CN108893204B - Method for synthesizing refined lanolin by inert gas with water method - Google Patents
Method for synthesizing refined lanolin by inert gas with water method Download PDFInfo
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- CN108893204B CN108893204B CN201810787505.5A CN201810787505A CN108893204B CN 108893204 B CN108893204 B CN 108893204B CN 201810787505 A CN201810787505 A CN 201810787505A CN 108893204 B CN108893204 B CN 108893204B
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- lanolin
- inert gas
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- decoloring
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B11/00—Recovery or refining of other fatty substances, e.g. lanolin or waxes
Abstract
The invention discloses a method for synthesizing refined lanolin by using an inert gas with a water method, which sequentially comprises the following steps: taking a mixture of wool acid and lanonol as a raw material, carrying out esterification reaction by adopting an inert gas water-carrying method under the catalysis of alkali, wherein the reaction temperature is 150-270 ℃, stopping the reaction after reacting for 4-22 h, and cooling to room temperature to obtain a wool grease solid; adding a decoloring agent, a decoloring activator and a solvent into the lanolin paste solid, and decoloring for 1-3 hours at 60-100 ℃; washing the decolorized product while the decolorized product is hot, cooling and drying to obtain the lanolin. The lanolin synthesized by the method has the technical advantages of high raw material conversion rate and high product quality (the chroma is less than or equal to 6).
Description
Technical Field
The invention relates to a method for synthesizing an organic compound, in particular to a method for synthesizing and refining lanolin by an inert gas with water method.
Background
Lanolin is a product with good water absorption, moistening, lipophilicity, emulsifying property and dispersibility, and is used in industries such as cosmetics, medicine, leather, agriculture and the like.
Lanolin is a natural substance secreted from sebaceous glands of sheep, and crude lanolin can be obtained by recovering waste water from wool washing. The hydrolysate of crude lanolin is rich in cholesterol, and the process for extracting cholesterol by hydrolyzing crude lanolin (for example, chinese patent CN103626820A) can produce a large amount of wool acid (about 50%) and lanolin alcohol (about 35%) as by-products, and at present, the by-products are treated by the following methods: various derivatives prepared by using wool acid and lanolin alcohol as raw materials, such as isopropyl lanolate, methyl lanolate, acetylated lanolin alcohol and the like, can be used as an emulsifier, a dispersant, a lubricant and the like of the toning lotion, but the economic value of the products is not high enough for refining lanolin. Therefore, a synthetic route is needed to be invented to produce synthetic refined lanolin with high raw material conversion rate and excellent product quality.
At present, no report is found in the existing method for preparing lanolin by taking wool acid and lanonol as raw materials. The main reason is that the raw material wool acid is a mixture of straight chain acid, branched chain acid and hydroxy acid, wherein the carbon chain length of the mixture is from eight carbons to forty carbons, the lanonol is also a mixture of aliphatic mono-alcohol, diol and polycyclic sterol with wide carbon number distribution, and the raw material structure is complex, so that complete esterification is difficult. The synthesis of lanolin requires high temperature and oxygen-insulating condition (high temperature, and the lanolin generates pigment molecules in the presence of oxygen to deepen the color), so that the azeotropic distillation method is not suitable for the synthesis system to remove water to push the equilibrium to move in the positive direction. Although the vacuum method can achieve the purposes of removing moisture and isolating oxygen generated by esterification reaction, the method has high energy consumption and high vacuum degree requirement, so a synthesis route with high raw material conversion rate and high product quality needs to be invented.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for synthesizing refined lanolin by an inert gas with water method, wherein the method has the advantages of high raw material conversion rate and good product quality (good color and luster and chroma less than or equal to 6).
