JPH0455412B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for separating higher alcohols from natural vegetable waxes or animal waxes.

In general, natural waxes (or waxes) are animal and vegetable waxes whose main components are esters of higher fatty acids and higher monohydric alcohols; mineral waxes such as montan wax; and petroleum waxes such as paraffin waxes. It is classified as deaf.

Among these, animal and plant waxes are found in the leaves, stems, pericarp, and seed coat of plants; the epidermis, brain, and secretions of animals; these waxes can be added directly to foods for gloss, moisture prevention, and foaming. It is widely used as a coating agent for candy products, a release agent for confectionery, a softener for chewing gum, etc., and its safety as a food additive has been fully confirmed in terms of food hygiene. It is. In addition to foods, it is also used as a raw material for pharmaceuticals, cosmetic bases, lubricants, stationery items, etc.

On the other hand, recently, the action of monohydric saturated alcohols with carbon numbers of 20 or more (hereinafter referred to as higher alcohols) as physiologically active substances has attracted attention, and tetracosanol (carbon number of 24) and hexacosanol (carbon number of
26), octacosanol (carbon number 28), triacontanol (carbon number 30), dotriacontanol (carbon number 32), tetratriacontanol (carbon number
34), among others, triacontanol is known to have a growth regulating effect on animals and plants, and octacosanol is known to increase muscle strength and vitality, strengthen virility, increase energy, improve endurance, and reduce basal metabolic energy. It has been introduced in the literature that it is effective for improvement (CTCuretone: Charles, C. Tomas,
Springfield, 1972).

In this way, higher alcohols have become attractive substances as their physiologically active effects have been elucidated, and the separation and utilization of these higher alcohols from the waxes of animals and plants that are abundant in the natural world is an important topic in the fields of food and pharmaceutical manufacturing. It has attracted a lot of attention in the field of fatty acid production, and is also attracting attention as it promotes the development of new applications.

[Prior Art] However, it is very difficult to industrially and efficiently separate higher alcohols from animal and plant waxes. The reason for this is that animal and plant waxes have long chain lengths (more than 50 carbon atoms), making them difficult to decompose in large quantities, and higher fatty acids and higher alcohols with 20 to 38 carbon atoms both have long chain lengths. This is because they have similar physical properties such as high melting point, high boiling point, and low solubility in solvents.

Under these circumstances, conventional methods for separating higher alcohols from animal and plant waxes have mainly involved analysis and identification methods as described below. (1) By saponifying and decomposing a small amount of animal and plant wax with a large amount of alkaline alcohol, it is made into a mixture of fatty acid salts and higher alcohols, and after acid decomposing the fatty acid salts into fatty acids, it is passed through an ion exchange resin column. Method of adsorbing fatty acid components and eluting and separating higher alcohol components (Oil Chemistry, Vol. 27,
5, 1978) is an analytical identification tool.

(2) The method of quantifying animal and plant waxes by transesterifying them into fatty acid esters and higher alcohols (JAOCS, Vol. 50, p. 367, 1977) is for analytical quantitative purposes and is not industrially applicable.

(3) By saponifying and decomposing whale oil and wool wax under high pressure,
The method for obtaining higher alcohols by steam distillation (Oil Chemistry, Vol. 5, No. 6, p. 355, 1956) is
This can be carried out because the higher alcohol contained in these is an unsaturated secondary alcohol, has a small number of carbon atoms, has a lower boiling point than the higher alcohol of the present invention, and is easy to distill. , like the higher alcohol of the present invention,
For those that are saturated and have high boiling and melting points,
It is not possible to separate in this way.

4 In enzymatic degradation, the action of porcine liver lipase on esters of long-chain fatty acids and short-chain primary alcohols (Biochimica, Et,
Biophysica, Acta, 248149, 1971), but these are purely academic studies, and their industrial use cannot be expected at this stage due to the abundance of enzymes and productivity of decomposed products.

In this way, in order to completely decompose animal and plant waxes with high chain length, it is necessary to decompose or transesterify them in an extremely large amount of solvent, or to decompose them under high pressure. Productivity is poor, and the latter is extremely dangerous due to the reaction in a solvent at high temperatures and high pressures.
Kg/cm ² or more was required, which involved high energy consumption, and there was a risk that decomposed products would be denatured due to high temperature and high pressure. Furthermore, as mentioned above, there is currently no suitable method for selectively and efficiently extracting and separating only higher alcohols from the decomposition products obtained by such decomposition.

