CN116589370A - Alpha-amino acid-metal phosphate co-salt compound, and preparation method and application thereof - Google Patents

Alpha-amino acid-metal phosphate co-salt compound, and preparation method and application thereof Download PDF

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CN116589370A
CN116589370A CN202310341300.5A CN202310341300A CN116589370A CN 116589370 A CN116589370 A CN 116589370A CN 202310341300 A CN202310341300 A CN 202310341300A CN 116589370 A CN116589370 A CN 116589370A
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amino acid
alpha
phosphate
salt compound
metal
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吴传隆
周振宇
彭启明
周荣超
邱小娟
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Tianbao Animal Nutrition Technology Co ltd
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Tianbao Animal Nutrition Technology Co ltd
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    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
    • 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
    • A23K20/142—Amino acids; Derivatives thereof
    • 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
    • A23K20/20—Inorganic substances, e.g. oligoelements
    • A23K20/24—Compounds of alkaline earth metals, e.g. magnesium
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    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
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    • A23K20/26—Compounds containing phosphorus
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    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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    • C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
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    • C07C229/34—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C07C229/36—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings with at least one amino group and one carboxyl group bound to the same carbon atom of the carbon skeleton
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    • C07C279/14—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton being further substituted by carboxyl groups
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Abstract

The invention relates to the technical field of feed additives, in particular to an alpha-amino acid-phosphoric acid metal salt compound and a preparation method and application thereof. The α -amino acid-phosphate co-salt compounds of the present invention deliver, for example, ca in a single water-soluble dosage unit +2 、Mg +2 Divalent metal, inorganic phosphorus and alpha-amino acid, and a plurality of components are not required to be mixed or combined, so that the phosphate radical and the alpha-amino acid in the feed can be prevented from dissolving and losing in the water environment, further the water pollution is avoided, and the feed has the characteristics of moderate stability and high bioavailability.

Description

Alpha-amino acid-metal phosphate co-salt compound, and preparation method and application thereof
Technical Field
The invention relates to the technical field of feed additives, in particular to an alpha-amino acid-metal phosphate co-salt compound and a preparation method and application thereof.
Background
The alpha-amino acid is a basic unit for composing protein, is composed of carbon, hydrogen, oxygen, sulfur and other elements, and is an amino-containing organic acid. After the chicken feeds, the protein in the feed is decomposed into alpha-amino acid by protease in the stomach and intestine, and enters into blood circulation to participate in the metabolic process in vivo, so as to synthesize chicken protein. The number of α -amino acids constituting proteins is 20 or more, and the number is divided into two major categories, i.e., essential α -amino acids and non-essential α -amino acids. For poultry, the necessary alpha-amino acids are alpha-amino acids which cannot be synthesized or are synthesized at a slow speed in the poultry body, cannot meet the requirements of the growth and development of the poultry, and must be fed by feed. There are 11 essential alpha-amino acids for poultry, namely methionine, lysine, arginine, threonine, isoleucine, leucine, tryptophan, phenylalanine, histidine, valine and glycine. Also, the aquatic animals have 10 essential α -amino acids, i.e., lysine, methionine, arginine, histidine, leucine, isoleucine, phenylalanine, valine, threonine and tryptophan, and ruminants have lysine, methionine, threonine, leucine, isoleucine, tryptophan, phenylalanine, valine and tyrosine. However, in aquatic feed, because the solubility of free alpha-amino acid in water is relatively high, the free alpha-amino acid in the feed is easy to dissolve out in water and is lost, and the dissolved alpha-amino acid also causes the problem of water pollution of aquaculture, therefore, the free alpha-amino acid generally needs to be treated and then can be absorbed by aquatic animals, such as physical coating technology treatment, alpha-amino acid dipeptide, metal chelate of the alpha-amino acid and the like. Since ruminants have a specific digestive system, especially the stomach, with tens of thousands of microorganisms, which are capable of decomposing and digesting free alpha-amino acids in the feed, converting the free alpha-amino acids into ammonia and organic acids, etc., resulting in a decrease in the utilization rate of free alpha-amino acids in the feed for absorption by ruminant bodies, it is also necessary for ruminant feed to subject the free alpha-amino acids to a specific treatment, mainly by physical means such as coating techniques and chemical treatments such as conversion of alpha-amino acids into metal chelates or metal salts.
