CN110128307B - A kind of preparation method of stable amino acid ferrous complex - Google Patents
A kind of preparation method of stable amino acid ferrous complex Download PDFInfo
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- CN110128307B CN110128307B CN201910504897.4A CN201910504897A CN110128307B CN 110128307 B CN110128307 B CN 110128307B CN 201910504897 A CN201910504897 A CN 201910504897A CN 110128307 B CN110128307 B CN 110128307B
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- GIPOFCXYHMWROH-UHFFFAOYSA-L 2-aminoacetate;iron(2+) Chemical compound [Fe+2].NCC([O-])=O.NCC([O-])=O GIPOFCXYHMWROH-UHFFFAOYSA-L 0.000 description 2
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- YHGPYBQVSJBGHH-UHFFFAOYSA-H iron(3+);trisulfate;pentahydrate Chemical compound O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YHGPYBQVSJBGHH-UHFFFAOYSA-H 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公布了一种稳定的氨基酸亚铁配合物的制备方法，在优化的氨基酸与亚铁盐按1:1摩尔比在铁粉存在下于水体系的条件下制备氨基酸亚铁配合物，通过使用一种助剂达到调节pH、消化铁粉、二次络合或螯合游离亚铁作用，使得所得反应液喷雾干燥后得到一种稳定的氨基酸亚铁配合物，具有高水平的亚铁含量和低水平的氧化率（三价铁含量），并在水溶液中具有较好的抗氧化能力，体现了优异的稳定性，提高了亚铁配合物产品在储运使用过程的抗氧化能力，有利于亚铁产品的高效利用。在本方法制备过程，优化了铁粉过滤和加无机酸消化铁粉步骤，无三废产生清洁可持续，额外地，使用的一种助剂还可提供有利的营养成分。The invention discloses a method for preparing a stable ferrous amino acid complex. The amino acid ferrous complex is prepared in the presence of iron powder in a water system with an optimized amino acid and ferrous salt in a molar ratio of 1:1. Use an auxiliary agent to adjust pH, digest iron powder, secondary complex or chelate free ferrous iron, so that after the obtained reaction solution is spray-dried, a stable amino acid ferrous complex with a high level of ferrous iron content is obtained and low level of oxidation rate (ferric iron content), and has good antioxidant capacity in aqueous solution, which reflects excellent stability and improves the antioxidant capacity of ferrous complex products during storage, transportation and use. Conducive to the efficient utilization of ferrous products. In the preparation process of the method, the steps of iron powder filtration and addition of inorganic acid to digest iron powder are optimized, no three wastes are produced, clean and sustainable, and additionally, an auxiliary agent used can also provide favorable nutrients.
Description
Technical Field
The invention belongs to the field of organic compound synthesis, and particularly relates to a preparation method of a stable amino acid ferrous complex.
Background
Ferrous iron is a necessary trace element for human and animals, is a component of hemoglobin, and can cause iron deficiency anemia in animals if food or feed is deficient. The traditional method adopts ferrous inorganic salt as a feed additive, and has the defects of instability in the adding process, easiness in oxidation, low absorption efficiency, large addition amount, low biological value, environment pollution caused by the discharge of most of excrement and the like, and animals need to pass through various biological barriers for absorption and utilization.
The ferrous amino acid complex or chelate is a ferrous mono-five-membered ring complex formed by ferrous ions and hydroxyl in amino groups and carboxyl groups in amino acids, while the ferrous bi-five-membered ring is a ferrous chelate, and the specific complex structure enables the intramolecular electrons to tend to be neutral, is easy to absorb and utilize in small intestines, and is a new generation feed additive. The amino acid ferrous chelate has an extremely stable double five-membered ring structure, is relatively stable in organisms, is not easy to interfere and antagonize with other feed raw materials or trace elements, has no anion interference, has higher purity, and is a good ferrous nutrient. Ferrous amino acid complexes also have unique advantages over ferrous amino acid chelates, with the single five-membered ring structure also having good stability but less molecular weight, and studies have shown (kirchgessner et al, 1967) that in a conjugate of an amino acid and a metal, the smaller the number of amino acids (the smaller the molecular weight), the better the absorption; meanwhile, the premise that the ferrous nutrient is absorbed and utilized by animals is that the compound must be dissolved in water within the physiological pH range of the animal body, and the amino acid ferrous complex is easily dissolved in water and has excellent solubility at the physiological pH of 2.0-7.4.
