阅读说明：本技术 饲料抗菌剂、其制备方法、牛至油添加剂及该添加剂在饲料中的应用 (Feed antibacterial agent, preparation method thereof, oregano oil additive and application of additive in feed ) 是由 粱丽娜 时惠敏 刘爱军 武晓瑞 于 2020-07-07 设计创作，主要内容包括：本发明实施例涉及将牛至油用于饲料添加剂技术领域,具体涉及一种饲料抗菌剂、其制备方法、牛至油添加剂及该添加剂在饲料中的应用,饲料抗菌剂由对牛至油先改性后包埋制得；改性为酯化或酰化；改性时使用催化剂；包埋使用乳化剂和吸附剂进行。本发明实施例的有益效果为：解决了牛至油适口性差、无气味残留和易挥发的问题；大大较少用于做预混剂的材料成本问题,使工艺简单化,便于操作；酰化用到的短链脂肪酸、中链脂肪酸都是改善动物肠胃的酸化剂,避免对肠胃的刺激；充分利用乳化剂对分子结构进行桥接的特性,充分保证产品的过胃率,从而不在胃部分解,达到最小剂量最好的效果。(The embodiment of the invention relates to the technical field of applying oregano oil to feed additives, in particular to a feed antibacterial agent, a preparation method thereof, an oregano oil additive and application of the additive in feed, wherein the feed antibacterial agent is prepared by modifying and embedding oregano oil; the modification is esterification or acylation; a catalyst is used for modification; the embedding is carried out using emulsifiers and adsorbents. The embodiment of the invention has the beneficial effects that: the problems of poor palatability, no odor residue and easy volatilization of the oregano oil are solved; the material cost problem for preparing the premixing agent is greatly reduced, so that the process is simplified and the operation is convenient; short-chain fatty acid and medium-chain fatty acid used for acylation are acidifiers for improving intestines and stomach of animals, so that the stimulation to the intestines and stomach is avoided; the characteristic that the emulsifier bridges the molecular structure is fully utilized, and the gastric-passing rate of the product is fully ensured, so that the product is not decomposed in the stomach, and the best effect of the minimum dosage is achieved.)

1. The feed antibacterial agent is characterized by being prepared by modifying and embedding oregano oil;

the modification is esterification or acylation;

a catalyst is used for modification;

the embedding is carried out using emulsifiers and adsorbents.

2. A method for preparing the feed antimicrobial agent according to claim 1, which comprises modifying and embedding oregano oil;

the modification is esterification or acylation;

a catalyst is used for modification;

the embedding is carried out using emulsifiers and adsorbents.

3. The method for preparing the feed antimicrobial agent according to claim 2, wherein the modification is esterification of at least one of aldehyde group and phenolic hydroxyl group in oregano oil or acylation of at least one of aldehyde group and phenolic hydroxyl group in oregano oil.

4. The method for producing an antibacterial agent for feed according to claim 3, wherein at least one of an aldehyde group and a phenolic hydroxyl group in oregano oil is acylated with a short-chain fatty acid, a medium-chain fatty acid, an acid anhydride corresponding to a short-chain fatty acid, or an acid anhydride corresponding to a medium-chain fatty acid.

5. The method for producing an antibacterial agent for feed according to claim 4, wherein the molar ratio of oregano oil to short-chain fatty acids, medium-chain fatty acids, anhydrides corresponding to short-chain fatty acids or anhydrides corresponding to medium-chain fatty acids is 1: 1.5-3.5;

the acylation temperature is 50-80 ℃.

6. The method for producing an antibacterial agent for feed according to claim 5, wherein the molar ratio of oregano oil to short-chain fatty acids, medium-chain fatty acids, anhydrides corresponding to short-chain fatty acids or anhydrides corresponding to medium-chain fatty acids is 1: 2;

the acylation temperature is 50-80 ℃.

7. The method for preparing the feed antimicrobial agent according to claim 1, wherein the catalyst is 4-dimethylaminopyridine, pyridine or sodium hydroxide;

the emulsifier is fatty acid monoglyceride and diglyceride, sucrose ester, modified starch, xanthan gum or polyglycerol ester;

the adsorbent is hydrogenated oil, dextrin, calcium carbonate or silicon dioxide.