Calcium and phosphorus have wide biological functions in animals, and common deficiency symptoms are as follows: appetite is reduced, and pica is avoided; growth is slowed down, productivity and feed utilization are reduced; skeletal abnormalities, and the like. Typical calcium and phosphorus deficiency of animals are rickets, osteoporosis and postpartum paralysis. The proper demand and supply of calcium and phosphorus is affected by a number of factors, the greatest of which is vitamin D. The absorption of calcium requires the presence of phosphorus at the same time, and the proper ratio of calcium to phosphorus in the animal feed is about 2:1, when the calcium is too high and the phosphorus is relatively low, the phosphorus is malabsorption, and when the calcium is too low and the phosphorus is relatively high, the calcium is precipitated due to the formed calcium phosphate and cannot be absorbed. Gu Jiangong et al have demonstrated that calcium and phosphorus in the appropriate ratio can inhibit bone resorption activity of osteoclasts, thereby regulating bone metabolism, primarily by inhibiting osteoclastogenesis and activation. Calcium and phosphorus are mineral elements with the highest content in the livestock and poultry bodies, and account for 1% -2% of the weight on average, wherein 98% -99% of the calcium and 80% of the phosphorus exist in bones. Under normal conditions, the ratio of calcium to phosphorus in the feed is about 2:1, and the ratio of calcium to phosphorus also changes to a certain extent due to different animal types, ages and nutritional conditions.
Phosphorus in animal feed is mainly 2: one is the direct addition of phosphorus, such as dibasic and monobasic, and the other is the addition of phytase to release phosphorus from the diet plant. The sources of calcium and magnesium in animal feed are mainly 2: organic calcium (magnesium) and inorganic calcium (magnesium). There are various inorganic calcium sources, mainly: calcium carbonate (magnesium), limestone powder (commonly known as stone powder) and shell powder. The shell powder is used for a lot of problems of raw material sources, crushed granularity, particle hardness and processing cost, and calcium carbonate and limestone powder are used more, but the digestion, absorption and utilization rate of inorganic calcium is lower. The organic calcium (magnesium) source has higher absorptivity and utilization rate than inorganic calcium (magnesium), and mainly comprises the following components: calcium (magnesium) gluconate, calcium (magnesium) lactate, calcium (magnesium) fumarate, calcium (magnesium) glycinate, calcium salt of methionine hydroxy analogue, etc. Calcium gluconate (8.5% of calcium) has too low calcium content and is added into feed at high cost. Calcium lactate (13% calcium content) is moderately priced, but bitter in taste, relatively sensitive to bitter taste in animals and less palatable. Whereas calcium fumarate has only a slight astringency, animals are not sensitive to astringency and have better palatability.
Therefore, research and development of an alpha-amino acid-phosphoric acid metal salt product which can contain calcium and phosphorus simultaneously and has the calcium-phosphorus ratio meeting the requirements is directed by the person skilled in the art as an animal feed additive by taking alpha-amino acid and phosphoric acid as main raw materials. At present, most of the feeds on the market directly mix calcium phosphate and alpha-amino acid into the feeds, the simple mixing mode has low bioavailability of the calcium phosphate and the alpha-amino acid, the animal absorption channel is single, the calcium phosphate and the alpha-amino acid can not promote absorption mutually, and a compound capable of delivering the alpha-amino acid, inorganic phosphorus, calcium and magnesium through ingestion is lacking. How to organically combine the alpha-amino acid, the calcium and the phosphorus to prepare the alpha-amino acid-metal phosphate co-salt composite product with low cost, safe product and higher purity has very important practical significance in the field.
Disclosure of Invention
It is therefore an object of the present invention to provide an alpha-amino acid-phosphoric acid metal co-salt, a process for its preparation and its use, which metal co-salt compound delivers, for example, ca in a single water-soluble dosage unit +2 、Mg +2 The metal ions, inorganic phosphate radicals and alpha-amino acids do not need to be mixed or combined with a plurality of components, so that the dissolution loss of the metal ions, inorganic phosphate radicals and alpha-amino acids in the feed in a water environment can be avoided, the water pollution is further avoided, or the decomposition in rumen of ruminants is avoided, and the bioavailability is low.
