JPS59161372A - Concentration of vitamin e - Google Patents

Abstract

PURPOSE:To separate and concentrate vitamin E compounds, especially alpha- tocopherol, from fresh vegetable tissue, without loss, in high efficiency, by a combination of the extraction with a specific solvent and the treatment with an ion exchange material. CONSTITUTION:A vegetable tissue containing vitamin E compounds (e.g. gramineous plant or arecaceous plant, especially leaves and stalks having high alpha- tocopherol content) is thoroughly crushed, and the exuded syrup is removed e.g. by pressure filtration, etc. The residue is mixed with a non-polar organic solvent which is water-insoluble and forms azeotropic mixture with water (e.g. n-hexane, carbon tetrachloride, etc.), and the mixture is heated at the azeotropic temperature to extract the vitamin E compounds to the solvent while removing the residual water by azeotropic distillation. The solution is separated by filtration, etc., and the solvent in the solution is distilled off to obtain the concentrate. The concentrate is heated in the presence of a lower alcohol to remove the alcohol-insoluble resinous material, and the resultant solution is treated with an ion exchange material (preferably a basic anion exchange material) to obtain concentrated vitamin E compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention ('': i) relates to a method for concentrating vitamin E. More specifically, the present invention ('': i) relates to a method for concentrating vitamin E. The present invention relates to a method for efficiently separating and concentrating vitamin E, especially α-tocopherol.

Conventionally, the physiological effects of vitamin E are only known to be on the gonads, for example, a deficiency of this vitamin can cause infertility or fetal absorption miscarriage in female mice, or atrophy of sperm-producing tissue and permanent infertility in males. However, in recent years, its antioxidant power has caused it to enter the animal body. It has become known that it exhibits strong antioxidant power, prevents cell damage caused by peroxidation, and plays an effective role in cell function and metabolism.

Therefore, vitamin E is currently available in pharmaceuticals, health foods,
It is attracting a lot of attention in the field of feed additives, and it is also attracting a lot of attention as a non-toxic antioxidant for food packaging plastic films and edible oils.

Natural vitamin E types include α, β-tocopherol Nohokani γ, δ, ε, ζ, η-tocopherol + 7)
Four types of cotrienols are known, which are species G and H. α, β, γ, and δ-tocopherol, with six hydrogen atoms removed from the molecule to introduce a double bond. Among these, the one with the strongest physiological activity (1-tocopherol,
Methods for efficiently extracting and synthesizing α-tocopherol, also known as Shitachiriki, from natural products are being actively researched. Note that while natural α-tocopherol is a d-unit, synthetic α-tocopherol is a racemic d, ]-unit.

These vitamin E types are wheat germ oil and cottonseed oil.

It is known to be contained in vegetable oils such as salad oil, as well as in the leaves and stems of plants of the succulent family and palm plants.

Since the content of vitamin E contained in plant tissues such as leaves and stems is minute, it is difficult to selectively concentrate vitamin E from the tissues. As a method of concentrating vitamin E from leaves and stems of KFD, the leaves and stems are first force-dried or sun-dried to remove water7, and then extracted and concentrated using an organic solvent. Alternatively, a method has been adopted in which water is removed using a water-soluble organic solvent such as a lower alcohol or ketone, and vitamin E is eluted into the solvent and concentrated.

However, the former forced drying or sun drying method has the drawback of loss of vitamin E in the drying process, while the latter method, which uses a water-soluble organic solvent, still
Since the solvent contains a large amount of water, it is difficult to recover the solvent, making it uneconomical.

The present inventors have overcame these drawbacks and have conducted extensive research into a method for efficiently separating and concentrating vitamin E, especially α-tocopherol, from fresh plant tissues such as leaves and stems without loss. As a result of repeated research, it was discovered that the objective could be achieved by combining extraction with a specific solvent (1) and treatment with an ion exchanger, and the present invention was completed.