[Problems to be Solved by the Invention] Therefore, in view of the current situation, the present inventors have decomposed animal and plant waxes completely, and efficiently and selectively extract and separate only higher alcohols from the decomposed products. The method was first applied for (patent application 1986-9404)
issue).

In this method, first, animal and plant waxes are dissolved in a solvent,
Next, a caustic potash-ethanol solution is added and the decomposition is repeated until no undegraded animal or plant wax is detected in the decomposed product, and the decomposed product is further desolvated and dehydrated to form an absolutely dry solid. The higher alcohols are separated by extraction with a specific solvent, but even with this method, the following problems still arose.

In other words, when an animal or plant wax is desolvated and dehydrated to an absolutely dry state after being decomposed with an alkali, the water used for the reaction to adjust the decomposition is incorporated into the decomposition product and the excess alkali, and the excess alkali absorbs moisture. Due to the nature of the water, it takes a very long time to dry and remove the water, and it is difficult to remove it completely.

If there is a lot of water in this way, when higher alcohols are extracted from bone-dry solids using a specific solvent, the extraction efficiency will be poor, and fatty acid salts, which are decomposition products, will be soluble in water and will be entrained in the higher alcohol extract. Therefore, it takes a lot of effort to remove it by washing with water.
This is especially true when a batch system is used in which the higher alcohol extract and undissolved cake are separated, and water and excess alkali form a film on the undissolved cake, significantly reducing the overrate. It turned out that it took a long time and was extremely inefficient.

[Means for Solving the Problems] The present inventors have solved the problems of this patent application No. 59-9404, and as a result of intensive research to further improve the problems, the present inventors have developed a method for decomposition of animal and plant waxes by alkali decomposition. By carbonating the excess alkali in the
It is possible to obtain bone-dry solids in a short time, and the grinding of bone-dry solids is easy, which improves the extraction efficiency of higher alcohols, shortens the purification time, and reduces hypersensitivity especially during batch extraction. They have found that this is a significant improvement and have completed the present invention.

That is, the present invention decomposes natural vegetable wax or animal wax using an alkali and a solvent to form excess alkali carbonate in the decomposition solution, and then removes the solvent to extract higher alcohols from the resulting bone-dry solid. This invention relates to a method for separating higher alcohols, which is characterized by extraction.

The animal and plant waxes used as raw materials in the present invention include rice bran wax, candelilla wax, carnauba wax, auricilla wax, wood wax, esparto wax, sugar wax, etc.
Examples of animal waxes include beeswax, serrata wax, Chinese insect wax, lanolin, spermaceti wax, and exposed beeswax. Among these, vegetable waxes have a high monoester content and higher alcohol content, and have a low content of other components other than monoesters such as free fatty acids, free alcohols, hydrocarbons, and unsaturated fatty acids. , rice bran wax is preferable, and among animal waxes, beeswax, shellfish wax, and Chinese insect wax are preferable because they have a high content of higher alcohols.

The alkali used to decompose animal and plant waxes is preferably an alkali metal hydroxide, with caustic soda and caustic potash being particularly preferred.

When converting excess alkali in the decomposition solution obtained by alkali decomposition of animal and plant waxes into carbonate, it is appropriate to use carbon dioxide. , or by converting frozen carbon dioxide into gas and blowing it into the gas.
Alternatively, it may be added in a solid form such as dry ice, but preferably, carbonation proceeds quickly by directly blowing carbon dioxide gas in the form of a gas to bring about vigorous contact.

The amount of carbon dioxide added is 2 to 5 times the amount corresponding to the excess alkali. If the amount is less than 2 times, the excess alkali will not be completely carbonated, resulting in poor extraction efficiency and excessiveness when extracting higher alcohols from bone-dry solids, and if it exceeds 5 times the amount, it will be uneconomical. be. However, in any case, they are used in excess to some extent, so it is preferable to recycle them for use.

