JP6256981B2 - Selective continuous recovery method of vitamin E from oil - Google Patents

Description

  The present invention relates to a method for selectively separating and recovering vitamin Es such as tocotrienols from oils, in particular natural oils such as palm oil and rice bran oil, without degradation loss.

Vitamin E (tocotrienol and tocopherol) has attracted attention as a health functional substance having high antioxidant activity. In particular, tocotrienol has the same basic structure as tocopherol and has three double bonds in the side chain, and therefore has an antioxidant activity 40 to 60 times higher than that of tocopherol (Non-patent Document 1). Recently, high physiological activities of tocotrienol such as an arteriosclerosis improving action and an anticancer action have been reported (Non-patent Document 2), and active use in the pharmaceutical and food fields is expected.

However, tocopherol is widely contained in various vegetable oils such as soybean, rapeseed, sunflower and corn, while tocotrienol is contained in some vegetable oils such as palm and rice bran at a very low concentration. In addition, tocotrienol easily undergoes oxidative degradation due to heat due to a double bond in the side chain, and easily loses physiological activity.

As a raw material for separating and recovering these vitamin Es, deodorized effluent (scum oil) discharged in a deodorizing process at the time of edible oil production is used. Table 1 shows the general composition of the deodorized effluent derived from soybean oil having a high tocopherol content and the deodorized effluent derived from rice bran having a high tocotrienol content in comparison with each crude oil. Although the content of vitamin E in scum oil is several tens of times higher than that in crude oil, the main component is free fatty acids, including triglycerides, sterols, and various hydrocarbons. Therefore, regardless of which vitamin E is targeted, a step of collecting a solution containing vitamin E rich from the raw material and a step of highly separating tocopherol, tocotrienol and other contaminants in the collected solution are required. . Various chromatographic separation methods have been proposed for the latter advanced separation step, and it is possible to separate α, β, γ, and δ isomers of tocopherol and tocotrienol as necessary. However, when the concentration of vitamin E in the recovered liquid is low and there are many other contaminants, a large amount of eluent supply and elution time are required, which increases the cost and environmental burden due to chromatographic separation. Therefore, in the process of recovering the vitamin E-rich solution from the former raw material, it is important how to suppress the degradation loss of vitamin E, increase the concentration, and reduce the amount of other impurities mixed.

Various studies have been conducted on tocopherol for the former vitamin E-rich solution recovery process. Most of the methods are molecular distillation of raw materials. Relaxing operating conditions to reduce thermal decomposition loss and additional operations to reduce the amount of impurities mixed (to remove free fatty acids with similar distillation properties) However, the process for removing sterols with similar separation properties has been studied and has already been industrialized, but the method of molecular distillation is applied to deodorized effluent derived from rice bran and palm containing tocotrienol. Then, in addition to the low content in the raw material itself, the thermal decomposition loss due to distillation is large, so the tocotrienol concentration and purity of the recovered liquid are also very low. However, it has become extremely expensive and has not yet been commercially available (Japanese Patent Laid-Open No. 8-100131, Patent Publication No. 10-508605, Japanese Patent Laid-Open No. 2002-194381, Japanese Patent Laid-Open No. 2002-3488, Japanese Patent Laid-Open No. 2003-171376, Japanese Patent Laid-Open No. 2004-30515 5, JP-A-2005-536191, JP-A-2007-521382, JP-A-2007-176801).

On the other hand, a recovery method by physical adsorption / desorption under mild conditions in which molecular distillation is not performed on deodorized effluent derived from palm containing tocotrienol has been studied. As the adsorbent, aluminum oxide, porous polymer, silica gel or the like is used, and it is shown that the recovery rate of vitamin E is high when silica gel is used. Although this method can avoid thermal decomposition loss due to distillation, it still requires a removal process of free fatty acids with similar adsorption properties and a removal process of sterols with similar separation properties, and tocotrienol is lost in these steps. There is no improvement.

