CN111534550A - Synthetic method and application of high-purity glyceryl monobutyrate - Google Patents
Synthetic method and application of high-purity glyceryl monobutyrate Download PDFInfo
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- CN111534550A CN111534550A CN202010510243.5A CN202010510243A CN111534550A CN 111534550 A CN111534550 A CN 111534550A CN 202010510243 A CN202010510243 A CN 202010510243A CN 111534550 A CN111534550 A CN 111534550A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6454—Glycerides by esterification
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/158—Fatty acids; Fats; Products containing oils or fats
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/70—Feeding-stuffs specially adapted for particular animals for birds
- A23K50/75—Feeding-stuffs specially adapted for particular animals for birds for poultry
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/80—Feeding-stuffs specially adapted for particular animals for aquatic animals, e.g. fish, crustaceans or molluscs
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Abstract
The invention discloses a synthetic method and application of high-purity glycerol monobutyrate, which comprises the following steps: (1) carrying out esterification reaction on butyric acid and glycerol; (2) reducing the temperature of the system to below 60 ℃, adding water with the weight of 0.2-5 times of that of the total product to obtain a reaction mixture, adding lipase, and stirring to perform hydrolysis reaction, so that the proportion of the dibutyrated glyceride in the total ester is reduced to 5-15%; the lipase is Novozym435, TL-100L, PL 20000L; (3) removing lipase in the reactant, and obtaining high-purity monobutyric acid glyceride through molecular distillation. The invention realizes the synthesis of high-purity glyceryl monobutyrate, and the glyceryl monobutyrate is applied to the preparation of feed additives.
Description
Technical Field
The invention relates to a method for synthesizing high-purity glycerol monobutyrate.
Background
The butyrin is a colorless oily liquid which is formed by butyric acid molecules and glycerol through chemical bonds, has a slightly special smell and is generally stable in structure. The butyrin exists in milk fat naturally in small amount, is neutral and stable in chemical property, and can release butyric acid under the action of lipase. Butyric acid has a powerful function, plays a great role in intestinal health, can directly or indirectly participate in the repair and renewal of digestive tract tissues, and rapidly provides energy for animal intestinal cells (particularly cecal and colonic cells). According to different proportions of butyric acid in the glycerol chain, the butyric acid can be divided into glycerol monobutyrate, glycerol dibutyrate and glycerol tributyrate. Butyrin has entered the field of animal health care products because of its unique biological activity. Glyceryl butyrate is an excellent butyrate supplement, and plays a significant role in intestinal health. Particularly, after China decides that the feed is prohibited from being added with antibiotic growth promoters in 2020, butyric acid products will meet a big outbreak. Research shows that the weight of the piglet is increased by adding the butyrin into the piglet feed with hypoevolutism, the growth of immune organs and small intestines is promoted, the intestinal villus form is improved, the villus surface area is increased, and the mucosal immunity level is increased.
Glyceryl monobutyrate makes it more widely used because of its unique water solubility. The butyrin can be mixed with water, and in the animal drinking water industry, the application is basically not limited, so that the feed can be used according to the demands of poultry and livestock to the maximum extent, the breeding efficiency is greatly improved, the breeding time is saved, and the cost is reduced. However, the current glyceryl monobutyrate product can not be completely dissolved in water due to the generation of more glyceryl dibutyrate in the synthesis process, and the use of drinking water for animals is seriously influenced.
Disclosure of Invention
Aiming at the defect of low purity of the monobutyric acid glyceride obtained by the existing synthesis method, the invention aims to provide the preparation method of the high-purity monobutyric acid glyceride. According to the invention, through the selective catalytic characteristic of lipase, lipophilic dibutyrin is hydrolyzed into hydrophilic monobutyyrin, so that the purpose of purification is achieved. After the product is separated and recovered, the purity of the monobutyric acid glyceride can be obviously improved.
This team research finds, directly esterify butyric acid and glycerine under certain temperature, always can have 20 ~ 40% dibutyrized glyceride to produce, because dibutyrized glyceride's lipophilicity, its solubility in water is not high, and this can lead to, conventional butyrin glyceride product dissolve in water after, dibutyrized glyceride can't dissolve, and these dibutyrized glycerides can produce very big inconvenience in actual application. Therefore, the method utilizes the characteristic of lipase interface catalysis, hydrolyzes the dibutyristate produced by the reaction into monobutyric acid glyceride under certain conditions, and does not hydrolyze the monobutyric acid glyceride, thereby achieving the purpose of purification, solving the problem that the dibutyristate cannot be dissolved in drinking water usage, greatly improving the culture efficiency and reducing the culture cost.
The purpose of the invention is realized by the following technical scheme:
a method for synthesizing high-purity glycerol monobutyrate comprises the following steps:
(1) carrying out esterification reaction on butyric acid and glycerol;
(2) reducing the temperature of the system to below 60 ℃, adding water with the weight of 0.2-5 times of that of the total product to obtain a reaction mixture, adding lipase, and stirring to perform hydrolysis reaction, so that the proportion of the dibutyrated glyceride in the total ester is reduced to 5-15%; the lipase is Novozym435, TL-100L, PL 20000L;
(3) removing lipase in the reactant, and obtaining high-purity monobutyric acid glyceride through molecular distillation.
