JP2002003488A - Method for producing fatty acid concentrate of tocopherol and tocotrienol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently concentrating and recovering tocopherol and tocotrienol from an oil and fat with 70-95% fatty acid content, especially a palm fatty acid distillate(PFAD). SOLUTION: The tocopherol and tocotrienol and free fatty acids in the oil and fat with 70-95% fatty acid content, especially the PFAD are esterified and subjected to distillation carried out thereafter or during the esterification to remove the unreacted free fatty acids and low-boiling substances. Thereby, a fatty acid concentrate of the tocopherol and tocotrienol is obtained in the residue.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for purifying and concentrating tocopherol and tocotrienol from fats and oils having a high fatty acid content, particularly palm oil fatty acid distillate (PFAD) which is a by-product of palm oil.

[0002]

2. Description of the Related Art Conventionally, as a method of concentrating tocopherol and tocotrienol from palm oil fatty acid distillate (PFAD), extraction with a solvent, fractionation of the solvent, treatment with an ion exchange resin, distillation and the like have been studied. However, these processes use large amounts of solvents and are not economical.

[0003] Further, as a purification method at an actual production level, as disclosed in Japanese Patent Application Laid-open No. 2-9875, free fatty acids and mixed glycerides are alkyl-esterified, and the alkyl esters are removed by distillation. Then, purification methods such as ion exchange and distillation are known, but they use a large amount of a solvent, and further, due to the effect of an acid catalyst used when esterifying free fatty acids, they are added to the side chain of tocotrienol. However, there is a disadvantage that denaturation due to the addition reaction of alcohol cannot be avoided. The denaturation of tocotrienol not only causes a decrease in the recovery rate, but also greatly affects the quality of the purified product.

[0004] As a pretreatment, a method of previously removing free fatty acids in palm oil fatty acid distillate (PFAD) by distillation has also been disclosed. However, defatty acid distillation is performed at a low concentration stage of tocopherol and tocotrienol. Despite this, a high-performance distillation apparatus such as a thin-film falling type or a centrifugal type is required, which is not economical.

Further, as a conventional technique which does not use a large amount of a solvent or an acid catalyst, as shown in US Pat. No. 5,660,691, tocopherol and tocotrienol such as sterol in a purified raw material containing tocopherol and tocotrienol are disclosed. There has also been proposed a method in which an alcohol having a similar boiling point is heated in advance to form an ester with a fatty acid to form a high-boiling compound, and tocopherol and tocotrienol are recovered as a fraction using a distillation operation.

However, in this method, when sterols or higher alcohols are esterified with fatty acids, tocopherol and tocotrienol also undergo an esterification reaction, and the recovery rate decreases. In particular, palm oil fatty acid distillate (PF
The tendency is remarkable in raw materials containing low concentrations of tocopherol and tocotrienol in a large amount of free fatty acids such as AD). Exam is refined from rice oil deodorized distillate.
The result shown in ple 1 is 7 at 200 ° C under nitrogen flow.
In Table-1, which is the result of distilling and recovering tocopherol and tocotrienol after performing the esterification reaction for a time, the recovery rates of tocopherol and tocotrienol in the fractions were calculated to be 81% and 67%, respectively. Is declining. Further, since tocopherol and tocotrienol have similar boiling points to fatty acids, separation by distillation is difficult, and a high-performance distillation apparatus must be used. In addition, a sophisticated rectification operation is required.

That is, when concentrating and recovering a small amount of tocopherol and tocotrienol from a large amount of fatty acid, the separation from the fatty acid is the most important. However, in the conventional technique, when the fatty acid is subjected to alkyl esterification, an acid catalyst is used. This causes an addition reaction to the side chain. In addition, when fatty acids are separated by distillation and tocopherols and tocotrienols are concentrated and recovered in the fraction, an esterification reaction between the fatty acids and tocopherols and tocotrienols occurs, and the recovery rate decreases.

In particular, when a palm oil fatty acid distillate (PFAD) containing a low concentration of tocopherols and tocotrienols of 0.01 to 2% and a large amount of fatty acids of 70 to 95% is used as a raw material, the reaction proceeds. early. The esterification reaction rate of each tocopherol and tocotrienol isomer with fatty acid,
δ-> β-, γ-> α-tocopherol / tocotrienol. Palm oil contains γ-tocotrienol most and δ-tocotrienol. From this, especially when palm oil fatty acid distillate (PFAD) is used as a raw material, the recovery rate is lowered.

Further, since the boiling points of tocopherol and tocotrienols and fatty acids are close to each other, it is difficult to completely separate them even with a high-performance distillation apparatus. in this way,
In the prior art, a method for effectively concentrating and recovering tocopherol and tocotrienol from a raw material containing a small amount of tocopherol and tocotrienol in a large amount of fatty acid has not been found.

