阅读说明：本技术 一种缬氨酸锰的制备方法及其应用 (Preparation method and application of manganese valine ) 是由 彭红星 黄逸强 陈娟 向阳葵 张亚伟 夏飞辉 苏军 于 2019-12-26 设计创作，主要内容包括：本发明公开了一种缬氨酸锰的制备方法,包括以下步骤：在搅拌下将缬氨酸溶解并升温,缓慢加入不溶性锰源进行反应,反应结束后将反应体系冷却、结晶、过滤分离、洗涤、干燥即得到缬氨酸锰。本发明还提供一种上述的缬氨酸锰作为动物饲料添加剂在动物中的应用。本发明的制备方法具有化学反应速率高、产品产率高、产品纯度高、无副产物等优点。(The invention discloses a preparation method of manganese valine, which comprises the following steps: and dissolving valine under stirring, heating, slowly adding an insoluble manganese source for reaction, and after the reaction is finished, cooling, crystallizing, filtering, separating, washing and drying a reaction system to obtain the manganese valine. The invention also provides application of the manganese valine as an animal feed additive in animals. The preparation method has the advantages of high chemical reaction rate, high product yield, high product purity, no by-product and the like.)

1. The preparation method of manganese valine is characterized by comprising the following steps: and dissolving valine under stirring, heating, slowly adding an insoluble manganese source for reaction, and after the reaction is finished, cooling, crystallizing, filtering, separating, washing and drying a reaction system to obtain the manganese valine.

2. The method of claim 1, wherein the insoluble manganese source is manganese carbonate and/or basic manganese carbonate.

3. The process according to claim 1, wherein the molar ratio of valine to manganese in the insoluble manganese source is (1.92-2.08): 1.

4. the method according to any one of claims 1 to 3, wherein the reaction temperature is controlled to 60 to 80 ℃ when the insoluble manganese source is added, and the reaction is continued for 1 to 2.5 hours after the insoluble manganese source is added.

5. The production method according to any one of claims 1 to 3, wherein the solid content of the reaction system is controlled to 12 to 28% when the insoluble manganese source is added.

6. The method according to any one of claims 1 to 3, wherein the insoluble manganese source is added in two portions; the amount of the insoluble manganese source added for the first time accounts for 30-60% of the total mass, and the rest insoluble manganese source is added after the reaction is carried out for 0.2-0.5 h.

7. The production method according to any one of claims 1 to 3, wherein an organic solvent is added to the reaction system during the crystallization of valine, the organic solvent is one or more selected from acetone, glycerol and ethanol, and the volume ratio of the organic solvent to water in the reaction system is (0.05-0.2): 1.

8. the production method according to any one of claims 1 to 3, wherein the filtrate obtained by the filtration separation is used as a mother liquor for dissolving valine in the next reaction.

9. Use of manganese valine as an animal feed additive according to any one of claims 1 to 8 in an animal which is a pig or a bird.

10. The use according to claim 9, wherein the manganese valine is added in an amount of 20-40ppm in terms of manganese element per ton of pig feed; the addition amount of the manganese-containing additive in each ton of poultry feed is 40-120ppm calculated by manganese element.

Technical Field

The invention belongs to the field of animal feed additives, and particularly relates to a preparation method and application of an amino acid chelate.

Background

Manganese is a component of arginase, prolidase, RNA polymerase, manganese-containing superoxide dismutase (Mn-SOD), pyruvate carboxylase, etc., and is also an activator of many enzymes in the body such as phosphorylase, aldolase, transferase, and hydrolase. Manganese deficiency in animals can lead to decreased feed intake, slower growth, decreased feed utilization, bone abnormalities, ataxia, and reproductive dysfunction.

Valine, as a branched chain amino acid essential to livestock and poultry, can significantly improve the growth performance of animals and provide energy for organisms to synthesize nutrient substances. In addition, valine has functions of synthesizing protein, providing oxidative energy supply in a special physiological period, mobilizing protein turnover of skeletal muscle, improving lactation performance, regulating nerves and endocrine, enhancing immune function, and the like.

