JP3428688B2 - Method for separating and purifying wool grease or lanolin - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for separating and purifying wool grease or lanolin. More specifically, when separating and purifying non-polar lanolin and a polar compound contained in wool grease or lanolin by an adsorption tower, the amount of the polar compound in the wool grease or lanolin remaining in the used adsorbent is a specific amount or less. And a method for repeatedly separating and purifying wool grease or lanolin. 2. Description of the Related Art Conventionally, a solution obtained by dissolving wool grease or lanolin in a nonpolar organic solvent is passed through an adsorption tower filled with an adsorbent, and a polar compound in the wool grease or lanolin is used as an adsorbent. By adsorbing and obtaining non-polar adsorption purified lanolin from the passing liquid, wool grease adsorbed on the adsorbent or a polar compound in lanolin is eluted and recovered by passing a polar organic solvent through wool grease or A method for separating and purifying lanolin is known (Japanese Patent Publication No. 54-21207). [0003] The adsorption tower filled with the adsorbent used for the separation and purification of the wool grease or lanolin elutes the polar compound in the wool grease or lanolin by passing a polar organic solvent through, and then removes nitrogen gas. It is dried by a method such as heating while flowing, and is used repeatedly for separation and purification of wool grease or lanolin. [0004] When the adsorption tower is regenerated and used repeatedly according to the method described above, it can be reused from the viewpoint of removing only allergens evaluated by total skin irritation. The number of times is at most 20 times. In addition to removing allergens, when trying to satisfy 5.0 or less of the standard value of the hydroxyl value of "Adsorbed and purified lanolin" of the Ministry of Health and Welfare "Permission criteria for cosmetic varieties", it is separated every time the number of repeated use of the adsorbent increases Problems such as a decrease in the amount of wool grease or lanolin that can be purified occur. For example, when the separation and purification of wool grease is carried out by the conventional method, if the yield of the first non-polar adsorptive purified lanolin is 100, the second purified adsorbed lanolin with a hydroxyl value of 5.0 or less is obtained. About 86.4, 1
The number decreases to about 47.6 at the 0th time and about 34.1 at the 20th time. [0005] The present invention solves the above-mentioned problems in the conventional method for separating and purifying wool grease or lanolin, and can increase the number of repeated use of the adsorption tower. The object of the present invention is to develop a method for separating and purifying wool grease or lanolin having such characteristics that the amount of wool grease or lanolin that can be separated and purified by repeated use can be kept small. A solution of grease or lanolin dissolved in a non-polar organic solvent is passed through an adsorption tower filled with an adsorbent to adsorb polar compounds in wool grease or lanolin to the adsorbent. And the polar compound in wool grease or lanolin adsorbed by the adsorbent In the separation and purification method of wool grease or lanolin that is eluted and recovered by passing through a polar organic solvent, the polar compound in the wool grease or lanolin adsorbed by the adsorbent is eluted by passing the polar organic solvent through,
At the time of recovery, the temperature of 35 ° C. or the boiling point of the polar organic solvent until the amount of the polar compound in the wool grease or lanolin adsorbed on the adsorbent becomes 2.5 % or less (wt%, the same applies hereinafter).