The invention solves the technical problems by the following technical means:
an aspect of the present invention is to provide an α -amino acid-phosphoric acid metal co-salt compound, characterized in that the metal co-salt compound has the following general structure:
wherein R and alpha-amino carboxyl form alpha-amino acid, M is calcium or magnesium, and when the alpha-amino acid in the metal salt compound is neutral or alkaline amino acid, x is 1, y is 1, z is 0.5, and n is 0-4; when the alpha-amino acid is an acidic amino acid, x is 1, y is 1, z is 1, and n is a number from 0 to 4.
Further, the neutral alpha-amino acid is any one of glycine, L-methionine, D, L-methionine, L-threonine, L-isoleucine, L-leucine, L-phenylalanine and L-valine; the basic alpha-amino acid is any one of L-lysine, L-arginine and L-histidine; the acid alpha-amino acid is L-glutamic acid or L-aspartic acid.
Further, the phosphate in the metal co-salt compound is one or two of calcium hydrophosphate and calcium dihydrogen phosphate, or the phosphate in the metal co-salt compound is one or two of magnesium hydrophosphate and magnesium dihydrogen phosphate.
The invention also provides a preparation method of the alpha-amino acid-metal phosphate co-salt compound, which is characterized by comprising the following steps of:
mixing and stirring phosphoric acid and alpha-amino acid, and reacting for 30-60 min at the temperature of 30-60 ℃ to obtain alpha-amino acid-phosphoric acid composite salt water solution;
adding alkaline earth metal compound into alpha-amino acid-phosphoric acid composite salt water solution, and reacting for 60-120 min at 70-90 ℃ to obtain alpha-amino acid-phosphoric acid metal co-salt compound mixed water solution, wherein the pH value of the alpha-amino acid-phosphoric acid metal co-salt compound mixed water solution is 4.0-8.5;
concentrating the mixed aqueous solution of the alpha-amino acid-metal phosphate co-salt compound under reduced pressure to be solid, drying to constant weight, grinding and sieving to obtain the alpha-amino acid-metal phosphate co-salt compound.
Further, the alkaline earth metal compound is any one of an oxide, hydroxide, and carbonate of calcium or magnesium.
Further, the phosphoric acid is wet-process phosphoric acid, wherein the phosphorus pentoxide in the phosphoric acid is 50-61.6 g/L, the fluorine ion content is less than 1000mg/kg, and the arsenic content is less than 10mg/kg.
Further, the molar ratio of the phosphoric acid to the alpha-amino acid is 0.5-1:1, and the molar ratio of the alpha-amino acid to the alkaline earth metal compound is 1:1.
In a further aspect the present invention provides the use of an alpha-amino acid-metal phosphate co-salt compound as described above as a feed additive in the preparation of aquatic feed, poultry feed and ruminant feed.
The invention has the following beneficial effects:
(1) The alpha-amino acid-phosphoric acid metal salt compound contains alpha-amino acid, calcium (magnesium) and inorganic phosphorus, can synergistically absorb the alpha-amino acid, the calcium (magnesium) and the phosphorus in animal bodies, can mutually promote absorption when nutrient elements are absorbed, and has good absorption effect.
(2) The alpha-amino acid-metal phosphate co-salt contains an alpha-amino acid ligand, can help to supplement the alpha-amino acid of the powder product, has moderate price and has lower cost than other single alpha-amino acid chelated calcium (magnesium); the premix feed additive has moderate fluidity, can not absorb moisture and agglomerate when pressed, is favorable for storage, can be used as a dispersing agent to be mixed with other feed additives, and can effectively prevent the premix feed from absorbing moisture and agglomerating so as to influence the feed quality.