In order to solve the problems, the invention provides a method for synthesizing and refining lanolin by an inert gas with a water method, which sequentially comprises the following steps:
1) and synthesis:
taking a mixture of wool acid and lanonol as a raw material, carrying out esterification reaction by adopting an inert gas water-carrying method under the catalysis of alkali, wherein the reaction temperature is 150-270 ℃ (preferably 150-200 ℃), stopping the reaction after reacting for 4-22 h, and cooling to room temperature to obtain a lanolin paste solid;
the mass ratio of the wool acid to the lanonol is 1: 0.6 to 1.8, wherein the dosage of the alkali is 0.05 to 10 percent (preferably 0.2 to 10 percent) of the total mass of the raw materials; the volume of inert gas flowing through the unit reaction volume in unit time is 0.1-10 ml/(ml · s);
2) and (3) decoloring:
adding a decolorizing agent, a decolorizing activator and a solvent into the lanolin pasty solid obtained in the step 1), and decolorizing for 1-3 h (preferably 2h) at 60-100 ℃ (preferably 70 ℃);
the mass ratio of the decoloring agent to the raw materials is 1.25-5: 10, the mass ratio of the decoloring activating agent to the raw materials is 0.25-1: 10;
remarks explanation: 40-60 ml of solvent is added for every 100g of raw materials;
3) and post-treatment:
washing the decolorized product obtained in the step 2) while the decolorized product is hot, cooling and drying to obtain the lanolin.
As an improvement of the method for synthesizing and refining lanolin by using an inert gas with water method, the alkali (as a catalyst) in the step 1) is any one of the following: sodium hydroxide, potassium hydroxide, sodium methoxide.
As a further improvement of the method for synthesizing and refining lanolin by using the inert gas with the water method, the decoloring agent is sodium chlorite, the decoloring activating agent is hydrochloric acid with the mass concentration of 37%, and the solvent is methanol.
As a further improvement of the method for synthesizing and refining lanolin by using the inert gas with water method, the inert gas in the step 1) is any one of the following gases: nitrogen, helium, argon, carbon dioxide.
As a further improvement of the method for synthesizing and refining lanolin by using the inert gas with water method, the step 3) is as follows: adding hot water (water with the temperature of 50-55 ℃) into the decolorized product obtained in the step 2) while the product is hot, washing for 3 times, wherein the dosage of the hot water is the same as that of the solvent (volume dosage) in the step 2), cooling, and drying in vacuum (drying at 70 +/-10 ℃ to constant weight) to obtain the lanolin serving as a product.
The water generated in the esterification reaction of the step 1) of the invention can be brought out of the reaction system by inert gas in real time, so the method is named as an inert gas water-carrying method. The advantages of discharging water out of the reaction system in real time are: removing byproduct water generated by esterification reaction, so that the reaction moves forward, and the conversion rate of raw materials and the yield of products are improved; meanwhile, in the process of carrying water by the inert gas, the reaction system can be isolated from oxygen, and a pigment structure is prevented from being generated in the esterification process, so that the color of the product is deepened.
In the present invention, 100g of raw materials are generally mixed in a container having a volume of 250 to 500 ml.
Compared with the existing lanolin refining method, the method of the invention has the following technical advantages:
1) the method of the invention is effective utilization of wool acid and lanonol which are byproducts of a process for extracting cholesterol by hydrolyzing lanolin.
2) Compared with the reaction of catalyzing esterification by strong acid, the method has the advantages of less catalyst consumption, good product color, simple process and the like.
3) Compared with the azeotropic distillation method, the method has the advantages of high synthesis conversion rate, high product yield and the like.
4) Compared with the esterification reaction without adding inert gas under normal pressure, the method has the advantages of short synthesis time, high conversion rate of raw materials, low acid value of products, excellent color and luster and the like.
5) Compared with the reaction adopting vacuum esterification, the method has the characteristics of low energy consumption, short reaction time, excellent product color and luster and the like. The acid value of the product can be substantially less than 1.
In conclusion, wool acid and lanonol are used as raw materials, and lanolin is synthesized by catalysis of inert gas with a water method under the action of trace inorganic base; the method for synthesizing and refining lanolin by the inert gas protection method has the advantages of no by-product, good product color, light smell and simple process.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1, a method for synthesizing refined lanolin with water under inert gas, using crude lanolin hydrolysate-wool acid and lanolin alcohol as raw materials, the following steps are carried out in sequence:
1) 50g each of wool acid and lanonol and 0.2g of potassium hydroxide are taken to be put in a 250ml single-mouth bottle, and N is continuously introduced into the system2The flow rate is 1ml/(ml · s), 190-200Reacting for 9h under the condition of temperature, cooling to room temperature to obtain lanolin paste solid (lanolin solid product);
that is, in the case of using a 250ml single-neck flask as a reaction vessel, N was introduced into the 250ml single-neck flask every second2The amount of (A) was 250 ml.
