JPWO2010125988A1 - Method for producing tocotrienol composition - Google Patents

Abstract

The present invention relates to a method for producing a tocotrienol-enriched tocotrienol composition comprising tocotrienol and 1% by weight or less of tocopherol based on said tocotrienol, comprising (1) coconut oil, (2) coconut oil and lower A raw material selected from a reaction product obtained by transesterification with alcohol, and (3) a distillation residue of a reaction product obtained by transesterification of coconut oil and a lower alcohol, is converted into an anion having a 2-hydroxyethyldimethylammonium group. A method for producing a tocotrienol-enriched tocotrienol composition comprising a step of adsorption treatment with an ion exchange resin.

Description

The present invention relates to a method for producing a tocotrienol composition enriched in tocotrienol.
Background art

  In recent years, it has been clarified that active oxygen and lipid peroxide are deeply involved in adult diseases and aging phenomena, and there is an interest in materials having antioxidant ability. Among them, tocopherol and tocotrienol are known as compounds having excellent antioxidant ability and radical scavenging ability.

  Tocopherol and tocotrienol are structurally similar, but because tocotrienol has three double bonds in the side chain, it has a particularly high affinity for adipose tissues such as cell membranes, and may have a stronger effect than tocopherol. It has been known. Moreover, tocotrienol has a diuretic, in addition to a preventive effect on heart disease due to cholesterol lowering action in serum (Non-Patent Document 1), a carcinogenesis-inhibiting action (Non-Patent Document 2), and an immunostimulatory action (Patent Document 1). Use as a sodium ion excretion agent, an antihypertensive therapeutic agent, and an ischemic heart disease preventive agent is expected (Patent Document 2). Therefore, in order to obtain the effect specific to tocotrienol more efficiently, it is desirable that tocotrienol can be obtained alone, and development of a simple and economical technique for that purpose has been desired.

  As a method for obtaining a mixture of tocopherol and tocotrienol, a method using a deodorized distillate obtained in a crude oil refining process as a raw material has been reported. For example, a method in which a fatty acid contained in a deodorized distillate is reacted with a lower alcohol in the presence of an acid catalyst, converted to a fatty acid alkyl ester, the fatty acid alkyl ester is removed by distillation, and the distillation residue is purified by molecular distillation. (Patent Document 3). However, in order to obtain a fatty acid distillate, a high temperature condition of 250 to 270 ° C. is required, and esterification reaction of tocopherol, tocotrienol and fatty acid occurs, and the recovery rate is lowered. In addition, since molecular distillation requires high temperature, high vacuum and precise distillation, heating for a long time is required, decomposition of tocotrienol, generation of undesired oxidation reaction products, and esterification reaction with remaining fatty acids. Progresses and the recovery rate decreases.

  On the other hand, after removing fatty acid alkyl ester by distillation, a method of performing an adsorption treatment with an anion exchange resin has been reported (Patent Document 4). However, since all isomers of the tocopherol family are adsorbed by this method, it is difficult to selectively separate only tocotrienol.

  Tocotrienols are contained in trace amounts in natural vegetable oils such as palm oil, rice bran oil, and barley oil. However, since many vegetable oils such as palm oil and rice bran oil contain both tocotrienol and tocopherol, a separation operation from tocopherol is necessary to obtain only tocotrienol. Crude palm oil contains about 600 to 1000 ppm of tocotrienol and tocopherol, and the constituent ratio is 20 to 30% for tocopherol and 80 to 70% for tocotrienol (Non-patent Document 3). Crude rice bran oil contains about 800 ppm of tocotrienol and tocopherol, of which about 50%. Coconut oil has a remarkably low content of these components, so that detailed research has been difficult so far, and industrialization has not been studied.

