CN1304362C - Prepn process of metal-amino acid chelate - Google Patents
Prepn process of metal-amino acid chelate Download PDFInfo
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- CN1304362C CN1304362C CNB2005100900716A CN200510090071A CN1304362C CN 1304362 C CN1304362 C CN 1304362C CN B2005100900716 A CNB2005100900716 A CN B2005100900716A CN 200510090071 A CN200510090071 A CN 200510090071A CN 1304362 C CN1304362 C CN 1304362C
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Abstract
The present invention discloses a preparation method of metal-amino acid chelate. According to the proportion of gram molecules, a metal compound in a reactant and ligand amino acid are prepared into water suspension. After pretreatment is carried out, the water suspension is injected into a nano mill of high-pressure liquid; very strong impact pressure is generated by making use of a collapse action principle of a gas cavity; momentary high temperature, supersonic waves of ultrahigh frequency, etc., commonly act on the suspension of the reactant to make the covalent bond of the ligand amino acid generate homolytic cleavage form free radical, and the metal-amino acid chelate is formed by the momentary combination of the free radical and metal ions which contain valence electrons which are not paired. The preparation method of metal-amino acid chelate of the present invention has the advantages of short production period, high yield, no generation of harmful impurities, such as sulphate, chloride, etc. The purity of reaction products is high; besides the amino acid chelate, only water is generated. After the dehydrating processing of the products is carried out, the products can be directly used as manufactured products of a chelate compound of the amino acid, and the present invention is used for medicine and food.
Description
Technical Field
The invention relates to a preparation method of a metal amino acid chelate.
Technical Field
Calcium, a metal element that is present in the largest amount in the human body. Generally, adult humans contain a total amount of calcium of about 1200 grams, of which about 99% is distributed in bones and teeth and the remaining 1% is present in the extracellular fluid, blood and soft tissues in free or bound ionic state. Calcium is not only a main component constituting bones and teeth of a human body, but also calcium ions have important roles in normal pulsation of the heart, coagulation of blood, conduction of normal excitability of muscles and nerves, maintenance of suitability for induction, permeability to cell membranes, activity of various enzymes, and other physiological functions. Calcium deficiency can cause a variety of diseases, and is particularly prominent in infants, pregnant women and the elderly. Typically, about 400 mg of calcium per day is renewed by adults, and therefore one must take this much calcium from food, in fact, typically one only takes 150 mg of calcium per day from food, and the remainder has to be supplemented by a calcium preparation.
Calcium products commonly used at home and abroad are not classified into three types: (1) inorganic salt-based products, such as calcium carbonate, calcium oxide, calcium chloride, calcium phosphate, calcium hydrogen phosphate, etc. The product has high calcium content, but low solubility, difficult absorption and great toxic and side effects; (2) common organic calcium products include calcium lactate, calcium acetate, calcium citrate, calcium gluconate, and the like. Compared with inorganic calcium, the product has the advantages of low calcium content, high solubility, low gastrointestinal irritation, low absorptivity, low bioavailability and large toxic and side effects: (3) organic calcium with biological activity, such as calcium threonate and L-aspartic acid chelated calcium. The product, especially L-aspartic acid chelated calcium, has the advantages of good solubility, easy absorption, high bioavailability, no toxic or side effect and the like. Therefore, the amino acid chelated calcium is the outstanding one among many calcium products and is widely favored.
What is an amino acid chelate, the american food management society, in 1987, has defined an amino acid chelate as: the molar ratio of the metal ions to the amino acid is 1: 2-1: 3, and the optimal ratio is 1: 2. The amino acids have an average molecular weight of about 150 and the chelates have a molecular weight of no more than 800. In brief, a chelate is a heterocyclic structure formed by a metal ion and an amino acid with an unpaired electron ligand. The structure of the chelate is determined by the synthesis conditions. The chelation reaction must be carried out under suitable conditions including molar ratios of metal ions to ligands, reaction medium, such as pH of aqueous solution and solubility of reactants, etc.
The amino acid chelate obtained by the correct synthetic method is a relatively stable compound in which the metal ion forms a five-membered ring structure with the α -amino acid carboxyl oxygen atom and the α -amino nitrogen, this five-membered ring structure being composed of the metal atom, the carboxyl oxygen atom, the carbonyl carbon atom, the α -carbon atom and the α -amino nitrogen atom the actual structure depends on the molar ratio of the metal ion to the ligand and whether the metal ion forms a coordinate bond with the carboxyl oxygen or not.
