CN116573999A - Alpha-hydroxy organic acid-amino acid and analogue divalent metal co-salt compound thereof, and preparation method and application thereof - Google Patents

Alpha-hydroxy organic acid-amino acid and analogue divalent metal co-salt compound thereof, and preparation method and application thereof Download PDF

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CN116573999A
CN116573999A CN202310341680.2A CN202310341680A CN116573999A CN 116573999 A CN116573999 A CN 116573999A CN 202310341680 A CN202310341680 A CN 202310341680A CN 116573999 A CN116573999 A CN 116573999A
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acid
divalent metal
alpha
hydroxy organic
amino acid
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吴传隆
彭启明
周荣超
周振宇
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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Abstract

The invention relates to the technical field of feed additives, in particular to an alpha-hydroxy organic acid-amino acid and analogue divalent metal salt compound, a preparation method and application thereof, wherein an alpha-hydroxy organic acid aqueous solution and a divalent metal compound react for 0.5-3 hours at the reaction temperature of 60-100 ℃, the alpha-amino acid and analogue thereof are added into the obtained mixed aqueous solution, the mixed aqueous solution reacts for 1-4 hours at the reaction temperature of 70-110 ℃, the reaction solution is decompressed and concentrated to be solid, the solid is dried to be constant weight, and the alpha-hydroxy organic acid-amino acid and analogue divalent metal salt compound thereof is obtained through grinding and sieving. The divalent metal, the alpha-hydroxy organic acid, the alpha-amino acid and the analogues thereof are delivered by a single water-soluble dosage unit, and a plurality of components are required to be mixed or combined, so that the dissolution loss of the alpha-hydroxy organic acid, the alpha-amino acid and the analogues thereof in the feed in a water environment can be avoided, the water pollution is further avoided, and the damage of the divalent metal to vitamins and fatty compounds in the feed is avoided.

Description

Alpha-hydroxy organic acid-amino acid and analogue divalent metal co-salt compound thereof, and preparation method and application thereof
Technical Field
The invention relates to the technical field of feed additives, in particular to an alpha-hydroxy organic acid-amino acid and analogue divalent metal salt compound thereof, and a preparation method and application thereof.
Background
Divalent metals (e.g., calcium, magnesium, zinc, copper, iron, manganese) are important to animal health. The importance of calcium in cell biochemistry is well known. Also well known is the importance of trace minerals (e.g., magnesium, zinc, copper, iron, manganese) to animal health. For example, many studies have shown that zinc has a direct relationship with animal immune organs and plays an important role in maintaining the structure and function of the animal central immune organs thymus, supraluminal and peripheral immune organs spleen, lymph nodes, tonsils. The growth and development are the basis of all production of poultry, and trace elements play a very important role in the production. Some trace elements are used as the material basis of growth and development to participate in organism constitution, such as manganese, copper, zinc and the like; some trace elements are used as main participants of cell growth metabolism in the growth and development process of poultry, for example, iron carries oxygen to participate in various chemical reactions in cells on one hand, and on the other hand, the iron is used as an output tool of carbon dioxide; some trace elements exist as promoters of various enzymes, hormones, etc. active substances in poultry, such as zinc, selenium, etc. In a word, the growth and development of the poultry are not separated from the participation of trace elements, and the body can only keep proper trace elements to ensure healthy growth and development.
At the same time, other compounds are also important, and the presence of these compounds can promote the absorption of the above divalent metal elements, especially in a manner of complexing (chelating) these compounds with the metal elements. D, L-2-hydroxy-4-methylthiobutanoic acid, also known as methionine hydroxy analogue (hydroxy methionine), is mainly used as feed supplement for methionine supplementation. Hydroxy methionine has been used in animal husbandry as early as fifty in the last century, and has been confirmed by feed industry, animal husbandry and pet manufacturers to be an excellent methionine source with biological effects equivalent to equimolar amounts of D, L-methionine and L-methionine. Other amino acids such as glycine are believed to help reduce oxidative stress by producing glutathione in the body. In addition, glycine is used by the body to produce creatine, a substance that has been shown to increase muscle size, strength and capacity. The beneficial effects of glycine on bone health, brain function and neurological conditions were also investigated. Glycine is the major component of collagen, which is known to promote skin health, relieve joint pain and prevent bone loss. The benefits of alpha-hydroxy organic acids such as malic acid, citric acid, gluconic acid are well known and documented.
The organic microelements (zinc, copper, iron and manganese) and the medium-major elements of calcium and magnesium can improve the growth performance of animals, enhance the immunity and the anti-stress capability, reduce the environmental pollution, and are a green and efficient feed additive with very broad application prospect. The use of alpha-hydroxy organic acid metal salts and bis alpha-amino acid metal chelates alone generally results in less desirable properties or performance. For example, organic acid salts such as tribasic magnesium citrate, calcium malate, etc., exhibit too high water solubility, while bis-alpha-amino acid metal chelates exhibit poor water solubility, either of which are difficult to compress in tableting applications due to low compressibility. Alpha-hydroxy organic acid metal salts such as magnesium citrate, calcium malate and zinc gluconate have poor stability and low metal content due to good water solubility, but are unfavorable for absorption by animals. The alpha-amino acid metal chelates, although poorly water soluble, have a lower dissolution rate in water, however, the molecular structure also shows a higher stability constant, which results in a slow rate of dissociation of such metal chelates into metal ions and free amino acids in animals, requiring dissociation under strong acid conditions, resulting in slower absorption, and ensuring sufficient residence time in animal intestines and stomach for adequate absorption, which may limit their use in feed applications. Currently, most of the feeds on the market are direct mixtures of divalent metal salts with organic acids or amino acids, and lack a compound which can deliver amino acids such as methionine and minerals by ingestion.