  In order to separate tocotrienol from a mixture of tocopherol and tocotrienol obtained from palm oil or the like, a more complicated purification process is required. For example, separation and concentration with tocopherol is difficult without using advanced chromatographic separation techniques such as multi-component separation type pseudo moving bed chromatography (Patent Document 5) and liquid chromatography (Patent Document 6). Patent Document 7 describes a method for producing a tocotrienol-enriched preparation, but the palm oil is only shown as the target oil and fat from a palm family plant. Patent Document 8 describes a method for recovering a small amount of a component such as tocotrienol from a vegetable oil such as coconut oil. Tocotrienol is recovered as a mixture with tocopherol or the like, and therefore contains a high concentration of tocotrienol. To obtain the composition, further processing steps are required. In Patent Document 9, fats and oils such as palm oil, soybean oil, coconut oil and wheat germ oil are dissolved in a nonpolar solvent, and ion exchange treatment with an anionic exchange resin is performed to separate and concentrate tocotrienols in the oil. The method of doing is disclosed.

J. et al. Biol. Chemm. , 261, p10554, 1986 Chem. Pharm. Bull. 37, p1369, 1989 Chemical industry data vol. 17, no. 6p225

JP 11-049767 A JP 2001-342133 A US Pat. No. 5,157,132 Japanese Patent Publication No.55-025189 JP 2002-153702 A Japanese Patent Laid-Open No. 2003-292489 International Publication No. 2003/092709 Pamphlet JP 2002-194381 A Summary of the invention of Japanese Patent Laid-Open No. 57-099583

The present invention relates to a method for producing a tocotrienol-enriched tocotrienol composition comprising tocotrienol and 1% by weight or less of tocopherol based on the tocotrienol,
It is selected from (1) coconut oil, (2) a reaction product obtained by transesterification of coconut oil and lower alcohol, and (3) a distillation residue of a reaction product obtained by transesterification of coconut oil and lower alcohol. The present invention relates to a method for producing a tocotrienol composition enriched in tocotrienol, which comprises a step of adsorbing a raw material with an anion exchange resin having a 2-hydroxyethyldimethylammonium group (hereinafter referred to as anion exchange resin (II)).
Detailed Description of the Invention

  The present invention provides a method capable of efficiently producing a tocotrienol-enriched tocotrienol composition having a high tocotrienol content by a simple operation.

  The production method of the present invention can produce a tocotrienol composition enriched in tocotrienol having a high tocotrienol content without requiring a complicated purification process or special equipment. Moreover, it can be carried out easily under mild conditions in terms of energy and cost, and is advantageous as an industrial production method. The high tocotrienol content prevents tocophenol from inhibiting the absorption of tocotrienol.

  Examples of the coconut oil used in the present invention include virgin coconut oil and coconut oil extracted from copula. Virgin coconut oil is obtained by squeezing the endosperm portion of coconut without drying and smoking, and is a raw material oil with less coloring. Coconut oil contains tocotrienol in low purity but high purity.

  The anion exchange resin (II) used in the present invention is a synthetic resin having a chemical structure in which a 2-hydroxyethyldimethylammonium group is introduced as an exchange group into a crosslinked polymer matrix. The polymer matrix is preferably a copolymer of styrene and divinylbenzene. The anion exchange resin (II) is usually used in the form of spherical particles having an average particle size of about 200 to 1200 μm, and further about 200 to 800 μm.

  The anion exchange resin (II) may be either gel type or porous, but is preferably porous. The porous anion exchange resin (II) has the same chemical structure as that of the gel type, but a large number of macropores are present in the polymer matrix, and the active surface becomes larger than that of the gel type. Macropores are pores present in the polymer matrix and are distinguished from micropores present in a water-containing state due to the network structure of the gel-type and porous anion exchange resin (II). As the porous anion exchange resin (II), a porous type or a high porous type (which is more porous than the porous type) can be used. Porous anion exchange resin (II) can be easily obtained as a commercial product and has a high adsorption capacity for tocotrienol, and therefore can be suitably used in the present invention.

  Commercially available products can be used as the anion exchange resin (II). For example, Diaion SA20A (Mitsubishi Chemical Co., Ltd.) is used for gel type, and Diaion PA408 (Mitsubishi Chemical Co., Ltd.) is used for porous porous type. ].