At this time, the temperature drops when carbon dioxide is added, so it is necessary to constantly heat the system.
It is preferred to maintain the temperature at 80°C.

In addition, with the addition of carbon dioxide, the inside of the system changes from brown and transparent to cloudy and some precipitation occurs. This is thoroughly desolvented and dehydrated using an evaporator or rotary evaporator under normal pressure or reduced pressure, and further dried in a drier in some cases to mix the fatty acid salt and higher alcohol in an absolutely dry state. Obtain solids.

This bone dry solid is pulverized and then the higher alcohol is extracted using a large Soxhlet type extractor or batchwise. In the former case, continuous extraction is carried out at the boiling point of the solvent using a solvent that does not dissolve the higher fatty acid salt but dissolves only the higher alcohol in an amount of 2 to 20 times the amount of the bone-dried solid that has been prepared, and in the latter case, is extracted in a dispersed state with stirring for 15 minutes to 5 hours at 40 to 65°C using a similar solvent in an amount of 3 to 15 times the amount of the bone-dried solid.

The higher alcohol extract is immediately filtered at the same temperature, but the filtering is preferably carried out under heating, and pressure filtering or filter press can be used.

It is sufficient to repeat this extraction and filtration twice; any more would be a waste of time.

The perfused mother liquor obtained by filtration can be decolored, deodorized, and purified in a conventional manner to obtain a crystalline higher alcohol, either in a solution state or after desolvation.

[Effects of the invention] The present invention provides the following advantages: After decomposing animal and plant waxes with alkali,
This method is characterized by carbonating excess alkali in the hydroxide state in the decomposition solution, and has the following advantages.

(1) The speed of desolvation and dehydration when desolventizing and dehydrating a decomposed solution to obtain an absolutely dry solid is extremely fast, and is 2 to 3 times faster than when carbonation is not performed.

Moreover, the bone-dry solid thus obtained is easy to grind and non-hygroscopic.

(2) In the decomposition solution, higher alcohols are not trapped in fatty acid salts, so the extraction efficiency when extracting higher alcohols from bone-dry solids is increased, and even higher alcohols are removed during batch extraction. The overrate of the extract becomes more than twice as fast as in the case without carbonation.

Specifically, in the case of the present invention, the extraction efficiency of higher alcohols is more than 70% by repeating the filtration twice after extraction for 1 hour, but in the case of no carbonation, the extraction time is only 40% after 2 hours of extraction. It only shows an extraction efficiency of about %.

As described above, the present invention improves the desolvation and dehydration properties of the decomposition solution and the hypersensitivity of the extracted higher alcohol extract by carbonating excess alkali in the hydroxide state in the decomposition solution, Furthermore, it improves the yield of higher alcohols, making it a major contribution to various fields such as food additives, pharmaceutical raw materials, and cosmetic bases.

[Examples and Comparative Examples] Next, the present invention will be specifically explained using Examples and Comparative Examples.

Example 1 Saponification value 85.5, acid value 8.3, iodine value 4.4, melting point
500 g of refined rice bran wax (manufactured by Noda Wax Co., Ltd.: No. 1) with a general characteristic value of 80.4°C was collected in a 10-capacity four-necked flask equipped with a stirrer, a thermometer, and a reflux tube, and 2 ethanol (reagent 1 grade) was added, stirred, and dissolved for 1 hour under refluxing of ethanol. To this, 165 g of 85% caustic potash grains (grade 1 reagent) were dissolved in 35 g of distilled water, and a caustic potash-ethanol solution diluted with ethanol was added, and the mixture was vigorously stirred for 2 hours under reflux, and the inside of the system turned reddish brown. It became.

In order to check the degree of decomposition after 2 hours, a portion of this solution was collected, and after desolvation, boron trifluoride-
When fatty acid potassium salt was methyl esterified with a methanol reagent and subjected to gas chromatography, a peak of undecomposed rice bran was observed.
In addition, the sample was decomposed for 2 hours and analyzed again, but a peak of undecomposed rice bran was still observed. The decomposition rate for the first two hours was 80.5%, and the decomposition rate for the next two hours was 92.8%.