Thus, there is no technology that can efficiently and stably recover a large amount of highly functional and high added value tocotrienol from natural oil, which is a major obstacle to industrialization. That is, the problems of the prior art are: 1) Tocotrienol is denatured and deteriorated due to extreme pH and temperature conditions, 2) Tocotrienol cannot be selectively recovered, and various impurities with similar separation properties are mixed (purity) 3) High molecular distillation process equipment and running cost. 4) Because there is no selective separation method, scum oil enriched with tocotrienol (tocotrienol content of about 2wt%) must be used as a raw material. The raw materials are limited.

  On the other hand, Kitagawa et al., The present inventor, developed the world's first fatty acid ester continuous synthesis technology that transesterifies triglycerides at a relatively low temperature (50 ° C) with an original idea using an anionic resin as a heterogeneous solid catalyst. (Non-patent document 2, Patent document 1, Patent document 2). Furthermore, a method for regenerating the catalytic activity of the anionic resin used for the fatty acid ester continuous synthesis by washing with a weak acid solution was also provided (Patent Document 3). In Patent Documents 1 and 2, it is described that fatty acid residues are adsorbed on the resin in parallel with the transesterification reaction, so that it is necessary to wash with an acid aqueous solution to desorb them. . Patent Document 3 discloses the removal of oil such as oleic acid residues adsorbed on a resin that causes deterioration of transesterification activity for the purpose of washing with a weak acid solution. However, these patent documents do not describe anything about the separation and recovery of vitamin E by an anion resin.

  Furthermore, the present inventors also developed the simultaneous production method of tocotrienol and biodiesel fuel from oil (patent document 4). Since this method does not require a molecular distillation step, deterioration of vitamin Es such as tocotrienol can be prevented under mild operating conditions such as room temperature.

JP 2006-104316 A JP 2007-297611 A JP 2007-14871 A JP 2009-190989

Biochem.Biophys.Res.Commun., 348,170 (2006) Bioresource Technol. 98,416 (2007)

In the method described in Patent Document 4, when vitamin Es are separated and recovered from palm oil or rice bran oil using a cation exchange resin and an anion exchange resin, vitamin Es are oxidatively decomposed and have low stability. In addition, since the adsorption proceeds more rapidly at a lower temperature, the reaction temperature during treatment such as adsorption / desorption using an anion exchange resin of vitamin E is preferably in the range of 0 ° C. to room temperature. The purity of vitamin E has not been studied. However, for efficient recovery of vitamin E, it has been desired not only to suppress thermal decomposition loss but also to increase the recovery amount and purity. Moreover, when using a deodorized effluent (scum oil) as a raw material, since many free fatty acids with low melting | fusing point are included, when the said process was performed below normal temperature, the raw material solidified and the problem which obstruct | occludes piping had arisen. Furthermore, when considering an actual industrialization process, it is preferable to carry out all the steps under the same conditions as much as possible from the economical and efficient viewpoints, and the temperature conditions in the above steps using an anion exchange resin are the same as before. In this process, the temperature conditions in the esterification reaction using a cation exchange resin (usually about 50 ° C.) are preferably arranged as much as possible.

The present inventor adsorbs vitamin E to an anion exchanger when the temperature of adsorption and separation of vitamin E using an anion exchanger such as an anion exchange tree is increased to about 45 ° C. to 55 ° C. At the same time, the fatty acid group which is a side chain of triglyceride (TG) contained in the raw material oil is also adsorbed to the anion exchanger, and when the adsorbed vitamin E is recovered, the fatty acid adsorbed in the same manner It was found for the first time that the group was incorporated as a free fatty acid.

As a result of intensive studies based on such new knowledge, the inventor of the present invention has considerably higher adsorption separation of vitamin E using an anion exchanger than the method disclosed in non-patent literature of about 45 ° C to 55 ° C. Performing under temperature conditions and setting the amount of alcohol added to the oil and the acid concentration in the desorbed liquid used to separate vitamin E adsorbed on the anion exchanger within a specific range In this way, we succeeded in increasing the recovery rate, amount and purity of vitamin E and solved the above problems.