(3) The preparation method has the advantages of simple process, convenient operation, low cost, safe product and small investment, is suitable for large-scale production, and ensures higher yield; the addition of the calcium (magnesium) source can not only regulate the pH value of the reaction system, but also avoid introducing new impurities in the process, reduce the difficulty of the subsequent purification process of the product, flexibly mix the alpha-amino acid with phosphoric acid and metal, and have simple synthesis and better effect than single alpha-amino acid complex (chelate) metal salt and calcium (magnesium) phosphate salt.
(4) The alpha-amino acid-metal phosphate co-salt compound is used as an additive for aquatic products, poultry and ruminants, and has better taste and less toxic and harmful substances than the conventional stone powder, calcium lactate, magnesium oxide, magnesium sulfate, magnesium carbonate and the like; the alpha-amino acid-metal phosphate co-salt added in the basic ration can be used as an alpha-amino acid supplement, can be used as inorganic phosphorus and metal element supplement, is flexibly matched, can greatly reduce alpha-amino acid loss and reduce animal body utilization rate caused by microbial decomposition when being particularly applied to aquatic feed and ruminant feed, reduces feed cost, improves the bioavailability of the alpha-amino acid, inorganic phosphorus and metal element, reduces phosphorus and metal content in livestock and poultry feces, reduces environmental pollution, and has promotion effect on animal growth performance.
Drawings
FIG. 1 is a general structure of an α -amino acid-metal phosphate co-salt compound of the present invention;
FIG. 2 is a chemical structure of a neutral alpha-amino acid-dibasic calcium phosphate co-salt compound of the invention;
FIG. 3 is a chemical structure of an acidic alpha-amino acid-dibasic calcium phosphate co-salt compound of the invention;
FIG. 4 is a chemical structure of a basic alpha-amino acid-dibasic calcium phosphate co-salt compound of the invention;
FIG. 5 is a chemical structure of a neutral alpha-amino acid-monocalcium phosphate co-salt compound of the present invention;
FIG. 6 is a chemical structure of an acidic alpha-amino acid-monocalcium phosphate co-salt compound of the present invention;
FIG. 7 is a chemical structure of a basic alpha-amino acid-monocalcium phosphate co-salt compound of the present invention;
FIG. 8 is a chemical structure of a neutral alpha-amino acid-magnesium hydrogen phosphate co-salt compound of the present invention;
FIG. 9 is a chemical structure of an acidic alpha-amino acid-magnesium hydrogen phosphate co-salt compound of the present invention;
FIG. 10 is a chemical structure of a basic alpha-amino acid-magnesium hydrogen phosphate co-salt compound of the present invention;
FIG. 11 is a chemical structure of a neutral alpha-amino acid-magnesium dihydrogen phosphate co-salt compound of the present invention;
FIG. 12 is a chemical structure of an acidic alpha-amino acid-magnesium dihydrogen phosphate co-salt compound of the present invention;
FIG. 13 is a chemical structure of a basic alpha-amino acid-magnesium dihydrogen phosphate co-salt compound of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The raw materials, equipment or instruments used are conventional products commercially available without identifying the manufacturer.
The alpha-amino acid-metal phosphate co-salt compound has a general structure shown in figure 1, wherein M is metal in the general structure shown in figure 1. Specifically, M is any one of calcium and magnesium, R and alpha-amino carboxyl form alpha-amino acid, the alpha-amino acid is further divided into neutral alpha-amino acid, acidic alpha-amino acid and alkaline alpha-amino acid, the neutral alpha-amino acid is any one of glycine, L-methionine, D, L-methionine, L-threonine, L-isoleucine, L-leucine, L-phenylalanine and L-valine, the alkaline alpha-amino acid is any one of L-lysine, L-arginine and L-histidine, and the acidic alpha-amino acid is any one of glutamic acid and aspartic acid. The alpha-amino acid-metal phosphate co-salt compound of the present invention is obtained in the form of particles containing the co-salt, and other biologically active substances dispersed in the particles, and can exhibit properties of being insoluble in neutral and alkaline water but soluble in acidic water.