Except for the reaction temperature, the reaction time, the raw material proportion and the like, the preparation of the amino acid ferrous complex and the chelate has the difficulties that the oxidation resistance of ferrous ions is realized, and the strong reducibility of the ferrous ions ensures that the ferrous ions are easily oxidized into ferric iron which is not utilized by an object, so the preparation process generally carries out deoxidation protection and uses an antioxidant. The earliest antioxidant mode has nitrogen protection in the reaction process and the addition of reducing antioxidants such as hydroxylamine hydrochloride, ascorbic acid, etc., which finally become impurities in the product and are not good for the product quality. Then, the reduced iron powder and carbonyl iron powder are used as reducing agents to reduce ferric iron in the system, and redundant reduced iron is filtered and removed. However, the iron powder impurity liquid which is filtered out is oxidized due to contact with air, and is difficult to be directly utilized, and a small amount of iron powder needs to be filtered, so that the cost is increased. In addition, at present, no antioxidant process consideration exists in the storage and use processes of the amino acid ferrous complex product, and when the moisture absorption and humidity of the storage are increased and water is added during feeding, the oxidation probability and oxidation speed of the amino acid ferrous complex are greatly improved, so that the loss of effective ferrous is actually caused, but the loss is neglected.
Chinese patent CN106187797 discloses dissolving glycine and ferrous sulfate heptahydrate in water, adding a small amount of iron powder and a few drops of concentrated sulfuric acid, rotating and reacting at 70-90 ℃ for 30-60 min, cooling to 50-65 ℃, crystallizing, filtering, washing the crystallized solid with absolute ethyl alcohol, and drying to obtain the product. The iron powder is added into the patent, concentrated sulfuric acid is added into the iron powder, the iron powder is digested by the added sulfuric acid, the acid and the iron powder can preferentially react at the moment, the added iron powder cannot play an anti-oxidation role at all, and the filtering step is omitted, so that the process is meaningless. Meanwhile, the dissolved iron powder causes relatively excessive free iron ions, and is more easily oxidized in the subsequent preparation process and the storage period to cause the quality reduction of products.
Chinese patent CN107118115 discloses that after glycine is dissolved in water, 0.1-5 per mill of ferrous carbonyl is added, the mixture is stirred at 50-70 ℃ for 10-30 min to remove dissolved oxygen, then ferrous sulfate heptahydrate with 0.95-1.1 molar proportion of glycine, maltodextrin with the weight of 10-50% of glycine and 0.1-5 per mill of silicon dioxide are added, the mixture is stirred and reacted at 50-85 ℃ for 20-40 min, and the reaction solution is filtered and then spray-dried to obtain the product. According to the patent, carbonyl iron powder is used as a deoxidizer and a reducing agent, dissolved oxygen in solvent water is considered, and removal of the dissolved oxygen is beneficial to reduction of oxidation in a ferrous reaction process, but in a glycine solution with the mass fraction of 20-25%, a considerable amount of carbonyl iron powder is directly consumed by reaction with hydrogen ions during heating deoxidation, and cannot well play a role in oxidation resistance. In addition, maltodextrin and silicon dioxide are added into the product, so that the effective content of the product is reduced, and the addition amount of the product in use is increased.
US4067994 discloses the synthesis of methionine iron complex salt with the mol ratio of methionine to iron element of 1:1 by methionine and ferrous, ferric sulfate or hydrochloride in 60 deg.C water solution. The method disclosed in the patent does not consider the problem of oxidation resistance of ferrous ions, and ferric iron is used as an effective component of the product, so the ferrous content is low. It is widely believed that the absorption of iron by animals is primarily ferrous, while there is little absorption of ferric.