Disclosure of Invention
In view of the above, the present invention aims to provide an α -hydroxy organic acid-amino acid and its analogues divalent metal co-salt compound, and a preparation method and application thereof, wherein divalent metals, α -hydroxy organic acids and α -amino acids and its analogues are delivered in a single water-soluble dosage unit, and multiple components are required to be mixed or combined, so that dissolution loss of α -hydroxy organic acids, α -amino acids and its analogues in a water environment in a feed can be avoided, and further water pollution is avoided, and damage of divalent metals to vitamins and fatty compounds in the feed is avoided.
The invention solves the technical problems by the following technical means:
an aspect of the present invention is to provide an α -hydroxy organic acid-amino acid and its analog divalent metal co-salt compound having the following general structure:
wherein M is any one of calcium, magnesium, zinc, copper, iron and manganese; r1 and alpha-hydroxy carboxyl can form alpha-hydroxy organic acid, R2 and alpha-amino carboxyl can form alpha-amino acid and amino acid analogues thereof, x is 0.5 or 1, y is 1 or 2, and z is 0-2.
Further, the alpha-hydroxy organic acid is any one of citric acid, malic acid and gluconic acid; the alpha-amino acid is any one of glycine, D, L-methionine, L-threonine, L-glutamic acid, L-lysine, L-tryptophan, L-phenylalanine, L-isoleucine, L-leucine and L-valine; the amino acid analogue is any one of 2-hydroxy-4-methylthiobutanoic acid and taurine.
In still another aspect of the present invention, there is provided a method for preparing the above-mentioned α -hydroxy organic acid-amino acid and its analog divalent metal co-salt compound, the method comprising the steps of:
reacting the alpha-hydroxy organic acid aqueous solution with the divalent metal compound for 0.5-3 h at the reaction temperature of 60-100 ℃ and the pH value of 7.0-12 to obtain a mixed aqueous solution of the divalent metal salt of the alpha-hydroxy organic acid and the divalent metal compound;
adding alpha-amino acid and analogues thereof into the mixed aqueous solution of the divalent metal salt and the divalent metal compound of the alpha-hydroxy organic acid, and reacting for 1-4 hours at the reaction temperature of 70-110 ℃ with the pH value of 6.0-11 to obtain the mixed aqueous solution of the divalent metal co-salt compound of the alpha-hydroxy organic acid-amino acid and analogues thereof;
concentrating the mixed aqueous solution of the alpha-hydroxy organic acid-amino acid and the analogue divalent metal co-salt compound to be solid under reduced pressure, drying to be constant weight, grinding and sieving to obtain the alpha-hydroxy organic acid-amino acid and the analogue divalent metal co-salt compound.
Further, the divalent metal compound is an oxide or hydroxide or carbonate of any one of calcium, magnesium, zinc, copper, iron, and manganese.
Further, the molar ratio of the alpha-hydroxy organic acid to the alpha-amino acid and the analogues thereof is 0.5-1:1, and the molar ratio of the ligand formed by the alpha-hydroxy organic acid to the alpha-amino acid and the analogues thereof to the divalent metal is 1:1-2.
Further, when the α -hydroxy organic acid is citric acid, the molar ratio of the α -hydroxy organic acid to the amino acid and analogs thereof is 1:1, and the molar ratio of the ligand to the divalent metal compound is 1:1.
Further, when the α -hydroxy organic acid is malic acid, the molar ratio of the α -hydroxy organic acid to the amino acid and analogues thereof is 0.5:1, and the molar ratio of the ligand to the divalent metal compound is 1.5:1.
Further, when the α -hydroxy organic acid is gluconic acid, the molar ratio of the α -hydroxy organic acid to the amino acid and the analogues thereof is 1:1, and the molar ratio of the divalent metal compound to the ligand is 2:1.
In a further aspect, the invention provides the use of the above-mentioned alpha-hydroxy organic acid-amino acid and analogues thereof as an additive in the preparation of aquatic feed or poultry feed.
The invention has the following beneficial effects:
(1) Compared with the monomer free amino acid, inorganic divalent metal salt and single alpha-hydroxy organic acid metal salt, the alpha-hydroxy organic acid-amino acid and analogue divalent metal salt compound has a special structure, the water solubility of the alpha-hydroxy organic acid-amino acid and analogue divalent metal salt compound is obviously reduced (the solubility of the alpha-hydroxy organic acid-amino acid and analogue divalent metal salt compound is less than 1.5 g/100 ml of water (20 ℃)), the dissolution loss of amino acid, alpha-hydroxy organic acid and divalent metal ions in the feed in the water environment is avoided, the water pollution is further avoided, and the damage of divalent metal to vitamins and aliphatic compounds in the feed is avoided.
(2) The alpha-hydroxy organic acid-amino acid and analogue divalent metal salt compound can be used as an alpha-hydroxy organic acid supplement, can be used as an amino acid supplement and a metal element supplement, is flexibly matched, and can greatly reduce the use of divalent metal elements in aquatic feeds and poultry feeds, reduce the feed cost, improve the bioavailability of the divalent metal elements, reduce the metal content in livestock manure and reduce the environmental pollution.
(3) Compared with the traditional single amino acid complex (chelate) divalent metal salt, the alpha-hydroxy organic acid-amino acid and analogue divalent metal salt compound of the invention takes the alpha-hydroxy organic acid as a base segment, can flexibly combine with other amino acids and analogues thereof, has simple synthesis and better effect than the single alpha-hydroxy organic acid or amino acid complex (chelate) divalent metal salt.