  When coconut oil is used as a raw material, it can be carried out in accordance with a general oil refining method. Specifically, a process of adsorbing coconut oil with an anion exchange resin (II) and a process of recovering tocotrienol from the anion exchange resin (II) adsorbed with tocotrienol are performed. Coconut oil is preferably mixed with a solvent such as n-hexane or ethanol and used for the adsorption treatment of the anion exchange resin (II). In that case, it is preferable that the weight ratio is coconut oil / solvent = 10/1 to 1/10, more preferably 5/1 to 1/5.

  When the coconut oil is brought into contact with the anion exchange resin (II) and adsorbed, tocotrienol is adsorbed on the anion exchange resin (II). For example, when coconut oil is passed through a column packed with an anion exchange resin (II), tocotrienol is adsorbed to the anion exchange resin (II), and nonpolar components such as glycerides, hydrocarbons and waxes are adsorbed. It flows out with coconut oil without being. Furthermore, only the nonpolar components can be washed away by passing a nonpolar solvent. The nonpolar solvent is preferably an n-hydrocarbon having 5 to 18 carbon atoms, more preferably n-pentane, n-hexane and n-octane, and even more preferably n-hexane. This step is important in increasing the tocotrienol ratio in the tocotrienol composition. The solubility of tocotrienol in these nonpolar solvents is not so high as to desorb tocotrienol adsorbed on the anion exchange resin, and only nonpolar components can be washed away. And the tocotrienol composition with much content of tocotrienol can be obtained by collect | recovering the tocotrienol adsorb | sucked by the anion exchange resin (II). The recovery of tocotrienol adsorbed on the anion exchange resin (II) is carried out by using an eluent such as a mixed solution of polar solvent and acid, for example, acetic acid-methanol solution, acetic acid-ethanol solution, formic acid-methanol solution, formic acid-ethanol solution. This can be done by passing through an anion exchange resin (II). Among these, it is preferable to use an acetic acid-methanol solution or an acetic acid-ethanol solution. Since the eluate contains tocotrienol and an eluent, the eluent can be removed by distillation or the like.

  The content of tocotrienol in coconut oil is extremely small, and is usually about 100 ppm or less. This is very little compared to palm palm oil containing about 400-800 ppm tocotrienol. In general, it is considered that such coconut oil is not suitable as a raw material for producing a composition containing tocotrienol, but the present invention is an adsorption treatment with a specific anion exchange resin called anion exchange resin (II). It has been found that tocotrienol can be selectively recovered and a tocotrienol composition having a high content can be obtained by performing the above. As is clear from the comparison between Examples and Comparative Examples described later, when an anion exchange resin having a polar group other than 2-hydroxyethyldimethylammonium group is used as the anion exchange resin, the recovery rate of tocotrienol is It is low and sufficient effect cannot be obtained.

  The adsorption treatment of coconut oil and anion exchange resin (II) can be performed using a glass column or a metal column. The anion exchange resin (II) is packed into a column, regenerated and conditioned according to a known method, and then coconut oil mixed with a solvent by the above-described method is preferably 15 to 50 ° C, more preferably 20 ° C to It can be passed at 40 ° C. The liquid passing speed is preferably SV = 0.1-5, and more preferably SV = 1-3. The volume ratio of the anion exchange resin (II) to the coconut oil solution is preferably anion exchange resin (II) / coconut oil solution = 100/1 to 1/1000, more preferably 10/1 to 1/100. After passing the coconut oil solution, 100 to 1000 g of the solvent is preferably passed at 15 to 50 ° C., more preferably at 20 to 40 ° C., whereby glycerides, hydrocarbons remaining in the resin, Nonpolar components such as waxes can be washed away.

  Moreover, the recovery process of the tocotrienol adsorbed on the anion exchange resin (II) can be performed continuously following the adsorption process. Specifically, tocotrienol can be eluted by passing an acid-polar solvent mixed solution such as an acetic acid-methanol solution preferably at 15 to 50 ° C., more preferably at 20 to 40 ° C. The liquid passing speed is preferably SV = 0.1-5, and more preferably SV = 1-3. The eluate (recovered product) can be made into a tocotrienol composition by removing the eluent by distillation or the like.

  Moreover, anion exchange resin (II) can be repeatedly used by reproducing | regenerating and conditioning the anion exchange resin (II) after a tocotrienol collection process by a well-known method.

