KR20010017635A - Production method of high-purity natural Tocopherol - Google Patents

Abstract

PURPOSE: A method for producing natural tocopherol is provided, thereby the higher purity natural tocopherol is simply isolated from soybean. CONSTITUTION: The method for producing natural tocopherol comprises the steps of: removing sterol mixture from soybean deodorized extract by low temperature distillation using an organic solvent; reacting fatty acid with alcohol in the presence of hydrogen sulfate for esterification; and dissolving the esterified compound into organic solvent and passing it through the column packed with basic anionic exchange resin to collect tocopherol, in which alcohol is monohydric alcohol such as ethanol, methanol, and isopropanol; dihydric alcohol such as ethyleneglycol or polyhydric alcohol, and the column consists of two columns, in which free fatty acid and pigment are removed in the first column and tocopherol is purified in the second column.

Description

Process for producing high purity natural tocopherol {Production method of high-purity natural Tocopherol}

In general, the soybean oil deodorant effluent contains about 8-15% of tocopherol, as well as sterols, free fatty acids, hydrocarbons, and glycerides. The content and composition of these ingredients may vary depending on the deodorization method, and even the same soybean is known to be different depending on the harvest time or the production region. Vegetable tocopherols are widely used as fats and oils and food additives as antioxidants. Especially, alpha-tocopherols, which are vitamin E, are widely used as pharmaceutical ingredients and cosmetic additives. .

According to U.S. Patent No. 3153055, sterol and tocopherol were separated from the deodorization effluent in soybean oil refining, and the fatty acid and glyceride were reacted under strong acid conditions to be converted into low molecular weight monohydric alcohol esters. Tocopherol and sterol were fractionally extracted with a solvent in which a polar solvent and a nonpolar solvent were combined.

According to Japanese Patent Application Laid-Open No. 57-59886, the palm oil or rice bran oil was neutralized with alkali, extracted with a fat-soluble organic solvent, and the solvent was removed to obtain a tocopherol concentrate.

According to US Pat. No. 2432181, tocopherol concentrates were isolated from vegetable oils and fats. According to these reactions, fatty acid glycerides contained in vegetable oils and fatty acids and low molecular weight monohydric alcohols were reacted under a basic polyalcoholization catalyst, followed by distillation to remove excess alcohol, glycerol, fatty acid esters, and the like, thereby obtaining a tocopherol concentrate. .

According to US Pat. No. 3,335,154, the deodorant effluent is saponified and acidified to convert glycerides and sterol esters contained in the deodorant effluent into alcohols such as fatty acids, glycerol, sterols and the like. The resulting fatty acid was reacted with a low molecular weight monohydric alcohol under acid catalysis to convert into fatty acid esters, and sterols were isolated through recrystallization, followed by molecular distillation to obtain a tocopherol concentrate.

According to US Pat. No. 4454329, the tocopherol concentrate was esterified by reacting the fatty acids in the deodorant effluent with dihydric or polyhydric alcohols under an acid catalyst and then by solvent extraction or molecular distillation.

According to Japanese Patent Application Laid-Open No. 56-12383, the soybean oil deodorization effluent was methyl esterified using methanol and toluene mixed solvent in the presence of sulfuric acid, and then the toluene layer was separated and the column column chromatography filled with a strong base anion exchange resin was used. After passing through to remove the non-adsorbed component, eluted with 10% toluene acetate solution, acetic acid in the eluate was washed with warm water at 80 ° C., and the solvent was removed to obtain a tocopherol concentrate.

According to Japanese Patent Application Laid-Open No. 59-212487, soybean oil was dissolved in a polar solvent and then passed through a column column chromatography filled with a non-polar polymer adsorption resin, and the non-adsorption portion was concentrated to obtain a tocopherol concentrate. In addition, cottonseed oil was dissolved in hexane and passed through a column column chromatography filled with a strong basic anion exchange resin to remove nonadsorbents such as glycerides, hydrocarbons, waxes and sterols, and eluted alpha-tocopherol by passing methanol. Non-alpha-tocopherol was eluted by passing through methanol dissolved in% acetic acid, and the eluate was passed through tube column chromatography filled with non-polar polymer resin to obtain non-alpha-tocopherol.

Tocopherol concentration by the solvent extraction method and saponification method is effective only when the tocopherol content in the raw material is high, and has many disadvantages in terms of purity and yield of the product, and molecular distillation method is also difficult to distill conditions and concentrated tocopherol The purity and yield are not high. Tocopherol concentration using ion-exchange resin is often used as a food additive or pharmaceutical raw material such as methanol or toluene, and it is problematic to recover solvent due to the mixed use of solvents. When free fatty acids may be mixed, there is a difficulty in removing acetic acid, and the yield is good, but there is a disadvantage in that high purity tocopherol cannot be obtained.

The present invention aims to provide a method for obtaining a high purity natural tocopherol from the soybean oil deodorization effluent in a simple process and high production in order to solve the above problems.

In order to achieve the above object, the present inventors have intensively studied and used organic solvents in two columns filled with basic anion exchange resin through simple desterol process and esterification process using soybean oil deodorant effluent. The present invention was completed by devising a technology to obtain high purity natural tocopherol by a simple process and high productivity by passing through the liquid.

