JPS60109586A - Purification of tocopherol - Google Patents

Abstract

PURPOSE:To separate and purify alpha-tocopherol and non-alpha-tocopherol from an oily material containing tocopherols, by using a strongly basic ion exchange resin and using methanol as the sole solvent. CONSTITUTION:An oily material containing tocopherols is dissolved in methanol, and the solution is developed in a column packed with a strongly basic ion exchange resin. The adsorbed alpha-tocopherol is eluted by passing methanol through the column. The remaining non-alpha-tocopherol adsorbed in the column is eluted by the treatment with methanol containing carbon dioxide gas. EFFECT:The methanol can be recovered and regenerated easily. The alpha-tocopherol and non-alpha-tocopherol can be separated from each other, and obtained in high recovery.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for separating and purifying oily substances containing tocopherols from non-α-tocopherols and non-α-tocopherols.

Conventionally, in these methods, oils and fats containing both α-tocopherol and non-α-tocopherols are used as a solvent for a basic anion exchange resin containing tocopherols (alcohols having aliphatic linear or side chains having 1 to 5 carbon atoms). ,
Aceto/.

A basic anion exchange resin is used to take advantage of the difference in adsorption capacity of ethylene glycol monomethyl ether or a mixed solvent consisting of one of these and one of benzene, petroleum ether, petroleum benzene, ligroin, and n-hexane. α-tocopherol! : non-α-)ff17
Method for separating each type of Erol (% Kosho 59-6
682) or methylated natural tocopherol concentrated oil is dissolved in a hydrocarbon solvent, and the resulting solution is OH
He was treated with a type of strongly basic ion exchange resin.

An alcoholic solvent selected from the group consisting of methanol, allylalcohol, solonolugylalcohol, benzylalcohol, and tetrahydrofurfurylalcohol, a mixed solvent of the alcoholic solvent and a hydrocarbon solvent, or a mixed solvent of the alcoholic solvent and the carbonized alcohol. A method for eluting α-tocopherol from the OH type strongly basic ion exchange resin using a '5f! mixed solvent formed by adding a third solvent to form a uniform mixed solution with a hydrogen soluble compound. (Refer to Japanese Patent Publication No. 45-5774).

However, these 8 manufacturing methods all use several types of solvents, so they are not only complicated to operate, but also have the drawbacks of expansion and contraction of the resin particles, which causes fluctuations in the column content and decreases separation performance. was there. Furthermore, it is known to use acetic acid as an acidic agent, but in this case non-α-
Industrialization of purification methods using strongly basic ion exchange resins has been difficult due to drawbacks such as difficulty in removing acetic acid from tocopherol eluates.

The present inventors conducted various studies to solve these conventional drawbacks, and as a result, we used a strongly basic ion exchange resin as an adsorbent and only methanol as a solvent, and used carbonic acid as an acidic agent, which is easy to separate from methanol. By using a gas, the separation ability between α-tocopherol and non-α-tocopherols can be improved, and the target substance can be obtained with a high recovery rate. Furthermore, after elution of α-tocopherol, other tocopherols ( The present invention was completed based on the discovery that highly pure non-α-tocopherols can be obtained by eluating and separating only the non-α-tocopherols (hereinafter referred to as "non-α-tocopherols").

Next, the present invention will be explained in detail.

First, an oil containing tocopherols (hereinafter referred to as "tocopherol oil") is a raw material for the method of the present invention.
Examples include soapstock obtained from the deodorizing process of cottonseed oil, soybean soapstock and their concentrates, or methylated natural tocopherol concentrated oil processed by the methylation method of non-α-tocopherol (β + r + '-tocopherol). These include natural tocopherols obtained from various vegetable soapstocks and processed products thereof, as well as synthetic tocopherols obtained by condensation of phytol and methyl group-substituted hydroquinone.

In the method of the present invention, these raw materials, tocopherol oils, are dissolved in methanol. The processing amount of tocopherol oil dissolved in methanol is 0 as total tocopherol for the strongly basic ion exchange resin described below.
．． A ratio of 6 to 0.01 w/v is preferred. Next, when a methanol solution containing this tocopherol oil is developed in a column filled with a strongly basic ion exchange resin, glycerides, steroids, hydrocarbons, higher alcohols, etc.
The fraction containing impurities such as wax flows out first. Furthermore, when methanol is passed through the column, an eluted fraction containing α-tocopherol is obtained.

Next, the non-α-tocopherol adsorbed on the column was treated with carbon dioxide gas-dissolved methanol to liberate the non-α-tocopherol from the strongly basic ion exchange resin.Then, the methanol was passed through to flow out the non-α-tocopherol. . The carbon dioxide concentration of the carbon dioxide dissolved methanol is 4 to 6.
A range of 1002/111 methanol is preferred. The treatment with methanol dissolved in carbon dioxide can be carried out by directly blowing carbon dioxide into the column, or by allowing methanol dissolved in carbon dioxide to flow down from the top of the column.

Next, a methanol solution of caustic alkali is passed through the column to regenerate the strongly basic porous synthetic resin. Usually, the concentration of caustic alkali used for this regeneration is preferably about 4 to 8 degrees.

Examples of the strong basic ion exchange resin used in the present invention include Dowext XL, Dowext 12% Dowext 14. Examples include Amberlite RA-401, Amberlite RA-411, Duolite A-40LO, and Duolite A-42LO.

According to the method of the present invention, (1) methanol used in each treatment can be easily recovered and regenerated; (2) α-tocopherols and non-α-tocopherols can be separated well and at a high recovery rate; (3) Non-α-tocopherols can be easily recovered from the non-α-tocopherol elution section because acidic agents that are difficult to remove such as acetic acid are not used, and there are no limitations on the material of the equipment; (4) Elution with methanol dissolved in carbon dioxide gas yields highly pure non-α-tocopherols with almost no impurities other than non-α-tocopherols; (5) Since the solvent used is a single solvent, expansion and contraction of the resin particles are avoided. There are various advantages such as good separation conditions due to less fluctuation within the column.