Therefore, when the caustic potash-ethanol solution (No. 2) was further added and decomposed for 2 hours, no peak of undecomposed rice bran was observed, indicating a 100% decomposition rate. On the other hand, no spots were observed at the corresponding positions where spots of undecomposed rice bran were confirmed by thin layer chromatography. That is,
Under these conditions and method, refined rice bran was completely decomposed in a total of 6 hours.

Next, transfer 4 from this decomposition solution to another 5-capacity four-necked flask, and while keeping it at 80°C and stirring, pass the carbon dioxide gas cylinder through the secondary valve and flow meter, and collect carbon dioxide gas with a glass tube. Blowing was carried out for 60 minutes at a rate of 300 ml/min. As carbon dioxide gas was blown into the solution, the decomposition solution became cloudy and appeared in a slurry state, and when left to stand for a while, it separated into upper and lower layers. Put this directly into a 10 capacity rotary evaporator,
Solvent removal and dehydration were carried out for 3 hours, first using an aspirator and finally under reduced pressure using a vacuum pump.

Next, take it out and keep it under 10mmHg at 60℃.
It was spread on a stainless steel tray and dried under the following conditions.
After drying for 5 hours, a bone-dry solid with a moisture content of 1% or less was obtained by the Karl Fischer method. This bone-dry solid was white and weighed 415 g.

This was crushed uniformly and used as an extraction raw material. 200 g of this extraction raw material was placed in a four-necked flask equipped with a 5-volume reflux tube, and heated at 50°C for 1 hour.
Higher alcohols were extracted with hexane. When this extract was passed through a cloth at a pressure of 1.5 kg/cm ² at 50° C. in a stainless steel pressurizer equipped with a jacket, it took 20 minutes. Furthermore, when the undissolved cake was extracted with 2 n-hexane and passed in the same manner, this time 15
It only took a minute. The combined concentration of the first and second concentrated mother liquors was 3.8.

This was washed three times with ion-exchanged water 1 at 60 to 70°C. The pH of the washing water from the three washes was 7.01, indicating neutrality. Next, it was dehydrated with anhydrous sulfur salt, decolorized with silica gel (trade name: Wako Gel C-200, manufactured by Wako Pure Chemical Industries, Ltd.), and then the solvent was removed under reduced pressure at 85°C using a rotary evaporator to make it almost colorless. crystal of
Got 36g. The yield of higher alcohol components in refined rice bran wax was 75%.

A portion of the crystals was collected, dissolved in chloroform, and subjected to gas chromatography analysis. As a result, no fatty acid component peak was observed, and most of the crystals were higher alcohols. Its composition is expressed in area% of the gas chromatogram: C ₂₄ −OH4.0%, C ₂₆ −
OH6.8%, _C28 -OH15.8%, _C30 -OH25.9%,
C ₃₂ −OH19.2%, C ₃₄ −OH16.9%, C ₃₆ −OH3.6
%, C ₃₈ -OH 0.9%, carbon water 24-38, even-numbered higher alcohols were 93.1%, and the remaining 6.9% were odd-numbered carbon alcohols, hydrocarbons, and others.

Example 2 Of the 415 g of absolute dry solid obtained by carbonating the decomposition solution in Example-1, 200 g of the remainder used in Example-1 was transferred to a 60 mmφ x 200 mm cylindrical paper (manufactured by Toyo Paper Co., Ltd.). The mixture was placed in a Soxhlet extractor and continuously extracted with 1 portion of n-hexane under reflux. Extraction was performed according to Example 1, replacing n-hexane every 8 hours, and 6.1 g of crystals were obtained after 8 hours, 16 hours, 24 hours, and 32 hours after the start of extraction.
8.0g, 8.0g, and 7.1g were obtained, respectively. The respective yields are 13%, 16%, 16%, 15%, and the cumulative yield is 60%.
It was hot. The composition of each crystal determined by gas chromatography was the first two, which showed almost the same value as in Example-1.
One had a slightly higher hydrocarbon content.

Example 3 500 g of Chinese insect wax (manufactured by Kato Yoko Co., Ltd.) having general characteristics of an acid value of 5.9 and a melting point of 81.8°C was decomposed according to Example-1.