The present invention relates to a method for separating and purifying a high purity tocopherol concentrate from a soybean oil deodorization effluent. The soybean oil deodorant effluent is subjected to a desterol process by recrystallization to remove sterols, and to produce fatty acids in the primary sample. It is characterized in that the tocopherol is eluted after it is introduced into the basic anion exchange resin and passed through an organic solvent in which carbonic acid gas is dissolved.

Hereinafter will be described in detail with respect to the present invention.

In the desterol process according to the present invention, 1 to 3 times of acetone is completely dissolved in the soybean oil deodorant effluent, and then 0.03 to 0.1 times of acetone is added to water, cooled to 5 ° C. or less, and crystallized sterol is filtered. Remove to obtain a primary sample.

0.7-5 times the monohydric, such as methanol, ethanol, or isopropanol, dihydric or polyhydric alcohol, such as ethylene glycol, was added to the primary sample obtained by the desterol process, and 1-5 with respect to the primary sample. A secondary sample is prepared by esterifying various fatty acids contained in the sample by stirring or refluxing at 30 to 80 ° C. using a sulfuric acid catalyst of%.

The esterification reaction by acid catalyst is a reversible reaction, so the amount of unreacted free fatty acids decreases as the amount of alcohol is used, but in this case, the amount of raw materials per reaction vessel decreases and the productivity decreases. Since it is difficult to recover, it is appropriate to use an alcohol of 0.7 to 5 times the volume ratio of the primary sample, and preferably, 0.7 to 1.5 times the volume ratio of alcohol. This method minimizes the decomposition of tocopherol that may occur during the reaction by using a small amount of acid catalyst compared to the existing method, and also facilitates the removal of the catalyst after the reaction.

Among the secondary sample constituents obtained in the esterification process, the adsorption capacity for basic anion exchange resin is the weakest in sterols, fatty acid esters, hydrocarbons and some pigments, the strong tocopherols and the strongest free fatty acids and some pigments. Two column column chromatography (column 1 and column 2) were prepared by using and the basic anion exchange resin was filled and used for separation.

The secondary sample obtained in the esterification step was dissolved in ethanol, and then filled with basic anion exchange resin and passed through the interconnected columns 1 and 2, and ethanol was passed through to remove sterols and fatty acid esters. And non-adsorbents such as hydrocarbons and some pigments are removed. When the non-adsorbents are removed, column 1, which contains free fatty acids and some pigments, is removed. In this case, the size of column 1 may be determined by calculating the amount of free fatty acids and pigments in the sample and the unit adsorption capacity for the anion exchange resin, and the size of column 1 should be as small as possible in consideration of the cost and work efficiency of the resin. Finally, the tocopherol mixture was eluted by passing ethanol saturated with carbon dioxide to column 2 to obtain a tocopherol with a purity of 85% or more with a recovery rate of 90% or more.

The ethanol used at this time may be 95% fermented ethanol, 95% synthetic ethanol, 99.5% anhydrous ethanol, 99.9% anhydrous ethanol, all of which can be used more than 95% pure ethanol, and solvents that can be used instead of ethanol include alcohols such as methanol, isopropyl alcohol; Ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran; Halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride; Ketones such as acetone and ethyl methyl ketone; Organic acid esters such as ethyl acetate and methyl acetate; Aromatic hydrocarbons, such as benzene and toluene, and hydrocarbons, such as pentane, hexane, cyclohexane, can be used, These can be used individually or in mixture of one or more.

In addition, the ion exchange resin is AMBERJET 4400, AMBERITE IRA-400, AMBERITE IRA-401, AMBERITE IRA-402, AMBERITE IRA-410, AMBERITE IRA-416, AMBERITE IRA-420C, AMBERITE IRA-458, AMBERITE IRA-900, AMBERITE IRN -78, DIAION PA408, DIAION PA418, DIAION SA10A, DIAION SA10AS, DIAION SA11A, DIAION SA20A, DIAION SA21A, DOWEX 1X2-100, DOWEX 1X2-200, DOWEX 1X2-400, DOWEX 1X8-50, DOWEX 1X8-100, DOWEX Basic anion exchange resins such as 1X8-200, DOWEX 1X8-400, DOWEX 2X8-100, DOWEX 2X8-200, DOWEX 2X8-400, DOWEX MSA-1, DOWEX MSA-2 and DOWEX G-55 can be used. It may be used alone or in combination of one or more.

Thus, by adsorbing free fatty acids and pigments with high adsorption in the first column using two columns in advance, free fatty acids eluted together with tocopherol during tocopherol concentration in a single column, which had a great effect on the yield and purity of the product. And it can solve the pigment removal problem efficiently.

In addition, by using a solvent in which carbon dioxide gas is dissolved in place of the conventional acetic acid mixed solvent as a tocopherol eluting solvent, a high purity tocopherol mixture can be obtained by increasing the selectivity of fatty acids and tocopherols, and unlike acetic acid, carbonic acid gas is very easy to remove. There is an advantage in that the process itself can be greatly reduced since a complicated process for removing acetic acid is not necessary.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are not intended to limit the invention only.