Drawings
FIG. 1 is a general structure of an α -hydroxy organic acid-amino acid and its analog divalent metal co-salt compound of the present invention;
FIG. 2 is a synthetic route diagram of the α -hydroxy organic acid-amino acid and its analog divalent metal co-salt compound of the present invention;
FIG. 3 is a chemical structure of a divalent metal co-salt compound of the present invention based on citric acid;
FIG. 4 is a chemical structure of a divalent metal co-salt compound of the present invention having malic acid as a base;
FIG. 5 shows the chemical structure of a divalent metal co-salt compound of the present invention having gluconic acid as a substrate.
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 divalent metal salt compound taking hydroxy methionine as a substrate has a general structure shown in figure 1, wherein M is metal and R in the general structure shown in figure 1 1 With alpha-hydroxy carboxyl groups to form alpha-hydroxy organic acids, or R 2 With the alpha-amino carboxyl group, to form alpha-amino acids and amino acid analogues, such as 2-hydroxy-4-methylthiobutanoic acid and taurine. Specifically, M is any one of calcium, magnesium, zinc, copper, iron and manganese, R 1 Can form any one of citric acid, malic acid and gluconic acid with alpha-hydroxy carboxyl; r is R 2 And the alpha-amino carboxyl group forms any one of glycine, D, L-methionine, L-threonine, L-lysine, L-glutamic acid, L-tryptophan, L-phenylalanine, L-isoleucine, L-leucine and L-valine. The molar ratio of the alpha-hydroxy organic acid to the amino acid in the divalent metal salt compound taking the alpha-hydroxy organic acid as the substrate is 0.5:1 or 1:1, the molar ratio of the ligand to the divalent metal is 1:1-2, and the number of crystal water in the compound is 0-2. The preparation method of the divalent metal co-salt compound of alpha-hydroxy organic acid-amino acid and the analogues thereof of the present invention follows the reaction route shown in fig. 2. Specific preparation methods are shown in examples 1-20.
EXAMPLE 1 preparation of calcium citrate-glycinate Co-salt
194.07 g (1.0 mol) of anhydrous citric acid crystal with the mass percent of 99% and 580 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and citric acid is completely dissolved, so that a citric acid aqueous solution with the mass percent of 24.82% is obtained. 116.67 g (2.0 mol) of calcium oxide powder with the mass percent of 96% is added into the citric acid aqueous solution, the reaction temperature is raised to 80 ℃, the reaction is carried out for 1h under the condition of heat preservation and stirring, and the pH value of the reaction system is 12, thus obtaining the milky calcium citrate aqueous solution. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the calcium citrate aqueous solution, the temperature is raised to 100 ℃, the temperature is kept, the stirring reaction is carried out for 2 hours, the pH value of the reaction system is 9, and the citric acid-calcium glycinate compound aqueous solution is obtained. The obtained aqueous solution of the citric acid-calcium glycine co-salt compound is directly concentrated to be solid under reduced pressure, then all the aqueous solution is transferred into a tray, and the tray is put into a blast drying oven at 105 ℃ to be dried to constant weight, thus 386.87 g of white solid powder of the citric acid-calcium glycine co-salt compound is obtained, the mass percentage of calcium in the product is 20.68%, and the yield is calculated to be 100%.
EXAMPLE 2 preparation of magnesium citrate-glycinate Co-salt
194.07 g (1.0 mol) of anhydrous citric acid crystal with the mass percent of 99% and 580 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and citric acid is completely dissolved, so that a citric acid aqueous solution with the mass percent of 24.82% is obtained. 81.42 g (2.0 mol) of magnesium oxide powder with the mass percent of 99% is added into the citric acid aqueous solution, the reaction temperature is raised to 75 ℃, the reaction is carried out for 1h under the condition of heat preservation and stirring, and the pH value of the reaction system is 11, thus obtaining milky magnesium citrate aqueous solution. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the magnesium citrate aqueous solution, the temperature is raised to 100 ℃, the temperature is kept, the stirring reaction is carried out for 2 hours, the pH value of the reaction system is 8.0, and the citric acid-magnesium glycinate compound aqueous solution is obtained. The obtained aqueous solution of the citric acid-magnesium glycinate compound is directly concentrated to be solid under reduced pressure, then all the aqueous solution is transferred into a tray, and the tray is put into a blast drying oven at 105 ℃ to be dried to constant weight, thus 354.21 g of white solid powder of the citric acid-magnesium glycinate compound is obtained, the mass percentage of magnesium in the product is 13.55%, and the yield is calculated to be 100%.
EXAMPLE 3 preparation of Zinc citrate-glycinate Co-salts
194.07 g (1.0 mol) of anhydrous citric acid crystal with the mass percent of 99% and 580 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and citric acid is completely dissolved, so that a citric acid aqueous solution with the mass percent of 24.82% is obtained. 164.42 g (2.0 mol) of zinc oxide powder with the mass percent of 99% is added into the citric acid aqueous solution, the reaction temperature is raised to 100 ℃, the reaction is carried out for 3 hours under heat preservation and stirring, and the pH value of the reaction system is 8.5, thus obtaining milky zinc citrate aqueous solution. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the zinc citrate aqueous solution, the temperature is raised to 110 ℃, the temperature is kept, the stirring reaction is carried out for 4 hours, the pH of the reaction system is 6.5, and the citric acid-zinc glycinate compound aqueous solution is obtained. The obtained aqueous solution of the citric acid-zinc glycinate compound is directly concentrated to be solid under reduced pressure, then the solid solution is completely transferred into a tray, and the tray is put into a blast drying oven at 100 ℃ to be dried to constant weight, thus 442.40 g of white solid powder of the citric acid-zinc glycinate compound is obtained, the mass percentage of zinc in the product is 29.38%, and the yield is calculated to be 100%.