That is, the present invention relates to the following aspects.
[Aspect 1] The following steps:
(1) Contact a mixed solution of oil and alcohol containing vitamin E with an anion exchanger,
(2) The triglyceride contained in the oil is converted into an adsorption-inactive fatty acid ester by transesterification using the anion exchanger as a catalyst, and at the same time, vitamin E contained in the oil is adsorbed on the anion exchanger. And (3) desorbing and recovering vitamin E from the anion exchanger using a desorbing solution containing acid and alcohol.
A method for selectively and highly producing vitamin E from the oil, comprising:
The mixed solution contains alcohol in an amount of 80 to 120% of the reaction stoichiometric amount with respect to the total amount of free fatty acid and triglyceride in the oil, and the concentration of acid in the desorbed solution is 2 to 5 wt%. The said method characterized by performing at 45 to 55 degreeC.
[Aspect 2] The method according to Aspect 1, wherein ethanol is used as the alcohol.
[Aspect 3] A method according to aspect 2, wherein acetic acid is used as the acid.
[Aspect 4] The method according to any one of Aspects 1 to 3, further comprising separating tocotrienol from the separated vitamin E.
[Aspect 5] The method according to aspect 4, wherein tocotrienol is separated from vitamin E by chromatographic separation.
[Aspect 6] The method according to any one of Aspects 1 to 5, wherein esterification of free fatty acids in the oil is performed before the vitamin E contained in the oil is brought into contact with the anion exchanger.
[Aspect 7] The method according to Aspect 6, wherein the free fatty acid is esterified using a cation exchanger.
[Aspect 8] The method according to any one of Aspects 1 to 7, wherein the anion exchanger is an anion exchange resin.
[Aspect 9] The method according to any one of Aspects 1 to 8, wherein a deodorized effluent (scum oil) is used as the oil.
[Aspect 10] The method according to any one of Aspects 1 to 9, wherein the reaction and / or adsorption separation is continuously performed using a reactor filled with a resin.
[Aspect 11] An apparatus for carrying out the method according to any one of Aspects 1 to 10, wherein the apparatus comprises a reactor filled with a resin, and the reaction and / or adsorptive separation is continuously performed.

The method of the present invention does not require a molecular distillation step. Therefore, since the cost (equipment and running cost) of the molecular distillation process is reduced, inexpensive production is possible. Further, only tocotrienol can be selectively recovered from the multi-component mixture with high purity by using a selective reaction between the resin and tocotrienol. Therefore, it does not contain impurities such as sterols that are difficult to separate from tocotrienol, and further high-level isomer separation is facilitated. Further, since the method of the present invention does not use a soaking catalyst, it is not necessary to perform a catalyst separation operation such as neutralization and desalting. Therefore, since tocotrienol can be recovered by a simple operation, inexpensive supply can be realized. Furthermore, since a solid catalyst called resin is used as an anion exchanger, it is possible to carry out reaction and adsorption separation with a simple operation by simply passing the reaction liquid through a reactor filled with resin. Will also be easier.

According to the present invention, when an alcohol is added to an oil containing vitamin E or the like to prepare a mixed solution, a reaction stoichiometric amount (for example, the reaction stoichiometric amount for the total amount of free fatty acids and triglycerides in the oil). (About 80 to 120%, preferably about 90 to 100%) of alcohol), the transesterification reaction of the triglyceride contained in the oil proceeds rapidly using the anion exchanger as a catalyst, The fatty acid group as a side chain becomes an adsorption-inactive ester, and when the vitamin E contained in the oil is adsorbed on the anion exchanger, the side chain fatty acid group of triglyceride is adsorbed on the anion exchanger at the same time. It became possible to prevent this.
Furthermore, in the continuous recovery method of vitamin E from oil using a cation exchanger and an anion exchanger, it is possible to increase the recovery amount and purity of vitamin E even under high temperature conditions of about 45 ° C to 55 ° C. It became.
In addition, the content of tocotrienol in the crude oil of rice bran and palm was as low as 0.1 wt%, which could not be recovered by the existing method. However, by the method of the present invention, only tocotrienol was removed from the multi-component mixture without thermal decomposition loss. Selective recovery with high purity became possible.