8. An oregano oil additive comprising the following components in respective weight ratios:

15% -30% of a feed antimicrobial made by the method of any one of claims 2 to 7;

42% -70% of inclusion agent;

10 to 30 percent of auxiliary material.

9. The oregano oil additive of claim 8 wherein the inclusion agent is a modified starch or a hydrogenated oil; the auxiliary materials comprise monoglyceride, alcohol, propylene glycol, water, gelatin, calcium carbonate and silicon dioxide.

10. Use of the oregano oil additive of claim 8 or 9 in feed.

Technical Field

The invention relates to the technical field of applying oregano oil to feed additives, and particularly relates to a feed antibacterial agent, a preparation method thereof, an oregano oil additive and application of the additive in feed.

Background

The antibiotic as a feed additive is widely used in animal husbandry to greatly reduce the attack rate and the death rate of animals, makes great contribution to the development of animal husbandry and brings unprecedented negative effects, namely, the drug resistance of bacteria is greatly improved. The continuous generation of superbacteria has seriously threatened the survival safety of human beings, and millions of people lose lives each year due to the infection of drug-resistant bacteria. Therefore, the abuse of antibiotics is being banned worldwide. Once the use of chemically synthesized antibiotics is banned, the antimicrobial components of herbs such as oregano oil are certainly a new favorite in the feed industry.

The oregano oil is yellow red or brown red essential oil, and mainly comprises carvacrol and thymol. Is one of the feed drug additives approved by the ministry of agriculture in China recently, has extremely strong sterilization and bacteriostasis effects of clearing heat, eliminating dampness, dispelling summer heat, relieving exterior syndrome and regulating qi, and is a safe, high-efficiency, green and pure natural traditional Chinese medicine additive with higher active ingredient ratio without incompatibility.

The oregano oil has special aromatic odor, poor animal palatability and strong irritation to mucous membranes and skin, is added into animal feed to seriously affect the appetite and food intake of animals, can only be added as auxiliary antibiotic at present, cannot be used singly in large quantities, and seriously limits the full play of the performance of the oregano oil.

In order to overcome the defect of the oregano oil, scholars mainly adopt an embedding method to prepare different formulations, such as patents: the method is suitable for the requirements of the breeding industry such as patent oregano oil feed additive powder (with the patent number of CN200510107322.7) and patent: a method for preparing origanum oil-B-cyclodextrin inclusion compound feed additive (patent No. CN201110125454.8) is disclosed, as is patent: a soluble origanum oil premix and a preparation method thereof (with the patent number of CN201610062014.5) and the like, which promote the development of the industry to a certain extent but can not thoroughly solve the problems of poor stability, residual smell, easy volatilization and the like. .

Therefore, there is a need for a solution that enables the use of oregano oil in feed to overcome the above problems.

Disclosure of Invention

In order to solve the problems, namely solving the problems of poor stability, odor residue and easy volatilization, the product of the origanum oil after acylation is digested by animal ingestion and degraded by pancreatic lipase to be converted into corresponding organic acid and origanum oil, thereby presenting a good slow release process. The released product can exert its bactericidal function in animal body, reduce irritation to stomach, and reduce regurgitation of animal. The origanum oil reacts with short carbon chain organic acid or acid anhydride and acyl chloride to carry out acylation, so that the volatility of the product can be effectively controlled. The product of the origanum oil after acylation is digested by animal ingestion and is degraded by pancreatic lipase to be converted into corresponding organic acid and origanum oil, and a good slow-release process is presented. The released product can exert its bactericidal function in animal body, reduce irritation to stomach, and reduce regurgitation of animal.

In a first aspect, embodiments of the present invention provide a feed antimicrobial agent prepared by modifying and then embedding oregano oil;

the modification is esterification or acylation;

a catalyst is used for modification;

the embedding is carried out using emulsifiers and adsorbents.

According to a second aspect of the embodiments of the present invention, there is provided a method for preparing the antibacterial agent for feed, the method comprising modifying and embedding oregano oil;

the modification is esterification or acylation;

a catalyst is used for modification;

the embedding is carried out using emulsifiers and adsorbents.

Further, the modification is esterification of at least one of aldehyde group and phenolic hydroxyl group in the oregano oil, or acylation of at least one of aldehyde group and phenolic hydroxyl group in the oregano oil.