EXAMPLE 4 preparation of copper citrate-glycinate Co-salts
194.07 g (1.0 mol) of anhydrous citric acid crystal with the mass percent of 99% and 580 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and citric acid is completely dissolved, so that a citric acid aqueous solution with the mass percent of 24.82% is obtained. 201.03 g (2.0 mol) of copper hydroxide blue powder with the mass percent of 97% is added into the citric acid aqueous solution, the reaction temperature is increased to 95 ℃, the reaction is carried out for 0.5h under the condition of heat preservation and stirring, and the pH value of the reaction system is 7.5, thus obtaining blue cupric citrate aqueous solution. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the cupric citrate aqueous solution, the temperature is raised to 110 ℃, the temperature is kept, the stirring reaction is carried out for 1h, the pH value of the reaction system is 6.0, and the blue citric acid-cupric glycinate common salt compound aqueous solution is obtained. The obtained aqueous solution of the citric acid-copper glycinate compound is directly decompressed and concentrated to be solid, then the solid is completely transferred into a tray, and the tray is put into a blast drying oven at 100 ℃ to be dried to constant weight, 439.41 g of blue solid powder of the citric acid-zinc glycinate compound is obtained, the mass percentage of copper in the product is 28.93%, and the yield is calculated to be 100%.
EXAMPLE 5 preparation of citric acid-ferrous Glycine Co-salt
194.07 g (1.0 mol) of anhydrous citric acid crystal with the mass percent of 99% and 580 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and citric acid is completely dissolved, so that a citric acid aqueous solution with the mass percent of 24.82% is obtained. 238.87 g (2.0 mol) of ferrous carbonate white powder with the mass percent of 97% is added into the citric acid aqueous solution, the reaction temperature is raised to 85 ℃, the reaction is carried out for 2 hours with heat preservation and stirring, and the pH value of the reaction system is 7.5, thus obtaining a light yellow ferrous citrate aqueous solution. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the ferrous citrate aqueous solution, the temperature is raised to 95 ℃, the temperature is kept, the stirring reaction is carried out for 2 hours, the pH value of the reaction system is 6.0, and the yellowish citric acid-ferrous glycine co-salt compound aqueous solution is obtained. The obtained aqueous solution of the citric acid-ferrous glycine co-salt compound is directly concentrated to be solid under reduced pressure, then the solid solution is completely transferred into a tray, and the tray is put into a blast drying oven at 100 ℃ to be dried to constant weight, thus 432.77 g of the citric acid-ferrous glycine co-salt compound light yellow solid powder is obtained, the mass percentage of iron in the product is 25.88%, and the yield is calculated to be 100%.
EXAMPLE 6 preparation of citric acid-manganese Glycine Co-salt
194.07 g (1.0 mol) of anhydrous citric acid crystal with the mass percent of 99% and 580 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and citric acid is completely dissolved, so that a citric acid aqueous solution with the mass percent of 24.82% is obtained. To the aqueous solution of citric acid, 187.26 g (2.0 mol) of 95% by mass of white manganese hydroxide powder was added, the reaction temperature was raised to 85 ℃, and the mixture was stirred at a constant temperature for 2 hours to obtain a pale gray aqueous solution of manganese citrate with a pH of 7.0. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the manganese citrate aqueous solution, the temperature is raised to 95 ℃, the temperature is kept, the stirring reaction is carried out for 2 hours, the pH value of the reaction system is 5.5, and the light gray citric acid-manganese glycinate co-salt compound aqueous solution is obtained. The obtained aqueous solution of the citric acid-manganese glycinate compound is directly concentrated to be solid under reduced pressure, then the solid solution is completely transferred into a tray, and the tray is put into a blast drying oven at 100 ℃ to be dried to constant weight, thus 426.18 g of the off-white solid powder of the citric acid-manganese glycinate compound is obtained, the mass percentage of manganese in the product is 25.81%, and the yield is calculated to be 100%.
According to the above method, a citric acid-methionine salt compound, a citric acid-threonine salt compound, a citric acid-glutamic acid salt compound, a citric acid-lysine salt compound, a citric acid-tryptophan salt compound, a citric acid-phenylalanine salt compound, a citric acid-isoleucine salt compound, a citric acid-leucine salt compound, a citric acid-valine salt compound, a citric acid-2-hydroxy-4-methylthiobutanoic acid salt compound, a citric acid-taurine salt compound are prepared, respectively, the structures of the above divalent metal salt compounds using citric acid as a substrate are shown in fig. 3, and the preparation conditions and results are shown in the following table 1:
TABLE 1
EXAMPLE 7 preparation of calcium malate-glycinate Co-salt
67.72 g (0.5 mol) of anhydrous malic acid white crystal with the mass percent of 99% and 200 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and malic acid is completely dissolved, so that an aqueous solution of malic acid with the mass percent of 25.0% is obtained. 77.08 g (1.0 mol) of calcium hydroxide powder with the mass percent of 96% is added into the malic acid water solution, the reaction temperature is increased to 80 ℃, the reaction is carried out for 0.5h under the condition of heat preservation and stirring, and the pH value of the reaction system is 12, thus obtaining the milky calcium malate water solution. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the calcium malate aqueous solution, the temperature is raised to 100 ℃, the temperature is kept, the stirring reaction is carried out for 4 hours, the pH value of the reaction system is 8.5, and the malic acid-calcium glycinate compound aqueous solution is obtained. The obtained malic acid-calcium glycine co-salt compound aqueous solution is directly decompressed and concentrated to be solid, then the solid is completely transferred into a tray, and is put into a blast drying oven at 105 ℃ to be dried to constant weight, 190.05 g of malic acid-calcium glycine co-salt compound white solid powder is obtained, the mass percentage of calcium in the product is 21.05%, and the yield is calculated to be 100%.