Disclosure of Invention

The technical problem to be solved by the invention is to overcome the defects and defects mentioned in the background technology, and provide a preparation method of manganese valine with the advantages of high chemical reaction rate, high product yield, high product purity, no by-product and the like and application thereof. In order to solve the technical problems, the technical scheme provided by the invention is as follows:

a preparation method of manganese valine comprises the following steps: and dissolving valine under stirring, heating, slowly adding an insoluble manganese source for reaction, and after the reaction is finished, cooling, crystallizing, filtering, separating, washing and drying a reaction system to obtain the manganese valine. In the present invention, manganese valine has the molecular formula of Mn (C)₅H₁₀NO₂)₂·H₂O。

In the above production method, preferably, the insoluble manganese source is manganese carbonate and/or basic manganese carbonate.

Because the manganese sulfate monohydrate or the manganese chloride can not be directly mixed with valine for reaction, alkali is required to be added, if the manganese chloride, the manganese sulfate monohydrate and the strong alkali are directly mixed, manganous hydroxide is firstly generated, then the manganous hydroxide is quickly oxidized by oxygen in water to generate manganese hydroxide, and finally the black manganese dioxide is generated by dehydration. Tetravalent manganese is much less available for absorption in animals than divalent manganese. In addition, when heating is performed at a high alkali concentration, other side reactions such as dehydration condensation reaction of valine and the like may occur.

In the invention, insoluble manganese salt is used for replacing soluble manganese salts such as manganese sulfate monohydrate, manganese chloride and the like, valine reacts with an insoluble manganese source, no by-product is generated, and the product purity is very high. And when the insoluble manganese source is manganese carbonate or basic manganese carbonate, the small bubbles of carbon dioxide released in the reaction process can temporarily change the viscosity of the reaction system, the materials in the reaction system are distributed more loosely, the reaction rate is more uniform, and the particle size of the generated product tends to be consistent. At this point, the insoluble manganese source cannot be added too quickly, otherwise the solution would be prone to bumping.

In the above production method, preferably, the molar ratio of valine to manganese in the insoluble manganese source is (1.92-2.08): 1.

in the preparation method, preferably, the reaction temperature is controlled to be 60-80 ℃ when the insoluble manganese source is added for reaction, and the reaction time is 1-2.5h after the insoluble manganese source is added. The reaction temperature cannot be too high because manganese carbonate and basic manganese carbonate undergo hydrolysis when azeotroped with water to form black manganese hydroxide, which then becomes manganese oxide.

In the above production method, it is preferable that the solid content of the reaction system is controlled to 12 to 28% by mass when the insoluble manganese source is added for the reaction. In the present invention, the solid content is related to the volume of the solvent added. If the addition amount of the solvent is too small, most raw materials cannot be uniformly diffused, and the raw materials are wrapped by the product, so that the collision reaction probability is reduced, and the reaction rate is very low; the solvent is added in too much amount, the probability of molecule collision combination is influenced because the raw materials are too dispersed in the solution, the positive influence on the reaction rate is not great, but the reaction system becomes more viscous because of the concentration problem, and the reaction rate is finally influenced because the reaction product wraps the raw materials. Meanwhile, too much addition will affect the subsequent crystallization yield and increase the filtration workload. Our studies show that it is the best choice to control the solid content of the reaction system to 12-28%.

In the above preparation method, preferably, the insoluble manganese source is added in two portions; the amount of the insoluble manganese source added for the first time accounts for 30-60% of the total mass, and the rest insoluble manganese source is added after the reaction is carried out for 0.2-0.5 h. The insoluble manganese source is added in two times, so that the reaction rate can be further controlled, the reaction is milder, and the solution can be better prevented from bumping. If the amount of the insoluble manganese source added is too large or too small, which is not favorable for controlling the reaction rate, we have found that the amount of the insoluble manganese source added for the first time is preferably 30 to 60% of the total amount.