Preferably, the molar ratio of butyric acid to glycerol in step (1) is 1: 0.5-1: 5.
Preferably, the reaction temperature in the step (1) is 150-180 ℃, and the reaction time is 2-8 hours
Preferably, the addition amount of the lipase in the step (1) is 10-100U/g of reaction mixture.
Preferably, the temperature of the hydrolysis reaction in the step (2) is 37 +/-5 ℃, and the reaction time is 4-8 hours.
The content of the monobutyric acid glyceride in the high-purity monobutyric acid glyceride prepared by the method is more than 90% of the total ester. The acid value of the glycerol monobutyrate is 1-5 mgKOH/g.
The high-purity glycerol monobutyrate is applied to preparing feed additives.
The high-purity glyceryl monobutyrate can be used as special drinking water oil for the aquatic product industry and poultry and livestock. Researches show that the grease can be used as an effective water-soluble butyric acid supplement, can effectively supplement butyric acid required in the growth process of animals, and is more beneficial to the growth of the animals.
Compared with the existing glyceryl butyrate, the glyceryl butyrate provided by the invention has the following characteristics:
(1) the water solubility of the high-purity glycerol monobutyrate is completely dissolved in water, so that the use in the culture process is greatly facilitated;
(2) according to the method, firstly, a mixture of the glyceryl monobutyrate is synthesized, then the selectivity of lipase is adopted, the hydrolysis activity of the lipase to the glyceryl monobutyrate is low, the hydrolysis activity of the lipase to the glyceryl dibutyrate is high, the glyceryl dibutyrate is converted into the glyceryl monobutyrate, and the synthesis of the high-purity glyceryl monobutyrate is realized.
(3) The product is enriched by adopting an enzyme method, is green, environment-friendly, safe and nuisanceless, and is more suitable for animals to eat.
Detailed Description
The practice of the present invention is described in more detail below by way of examples in which all percentages are by mass.
Example 1
1000g of glycerin and 1000g of butyric acid were charged into a reaction vessel, and reacted at a temperature of 150 ℃ for 6 hours, and the content of monobutyric acid glyceride was 53.7%, the content of dibutyric acid glyceride was 35.4%, and the content of butyric acid was 9.9% as measured by gas chromatography (this composition excludes glycerin, the same applies hereinafter). Then the temperature of the material is reduced to 60 ℃, 2000g of water is added, 10g (about 50U/g of reactant, the same is applied below) of lipase TL100L (purchased from Novit company) is added, the mixture is stirred and reacted for 6 hours at 37 ℃, the enzyme is filtered, and residual water, butyric acid and glycerol are removed by molecular distillation (the main parameters are that the evaporation temperature is 140 ℃ and the vacuum degree is 100pa), thus obtaining the high-purity glycerol monobutyrate. The results of the gas chromatography analysis show that the main components are as follows: the content of monobutyric acid glyceride is 90.1%, and the content of dibutyric acid glyceride is 9.5%. The acid value is 3.2 mgKOH/g.
Example 2
2000g of glycerol and 1000g of butyric acid were charged into a reaction vessel, and reacted at a temperature of 160 ℃ for 5 hours, whereby the content of glycerol monobutyrate was 55.6%, the content of glycerol dibutyrate was 35.7%, and the content of butyric acid was 7.8%, as measured by gas chromatography. Then, the temperature of the material is reduced to 60 ℃, 3000g of water is added, 15g of lipase TL100L (purchased from Novitin company) is added, after stirring and reacting for 6 hours at 37 ℃, the enzyme is filtered, and residual water, butyric acid and glycerol are removed by molecular distillation (the main parameters are that the evaporation temperature is 140 ℃ and the vacuum degree is 100pa), so that the high-purity glyceryl monobutyrate is obtained. The results of the gas chromatography analysis show that the main components are as follows: the content of monobutyric acid glyceride is 90.7%, and the content of dibutyric acid glyceride is 8.8%. The acid value is 3.8 mgKOH/g.
Example 3
3000g of glycerol and 1000g of butyric acid are added into a reaction vessel, and the mixture is reacted for 4 hours at the temperature of 165 ℃, and the content of the glycerol monobutyrate, the content of the glycerol dibutyrate and the content of the butyric acid are respectively 58.7%, 34.4% and 6.0% by gas chromatography. Then, the temperature of the material is reduced to 60 ℃, 3000g of water is added, 15g of lipase PL20000L (purchased from Novitin company) is added, the mixture is stirred and reacts for 5 hours at 37 ℃, the enzyme is filtered, and residual water, butyric acid and glycerol are removed by molecular distillation (the main parameters are that the evaporation temperature is 140 ℃ and the vacuum degree is 100pa), thus obtaining the high-purity glyceryl monobutyrate. The results of the gas chromatography analysis show that the main components are as follows: the content of monobutyric acid glyceride is 91.7%, and the content of dibutyric acid glyceride is 8.0%. The acid value was 4.3 mgKOH/g.