EXAMPLE 1 preparation of Glycine-dibasic calcium phosphate Co-salt
75.76 g (1.0 mol) of glycine crystal with the mass percent of 99% and 118.36 g of phosphoric acid (0.5 mol) (the phosphorus pentoxide content is 30%) are added into a reaction bottle, heated to 50 ℃, stirred and fully dissolved, and reacted at constant temperature for 50min to obtain glycine-phosphoric acid composite salt water solution. 77.08 g (1.0 mol) of calcium hydroxide powder with the mass percent of 96% is weighed and added into the glycine-phosphoric acid composite salt water solution, the reaction temperature is controlled to be 80 ℃, the reaction time is controlled to be 60 minutes, and the glycine-calcium hydrophosphate water solution containing milky precipitate is obtained, and the pH value of the reaction solution is 7.0. Concentrating the obtained glycine-calcium hydrophosphate aqueous solution containing the milky white precipitate into a solid, transferring the solid into a tray, and drying at 100 ℃ to constant weight to obtain 208.42 g of white glycine-calcium hydrophosphate common salt powder, wherein the yield is 100%, the product purity is 95%, the glycine content in the product is 35.98%, the phosphate content is 23.03%, and the calcium content is 19.19%.
EXAMPLE 2 preparation of Glycine-dibasic calcium phosphate Co-salt
75.76 g (1.0 mol) of glycine crystals with the mass percent of 99% and 57.65 g of phosphoric acid (0.5 mol) (with the phosphorus pentoxide content of 61.6%) are added into a reaction bottle, heated to 35 ℃, stirred and fully dissolved, and reacted at constant temperature for 30min to obtain glycine-phosphoric acid composite salt water solution. 62.22 g (1.0 mol) of calcium oxide powder with the mass percent of 90% is weighed and added into the glycine-phosphoric acid composite salt water solution, the reaction temperature is controlled to be 90 ℃, the reaction time is controlled to be 90min, and the glycine-calcium hydrophosphate water solution containing milky precipitate is obtained, and the pH value of the reaction solution is 7.5. Concentrating the obtained glycine-calcium hydrophosphate aqueous solution containing the milky white precipitate into a solid, transferring the solid into a tray, and drying at 100 ℃ to constant weight to obtain 208.42 g of white glycine-calcium hydrophosphate common salt powder, wherein the yield is 100%, the purity of the product is 95%, the glycine content in the product is 35.98%, the phosphate content is 23.03%, and the calcium content is 19.19%.
EXAMPLE 3 preparation of Glycine-dibasic calcium phosphate Co-salt
75.76 g (1.0 mol) of glycine crystal with the mass percent of 99% and 71.02 g of phosphoric acid (0.5 mol) (the phosphorus pentoxide content is 50%) are added into a reaction bottle, heated to 35 ℃, stirred and fully dissolved, and reacted at constant temperature for 50min to obtain glycine-phosphoric acid composite salt water solution. 101.01 g (1.0 mol) of calcium carbonate powder with the mass percent of 99 percent is weighed and added into the glycine-phosphoric acid composite salt water solution, the reaction temperature is controlled to be 90 ℃, the reaction time is controlled to be 120min, and the glycine-calcium hydrophosphate water solution containing milky precipitate is obtained, and the pH value of the reaction solution is 7.0. Concentrating the obtained glycine-calcium hydrophosphate aqueous solution containing the milky white precipitate into a solid, transferring the solid into a tray, and drying at 100 ℃ to constant weight to obtain 208.42 g of white glycine-calcium hydrophosphate common salt powder, wherein the yield is 100%, the purity of the product is 95%, the glycine content in the product is 35.98%, the phosphate content is 23.03%, and the calcium content is 19.19%.
According to the method, methionine-calcium hydrophosphate common salt compound, L-threonine-calcium hydrophosphate common salt compound, L-isoleucine-calcium hydrophosphate common salt compound, L-leucine-calcium hydrophosphate common salt compound, L-phenylalanine-calcium hydrophosphate common salt compound, L-valine-calcium hydrophosphate common salt compound, L-glutamic acid-calcium hydrophosphate common salt compound, L-aspartic acid-calcium hydrophosphate common salt compound, L-lysine-calcium hydrophosphate common salt compound, L-arginine-calcium hydrophosphate common salt compound and L-histidine-calcium hydrophosphate common salt compound are respectively prepared. The chemical structures of the methionine-calcium hydrophosphate co-salt compound, the L-threonine-calcium hydrophosphate co-salt compound, the L-isoleucine-calcium hydrophosphate co-salt compound, the L-leucine-calcium hydrophosphate co-salt compound, the L-phenylalanine-calcium hydrophosphate co-salt compound and the L-valine-calcium hydrophosphate co-salt compound are shown in the figure 2, the chemical structures of the L-glutamic acid-calcium hydrophosphate co-salt compound and the L-aspartic acid-calcium hydrophosphate co-salt compound are shown in the figure 3, and the chemical structures of the L-lysine-calcium hydrophosphate co-salt compound, the L-arginine-calcium hydrophosphate co-salt compound and the L-histidine-calcium hydrophosphate co-salt compound are shown in the figure 4.