Chinese patent CN1112115 discloses that hydroxy methionine and ferrous inorganic salt are reacted for 0.8 to 1.2 hours in 50 to 100 ℃ aqueous solution by adjusting the pH of the system to be 6 to 8 with sodium hydroxide according to the molar ratio of 1:1 to 2, and then cooled and centrifugally separated to obtain a hydroxy methionine ferrous product. The method disclosed in the patent uses hydroxymethionine and ferrous sulfate as main complexing raw materials, and prepares the ferrous hydroxymethionine after adjusting alkali. Hydroxymethionine is a methionine analogue in which the amino group of methionine is substituted with a hydroxyl group, and has a methionine-like nutritional effect. However, the hydroxyl of the hydroxy methionine is weaker than the amino in complexing stability, the liquid methionine is stronger in acidity, and hydrogen ions and ferrous iron compete. The pH adjustment by using sodium hydroxide can enhance the complexation reaction of liquid methionine, but the adjustment process has the defects that the local pH is too large, so that ferrous iron is easy to oxidize, and in addition, sodium sulfate wastewater is generated.
Generally, besides the above preparation processes mainly facing the improvement of effective ferrous iron content by oxidation resistance and the environmental protection of products and production processes, the stability of the products during drying, storage, transportation and use is also considered at present. Particularly, some amino acid ferrous complex products which are easy to absorb moisture not only have poor caking and poor flowability after absorbing moisture, but also are easy to be instable and oxidized, such as ferrous glycine complexes and hydroxymethionine complexes, so the stability of the storage process of the amino acid ferrous complex products needs to be considered.
In summary, the current preparation technology of ferrous amino acid complexes mainly has the following problems:
(1) the preparation process using water as a solvent does not consider the removal of impurity ions and the removal of dissolved oxygen in water, which increases the difficulty and workload of ferrous oxidation resistance in the subsequent preparation process.
(2) Antioxidant selection or use presents problems, such as: heterogeneous antioxidants such as hydroxylamine hydrochloride and ascorbic acid are used to bring in the final product to influence the product quality; when iron powder is used as a reducing agent, the iron powder needs to be filtered to remove unreacted iron powder and recovered iron powder and is difficult to utilize, or the iron powder is preferentially contacted with acid or stronger acid, so that the iron powder is consumed and does not play an actual reducing role; all the above problems directly affect the quality and stability of the final product.
(3) Stability control of subsequent links such as storage, transportation and use of ferrous amino acid products is not considered (Chinese patent CN107118115 adds maltodextrin with 10-50% of weight of glycine to prevent moisture absorption in the storage and transportation process, but the problems are described above and the stability is not helpful when the feed additive is prepared for use).
(4) Part of the product preparation process also produces salt-containing wastewater.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a preparation method of a stable amino acid ferrous complex, which can remove impurity ions and dissolved oxygen in preparation water, greatly reduce the ferrous oxidation rate in the preparation process, improve the product quality and correspondingly reduce the dosage of antioxidant reduced iron powder.
The object of the invention is achieved in particular in that:
a preparation method of a stable amino acid ferrous complex is characterized by comprising the following steps:
(1) removing dissolved oxygen from preparation water, adding amino acid and ferrous salt, controlling the temperature to be 40-95 ℃, stirring until the amino acid and the ferrous salt are completely dissolved, adding reduced iron powder, and carrying out heat preservation reaction for 20-60 min;
(2) and after the reaction is finished, adding an auxiliary agent to control the pH to be = 2-5, stirring for 10-30 min, digesting residual reduced iron powder, directly or after concentrating the reaction solution, carrying out spray drying, collecting and packaging to obtain the finished product of the amino acid ferrous complex.
The auxiliary agent is 2-hydroxy-4-methylthiobutyric acid, but can also be replaced by lactic acid, fumaric acid, citric acid, tartaric acid and the like.
Further, the amino acid is one or more of methionine, threonine, glycine, leucine, serine, lysine and phenylalanine.
Further, the amino acid is methionine, glycine.
The dosage of the reduced iron powder is 0.001-0.01 of the molar weight of the ferrous salt.
The molar ratio of the amino acid to the ferrous salt is 0.9-1: 1, and the dosage of the auxiliary agent is 0.05-0.2 amino acid molar equivalent.
Further, the ferrous salt is ferrous sulfate, ferrous chloride and various hydrates thereof.
In particular, the means for removing dissolved oxygen by the preparation water is ultrasonic deoxidation, thermal deoxidation and/or nitrogen blowing.