[0010]

An object of the present invention is to develop a method for effectively concentrating and recovering high-quality tocopherol and tocotrienol.

[0011]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems. Specifically, (1) a large amount of a solvent is not used, and (2) a strong acid catalyst that causes denaturation of tocotrienol is not used. (3) In the stage where the content of tocopherol and tocotrienol is low, a high-precision device that causes an increase in purification cost is not used. (4) There is no significant decrease in the recovery rate. (5) Obtain a purified concentrate that is preferred for subsequent purification steps.

As a result of repeated studies on methods satisfying these five items, the present inventor has conducted an esterification reaction of tocopherol and tocotrienols, which are the substances to be concentrated and recovered, with a fatty acid present in a large amount in the raw material. Let
Fatty acid and fatty acid esters of tocopherols and tocotrienols, which are non-volatile substances that are easily separated by distillation,
Through distillation, the majority of free fatty acids not used in the reaction were separated as fractions, and the objective was achieved by concentrating and recovering tocopherols and tocotrienols, which are non-volatile substances, to residues. Thus, the present invention has been completed.

That is, the present invention relates to (1) using an oil or fat having a fatty acid content of 70 to 95%, and subjecting the tocopherol and tocotrienol contained therein to an esterification reaction with a free fatty acid or after the esterification reaction. A method for producing tocopherol and tocotrienol fatty acid ester concentrates in the residue by removing unreacted free fatty acids and low-boiling substances by distillation, (2) fatty acid content of 70 to 95%
Wherein the fat or oil is a palm oil fatty acid distillate (PFAD), and (3) the content of tocopherol and tocotrienol is 0.01 to 2%. (1) or the production method according to (2),
(4) The method according to any one of (1), (2) and (3), wherein the reaction temperature is 180 to 270 ° C., (5) Weight of fatty acid and the contents of tocopherol and tocotrienol. The production method according to any one of (1), (2), (3) and (4), wherein the ratio is 35 to 950.

Tocopherol is

Embedded image and

It has the structure shown in Table 1 and naturally has four homologs. Also, tocotrienol is

Embedded image and

It has the structure shown in Table 2 and naturally has four homologs.

[0015]

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[0016]

[Table 1]

[0017]

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[0018]

[Table 2]

Tocopherols are widely used in medicines, health foods, cosmetics, etc. due to their excellent physiological activity and antioxidant power. The main physiological activities are anti-fertility activity, anti-muscular atrophy activity, anti-hemolytic activity, aging prevention, etc., and the main use is to prevent diseases caused by active oxygen due to antioxidant power in vivo. The antioxidant power of tocopherols is not limited to living organisms, and is widely used as an antioxidant for easily oxidizable foods.

In a recent study, tocotrienol was
Serum cholesterol lowering effect (J. Biol. Chem., 261, p.
10544, 1986), a heart disease preventive effect, a carcinogenesis inhibitory effect (Chem. Pharm. Bull., 37, p1369, 1989), and an immunostimulatory effect (JP-A-11-49767). , Its usefulness has been recognized. Tocopherol is contained in many vegetable oils such as soybeans and rapeseed, and purified tocopherol is produced from deodorized distillate discharged from these purification steps.

On the other hand, palm oil contains both tocopherol and tocotrienol. 600 for crude palm oil
Tocotrienol occupies 70-80% in the composition ratio (Chemical Industrial Data vol.17, No.6
p225). Crude rice oil contains about 800 ppm, of which tocotrienol is about 50%.

Palm oil fatty acid distillate (PFAD) is a by-product of palm oil discharged from a palm oil refining process, and is a total of 0.01 to 2% of tocopherol and tocotrienols.
Is generally contained. The palm oil refining method comprises a degumming step, a deacidifying step, a decolorizing step, and a deodorizing step as basic steps, and is classified into a physical refining method and a chemical refining method according to the method of removing free fatty acids.

The physical purification method is characterized in that free fatty acids are removed at the same time as deodorization in the deodorization step. In recent years, the physical purification method has become mainstream. The deodorization by the physical refining method is carried out by steam distillation, and the obtained palm oil fatty acid distillate (PFAD) is mainly fatty acid and contains 70-95% of free fatty acids, and is light-colored and fatty acid purity Because of its high cost, it is used for feed and detergent raw materials.

That is, the present invention relates to a method for producing palm oil fatty acid distillate (PFAD) under a pressure of 5 mmHg to 760 mmHg within a range not involving fatty acid distillation at a temperature of about 150 ° C. to 300 ° C., preferably 18 ° C.
Heat at 0 ° C. to 270 ° C. to esterify tocopherols and tocotrienols with fatty acids. At this time, it is desirable to use a means for preventing the degradation of tocopherol and tocotrienol, such as performing the reaction under an inert gas stream. In particular, conducting the reaction in an inert gas stream is advantageous for the progress of the reaction because it has an effect of discharging water generated in the esterification reaction to the outside of the reaction system.