The preparation conditions and results of the above co-salt compounds are described in table 1 below:
TABLE 1
EXAMPLE 4 preparation of Glycine-monocalcium phosphate Co-salt
75.76 g (1.0 mol) of glycine crystal with the mass percent of 99% and 236.72 g of phosphoric acid (1.0 mol) (the phosphorus pentoxide content is 30%) are added into a reaction bottle, heated to 50 ℃, stirred and fully dissolved, and reacted at constant temperature for 60min to obtain glycine-phosphoric acid composite salt water solution. 77.08 g (1.0 mol) of calcium hydroxide powder with the mass percent of 96% is weighed and added into the glycine-phosphoric acid composite salt water solution, the reaction temperature is controlled to be 80 ℃, the reaction time is controlled to be 60 minutes, and the glycine-phosphoric acid monocalcium water solution containing milky precipitate is obtained, and the pH value of the reaction solution is 5.0. The obtained glycine-monocalcium phosphate aqueous solution containing the milky white precipitate is concentrated to be solid, the solid is transferred into a tray and dried to constant weight at 100 ℃ to obtain 241.05 g of white glycine-monocalcium phosphate common salt powder, the yield is 100%, the purity of the product is 95%, the glycine content in the product is 31.11%, the phosphate content is 40.24%, and the calcium content is 16.59%.
According to the above method, methionine-monocalcium phosphate, L-threonine-monocalcium phosphate, L-isoleucine-monocalcium phosphate, L-leucine-monocalcium phosphate, L-phenylalanine-monocalcium phosphate, L-valine-monocalcium phosphate, L-glutamic acid-monocalcium phosphate, L-aspartic acid-monocalcium phosphate, L-lysine-monocalcium phosphate, L-arginine-monocalcium phosphate, L-histidine-monocalcium phosphate, the structures of the above-mentioned co-salts are shown in FIG. 5, FIG. 6 and FIG. 7, and the preparation conditions and results are shown in Table 2 below:
TABLE 2
EXAMPLE 5 preparation of Glycine-magnesium Hydrogen phosphate Co-salt
75.76 g (1.0 mol) of glycine crystal with the mass percent of 99% and 118.36 g of phosphoric acid (0.5 mol) (the phosphorus pentoxide content is 30%) are added into a reaction bottle, heated to 50 ℃, stirred and fully dissolved, and reacted at constant temperature for 50min to obtain glycine-phosphoric acid composite salt water solution. 58.59 g (1.0 mol) of magnesium hydroxide powder with the mass percent of 99 percent is weighed and added into the glycine-phosphoric acid composite salt water solution, the reaction temperature is controlled to be 90 ℃, the reaction time is controlled to be 60 minutes, and the glycine-magnesium hydrogen phosphate water solution containing milky precipitate is obtained, and the pH value of the reaction solution is 7.5. The obtained glycine-magnesium hydrogen phosphate aqueous solution containing the milky white precipitate is concentrated to be solid, the solid is transferred into a tray and dried to constant weight at 100 ℃ to obtain 170.83 g of white glycine-magnesium hydrogen phosphate common salt powder, the yield is 100%, the product purity is 96%, the glycine content in the product is 43.90%, the phosphate content is 28.10%, and the magnesium content is 14.05%.