  Moreover, in this invention, the reaction product (henceforth transesterification reaction product) which transesterified coconut palm oil and a lower alcohol can be used as a raw material. In this case, as in the case of using coconut oil as the raw material, the step of adsorbing the transesterification reaction product with the anion exchange resin (II) and the recovery of the tocotrienol from the anion exchange resin (II) on which the tocotrienol is adsorbed The process to perform can be performed.

  The transesterification product is obtained by transesterification of coconut oil and a lower alcohol (preferably a monohydric alcohol having 1 to 5 carbon atoms), and includes fatty acid alkyl ester, glycerin, lower alcohol, triglyceride, diglyceride, Contains monoglycerides and the like. Specific examples of the lower alcohol having 1 to 5 carbon atoms include methanol, ethanol, propanol, and the like. From the industrial viewpoint, methanol is preferable because of low cost and easy recovery. This transesterification product also contains tocotrienol.

  The transesterification reaction between coconut oil and lower alcohol can be carried out by a known method. The reaction can be performed in either a continuous or batch mode, but a continuous reaction is advantageous when a large amount of ester is produced. As the catalyst, a homogeneous alkaline catalyst such as sodium hydroxide, potassium hydroxide or sodium alcoholate is generally used, but solid catalysts such as ion exchange resin, hydrous zirconium oxide, aluminum phosphate, sulfuric acid-supported zirconia, titanosilicate, etc. Can also be used. When using a homogeneous alkali catalyst, the reaction is generally carried out under the following conditions. The reaction temperature is 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction pressure is in the range of normal pressure to 0.5 MPa, preferably normal pressure.

  The adsorption treatment of the transesterification product and the anion exchange resin (II) can be performed using a glass column or a metal column. The anion exchange resin (II) is packed in a column, regenerated and conditioned according to a known method, and then 100 to 1000 g of an ester exchange reaction product mixed with a solvent, preferably 15 to 50 ° C., more preferably 20 The liquid can be passed at a temperature of from 40 ° C to 40 ° C. The transesterification reaction product is preferably mixed with a solvent such as n-hexane or ethanol and used for the adsorption treatment of the anion exchange resin (II). In that case, the weight ratio of transesterification product / solvent = 10/1 to 1/10, more preferably 5/1 to 1/5 is preferable. The liquid passing speed is preferably SV = 0.1-5, and more preferably SV = 1-3. The volume ratio of the anion exchange resin (II) to the transesterification reaction product solution is as follows: anion exchange resin (II) / transesterification reaction product solution = 100/1 to 1/1000, and further 10/1 to 1/100. It is preferable that After passing the solution, 100 to 1000 g of the solvent is preferably passed at 15 to 50 ° C., more preferably at 20 to 40 ° C., thereby transesterification reaction products, glycerides remaining in the resin, Nonpolar components such as hydrocarbons and waxes can be washed away.

  The recovery process of tocotrienol adsorbed on the anion exchange resin (II) can be performed in the same manner as in the case of the coconut oil described above.

  In the present invention, the distillation residue of the transesterification product can be used as a raw material. In this case, as in the case of using coconut oil as the raw material, the step of adsorbing the distillation residue of the transesterification reaction product with the anion exchange resin (II) and the anion exchange resin (II) adsorbed with the tocotrienol are performed. A step of recovering tocotrienol can be performed.

  The distillation residue of the transesterification reaction product is obtained by distilling the transesterification reaction product of coconut oil and a lower alcohol (preferably a monohydric alcohol having 1 to 5 carbon atoms). Fatty acid alkyl ester, glycerin , Lower alcohols, triglycerides, diglycerides, monoglycerides and the like. Tocotrienol is also contained in the distillation residue of the transesterification product.

  The transesterification reaction product is desirably distilled under reduced pressure, and the pressure is preferably 0.1 to 10 kPa. When the pressure is 0.1 kPa or less, the burden on the equipment increases in order to maintain a high degree of vacuum. If it is 10 kPa or more, the temperature of the distillation bottom becomes too high, and there is a concern that the fatty acid ester is decomposed. The distillation column used in the distillation process is a column packed with a regular packed plate of metal plate or wire mesh for contact with gas and liquid, or an irregular packing such as Raschig ring or pole ring, or perforated plate tray, foam Either a rectifying column provided with a shelf such as a bell-type tray or a flash column not provided with a gas-liquid contact portion in the column may be used. The distillation operation of the present invention can be carried out continuously, batchwise, or semi-batch.