Example

<< Example 1 >>

1 kg of soybean oil deodorant effluent (containing 8.13% tocopherol) is added to the reaction vessel, and dissolved by adding 3 L of acetone. 150 ml of distilled water is added thereto, cooled to -5 ° C, and left for 1 hour. The precipitated sterol was removed by filtration and the filtrate was distilled under reduced pressure to remove acetone. The filtrate was transferred to a separatory funnel, and left standing to remove water from the separated lower layer to obtain 759 g of desterolized primary sample (containing 10.54% of tocopherol).

<< Example 2 >>

760 ml of methanol is added to 759 g of the primary sample prepared in Example 1, and 7.6 g of sulfuric acid is added to reflux for 2 hours. After the reaction was completed, 760 ml of water and 760 ml of hexane were added, stirred for 1 minute, and left to stand. The water layer of the lower layer was removed, and the organic layer was washed three times with 1100 ml of water to completely remove the acid catalyst, and then concentrated under reduced pressure to be methyl esterified. 765 g of a secondary sample (containing 10.33% of tocopherol) was obtained.

<< Example 3 >>

AMBERITE IRA-401, a strong base anion exchange resin, prepared two columns (columns 1 and 2, respectively) having a diameter of 6.5 cm, filled with 150 ml for column 1 and 1.5 L for column 2, and connected thereto. 1.6 L of 99.5% ethanol was added to 530 g of the secondary sample prepared in, dissolved in 50 ml / min, and then passed through 2.0 L of 99.5% ethanol to remove non-adsorbed content. The column 1 was separated and removed, and 7 L of ethanol saturated with carbon dioxide was passed through the column 2 at a rate of 50 ml / min, and the resulting solution was distilled under reduced pressure to obtain 58.5 g of tocopherol concentrate (purity 89.9%, yield 93.38%). .

<< Example 4 >>

AMBERITE IRA-410, a strong basic anion exchange resin, was prepared with two columns (column 1 and column 2) each having a diameter of 4.0 cm, filled with 20 ml for column 1 and 220 ml for column 2, and then connected in Example 2. 200 ml of 95% fermented ethanol was added to 100 g of the prepared secondary sample, mixed and passed through at a rate of 5 ml / min, and 300 ml of fermented ethanol was passed through at a rate of 5 ml / min to remove non-adsorbed powder. The column 1 was separated and removed, and 600 ml of fermented ethanol saturated with carbon dioxide gas was passed through at a rate of 7 ml / min, and 400 ml of fermented ethanol was passed through at a rate of 7 ml / min. 11.44 g (purity 85.66%, 92.2% yield) of the concentrate were obtained.

As described above, in the present invention, the soybean oil deodorant effluent is subjected to a low temperature fractionation process using an organic solvent to remove the sterol mixture, esterified fatty acid with alcohol under sulfuric acid catalyst, and then dissolved in an organic solvent to give a basic anion exchange resin. Tocopherol is eluted with an organic solvent in which carbonic acid gas is dissolved by flowing into a column device packed with a gas.In order to separate and purify natural tocopherol, a method of obtaining a high purity natural tocopherol from a soybean oil deodorant effluent with a simple process and high productivity to provide.

Claims (5)

In separating and purifying natural tocopherol from soybean oil deodorization effluent, (A) Sterols through a low temperature fractionation process using organic solvents Remove the mixture (B) esterify the fatty acid by reacting it with alcohol under sulfuric acid catalyst (C) Column apparatus filled with basic anion exchange resin by dissolving it in organic solvent To elute the tocopherols with an organic solvent in which Separation and purification of natural tocopherols from soybean oil deodorization How to In the step (b) of claim 1, the alcohol used is monohydric alcohols such as ethanol, methanol, isopropanol, dihydric alcohols such as ethylene glycol, or polyhydric alcohols having three or more OH- groups, and added. The ratio is 0.7 to 5 times by volume ratio relative to the first sample, and as a catalyst, sulfuric acid is added at a weight ratio less than 5% relative to the first sample, and the fatty acid is esterified by heating and stirring at a temperature in the range of 30 to 80 ° C. Way In the process of claim 1, the column apparatus comprises two columns (columns 1 and 2), each column is filled with a basic anion exchange resin, and the remaining free fatty acids and pigments in the sample are removed from the column 1, and Separation and purification method of natural tocopherol, characterized in that tocopherol is separated and concentrated in high purity in column 2 Separation and purification method of natural tocopherol, characterized in that eluting natural tocopherol through the organic solvent in which carbonic acid gas is dissolved in step (c) of claim 1 In the step (c) of claim 1, the organic solvent is alcohol such as ethanol, methanol, isopropyl alcohol; Ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran; Ketones such as acetone and ethyl methyl ketone; Organic acid esters such as ethyl acetate and methyl acetate; And hydrocarbons such as pentane, hexane, cyclohexane, and the like, and to separate and purify natural tocopherols, which are used alone or in combination.