According to the above method, methionine-magnesium hydrogen phosphate, L-threonine-magnesium hydrogen phosphate, L-isoleucine-magnesium hydrogen phosphate, L-leucine-magnesium hydrogen phosphate, L-phenylalanine-magnesium hydrogen phosphate, L-valine-magnesium hydrogen phosphate, L-glutamic acid-magnesium hydrogen phosphate, L-aspartic acid-magnesium hydrogen phosphate, L-lysine-magnesium hydrogen phosphate, L-arginine-magnesium hydrogen phosphate and L-histidine-magnesium hydrogen phosphate are prepared, respectively, wherein the structures of the above co-salt compounds are shown in FIG. 8, FIG. 9 and FIG. 10, and the preparation conditions and results are shown in Table 3 below:
TABLE 3 Table 3
EXAMPLE 6 preparation of Glycine-magnesium dihydrogen phosphate Co-salt
75.76 g (1.0 mol) of glycine crystal with the mass percent of 99% and 236.72 g of phosphoric acid (1.0 mol) (the phosphorus pentoxide content is 30%) are added into a reaction bottle, heated to 50 ℃, stirred and fully dissolved, and reacted at constant temperature for 50min to obtain glycine-phosphoric acid composite salt water solution. 58.59 g (1.0 mol) of magnesium hydroxide powder with the mass percent of 99 percent is weighed and added into the glycine-phosphoric acid composite salt water solution, the reaction temperature is controlled to be 80 ℃, the reaction time is controlled to be 60 minutes, and the glycine-magnesium dihydrogen phosphate water solution containing milky precipitate is obtained, and the pH value of the reaction solution is 5.0. The obtained glycine-magnesium dihydrogen phosphate aqueous solution containing the milky white precipitate is concentrated to be solid, the solid is transferred into a tray and dried to constant weight at 100 ℃ to obtain 221.88 g of white glycine-magnesium dihydrogen phosphate common salt powder, the yield is 100%, the purity of the product is 96%, the glycine content in the product is 33.80%, the phosphate content is 43.72%, and the magnesium content is 10.82%.
According to the above method, methionine-magnesium dihydrogen phosphate, L-threonine-magnesium dihydrogen phosphate, L-isoleucine-magnesium dihydrogen phosphate, L-leucine-magnesium dihydrogen phosphate, L-phenylalanine-magnesium dihydrogen phosphate, L-valine-magnesium dihydrogen phosphate, L-glutamic acid-magnesium dihydrogen phosphate, L-aspartic acid-magnesium dihydrogen phosphate, L-lysine-magnesium dihydrogen phosphate, L-arginine-magnesium dihydrogen phosphate, L-histidine-magnesium dihydrogen phosphate, and the structures of the above-mentioned co-salts are shown in FIG. 11, FIG. 12, and FIG. 13, and the preparation conditions and results are shown in Table 4 below:
TABLE 4 Table 4
EXAMPLE 7 comparison of biological Effect of alpha-amino acid-phosphate Metal Co-salt Compounds
Rainbow trout is used as an experimental feeding target, and free amino acids, single calcium (magnesium) phosphate and single amino acid chelated calcium (magnesium) are used as comparison. The results show that: the bioavailability of metals, amino acids and phosphorus in the alpha-amino acid-metal phosphate co-salts is significantly higher than that of the ionized amino acids, the single calcium (magnesium) phosphate salts and the single amino acid chelated calcium (magnesium). The experimental results are shown in table 5:
TABLE 5
Example 8 comparison of biological Effect of alpha-amino acid-calcium phosphate Co-salt Compounds
White feather chickens are used as experimental feeding targets, and free amino acids, single calcium phosphate salt and single amino acid chelated calcium are used as comparison. The results show that: the bioavailability of metals, amino acids and phosphorus in alpha-amino acid-calcium phosphate co-salts is significantly higher than that of ionized amino acids, single calcium phosphate salts and single amino acid chelated calcium. The experimental results are shown in table 6:
TABLE 5
EXAMPLE 7 comparison of biological Effect of alpha-amino acid-phosphate Metal Co-salt Compounds
Cattle were used as the experimental feeding targets, and free amino acids, single calcium (magnesium) phosphate salts and single amino acid chelated calcium (magnesium) were used as comparisons. The results show that: the bioavailability of metals, amino acids and phosphorus in the alpha-amino acid-metal phosphate co-salts is significantly higher than that of the ionized amino acids, the single calcium (magnesium) phosphate salts and the single amino acid chelated calcium (magnesium). The experimental results are shown in table 7:
TABLE 7
In conclusion, the alpha-amino acid-metal phosphate co-salt compound has higher bioavailability, can avoid the dissolution loss of alpha-amino acid, metal ions and inorganic phosphorus in the feed in a water environment, further avoids the water pollution, and can be used as an additive in aquatic feed or poultry feed. As a ruminant feed additive, the alpha-amino acid-metal phosphate co-salt compound has good rumen bypass effect, achieves ideal absorption, and has higher bioavailability than free alpha-amino acid and phosphate.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention. The technology, shape, and construction parts of the present invention, which are not described in detail, are known in the art.