The present invention relates to a method for separating and purifying wool grease or lanolin by repeatedly using an adsorbent through which a polar organic solvent having a water content of less than 5% is passed. In the present invention, a solution of wool grease or lanolin dissolved in a non-polar organic solvent is passed through an adsorption tower filled with an adsorbent, and the polar compound in the wool grease or lanolin is adsorbed. And non-polar adsorbed purified lanolin is obtained from the passing solution. [0007] The wool grease is obtained by separating and recovering a brownish animal odor attached to wool from a waste solution for washing wool. It contains impurities and free lanolin alcohol and free lanolin fatty acids as wool grease components. Polar compounds such as free lanolin fatty acids and lanolin alcohol among the above-mentioned components have a sticky feeling unique to wool grease, smell,
It is known that when used as a cosmetic raw material, it may cause skin irritation. The lanolin is a yellow-yellow-brown, highly viscous ointment-like substance obtained by subjecting wool grease to acid treatment, alkali treatment, water washing, decoloring, and then performing a treatment such as steam deodorization. It is commercially available as a raw material for pharmaceuticals and cosmetics. The non-polar organic solvent used for dissolving the wool grease or lanolin preferably dissolves components other than impurities (proteins, hair pieces, dust, earth and sand, etc.) contained in the wool grease or lanolin, and is preferably used. Non-polar organic solvents having a boiling point of about 40 to 120 ° C. are exemplified, but not limited thereto. Specific examples of such non-polar organic solvents include aliphatic or aromatic hydrocarbons such as n-hexane, 3-methylpentane, petroleum ether, benzene, toluene and cyclohexane, chloroform, tetrachloride Examples include, but are not limited to, halogenated hydrocarbons such as carbon, mixtures thereof, and the like. Of these, n-hexane, petroleum ether,
Cyclohexane and the like are preferred from the viewpoint of safety for the human body, ease of distillation, and the like. When the wool grease or lanolin is dissolved in the non-polar organic solvent, the ratio of the wool grease or lanolin to the non-polar organic solvent is based on 1 part of wool grease or lanolin (parts by weight, hereinafter the same). And 1.5 to 7.5 parts by volume, preferably 2.5 to 4 parts by volume of the nonpolar organic solvent. If the solution contains contaminants as insolubles, the insolubles are removed by a method such as filtration (eg, filter press) or decantation, and then an adsorption tower filled with an adsorbent. It is preferable that the liquid is passed through. As the adsorbent, any one having a difference in the adsorbability between a polar substance and a non-polar substance can be used. Specific examples thereof include activated clay, acid clay, bentonite, activated alumina and silica gel. , Aluminum silicate, magnesium silicate, zeolite, and mixtures thereof, among which activated alumina,
Silica gel and magnesium silicate are preferred. The particle size of these adsorbents is preferably from 16 to 200 mesh from the viewpoint of having a desired strength in the adsorption tower and facilitating uniform filling, and more preferably from 30 to 200 mesh. As the shape of the adsorption tower filled with the adsorbent, any shape can be used as long as it is a commonly used shape. However, there is a case where heating is required in an adsorbate elution step described later. Since heating is required in the regeneration step, for example, those having heating and heating means such as a steam jacket and an electric heater are preferable. There is no particular limitation on the method of filling the adsorbent, but in order to prevent clogging and uneven drying when heating and drying while passing nitrogen gas during regeneration of the adsorption tower. Is preferably filled as uniformly as possible. A solution obtained by dissolving wool grease or lanolin in the non-polar organic solvent is passed through the adsorption tower prepared in this way.
Usually, at room temperature, the amount of the adsorbent is 1 to 10 parts, preferably about 4 to 7.5 parts per 1 part of wool grease or lanolin, and the liquid is adsorbed for about 10 to 30 minutes. It is preferable to pass the solution so as to come into contact with the agent. After passing the above solution, 1 part of adsorbent is
By washing with about 3 parts by volume of a non-polar solvent, and distilling off the non-polar solvent by combining the flow-through and the washing liquid, a non-polar adsorption-purified lanolin can be obtained. On the other hand, the polar compound in wool grease or lanolin adsorbed on the adsorbent is eluted by passing a washing solution and then a polar organic solvent. The polar compound in wool grease or lanolin is recovered by distilling off the solvent from the obtained eluate. In the present invention, when the polar compound in the wool grease or lanolin adsorbed on the adsorbent is eluted and recovered by passing a polar organic solvent through, the polar compound in the wool grease or lanolin adsorbed on the adsorbent is recovered. The amount of the compound is 2 . The polar organic solvent is passed so as to be 5% or less. As a method of reducing the amount of the polar compound in the wool grease or lanolin adsorbed on the adsorbent to 2.5 % or less, the temperature at which the adsorbent comes into contact with the polar organic solvent is 35%.
