JPS6287537A - Extraction of straight-chain primary aliphatic higher alcohol - Google Patents

Abstract

PURPOSE:To industrially and advantageously extract only a straight-chain primary aliphatic higher alcohol from a mixture of higher fatty acid with a higher alcohol obtained by decomposing animal and vegetable natural waxes with saponification, by using a fluid in sub- or super-critical state as an extractant. CONSTITUTION:Animal and vegetable natural waxes (example; carnauba wax, candelilla wax, rice bran wax, etc.) is decomposed by saponification, and the obtained mixture of higher fatty acid salt with higher alcohol is extracted by using a fluid in sub- or super-critical state, i.e. a fluid in the state at near the critical temperature and the critical pressure or above (example; ethylene and CO2, especially CO2 under 60-300kg/cm<2> at 25-100 deg.C is preferred), to separate and obtain the straight chain primary aliphatic higher alcohol (example; triacontanol, etc.). EFFECT:Separation of an extract from an extractant is readily carried out and the product is of high purity. USE:A health food, remedial purpose food, etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention aims at producing straight-chain primary fat adult grade from a mixture of higher fatty acid salts and higher alcohols obtained by saponifying and decomposing animal/vegetable natural waxes. This invention relates to a method for extracting and separating alcohol. In more detail, linear primary fatty adult alcohol is produced from a mixture of higher fatty acid salts and higher alcohols obtained by saponifying and decomposing natural waxes derived from plants and plants using a fluid in a subcritical or supercritical state as an extractant. This relates to a method for extracting and separating. The straight chain primary fatty adult alcohol to be extracted is about C20 to 036,
Among them, octacosanol (028) and triacontanol (C30) are important substances that are expected to be used in many fields as physiologically active substances. That is, octacosanol is C
Molecule represented by H3(CH2)26CH20H! 41
0.74, melting point 83.2-83.4°C1 It is a white crystalline linear saturated 1(llIi alcohol), and is found in nature as a component of vegetable waxes, especially wax extracted from wheat leaves, and apples. Candelilla wax, the wax that covers the epidermis of
Contained in cotton wax, etc. In addition, they are widely present in the epidermis of vegetable oils, grains, nuts, plant leaves, stems, fruits, etc., but in all cases, their content is extremely small.

Octacosanol has a large part (1 pu to increase physical strength and a
It is known that it has two effects: repair of damaged nerve cells. For example, ■ Increased endurance, energy, and physical strength ■ Improved reflexes and agility ■ Improved resistance to the effects of stress ■ Stimulated sex hormones, muscle spasms? It has been confirmed to have effects such as reduction in muscle function, improvement in muscle function including myocardium, reduction in systolic blood pressure, improvement in basal metabolic power, etc., and is used as a health food and for therapeutic purposes. Approximately 1 mfJ/daV is appropriate for the purpose of increasing physical strength, but for therapeutic purposes, approximately 401 tl for minerals and vitamins! It is said that it is best to take an additional dose of about J/day.

Triacontanol is also called mericyl alcohol.
Molecule ff represented by CH3(CH2)28cH20H
1438.80, 9 points, 86.5°C, white crystalline linear saturated alcohol. Like octacosanol, it is found in nature in minute amounts as a component of vegetable waxes. Triacontanol is known to have similar effects to octacosanol, and has also been recognized to have an extremely significant plant growth promoting effect.

(Prior art) Methods for producing octacosanol, which are useful as described above, include chemical synthesis using behenic acid CH3(CH2)2oCOOH as a starting material, and 1,18-octadecanedicarboxylic acid obtained from cyclohexane and butadiene. There is a method of electrochemical synthesis from monoethyl ester and capric acid, but there is also an extraction method that uses natural vegetable oils and waxes as raw materials (1) Among natural vegetable oils, waxes, etc., 12) wheat germ oil. It is known that approximately 100 poii○ is contained in the sulfuric acid, and this is said to be the best raw material for extraction on a commercial basis. Triacontanol is synthesized using lauric acid instead of capric acid in the same manner as the electrochemical synthesis method of octacosanol. However, extraction methods from vegetable waxes have not yet been commercially implemented.