Claims (8)

1. An α -amino acid-phosphate metal co-salt compound, characterized in that the metal co-salt compound has the general structure:
wherein R and alpha-amino carboxyl form alpha-amino acid, M is calcium or magnesium, and when the alpha-amino acid in the metal salt compound is neutral or alkaline amino acid, x is 1, y is 1, z is 0.5, and n is 0-4; when the alpha-amino acid is an acidic amino acid, x is 1, y is 1, z is 1, and n is a number from 0 to 4.
2. The α -amino acid-metal phosphate co-salt compound of claim 1, wherein the neutral α -amino acid is any one of glycine, L-methionine, D, L-methionine, L-threonine, L-isoleucine, L-leucine, L-phenylalanine, L-valine; the basic alpha-amino acid is any one of L-lysine, L-arginine and L-histidine; the acid alpha-amino acid is L-glutamic acid or L-aspartic acid.
3. The α -amino acid-phosphoric acid metal co-salt compound according to claim 1 or 2, wherein the phosphate in the metal co-salt compound is one or both of calcium hydrogen phosphate and calcium dihydrogen phosphate, or wherein the phosphate in the metal co-salt compound is one or both of magnesium hydrogen phosphate and magnesium dihydrogen phosphate.
4. The preparation method of the alpha-amino acid-metal phosphate co-salt compound is characterized by comprising the following steps:
mixing and stirring phosphoric acid and alpha-amino acid, and reacting for 30-60 min at the temperature of 30-60 ℃ to obtain alpha-amino acid-phosphoric acid composite salt water solution;
adding alkaline earth metal compound into alpha-amino acid-phosphoric acid composite salt water solution, and reacting for 60-120 min at 70-90 ℃ to obtain alpha-amino acid-phosphoric acid metal co-salt compound mixed water solution, wherein the pH value of the alpha-amino acid-phosphoric acid metal co-salt compound mixed water solution is 4.0-8.5;
concentrating the mixed aqueous solution of the alpha-amino acid-metal phosphate co-salt compound under reduced pressure to be solid, drying to constant weight, grinding and sieving to obtain the alpha-amino acid-metal phosphate co-salt compound.
5. The method for producing an α -amino acid-metal phosphate co-salt compound according to claim 4, wherein the alkaline earth metal compound is any one of an oxide, hydroxide, and carbonate of calcium or magnesium.
6. The method for producing an α -amino acid-metal phosphate co-salt compound according to claim 5, wherein the phosphoric acid is wet phosphoric acid, wherein phosphorus pentoxide in the phosphoric acid is 50 to 61.6g/L, the fluorine ion content is less than 1000mg/kg, and the arsenic content is less than 10mg/kg.
7. The method for producing an α -amino acid-phosphoric acid metal salt compound according to claim 6, wherein the molar ratio of phosphoric acid to α -amino acid is 0.5 to 1:1, and the molar ratio of α -amino acid to alkaline earth metal compound is 1:1.
8. Use of an alpha-amino acid-metal phosphate co-salt compound according to claim 1 or 2 as feed additive in the preparation of aquatic feed, poultry feed and ruminant feed.
CN202310341300.5A 2023-03-31 2023-03-31 Alpha-amino acid-metal phosphate co-salt compound, and preparation method and application thereof Pending CN116589370A (en)

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