Or a temperature lower than the boiling point of the polar organic solvent. The temperature at which the adsorbent comes into contact with the polar organic solvent at 35 ° C. to a temperature lower than the boiling point of the polar organic solvent, preferably about 40 to 120 ° C., depends on the amount of the polar compound adsorbed on the adsorbent. The temperature is set to 35 ° C. or more near the melting point to speed up elution and recovery of the polar compound, and to reduce the amount of residual adsorption to the adsorbent. By adopting such a method, the amount of the polar compound in wool grease or lanolin remaining in the adsorbent even when the amount of the polar organic solvent used is equal to the amount of the conventional polar organic solvent is 2 . It can be 5% or less. The temperature at which the adsorbent comes into contact with the polar organic solvent may be the same temperature from the beginning to the end. For example, at first, the heating of the adsorption tower is not sufficient, and then the temperature is gradually increased. When passing through a heated polar organic solvent, first contact with a non-polar organic solvent at room temperature at a lower temperature, but then first and last, as when the temperature is gradually increased. May be different. The proportion of the polar compound in the wool grease or lanolin remaining in the adsorbent can be determined by weighing about 20 g after taking out the adsorbent after passing a predetermined amount of polar solvent and thoroughly mixing the adsorbent. Take a cylindrical filter paper, cover the top with absorbent cotton, and add water-saturated methyl ethyl ketone (water content 12
%) Extracted with 200 mL for 5 hours, the amount of the polar compound eluted was determined, and the ratio to the adsorbent dried at 105 ° C. for 3 hours was calculated. As a result, the amount of wool grease or lanolin that can be separated and purified by one separation and purification can be reduced, and problems such as a decrease in the purity of the obtained nonpolar adsorbed and purified lanolin can be improved. The polar organic solvent used for the above purpose includes, for example, alkanols such as methanol, ethanol and isopropanol, their esters such as ethyl acetate, and mixtures thereof.
To some extent, but not limited thereto. The amount of the polar solvent used is such that the temperature at which the adsorbent comes into contact with the polar organic solvent is 35 ° C. per part of the adsorbent.
When the temperature is lower than the boiling point of the polar organic solvent, 0.6 to 1.5 parts by volume, more preferably 0.9 to 1.1 parts by volume is appropriate. Although the elution of the polar compound in the wool grease or lanolin adsorbed on the adsorbent, and the higher the polarity of the polar organic solvent flowing to regenerate the adsorbent, the residual ratio of the polar compound decreases, The subsequent drying takes time. One method of increasing the polarity of the polar organic solvent is to increase the water content of the polar organic solvent, but it is preferable to reduce the water content to about 5% or less in consideration of the time required for drying. The polar organic solvent is adsorbed on the adsorbent after eluting and recovering the polar compound in the wool grease or lanolin adsorbed on the adsorbent. Is heated to 100 to 150 ° C by a steam jacket attached to
By drying for 20 hours, it can be regenerated into an adsorption tower that can be used for separation and purification of wool grease or lanolin. By employing such a method, the number of times the adsorbent is used repeatedly can be increased, and
Even if the number of times of repeated use increases, the throughput per one treatment can be kept large, and therefore, the yield of the obtained non-polar adsorbed and purified lanolin can be increased, and the hydroxyl value can be lowered. . The obtained non-polar adsorbed and purified lanolin is equivalent to or more than the adsorbed and purified lanolin obtained by the conventional method in terms of hue, odor and skin irritation, allergic properties, etc., and is used for cosmetics, pharmaceuticals, etc. It is preferably used. The polar compound obtained by elution (eluted polar lanolin) is also equivalent to a conventional product and can be suitably used as an industrial raw material. Next, the method of the present invention will be described more specifically based on Examples and Comparative Examples. Example 1 Unused activated alumina (alumina gel manufactured by Japan Activated Shirato Co., Ltd., having an average particle size of 30 mesh and a moisture content of 0.2%)
100 kg was packed in the adsorption tower, and a solution obtained by dissolving 20 kg of wool grease (acid value 0.8, hydroxyl value 35.6, hue Gardner 7) in 50 L of n-hexane was passed over about 20 minutes. 100 L of hexane was passed over about 20 minutes, and the passed liquids were combined and the solvent was distilled off to obtain non-polar adsorption purified lanolin. In addition, moisture content 0.5%,
100 L of warm ethanol at 40 ° C. was passed over about 20 minutes to elute the polar compound adsorbed on the adsorbent,
The solvent was distilled off to obtain eluted polar lanolin. The adsorbent was sufficiently dried by passing nitrogen gas from the upper part of the adsorption tower for 6 hours while heating to 140 ° C. with a steam jacket attached to the adsorption tower.