In order to accelerate the progress of the reaction, a mild catalyst such as ammonium acid sulfate or isopropyl titanate may be used without fear of denaturing tocotrienol, or a free fatty acid may be added. By this esterification reaction, tocopherols and tocotrienols become non-volatile fatty acid esters, and are easily separated from unreacted free fatty acids and other low-boiling compounds in the distillation operation.

Subsequently, the reactant containing the obtained tocopherol and tocotrienol fatty acid ester is roughly
By performing simple distillation such as simple distillation or steam distillation at a pressure of 0.01 mmHg to 20 mmHg at 150 ° C to 300 ° C to distill off unreacted free fatty acids and other low boiling compounds, tocopherol and tocotrienol Fatty acid esters and other non-volatile components can be left in the residue.

The tocopherol and tocotrienol fatty acid ester concentrate obtained as a residue has a content of tocopherol and tocotrienol of 7
It can be concentrated up to 倍 10-fold with little loss of tocopherols and tocotrienols.

As another method of leaving fatty acid esters of tocopherol and tocotrienol in the residue, palm oil fatty acid distillate (PFAD) is used in an amount of 0.01 mmHg to 20 mm.
Under pressure of Hg, approximately 150-300 ° C, preferably 180 ° C
Unheated free fatty acids and low-boiling compounds are distilled off by heating at -270 ° C. to esterify almost all of the tocopherols and tocotrienols with fatty acids and at the same time perform distillation.

At this time, the degree of vacuum and the temperature are adjusted to avoid distilling out tocopherol and tocotrienols.
It is also desirable to use a means for preventing the degradation of tocopherol and tocotrienol, such as performing the reaction under an inert gas stream. In order to accelerate the progress of the reaction, a mild catalyst which does not have to worry about denaturing tocotrienol may be used, or a free fatty acid may be added. Even if this method is used, the same fatty acid ester concentrate of tocopherol and tocotrienol as the method described in the preceding section can be left in the residue. The above steps are represented by the following flow.

That is, for the purpose of the present invention, tocopherol and tocotrienol in palm oil fatty acid distillate (PFAD) are esterified with fatty acids to distill excess fatty acids, or to distill while proceeding the esterification reaction. By removing most of the free fatty acids and low-boiling compounds, most of the tocopherol and tocotrienol fatty acid esters can be left in the residue.

There is no need to use a large amount of solvent, to cause denaturation of the target substance, and to require a high-performance distillation apparatus. Moreover, the residues are fatty acid esters of tocopherol and tocotrienol, hydrocarbons,
The sterol fatty acid ester and glyceride are the main components, resulting in a simple composition in which the subsequent purification step is very advantageous.

The concentrate obtained as a residue is subjected to steps such as steam distillation and alkali deacidification to remove free fatty acids, if necessary, and is subjected to transesterification or the like to remove the tocopherol and tocotrienol fatty acid ester from the original free form. After that, various purification steps, such as ion exchange resin treatment and molecular distillation, which are conventional methods, are performed, whereby a highly purified product can be economically produced.

In the prior art, the addition of alcohols to the side chains of tocotrienol, especially from feedstocks such as palm oil fatty acid distillate (PFAD) containing low levels of tocopherol and tocotrienol in large amounts of free fatty acids Although it was difficult to concentrate and recover industrially without causing a reaction, according to the present invention, palm oil fatty acid distillate (PF
AD) can be concentrated and purified at low cost without denaturation of the target product.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in more detail with reference to the following Examples and Comparative Examples, but it goes without saying that the present invention is not limited thereto. [Example 1] In a 1 L four-necked flask, palm oil fatty acid distillate (PFAD, fatty acid 83.3%, tocopherol concentration 0.07%,
768.4 g of tocotrienol concentration (0.22%) was charged, and an esterification reaction was carried out at 220 ° C. for 2 hours and 30 minutes under a nitrogen stream. At this time, the esterification reaction rate of tocopherol and tocotrienol was 72%. In the same flask, the esterification reaction product was subjected to defatty acid distillation at 190 to 230 ° C. under a reduced pressure of 5 mmHg to obtain 655.2 g of a fraction and 107.0 g of a residue (Table 3). 95.5% (* 1) of residual tocopherol and tocotrienol
Was a fatty acid ester.