EXAMPLE 8 preparation of malic acid-magnesium Glycine Co-salt
67.72 g (0.5 mol) of anhydrous malic acid white crystal with the mass percent of 99% and 200 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and malic acid is completely dissolved, so that an aqueous solution of malic acid with the mass percent of 25.0% is obtained. 63.04 g (1.0 mol) of 92% magnesium hydroxide powder is added into the malic acid aqueous solution, the reaction temperature is raised to 85 ℃, the mixture is stirred and reacted for 1h while keeping the temperature, and the pH of the reaction system is 12, thus obtaining a milky magnesium malate aqueous solution. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the magnesium malate aqueous solution, the temperature is raised to 100 ℃, the temperature is kept, the stirring reaction is carried out for 2 hours, the pH value of the reaction system is 8.0, and the malic acid-magnesium glycinate compound aqueous solution is obtained. The obtained malic acid-magnesium glycinate compound aqueous solution is directly decompressed and concentrated to be solid, then the solid is completely transferred into a tray, and the tray is put into a blast drying oven at 100 ℃ to be dried to constant weight, 169.63 g of malic acid-magnesium glycinate compound white solid powder is obtained, the mass percentage of magnesium in the product is 14.15%, and the yield is calculated to be 100%.
EXAMPLE 9 preparation of malic acid-Zinc glycinate Co-salt
67.72 g (0.5 mol) of anhydrous malic acid white crystal with the mass percent of 99% and 200 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and malic acid is completely dissolved, so that an aqueous solution of malic acid with the mass percent of 25.0% is obtained. 101.45 g (1.0 mol) of zinc hydroxide powder with the mass percent of 98% is added into the malic acid water solution, the reaction temperature is raised to 85 ℃, the reaction is carried out for 2 hours under heat preservation and stirring, and the pH value of the reaction system is 8.0, thus obtaining milky zinc malate water solution. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the zinc malate aqueous solution, the temperature is raised to 110 ℃, the temperature is kept, the stirring reaction is carried out for 2 hours, the pH of the reaction system is 6.5, and the malic acid-zinc glycinate compound aqueous solution is obtained. The obtained malic acid-zinc glycinate compound aqueous solution is directly decompressed and concentrated to be solid, then the solid is completely transferred into a tray, and the tray is put into a blast drying oven at 100 ℃ to be dried to constant weight, 209.23 g of malic acid-zinc glycinate compound white solid powder is obtained, the mass percentage of zinc in the product is 31.07%, and the yield is calculated to be 100%.
EXAMPLE 10 preparation of copper malate-glycinate Co-salt
67.72 g (0.5 mol) of anhydrous malic acid white crystal with the mass percent of 99% and 200 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and malic acid is completely dissolved, so that an aqueous solution of malic acid with the mass percent of 25.0% is obtained. 80.35 g (1.0 mol) of copper oxide black powder with the mass percent of 99% is added into the malic acid water solution, the reaction temperature is raised to 85 ℃, the reaction is carried out for 2 hours under heat preservation and stirring, and the pH value of the reaction system is 7.5, thus obtaining the blue copper malate water solution with black precipitate. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the copper malate aqueous solution, the temperature is raised to 110 ℃, the temperature is kept, the stirring reaction is carried out for 4 hours, the pH value of the reaction system is 6.0, and the blue malic acid-copper glycinate co-salt compound aqueous solution is obtained. The obtained malic acid-copper glycinate compound aqueous solution is directly decompressed and concentrated to be solid, then the solid is completely transferred into a tray, and the tray is put into a blast drying oven at 105 ℃ to be dried to constant weight, 209.84 g of malic acid-copper glycinate compound blue solid powder is obtained, the mass percentage of copper in the product is 30.26%, and the yield is calculated to be 100%.
EXAMPLE 11 preparation of malic acid-ferrous Glycine Co-salt
67.72 g (0.5 mol) of anhydrous malic acid white crystal with the mass percent of 99% and 200 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and malic acid is completely dissolved, so that an aqueous solution of malic acid with the mass percent of 25.0% is obtained. 72.73 g (1.0 mol) of ferrous oxide black powder with the mass percent of 99 percent is added into the malic acid water solution, the reaction temperature is raised to 70 ℃, the reaction is carried out for 1h under the condition of heat preservation and stirring, and the pH value of the reaction system is 7.5, thus obtaining the yellowish ferrous malate water solution with black sediment. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the ferrous malate aqueous solution, the temperature is raised to 70 ℃, the temperature is kept, the stirring reaction is carried out for 2 hours, the pH value of the reaction system is 7.0, and the yellowish malic acid-ferrous glycinate compound aqueous solution is obtained. The obtained malic acid-ferrous glycine co-salt compound aqueous solution is directly decompressed and concentrated to be solid, then the solid is completely transferred into a tray, and is put into a blast drying oven at 105 ℃ to be dried to constant weight, 204.21 g of malic acid-ferrous glycine co-salt compound blue solid powder is obtained, the mass percentage of iron in the product is 27.42%, and the yield is calculated to be 100%.
