阅读说明：本技术 利用甘氨酸母液制备甘氨酸螯合物及微量元素肥/高效缓释肥的方法 (Method for preparing glycine chelate and microelement fertilizer/efficient slow-release fertilizer by using glycine mother liquor ) 是由 周荣超 廖常福 彭启明 吴传隆 唐东艳 邓志强 王发昌 杜丕姬 于 2020-05-27 设计创作，主要内容包括：本发明涉及一种甘氨酸螯合物的制备方法,所述方法是利用直接海因法合成的甘氨酸母液制备甘氨酸螯合物,具体包括以下步骤：(1)直接海因法合成甘氨酸母液；(2)将所述的甘氨酸母液加碱反应,得甘氨酸盐水溶液；(3)将所述甘氨酸盐水溶液与无机金属盐反应,得甘氨酸螯合物。本发明利用直接海因法甘氨酸母液制备甘氨酸金属螯合物,再使用剩余母液制备微量元素肥,实现了甘氨酸、无机盐、溶解甘氨酸螯合物的分级回收和完全利用,无废弃物排放。本发明生产工艺具有清洁环保,具有操作简单,装备容易维护,收率高,产品稳定性高,母液中甘氨酸回收利用率高。(The invention relates to a preparation method of glycine chelate, which is characterized in that glycine mother liquor synthesized by a direct hydantoin method is used for preparing the glycine chelate, and the preparation method specifically comprises the following steps: (1) synthesizing glycine mother liquor by a direct hydantoin method; (2) adding alkali into the glycine mother liquor for reaction to obtain a glycine salt aqueous solution; (3) and reacting the glycinate salt aqueous solution with inorganic metal salt to obtain the glycine chelate. The invention utilizes the direct hydantoin method glycine mother liquor to prepare the glycine metal chelate, and then uses the residual mother liquor to prepare the microelement fertilizer, thereby realizing the graded recovery and the complete utilization of the glycine, the inorganic salt and the dissolved glycine chelate, and having no waste discharge. The production process has the advantages of cleanness, environmental protection, simple operation, easy equipment maintenance, high yield, high product stability and high recovery rate of the glycine in the mother liquor.)

1. Composition for the preparation of glycine chelate containing trace elements, characterized in that it comprises glycine mother liquor and a base.

2. The composition of claim 1, wherein the glycine mother liquor is a raffinate from a direct hydantoin synthesis of a glycine product.

3. The composition of claim 1, wherein the glycine mother liquor comprises the following components in parts by mass: 10 to 20 parts of glycine, 0.5 to 1.5 parts of glycine dipeptide, 0.5 to 1.0 part of 2, 5-diketopiperazine, 0.5 to 1.0 part of hydantoin, 0.4 to 0.8 part of glycinamide, 0.5 to 0.8 part of glycine trimer, 0.1 to 0.6 part of hydantoin amide, 0.1 to 1.0 part of ammonium sulfate, 0.0001 to 0.1 part of hydantoin, 0.0001 to 50ppm of ammonia and water.

4. A method for preparing a glycine chelate complex containing trace elements using the composition as set forth in any one of claims 1 to 3, characterized in that the method specifically comprises the steps of:

(1) adding the glycine mother liquor into the alkali for reaction to obtain a glycine salt aqueous solution;

(2) and reacting the glycinate salt aqueous solution with inorganic metal salt to obtain the glycine chelate.

5. The method according to claim 4, wherein the alkali in the step (1) is one or more of calcium oxide, calcium hydroxide, potassium carbonate, sodium hydroxide, sodium carbonate and ammonia, and the molar ratio of the alkali to the total amino acids in the glycine mother liquor is 0.55-1.5: 1.

6. The method according to claim 4, wherein the reaction in step (1) is specifically: reacting for 1-30 min at the temperature of 120-170 ℃.

7. The method according to claim 4, wherein the glycine salt aqueous solution in the step (1) has a mass concentration of 15 to 45%.

8. The method according to claim 4, wherein the inorganic metal salt in the step (2) is an anhydrous compound or hydrate of sulfate or hydrochloride of zinc, iron, copper, manganese, magnesium, nickel and chromium, and the molar ratio of the glycine to the metal ions of the inorganic metal salt is 1.8-3.1: 1.

9. The method according to claim 4, wherein the reaction in step (2) is specifically: reacting at 40-100 ℃ for 10-120 min.

10. A glycine chelate prepared by the process of any one of claims 4 to 9.

11. Glycine chelate according to claim 10, characterized in that it contains any of the trace elements zinc, iron, copper, manganese, magnesium, nickel, chromium.