%), Cooled to room temperature, and reused under the same conditions. The number of times the adsorbent was used, the ratio of the polar compound in the wool grease remaining in the adsorbent (residual oil fraction), the ratio of the obtained adsorbed purified lanolin and the eluted polar lanolin to the wool grease, and the adsorption Table 1 shows the relationship with the analysis results (acid value, hydroxyl value, hue) of the purified lanolin. The residual oil content in the adsorbent was determined by the method described above. [Table 1] From the results shown in Table 1, the residual oil content in the adsorbent hardly increased even after 50 times of use, and the hydroxyl value of the obtained adsorbed and purified lanolin was also determined according to the "Permission criteria for cosmetic varieties" (examined by the Pharmaceutical Affairs Bureau, Ministry of Health and Welfare). It can be seen that the standard value of "adsorbed and refined lanolin" of the second section supervision, published by Yakuji Nippo is 5.0 or less. COMPARATIVE EXAMPLE 1 100 kg of activated alumina used in Example 1 was charged into an adsorption tower, and the wool grease (acid value of 0.1 g) was added to 50 L of n-hexane.
8. Hydroxyl value 35.6, Hue Gardner 7) 20 kg of a solution was dissolved therein, and 100 L of n-hexane was passed therethrough. The passed solutions were combined and the solvent was distilled off to obtain adsorbed purified lanolin. . Further, methanol 1 at room temperature (23 ° C.)
After passing through 00 L, the polar compound adsorbed on the adsorbent was eluted, and the solvent was distilled off to obtain eluted polar lanolin. The adsorbent was sufficiently dried by passing nitrogen gas from the top of the adsorption tower for 6 hours while heating to 140 ° C. with a steam jacket attached to the adsorption tower (volatility: 1.0%).
%), Cooled to room temperature, and reused under the same conditions. Table 2 shows the results. [Table 2] From the results shown in Table 2, the residual oil content of the adsorbent exceeds 3.0% after one use, and the purified lanolin obtained by using this adsorbent (the second use of the adsorbent) was obtained. It can be seen that the hydroxyl value already exceeds the standard value of 5.0 for "adsorbed and refined lanolin" in the "permission criteria for cosmetic varieties", and it cannot be used as a cosmetic raw material. Comparative Example 2 A solution prepared by dissolving 100 kg of the activated alumina used in Comparative Example 1 in an adsorption tower and dissolving wool grease (acid value 0.8, hydroxyl value 35.6, hue Gardner 7) in 50 L of n-hexane. Then, 100 L of n-hexane was passed, and the passed liquids were combined and the solvent was distilled off to obtain purified lanolin. Further, room temperature (23 ° C.) methanol 10
After passing through 0 L, the polar compound adsorbed on the adsorbent was eluted, and the solvent was distilled off to obtain eluted polar lanolin. The adsorbent was thoroughly dried by passing nitrogen gas from the upper part of the adsorption tower for 6 hours while heating to 140 ° C. with a steam jacket attached to the adsorption tower.
