In a previous paper, some experimental results were shown relating to the adaptabiliuy of liquid butane as an extraction solvent for soybean extraction, the extraction condition and the quality of the products. The present study has been done in order to confirm these results in a series of bench scale experimentation under increased pressure using an extractor of about 1015kg charge of soybean flakes per batch. The results of the present study are as follows : 1. The soybean meals of residual oil content of about 1% are obtained by extracting soybean flakes of about 0.4mm thickness for 2 hours at 40°C. 2. Since the solvent of the meals is easily removed at a slightly elevated temperature (5060°C), the meals can be completely freed from the solvent without causing any denaturation of the protein in the meals. 3. Butane extracted oil is light-colored and has a low acid value and lecithin content, so that the oil is refined easily with only a smaller loss and the deodorized oil has a good flavor and a good stability in the A.O.M. test.
Bleaching agents and conditions for bleaching extracted soybean oil gums under ordinary pressure have been studied. By removing the aqueous phase separated after bleaching, the use of sodium chlorite and phosphoric acid as a bleaching-aid was effective for lowering the water content of gum and for reducing the amount of bleaching agent remaining in the treated gum. The amount of necessary bleaching agent actually consumed in the bleaching was very little, however, a large excess of bleaching agent was necessary and “Aging” process was also necessary in order to achieve a good bleaching effect. Use of hydrogen peroxide concurrently with benzoyl peroxide was also proved to be effective. In the preparation of paste lecithin, bleaching and simultanous drying could be achieved by adding the bleaching agent to the gum and by subsequent evaporation under vacuum. Sodium chlorite with acetic acid, phosphoric acid or citric acid as a bleaching-aid was proved effective. In this case, simultaneous use of hydrogen peroxide and benzoyl peroxide gave a better result. This was ascribed to the preferential bleaching function of these bleaching agents for different coloring substances in the gum, from the result of spectrophotometric analysis of the gums before and after bleaching.
In order to prevent the deterioration of edible oils during frying, the preventing effect of protection from exposure to air was examined. In soy bean oil, 24 pieces of tofu (soy protein curd, 70g weight and 75% moisture) were continuously fried during 7 hours at 110°C and 185°C under the condition that the oil surface was covered and protected from exposure to air by means of metal float. The same oil was repeatedly treated under the above mentioned condition, and after ten times of treatment the chemical and physical properties of the treated oil were compared with the case of frying without the protection. As a result, it was confirmed that the oxidation and the polymerization of the oil could be almost prevented, but hydrolysis of the oil has been promoted, contradictorily.
Authors made research to find the structure of the four kinds of hydrogenated fats (whale oil, fish oil, soybean oil, rapeseed oil) which are most useful glycerides in our edible fat and oil industries. Each fat was separated by fractional crystallization and the typical fractions were analyzed by means of pancreatic lipase hydrolysis. As a result, the main structure of each fat was determined and it was concluded that the predominant isomer was unsymmetrical in both disaturated-monounsaturated and the monosaturated-diunsaturated glycerides.
(1) The characteristics of the various lipids (acetone-soluble lipid, lecithin, cephalin and sphingolipid) contained in the liver of yellowtail, Seriola quinqueradiata, were studied from the view point of lipid metabolism of fish. (2) Fresh livers of the fifty five fish caught in the Koyawata fishing ground near Odawara City (west part of Kanagawa Prefecture, Japan) on the 12th of April, 1959 were extracted with acetone. The acetone extract was further treated with acetone to yield the fatty oil as acetone-soluble lipid. (3) The acetone-soluble lipid was obtained at yield of 8.84% to the fresh livers. (4) Lecithin purified from the alcohol soluble fraction was obtained at yield of 0.22% to the fresh livers. Spectrophotometry of the alkali-isomerized liquid acids indicated the presence of conjugated tri- to pentaenoic acids in the lecithin. According to rough calculation, composition of the conjugated fatty acids of the lecithin in the livers seems to consist of 34.98% saturated and 65.02% unsaturated acids. (5) Cephalin purified from the alcohol insoluble fraction was obtained at yield of 0.72% to the fresh livers. Fractional precipitation of the purified cephalin from chloroform with absolute ethanol yielded five groups and showed the presence of phosphatidyl serine, phosphatidyl ethanolamine and inositol phosphatide in the cephalin. Spectrophotometry of the alkali-isomerized liquid fatty acids showed no presence of polyenoic acids. According to simple calculation the conjugated fatty acids of the cephalin in livers consist of 30.13% saturated acids and 69.87% unsaturated acids. The paper chromatography indicated the presence of myristic, palmitic, stearic, zoomaric, oleic, erucic, linolic and linolenic acids in the lecithin and cephalin obtained from the livers.