Example 4
4000g of glycerol and 1000g of butyric acid are added into a reaction vessel, and the mixture is reacted for 4 hours at the temperature of 165 ℃, and the content of the glycerol monobutyrate, the content of the glycerol dibutyrate and the content of the butyric acid are respectively 58.6%, 34.4% and 5.9% through gas chromatography. Then the temperature of the material is reduced to 60 ℃, 2000g of water is added, 20g of lipase Novozym435 (purchased from Novixin company) is added, the mixture is stirred and reacts for 5 hours at 37 ℃, the enzyme is filtered, and residual water, butyric acid and glycerol are removed by molecular distillation (the main parameters are that the evaporation temperature is 140 ℃ and the vacuum degree is 100pa), thus obtaining the high-purity glycerol monobutyrate. The results of the gas chromatography analysis show that the main components are as follows: the content of monobutyric acid glyceride was 93.5%, and the content of dibutyric acid glyceride was 6.3%. The acid value was 3.6 mgKOH/g.
Example 5
A1.5L beaker was charged with 1kg of water, and 10g of the high-purity glycerol monobutyrate of example 1 was added thereto, and the mixture was stirred and allowed to stand, whereupon the solution was observed to be clear and transparent and free of precipitates. The result shows that the high-purity glyceryl monobutyrate produced by the patent can be completely dissolved in water, and is more suitable for animal drinking water addition.
Example 6
A1.5L beaker was charged with 1kg of water, and then 100g of the high-purity monobutyric acid glyceride of example 2 was added thereto, and the mixture was stirred and allowed to stand, whereupon it was observed that the solution was clear and transparent and no precipitate was formed. The result shows that the high-purity glyceryl monobutyrate produced by the patent can be completely dissolved in water, and is more suitable for animal drinking water addition.
Example 7
A1.5L beaker was charged with 1kg of water, and 200g of the high-purity monobutyric acid glyceride of example 3 was added thereto, and the mixture was stirred and allowed to stand, whereupon it was observed that the solution was clear and transparent and had no precipitate. The result shows that the high-purity glyceryl monobutyrate produced by the patent can be completely dissolved in water, and is more suitable for animal drinking water addition.
Claims (9)
1. A method for synthesizing high-purity glycerol monobutyrate is characterized by comprising the following steps:
(1) carrying out esterification reaction on butyric acid and glycerol;
(2) reducing the temperature of the system to below 60 ℃, adding water with the weight of 0.2-5 times of that of the total product to obtain a reaction mixture, adding lipase, and stirring to perform hydrolysis reaction, so that the proportion of the dibutyrated glyceride in the total ester is reduced to 5-15%; the lipase is Novozym435, TL-100L, PL 20000L;
(3) removing lipase in the reactant, and obtaining high-purity monobutyric acid glyceride through molecular distillation.
2. The synthesis method according to claim 1, wherein the molar ratio of butyric acid to glycerol in step (1) is 1:0.5 to 1: 5.
3. The synthesis method according to claim 1 or 2, wherein the reaction temperature in step (1) is 150 to 180 ℃ and the reaction time is 2 to 8 hours.
4. The synthesis method according to claim 3, wherein the lipase is added in the step (1) in an amount of 10 to 100U/g of the reaction mixture.
5. The synthesis method of claim 4, wherein the hydrolysis reaction in step (2) is carried out at 37 ± 5 ℃ for 4-8 hours.
6. High purity glycerol monobutyrate obtained by the process according to any one of claims 1 to 5.
7. The high purity glycerol monobutyrate of claim 6 wherein the glycerol monobutyrate content is greater than 90% of the total esters.
8. The high-purity glycerol monobutyrate according to claim 6 or 7, wherein the acid value of glycerol monobutyrate is 1 to 5 mgKOH/g.
9. Use of the high purity glycerol monobutyrate according to claim 6 or 7 or 8 for the preparation of a feed additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010510243.5A CN111534550A (en) | 2020-06-08 | 2020-06-08 | Synthetic method and application of high-purity glyceryl monobutyrate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010510243.5A CN111534550A (en) | 2020-06-08 | 2020-06-08 | Synthetic method and application of high-purity glyceryl monobutyrate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112666301A (en) * | 2020-12-17 | 2021-04-16 | 太仓安佑生物科技有限公司 | Method for measuring content of tributyrin |
| CN114456066A (en) * | 2022-01-29 | 2022-05-10 | 山东成武易信环保科技有限公司 | Distillation method for purifying glycerol monobutyrate |
-
2020
- 2020-06-08 CN CN202010510243.5A patent/CN111534550A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112666301A (en) * | 2020-12-17 | 2021-04-16 | 太仓安佑生物科技有限公司 | Method for measuring content of tributyrin |
| CN114456066A (en) * | 2022-01-29 | 2022-05-10 | 山东成武易信环保科技有限公司 | Distillation method for purifying glycerol monobutyrate |
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Application publication date: 20200814 |