In the above formula (1), M is a divalent metal ion, the dotted line represents a coordinate bond, a covalent bond or an ionic bond, and the solid line represents a covalent bond or a coordinate bond formed by the metal ion and α -amino group, it is possible for the metal ion to be bonded to carboxyl oxygen through a coordinate bond or an ionic bond, however, most typically only α -amino acid is bonded to the metal ion through a coordinate bondAfter this, four chemical bonds can be formed. When R in the structural formula is H, the amino acid is glycine with the simplest structure, R can be any one of more than twenty amino acids, and when L-aspartic acid is used as a ligand, R is-CH2In other words, when different amino acids are used as ligands for the metal ions, even though the R groups are different, they all form chelate rings having the same composition of atoms at the same position.
Since the 1979 that calcium amino acid chelate was used as a calcium supplement, the research on the preparation method of metal amino acid chelate has been a focus of attention. To date, amino acid chelate production methods, mainly chemical synthesis and electrolytic-semipermeable membrane methods, have major problems with these methods: slow reaction, long time, low yield, incomplete reaction, and difficult removal of residual reactants not involved in synthesis, thus difficult large-scale production. The invention aims to provide a method for preparing an amino acid chelate with high efficiency, rapidness and scale.
Disclosure of Invention
The invention aims to provide a preparation method of a metal amino acid chelate, which overcomes the defects of the existing preparation method of a metal amino acid integral compound.
The invention is based on the following principle: the synthesis of the metal amino acid chelate is carried out in a high-pressure fluid nanometer mill, a metal compound and ligand amino acid suspension with certain concentration after crushing, homogenizing and filtering are injected into the fluid nanometer mill by a high-pressure pump, and ultrasonic waves with strong impact pressure, instantaneous high temperature and ultrahigh frequency are generated by utilizing the cavitation collapse principle of the equipment and jointly act on the metal compound and the ligand amino acid, so that amino acid covalent bonds are uniformly cracked to form free radicals and metal ion structures to generate the metal amino acid chelate.
The invention is realized by the following technical scheme:
a preparation method of a metal amino acid chelate comprises the following steps: mixing metal compound and ligand amino acid with water, stirring, making into suspension, adjusting pH to neutral or slightly alkaline (such as pH 7.0-8.0), pulverizing, homogenizing, and filtering to obtain suspension with solid particle size less than 30 μm; injecting the suspension into a high-pressure liquid nano mill, wherein the pressure is 90-130MPa, preferably 110MPa, the feeding speed is 100-300 liters and preferably 200 liters per hour, reacting for 0.5-1.5 hours, preferably 1 hour to obtain an amino acid chelate clear solution, and performing spray dryingto obtain a metal amino acid chelate finished product;
the metal compound is a metal oxide or a metal hydroxide;
the ligand amino acid is any one of known amino acids, or a combination thereof, or a small molecule peptide formed by the amino acids.
The metal compound is preferably a divalent metal compound.
The divalent metal ion is especially calcium, magnesium, copper, zinc, cobalt, manganese, or a combination thereof.
The metal compound is preferably Ca (OH)2、CaO、Mg(OH)2Or MgO.
The ligand amino acid is especially alanine, aspartic acid, asparagine, glutamic acid, glutamine, arginine, lysine, histidine, glycine, proline, hydroxyproline, leucine, isoleucine, cysteine, cystine, methionine, tryptophan, tyrosine, valine, phenylalanine, threonine, serine or ornithine, or a combination thereof, or a small peptide formed thereof.
The molar ratio of the metal compound to the ligand amino acid is preferably 1: 2 to 1: 3, preferably 1: 2.
When the metal ion in the amino acid chelate is divalent, e.g., metal compound Ca (OH)2、CaO、Mg(OH)2Or the molar ratio of MgO to ligand L-aspartic acid is preferably 1: 2-1: 3, preferably 1: 2.
In the above preparation method, the pH of the suspension is preferably adjusted to 7.4.
The ratio of the metal compound, ligand amino acid reactant and water is preferably in the range 18-30: 70-82, preferably 20: 80 or 25: 75.
