阅读说明：本技术 一种高纯度一丁酸甘油酯的合成方法和应用 (Synthetic method and application of high-purity glyceryl monobutyrate ) 是由 杨博 刘峥 陈华勇 蓝东明 田爱民 曾煜辉 于 2020-06-08 设计创作，主要内容包括：本发明公开了一种高纯度一丁酸甘油酯的合成方法和应用,包含以下步骤：(1)将丁酸和甘油进行酯化反应；(2)降低体系温度至60℃以下,加入总产物0.2～5倍重量的水,再得到反应混合物,加入脂肪酶,搅拌进行水解反应,使得二丁酸甘油酯占总酯的比例降低至5～15％；所述脂肪酶为Novozym435、TL-100L、PL20000L；(3)去除反应物中的脂肪酶,经分子蒸馏,得到高纯度一丁酸甘油酯。本发明实现了高纯度一丁酸甘油酯的合成,所述丁酸甘油酯在制备饲料添加剂中应用。(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.)

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.

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.