An example of the method of the present invention is shown in a flowchart.

The oil used as a raw material in the method of the present invention is not particularly limited as long as it contains vitamin E such as tocotrienol, and may be natural oil (crude oil), synthetic oil, or a mixture thereof. Furthermore, modified oils obtained by modifying a part of these oils by oxidation, reduction, or the like, and oil processed products containing these oils as the main component can also be used as raw materials.

  That is, as already described, deodorized effluent (scum oil) that is by-produced in the refining process of rice bran oil and palm oil, which is used as a raw material in the conventional method, and is not effectively used can be used. Furthermore, it is preferable to use rice bran and palm crude oil from the viewpoint of production. As a result, the amount of tocotrienol supplied to the market is increased by about 50 times.

It is also possible to use oil in which any foreign component other than oil is mixed. These foreign components are preferably removed by an appropriate means known to those skilled in the art, such as sedimentation, filtration, and liquid separation, and then used in the method of the present invention.

Vitamin E includes α-, β-, γ-, and δ-tocotrienol, and α-, β-, γ-, and δ-tocophenol.

As already described, since the anion exchanger also adsorbs free fatty acids contained in the oil and fatty acids that are the side chains of triglycerides, when these oils containing a large amount thereof are directly treated, these free fatty acids are adsorbed. It is important that fatty acids and side chain fatty acid groups are not adsorbed on the anion exchanger.

Therefore, the feature of the present invention is that when an alcohol is added to an oil containing vitamin E or the like to prepare a mixed solution, an amount equivalent to a stoichiometric amount with respect to the total amount of free fatty acids and triglycerides in the oil (for example, By adding about 80 to 120%, preferably about 90 to 100%, of the reaction stoichiometric amount of alcohol), the transesterification reaction of the triglyceride contained in the oil can be accelerated by using the anion exchanger as a catalyst. When the fatty acid group which is the side chain of triglyceride becomes an adsorption-inactive ester and the vitamin E contained in the oil is adsorbed to the anion exchanger, the side chain fatty acid group of the triglyceride becomes the anion. It is to prevent simultaneous adsorption on the exchanger. This makes it possible to increase the recovery amount and purity of vitamin Es.

When the amount of alcohol added is larger than the amount corresponding to the above reaction stoichiometry, the transesterification reaction of the triglyceride progresses slowly. On the contrary, when the alcohol addition amount is low, the transesterification reaction of the triglyceride does not proceed sufficiently. In either case, the fatty acid group, which is a side chain of triglyceride, cannot be sufficiently prevented from adsorbing to the anion exchange resin, resulting in a decrease in the recovery amount and purity of vitamin Es.

Further, when free fatty acid is contained in the oil, it is preferentially adsorbed to the anion exchanger over vitamin E, resulting in a decrease in the amount of vitamin E recovered and purity. Therefore, before the oil is brought into contact with the anion exchanger, it is necessary to advance the esterification reaction of the free fatty acid contained in the oil by the cation exchanger to obtain an adsorption-inactive ester. For this purpose, first, an oil containing vitamin E is treated with a cation exchanger with an alcohol in a reaction stoichiometric amount with respect to the total amount of free fatty acids.

As the cation exchanger, for example, a cation resin known to those skilled in the art such as Diaion PK-208LH (manufactured by Mitsubishi Chemical Corporation) can be used. The esterification of the free fatty acid contained in the oil by the cation exchanger prevents the heat loss of the tocotrienol and allows the reaction to proceed rapidly, so that each operation such as adsorption and separation using an anion exchanger is performed. It is preferable to carry out at the same temperature range as, for example, about 45 ° C to 55 ° C, for example, about 50 ° C. Further, in order to minimize the residual amount of free fatty acid, the conversion rate of esterification is preferably 97% or more. Such high conversion rate can be achieved under the above-mentioned mild conditions. It is an excellent feature of the body.

The other conditions in the above reaction by the above cation exchanger, for example, the reaction time and the reaction pressure are appropriately selected from those known to those skilled in the art as described in Patent Document 1 and Patent Document 2. It can be set.

