 210 Sodium Chloride 5.0 Oil hardened 2 1/2 210 5.0 Zinc Chloride Oil polymerized 21/2 7 1 .O 200 Slight hardening 2 1/2 1.0 200 Oil Hardened 2v2 7 (CH) 200 0.5 8 2'/2 Tin Chloride 1 . 0 200 9 2 0 ,5 200 10 Sulfur Slight hardening 21/2 0.5 200 Oil hardened 10 (CH) 2li2 200 11 1.0 X o hardening 21'2 200 1.0 Oil hardened 11 (CH) 21/2 . . . 200 Blank 21/2 Sulfur 0.1 210 3 112 12 1.0 200 R e d Phosphorus 13 2 Slight hardening Oil hardened 1.0 200 2 13 (CH) 0.5 200 Slight hardening 2 14 Oil hardened 0.5 200 14 (CH) Sulfur Chloride 1.0 200 15 1.o 200 15 (CH) 200 1.0 16 (AS2031 200 1.0 L Mercury 17 , . . 200 Blank 21/2 1.0 200 21/2 No hardening 18 Lead Stearate 1 .o 200 Lead Oleate 19 21/2 1.0 200 2112 19 (CHI (CH) after a n experiment number indicates treatment with copper hydrate before hydrogenation.
of tests with such bodies and in some cases t h e effect of copper hydrate thereon is indicated.
through t h e oil, t h e temperature of t h e oil being held a t z j o 0 C. for ' / 2 hr., then lowered t o 190 t o zoo' C. and maintained a t t h a t point for 3 hrs. The oil hardened to a melting point of 4 j' C. Probably t h e most difficult t o handle of all the lowgrade oils is t h a t derived from city garbage. There are two methods of reclaiming this grease, one b y boiling t h e garbage with water and allowing the oil t o rise t o t h e t o p when it is dramx off, t h e other b y extracting t h e oil with solvents. This oil is usually denatured with or contains t a r , and as it is derived from all manner of materials which would vary from d a y t o d a y it is quite probable t h a t no fixed method of treatment can b e employed. Up t o t h e present time no entirely satisfactory method has been found t o refine and successfully harden this material in a manner capable of general commercial application. EXARIIZATION
O F COPPER HYDRATE
The copper hydrate which had been used t o detoxicate the cod and other oils was examined t o determine what bodies qrere taken u p from the oils b y t h e treatment. F a t t y material was remoxTed from the copper hydrate by extraction with solvents and the residue was analyzed. Sulfates \\-ere found but no evidence
O T H E R CATALYZER P O I S O K S
NEW JERSEY
TESTING LABOR.4TORIES. MONTCLAIR
EXPERIMENTAL NOTES ON THE PREPARATION OF FIRE-PROOF WRITING PAPER By ROLLING. MYERS Received M a y 22, 1916
The writer made a careful study of t h e methods for t h e preparation of fire-proof writing paper, as well as of t h e character of t h e paper obtained b y such processes. H e extended this work t o include the paper produced from crysotile fiber when this was combined, as pulp, with white or lightly tinted precipitated compounds of t h e metals. These pulps were prepared a t about 100' C. The method used in t h e preparation of the paper was identical, in many respects, t o t h a t employed by t h e Japanese in t h e preparation of their hand-made paper from t h e vegetable and animal fibers. Each sample prepared was tested for porosity, tensile strength and permanence t o temperatures varying from 900-1000° C. during a period of about I O hours: 80 or 90 samples of paper were prepared. T h e following inferences appear t o be truthful interpretations of t h e experimental studies: I-The commercial varieties of crysotile fiber used as raw material in t h e preparation of the paper were not to be distinguished in respect t o mutability a t high temperature, porosity, tensile strength and flexibility. z-T'l'ithin certain limits, variations in the quantity of t h e chemical reagents used for a given weight of fiber produced no observable gain in tensile strength and t h e reduction of porosity in the paper prepared. 3-Tensile strength and closeness of texture of t h e paper prepared appears t o be obtained best from pulps containing precipitated hydroxides, arsenites, silicates and tungstates. Perhaps the best paper prepared, in respect t o t h e properties referred to, was t h a t obtained from a pulp containing a considerable excess of magnesium arsenite in a n alkaline mixture. This paper was far in advance of any of t h e commercial papers examined. It might be well t o note t h a t most of t h e above
Oct., 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 E N G I N E E R I N G C H E M I S T R Y
precipitates are flocculent i n character, a n d t h a t increase in closeness of texture a n d tensile strength is not always concurrent. 4-Substances like kaolin or pulverized mica, when incorporated with t h e pulps, do not seem t o a d d anything t o t h e paper produced. 5-In all t h e pulps, there exists a certain amount of adhesion between t h e fiber a n d t h e precipitated substance. This attraction is greatest for t h e precipitated salts of t h e more basic metals like calcium a n d magnesium, a n d least for t h e more acid metals like silver or lead. This adhesive effect may be due t o some chemical action between t h e fiber a n d t h e precipitate. 6-The degree of porosity of all samples increased rapidly when t h e y were heated for a n y length of time above 100’ C., t h e cause of t h e increase of porosity being undoubtedly t h e contraction i n bulk of t h e precipitated substance in t h e paper. 