In addition, animal and vegetable natural waxes contain these higher alcohols in the form of higher fatty acids and esters, so after saponifying and decomposing these waxes in an ethanol/caustic solution, A method has been proposed in which a bone-dry solid is obtained and extracted with a non-polar solvent to obtain a higher alcohol. (Unexamined Japanese Patent Publication No. 60-155143> (Problems to be Solved by the Invention) Octacosanol obtained by chemical synthesis seems to be similar in effect to natural products, but for example, it is difficult to extract behenic acid itself, which is used as a raw material. 17 is difficult, and the electrochemical method involves complicated synthesis and purification processes, resulting in an expensive product.Furthermore, there remain concerns about the safety of human administration as a synthetic chemical. The extraction of natural octacosanol is 100pp even in wheat germ oil, which is said to have the highest content.
In other cases, the content is only extremely small. In addition, octacosanol is insoluble in water and has low solubility in battering machine solvents, making its extraction difficult and therefore very expensive. Triacontanol is almost the same and is very expensive.

The method of extracting and separating higher alcohols with a non-polar solvent after saponifying and decomposing natural waxes of animal and vegetable origin is efficient in terms of raw materials because the higher alcohols exist in a relatively concentrated form. It can be said. In this method, wax is dissolved in a solvent and then ethanol and caustic alkali are added to perform saponification and decomposition under reflux. This requires addition and is very inefficient in volume, and if undecomposed wax remains, it will be extracted into higher alcohol components during subsequent solvent extraction, making it difficult to remove. Also,
(Desolvent removal) If dehydration is not performed completely, higher fatty acid salts will be solubilized in the extraction process with non-polar solvents and extracted together with higher alcohols, making the separation and purification process complicated and affecting the purity of the final product. There is a large possibility of lowering the yield. others,
There are many problems such as high energy consumption and complicated operations such as the need for post-treatment such as desolvation as the extraction is carried out using an organic solvent.

(Means for Solving the Problem) Therefore, the present inventors have conducted intensive studies on an industrially advantageous method for extracting and separating linear primary fatty free-range alcohols such as octacosanol and triacontanol from naturally occurring raw materials. As a result, if a fluid in a subcritical or supercritical state is used as an extractant, a mixture of higher fatty acid salts and aliphatic higher alcohols obtained by saponifying and decomposing animal and vegetable natural waxes using ethanol and caustic alkali can be extracted. The present invention was achieved by discovering that only these higher alcohols can be extracted and separated. Furthermore, the present invention was completed by studying the types of raw materials, types of extractants, extraction and separation conditions, etc.

The configuration of the present invention will be explained below.

The animal and vegetable natural waxes used as raw materials are esters of higher fatty acids and higher aliphatic alcohols, and are decomposed into higher fatty acid salts and higher aliphatic alcohols through a saponification reaction with caustic alkali. For decomposition, the raw material is dissolved in refluxed ethanol in advance, and an excess ethanol/caustic alkaline solution (the amount of alkali added is about 3 to 5 times the mole of raw wax) is added in several portions. Let's do it. Although good results can be obtained by using caustic potash as the caustic alkali, it is also possible to use caustic soda. The degree of progress of wax decomposition is estimated by measuring the peak area of undecomposed wax by gas chromatography and determining the degree of decrease in the area. Ideally, the wax should be decomposed until no undecomposed wax is observed, but in the method of the present invention, which uses a subcritical or supercritical fluid as an extractant, even if a peak of undecomposed wax is observed in gas chromatography, , distill off some of the water used in the preparation of ethanol and ethanol/casei alkaline solution, dry and remove a small amount of water.
Even if the wax still contains undecomposed wax, that is, the decomposition is incomplete, it can proceed to the next extraction step.