In the method of the present invention, the amount of the “reaction stoichiometric amount relative to the total amount of free fatty acids and triglycerides” means that when the alcohol used is a monohydric alcohol such as ethanol, [(free fatty acid Mole number) + (number of moles of triglyceride) × 3].

The amount of free fatty acid and triglyceride contained in the raw oil is determined by any method / means known to those skilled in the art, for example, the method described in the test method used in the standard of biofuel (JIS K 2390). Can be sought.

Alternatively, instead of actually measuring the amount of free fatty acid and triglyceride contained in the oil, it is generally known in the art as the total amount of free fatty acid and triglyceride contained in the starting oil. Range, for example, in the case of scum oil, free fatty acid: about 30 to 50 wt% and triglyceride: about 10 to 20 wt%. You can ask. For example, in the case of the scum oil, the reaction stoichiometry is about 6 to 10 wt% with respect to the oil.

In the method of the present invention, adsorption and separation of vitamin Es on an anion exchanger, and desorption and recovery therefrom are performed. For example, the vitamin E contained in the oil is adsorbed on the anion exchanger by bringing the oil into contact with the anion exchanger, and then the anion exchanger on which the vitamin E is adsorbed is subjected to an appropriate filtration such as oil and filtration. Isolate by method. Then, vitamin Es are desorbed by washing the anion exchanger using an alcoholic acid solution as a desorbing solution.

As the anion exchanger (anion exchanger), any of those known to those skilled in the art described in JP-A-2006-104316 and JP-A-2007-297611 can be used. In particular, strong basic anion exchange resins are preferred. When the anion exchange resin is classified by the degree of crosslinking or porosity, a gel type, a porous type, a high porous type and the like can be mentioned, and a porous type and a high porous type are preferable.

Incidentally, as commercially available products, for example, Diaion PA-306 (manufactured by Mitsubishi Chemical Corporation), Diaion PA-306S (same), Diaion PA-308 (same), Diaion HPA-25 (same) Dowex 1 -X2 (manufactured by Dow Chemical Company), Amberlite IRA-45 (manufactured by Organo), Amberlite IRA-94 (same), etc. can be used.

Furthermore, examples of commercially available anion exchange resins satisfying pKa of 9.8 or less include Diaion SA20A (manufactured by Mitsubishi Chemical Corporation), Diaion SA21A (same), and porous type II strong base anions. As an exchange resin, Diaion PA408 (same), Diaion PA412 (same), Diaion PA418 (same), and the like can be used. Here, the type II strong base anion exchange resin refers to the above-described anion exchange resin having a dimethylethanolammonium group.

Since a commercial product of an anion exchange resin is Cl type at the time of purchase, it is used in the present invention after being substituted with an OH group. For example, a 0.5 to 2 mol / dm ³ aqueous NaOH solution is used as the replacement agent, and the flow rate of the replacement agent is preferably about 2 to 10 ml-NaOH / min per 1 ml of anion exchange resin. The flow rate is 5 to 20 ml per 1 ml of anion exchange resin. After the substitution is completed, the resin is taken out from the column and thoroughly washed with distilled water so that the substitution agent does not remain. The pH of the resin cleaning solution is measured to confirm that it has the same pH as that of distilled water, and finally washed with a predetermined alcohol and used in the present invention.

In the case of a stirred tank reactor, the amount of the anion exchange resin used is usually selected from the range of 100 to 1000 g, preferably 200 to 800 g, per mole of oil. After use, it can be used repeatedly for the same reaction, but it is preferable to regenerate the resin as appropriate. When using an ion exchange resin as a packed bed, the oil flow rate per liter of resin is usually 10 to 100 mL, preferably about 15 to 60 mL.