That is, in the present invention, after pulverizing a plant tissue containing vitamin E and removing the water generated at the time, using a non-polar organic solvent that is insoluble in water and forms an azeotrope with water, The water remaining in the plant tissue is azeotropically distilled off with the solvent, and the vitamin E contained in the plant tissue is eluted into the solvent, and then the solvent is distilled off, and then from the residual liquid. Vitamin E using ion exchanger
The present invention provides a method for concentrating vitamin E, which is characterized by obtaining a concentrate of vitamin E.

The plant tissues containing vitamin E used in the present invention include, for example, grains such as rice, wheat, and corn, plants of the legaceae family such as bald grass that grow naturally in the wilderness, and leaves and stems of palm plants. is suitable.

These leaves and stems contain less mold containing vitamin E compounds than their fruits, but are characterized by an extremely high content ratio of α-tocopherol in vitamin E compounds.

The non-polar organic solvent used in the present invention is water-insoluble and forms an azeotrope with water, such as n-hexano, n-hebutane, Examples include hydrocarbon solvents such as benozeno and toluene, and halogen solvents such as trichlene carbon tetrachloride.

Next, as the ion exchanger used in the present invention, a basic anion exchanger is suitable, and this one can be in the form of a membrane, a fiber,
It can be used in any shape such as granules. Particularly suitable are EF-8A-CL type anion exchange fiber manufactured by Nichibi Corporation, Amberlite IRA 401CL type anion exchange resin manufactured by Organo Corporation, and Amberlys A-26 anion exchange resin for non-aqueous solutions manufactured by Organo Corporation.

Next, an example of an embodiment of the present invention is shown. First, vitamin E
Fresh leaves and stems of a plant belonging to the family Araceae or a plant belonging to the palm family are used as the plant tissue containing the species, and after sufficiently pulverizing these leaves and stems, the water produced at that time is removed by compression filtration or the like. Next, the above-mentioned non-polar organic solvent is added and heated at an azeotropic temperature, and while water remaining in the plant tissue is azeotropically distilled off together with the solvent, vitamin E contained in the plant tissue is added to the solvent. Let it elute. Next, the fibers and the vitamin E-containing solution are separated by filtration or the like, and then the solvent in the solution is distilled off to obtain a concentrate.

This concentrate contains components other than vitamin E, so lower alcohols such as methanol and ethanol are added and heated to remove alcohol-insoluble resinous substances, and then the alcohol solution is converted into an ion exchanger. contact with
The vitamin E contained therein is adsorbed, and then the vitamin E adsorbed on the ion exchanger is eluted using, for example, an ethanol solution containing acetic acid as an eluent. Next, a non-aqueous solvent such as n-hexane is added to this vitamin E-containing solution, which is thoroughly washed with water using saturated saline, etc., then dried over anhydrous sodium sulfate, etc., and the solvent is distilled off to achieve the desired purpose. A concentrate containing vitamin E is obtained.

The concentrate thus obtained contains about 70% or more of vitamin E, mainly α-tocopherol.

According to the method for concentrating vitamin E of the present invention, vitamin E, especially α-tocopherol, can be separated and concentrated very efficiently from plant tissue containing vitamin E.

The resulting concentrate contains approximately 70 φ or more of vitamin E, mainly α-tocopherol, and can be used as it is as a pharmaceutical, health food, or feed additive, or as edible oil, food packaging film, etc. It can be used as a non-toxic antioxidant.

Next, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to this example.

Example 1 Fresh leaves of Hikeshiba, a plant belonging to the family Helicoptera that grows naturally in the wilderness IK
After pulverizing 9 and removing the water produced at that time by compression filtration, the pulverized fibers were placed in a 3L Ninoro flask (a reflux condenser was attached to the top, and a separatory funnel for moisture separation was attached to the bottom of this condenser). Put it inside and add benzene 70
70℃ and heated at around 70℃ for 2 hours, distilled water and benzene were introduced into a separatory funnel attached to the bottom of the condenser, and the water was taken out of the system [7. The Hensen's soluble portion in the fiber was extracted.