  The adsorption treatment of the distillation residue of the transesterification reaction product and the anion exchange resin (II) can be performed using a glass column or a metal column. After anion-exchange resin (II) is packed in a column and regenerated and conditioned according to a known method, 100 to 1000 g of distillation residue of the transesterification product mixed with a solvent is preferably 15 to 50 ° C. Preferably, the liquid can be passed at 20 to 40 ° C. The transesterification reaction product is preferably mixed with a solvent such as n-hexane or ethanol and used for the adsorption treatment of the anion exchange resin (II). In this case, it is preferable that the distillation residue / solvent of the transesterification reaction product = 10/1 to 1/10, and more preferably 5/1 to 1/5. The liquid passing speed is preferably SV = 0.1-5, and more preferably SV = 1-3. The volume ratio of the distillation residue solution of the anion exchange resin (II) and the transesterification reaction product was an anion exchange resin (II) / distillation residue solution of the transesterification reaction product = 100/1 to 1/1000, and further 10 / 1 to 1/100 is preferable. After passing the solution, 100 to 1000 g of solvent is preferably passed at 15 to 50 ° C., more preferably at 20 to 40 ° C., so that glycerides, hydrocarbons, wax, etc. remaining in the resin Non-polar components can be washed away.

  The recovery process of tocotrienol adsorbed on the anion exchange resin (II) can be performed in the same manner as in the case of the coconut oil described above.

When the transesterification reaction product or the distillation residue of the transesterification reaction product is used, it can be implemented as a method for producing a tocotrienol composition having the following steps 1 and 2.
Step 1: Obtain a reaction product containing a fatty acid alkyl ester by transesterification of coconut oil and a lower alcohol Step 2: Distill the reaction product containing the fatty acid alkyl ester obtained in Step 1 or the reaction product The distillation residue obtained by adsorption with an anion exchange resin having a 2-hydroxyethyldimethylammonium group

  Step 1 can be performed by a known method. The reaction can be performed in either a continuous or batch mode, but a continuous reaction is advantageous when a large amount of ester is produced. As the catalyst, a homogeneous alkaline catalyst such as sodium hydroxide, potassium hydroxide or sodium alcoholate is generally used, but solid catalysts such as ion exchange resin, hydrous zirconium oxide, aluminum phosphate, sulfuric acid-supported zirconia, titanosilicate, etc. Can also be used. When using a homogeneous alkali catalyst, the reaction is generally carried out under the following conditions. The reaction temperature is 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction pressure is in the range of normal pressure to 0.5 MPa, preferably normal pressure.

  The distillation in step 2 is desirably performed under reduced pressure, and the pressure is preferably 0.1 to 10 kPa. When the pressure is 0.1 kPa or less, the burden on the equipment increases in order to maintain a high degree of vacuum. If it is 10 kPa or more, the temperature of the distillation bottom becomes too high, and there is a concern that the fatty acid ester is decomposed. The distillation column used in the distillation process is a column packed with a regular packed plate of metal plate or wire mesh for contact with gas and liquid, or an irregular packing such as Raschig ring or pole ring, or perforated plate tray, foam Either a rectifying column provided with a shelf such as a bell-type tray or a flash column not provided with a gas-liquid contact portion in the column may be used. The distillation operation of the present invention can be carried out continuously, batchwise, or semi-batch.

  The tocotrienol composition is obtained by subjecting the reaction product containing the fatty acid alkyl ester obtained in step 1 or the distillation residue obtained by distillation of the reaction product as described above to adsorption treatment in the same manner as described above. be able to.

  The inventors have found that coconut oil contains little tocophenol. Therefore, in the present invention, a composition having a high tocotrienol content and a very low tocophenol content can be obtained. The tocotrienol composition prepared according to the present invention has a tocophenol content of 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.1% by weight or less, and still more preferably to tocotrienol. Below the detection limit (this level may be perceived as substantially 0% by weight).