EXAMPLE 12 preparation of citric acid-manganese Glycine Co-salt
67.72 g (0.5 mol) of anhydrous malic acid white crystal with the mass percent of 99% and 200 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and malic acid is completely dissolved, so that an aqueous solution of malic acid with the mass percent of 25.0% is obtained. 71.65 g (1.0 mol) of manganese monoxide gray green powder with the mass percent of 99% is added into the malic acid water solution, the reaction temperature is increased to 90 ℃, the reaction is carried out for 4 hours under the condition of heat preservation and stirring, and the pH value of the reaction system is 7.0, thus obtaining the light gray manganese malate water solution. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the manganese malate aqueous solution, the temperature is raised to 100 ℃, the temperature is kept, the stirring reaction is carried out for 2 hours, the pH value of the reaction system is 6.0, and the light gray malic acid-manganese glycinate co-salt compound aqueous solution is obtained. The obtained malic acid-manganese glycinate compound aqueous solution is directly decompressed and concentrated to be solid, then the solid is completely transferred into a tray, and the tray is put into a blast drying oven at 100 ℃ to be dried to constant weight, 201.08 g of malic acid-manganese glycinate compound off-white solid powder is obtained, the mass percentage of manganese in the product is 27.35%, and the yield is calculated to be 100%.
The structures of the malic acid-methionine co-salt compound, the malic acid-threonine co-salt compound, the malic acid-glutamic acid co-salt compound, the malic acid-lysine co-salt compound, the malic acid-tryptophan co-salt compound, the malic acid-phenylalanine co-salt compound, the malic acid-isoleucine co-salt compound, the malic acid-leucine co-salt compound, the malic acid-valine co-salt compound, the malic acid-2-hydroxy-4-methylthiobutanoic acid co-salt compound, and the malic acid-taurine co-salt compound are shown in fig. 4, and the preparation conditions and the results are shown in the following table 2:
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TABLE 2
EXAMPLE 13 preparation of calcium gluconate-glycinate Co-salts
198.14 g (1.0 mol) of anhydrous gluconic acid crystal with the mass percent of 99% and 580 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and the gluconic acid is completely dissolved, so as to obtain an aqueous solution of the gluconic acid with the mass percent of 25.21%. 101.0 g (1.0 mol) of calcium carbonate powder with the mass percent of 99 percent is added into the gluconic acid aqueous solution, the reaction temperature is increased to 90 ℃, the temperature is kept, the stirring reaction is carried out for 3 hours, the pH of the reaction system is 7.5, and the milky white calcium gluconate aqueous solution is obtained. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the calcium gluconate aqueous solution, the temperature is raised to 110 ℃, the temperature is kept, the stirring reaction is carried out for 4 hours, the pH value of the reaction system is 7.0, and the calcium gluconate-calcium glycinate compound aqueous solution is obtained. The obtained aqueous solution of the citric acid-calcium glycine co-salt compound is directly concentrated to be solid under reduced pressure, then all the aqueous solution is transferred into a tray, and the tray is put into a blast drying oven at 105 ℃ to be dried to constant weight, thus 344.37 g of white solid powder of the gluconic acid-calcium glycine co-salt compound is obtained, the mass percentage of calcium in the product is 11.61%, and the yield is calculated to be 100%.
EXAMPLE 14 preparation of magnesium gluconate-glycinate Co-salt
198.14 g (1.0 mol) of anhydrous gluconic acid crystal with the mass percent of 99% and 580 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and the gluconic acid is completely dissolved, so as to obtain an aqueous solution of the gluconic acid with the mass percent of 25.21%. 63.04 g (1.0 mol) of 92% magnesium hydroxide powder is added into the aqueous solution of gluconic acid, the reaction temperature is increased to 90 ℃, the mixture is stirred and reacted for 1h while keeping the temperature, and the pH of the reaction system is 12, thus obtaining the milky aqueous solution of magnesium gluconate. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the magnesium gluconate aqueous solution, the temperature is raised to 100 ℃, the temperature is kept, the stirring reaction is carried out for 2 hours, the pH value of the reaction system is 7.5, and the magnesium gluconate-glycinate compound aqueous solution is obtained. The obtained aqueous solution of the citric acid-magnesium glycinate compound is directly concentrated to be solid under reduced pressure, then all the aqueous solution is transferred into a tray, and the tray is put into a blast drying oven at 105 ℃ to be dried to constant weight, thus 317.51 g of white solid powder of the gluconic acid-magnesium glycinate compound is obtained, the mass percentage of magnesium in the product is 7.6%, and the yield is calculated to be 100%.
EXAMPLE 15 preparation of gluconic acid-zinc glycinate Co-salt
198.14 g (1.0 mol) of anhydrous gluconic acid crystal with the mass percent of 99% and 580 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and the gluconic acid is completely dissolved, so as to obtain an aqueous solution of the gluconic acid with the mass percent of 25.21%. 82.20 g (1.0 mol) of zinc oxide powder with the mass percent of 99 percent is added into the aqueous solution of the gluconic acid, the reaction temperature is raised to 100 ℃, the temperature is kept, the stirring reaction is carried out for 3 hours, the pH of the reaction system is 8.0, and the milky aqueous solution of the zinc gluconate is obtained. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the zinc gluconate aqueous solution, the temperature is raised to 100 ℃, the temperature is kept, the stirring reaction is carried out for 3 hours, the pH of the reaction system is 6.5, and the zinc gluconate-zinc glycinate compound aqueous solution is obtained. The obtained aqueous solution of the citric acid-zinc glycinate compound is directly concentrated to be solid under reduced pressure, then all the aqueous solution is transferred into a tray, and the tray is put into a blast drying oven at 105 ℃ to be dried to constant weight, thus 360.36 g of white solid powder of the gluconic acid-zinc glycinate compound is obtained, the mass percentage of zinc in the product is 18.04%, and the yield is calculated to be 100%.