Furthermore, according to Example 1, this decomposition solution was
℃ and carbon dioxide gas at a speed of 300 m/min at 120 m/min.
After blowing for a minute, remove solvent, dehydrate, and dry.
688g bone dry solid was obtained.

This material was pulverized, 200g of which was used as an extraction raw material, extracted with n-hexane (2) according to Example 1, and the extracted liquid was filtered. A yield of 79% based on the higher alcohol component in insect wax was obtained.

This crystal was subjected to gas chromatography analysis according to Example 1, and the composition of the higher alcohol was determined from the area percentage of the gas chromatogram: _C24 -OH4.8%, _C26 -OH47.3%, ₂₈ −
OH40.1%, _C30 -OH5.4%, _C32 -OH0.4%,
Even-numbered higher alcohols with 24 to 32 carbon atoms are 98.0
%, and the remaining 2.0% was odd-numbered carbon alcohols, hydrocarbons, and others.

Comparative Example 1 The decomposed solution 4 obtained by decomposing refined rice bran wax in Example-1 was put into a rotary evaporator as it was, and the solvent was removed and dehydrated under reduced pressure using an aspirator and a vacuum pump at 60 to 80°C for 6 hours. It cost. Furthermore, take this out and apply 10mmHg
Thereafter, it was spread on a stainless steel tray and dried at 60°C. After 8 hours of drying, the moisture content is 10% by the Karl-Fitscher method, 5% after 16 hours, and 3% after 24 hours.
It hardly decreased any further. The absolute dry solid weight at this time was 482 g. This was crushed uniformly and used as an extraction raw material in the same manner as in Example-1. Because this product is hygroscopic, it had to be stored in a glass bottle with a lid.

200 g of this extraction raw material was placed in a four-necked flask similar to that in Example 1, and extraction was performed in accordance with Example 11. However, the extraction time was 2 hours.
Furthermore, this was subjected to pressure filtration according to Example-1. First, to obtain 1.5% mother liquor, 90
minutes, and then to dispose of that undissolved cake.
It took 65 minutes to obtain a mother liquor with a concentration of 2.0. The total amount of this concentrated mother liquor was 3.5% according to Example-1.
When washed with ion-exchanged water 1 at 60-70℃,
It took five washes for the wash water to become completely neutral.

Next, dehydration with anhydrous rice bran salt and decolorization with silica gel were performed according to Example 1, and the solvent was removed with a rotary evaporator to obtain 17.8 g of white crystals (yield based on the higher alcohol component in refined rice bran wax).
42%). The composition in terms of area % of the gas chromatogram of this crystal is C ₂₄ −OH3.8%, C ₂₆ −
OH7.0%, _C28 -OH14.9%, _C30 -OH27.1%,
C ₃₂ −OH19.5%, C ₃₄ −OH15.9%, C ₃₆ −OH2.8
%, C ₃₈ -OH 1.1%, 92.1% is higher alcohol with even carbons having 24 to 38 carbon atoms, and the remaining 7.9% is alcohol with odd carbons, hydrocarbons, etc. obtained in Example-1. The composition was almost the same.

Comparative Example 2 200g of the remaining 482g of bone dry solid obtained in Comparative Example-1 used in Comparative Example-1 was added to Example-2.
8 hours, 16 hours after the start of extraction,
Crystals 5.1g, 6.0g, 5.9g after 24 hours and 32 hours,
7.5g each was obtained. The yield of each is 12%,
The yield was 14%, 14%, 18%, and the cumulative yield was 58%.
The composition of each crystal determined by gas chromatogram was almost the same as that of Comparative Example-1.

Claims (1)

[Claims] 1. Decompose natural vegetable wax or animal wax using an alkali and a solvent, convert excess alkali in the decomposition solution into carbonate, and then remove the solvent to obtain a high grade solid product. A method for separating higher alcohols 2 characterized by extracting alcohol In claim 1, a method for separating higher alcohols 3 using carbon dioxide to convert excess alkali in a decomposition solution into carbonate. In range 1 or 2,
Method for separating higher alcohols in which carbon dioxide is in gaseous or solid form 4 In claim 1, 2 or 3, it is provided that the natural plant wax or animal wax is rice bran wax, beeswax, shellfish wax, or china wax. Separation method for higher alcohols, which are insect waxes