Particularly, the preparation water is desalted water or softened water which is obtained by one or more water treatment means such as anion resin exchange, cation resin exchange, ultrafiltration, nanofiltration, reverse osmosis and the like and is free of impurity ions, and the water quality meets the requirement that the conductivity is 1-10 us/cm.
Compared with the prior art, the invention has the following advantages:
the method has the advantages that the oxidation risk of ferrous iron is reduced by removing impurity ions and dissolved oxygen in the prepared water, the reduced iron powder used as antioxidant is reserved to the later stage of reaction, 2-hydroxy-4-methylthiobutyric acid used as an auxiliary agent is used for digestion, the antioxidant function of the iron powder in the whole reaction process is guaranteed, meanwhile, filtering equipment and operation are optimized, the lower pH (2-5) is favorable for protecting the ferrous iron from being oxidized, a small amount of digested iron powder and the auxiliary agent form a stable chelate, and the obtained reaction liquid is subjected to spray drying and packaging to obtain the product. The whole process avoids the oxidation reaction of ferrous iron and oxidizing substances as far as possible, and ensures the high ferrous quality of the amino acid ferrous iron. Meanwhile, a certain amount of added auxiliary agent is used for digestion and chelation of the reduced iron powder in the reaction process, and the secondary coordination or chelation of free ferrous iron is provided to inhibit ferrous oxidation and resolution of a ferrous complex at a lower pH value during storage, transportation and use, so that the stability of the product is achieved. When 2-hydroxy-4-methylthiobutyric acid is used as an adjuvant, an additional methionine supplement can be provided for the animal body.
(1) Impurity ions and dissolved oxygen in the preparation water are removed, the ferrous oxidation rate in the preparation process is greatly reduced, the product quality is improved, and the dosage of the antioxidant reduced iron powder is correspondingly reduced.
(2) The antioxidant reduced iron powder exists until the main reaction is finished, and then is digested by using an auxiliary agent, so that the whole process is ensured to be antioxidant, and meanwhile, the filtering operation is omitted.
(3) 2-hydroxy-4-methylthiobutyric acid is used as an auxiliary agent and has the functions of residual iron powder digestion, secondary chelation of free ferrous ions and a stabilizer in the processes of storage, transportation and use.
(4) The whole process basically has no three wastes, and is clean and sustainable.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention will now be described with reference to the following examples, which are set forth as a method of the invention and are not intended as a limitation on the scope of the method or practice of the invention.
Example 1
Preparation of ferrous methionine complex: 602.02kg of industrial desalted water (the conductivity is 2.8 us/cm) is added into a 2000L reaction kettle, then the temperature is raised to 95 ℃, the temperature is kept for 30-60 min, nitrogen is introduced for 5-15 min at the later stage, and the residual amount of oxygen in water is analyzed and is not detected. Then 301.01kg of DL-methionine crystal (2000 mol) with the content of 99wt% and 310.02kg of anhydrous ferrous sulfate (2000 mol) with the content of 98wt% are added, stirring is carried out to completely dissolve the DL-methionine crystal, 0.448kg of reduced iron powder (8 mol) is added, the temperature is kept for 20-60 min at 40-95 ℃, 3.41kg of auxiliary agent 2-hydroxy-4-methylthiobutyric acid (20 mol) is added, the pH = 2-5 of the reaction liquid is adjusted, residual reduced iron powder is digested, stirring is carried out for 10-30 min, and DL-methionine complex ferrous salt water solution is obtained, wherein the concentration of DL-methionine complex ferrous salt in the water solution is 49.7wt%.
Spray drying treatment of the ferrous methionine complex: carrying out reduced pressure concentration treatment on the obtained DL-ferrous methionine complex aqueous solution in a reaction kettle, concentrating the DL-ferrous methionine complex aqueous solution to a concentration of about 70wt%, wherein the concentrated solution has good fluidity at 60 ℃, condensed water circulates to production water of the next batch, the concentrated solution is subjected to spray drying treatment, the nitrogen preheating temperature is 115 ℃, 607.22kg of DL-ferrous methionine complex product is obtained after the spray drying treatment, the product has good fluidity, the color of the product is light brown powder, the product passes through a 0.25mm aperture analysis sieve, the product passing rate is more than 99%, the ferrous iron content in the product is 18.25%, and ferric iron: 0.08 percent, the complexing rate of ferrous is 99 percent, and the yield of the DL-methionine ferrous complex is 99.8 percent. The condensed water recovered by spray drying and condensation is recycled to the next batch of water for dissolving DL-methionine, and the nitrogen is recycled to the next batch of gas for spray drying.