The order of reaction and reaction velocity constants were sought by comparing esterification velocity by adding dilute aqueous solutions of mono-, di- and trihydric aliphatic alcohols to different kinds of rice brans containing various degree of free fatty acid. Change in properties of fatty matter and its composition were also examined by adding aqueous solutions of either methanol or ethanol to a large quantity of rice bran. As a result it was found that the apparent ester formation reaction due to the addition of monohydric alcohol is in accordance with the secondary reaction and that the velocity is in the order of n-butanol_??_n-propanol>ethanol_??_methanol. As the dihydric alcohol ethylene glycol and 1, 3 butylene glycol were employed, and as the trihydric alcohol glycerin was used. In this case ester formation reaction velocity was in the order of ethylene glycol>1, 3 butylene glycol>glycerin and was only 1/51/10 of monohydric alcohol. Especially slow is the esterification velocity of glycerin. Change in properties of the fatty matter due to the lapse of reaction time and its composition were examined by adding aqueous solution of 20wt% of either methanol or ethanol to a large quantity of rice bran. As a result the presence of about 50% methyl or ethyl ester was observed. From this result the possibility of high yield esterification was proved. It became apparent that the lipase which exists in rice bran performs the hydrolysis of fatty matter and that it carries out concurrently the ester synthesis of free fatty acid and monohydric alcohol.
Shea butter was molecularly distilled by the centrifugal molecular distillation apparatus, and unsaponifiable matters contained in each fractions were determined. Concentrated unsaponifiable matters were found in both the first fraction and the residue. The main fraction was obtained with 72per cent yield, which contained only a little unsaponifiable matter. It was comfirmed that β-amyrine and lupeol existed in the first fraction and poly-isoprene in the residue.
Various polyoxyethylene (POE) sorbitan fatty acid esters were synthesized, and some properties of these reaction products were studied. Solubilizing powers of azobenzene and clouding points of aq. solutions of POE sorbitan monolaurates were greatly affected by not only the amounts of added ethyleneoxide (EO), but also the constituents of used sorbitan monolaurates as raw materials and reaction conditions of additional polymerization of EO. O/W emulsions of liquid paraffin were prepared by various POE sorbitan fatty acid esters combined with Arlacel 60 (sorbitan monostearate) in various ratio, and were studied about viscosities of emulsions, HLB values and inversion temperatures. Viscosities of emulsions were measured by MacMichael's rotating cup viscometer and were compared by the torsional angles of viscometer at 50 r.p.m. with each sample. From the diagrams of viscosities of O/W emulsions vs. combination ratio of two emulsifiers, there were two maximum values, except POE sorbitan trioleate. Deviations between experimental values of HLB and calculated values by Griffin's equation were not so great as that of sorbitan fatty acid esters. Inversion temperatures became higher when ratio of POE sorbitan fatty acid esters increased. When ratio of emulsifiers to oil phase or ratio of oil phase to water phase were increased, inversion temperatures became lower and their ranges became wider.
The quarternary ammonium salts were obtained by treating α, β-unsaturated compounds such as N-dodecylacrylamide and dodecyl acrylate with hydrochloride of tert-amines such as pyridine and trimethylamine. The reaction was carried out by heating an alcoholic solution of an equimolar mixture of tert-amine salt and α, β-unsaturated compound in a sealed tube for 1014 hours. However, triethylamine hydrochloride was unreactive. Its nonreactivity is propably due to steric hindrance. The structure of reaction product of dodecyl acrylate and pyridinium chloride was proved by comparing with that obtained directly from dodecyl β-chloropropionate and pyridine. Therefore, it is expected that the other products had similar structure. It was found that these products were surface active.
We have succeeded in hydrogenation of nitrobenzene to aniline in quantitative yield in the vapor phase on the same hydrogenation condition mentioned in the previous report (27) by using pilled copperchromium-manganese oxide catalyst, prepared by the new method. The preparation of the catalyst (KW-11) is as follows; the copper-chromium-manganese oxide powder (KW-1) is mixed with the water solution of chromic acid anhydride. In this procedure copper oxide contained in KW-1 reacts with cromic acid to produce a compound of copper-chromium oxide (CuCr2O7·2H2O), and this may act as a binder of the copper-chromium-manganese oxide powder. Then these mixture are pilled 3mm×3mm size by ordinary pilling machine. In this experiment the amount of chromic acid is regulated to be the same mols of CuO contained in KW-1. The crushing strength of KW-11 is 100kg/cm2, and the KW-11 used in the hydrogenation is 250kg/cm2. From X-ray diffraction data, the type of combination of metallic oxide present in the used catalyst is as follows; the catalyst consists of reduced copper, CuCr2O4 combined with manganese oxide and may be amorphous CuCr2O4 which is reduced from CuCr2O7·2H2O.
It is said that X-ray diffraction broadening is decided by crystallite-size, form, and internal disorder of crystals under constant conditions of experiment. It has been known in general to determine crystallite-size by line-broadening according to the equation proposed by Scherrer. The authors calculated crystallite-size of various paraffins by means of the above method, from the recorded figures of automatic X-ray diffractometer (Geiger Flex). As a result, it was found that the crystallite-size of various paraffins was 250600Å, for which much differences could be by the preparation methods of paraffin samples for the diffractometer.