JPS6081200A - Method for separating and purifying sterol ester - Google Patents

Abstract

PURPOSE:To separate and purify the titled compound useful as a base material for cosmetics and raw material for medicines, etc. industrially in high yield, by dissolving a deodorization distillate formed as a by-product in the deodorization step of a fat or oil in an aromatic solvent, removing the resultant insoluble free sterol, and adding a saturated aliphatic lower alcohol thereto. CONSTITUTION:A deodorization distillate formed as a by-product in the deodorization step of a fat or oil is dissolved in an aromatic solvent, preferably toluene or xylene, in an amount of 1-3 times of that of the distillate under heating, and the resultant solution is slowly cooled to a temperature, e.g. 5-10 deg.C, to deposite primarity free sterol, which is then removed. A 1-3C saturated aliphatic alcohol is then added thereto to deposite only the sterol ester as a secondary deposit. The above-mentioned operation is repeated to further recrystallize the sterol ester and give the aimed compound in high purity (>=97%).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a method for effectively dispensing sterol nisdel from the deodorized distillate produced during deodorization treatment during the refining process of fats and oils.

Sterol esters, which are contained in deodorized distillates from 1 to 25%, are used as cosmetic bases due to their emulsion-stabilizing effects and moisturizing properties on the skin, as well as sterols.
Use as a raw material for the synthesis of steroid-type medical products, and
, 'J car press ζ] It can be expected to be used as a lubricating oil additive and liquid crystal.

Conventionally, separation of sterols from deodorized distillates has been carried out industrially, but the method for segmenting sprawl esters has not yet been industrialized. This is due to the physical and chemical properties unique to sterol esters, such as castyrol,
sterol ester, fatty acid,) literpene, glycerin I
This is probably because it is technically difficult to separate sterol esters alone from deodorized distillates consisting of a multicomponent system such as copherol.

The present inventors have conducted various studies on a method for efficiently producing 1lff molecules of sterol ester from deodorized distillates of fats and oils in consideration of the above points, and as a result, the above objective can be achieved by selecting a specific solvent. We have discovered what can be achieved and completed the present invention.

That is, in the present invention, the deodorized distillate by-produced in the process of removing oil 1]'J is dissolved in an aromatic solvent, and after removing the sterol as an insoluble component, this solution is added with a carbon number. 1
QV indicates that sterol esters can be precipitated as 30% by adding 3 saturated aliphatic alcohols.
This is a separation and purification method for the characteristic sprawl ester.

The method of the invention is carried out as follows.

First, 1 to 3 times more aromatic solvent is added to the deodorized distillate III and dissolved by heating. The temperature at this time is not limited to 1'\ as long as the raw material is dissolved in the solvent.

After heating and dissolving, the mixture is slowly cooled to 5 to 10°C to primarily precipitate free sterols. If it is rapidly cooled during cooling, the precipitate becomes gel-like and it becomes difficult to remove the sterol, so the slow cooling time is preferably 5 to 24 hours.

Next, after removing the free sterols, if a saturated aliphatic alcohol, preferably 1 to 1 to 2 carbons of charcoal above 100% is added to the p-liquid, only sterol esters are efficiently precipitated. Since this secondary precipitate has large crystals, it is easy to filter. Furthermore, regarding the obtained precipitate, the same 4 children's Sugo 1
Purity improves by repeating the process and recrystallizing.

In addition, for the purpose of concentrating sterol nisdels, alcohol (1 to 3 saturated aliphatic alcohols) is added to the deodorized distillate and dissolved by heating, and then slowly cooled to precipitate the fraction containing sterols and sterol nisdels. When the above-mentioned operation is carried out using it as a raw material, a purity of 90% or more of sterol Nisdel can be obtained, and when recrystallization is performed using the same shuttle, the purity becomes more than 97%.

The oil and fat deodorizing distillate used in the present invention is preferably one containing as much sterol ester as possible, and is a deodorizing distillate of vegetable oils such as rapeseed, soybean, cottonseed, safflower, sunflower, corn, rice bran, and sesame. Extracts can be used as raw materials.

As the aromatic agent, benzene, toluene, and xylene are suitable for use, and toluene and xylene are practically preferred.

Furthermore, the type of alcohol used for crystal precipitation
The alcohol may be any of saturated aliphatic alcohols such as methanol, ethanol, n-7' lovanol, and impropanol. However, those having 4 or more charcoal tips are not suitable because the precipitation of sterol esters does not occur even if the amount added is increased.

The present invention is carried out as described above, and according to this, it is possible to industrially and efficiently produce the sprawl ester fraction NI'A"3 from deodorized distillate, for which there was no practical method to date. This method is extremely meaningful in that it can be carried out and the desired product of high purity can be obtained.Examples of the present invention will be described below.

Example 1 2 oor of soybean deodorized distillate (containing 99% sterol esters and 13.5% free sterols) was hot-dissolved in 400 d of xylene. The mixture was slowly cooled to 5° C., left to stand for 5 hours, and the precipitate was separated by filtration to obtain i-th order product 252. Add methanol to the p liquid after removing this primary precipitate.
Add me and leave it at 5℃ for a while and separate the precipitate by filtration! 'J l, a secondary precipitate 162 was obtained. The precipitate was briefly soaked in xylene, 8', Ll''j of methanol was added, and the precipitate was gradually cooled to 5°C, and the precipitate was dissolved in a rice cooker.
Sterol ester with a degree of 95 or higher (medium-colored plate crystals) 1
I got 37.