After the extraction, the benzene solution is cooled to room temperature, filtered under suction to separate the fibrous material and the benzene solution, and then the benzene solution is concentrated using a 300 d sieve, and then cooled to room temperature to remove the precipitated gel-like substance. After sedimentation and removal using a centrifuge at 7000 r, p, m, benzene was distilled off (~ to obtain a greenish brown benzene extract 807. Ethanol 100 m/! was added to this extract and heated with stirring. Thereafter, the resinous compounds precipitated by cooling at around 0°C were separated by suction filtration.The ethanol solution was heated to around room temperature (25°C), and then heated to around room temperature (25°C). Lighte R-A 401 C
Vitamin E was adsorbed by passing through a glass column layer filled with L-type anion exchange resin). Next, after washing this ion exchange resin with 300ml of ethanol,
Desorb vitamin E from the ion exchange resin with 300 ml of ethanol solution containing 10% acetic acid, and add n-
After adding 300 ml of hexane, washing with saturated brine to remove acetic acid and ethanol, adding anhydrous sulfur salt to the n-hexane solution and drying, distilling off n-hexane (-
A viscous liquid of 2.52% was obtained. The content of vitamin E in this viscous liquid was determined by high performance liquid chromatography, and was found to be about 70%, mainly consisting of α-tocopherol.

Example 2 Fresh leaves of oil palm, a tropical palm tree, were thoroughly crushed, and the water produced at that time was removed by compression filtration, and then placed in the same extraction flask as used in Example 1. Then, 700 g of n-heptane was added and heated at around 80° C. for 2 hours, and vitamin F2 was extracted while removing water that azeotroped with n-heptane from the system.

After the extraction, the n-hexane solution was cooled to room temperature, filtered under suction to separate the fibrous material from the n-hexane solution, and the n-hexane solution was concentrated to obtain a dark greenish brown viscous residue. I got it. Add 400 ml of ethanol to this viscous residue, heat while stirring, and heat to 0°C.
The solid that precipitated after cooling to a certain temperature was separated using a centrifuge. The ethanol solution was passed through a 300 ml layer of the same ion exchange resin as in Example 1 to adsorb vitamin E.

Next, this ion exchange resin was purified with 500 ml of ethanol, and then ethanol 'A' containing 1 JO% of acetic acid was added.
Vitamin E was eluted from the ion exchange resin at 300 yd of nl:', 300 yd of n-hexano was added to this solution, and washed with saturated saline solution until the washing solution became neutral. Next, anhydrous sodium sulfate is added to the 11-hexano solution, and after drying, activated clay 37 is added and stirred sufficiently to adsorb the green pigment, followed by fractional filtration. The filtered activated clay is 1
Wash with 0.00 g of n-hexano, combine the washing liquid and the liquid, distill off the n-hexano, and obtain 2.5 ml of viscous pale green liquid.
I got a 7. When this product was analyzed by high performance liquid chromatography, the content of vitamin E: ψ, whose main component is α-tocopherol, was about 70%.

Agent Akira Agata Procedural Amendment 3, Relationship to the case of the person making the amendment Patent applicant Address 4-8-17 Shimoigusa, Suginami-ku, Tokyo Name
Shibu Koto (and 1 other person) 4 Agents 5 Date of amendment order Item 6 Number of inventions increased by amendment Column 8 Detailed explanation of the invention in the specification subject to amendment 07 Contents of amendment (1) Description No. “Nichibi IE” on page 6, lines 3-4
Delete "F -S p, -CL type anion exchange fiber".

(2) On page 11, line 13, “It was about 70%.

”, then add the following sentence on a new line.

“Example 3 Angelica utilis leaves I
By using Ky and carrying out the same treatment as in Example 1, a viscous dark and colored liquid containing 20% in situ v and 12% α-tocopherol was obtained. ” 614

Claims (1)

[Claims] 1. After crushing a plant tissue containing vitamins 1°C and removing the insect-repelling water, the plant tissue is crushed using a non-polar organic solvent that is water-insoluble and forms an azeotrope with water. While the water remaining in the tissue is azeotropically distilled off with the above-mentioned method, the vitamin E contained in the plant tissue is eluted into the solvent, and then the solvent is distilled off, and the remaining liquid is A method for concentrating vitamin F2, which comprises obtaining a concentrate of vitamin E using an ion exchanger.