12. Glycine chelate according to claim 10, characterized in that it is obtained by concentration and crystallization of the aqueous glycine salt solution prepared by the process according to any one of claims 4 to 9.

13. The trace element fertilizer is characterized by comprising one or more than two trace elements of zinc, iron, copper, manganese, magnesium, nickel and chromium.

14. The method for preparing the trace element fertilizer of claim 12, wherein the glycine salt aqueous solution in the step (1) of claim 4 is concentrated, crystallized and separated to obtain a glycine chelate crystal and a crystallization mother liquor a, the glycine chelate in the step (2) is concentrated, crystallized and separated to obtain a glycine chelate crystal and a crystallization mother liquor B, and the concentration, spray drying and the concentration of the a and/or the B are/is carried out to obtain the trace element fertilizer of claim 12.

15. The preparation method of the high-efficiency slow-release fertilizer is characterized by separating insoluble matters after the reaction in the step (1) of claim 4, centrifuging the glycinate aqueous solution to obtain filtrate, mixing the insoluble matters and the filtrate, concentrating, and performing spray drying to obtain the high-efficiency slow-release fertilizer.

16. The efficient slow-release fertilizer prepared by the method of claim 15, wherein the efficient slow-release fertilizer is an efficient slow-release calcium fertilizer.

17. The production system for producing the glycine chelate is characterized in that the production system is sequentially connected with a production system for synthesizing the glycine mother liquor by a direct hydantoin method, a reaction device 1 and a reaction device 2, the production system for synthesizing the glycine mother liquor by the direct hydantoin method is provided with more than two output pipelines, at least one output pipeline is connected with the reaction device 1, and one part of the glycine mother liquor is input into the reaction device 1 for reaction.

18. The production system according to claim 17, wherein the reaction device 1 is a high-pressure reaction kettle, and the reaction device 2 is further connected with a separation device and a drying device.

Technical Field

The invention belongs to the field of organic complex preparation, and particularly relates to a method for preparing feed-grade glycine chelate and a byproduct trace element fertilizer thereof by using glycine mother liquor.

Background

The trace elements are very important nutritional additives, and the trace element additives commonly used in feed and premix at present mainly comprise inorganic salts such as sulfate, chloride, oxide and the like, and have a plurality of defects, such as: in animal nutrition, due to the complex chemical reaction in the digestion process, the feed is easily affected by phosphate (such as calcium hydrophosphate, calcium dihydrogen phosphate), phytic acid and other components in the feed, so that insoluble precipitates are formed, the biological potency is reduced, and the absorption and utilization are affected; in feed processing, inorganic salt generally contains crystal water and is easy to absorb moisture and agglomerate; the inorganic salt has strong destructive effect on vitamins, grease and the like; some feed factories adopt high-manganese and high-zinc feed, the yield is low, and the environment is seriously polluted.

The test result of the glycine chelate metal compound for broiler shows that the weight gain speed of the test group is increased by 5.28% compared with the control group, the feed conversion rate is increased by 2.59%, 1500 glycine chelate metal compounds are fed in one batch, and 2100 yuan can be increased for 5 batches of breeders in the year. The test results of Sundecheng et al (1995) on the layers of the Deck indicate that the total egg weight and the egg laying rate of the test group are respectively improved by 21.02% and 12.80% compared with the control group, and the feed-egg ratio and the soft-breaking egg rate are respectively reduced by 20.74% and 31.79%; the metabolism test also shows that the absorption utilization rates of the iron, copper, manganese and zinc elements in the test group are respectively improved by 71.65%, 93.07%, 188.08% and 107.42% compared with the control group.

The ferrous glycine chelate can obviously improve the reproductive performance of sows, improve the body conditions of the sows, reduce the elimination rate of the sows during the birth, prevent the anemia and diarrhea of piglets and reduce the death rate of the piglets. The feed added with glycine chelated iron (500ppm) is fed 21-28 days before the birth of the sow, so that the postpartum piglets do not need to be supplemented with iron, the death rate of the piglets is obviously reduced, the weaning weight is larger, and the breeding rate of the weaning piglets can reach 94%. The experimental study of the compound amino acid chelate and the ecological preparation feed additive on the fattening pigs shows that the daily gain ratio is improved by 17.82 percent compared with the control, the feed conversion ratio is reduced by 14.43 percent, and the economic benefit is improved by 70.38 percent.

