JPH0524914B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a method for separating and refining tocotrienols and tocopherols to high purity from raw materials in which they coexist.

(b) Prior Art Tocopherols are contained in many oils and fats, usually in a content of 1% or less, and are widely used in medicines as vitamin E and in foods as antioxidants. Tocotrienol, which has three double bonds in its side chain, is known as a substance related to tocopherol, and various studies have revealed that it has the same effects as tocopherol, and at the same time, it has also been found to have properties that compensate for the shortcomings of tocopherol. As a result, the importance of tocotrienols is expected to increase.

Many fats and oils contain only tocopherols, but tocotrienols coexist with tocopherols in palm oil, rice bran oil, wheat germ oil, etc.

The behavior of tocotrienols is strikingly similar to that of tocopherols, so it is difficult to industrially produce high-purity concentrates of tocotrienols or tocopherols from these oils, which inevitably results in high processing costs. .

Special Publication No. 59-34191 and Special Publication No. 59-34192
Although the publication discloses a method for concentrating tocopherols and tocotrienols, these are methods for concentrating a mixture of the two, and so far no effective method for separating and concentrating the two has been known.

(c) Problems to be Solved by the Invention An object of the present invention is to eliminate the above-mentioned drawbacks and provide a method for separating and concentrating tocotrienols and tocopherols with high purity at low cost.

(d) Means for Solving the Problems As a result of intensive research, the present inventors have discovered that the above object can be achieved by using a specific adsorbent.

The present invention has been completed based on this knowledge, and involves contacting a distillate obtained in a deodorizing process or a distillation deacidification process of fats and oils in which tocotrienols and tocopherols coexist with a reverse phase partition type adsorbent. , a method for concentrating tocotrienols and tocopherols, which is characterized by sequentially extracting tocotrienols and tocopherols by contacting them with a solvent.

The starting material of the present invention is a distillate of palm oil, rice bran oil, wheat germ oil, etc. in a deodorizing process or distillation deacidification process.

If this distillate contains a large amount of free fatty acids, an anion exchange resin,
It is preferable to remove free fatty acids by means such as distillation or solvent fractionation.

An example of operation using an anion exchange resin is as follows. That is, the distillate is first esterified using a monohydric alcohol. Methanol or ethanol is usually used as the monohydric alcohol. Sulfuric acid or the like is used as the esterification catalyst.

The esterified product obtained above is brought into contact with an anion exchange resin to adsorb tocotrienols and tocopherols contained in the treated product.

Next, the adsorbent is brought into contact with a solvent to extract fatty acid esters. In this case, water-free ethanol is used as the solvent. Subsequently, tocotrienols and tocopherols are simultaneously extracted by contacting with ethanol containing water as a second solvent. The solvent is removed from the obtained extract under reduced pressure.

Note that the method for removing free fatty acids is not limited to the above.

The above-mentioned distillate or the above-treated distillate is then contacted with a reverse phase distribution type adsorbent. As the reverse phase distribution type adsorbent, silica gel to which an alkyl group having 6 to 28 carbon atoms is chemically bonded is preferred, and silica gel to which an aminopropyl group, cyanopropyl group, or phenyl group is bonded can also be used.

Through this operation, the material to be treated is adsorbed on the adsorbent and then brought into contact with a solvent to first extract tocotrienols and then tocopherols. Suitable solvents are lower alkanols such as methanol and ethanol, highly polar solvents such as acetonitrile, or mixed solvents of these with weakly polar solvents such as chloroform, methylene chloride, and tetrahydrofuran. The categories in which tocotrienols and tocopherols are extracted vary depending on various conditions, but in general, tocotrienols are extracted when 3 to 6 times the amount of the adsorbent is used, and tocopherols are extracted when 10 to 30 times the amount of the adsorbent is used.