EXAMPLE 16 preparation of copper gluconate-glycinate Co-salts
198.14 g (1.0 mol) of anhydrous gluconic acid crystal with the mass percent of 99% and 580 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and the gluconic acid is completely dissolved, so as to obtain an aqueous solution of the gluconic acid with the mass percent of 25.21%. 80.35 g (1.0 mol) of copper oxide black powder with the mass percent of 99 percent is added into the aqueous solution of the gluconic acid, the reaction temperature is raised to 100 ℃, the temperature is kept, the stirring reaction is carried out for 3 hours, the pH value of the reaction system is 7.5, and the blue aqueous solution of the copper gluconate with black sediment is obtained. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the copper gluconate aqueous solution, the temperature is raised to 100 ℃, the temperature is kept, the stirring reaction is carried out for 3 hours, the pH value of the reaction system is 6.5, and the copper gluconate-glycinate compound aqueous solution is obtained. The obtained aqueous solution of the citric acid-copper glycinate compound is directly concentrated to be solid under reduced pressure, then all the aqueous solution is transferred into a tray, and the tray is put into a blast drying oven at 105 ℃ to be dried to constant weight, thus 361.50 g of blue solid powder of the gluconic acid-copper glycinate compound is obtained, the mass percentage of copper in the product is 17.56%, and the yield is calculated to be 100%.
EXAMPLE 17 preparation of gluconic acid-ferrous Glycine Co-salt
198.14 g (1.0 mol) of anhydrous gluconic acid crystal with the mass percent of 99% and 580 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and the gluconic acid is completely dissolved, so as to obtain an aqueous solution of the gluconic acid with the mass percent of 25.21%. 72.73 g (1.0 mol) of ferrous oxide black powder with the mass percent of 99 percent is added into the gluconic acid aqueous solution, the reaction temperature is increased to 80 ℃, the reaction is carried out for 3 hours under the condition of heat preservation and stirring, and the pH value of the reaction system is 7.0, thus obtaining the light yellow ferrous gluconate aqueous solution with black sediment. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the ferrous gluconate aqueous solution, the temperature is raised to 100 ℃, the temperature is kept, the stirring reaction is carried out for 3 hours, the pH value of the reaction system is 6.5, and the aqueous solution of the gluconic acid-ferrous glycinate compound is obtained. The obtained aqueous solution of the citric acid-ferrous glycine co-salt compound is directly concentrated to be solid under reduced pressure, then all the aqueous solution is transferred into a tray, and the tray is put into a blast drying oven at 105 ℃ to be dried to constant weight, thus 353.77 g of pale yellow solid powder of the gluconic acid-ferrous glycine co-salt compound is obtained, the mass percentage of iron in the product is 15.83%, and the calculated yield is 100%.
EXAMPLE 18 preparation of gluconic acid-manganese glycinate Co-salt
198.14 g (1.0 mol) of anhydrous gluconic acid crystal with the mass percent of 99% and 580 g of deionized water are weighed into a reaction bottle with a stirrer, stirred and heated to 50 ℃, and the gluconic acid is completely dissolved, so as to obtain an aqueous solution of the gluconic acid with the mass percent of 25.21%. 93.63 g (1.0 mol) of white manganese hydroxide powder with the mass percent of 95 percent is added into the aqueous solution of the gluconic acid, the reaction temperature is increased to 80 ℃, the reaction is carried out for 3 hours under the condition of heat preservation and stirring, and the pH value of the reaction system is 7.5, thus obtaining the aqueous solution of the manganese gluconate with light green precipitation. 75.76 g (1.0 mol) of glycine crystal with the mass percent of 99 percent is added into the manganese gluconate aqueous solution, the temperature is raised to 100 ℃, the temperature is kept, the stirring reaction is carried out for 3 hours, the pH value of the reaction system is 6.0, and the aqueous solution of the gluconic acid-manganese glycinate compound is obtained. The obtained citric acid-manganese glycinate compound aqueous solution is directly concentrated to be solid under reduced pressure, then all the solid solution is transferred into a tray, and the tray is put into a blast drying oven at 105 ℃ to be dried to constant weight, thus 356.41 g of off-white solid powder of the gluconic acid-manganese glycinate compound is obtained, the mass percentage of manganese in the product is 15.43%, and the yield is calculated to be 100%.
The structures of the gluconic acid-methionine salt compound, the gluconic acid-threonine salt compound, the gluconic acid-glutamic acid salt compound, the gluconic acid-lysine salt compound, the gluconic acid-tryptophan salt compound, the gluconic acid-phenylalanine salt compound, the gluconic acid-isoleucine salt compound, the gluconic acid-leucine salt compound, the gluconic acid-valine salt compound, the malic acid-2-hydroxy-4-methylthiobutanoic acid salt compound and the gluconic acid-taurine salt compound, which are shown in the figure 5, are prepared under the following conditions and with the following results
The table 3 describes:
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TABLE 3 Table 3
In tables 1 to 3, the values before the slash are the temperature, time and pH at which the α -hydroxy organic acid reacts with the divalent metal compound in the first reaction, and the values after the slash are the temperature, time and pH at which the α -amino acid and the like are added in the second reaction. The products prepared in examples 1-18 were tested for solubility and were found to all have a solubility of less than 1.5 g/100 ml water (20 ℃).