The glycine chelate metal compound has obvious effects on promoting the growth of fish, improving the feed conversion rate and the survival rate of fish, and is an ideal nutritional feed additive suitable for the nutritional requirements of fish. A feeding test of Zhao Yuanfeng et al (1994) on carps shows that the weight gain of a comparison group added with the glycine chelate metal compound is improved by 37.2-68.1%, and the bait coefficient is reduced to 1.4-1.7 from 2.4 of the comparison group. Liaijie et al (1994) adds glycine chelate metal compound, Cu 2Mg, Zn 30Mg, Mn 12Mg, Fe 150Mg, Co 2Mg and Mg 400Mg in each kilogram of feed, can accelerate the growth of tilapia, and improves the weight gain rate by 17.84-25.84% compared with inorganic trace elements; for crucian carp, the digestibility of trace elements Cu and Co can be improved by 41-58%, the digestibility of Fe and Zn can be improved by 14-16%, and the digestibility of Mn can be improved by 5-7%.

Therefore, the glycine chelate metal compound has stable chemical performance, high biological value, no toxicity, no stimulation, good palatability, no incompatibility with vitamins, antibiotics and the like, has certain functions of sterilizing and improving immunologic function, has curative effect on enteritis, dysentery and anemia, and has stable chemical properties. As a feed additive, the compound feed additive has the double functions of supplementing trace elements and amino acids, can reduce the feed consumption and improve the feed conversion utilization rate, and has obvious economic benefit.

The direct hydantoin method is an important production method of glycine, the method takes hydroxyl acetonitrile and ammonium bicarbonate as raw materials, the hydroxyl acetonitrile, ammonia, carbon dioxide and water are reacted at high temperature and high pressure according to the feeding molar ratio of 1:4:2:46, ammonia and carbon dioxide are discharged to generate glycine aqueous solution, and glycine products are obtained through decoloring, concentrating, cooling and crystallizing. However, there is also a problem that some organic impurities such as hydantoin, hydantoin acid amide, glycine dipeptide, glycine tripeptide, 2, 5-diketopiperazine, glycine amide, and unreacted hydantoin are generated during the production of glycine, and the structural formula is as follows:

the reason for generating the impurities is that the hydroxyacetonitrile firstly reacts with ammonia to generate aminoacetonitrile, then the aminoacetonitrile forms a ring under the action of carbon dioxide, and the hydantoin ring is unstable and decomposed into glycine, carbon dioxide and ammonia after a small amount of aminolysis and high temperature and high pressure. However, in this process, impurities such as hydantoin acid, hydantoin acid amide, glycine dipeptide, glycine tripeptide, 2, 5-diketopiperazine, and glycinamide are generated due to incomplete decomposition of the hydantoin ring, and in addition to the above impurities, ammonium sulfate is also generated in the mother liquor because hydroxyacetonitrile is easily decomposed and polymerized during storage or transportation, and therefore, it is necessary to perform an acidification treatment in which a small amount of sulfuric acid is added to hydroxyacetonitrile to lower the pH of the hydroxyacetonitrile to 2 to 3, but the added sulfuric acid is finally converted into ammonium sulfate and remains in the mother liquor, thereby affecting the recycling of the glycine mother liquor. In industrial processes, in order to prevent the accumulation of these impurities, a part of glycine crystallization mother liquor is generally extracted and incinerated, and the amount of the mother liquor extracted and incinerated is generally about 10% of the mass of the mother liquor, which inevitably results in a great amount of glycine loss. Although impurities such as hydantoin acid, hydantoin acid amide, glycine dipeptide, glycine tripeptide, 2, 5-diketopiperazine, glycine amide and the like exist in the glycine mother liquor, the impurities can be converted into glycine under conditional conditions, and the conversion is sometimes thorough, such as under high-temperature conditions or alkaline conditions, but only under high-temperature conditions, the conversion is incomplete, and even reversible reaction is possible, and under alkaline conditions, the impurities can be hydrolyzed completely and converted into glycine, and the alkaline treated mother liquor cannot be recycled to the original reaction system. The disposal by incineration is therefore directly effective, at least in the present case analyzed. However, the method wastes resources, pollutes the environment and causes the increase of the production cost of the glycine.

Therefore, a method for producing valuable products by comprehensively utilizing the glycine mother liquor by the direct hydantoin method is urgently needed, so that the method not only prevents the accumulation of impurities in the mother liquor from influencing the recycling of the mother liquor, but also fully recycles the impurities such as glycine and glycine derivatives in the mother liquor, avoids direct incineration treatment and achieves the purpose of fully utilizing wastes.