In the method of the present invention, the operations of adsorption and separation of vitamin E on the anion exchanger, desorption and recovery from the anion exchanger are performed within a range not higher than the heat resistant temperature of the anion exchanger, for example, about 45 C. to 55.degree. C., preferably about 50.degree. C. As a result, the above-described process using an anion exchange resin can be performed in the same temperature range for all the processes using a cation exchange resin and an anion exchange resin, which are the previous processes, and the actual industrialization process can be performed. When considered, it is preferable from the viewpoint of economy and efficiency, and further, there is no possibility that the raw material is solidified to block the piping.

Furthermore, one of the technical features of the present invention is that the acid concentration in an acid solution used as a desorbing solution to desorb vitamin E by washing an anion exchanger is 2 to 5 wt%, Preferably, it is 3.0 to 3.5 wt% (0.40 to 0.45 mol / L), more preferably about 3.3 wt% (0.43 mol / L). In this way, by setting the acid concentration in the desorbed liquid within a specific range, the elution time of free fatty acid adsorbed on the anion exchanger together with vitamin E can be shifted from the elution time of vitamin E, It becomes possible to increase the recovery amount and purity of Es.

The alcohol used in the method of the present invention is not particularly limited, and examples thereof include alcohols having a saturated linear or branched hydrocarbon skeleton having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. For example, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol and the like can be mentioned. These alcohols can be used alone or in admixture of two or more. In the present invention, it is preferable to use methanol and / or ethanol from the viewpoint of availability and availability of the obtained fatty acid ester. In this operation, the alcohol acts as a reaction substrate for subjecting the oil to alcoholysis (transesterification reaction), and also has a solvent action for adjusting the dilution and viscosity of the oil.

As such an acid, an organic acid such as formic acid, acetic acid, citric acid or a salt thereof, or a mixture thereof can be used. In particular, the acid solution is preferably a weak acid or weak acid salt solution such as a mixed solution of acetic acid and an alcohol such as ethanol.

Other conditions / means for each of the above operations can be appropriately selected from any known to those skilled in the art. For example, each reaction time (contact time, desorption time) can be appropriately set by those skilled in the art depending on the reaction temperature, the amount of ion exchange resin used, and the like. For example, the stirring is usually performed for 1 to 10 hours, preferably 3 to 5 hours, and in the flow system for 5 minutes to 2 hours, preferably 10 minutes to 1 hour.

Furthermore, the reaction pressure is not particularly limited. Although it is easy to operate under normal pressure, the pressure may be increased to about 1 to 10 atm if necessary.

Tocotrienol contained therein can be separated from the separated vitamin E by any method known to those skilled in the art, such as chromatographic separation. It should be noted that when a column or the like is filled with an anion exchanger adsorbed with vitamin E and an acid solution is used to elute vitamin E from the anion exchanger, various conditions (for example, the type of acid, By appropriately setting the treatment flow rate, time, etc., the desorption (elution) time peak of each component in vitamin E adsorbed on the anion exchanger can be shifted. No chromatographic separation is required.

In each operation step in the method of the present invention, the contact method between the reaction substrate and the ion exchanger is not particularly limited, such as a batch method or a continuous method. Examples of the apparatus include a device provided with a treatment tank, and a device for transferring resin in a circulation system or a countercurrent system. Examples of the contact method include circulation (method of passing through a packed bed of ion exchange resin), stirring (method using a stirring tank), flow (fluidized bed reactor), shaking (shaking reactor), and the like. . In addition to a column-flowing type and a developing bed (expanded column) in which the raw material introduction port and the product collection port are fixed, a batch type can also be used. In particular, a method in which each operation such as reaction or adsorption separation is continuously performed using a reactor filled with a resin is preferable.