In particular, in the invention, when the amino acid chelated calcium is prepared, the metal compound can adopt Ca (OH)2Or CaO. For example, in the preparation of calcium L-aspartate chelate, Ca (OH)2Or the optimal molar ratio of CaO to ligand L-aspartic acid is 1: 2. The reaction formula is as follows:
when the L-aspartate chelated magnesium is prepared by the invention, the metal compound can adopt Mg (OH)2Or MgO. For example, the optimal molar ratio of both to ligand amino acids is 1: 2. The reaction formula is as follows:
for another example, in the present invention, when wet process is used to prepare calcium aspartate and magnesium aspartate, water is used as reaction medium, carrier and kinetic energy carrier, and the metal compound is Ca (OH)2And Mg (OH)2The optimal gram molecular ratio of the amino acid to the ligand aspartic acid is 1: 2; the ratio of reactant to water is 20-30: 70-80, and the optimal ratio is 25: 75. Suspension of reactantsThe optimum pH of (1) is neutral or slightly alkaline. When preparing calcium aspartate or magnesium aspartate, metal compounds Cao and MgO are adopted, and the optimal gram-molecule ratio of the metal compounds Cao and MgO to ligand aspartate is 1: 2; the ratio of the reactant to the water is 18-25: 75-82, and the optimal ratio is 20: 80; the optimum pH of the reaction suspension is neutral or slightly alkaline.
According to the invention, the prepared L-aspartate chelated calcium and L-aspartate chelated magnesium have the advantages of stable molecular structure, good solubility, easy absorption and high bioavailability, and are analyzed: the calcium content in the L-aspartate chelated calcium is 11.5-13.5%, the magnesium content in the L-aspartate chelated magnesium is 7.0-9.0%, the content of harmful metal elements such as mercury, lead, arsenic, chromium and the like is far lower than the national standard, and impurities such as chloride, sulfate and the like are basically not contained; all microbiological indexes reach the national standard.
The preparation method of the metal amino acid chelate has the advantages of short production period, high yield, no generation of sulfate and chloride harmful impurities and the like, the reaction product has high purity, and only water is generated except the amino acid chelate, so that the product can be directly used as an amino acid chelate product after dehydration treatment and can be used for medicines and foods.
Detailed Description
Example 1
Selecting Ca (OH)2And L-aspartic acid, burdening according to a molar ratio of 1: 2, mixing the reactants and purified water according to a ratio of 25: 75, fully stirring, adjusting the acidity of the suspension to pH7.4, treating by a colloid mill and a homogenizer to fully dissolve and disperse the reactants, filtering out larger particles in the suspension by a filter to ensure that the particle size of solid matters in the suspension is less than 30 micrometers, then injecting the reactant suspension into a high-pressure liquid nano mill, controlling the working pressure of the nano mill to be 110MPa, controlling the feeding speed to be 200 liters per hour, reacting for 1 hour, completing all chelation reaction processes in a nano mill materialization chamber, and finally obtaining a clear L-aspartic acid chelated calcium solution, wherein the clear L-aspartic acid chelated calcium solution does not produce impurities such as sulfate, chloride and the like, and the reaction liquid is spray-dried to obtain a white crystalline powder product.
After analysis: the calcium content in the product is 11.5-13.5%, and the content of harmful metal elements such as lead, mercury, arsenic and the like is less than 1 mg/kg; the microbiological indexes meet the national standard. Therefore, the dehydrated product can be directly used for food or medicine.
Example 2
For the preparation of L-aspartate chelated calcium, CaO is substituted for Ca (OH)2The charging proportion of CaO and L-aspartic acid is still 1: 2, the proportion of reactants and water is 20: 80, the reaction time is 0.5 hour, and other conditions and operation procedures are the same as those in the embodiment 1. The results of the quality analysis of the obtained product were in accordance with those of example 1.
Example 3
Selected Mg (OH)2And L-aspartic acid, mixing the raw materials according to the weight ratio of 1: 2, mixing the reactant and the purified water according to the weight ratio of 25: 75, fully stirring, adjusting the acidity of the suspension to pH7.4, treating the suspension by a colloid mill and a homogenizer to fully disperse the reactant, filtering out larger particles in the suspension by a filter to ensure that the granularity of solid matters in the suspension is less than 30 micrometers, then injecting the reactant suspension into a high-pressure liquid nano mill, controlling the working pressure of the nano mill to be 110MPa, and controlling the feeding speed to be 110MPa200 liters per hour, the reaction time is 1.5 hours, all the chelation reaction processes are finished in a nano mill chemical chamber, and finally, the clear L-aspartic acid chelated magnesium is obtained. In the same way, impurities such as sulfate, chloride and the like are not generated in the process, and the reaction liquid is sprayed and dried to obtain a white crystal powder product.