As shown by the acid value, saponification value and unsaponifiable substance (Table 4), the obtained residue is mostly fatty acid-related substances such as fatty acid esters and unsaponifiable substances. % Tocopherol and tocotrienol, plus hydrocarbons and sterols, for a total of 71.5
% (* 2) (Table 5). * 1 Content of residual tocopherol and tocotrienol 0.50 + 1.52 = 2.02% Breakdown of 2.02% 0.09% Free form of tocopherol and tocotrienol 0.09% Fatty acid ester of tocopherol and tocotrienol 1.93% 1.93 ÷ 2.02 × 100 = 95.5% * 2 27.9 + 28 0.0 + 15.6 = 71.5%

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

[Table 5]

Example 2 A 1 L four-necked flask was charged with 631.6 g of the same PFAD as in Example 1, and heated under a reduced pressure of 4 mmHg. At 190 ° C., the degree of decompression decreased due to the generation of water by the esterification reaction, and the pressure changed around 10 mmHg. Further heating was carried out, distillation of free fatty acids and other low-boiling substances started at 220 ° C, and distillation was completed at 240 ° C. The pressure at the end of the distillation was 5 mmHg. Esterification / distillation took 4 hours to obtain 542.4 g of a fraction and 83.4 g of a residue (Table 6). 95.7% of residual tocopherol and tocotrienol (* 3)
Was a fatty acid ester.

As shown by the acid value, saponification value and unsaponifiable matter (Table 7), the obtained residue is mostly fatty acid-related substances such as fatty acid esters and unsaponifiable substances. , Containing 25.6% tocopherol and tocotrienol, plus hydrocarbons and sterols,
It was 67.1% (* 4) (Table 8). * 3 0.49 + 1.60 = 2.09% Breakdown of 2.09% Free form 0.09% Fatty acid ester 2.00% 2.00 ÷ 2.09 ×
100 = 95.7 * 4 25.6 + 27.2 + 14.3 = 67.1%

[0041]

[Table 6]

[0042]

[Table 7]

[0043]

[Table 8]

[0044]

According to the present invention, tocopherol and tocotrienol can be efficiently and economically purified from fats and oils having a high fatty acid content, in particular, palm oil fatty acid distillate (PFAD), and there is no generation of modified products.

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[Procedure amendment]

[Submission date] June 1, 2001 (2001.6.1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0003

[Correction method] Change

[Correction contents]

[0003] Further, as a purification method at an actual production level, as disclosed in Japanese Patent Application Laid-open No. 2-9875, free fatty acids and mixed glycerides are alkyl-esterified, and the alkyl esters are removed by distillation. Although then a method of performing ion exchange and distillation purification are known, they are under the influence of an acid catalyst to be used when using a large amount of solvent, addition esterifying the free fatty acids, Tokoto
There is a disadvantage that modification of lienol is inevitable to some extent . The denaturation of tocotrienol not only causes a decrease in the recovery rate, but also greatly affects the quality of the purified product.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

That is, when concentrating and recovering a small amount of tocopherol and tocotrienol from a large amount of fatty acid, separation from the fatty acid is the most important. However, in the prior art, when the fatty acid is subjected to alkyl esterification, an acid catalyst is used. The effect causes denaturation of tocotrienol. In addition, when fatty acids are separated by distillation and tocopherols and tocotrienols are concentrated and recovered in the fraction, an esterification reaction between the fatty acids and tocopherols and tocotrienols occurs, and the recovery rate decreases.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction contents]

In the prior art, particularly from raw materials such as palm oil fatty acid distillate (PFAD), which contain low levels of tocopherol and tocotrienol in large amounts of free fatty acids, the modification of the tocotrienol without causing denaturation of the tocotrienol According to the present invention, it is possible to concentrate and purify from palm oil fatty acid distillate (PFAD) at low cost without denaturing the target product.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Satoshi Ueishi 60-1 Higashi-Hanawa, Tatomi-cho, Nakakoma-gun, Yamanashi Prefecture Lighttopia Hanawa 206 F-term (reference) 4C062 FF16 FF25

Claims (5)

[Claims] Claims 1. Using an oil or fat having a fatty acid content of 70 to 95%, tocopherol and tocotrienol contained therein are subjected to an esterification reaction with a free fatty acid or while the esterification reaction is being carried out, while the unreacted free fatty acid and A method for producing a tocopherol and tocotrienol fatty acid ester concentrate in a residue by removing low-boiling substances by distillation. 2. The method according to claim 1, wherein the fat having a fatty acid content of 70 to 95% is a palm oil fatty acid distillate (PFAD). 3. The method according to claim 1, wherein the content of tocopherol and tocotrienol is 0.01 to 2%.
Or the production method according to 2. 4. The production method according to claim 1, wherein the reaction temperature is from 180 to 270 ° C. 5. The method according to claim 1, wherein the weight ratio of the fatty acid to the contents of tocopherol and tocotrienol is 35 to 950.