Example 19: biological effect experimental comparison of divalent Metal Co-salt Compounds of partial alpha-hydroxy organic acids-amino acids and analogs thereof
The rainbow trout is taken as an experimental feeding target, and free amino acids (calcium salt compounds and magnesium salt compounds are not microelements, so that the comparison is mainly free amino acids) and inorganic salt microelements are taken as comparison. The rainbow trout is fed by using the divalent metal trace element co-salt compound of the trace elements in the form of sulfate and the alpha-hydroxy organic acid-amino acid and analogues thereof respectively, and the result shows that: the deposition amount of trace elements in divalent metal trace element co-salt compounds of alpha-hydroxy organic acid-amino acid and analogues thereof is significantly higher than that of inorganic salt groups. The effective utilization rate of amino acids for alpha-hydroxy organic acid-amino acid and its analog calcium co-salt compound and alpha-hydroxy organic acid-amino acid and its analog magnesium co-salt compound is significantly higher than that of the free amino acid group. The experimental results are shown in Table 4.
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TABLE 4 Table 4
Example 20: experiment of stability of partial alpha-hydroxy organic acid-amino acid and its analog divalent Metal Co-salt Compound against vitamin A and B1
The effect of trace elements in the premix on vitamin A and B1 stability is shown in Table 5.
TABLE 5
The data in table 5 shows that the alpha-hydroxy organic acid-amino acid and its analog divalent metal co-salt compounds of the present invention are less damaging to vitamins a and B1 than the inorganic salt group and significantly reduce the loss of vitamins a and B1 in the premix.
In conclusion, the alpha-hydroxy organic acid-amino acid and analogue divalent metal salt compound thereof has higher bioavailability, can avoid the dissolution loss of amino acid and alpha-hydroxy organic acid in feed in water environment, further avoid water pollution, and avoid the damage of divalent metal to vitamins and fatty compounds in feed, and can be applied to aquatic feed or poultry feed as an additive.
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 (9)

1. An α -hydroxy organic acid-amino acid and analogs thereof divalent metal co-salt compound, characterized in that said divalent metal co-salt compound has the general structure:
wherein M is any one of calcium, magnesium, zinc, copper, iron and manganese; r is R 1 Can form an alpha-hydroxy organic acid with an alpha-hydroxy carboxyl group, R 2 Can form alpha-amino acid and amino acid analogues thereof with alpha-amino carboxyl, x is 0.5 or 1, y is 1 or 2, and z is 0-2.
2. The α -hydroxy organic acid-amino acid and analog divalent metal co-salt compound according to claim 1, wherein the α -hydroxy organic acid is any one of citric acid, malic acid, gluconic acid;
the alpha-amino acid is any one of glycine, D, L-methionine, L-threonine, L-glutamic acid, L-lysine, L-tryptophan, L-phenylalanine, L-isoleucine, L-leucine and L-valine;
the amino acid analogue is any one of 2-hydroxy-4-methylthiobutanoic acid and taurine.
3. A process for the preparation of divalent metal co-salt compounds of α -hydroxy organic acids-amino acids and analogues thereof, said process comprising the steps of:
reacting the alpha-hydroxy organic acid aqueous solution with the divalent metal compound for 0.5-3 h at the reaction temperature of 60-100 ℃ and the pH value of 7.0-12 to obtain a mixed aqueous solution of the divalent metal salt of the alpha-hydroxy organic acid and the divalent metal compound;
adding alpha-amino acid and analogues thereof into the mixed aqueous solution of the divalent metal salt and the divalent metal compound of the alpha-hydroxy organic acid, and reacting for 1-4 hours at the reaction temperature of 70-110 ℃ with the pH value of 6.0-11 to obtain the mixed aqueous solution of the divalent metal co-salt compound of the alpha-hydroxy organic acid-amino acid and analogues thereof;
concentrating the mixed aqueous solution of the alpha-hydroxy organic acid-amino acid and the analogue divalent metal co-salt compound to be solid under reduced pressure, drying to be constant weight, grinding and sieving to obtain the alpha-hydroxy organic acid-amino acid and the analogue divalent metal co-salt compound.
4. A method of preparation according to claim 3, wherein the divalent metal compound is an oxide or hydroxide or carbonate of any one of calcium, magnesium, zinc, copper, iron, manganese.
5. The method according to claim 3, wherein the molar ratio of the α -hydroxy organic acid to the α -amino acid and the like is 0.5 to 1:1, and the molar ratio of the ligand consisting of the α -hydroxy organic acid to the α -amino acid and the like to the divalent metal is 1:1 to 2.
6. The method according to claim 5, wherein when the α -hydroxy organic acid is citric acid, the molar ratio of the α -hydroxy organic acid to the amino acid and the like is 1:1, and the molar ratio of the ligand to the divalent metal compound is 1:1.
7. The method according to claim 5, wherein when the α -hydroxy organic acid is malic acid, the molar ratio of the α -hydroxy organic acid to the amino acid and the analogues thereof is 0.5:1, and the molar ratio of the ligand to the divalent metal compound is 1.5:1.
8. The method according to claim 5, wherein when the α -hydroxy organic acid is gluconic acid, the molar ratio of the α -hydroxy organic acid to the amino acid and the analogues thereof is 1:1, and the molar ratio of the divalent metal compound to the ligand is 2:1.
9. Use of an α -hydroxy organic acid-amino acid and its analogue divalent metal co-salt compound according to claim 1 or 2 or prepared according to the preparation method of any one of claims 3-8 as an additive in the preparation of aquatic feed or poultry feed.
CN202310341680.2A 2023-03-31 2023-03-31 Alpha-hydroxy organic acid-amino acid and analogue divalent metal co-salt compound thereof, and preparation method and application thereof Pending CN116573999A (en)

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