A conventional method for separating higher alcohols from a mixture of higher fatty acid salts and higher alcohols using nonpolar solvents such as n-hexane and n-pentane (Japanese Patent Application Laid-Open No. 1986-1
55143>, if undecomposed wax remains, the wax will be extracted into higher alcohol components during solvent extraction, making removal difficult and causing a decrease in purity and yield. However, in the method of the present invention, by selecting the type of subcritical or supercritical fluid and extraction conditions, it is possible to selectively extract only higher alcohols from a mixture of higher fatty acid salts and higher alcohols. This is superior to the conventional method.

Generally, a method for separating an organic compound from a mixture containing it using a subcritical or supercritical fluid is known, for example, as described in Japanese Patent Publication No. 54-10539. A fluid in a subcritical or supercritical state refers to a fluid in a state near or exceeding critical temperature and pressure. For example, ethylene (9.9℃, 50atm),
It is a fluid like carbon dioxide (31.0°C, 72.9 atm) that is near or above the critical state, and has a density close to that of a liquid and a large diffusion coefficient close to that of a gas. Because of this characteristic, various compounds can be extracted quickly and efficiently in large quantities, and the extractant can be easily separated. Furthermore, because the ability to dissolve various compounds can be drastically changed by changing the pressure or temperature slightly, it also has the characteristic of being able to perform selective extraction.

Generally, in the present invention, any of the above-mentioned fluids in a subcritical or supercritical state can be used, but in general, the separation ability between higher fatty acid salts and straight chain primary fatty free grade alcohols is excellent. Carbon dioxide is usually used as the extraction agent because it can be processed at relatively low temperatures, is easy to handle and operate, and is economically advantageous.

In the extraction method using a solvent such as n-hexane or n-pentane, the extract is colored and contains an alkaline component. Therefore, colorless higher alcohols cannot be obtained by performing the dealkalization, dehydration, and decolorization processes with hot water. However, when supercritical or subcritical carbon dioxide is used as an extractant, When the CO2 used in the agent is separated, a colorless aliphatic first-class higher alcohol is isolated.
There is no need for troublesome post-operations such as dealkalization, dehydration, and decolorization.

Embodiments of the present invention will be described below based on a flow sheet. In Figure 1: Compression line 2 from 002 cylinder 1
C02 compressed to a predetermined pressure using a heat exchanger 3 is brought to a predetermined extraction temperature and brought into a subcritical or supercritical state and introduced into an extraction column 4. The extraction tower 4 is charged with a mixture (dry solid) of higher fatty acid salts and higher alcohols obtained by saponification and decomposition of animal and vegetable natural waxes, and extracted by contacting with subcritical or supercritical CO2. Perform the operation. Next, the pressure of the CO2 phase containing the extract is reduced through a pressure reducing valve 5, and the extract is separated from 002 by passing into a separator 6. The C02 separated from the extract is cooled and liquefied in the condenser 7, and is recycled via the compressor 2. In the above process, the pressure of CO2 in the extraction column is 50 to 500 KI/
CIt, preferably 60-300 to 3/Ci, temperature 2
It is necessary to perform extraction while maintaining the temperature in the range of 5 to 100°C, preferably 25 to 70°C. If it is too low, it becomes liquefied CO2, which requires energy to separate the extractant from the extract.

On the other hand, if it is too high, the cost of the equipment will increase, causing problems in terms of economic efficiency, and may also cause adverse effects such as thermal deterioration. Separator 6
The conditions for separating the extract from the extraction phase are that the pressure is 1
Preferable results can be obtained by setting the temperature in the range of 9/ci to 200 to 30 to 100°C. Incidentally, stepwise extraction can also be carried out by introducing the extracting agent into the extraction column while increasing the pressure stepwise. In addition to the above-mentioned pressure reduction method, separation from the extractant may be performed by a temperature change method, and by installing a plurality of separators in series, it is also possible to perform fractional separation by lowering the pressure stepwise. In the process shown in Figure 1, the separator 6
Although the extract is separated over time, the components of the extracted extract differ depending on the method of fractionation, so it is also possible to separate the desired active ingredients.