Further, at least one of the aldehyde group and the phenolic hydroxyl group in the oregano oil is acylated with a short-chain fatty acid, a medium-chain fatty acid, an acid anhydride corresponding to a short-chain fatty acid, or an acid anhydride corresponding to a medium-chain fatty acid.

Further, the mol ratio of the oregano oil to the short-chain fatty acid, the medium-chain fatty acid, the acid anhydride corresponding to the short-chain fatty acid or the acid anhydride corresponding to the medium-chain fatty acid is 1: 1.5-3.5;

the acylation temperature is 50-80 ℃.

Further, the molar ratio of the oregano oil to short-chain fatty acids, medium-chain fatty acids, anhydrides corresponding to the short-chain fatty acids or anhydrides corresponding to the medium-chain fatty acids is 1: 2;

the acylation temperature is 50-80 ℃.

Further, the catalyst is 4-dimethylaminopyridine, pyridine or sodium hydroxide;

the emulsifier is fatty acid monoglyceride and diglyceride, sucrose ester, modified starch, xanthan gum or polyglycerol ester;

the adsorbent is hydrogenated oil, dextrin, calcium carbonate or silicon dioxide.

The third aspect of the embodiment of the invention discloses an oregano oil additive, which comprises the following components in parts by weight:

15% -30% of a feed antimicrobial made by the method of any one of claims 1 to 7;

42% -70% of inclusion agent;

10 to 30 percent of auxiliary material.

Further, the clathrating agent is modified starch or hydrogenated oil; the auxiliary materials comprise monoglyceride, alcohol, propylene glycol, water, gelatin, calcium carbonate and silicon dioxide.

In a fourth aspect of the embodiments of the present invention, there is disclosed a use of the oregano oil additive as claimed above in feed.

The embodiment of the invention has the beneficial effects that:

through the modification and embedding of the oregano oil, the problems of poor palatability, no odor residue and easy volatilization of the oregano oil are solved;

the material cost problem for preparing the premixing agent is greatly reduced, so that the process is simplified and the operation is convenient;

short-chain fatty acid and medium-chain fatty acid used for acylation are acidifiers for improving intestines and stomach of animals, so that the stimulation to the intestines and stomach is avoided;

the characteristic that the emulsifier bridges the molecular structure is fully utilized, and the gastric-passing rate of the product is fully ensured, so that the product is not decomposed in the stomach, and the best effect of the minimum dosage is achieved.

Detailed Description

In a first aspect, embodiments of the present invention provide a feed antimicrobial agent prepared by modifying and then embedding oregano oil;

the modification is esterification or acylation;

a catalyst is used for modification;

the embedding is carried out using emulsifiers and adsorbents.

According to a second aspect of the embodiments of the present invention, there is provided a method for preparing the antibacterial agent for feed, the method comprising modifying and embedding oregano oil;

the modification is esterification or acylation;

a catalyst is used for modification;

the embedding is carried out using emulsifiers and adsorbents.

Further, the modification is esterification of at least one of aldehyde group and phenolic hydroxyl group in the oregano oil, or acylation of at least one of aldehyde group and phenolic hydroxyl group in the oregano oil.

Further, at least one of the aldehyde group and the phenolic hydroxyl group in the oregano oil is acylated with a short-chain fatty acid, a medium-chain fatty acid, an acid anhydride corresponding to a short-chain fatty acid, or an acid anhydride corresponding to a medium-chain fatty acid. The acylating agent may be acetic anhydride, acetyl chloride, glacial acetic acid, propionic acid, propionyl chloride, butyric acid, butyryl chloride, caproic acid, caprylic acid, capric acid, and other organic acids and corresponding acid anhydrides. Among them, acetic acid and butyric acid are preferred.

Further, the mol ratio of the oregano oil to the short-chain fatty acid, the medium-chain fatty acid, the acid anhydride corresponding to the short-chain fatty acid or the acid anhydride corresponding to the medium-chain fatty acid is 1: 1.5-3.5;

the acylation temperature is 50-80 ℃.

Further, the molar ratio of the oregano oil to short-chain fatty acids, medium-chain fatty acids, anhydrides corresponding to the short-chain fatty acids or anhydrides corresponding to the medium-chain fatty acids is 1: 2;

the acylation temperature is 50-80 ℃.

The solvent can be used or not used in the modification process, and the solvent can be toluene, isopropyl ether, benzene, trichloromethane and the like.