Disclosure of Invention

In view of the above, an object of the present invention is to provide a composition for preparing glycine chelate complexes containing trace elements.

Further, the composition includes a glycine mother liquor and a base.

Further, the glycine mother liquor is a residual liquor obtained by synthesizing the glycine product by using a direct hydantoin method.

Further, the glycine mother liquor comprises the following components in percentage by mass: 10 to 20 parts of glycine, 0.5 to 1.5 parts of glycine dipeptide, 0.5 to 1.0 part of 2, 5-diketopiperazine, 0.5 to 1.0 part of hydantoin, 0.4 to 0.8 part of glycinamide, 0.5 to 0.8 part of glycine trimer, 0.1 to 0.6 part of hydantoin amide, 0.1 to 1.0 part of ammonium sulfate, 0.0001 to 0.1 part of hydantoin, 0.0001ppm < 50ppm of ammonia and water.

The invention also aims to provide a preparation method for preparing glycine chelate by using the composition, which comprehensively utilizes the glycine mother liquor synthesized by a direct hydantoin method and comprehensively utilizes waste.

Further, the method is to prepare the glycine chelate by utilizing the residual mother liquor of the glycine product synthesized by the direct hydantoin method.

Specifically, in some embodiments, the synthesis method of the glycine mother liquor synthesized by the direct hydantoin method is as follows: feeding the hydroxyl acetonitrile, the ammonium carbonate and the water according to the feeding ratio of 1:3: 45-50, wherein the reaction temperature is 160-165 ℃, and the reaction time is 3.5-4 hours; after the reaction is finished, carbon dioxide and ammonia which do not participate in the reaction are stripped to obtain a glycine aqueous solution, and the glycine aqueous solution is decolored, concentrated, cooled and crystallized, and mother liquor obtained after the glycine is centrifuged is hydantoin method glycine mother liquor. The glycine mother solution comprises the following components in percentage by mass: 10 to 20 parts of glycine, 0.5 to 1.5 parts of glycine dipeptide, 0.5 to 1.0 part of 2, 5-diketopiperazine, 0.5 to 1.0 part of hydantoin, 0.4 to 0.8 part of glycinamide, 0.5 to 0.8 part of glycine trimer, 0.1 to 0.6 part of hydantoin amide, 0.1 to 1.0 part of ammonium sulfate, 0.0001 to 0.1 part of hydantoin, 0.0001ppm < 50ppm of ammonia and water.

Further, the method specifically comprises the following steps:

(1) adding the glycine mother liquor into the alkali for reaction to obtain a glycine salt aqueous solution;

(2) and reacting the glycinate salt aqueous solution with inorganic metal salt to obtain the glycine chelate.

Further, in the step (1), the alkali is one or more of calcium oxide, calcium hydroxide, potassium carbonate, sodium hydroxide, sodium carbonate and ammonia, and the molar ratio of the alkali to the total amino acids in the glycine mother liquor is 0.55-1.5: 1.

Further, the total amino acids were measured by the Kjeldahl method.

Further, the reaction in the step (1) is specifically as follows: reacting for 1-30 min at the temperature of 120-170 ℃.

Preferably, the temperature is 150-170 ℃, and the reaction time is 5-15 min.

Further, the mass concentration of the glycinate salt aqueous solution in the step (1) is 15-45%.

Preferably, the mass concentration of the glycinate salt aqueous solution in the step (1) is 35-40%.

Further, the inorganic metal salt in the step (2) is an anhydrous compound or hydrate of sulfate or hydrochloride of zinc, iron, copper, manganese, magnesium, nickel and chromium, and the molar ratio of the glycine to the inorganic metal salt is 1.8-3.1: 1.

Further, the inorganic metal salt in the step (2) may be an anhydrous compound or hydrate of sulfate or hydrochloride of trace metal elements required by animals and plants except zinc, iron, copper, manganese, magnesium, nickel and chromium.

Further, the reaction in the step (2) is specifically as follows: reacting at 40-100 ℃ for 10-120 min.

Preferably, the temperature is 60-95 ℃, and the reaction time is 30-100 min.

Further, filtering the glycine salt water solution obtained in the step (1) to remove insoluble substances, concentrating to a certain degree, cooling for crystallization, separating to obtain chelate crystals and crystallization mother liquor, and washing and drying the crystals to obtain the feed-grade glycine chelate.

Further, cooling and crystallizing the glycine chelate in the step (2), separating to obtain a chelate crystal and a crystallization mother liquor, and washing and drying the crystal to obtain the feed-grade glycine chelate.