% Or less), cooled to room temperature, and reused under the same conditions except that the amount of wool grease used was changed as shown in Table 3. Table 3 shows the results. [Table 3] From the results shown in Table 3, the amount of wool grease used must be greatly reduced from the second time in order to reduce the hydroxyl value to 5.0 or less, and the yield of adsorbed and purified lanolin per one treatment is reduced. It can be seen that the price has decreased significantly and the product price has increased significantly. Comparative Example 3 Adsorbed and purified lanolin was obtained in the same manner as in the first use of Comparative Example 2, and then methanol 200 at room temperature (23 ° C.) was obtained.
L was passed therethrough to elute the polar compound adsorbed on the adsorbent, and the solvent was distilled off to obtain eluted polar lanolin. on the other hand,
The adsorbent was sufficiently dried (at a volatile content of 1.0% or less) by passing nitrogen gas from the top of the adsorption tower for 6 hours while heating to 140 ° C. with a steam jacket attached to the adsorption tower. The residual oil content in the adsorbent was 3.4%. Using this adsorbent, wool grease was separated and purified under the same conditions. As a result, the hydroxyl value of the obtained purified lanolin was 5.5, and the yield was 48.7%. Further, the residual oil content in the adsorbent was 3.5%. As described above, double the amount of the polar solvent to 200 L
(The polar compound in the wool grease adsorbed by the adsorbent with 100 L of polar solvent is almost eluted, so the 200 L amount is a large excess.) It did not pass the standard of the hydroxyl value of 5.0 or less. Comparative Example 4 The same method as in Comparative Example 2 was repeated except that the second use of the adsorbent was repeated to produce 20 kg of adsorbed and purified lanolin having a hydroxyl value of 5.9. ℃)
Was passed through 100 L of methanol to elute the polar compound adsorbed on the adsorbent, and the solvent was distilled off to obtain eluted polar lanolin. On the other hand, while the adsorbent was heated to 140 ° C. with a steam jacket attached to the adsorption tower, nitrogen gas was passed through the upper part of the adsorption tower for 6 hours to be sufficiently dried (volatile content: 1.0% or less). The residual oil content in the adsorbent is 3.6
%Met. Using this adsorbent, the previously obtained adsorbed and purified lanolin having a hydroxyl value of 5.9 was again separated and purified under the same conditions, and as a result, the obtained readsorbed and purified lanolin had a hydroxyl value of 3.
However, the yield with respect to the first wool grease was extremely low at 29.4%, which was unsatisfactory as an industrial production method. According to the method of the present invention, the number of reusable times of the adsorbent used for separating and purifying wool grease or lanolin can be increased. The amount of wool grease or lanolin that can be separated and purified at one time for each layer decreases,
Although the purity of the obtained adsorbed and purified lanolin decreases,
The decrease in the amount and the decrease in the purity can be reduced.

Claims (1)

(57) [Claim 1] A solution obtained by dissolving wool grease or lanolin in a non-polar organic solvent is passed through an adsorption tower filled with an adsorbent, and the polar compound in the wool grease or lanolin is removed. Wool that is adsorbed on an adsorbent to obtain non-polar adsorbed and purified lanolin from the passing solution, and is recovered by eluting the polar compound in wool grease or lanolin adsorbed on the adsorbent by passing it through a polar organic solvent In the separation and purification method of grease or lanolin, when the polar compound in wool grease or lanolin adsorbed on the adsorbent is eluted and recovered by passing a polar organic solvent through, the polarity in wool grease or lanolin adsorbed on the adsorbent is recovered. 35 ° C to polar until the amount of compound is less than 2.5 % by weight
A method of separating and purifying wool grease or lanolin by repeatedly using an adsorbent which has passed a polar organic solvent having a water content of 5% by weight or less at a boiling point lower than the organic solvent.