In particular, a reactor having a reaction substrate introduction port on one side of a container (reactor) filled with a predetermined ion exchanger and a product recovery port on the other side is desirable. Although the said container may have individually, you may have the structure formed by connecting two or more in parallel and / or in series. The shape of the container is not particularly limited, but a column is usually used. When an ion exchange resin is packed in a column and used, an embodiment using an expanded bed column packed layer having a high porosity is preferable in order to prevent the resin from swelling and being damaged. Here, an expanded bed column is used in a separation and purification method in which a target component dissolved in a fluid having a high viscosity or a solid content is adsorbed and recovered by adsorbent particles. This refers to those in which fluid is flowed upward, adsorbent particles having a large specific gravity are suspended in a stationary state, and column chromatography operation is performed while maintaining a large porosity. For example, Chemical Engineering Papers Vol. 27, No. 2 (2001) Known methods described in pages 145-148 and the like can be used. In the range where the molar ratio of oils to alcohols is large, the problem of breakage of the ion exchange resin due to swelling is likely to occur, so care is taken in designing the reactor. The invention therefore also relates to an apparatus for carrying out such a method of the invention. However, for efficient operation, an upward flow is used during an adsorption operation for passing a liquid mixture of oil and alcohol, and a downward flow is used for a desorption operation for passing a liquid mixture of acid and alcohol. It is preferable.

EXAMPLES Hereinafter, although this invention is concretely demonstrated according to an Example, the technical scope of this invention is not restrict | limited at all by these description. The following examples were carried out according to general methods known to those skilled in the art unless otherwise specified.

Simulation experiment with model scum oil system (1)
The following experiments evaluated the influence of the amount of triglyceride and added alcohol contained in the oil raw material after esterification of fatty acids on the free fatty acid efflux.
Experimental conditions:
Raw material 1: Vitamin E (V _E H) δ-Tocophenol 3wt%-Ethanol solution Raw material 2: Model oil assuming post-esterification of fatty acid (δ-Tocophenol 3wt%, Triglyceride 14wt%, Fatty acid ester 83wt%) And ethanol mixture (triglyceride: ethanol mixture molar ratio = 1: 3, 1: 6 and 1:20)
Resin column: DiaionPA306S packed with 6.7g Adsorption experiment: Raw material solution is supplied to the column (Φ1.1 cm x 10 cm) at a rate of 1 cm ³ / min (50 ° C)
Desorption experiment: After feeding ethanol in the downward flow at the same rate to flow out the raw material in the column, 0.43 mol / L acetic acid-ethanol solution was similarly supplied Temperature condition: 50 ° C
result:
As shown in Table 2, if triglyceride (GF ₃ ) was not present in the raw material (raw material 1), the free fatty acid did not flow out (purity 100%) although there was a mixture of weak acid in the effluent. On the other hand, when triglyceride is present in the raw material (raw material 2), as shown in Chemical Formula 1, adsorption of side chain fatty acid groups occurs competitively and is released together with tocopherol (V _E H) during the desorption experiment. Fatty acid (FH) flowed out, making it difficult to recover tocopherol (Table 3). In this experiment, the triglyceride of the raw material is set to 14 wt%, which is the same low value as in scum oil, but the higher the concentration, the greater the amount of contamination.

Here, the recovery rate and purity of vitamin E are defined by the following equations, respectively.
Recovery [%] = Vitamin E desorption amount / (Total amount of vitamin E in the supplied raw material−Total amount of vitamin E in the raw material flowing out from the column) × 100
Purity [wt%] = Vitamin E elimination amount / (Vitamin E elimination amount + free fatty acid elimination amount) x 100
(* 90% of total desorption amount)

Simulation experiment with model scum oil system (2)
Next, the influence of the acid concentration in the detachment solution on the free fatty acid efflux was evaluated by the following experiment.
Experimental conditions:
Desorption experiment: After supplying ethanol to drain the raw material in the column, the acetic acid concentration in the desorption solution (acetic acid-ethanol solution) was changed to 0.86 mol / L, 0.43 mol / L and 0.22 mol / L. Except for the point, it is the same as Example 1.
result:
As shown in Table 4, by using a desorbed solution having an acetic acid concentration of 0.43 mol / L, the recovery amount, recovery rate, and purity of vitamin E were successfully increased.