The invention also aims to provide a glycine chelate prepared by the method, wherein the chelate contains one or more metal trace elements.

Further, the glycine chelate contains any one of trace elements of zinc, iron, copper, manganese, magnesium, nickel and chromium.

Further, the glycine chelate is prepared by concentrating and crystallizing the glycine salt aqueous solution prepared by the method.

The invention also provides a trace element fertilizer which contains one or more than two trace elements.

Further, the trace element fertilizer contains one or more than two trace elements of zinc, iron, copper, manganese, magnesium, nickel and chromium.

The invention also provides a preparation method of the trace element fertilizer, which comprises the steps of concentrating, crystallizing and separating the glycinate salt aqueous solution to obtain a glycine chelate crystal and a crystallization mother liquor A, concentrating, crystallizing and separating the glycine chelate to obtain a glycine chelate crystal and a crystallization mother liquor B, and concentrating, spraying and drying the A or/and the B to obtain the trace element fertilizer.

Furthermore, the main component of the trace element fertilizer is one or more of sulfate or hydrochloride of potassium, sodium and ammonium, and the trace element fertilizer also comprises at least more than one trace element component, wherein the trace element component mainly exists in the form of glycine chelate.

The invention also provides a preparation method of the efficient slow-release fertilizer.

Separating out insoluble substances after the reaction with the alkali, centrifuging the glycinate aqueous solution to obtain filtrate, mixing the insoluble substances with the filtrate, concentrating, spraying and drying to obtain the efficient slow-release fertilizer.

Further, the high-efficiency slow-release fertilizer is a high-efficiency slow-release calcium fertilizer.

The invention aims to further provide a production system for producing glycine chelate, the production system utilizes waste glycine mother liquor for recycling, and the process is environment-friendly.

Further, the production system is sequentially connected with a production system for synthesizing the glycine mother liquor by the direct hydantoin method, a reaction device 1 and a reaction device 2, the production system for synthesizing the glycine mother liquor by the direct hydantoin method is provided with more than two output pipelines, at least one output pipeline is connected with the reaction device 1, and one part of the glycine mother liquor is input into the reaction device 1 for reaction.

Further, reaction unit 1 is high pressure batch autoclave, reaction unit 2 still connects separator and drying device.

The invention has the beneficial effects that:

the invention utilizes the direct hydantoin method glycine mother liquor to prepare the glycine metal chelate, and then uses the residual mother liquor to prepare the microelement fertilizer, thereby realizing the graded recovery and the complete utilization of the glycine, the inorganic salt and the dissolved glycine chelate, and having no waste discharge.

The invention converts impurities in the glycine mother liquor into beneficial glycine to be utilized by alkaline hydrolysis; compared with the traditional method of using commercial grade glycine, the method has low production cost and realizes the comprehensive utilization of wastes.

The production process has the advantages of cleanness, environmental protection, simple operation, easy equipment maintenance, high yield, high product stability and high recovery rate of the glycine in the mother liquor.

Drawings

FIG. 1 is a schematic diagram of a glycine chelate process flow.

Detailed Description

The examples are given for the purpose of better illustration of the invention, but the invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.

In the embodiment of the invention, the content of glycine is detected by using ion chromatography; organic impurities in the glycine mother liquor are detected by a high performance liquid chromatography, and the total glycine content is obtained by converting and accumulating various reversible glycine derivative impurities detected by the high performance liquid chromatography or directly determined by a Kjeldahl method.

In the embodiment of the invention, the process flow of the production process of the glycine chelate is shown in figure 1. In the glycine mother liquor, one part of the mother liquor returns to the preparation step for circulation, and the other part of the mother liquor is added with alkali, so that the scheme of the invention is applied for reaction, the waste is recycled, and the process is environment-friendly.

In the embodiment of the invention, the change condition of the components of the glycine mother liquor is analyzed by using the high performance liquid chromatography, but the problems of high personnel operation requirement, complex conversion and large investment of analysis equipment exist in a production field, after the glycine mother liquor hydrolysis experiment performed in the embodiment 1, the condition for converting impurities in the completely hydrolyzed glycine mother liquor into glycine is clear, the following part of experiments try to determine the content of total glycine by adopting a Kjeldahl method, and the subsequent experiment is performed by taking the data as the feeding basis (after the analysis and the method of the total glycine are replaced, in the first experiment example 5, the components of the hydrolyzed glycine mother liquor are still verified by using the high performance liquid chromatography).