KR810000104B1 - Method for preparing pure squalan from shark-liver oil - Google Patents

Abstract

Squalane was prepared from squalene in a way as follows: squalene prepared from the liver oil of shark by deoxidation, decoloration and fractionary vacuum distillation was treated with alkali and water washing treatment to removes impurities and was put into autoclave attached on agitator with a porous rotor. Mixed catalyst(Ni and active carbon 1:1) of about 1.0% by weight of above squalene was added to it. After adding H for 5 hrs., obtained squalane was treated with metal Na and then was purified by fractionary vacuum distillation and deodorization.

Description

Method for producing high purity squalane from shark liver oil

The present invention has a coagulation point of -60 ℃ in deep sea shark liver oil and excellent lubricity, so it can be used as an advanced lubricant of precision machinery. It has good osmotic power to the skin and gives activity without irritating the subcutaneous tissue. The present invention relates to a high-purity squalane preparation having a good effect as a basic raw material for cosmetics.

Shark liver oil caught in the deep sea (200-1,000m) contains about 15-80% of squaraine, while shark liver oil caught near Korea contains about 20-30% of squaraine.

Squalene is a molecular formula of C ₃₀ H ₅₀ , a compound belonging to terepins with six double bonds in its molecule, and its oxo number is 372. Aran has a solidification point of -60 ℃ and has good lubricity and does not change very much at low temperatures and low temperatures. It is extremely suitable as a lubricant for precision machinery. It also has an excellent effect as a basic raw material of cosmetics.

Conventionally, a method of producing squaraine from deep sea liver oil is known. Such a method removes a double bond of squaraine containing a considerable amount of impurities by hydrogenation, and also contains a large amount of impurities and a non-squalane squaraine derivative. Although it is somewhat suitable as a lubricating oil, it was difficult to use as a raw material for basic cosmetics.

1) A method of preparing high-purity squaraine from Japanese Patent Publication No. 26-3275, the method comprising distilling black fish shark oil as a raw material under reduced pressure of 0.1-0.5 mm / Hg to collect effluent at 230-235 ° C. and hydrogenating it. After adding caustic soda by the conventional method, saponification sufficiently, and distilled what was obtained by washing with water and dehydrating. Then, about 5% of concentrated sulfuric acid was added and stirred for about 3 hours to fully react. After cooling, the mixture was separated and 5% of clay was added. It is a manufacturing method of high purity squalane characterized by combining the process of filtration under reduced pressure at -20 ° C through a filtration layer filled with alumina and silica gel after filtration after heating and stirring at ° C.

2) A method of preparing squaraine oil of Japanese Patent Publication No. 26-4125, which is a method of producing squaraine oil obtained by fractional distillation of surplus shark oil, adding a nickel catalyst and hydrogenating at a hydrogen pressure of 50 kg / cm 2 and a temperature of 156 ° C. Oxo obtains 98.7 of the product, adds 30 parts of hydrogen peroxide of 30% glacial acetic acid to the product, heats and reacts with stirring at 100 ° C. for about 8 hours, removes acetic acid of acetic acid, washes with sodium carbonate solution, and washes with water to obtain a product. It can be seen from the description of both publications that the invention relates to a process for producing a liquor oil from squalene produced by cooling the product to remove precipitates as much as possible.

However, as described above, the manufacturing method of each squaraine has a freezing point of -60 ℃ and the final product has a precipitate at -20-30 ℃. It can be seen that many impurities are contained.

Therefore, Squalane made as such has some value as a lubricating oil of precision machinery, but it is not suitable as a lubricating oil used in extremely cold fats and contains a lot of impurities, so it can cause side effects when osmotically subcutaneous. Not suitable as

The inventors of the present invention have completed the present invention as a result of many studies to prepare squaraine, which can be used as a precision machinery lubricant even in extreme regions and as a basic raw material of cosmetics, from cod liver oil with a low content of squalene, such as fish shark. The details are as follows.