In the above preparation method, preferably, an organic solvent is added to the reaction system during the crystallization of valine, the organic solvent is one or more of acetone, glycerol and ethanol, and the volume ratio of the organic solvent to water in the reaction system is (0.05-0.2): 1. the manganese valine can be crystallized out by uniformly dispersing in the reaction system by utilizing the characteristic of low solubility of the manganese valine in the organic solvent. Considering the factors of cost, crystallization efficiency, volume size of a reaction kettle and the like, the volume ratio of the added organic solvent to the water in the reaction system is (0.05-0.2): 1 is preferred.

In the above production process, it is preferable that the filtrate obtained by the filtration separation is used as a mother liquor for dissolving valine in the next reaction. The preparation method provided by the invention has no by-product, does not need to discharge waste water, can recycle the mother liquor, and is greatly beneficial to plant areas which are strictly controlled by environmental protection and do not allow waste water to be discharged. In addition, the mother liquor is recycled, except the drying and transferring process, almost no material loss exists, and the yield of the multi-batch product can be more than 99.5 percent.

As a general technical concept, the invention also provides application of the manganese valine as an animal feed additive in animals, wherein the animals are pigs or poultry.

In the application, preferably, the addition amount of the manganese valine in each ton of pig feed is 0-40ppm calculated by manganese element; the addition amount of the manganese-containing additive in each ton of poultry feed is 0-100ppm calculated by manganese element.

In the invention, manganese carbonate or basic manganese carbonate reacts with valine under the heating condition to generate manganese valine, and the chemical reaction equation is as follows:

MnCO₃+2C₅H₁₁NO₂＝Mn(C₅H₁₀NO₂)₂·H₂O+CO₂↑；

xMnCO₃·yMn(OH)₂+2(x+y)C₅H₁₁NO₂＝(x+y)[Mn(C₅H₁₀NO₂)₂·H₂O]+xCO₂↑；

wherein the molecular formula of the basic manganese carbonate is xMnCO₃·yMn(OH)₂；x、y≥0。

The amino acid complex is used as a 3 rd generation trace element additive, and the excellent biological functions of the amino acid complex are proved by a large number of tests, compared with an inorganic trace element additive, the amino acid complex has better chemical stability, can obviously improve the bioavailability of trace elements, improve the growth performance of animals, enhance the immunity and the anti-stress capability and improve the quality of animal products, and the application of the amino acid complex can reduce the addition of the trace elements and reduce the pressure on the environment while storing the trace elements in high level in the animals. The invention utilizes the combination of valine and inorganic manganese salt to exert the advantages of the valine and the inorganic manganese salt.

Compared with the prior art, the invention has the advantages that:

1. compared with other manganese products, the manganese valine product is a limited manganese amino acid product, can be preferentially absorbed by animals, has higher yield and utilization rate, and has good application prospect.

2. In the invention, insoluble manganese salt is used for replacing soluble manganese salts such as manganese sulfate monohydrate, manganese chloride and the like, so that side reactions are less, and the product purity is higher.

3. The invention only needs to calculate the weight of the added insoluble manganese source, does not need to adjust the pH value in the reaction and reduces the workload.

4. The preparation method has the advantages of high chemical reaction rate, high product yield, high product purity, no by-product and the like.

5. The method of the invention can also reduce energy consumption, simplify the process and avoid waste liquid discharge and environmental pollution.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

Fig. 1 is an XRD pattern of manganese valine prepared in example 1.

Detailed Description

In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.

Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.

Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.

The manganese content of the product of the following example is determined by ammonium ferrous sulfate titration, the valine content is determined by nitrogen determination, and the loss of water of crystallization is realized when water is lost at 180 ℃ and the loss of free water is realized when water is lost at 104 ℃.