(Example) The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to this.

Example 1 Oxidation (AV) 9.5 Saponification value (SV) 89.4 Iodination (
IV) 350 g of refined rice bran wax (Rice Plan Wax) with a melting point of 4.8 (m/p/>81.2°C) was added under stirring to a 10 U 4-ton flask containing 2 breaths of ethanol, and 1 It was dissolved under ethanol reflux for an hour.The ethanol/caustic potash solution was prepared by adding raw mother water to 2009 solid potash to make it wet, and then dissolving it in the second ethanol.This ethanol/caustic potash solution was A portion was gradually added dropwise to the ethanol solution of rice bran wax and stirred under reflux for 5 hours to perform a decomposition reaction. The reaction was carried out under reflux for 5 hours to complete the decomposition reaction.A portion of the decomposition product was collected and analyzed by gas chromatography, and a small amount of undecomposed wax components were found. Ethanolization and dehydration were carried out under vacuum.The yield of the dry solid was 3809. This solid was crushed and used as a raw material in the process shown in Figure 1 to produce 20 ONy/CI! Critical C
Extraction was performed using O2 as an extractant, and the extract was separated at room temperature and atmospheric pressure to obtain 1023 as a white solid. As a result of analyzing this white solid by gas chromatography, it was found to be a highly pure higher alcohol composition, and the raw material wax and higher fatty acid salts present therein were very small. The results of analysis of a higher alcohol composition by gas chromatography are shown.

C24: 5.5%, C26: 7.2%, 028
:16.5%C3o: 24.3%, C34: 18
．． 0%, 036: 3.8% Example 2 The same rice bran wax 350 used in Example 1! ? was subjected to the same decomposition treatment as in Example 1, followed by removal of ethanol and dehydration in the same manner as in Example 1 to obtain 378 g of dry solid. Using the pulverized solid material as a raw material, extraction was performed using supercritical CO2 at 250 KI/ai and a temperature of 40°C as an extractant in the process shown in Figure 1.
After partially separating the extract containing undecomposed wax at 40° C., higher alcohols were separated at 140 kg/cIi at 35° C. to obtain 97 g of a white solid. When this white solid was analyzed by gas chromatography,
The presence of raw material wax and fatty acids was not detected, indicating that the composition was a highly pure higher alcohol composition. The results of analysis of the higher alcohol composition by gas chromatography are shown below.

C24: 3.7%, C26: 8.3%, 02B: 2
1.6%.

C30: 28.4%, C32: 19.1%, C
34: 15.3%.

C36: 1.5% Example 3 Sugar wax (>200g) imported from Kini I-Ba was subjected to alkaline decomposition for about 3 hours in the same manner as in Example 1, and the resulting decomposition solution was also subjected to the same treatment. Example] was dried in the same manner as above to obtain a dry solid of 213 mm.This dry solid was pulverized and used as a raw material in the process shown in Figure 1 at a pressure of 220'J/cut and fA of 38°C Extracted using supercritical CO2 as an extractant to 150'!
The extract was separated at 35° C. to obtain 359 as a white fine powder. When this fine powder was analyzed by gas chromatography, it was found to be a 02B A-phthalate (high WA degree n-class resin group III group containing sanol as a main component) nordyl-1-l composition. The following are the results of the analysis of the extract by Gask.

C24: 3. , i%, C26: 7.6%, 02
8: 70.3%.

c3o: 12.1%, C32: 2.2%.

Example 4 AV2. O,5V80.3. IVl　1.5. m.

250 g of carnauba wax at p87.8° C. was saponified and decomposed according to Example 1, and then dried to obtain 265 g of a dry solid. Using the pulverized dry solid as a raw material, extraction was carried out in the process shown in Figure 1 using supercritical CO2 at a pressure of 20Q Kg/cti and a temperature of 40°C as an extractant.
Separation under atmospheric pressure yielded 879 as a white fine powder. When this extract was analyzed by gas chromatography, it was found that the presence of raw material wax and fatty acids was extremely small, making it a highly pure higher alcohol composition. The analysis results of higher alcohol components are shown below.