Example 2 Rapeseed de-A distillate (contains 21.3 sterol esters and 6.7% free sterols) 200 y f, 400
The mixture was hot-digested in toluene at RSE. Cool slowly to 5℃,
After standing for 5 hours, the precipitate was separated by filtration to obtain primary precipitate 122. Add 600 ml of ethanol to the p-liquid from which the primary precipitate has been removed, let it stand for a while at 5°C, and filter the precipitate to obtain molecules iit L, secondary precipitate 40.
I got 51. This precipitate was dissolved in hot toluene, an appropriate amount of ethanol was added, and the mixture was slowly cooled to 5°C. The precipitate was separated by filtration to obtain sterol ester (colorless plate-like crystals) 302 with a purity of 95 or higher. Example 5 200 g of cottonseed deodorized distillate (containing 2% sterol esters and 91% free sterols) was hot-dissolved in 400 g. The mixture was slowly cooled at 5°C and left to stand for 5 hours, and the precipitate was separated by filtration to obtain 13.5F of primary precipitate.

Add isopropanol to the filtrate after removing this primary precipitate.
00 m0JOL, the mixture was allowed to stand for a while at 5°C, and the precipitate was separated by filtration to obtain a second precipitate 13F. Dissolve this precipitate in hot benzene, add an appropriate amount of impropatol, slowly cool to 5°C, separate the precipitate by filtration, and prepare sterol ester (colorless plate-like crystals) with a purity of 95 or higher.
．． 5g was obtained.

Example 4 Methanol was added to a deodorized soybean distillate in double portions, dissolved by heating, and then slowly cooled to 5° C. to precipitate a fraction containing sterols and sterol esters. This is separated by centrifugation and used as a raw material (containing 50% sterol ester and 40% free sterol). 200v of this raw material is thermally decomposed into 400 units of xylene. It was slowly cooled to 5°C, left to stand still for 5 hours, and the precipitate was separated by filtration.
I got 02. This primary precipitate was removed, 600 d of methanol was added to the 7'CP liquid, and the mixture was allowed to stand at 5° C. for a while, and the precipitate was separated by filtration to obtain 50 f of secondary precipitate. (Purity 90% or more). This product was dissolved in hot xylene, an appropriate amount of methanol was added, and the mixture was slowly cooled to 5°C. The precipitate was evaporated by passing to obtain 45v of sterol ester (colorless plate-like crystals) with a purity of 97% or higher.

r0 Permit Applicant Nippon Refining Yurin Shiki Co., Ltd.] Shi'L 1. ili Masashi Shouma 11J5B December 1. ilJ Special J+ Agency Director Name: Sugi [11 people 1. (μm, thing+'
+ Indication 1982 special a'l'1 AJf No. 189344-5] 2
, Name of the invention Ste1 Nornisgur no Ui1 TurtleIL: l'i1M method 3
, 7+Ii is correct. and 1 thing 1'1 leap 1 thread 21 Shin'l'ii + petitioner 4, fi
ll stop target il+ light? Il:'J(2) 明A11l'J,:'1. Claim 5
, Correction details +11 Details 1! +21st 'L 5 f'l' 1 no! M 25 % J to 1 about 1 to about 25 % J toil
l Correct.

(2) Page 2, line 12, 1--... Although it is carried out, insert "1 in the deodorized distillate" after "."

(3) Correct 1-(saturation of 1 to 3 carbon atoms) to 1 (saturation of carbon number 1.-4) in line 9 of shell number 4.

(4) As per attached sheet.

Attachment Claims (1) Oils and fats; 2. Dissolving the deodorized distillate by-produced in the odor process in an aromatic solvent 1) '+-L, free sterile 1'-ol as insoluble matter and removing 'C' Then, a saturated aliphatic alcohol having 1 to 3 carbon atoms is added to this solution, thereby converting the sterol ester into an insoluble component and precipitating it.

(2) The deodorized distillate was preliminarily treated with charcoal, saturated aliphatic alcohol having a number of 1 to 4 was added, and a fraction containing esters and esters was extracted.
;l'l request (D Fl(n 1111 th fil
qi description 0. ) Method.

(3) The method according to claim (1).

(4) The method according to item III, item fi1 of claim 'I', wherein the alcohol (saturated aliphatic) is methanol.

Claims (1)

[Scope of Claims] (1) After dissolving the deodorizing distillate by-produced in the deodorizing process of oils and fats in an aromatic solvent and removing free sterols as insoluble matter, this solution is added to A method for separating sterol esters, which involves adding saturated aliphatic alcohol to precipitate sterol esters as insoluble matter. (2) Drying 11 of the special request in which a saturated aliphatic alcohol having 1 to 5 carbon atoms is added to the deodorized distillate in advance to separate the sterols and sterol esters.
The method described in Box 11 (1). (5) The method according to claim (1), wherein the aromatic bath agent is xylene. (4) The method according to claim (1), wherein the saturated aliphatic alcohol is methanol.