  In the production method of the present invention, the recovery rate of tocotrienol is preferably 50 to 100%, more preferably 75 to 100%. In the present invention, the recovery rate (%) of tocotrienol is determined as follows. Moreover, the content of tocotrienol was measured by the method of Examples described later.

Tocotrienol recovery rate (%) = [tocotrienol content in recovered material / tocotrienol content in treated object] × 100
* Tocotrienol content in the collected product: after adsorption treatment with anion exchange resin (II), and total mass containing tocotrienol in the collected collected material * Tocotrienol content in treated material: adsorbed with anion exchange resin (II) Tocotrienol-containing total mass in the distillation residue of coconut palm oil or transesterification product or transesterification product before treatment

  The tocotrienol composition produced by the production method of the present invention has a remarkably high tocotrienol-containing concentration as compared with raw material coconut oil and the like, and thus is useful as an intermediate material for various uses. The composition of the tocotrienol composition produced by the production method of the present invention varies depending on the method for recovering tocotrienol from the anion exchange resin (II) and the subsequent treatment. For example, when an acetic acid-methanol solution is used as an eluent during recovery, a composition containing tocotrienol, acetic acid and methanol, and a composition obtained by distilling off acetic acid and methanol from the composition are obtained. The composition from which the eluent (eg acetic acid and methanol) has been distilled off is available as coconut oil concentrated for tocotrienol. The same applies to the case where the transesterification product or the distillation residue of the transesterification product is used as a raw material.

In the production method of the present invention, a tocotrienol composition with higher purity can be produced by further comprising the following step 3 and step 4.
Step 3: A step of washing away glycerides, hydrocarbons, waxes, etc. remaining in the resin by passing a nonpolar solvent.
Step 4: A step of recovering tocotrienol adsorbed on the resin by passing a mixed solution of a polar solvent and an acid after Step 1.

In the manufacturing method of this invention, it is preferable to carry out at the following processes according to the raw material to be used. (1) When coconut oil is used as a raw material, after the step of adsorbing the raw material with an anion exchange resin having a 2-hydroxyethyldimethylammonium group, the steps 3 and 4 are performed in this order. (2) When a reaction product obtained by transesterification of coconut oil and lower alcohol is used as a raw material, and (3) A distillation residue of a reaction product obtained by transesterification reaction between coconut oil and lower alcohol is used as a raw material. In this case, the process is performed in the order of process 1, process 2, process 3, and process 4.
Examples The following examples describe the practice of the present invention. The examples are illustrative of the invention and are not intended to limit the invention.

(1) Tocotrienol content Agric. Food Chem. 54, p3351, 2006.

(2) Ion exchange resin As ion exchange resins, various types of diamond ions manufactured by Mitsubishi Chemical Corporation were used (Table 1).

(3) Raw material fats and oils The raw material fats and oils of Table 2 were used.

Example 1
100 g of virgin coconut oil was dissolved in 100 mL of n-hexane to prepare an n-hexane solution. The n-hexane solution was passed through a 3 cmφ × 50 cm glass column filled with 100 mL of Diaion PA408 substituted with n-hexane, pretreated in advance, and passed at a rate of SV = 2. Washing was performed by passing 200 mL of n-hexane at SV = 2 to remove impurities such as glycerides hydrocarbons and waxes as non-adsorbed fractions. Subsequently, 250 mL of acetic acid methanol solution (containing 5% acetic acid) was passed at a rate of SV = 2, and further 150 mL of methanol was passed at a rate of SV = 2 to perform washing, and the tocotrienol fraction was eluted. The acetic acid methanol solution was distilled off to obtain a tocotrienol composition. The tocotrienol content of the composition was measured and the recovery was determined by comparison with that of virgin coconut oil before the adsorption treatment. The results are shown in Table 3. The virgin coconut oil used in this example contained 37 ppm of tocotrienol.