2) Adding 25g of sodium chlorite and 50ml of methanol into the lanolin pasty solid obtained in the step 2), slowly dropwise adding 5g of 37% hydrochloric acid (the temperature is controlled to be less than or equal to 70 ℃ in the dropwise adding process), and decoloring for 2 hours at 70 ℃;
3) and 2) adding 50ml of hot water (water with the temperature of 50-55 ℃) into the decolorized product obtained in the step 2) for washing while the product is hot, carrying out phase separation to obtain an upper oil phase, repeatedly washing for three times (the washing conditions are the same), cooling to room temperature to obtain a light yellow solid product, and drying in vacuum (the vacuum degree is 0.096Mpa) (drying at 70 ℃ to constant weight) to obtain 96.1g of lanolin, wherein the yield is 96.1% and the acid value is 0.89.
Examples 2 to 6, the reaction conditions in example 1 were changed, that is, the type and flow rate of the inert gas in step 1) were changed, and the rest was the same as example 1, thereby obtaining examples 2 to 6, and the obtained total yield and performance parameters were as shown in table 1 in comparison with example 1.
TABLE 1
Examples 7 to 10 were obtained by changing the reaction conditions in example 1, i.e., changing the kind and amount of the base catalyst in step 1), and the remainder was the same as in example 1, and the total yield and performance parameters obtained by comparing with those of example 1 are shown in Table 2.
TABLE 2
Examples 11 to 12, the reaction conditions in example 1 were changed, that is, the reaction temperature and reaction time in step 1) were changed, and the rest was the same as in example 1, thereby obtaining examples 11 to 12, and the obtained total yield and performance parameters were as shown in Table 3 for example 1.
TABLE 3
| Examples | 1 | 11 | 12 |
| Reaction temperature/. degree.C | 190～200 | 150～160 | 260～270 |
| Reaction time/h | 9 | 22 | 4 |
| Yield/% | 96.1 | 89.4 | 96.7 |
| Acid value of the product | 0.89 | 3.1 | 0.50 |
| Product color | 6 | 5 | 8+ |
Comparative example 1-1, the use of the base in example 1 was eliminated, i.e., the amount of potassium hydroxide used was changed from 0.2g to 0, and the remainder was identical to example 1.
The results obtained were: the yield was 0%, and the acid value of the product obtained after the reaction in step 1) was 54.0.
Comparative example 1-2, the catalyst in example 1 was changed from potassium hydroxide to concentrated sulfuric acid, with the weight unchanged; the rest is equivalent to embodiment 1.
The results obtained were: the product had a color of 10, a yield of 80% and an acid value of 9.2.
Comparative example 2-1, the condition of the inert gas with water in example 1 was changed to azeotropic distillation (toluene solvent equal in mass to the raw material was added), and the reaction temperature was reflux temperature (110 ℃); the rest is equivalent to embodiment 1.
The results obtained were: the yield was 0, and the acid value of the product obtained after the reaction in step 1) was 54.1.
Comparative example 2-2, the inert gas water-carrying condition in example 1 was changed to the inert gas-free condition; namely, the step 1) is changed into the following steps: 50g of each of wool acid and lanolin alcohol and 0.2g of potassium hydroxide are taken to be put into a 250ml single-mouth bottle, reacted for 10 hours at the temperature of 190-200 ℃, and cooled to room temperature to obtain a lanolin solid product (brown pasty solid); the rest is equivalent to embodiment 1.
The results obtained were: the product had a color of 10, a yield of 30% and an acid value of 37.8.
Comparative examples 2 to 3, the condition of the inert gas with water in example 1 was changed to a vacuum condition; namely, the step 1) is changed into the following steps: 50g of each of wool acid and lanolin alcohol and 0.2g of potassium hydroxide are taken to be put in a 250ml single-mouth bottle, the system is vacuumized (the vacuum degree is 0.9bar), the reaction is carried out for 10 hours at the temperature of 190-200 ℃, and after the reaction is cooled to the room temperature, a lanolin solid product (brown pasty solid) is obtained; the rest is equivalent to embodiment 1.
The results obtained were: the product had a color of 7, a yield of 95.2% and an acid value of 0.97.
Comparative example 3-1, the reaction time of "190-200 ℃ for 9 h" in example 1 was changed to "120-130 ℃ for 24 h", and the rest was the same as in example 1.
The results obtained were: the product had a color of 5, a yield of 71.5% and an acid value of 15.0.