Example 2
Preparing a ferrous glycine complex: 451.52kg of industrial desalted water (the conductivity is 3.2 us/cm) is added into a 2000L reaction kettle, then the temperature is raised to 95 ℃, the temperature is kept for 30-60 min, nitrogen is introduced for 5-15 min at the later stage, and the residual amount of oxygen in water is analyzed and is not detected. Then 151.66kg of glycine crystals (2000 mol) with the content of 99wt% and 573.22kg of ferrous sulfate heptahydrate (2000 mol) with the content of 97wt% are added, stirring is carried out to completely dissolve the glycine crystals, 0.448kg of reduced iron powder (8 mol) is added, the temperature is kept at 40-95 ℃ for 20-60 min, 2.56kg of auxiliary agent 2-hydroxy-4-methylthiobutyric acid (15 mol) is added, the pH = 2-5 of the reaction liquid is adjusted, residual reduced iron powder is digested, stirring is carried out for 10-30 min, and a ferrous glycine complex water solution is obtained, wherein the concentration of the ferrous glycine complex in the water solution is 45.53 wt%.
Spray drying treatment of ferrous glycine complex: concentrating the obtained ferrous glycine complex aqueous solution in a reaction kettle, concentrating the ferrous glycine complex aqueous solution to about 85wt% of the concentration of the ferrous glycine complex, enabling the concentrated solution to have good fluidity at 75 ℃, circulating condensed water to production water of the next batch, performing spray drying on the concentrated solution, preheating nitrogen at 105 ℃, obtaining 607.22kg of ferrous glycine complex product after spray drying, enabling the product to have good fluidity, enabling the product to be in a brown powder color, enabling the product to pass through a 0.25mm pore size analysis sieve, enabling the product passing rate to be more than 99%, enabling the ferrous iron content in the product to be 20.82wt%, and enabling ferric iron: 0.06 percent, the complexing rate of ferrous iron is 99 percent, and the yield of the ferrous glycine complex is 99.8 percent. The condensed water recovered by spray drying condensation is recycled to the glycine dissolving water of the next batch, and the nitrogen is recycled to the gas for spray drying of the next batch.
Comparative example 3
According to the method, a ferrous methionine complex is prepared by a method without considering antioxidation, methionine and ferrous salt react directly at the temperature of 60 ℃ in the molar ratio of 1:1, and then the product is obtained after concentration, taking out and drying. The content of detected ferrous iron is 17.65%, and the content of detected ferric iron is as follows: 0.64 percent, and the yield of the DL-methionine ferrous complex is 98.6 percent.
Comparative example 4
Preparing ferrous glycine complex according to a common reduced iron powder excess oxidation resistance method, feeding methionine and ferrous salt according to the molar ratio of 1:1, adding reduced iron powder, filtering excessive iron powder after reaction is finished, and treating reaction liquid to obtain the product. Detecting that the content of ferrous is 20.62wt%, and the content of ferric iron: 0.10 percent, and the yield of the ferrous glycine complex is 98.1 percent.
Example 5
Stability test 1:
when ferrous ions exist in a stable complex and a stable chelate, the ferrous ions are not easily oxidized whether in a solid state or in an aqueous solution, but the dissociated ferrous ions are easily oxidized into ferric iron by air or oxygen in the solution, the ferrous iron is oxidized and consumed, the forward progress of the resolution is further promoted, and the consumption of the ferrous complex and the conversion of the ferrous iron to the unusable ferric iron are caused. The stability of the test is judged by tracking the product analysis reaction mainly through measuring the content of ferric iron in the solution.
And (3) transferring 20g of the ferrous complexes obtained in the examples 1, 2, 3 and 4 into a 100ml beaker, adding 20ml of room-temperature deoxidized deionized water respectively, stirring and dissolving, marking as A, B, C, D groups respectively, placing the beaker on an operation platform in an open mode, and sampling each group for 10min, 60min and 90min respectively to analyze the content of the ferric iron in the sample.