Further, the catalyst is 4-dimethylaminopyridine, pyridine or sodium hydroxide, preferably 4-dimethylaminopyridine;

the emulsifier is fatty acid monoglyceride and diglyceride, sucrose ester, modified starch, xanthan gum or polyglycerol ester;

the adsorbent is hydrogenated oil, dextrin, calcium carbonate or silicon dioxide.

The third aspect of the embodiment of the invention discloses an oregano oil additive, which comprises the following components in parts by weight:

15% -30% of a feed antimicrobial made by the method of any one of claims 1 to 7;

42% -70% of inclusion agent;

10 to 30 percent of auxiliary material.

Further, the clathrating agent is modified starch or hydrogenated oil; the auxiliary materials comprise monoglyceride, alcohol, propylene glycol, water, gelatin, calcium carbonate and silicon dioxide.

In a fourth aspect of the embodiments of the present invention, there is disclosed a use of the oregano oil additive as claimed above in feed.

Examples of acylation of oregano oil

Example 1

200kg of oregano oil is pumped in under the protection of nitrogen, 1kg of pyridine is added into a reaction kettle, 150kg of acetic anhydride is added, stirring is started, and heating reflux is carried out for 5.5 hours. After the reaction is finished, stopping introducing nitrogen, and distilling off acetic acid and anhydride which do not participate in the reaction under reduced pressure at 65-70 ℃ until no acetic acid flows out. 50kg of 5% sodium bicarbonate aqueous solution was added, stirred to neutralize, and then allowed to stand for layering, after separating the aqueous layer, the aqueous layer was washed twice until the pH became neutral, and 290kg of the product having residual water was dried. 98% of the phenolic compounds were converted to ester compounds by gas chromatography.

Example 2

200kg of oregano oil is pumped in under the protection of nitrogen, DMAP1kg is added into the reaction kettle, 150kg of butyric acid is added, stirring is started, and heating reflux is carried out for 6.5 hours. After the reaction is finished, stopping introducing nitrogen, and distilling off butyric acid which does not participate in the reaction at 80-90 ℃ under reduced pressure until no liquid flows out. Adding 50kg of 5% sodium bicarbonate aqueous solution, stirring for neutralization, standing for layering, separating a water layer, washing twice until the pH value is neutral, and drying 320kg of a product with residual water.

Example 3

200kg of oregano oil is pumped in under the protection of nitrogen, 0.5kg of sulfuric acid is added into a reaction kettle, 220kg of butyric anhydride is added, stirring is started, and heating reflux is carried out for 3.5 hours. After the reaction is finished, stopping introducing nitrogen, and distilling off butyric acid which does not participate in the reaction at 80-90 ℃ under reduced pressure until no liquid flows out. Adding 50kg of 5% sodium bicarbonate aqueous solution, stirring for neutralization, standing for layering, separating a water layer, washing twice until the pH value is neutral, and drying 320kg of a product with residual water.

Preparation method of feed antibacterial agent production example

Example 1

200kg of hydrogenated oil, 20kg of monoglyceride, 5kg of phospholipid, 10kg of propylene glycol, 80kg of water and 60kg of dextrin, wherein 100kg of modified origanum oil is heated to 70 ℃, uniformly stirred, enters a homogenizer for homogenization and then enters a spray tower for powder spraying. The powder spraying process parameters comprise the air inlet amount of 100m3/s, the air inlet temperature of 65 ℃, the feeding amount of 200kg/h and the air outlet temperature of 30 ℃, and the volatilization loss analysis result of the granulated premix is less than 0.5 percent. Completely meets the product requirements.

Example 2

600kg of hydrogenated oil, 40kg of monoglyceride, 30kg of polyglycerol ester, 10kg of xanthan gum, 60kg of modified starch, 100kg of modified origanum oil and 50kg of calcium carbonate are heated to 70 ℃, stirred uniformly, enter a homogenizer for homogenization and then enter a spray tower for powder spraying. The powder spraying process parameters comprise the air inlet amount of 100m3/s, the air inlet temperature of 55 ℃, the feeding amount of 200kg/h and the air outlet temperature of 30 ℃, and the volatilization loss analysis result of the granulated premix is less than 0.3 percent. The product requirement can be completely met.

In addition, it is readily understood by those skilled in the art that the scope of the present invention is obviously not limited to these specific embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.