Note that the tocotrienol fraction and tocopherol fraction may contain impurities such as sterols, hydrocarbons, and fatty acids; in this case, the fraction containing impurities is adsorbed by contacting with silica gel, for example, before or after treatment with a reversed-phase partition type adsorbent. 5-20% later
Impurities can be removed by a method such as extracting tocotrienols and/or tocopherols with hexane containing ethyl ether.

Example 1 10 kg of methanol containing 1% sulfuric acid was added to 10 kg of the distillate obtained in the deodorizing step during the refining of rice bran oil, and after heating for 1 hour, most of the methanol was distilled off under reduced pressure. After washing the residue with water and dehydrating it, it is applied to a column filled with anion exchange resin 5 for adsorption, and then 99.5% ethanol 30 is passed through it to elute most of the fatty acid methyl. Subsequently, 20 g of 94% aqueous ethanol was poured into the flask, and the fractions were collected and the solvent was removed under reduced pressure to obtain 442 g of an extract. This category contained 15.5% tocotrienols and 14.0% tocopherols.

Next, this eluate was adsorbed on a column filled with silica gel 5 to which alkyl groups having 18 carbon atoms were chemically bonded, and acetonitrile was passed through the column for 20
Collect categories ~25 (category 1) and 30-45 (category 2). Section 1 and Section 2 were desolvated under reduced pressure to give Section 1 α-tocotrienol and β-tocotrienol.
31g extract containing 91% total tocotrienols
In Category 2, 28.5 g of extract containing 85% α-tocopherol was obtained.

Example 2 Distillate 10 obtained during distillation deacidification of palm oil
After adding 10 kg of methanol containing 1% sulfuric acid to kg and heating for 1 hour, most of the methanol is distilled off under reduced pressure. After washing the residue with water and dehydrating it, it was subjected to a column packed with anion exchange resin 5 to be adsorbed.
Flow 99.5% ethanol 30 to elute most of the fatty acid methyl. Next, 94% hydrated ethanol
20 was poured, the fractions were collected, and the solvent was removed under reduced pressure to obtain 825 g of extract (1). This category contained 4.5% tocotrienols and 5.3% tocopherols.

The extract (1) is applied to a column packed with silica gel column 10 to adsorb it, and then 30 g of hexane containing 5% ethyl ether is passed through the column and the fraction is collected. The solvent was removed under reduced pressure to obtain 101 g of extract (2). This extract (2) contains 44% tocotrienols and 36% tocopherols.
It contained %.

Next, the extract (2) was adsorbed on a column filled with silica gel 5, in which alkyl groups having 8 carbon atoms were chemically bonded, and ethanol was passed through the column for 15 to 30 minutes.
(Category 1) and 30 to 50 (Category 2). After removing the solvent from Category 1 and Category 2 under reduced pressure, Category 1 is an extract containing 98% tocotrienols.
43g and Category 2 yielded 33g of extract containing 95% tocopherols.

(e) Effects of the invention Tocotrienols and tocopherols are both useful substances as medicines, foods, etc., but since their behavior is extremely similar to each other, it is necessary to separate each of them with high purity from substances containing both. It was difficult to do so.

However, according to the present invention, both of these can be separated and concentrated to a high degree of purity, and the processing cost is low, so that industrial implementation is possible.

Claims (1)

[Scope of Claims] 1. A distillate obtained in a deodorizing process or distillation deacidification process of fats and oils in which tocotrienols and tocopherols coexist is brought into contact with a reversed phase distribution type adsorbent, and then brought into contact with a solvent to produce tocotrienols. A method for concentrating tocotrienols and tocopherols, the method comprising sequentially extracting tocotrienols and tocopherols. 2. The concentration method according to claim 1, wherein the reversed phase partition type adsorbent is silica gel to which alkyl groups having 6 to 28 carbon atoms are chemically bonded. 3. The concentration method according to claim 1 or 2, wherein after free fatty acids in the distillate are removed, the distillate is brought into contact with a reverse phase partition type adsorbent.