EXAMPLES Next, Examples will be given to further specifically explain the present invention, but the present invention is not limited to the following Examples.

Example 1 25 Qtl of methanol was added to soapstock 5031 obtained from the deodorizing process of cottonseed oil, and the mixture was stirred at 5° C. for 1 hour using r#IJ. After removing insoluble matter, the methanol solution was distilled off under reduced pressure to obtain oily substance 218j1 (non-α-tocopherol 14.6
%, α-tocopherol (14.3%).

Next, a glass column (3,251 x 30 m) was filled with Dowext x 2 (OHHQ 5
100 to 200 mesh) To 150-ml, add 12.8 ml of the previously obtained oily substance dissolved in 80 ml of methanol.
The flow rate was 3 d/min. Furthermore, methanol was passed through at a rate of 2 I]2 d/min, and the elution section containing α-tocopherol (400
*/~580g) 180- is distilled off under reduced pressure to obtain oily substance 3
．． 639 (85.0% α-tocopherol, 05% r-tocopherol) was obtained. Next, carbon dioxide gas of 1'00 rug/min was blown into the resin packed in the lower part of the column for 15 minutes, then methanol was passed through at 2.53 wrl for 7 minutes, and the resulting eluate 250 */ was evaporated under reduced pressure. 3.28 jl of oil (non-α-tocopherol 96.'>%,
α-Tocopherol xerone was obtained.

The column was filled with 1N caustic potash-methanol solution 50011/
was first washed with methanol 5DO+wj to regenerate the resin.

Example 2 Tocopherol concentrate obtained from soybean soapstock was extracted with methanol at 5°C, and the methanol-insoluble matter was extracted with methanol (μm: 7'm). Cohuerol concentrate (total) copherol 6aO1, of which α-
Tocopherol 7.5%) was obtained.

Tocopherol concentrate (6aO% total tocopherol,
Of which α-tocopherol 7.5%) 25.0p to 1
．． 23d/min flow rate, 2.00*/min methanol
/min. Eluate containing α-tocopherol <4
05d~570t/) 167Al was distilled off under reduced pressure to obtain 2.249 of an oil (83.2H of α-tocopherol, 3.0H of non-(1-) copherol σ). Next, methanol 1 and DOOd saturated with carbon dioxide gas were introduced, and the methanol was distilled off under reduced pressure to obtain a fraction containing tocopherol.
h, α-tocopherol 0 h) was obtained. The resin was regenerated in the same manner as in Example 1.

Example 6 The same procedure as in Example 2 was carried out, except that Amberlight Element RA-401 (OH type) 150- was used instead of Dowext X2 (OH type). Tocopherol concentrate (6aO% total tocopherols, including 75% α-tocopherol) 25. Op Yoshi, oil containing 79.4% α-tocopherol and 3.6% non-α-tocopherol 2.31
P, and an oil is, sp containing 93.8% non-α-tocopherol was obtained.

Example 4 Tocopherol concentrate obtained from soybean soapstock (46.2% total tocopherol) 809 was dissolved in isopropyl ether 4
00- dissolved in phosphorus oxychloride 509 and paraformaldehyde 15. Ojl was added and reacted at 40°C for 5 hours. Next, 160 d of concentrated hydrochloric acid was added, and 602 d of zinc powder was added over 1 hour while stirring vigorously at 30 to 57°C. After removing insoluble materials, the inpropyl ether layer was washed with water, dehydrated, and the solvent was distilled off to produce a pale yellow oil (tocopherol 4
2.2%% of which α-tocopherol 41.3%) 47
I got 2. Extract with 30ONt of methanol at 5°C.

27.49 of a tocopherol concentrate (tocopherol 5a 6%, of which α-tocopherol 57.3%) was obtained.

α-tocopherol 87,3 was treated in the same manner as in Example 2.
Oil I containing m and non-α-tocopherols [14%
I got Z20j'.

Example 5 Jacketed glass column (3,2zX 30t1n
) to Downic 7, 1-12 (OH type, 100-20
0 mesh) was filled with 80 ml of methanol, and warm water was circulated inside the jacket to maintain the temperature at around 40°C.

Tocopherol concentrate obtained from soybean soapstock (
A solution in which 13.9 jl of 63.5% total tocopherol (of which 7.1% α-tocopherol) was dissolved in methanol was poured in at a rate of 0.67 ml and 11 minutes. Furthermore, methanol was passed at a rate of 114 d/min, - 420d of the elution fraction (200-620ml) containing tocopherol was distilled off under reduced pressure to obtain an oily product of 1.879Cα-) = r7 Erol 47
．． 7%, r-)copherol (10%) was obtained. Next, carbon dioxide gas was blown into the resin in the same manner as in Example 1, and then methanol was passed through the resin.

200 d of the obtained eluate was distilled off under reduced pressure to obtain an oily substance 6.
979 (all): ff Ferro: 1-le 97.6%,
C1-) Copherol 0) was obtained. The column was regenerated in the same manner as in Example 1.

Patent applicant: Nisshin Seifun Co., Ltd.

Claims (1)

[Claims] An oily substance containing tocopherols was dissolved in methanol, and this was applied to a column filled with a strong base ion exchange resin. After methanol was passed through the column to elute α-tocopherol, the column was filled with carbon dioxide gas-dissolved methanol. 1. A method for purifying tocopherols, which comprises treating to free elute non-α-tocopherols.