Experiment using practical system (scum oil)
Experimental conditions:
Oil raw material: Rice bran-derived scum oil (provided by Sanwa Yushi Co., Ltd.): Vitamin E (V _E H) (tocophenol (T1) 1.5 wt% and tocotrienol (T3) 1.5 wt%), triglyceride (GF ₃ ) 14 wt%, free fatty acid (FH) 44 wt%
Added ethanol: stoichiometric amount for triglycerides and free fatty acids (8.6 wt% of oil)
Esterification of free fatty acids: A batch reaction was performed by adding 33.3% (w / w) resin (Diaion PK208LH) to a mixed solution of oil raw material and alcohol, and shaking at 150 spm for 36 hours in a 50 ° C constant temperature bath. And esterification (conversion> 97%) was carried out.
Adsorption: The raw material solution was supplied (50 ° C.) in an upward flow at 1 cm ³ / min to a resin column (6.7 g of DiaionPA306S: Φ1.1 cm × 10 cm).
Desorption: After feeding ethanol in the downward flow at the same rate to flow out the raw material in the column, 0.43 mol / L acetic acid-ethanol solution is similarly fed (50 ° C), and the adsorbed vitamin E is removed. Desorbed.
result:
As a result, as shown in Table 5, in the conventional method (method of separating vitamin Es and esters by stepwise molecular distillation at 100-250 ° C (5,6 times)), the recovery rate of vitamin Es and Purity was about 35% and 20% by weight, respectively, and the method of the present invention achieved a recovery rate of 100% of vitamin E (particularly, recovery rate of tocotrienol with a large thermal decomposition loss). Furthermore, the purity increased more than 3 times, and the impurities contained were only free fatty acids that were easily chromatographically separated.

In each experiment, after collecting the solution and diluting with ethanol as necessary, the concentrations of tri, di, monoglyceride, free fatty acid, sterol, squalene, and fatty acid ester were determined by HPLC equipped with a UV detector. The concentration of each compound was measured by HPLC equipped with a fluorescence detector.

The present invention has the following industrial applicability.
(1) Vitamin E such as tocotrienol can be supplied to society at lower cost and more stably.
(2) Since high-purity products of tocotrienol can be easily mass-produced, specialized function evaluations and human tests can be performed.
(3) If palm coconut oil or rice bran crude oil with higher production volume is used as a raw material, it will be possible to collect tocotrienol and produce biodiesel fuel and glycerin at the same time, creating a vibrant society that takes into consideration human health and the environment. Can contribute.

Claims (11)

The following steps:
(1) Contact a mixed solution of oil and alcohol containing vitamin E with an anion exchanger,
(2) The fatty acid group which is the side chain of the triglyceride contained in the oil is converted into an adsorption-inactive fatty acid ester by transesterification using the anion exchanger as a catalyst, and at the same time, vitamin E contained in the oil Adsorbed and separated on the anion exchanger, and then (3) desorbing and recovering vitamin E from the anion exchanger using a desorption solution containing acid and alcohol.
A method for selectively and highly producing vitamin E from the oil, comprising:
The mixed solution contains alcohol in an amount of 80 to 120% of the reaction stoichiometric amount with respect to the total amount of free fatty acid and triglyceride in the oil, and the concentration of acid in the desorbed solution is 2 to 5 wt%. The said method characterized by performing at 45 to 55 degreeC. The process according to claim 1, wherein ethanol is used as the alcohol. 3. A process according to claim 2, wherein acetic acid is used as the acid. The method according to any one of claims 1 to 3, further comprising separating tocotrienol from the separated vitamin E. The method according to claim 4, wherein tocotrienol is separated from vitamin E by chromatographic separation. The method according to any one of claims 1 to 5, wherein esterification of free fatty acids in the oil is performed before the vitamin E contained in the oil is brought into contact with the anion exchanger. The method of Claim 6 which esterifies a free fatty acid using a cation exchanger. The method according to any one of claims 1 to 7, wherein the anion exchanger is an anion exchange resin. The method according to any one of claims 1 to 8, wherein a deodorized effluent (scum oil) is used as the oil. The method as described in any one of Claims 1-9 which perform reaction and / or adsorption separation continuously using the reactor filled with resin. The apparatus for carrying out the method according to any one of claims 1 to 10, wherein the apparatus comprises a reactor filled with a resin, and the reaction and / or adsorption separation is continuously performed.