In general, when hydrogenating a double bond of an organic compound, a nickel catalyst is used as a catalyst and hydrogenation is performed under high pressure. As described above, a nickel catalyst is added to squalene and a hydrogen pressure is applied at a high pressure of 50 atm. When the product is heated to 150 ° C and hydrogenated at, the product has an oxo number of 98.7, which indicates that the above-mentioned product contains many other impurities. Applicants can mix the same amount of fine powder of activated carbon with a nickel catalyst to activate the catalyst. In the hydrogen addition of squalene under high pressure hydrogen, the hydrogenation reaction was found to proceed well when a large number of holes were installed in the rotor blades of the stirrer, and the present invention was described. .

EXAMPLE

[Step 1]

After deoxidation and decolorization of the raw liver oil by a known method, it is put in a fractional distillation tube and vacuum distilled by a known method, and supernatants (mainly pristane and higher alcohols) flowing out at 50-200 ° C. at a vacuum degree of 2 mm / Hg are separately collected. Prepared squalene for 200-250 ° C. flow is obtained, and the following electrically prepared squalene is subjected to a known alkali treatment and washed with water to remove impurities such as free fatty acids. The resids are mainly neutral oils and lead streams.

[Step 2]

Put the electric preparation squalene in a special autoclave equipped with a rotor blade and add a similar amount of activated carbon and nickel catalyst of about 1% of crude squalene to the hydrogen pressure at 180-220 ℃. After hydrogenation at 30-40 kg / cm 2 for 5 hours, the catalyst is separated to obtain squaran.

[Step 3]

The electrosquarane is placed in a reactor equipped with a stirrer, and about 1% by weight of sodium metal is added, followed by heating and stirring at 140-150 ° C. for about 3 hours (at this time, a small amount of higher alcohol and fatty acid Combined with sodium metal to form alkalade and fatty acid soda).

Next, after cooling, the above-mentioned squalane is put in a vacuum fractional distillation tube, and the purified fraction of squalene is collected by collecting a stream having a flow rate of 200-240 ° C. at a vacuum degree of 2 mm / Hg. At this time, the flow rate and the residual amount of each flow temperature is as follows.

Initial flow rate 200 ℃ or less 10-15%

Next flow rate 200-240 ° C 70-80% (purified squalane)

Residue 10-15%

Next, the purified squaraine is put in a deodorization tube and subjected to a known deodorization operation through steam for 1-2 hours while heating at a vacuum degree of about 2 mm / Hg temperature of 150-170 ° C. to produce high purity squalane of the present invention. It is less than 1 to go.

The crude squalene obtained in the first step is mainly composed of squalene, a small amount of fatty acid higher alcohol pristane, and a small amount of neutral oils and odorants, but it does not interfere in the subsequent step.

Metal treatment of squalene obtained in the third and second steps is carried out by vacuum fractionation with the use of a small amount of free fatty acid and trace neutral oil contained in the squalane as fatty acid salt and a small amount of alcohol as alcorad. This is to completely remove it.

As described above, the present invention can increase the hydrogenation rate while the hydrogenation pressure is lower than that of the conventional squaraine production method, and thus the production method is easy and the purity of the squaraine obtained is higher than that of the conventionally known squaraine production method. It can be manufactured, and the product relates to the manufacturing method of Squalane, which can be used as a lubricant for precision machinery even in extremely cold fats (because it should be solidified at -60 ℃) and can be used with confidence as a cosmetic raw material.

Claims (1)

As described above, the known process of alkali-washing and washing the crude squalene obtained by deoxidizing, decolorizing, and fractional vacuum distillation of the molten shark liver oil is carried out on the square on an autogreb equipped with a stirrer with a porous rotor blade. Squeeze characterized by combining the process of adding sodium catalyst with about 1.0% of nickel and a catalyst for the same amount of activated carbon, and hydrogenating the squalane obtained by hydrogenation by a conventional method for about 5 hours, followed by deodorization of a known vacuum fractional distillation. Aran's recipe.