C22: 1.2%, C24: 2.5%, c26
'7.1%.

C28: 7.3%, C3o: 17.8%, C32
: 43.5%.

C36: 15.7%, others 4.9% [Effects of the invention] The method of the present invention industrially advantageously produces octacosanol,
It is possible to obtain useful linear primary fatty alcohols such as triacontanol, and the following superior effects can be achieved compared to conventional methods.

■ In the conventional method, animal and vegetable natural waxes are mixed with ethanol and
Through the saponification reaction with caustic alkali, it is almost completely decomposed into higher fatty acid salts and aliphatic higher alcohols, and only the higher alcohols are extracted and separated from the reactants using nonpolar solvents such as n-hexane and n-pentane. Ta. However, in the method of the present invention, subcritical or supercritical fluids whose ability to dissolve various organic compounds changes simply by changes in temperature and pressure,
In particular, since carbon dioxide is used as an extractant, even if saponification and decomposition are not completely carried out, linear
Only grade fatty alcohols can be selectively extracted.

Similarly, even if ethanol and some water are incompletely distilled off after the decomposition reaction, the extraction step can still be carried out for the same reason as described above.

■ In conventional methods, for example, when extraction is performed using n-hexane, the extract is colored and contains a large amount of alkali, so after the complicated steps of washing, dehydration, and decolorization, the extractant is distilled off. The target object was separated. However, in the method of the present invention, since a subcritical or supercritical fluid is used as the extractant, separation of the extract and the extractant is very easy, and only the target product can be obtained after separation. Therefore, there is no need for a complicated post-treatment process as in the conventional method, and linear primary fatty adult-grade alcohols can be efficiently separated in a simple process. Furthermore, unlike conventional methods, large amounts of organic solvents are not used, so there are no operational risks, environmental pollution, or other problems.

■ Because the extraction operation is performed at low temperatures and in an inert atmosphere, there is no deterioration, and there is no problem of residual bacteria in the organic solvent in the extract, so it is possible to extract and separate highly pure linear primary fatty free-range alcohol. can.

[Brief explanation of drawings]

FIG. 1 is a flow sheet showing an embodiment of the present invention.

Claims (9)

[Claims] (1) When separating higher alcohols from a mixture of higher fatty acid salts and higher alcohols obtained after saponifying and decomposing animal and vegetable natural waxes, it is recommended to use a subcritical or supercritical fluid as an extractant. Characteristic method for extracting linear primary aliphatic higher alcohols. (2) Carnauba wax (animal/vegetable natural wax)
Carnaba Wax), Candelilla Wax (C
andelilla Wax), Rice-Bran Wax, Bees Wax (
Bees Wax), Shell Wax
lac Wax), Shugar Cane Wax (Sug
Claim (1) which is (cane wax)
Method described. (3) The method according to claim (1), wherein the saponification and decomposition is carried out using an ethanol/caustic acid solution. (4) The method according to claim (1), wherein the fluid in a subcritical or supercritical state is carbon dioxide. (5) The fluid in subcritical or supercritical state has a pressure of 60 to 3
The method according to claim (4), wherein carbon dioxide is used at a temperature of 00 Kg/cm^2 and a temperature of 25 to 100°C. (6) The method according to claim (1), (4) or (5), wherein the conditions for separating the extract from the extraction phase are a pressure of 1 to 200 Kg/cm^2 and a temperature of 30 to 100°C. . (7) Claims (1) and (4) obtained by dividing the extracted components by performing stepwise extraction in the extraction process or fractionally separating them in the separation process.
The method described in (5) or (6). (8) The main component of the linear primary aliphatic higher alcohol to be extracted and separated is octacosanol (Octacosanol).
) The method according to claims (1) to (7). (9) The main component of the linear primary aliphatic higher alcohol to be extracted and separated is triacontanol (Tria-conta-contanol).
The method according to claims (1) to (7), wherein the method is: