JPS5822078B2 - Advanced refining method for wool wax - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for highly refining wool wax, which comprises treating crude wool wax as a solution of a non-polar organic solvent with a combination of a cation exchange resin and/or anion exchange resin and light irradiation.

Refined wool wax is a useful substance used as a base for pharmaceutical ointments and cosmetic creams, lotions, shampoos, conditioners, etc.

Crude wool wax, which is the raw material, recovered from wool washing waste liquid contains impurities such as: ■ Contaminants such as dust, earth and sand, and vegetable matter ■ Inorganic salts that are thought to be components of sheep sweat ■ Manure, blood, and other oxides Contains a large amount of free fatty acids, free alcohols, etc., which are the decomposed products of wax ester, the main ingredient.

Because of this, it has a significant coloration and animal odor, and has low utility value as it is, so it needs to be purified.

Conventionally, this crude wool wax is purified by: (1) Mixing with warm water and centrifuging to remove impurities and water-soluble impurities.

(2) Add warm water containing acids such as phosphoric acid and sulfuric acid, and bleaching agents such as sodium hypochlorite, heat and mix, and remove the aqueous layer by centrifugation.

(3) Add warm water containing alkalis such as caustic soda and soda carbonate, and bleaching agents such as hydrogen peroxide, heat and mix, and remove the aqueous layer by centrifugation.

(4) Wash with warm water to remove excess alkali, bleach, etc.

(5) After that, perform white clay treatment as necessary.

This was done through a series of operations.

In general, when refining wool wax, coloring and reducing the acid value are the most important.Especially, with the conventional refining methods such as those mentioned above, (1) the degree of purification of the product is greatly influenced by the quality of the crude wool wax that is the raw material; Ru.

(2) The operation is extremely complicated and takes a lot of time.

(3) Impurities with large molecular weights such as proteins are difficult to remove.

(4) The yield of wool wax is as low as about 70%.

(5) A large amount of contaminated wastewater is produced.

(6) Difficult to remove animal odor.

There are drawbacks such as.

The present inventors conducted research to find a method for solving these problems and easily obtaining high-purity wool in a high yield, and as a result, they arrived at the method of the present invention.

That is, the present invention is characterized in that when refining a wool region, the wool region is made into a solution of a non-polar organic solvent, and after being irradiated with light, the solution is passed through a cation exchange resin and/or a weakly basic anion exchange resin. This is an advanced refining method for wool.

The invention is carried out in a conventional manner.

The wool region is treated with a solution of an organic solvent, a cation exchange resin regenerated into an H type after removing insoluble matter and/or an anion exchange resin regenerated into an OH type, and a combination of light irradiation.

The treatment temperature is in the range of 20 to 60°C, preferably 30 to 4°C.
In the range of 0°C, the concentration of the solution is in the range of 5 to 50 wt%, preferably in the range of 5 to 30 wt%.

Further, the liquid passing rate through the resin layer is preferably in the range of 0.5 to 2C1/l exchanged resin/)1r).

In the case of light treatment, 300-450 nm as a light source
It is preferable to use light having a wavelength of 5 to 15 minutes.

Furthermore, the light irradiation is performed in the presence of air or oxygen.

A purified wool wax is obtained by distilling off the organic solvent from the solution of the organic solvent in the wool region obtained by the above treatment.

The treatment using a combination of a cation exchange resin and/or anion exchange resin and light irradiation is the following five types of combination treatment.

(1) After irradiating the organic solvent solution in the wool area with light,
(2) After irradiating the organic solvent solution in the wool region with light, the solution is passed through the anion exchange resin layer, and then the cation exchange resin layer. (3) After irradiating a solution of an organic solvent in the wool region with light, a treatment in which the solution is passed through a resin layer made of a mixture of an anion exchange resin and a cation exchange resin; (4) A treatment in which a solution of an organic solvent in the wool region A process of irradiating a solvent solution with light and then passing the liquid through a cation exchange resin layer; (5) A process of irradiating a solution of an organic solvent in the wool region with light and then passing the liquid through an anion exchange resin layer; all of the above. By the combined treatment, extremely high-quality purified wool wax can be obtained in high yield with a much simpler operation than conventional methods.

When light is irradiated onto wool, the peroxide value increases, which can have an unfavorable effect on the quality of the wool.Ion exchange resins, especially strongly acidic ion exchange resins, reduce this peroxide value. have an effect.

The ion exchange resin used in the present invention is preferably a strongly acidic MR type resin such as Amberlyst 15, Amberlyst) As a weakly basic MR type resin (
For example, Amberlight IRA94, Amberlight IR
A93, Amberlis) A-21, etc. (all manufactured by Nippon Organo) are desirable.

The solvent used in the present invention must be a non-polar organic solvent such as benzene or n-hexane that can dissolve wool, ketones such as methyl ethyl ketone, chlorinated solvents such as chloroporm, alcohol-based solvents such as butanol, etc. When using a solvent, good results cannot be obtained because impurities once adsorbed are likely to be eluted due to the polarity of the solvent.

Regeneration of the cation exchange resin used in the present invention includes:
It is preferable to use a lower alcohol such as methanol or ethanol (and more preferably a lower alcohol containing an acid such as hydrogen chloride or sulfuric acid).

Further, the anion exchange resin is preferably regenerated using a lower alcohol such as methanol or ethanol, and more preferably using a lower alcohol containing a base such as caustic soda or caustic potash.

For both cation exchange resins and anion exchange resins, non-polar organic solvents are replaced with methanol, etc., and cation exchange resins are regenerated with acid aqueous solutions such as hydrochloric acid and sulfuric acid, and anion exchange resins are regenerated with base aqueous solutions such as caustic soda and caustic potash. However, the regeneration ability is lower than that of lower alcohols containing acids or bases (and wastewater treatment is required).

The wool region obtained by the present invention has a much better hue than the wool region obtained by conventional methods, has less animal odor, and has a lower ash content.
It has low acid value and peroxide value, and is of excellent quality.

Next, the present invention will be explained in more detail with reference to Examples, which are not intended to limit the present invention, but may be modified without changing the nature of the present invention.

All percentages in the following Examples and Comparative Examples indicate weight percent, and Gardner chromaticity, acid value, and peroxide value were measured using the methods described in Standard Oil and Fat Analysis Test Methods (edited by Japan Oil Chemists' Association). .

Comparative example 1 10% n-hexane solution of crude wool wax at 1600P per minute
．． The mixture was irradiated with a high-pressure mercury lamp (100 W) at room temperature for 10 minutes while bubbling air of 41, and then the solvent was distilled off to obtain wool wax.

Table 1 shows the Gardner color, acid value, and peroxide value of the raw wool wax and the wool wax obtained by the above method.

Comparative Example 2 Strongly acidic MR type ion exchange resin (Amberlyst 15) 1601 was made into a methanol slurry with an inner diameter of 22 mmφ.
It was packed into a jacketed column.

After washing the resin by passing methanol through it, about 3 liters of a methanol solution of IN hydrogen chloride was passed therethrough to regenerate the resin into H type.

Thereafter, hydrogen chloride in the resin layer was removed with methanol, and finally methanol was replaced with n-hexane.

Weakly acidic M was added to another jacketed column (inner diameter 22 mmφ).
R-type ion exchange resin (Amberlite IRA94) 16
The resin was regenerated into an OH type by the same treatment as above except that 0r was filled as a methanol slurry and a methanol solution of IN caustic soda was used instead of a methanol solution of IN hydrogen chloride.

16002, a 10% n-hexane solution of crude wool wax, was first passed through the above-mentioned strongly acidic ion exchange resin layer, and then passed through the weakly basic ion exchange resin layer.

During liquid passage, the temperature of the resin layer was kept at 30°C, and the liquid passage rate was 20°C.
It was carried out at 0cc/hr.

The effluent was collected and n-hexane was distilled off, and the Cardner color, acid value, peroxide value, and yield of the wool wax obtained are shown in Table 1.

The raw material crude wool wax used was the same as in Comparative Example 1.

Example 1 In the same manner as in Comparative Example 2, a strongly acidic ion exchange resin (Amberlyst 15) was regenerated into H type, and a weakly basic ion exchange resin (Amberlyst IRA94) was regenerated into OHW.

A high-pressure mercury lamp (10%
0W) for 10 minutes, then the solution was passed through the above-mentioned strongly acidic ion exchange resin layer, and finally the solution was passed through the weakly basic ion exchange resin layer.

The liquid flow rate was 200 cc/hr, and the temperature was 30°C.

After passing the 10% n-hexane solution of crude wool wax, about 500 cc of hexane is passed through.

All the effluents were collected and n-hexane was distilled off, and the Gardner color, acid value, peroxide value, and yield of the wool wax obtained are shown in Table 1.

Comparative Example 3 The order in which a 10% n-hexane solution of crude wool wax was passed was changed to first a photoreaction tank, then a strongly acidic ion exchange resin layer, and finally a weakly basic ion exchange resin layer. Purification was carried out in the same manner as in Example 1, except that the ion exchange resin layer was followed by the photoreaction tank, and finally the weakly basic ion exchange resin layer.

Cardner chromaticity, acid value, peroxide value of the obtained wool wax,
The yield is shown in Table-1.

Comparative Example 1 has a very high peroxide value and a high Gardner chromaticity, and Comparative Example 2 also has a high Gardner chromaticity.

In Comparative Example 3, the Gardner chromaticity and acid value are extremely low, but the peroxide value is higher than that of the raw material.

In comparison, in Example 1, a high-quality wool wax with extremely low Gardner chromatic acid value and low peroxide value was obtained.

Example and Comparative Example 3 Differences in performance depending on the combination of ion exchange resin and light irradiation were compared.

In the same manner as in Comparative Example 2, the strongly acidic ion exchange resin (Amberlyth) 15) was regenerated into the H type, and the weakly basic ion exchange resin (Amberlite IRA94) was regenerated into the OH type, and the following combinations were carried out and examples. (Used in the experiments of 1-pack (2) and combinations (3) to (5) as comparative examples.

In combination (1), 20% of crude wool wax is made into a 10% n-hexane solution, first irradiated with light using a high-pressure mercury lamp, then passed through strong acidic ion exchange resin 301, and finally weakly basic ion The solution was passed through exchange resin 301.

In combination (2), crude wool wax 209 was made into a 10% n-hexane solution, first irradiated with light using a high-pressure mercury lamp, and then strongly acidic ion exchange resin 302 and weakly basic ion exchange resin 301 were mixed. A liquid was passed through the resin layer.

In combination (3), crude wool wax 202 is made into a 10% n-hexane solution, and then strongly acidic ion exchange resin 309 is added.
The solution was then irradiated with light from a high-pressure mercury lamp, and finally the solution was passed through a weakly basic ion exchange resin 301.

In combination (4), crude wool wax 202 is made into a 10% n-hexane solution, and then strongly acidic ion exchange resin 302 is added.
The solution was then passed through a weakly basic ion exchange resin 301, and finally irradiated with light using a high pressure mercury lamp.

In combination (5), crude wool wax 202 is made into a 10% n-hexane solution, and then strongly acidic ion exchange resin 30?
and 30f of weakly basic ion exchange resin! A liquid was passed through the resin layer mixed with ', and then light was irradiated with a high-pressure mercury lamp.

N-hexane was distilled off from the solutions treated with combinations (1) to (5), and the Gardner color, acid value, and peroxide value of the wool wax obtained are shown in Table 2.

In each combination, light irradiation was performed for 10 minutes using a 100 W high pressure mercury lamp.

In addition, when passing wool wax through an ion exchange resin, the resin is 17 m
Packed in mφ column and 100cc/hr at 30℃
was done at a speed of

In any combination, the Gardner chromaticity is significantly improved and the acid value is reduced to 1 or less, but combinations (3) to
In (5), the peroxide value is not sufficiently reduced, or rather increases.

Combinations (1) and (2) showed significantly low values not only in Gardner chromaticity but also in acid value and peroxide value, indicating that it is desirable to perform treatment with a cation and/or anion exchange resin after light irradiation. ing.

Claims (1)

[Claims] 1. To purify wool wax, wool wax is made into a solution of a non-polar organic solvent, and after being irradiated with light, a cation exchange resin and/or
Alternatively, an advanced purification method for wool wax characterized by passing the solution through a weakly basic anion exchange resin. 2. The method for highly refining wool wax according to claim 1, wherein light having a wavelength of 300 to 450 nm is used as a light source.