The analytical data are as follows:
table 1: change of content of ferric iron in 50% concentration ferrous complex solution
A: the ferrous methionine complex is prepared by the method;
b: the ferrous glycinate complex is prepared by the method;
c: directly reacting methionine and ferrous sulfate in a ratio of 1:1 to prepare a ferrous methionine complex;
d: and (3) a ferrous glycine complex prepared by reacting glycine and ferrous sulfate under excessive iron powder.
Example 6
Stability test 2:
since ferrous iron is added in very small amounts as a micronutrient, and should be actually present at lower concentrations in wet solid or liquid feeds, the 25% concentration ferrous amino acid complex stability was tested for reference.
60g of the ferrous complexes obtained in the examples 1, 2, 3 and 4 are respectively transferred into a 250ml beaker, 180ml of room-temperature deoxidized deionized water is respectively added to be stirred and dissolved, the groups a, b, c and d are respectively marked, the operation platform is opened, and each group is sampled for 10min, 60min and 90min respectively to analyze the content of the ferric iron in the groups.
The analytical data are as follows:
table 2: change of content of ferric iron in 25% concentration ferrous complex solution
a: the ferrous methionine complex is prepared by the method;
b: the ferrous glycinate complex is prepared by the method;
c: directly reacting methionine and ferrous sulfate in a ratio of 1:1 to prepare a ferrous methionine complex;
d: and (3) a ferrous glycine complex prepared by reacting glycine and ferrous sulfate under excessive iron powder.
Claims (5)
1. A preparation method of a stable amino acid ferrous complex is characterized by comprising the following steps:
(1) removing dissolved oxygen from preparation water, adding amino acid and ferrous salt, controlling the temperature to be 40-95 ℃, stirring until the amino acid and the ferrous salt are completely dissolved, adding reduced iron powder, and carrying out heat preservation reaction for 20-60 min;
(2) after the reaction is finished, adding an auxiliary agent to control the pH to be = 2-5, stirring for 10-30 min, digesting residual iron powder, directly or after concentrating the reaction solution, performing spray drying, collecting and packaging to obtain a finished product of the amino acid ferrous complex;
the auxiliary agent is 2-hydroxy-4-methylthio butyric acid;
the amino acid is methionine and glycine;
the dosage of the reduced iron powder is 0.001-0.01 of the molar weight of the ferrous salt;
the molar ratio of the amino acid to the ferrous salt is 0.9-1: 1, and the dosage of the auxiliary agent is 0.05-0.2 amino acid molar equivalent.
2. The method for preparing the stable amino acid ferrous complex according to claim 1, wherein the iron powder is one or more of activated iron powder, reduced iron powder and carbonyl iron powder.
3. The method for preparing the stable ferrous amino acid complex as claimed in claim 2, wherein the ferrous salt is ferrous sulfate, ferrous chloride or their hydrates.
4. The method for preparing the stable ferrous amino acid complex as claimed in claim 2, wherein the means for removing dissolved oxygen by using water is ultrasonic deoxidation, thermal deoxidation and/or nitrogen gas blowing.
5. The method for preparing the stable amino acid ferrous complex as claimed in claim 2, wherein the preparation water is desalted water or softened water without impurity ions, which is obtained by one or more water treatment means of anion resin exchange, cation resin exchange, ultrafiltration, nanofiltration and reverse osmosis, and the water quality is 1-10 us/cm.
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| CN112028782B (en) * | 2020-08-25 | 2023-11-21 | 重庆森乐美生物科技有限公司 | Production system and method of glycine complex chromium salt |
| CN112028781B (en) * | 2020-08-25 | 2023-08-29 | 重庆森乐美生物科技有限公司 | Production system and method of glycine complex cobalt salt |
| CN114957687A (en) * | 2022-05-17 | 2022-08-30 | 桂林理工大学 | Tri (p-carboxyphenyl) amino-triazine and ferrous ion constructed complex and synthetic method thereof |
| CN115260068A (en) * | 2022-07-20 | 2022-11-01 | 天宝动物营养科技股份有限公司 | Divalent metal co-salt compound with hydroxymethionine as base and preparation method and application thereof |
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