Example 2 and Comparative Examples 1 to 4
In Example 1, instead of Diaion PA408, SA20A (Example 2), PA306S (Comparative Example 1), SA11A (Comparative Example 2), HPA25 (Comparative Example 3), and WA10 (Comparative Example 4) were used. Obtained a tocotrienol composition in the same manner as in Example 1. In the same manner as in Example 1, the tocotrienol content and the recovery rate were determined. The results are shown in Table 3.

Example 3
In Example 1, the tocotrienol composition was obtained like Example 1 except having used the coconut crude oil squeezed from the copra instead of the virgin coconut oil. The tocotrienol content of the composition was measured, and the recovery rate was determined by comparison with that of coconut crude oil before the adsorption treatment. The results are shown in Table 4. The coconut oil used in this example contained 48 ppm of tocotrienol.

Example 4
Seven equivalents of methanol was added to the crude coconut oil as a starting material, and 0.1 wt% (vs. crude coconut oil) of an acid catalyst (sulfuric acid) was added and heated to reflux. Subsequently, 0.5% by weight (vs. crude palm oil) of an alkali catalyst (sodium hydroxide) was added and heated to reflux to obtain a mixture of crude coconut fatty acid methyl ester and glycerin. The mixture was allowed to stand and separated to separate glycerin, and then washed with water to remove the catalyst and glycerin. The reaction product containing the crude coconut fatty acid methyl ester obtained by this step contained 16 ppm of tocotrienol. The purity of the crude coconut fatty acid methyl ester was 95%.

 In Example 1, a tocotrienol composition was obtained in the same manner as in Example 1 except that the reaction product containing the crude coconut fatty acid methyl ester was used instead of virgin coconut oil. The tocotrienol content of the composition was measured, and the recovery rate was determined by comparison with that of the reaction product containing the crude coconut fatty acid methyl ester before the adsorption treatment. The results are shown in Table 5.

Example 5
The crude coconut fatty acid methyl ester synthesized in the same manner as in Example 4 was distilled under reduced pressure at 150 ° C. and 400 Pa to distill off the coconut fatty acid methyl ester. The obtained distillation residue contained 1300 ppm of tocotrienol. In Example 1, a tocotrienol composition was obtained in the same manner as in Example 1 except that this distillation residue was used instead of virgin coconut oil. The tocotrienol content of the composition was measured, and the recovery rate was determined by comparison with that of the distillation residue before the adsorption treatment. The results are shown in Table 6.

Claims (5)

A method for producing a tocotrienol-enriched tocotrienol composition comprising tocotrienol and 1% by weight or less of tocopherol based on said tocotrienol, comprising:
It is selected from (1) coconut oil, (2) a reaction product obtained by transesterification of coconut oil and lower alcohol, and (3) a distillation residue of a reaction product obtained by transesterification of coconut oil and lower alcohol. A method for producing a tocotrienol-enriched tocotrienol composition, comprising a step of subjecting a raw material to an anion exchange resin having a 2-hydroxyethyldimethylammonium group. The method for producing a tocotrienol-enriched tocotrienol composition according to claim 1, comprising the following steps 1 and 2.
Step 1: Obtain a reaction product containing a fatty acid alkyl ester by transesterification of coconut oil and a lower alcohol Step 2: Distill the reaction product containing the fatty acid alkyl ester obtained in Step 1 or the reaction product The distillation residue obtained by adsorption with an anion exchange resin having a 2-hydroxyethyldimethylammonium group  The method for producing a tocotrienol-enriched tocotrienol composition according to claim 1 or 2, wherein the anion exchange resin is a porous type.  The method for producing a tocotrienol-enriched tocotrienol composition according to any one of claims 1 to 3, further comprising a step of recovering tocotrienol adsorbed on the anion exchange resin. The method for producing a tocotrienol-enriched tocotrienol composition according to any one of claims 1 to 4, further comprising the following step 3 and step 4 as a step of recovering the tocotrienol adsorbed on the anion exchange resin. .
Step 3: A step of washing away glycerides, hydrocarbons, waxes, etc. remaining in the resin by passing a nonpolar solvent.
Step 4: A step of recovering tocotrienol adsorbed on the resin by passing a mixed solution of a polar solvent and an acid.