Comparative example 3-2, the reaction time of "190-200 ℃ for 9 h" in example 1 was changed to "300-320 ℃ for 4 h", and the rest was the same as example 1.
The results obtained were: the product had a color of 10, a yield of 95.9% and an acid value of 0.94.
Finally, it is also noted that the above-mentioned illustrations are only a few specific embodiments of the present invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (5)
1. The method for synthesizing and refining lanolin by using inert gas with water is characterized by sequentially comprising the following steps of:
1) and synthesis:
taking a mixture of wool acid and lanonol as a raw material, carrying out esterification reaction by adopting an inert gas water-carrying method under the catalysis of alkali, wherein the reaction temperature is 150-270 ℃, stopping the reaction after reacting for 4-22 h, and cooling to room temperature to obtain a wool grease solid;
the mass ratio of the wool acid to the lanonol is 1: 0.6-1.8, wherein the using amount of the alkali is 0.05-10% of the total mass of the raw materials; the volume of inert gas flowing through the unit reaction volume in unit time is 0.1-10 ml/(ml · s);
2) and (3) decoloring:
adding a decoloring agent, a decoloring activating agent and a solvent into the lanolin pasty solid obtained in the step 1), and decoloring for 1-3 h at 60-100 ℃;
the mass ratio of the decoloring agent to the raw materials is 1.25-5: 10, the mass ratio of the decoloring activating agent to the raw materials is 0.25-1: 10;
3) and post-treatment:
washing the decolorized product obtained in the step 2) while the decolorized product is hot, cooling and drying to obtain the lanolin.
2. The method for synthesizing refined lanolin by using inert gas with water method as claimed in claim 1, wherein: the alkali in the step 1) is any one of the following alkali: sodium hydroxide, potassium hydroxide, sodium methoxide.
3. The method for synthesizing refined lanolin by using inert gas with water method as claimed in claim 2, wherein:
the decolorizing agent is sodium chlorite, the decolorizing activator is hydrochloric acid with the mass concentration of 37%, and the solvent is methanol.
4. The method for synthesizing refined lanolin with water through inert gas according to claim 3, wherein the inert gas in step 1) is any one of the following: nitrogen, helium, argon, carbon dioxide.
5. The method for synthesizing and refining lanolin by using inert gas with water method according to any one of claims 1 to 4, wherein the step 3) is as follows:
adding hot water with the temperature of 50-55 ℃ into the decolorized product obtained in the step 2) while the product is hot, washing for 3 times, wherein the amount of the hot water is the same as that of the solvent in the step 2), cooling, and then drying in vacuum to obtain the lanolin serving as the product.
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| CN114196480B (en) * | 2020-09-17 | 2023-11-07 | 武汉华谱生物科技有限公司 | Preparation method of ultrapure lanolin |
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|---|---|---|---|---|
| CN1911881A (en) * | 2006-08-18 | 2007-02-14 | 浙江大学 | Method of separating wool acid and lanonol from wool grease |
| CN101531747A (en) * | 2009-04-20 | 2009-09-16 | 安徽中铁工程材料科技有限公司 | Preparation method of polycarboxylic acids high efficiency water reducer |
| CN101914014A (en) * | 2010-09-03 | 2010-12-15 | 北京博瑞创奇科技有限公司 | Method for synthesizing and purifying synthetic ester oil for cosmetics and synthetic ester oil for cosmetics obtained by same |
| CN102863315A (en) * | 2012-09-29 | 2013-01-09 | 杭州下沙生物科技有限公司 | Method of using lanolin to prepare wool acid metal soap and lanonol |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911881A (en) * | 2006-08-18 | 2007-02-14 | 浙江大学 | Method of separating wool acid and lanonol from wool grease |
| CN101531747A (en) * | 2009-04-20 | 2009-09-16 | 安徽中铁工程材料科技有限公司 | Preparation method of polycarboxylic acids high efficiency water reducer |
| CN101914014A (en) * | 2010-09-03 | 2010-12-15 | 北京博瑞创奇科技有限公司 | Method for synthesizing and purifying synthetic ester oil for cosmetics and synthetic ester oil for cosmetics obtained by same |
| CN102863315A (en) * | 2012-09-29 | 2013-01-09 | 杭州下沙生物科技有限公司 | Method of using lanolin to prepare wool acid metal soap and lanonol |
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