7-Tensile strength, a n d smoothness of surface only, seem t o be enhanced b y pressing with a warm iron. 8-From t h e identity of crysotile t o “ t r u e asbestos” a n d t h e general character of t h e foreign substances used, t h e indications are p r e t t y clear t h a t no foreign substance either acting b y itself or with others can increase t h e chemical stability of asbestos towards fire. 9-Under the e x p e r i m e n t a l c o n d i t i o n s set f o r the heat or “fire test,” i. e., a t e m p e r a t u r e v a r y i n g f r o m 9001000’ C . w i t h a t i m e i n t e r v a l of I O h o u r s , i t s e e m s probable t h a t n o p a p e r c o m p o s e d of i n c o m b u s t i b l e s u b s t a n c e s c o n t a i n i n g m o l e c u l a r water i s fire-proof or c a n be made fre-proof. This inference c a n be extended t o “ t r u e asbestos” on account of its general similarity in properties a n d composition t o crysotile. It i s t r u e , however, t h a t several samples of paper prepared b y t h e writer, were not seriously impaired when exposed t o a dull red heat for a n hour or so. These samples still possessed considerable flexibility a n d could be handled, if a certain degree of care was used. There are some varieties of “ t r u e asbestos” which cling t o their zeolitic(?) water with a great deal more persistence t h a n crysotile. Paper made from asbestos of this sort would of course be quite well adapted for t h e preparation of, e. g., fire-proof records. I n general t h e n , when lower temperatures a n d shorter time limits are considered, it is very probable t h a t a n entirely satisfactory fire proof paper can be prepared. Io-In respect t o fire-proof inks, solutions of ferric, chromic a n d cobaltous nitrates a n d chlorides were used. They stood t h e “fire test” well. According t o Franz Cirkel in t h e Canadian Government bulletin “Asbestos-Its E x p l o i t a t i o n a n d Uses” no inks up t o t h a t time prepared would s t a n d a red heat-excepting perhaps those produced from platinum. For inks other t h a n those prepared from platinum, one condition seems t o be necessary, t h a t t h e acid oxides in t h e paper should be kept in excess. T U L A NUEN I V E R S I T Y OF LOUISIANA, N E W ORLEANS
889
A HIGHLY UNSATURATED HYDROCARBON IN SHARK LIVER OIL By MITSUMARUTSUJIMOTO Received March 21, 1916
Although usually small i n their quantities, hydrocarbons seem t o occur i n f a t t y oils more frequently t h a n hitherto considered. Some of t h e m may possibly be utilized for t h e identification of individual fats a n d oils. P. Matthes a n d 0. Rohdeckl isolated a hydrocarbon of t h e composition C30H48 from cacao butter. I t was considered most likely identical with amyrilene. T h e former chemist, together with H. Sander,2 obtained a hydrocarbon from laurel oil a n d named i t a n d formed laurane. It h a d t h e composition CQ0Hd2 a fine needle crystal of m. p. 69” C. from its alcoholic solution. According t o another investigation of Matthes a n d W. Heintz,3 a hydrocarbon of t h e composition C20H42(m. p. 6 9 ” C.) occurs in parsley seed oil a n d was named b y t h e m petrosilene. A hydrocarbon, CB1HG4 (m. p . 67-68” C.), is s t a t e d t o occur in kbsam seed oil (Power a n d Lees). I n t h e domain of animal oils, especially in insect oils, hydrocarbons occur in considerable amounts a n d are characteristic of them. So, from chrysalis oil, Menozzi a n d Moreschi4 isolated two hydrocarbons: one of t h e m had t h e composition C28H58, melted a t 62. j” C. a n d was optically active, while t h e other melted a t 41-42’ C. Further, hydrocarbons were obtained from cantharide and Melolontha oils.’ T h e s t u d y of substances, beside sterols, in t h e unsaponifiable m a t t e r of oils and fats, so-called “stearolfree unsaponifiable matter,” has lately much attracted t h e interest of t h e oil chemist. These substances consist mainly of hydrocarbons, alcohols a n d ketones. Thanks t o t h e classical researches of Windaus, a n effectual means for t h e separation of sterols from these substances was int‘roduced into f a t analysis b y t h e use of digitonin. T h e reports of J. Marcusson a n d G. Meyerheim,e as well as P. Berg a n d J. Angerhausen,? have satisfactorily confirmed t h e importance of t h e investigation of a stearol-free unsaponifiable matter. T h e latter chemists have devised, on t h e ground of t h e examination of this matter, a differentiation method of mowrah a n d shea butters, t h e distinction of which is not feasible by ordinary f a t analysis. Of marine animal oils, shark liver oil contains, as is well known, a high percentage of unsaponifiable matter, and appears t o furnish a very suitable material for t h e above-mentioned investigation. I n t h e literat u r e of fats, however, we find b u t meagre descriptions of t h e oil; some statements even appear t o be conflicting a t a glance. Ber.. 1908, 41. Arch. d . Pharm., 1908, 165. a Be?., 1909, 325. ‘ R e n d . accad. dei Lincei, 1908, 95. Mosquito fat is likely to contain hydrocarbon (W Normann, Chem. Rev., 1913, 187). 6 Z . angew. Chem.. 1914, 201. 7 Z . Nahr. Genussm., 1914, Bd. 27, 723; Bd. 28. 73, 145. 1
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