After analysis: the magnesium content in the product is 7.0-9.0%, and the content of harmful metal elements such as lead, mercury, arsenic and the like is less than 1 mg/kg; the microbiological indexes meet the national standard. Therefore, the dehydrated product can be directly used for food or medicine.
Example 4
For the preparation of L-magnesium aspartate, MgO is used instead of Mg (OH)2The ratio of MgO to L-aspartic acid was still 1: 2, the ratio of the reactants to water was 20: 80, the other regulations and procedures were the same as in example 3, and the results of quality analysis of the obtained product were the same as in example 3.
Example 5
In order to simultaneously obtain the L-aspartate chelated calcium and the L-aspartate chelated magnesium, Ca (OH) is selected2、Mg(OH)2And L-aspartic acid, the mixture ratio of the hydroxide of the L-aspartic acid and the hydroxide of the amino acid is 1: 2, the ratio of the reactant to water is 25: 75, the mixture is fully stirred, the pH of the suspension is 7.4, the suspension is treated by a colloid mill and a homogenizer to fully disperse the reactant, larger particles in the suspension are filtered out by a filter to ensure that the particle size of solid matters in the suspension is less than 30 microns, then the suspension is injected into a nano mill, the working pressure of the nano mill is controlled to be about 110MPa, the feeding speed is 200 liters per hour, and the reaction time is shortenedAnd 1 hour, and the whole chelation reaction process is finished in the nano mill chemical chamber. Finally, a clear chelate solution is obtained, impurities such as sulfate, chloride and the like are not generated in the process, and the reaction solution is spray-dried to obtain a white crystal powder product.
The amount of the calcium L-aspartate and the magnesium L-aspartate in the product is determined by the amount of Ca (OH) added during feeding2And Mg (OH)2The amount is determined, and the feeding amount of the two can be adjusted according to the requirement.
Example 6
In order to simultaneously obtain amino acid chelate containing a plurality of metal elements at one time, for example, in order to simultaneously obtain a plurality of metal elements necessary for human body such as calcium, magnesium, zinc, cobalt, manganese and the like at one time, metal compounds of the metal elements are mixed and fed, the gram-molecule ratio of the total amount of the plurality of element mixtures Schranicke of the plurality of element mixtures to amino acid is 1: 2, the ratio of reactants to water is 25: 75, the optimum pH of the suspension is 7.4, and other conditions and operation procedures are the same as those of example 1.
The content of various metal elements in the amino acid chelate depends on the feeding amount of various metal compounds, and different types and proportions of the metal compounds are added according to requirements, so that the metal amino acid chelates with different combinations and different contents can be obtained.
Example 7
The same as example 1, except that the molar ratio 1: 3 was formulated: the ratio of the reactant to the purified water is 20: 80; the acidity of the suspension is adjusted to pH 7.0; the working pressure of the nano mill is 90 MPa; the feed rate was 100 liters per hour.
Example 8
The same as example 3, except that the ratio of the reactants to purified water was 18: 82; adjusting the acidity of the suspension to pH 8.0; the working pressure of the nanomill is 130 MPa; the feed rate was 300 liters per hour.
Example 9
The same as example 3, except that the ratio of the reactant to the purified water was 30: 70; the acidity of the suspension was adjusted to pH 7.8.
Claims (4)
1. A preparation method of a metal amino acid chelate comprises the following steps: respectively taking a metal compound and ligand amino acid, adding water, mixing, fully stirring to prepare a suspension, adjusting the pH to 7.4, crushing, homogenizing, and filtering to obtain a suspension with a solid particle size of less than 30 microns; injecting the suspension into a high-pressure liquid nano mill, reacting for 0.5-1.5 hours at the pressure of 90-130MPa and the feeding speed of 100 liters per hour to obtain amino acid chelate clear liquid, and spray drying to obtain a finished product of the metal amino acid chelate;
the metal compound is Ca (OH)2、CaO、Mg(OH)2Or MgO;
the ligand amino acid is L-aspartic acid;
the ratio of the metal compound, ligand amino acid reactant and water is 18-30: 70-82.
2. The method for preparing a metal amino acid chelate according to claim 1, wherein the ratio of the metal compound, the ligand amino acid reactant and water is 20: 80 or 25: 75.
3. The method for preparing a metal amino acid chelate according to claim 1 or 2, wherein the molar ratio of the metal compound to the ligand amino acid is 1: 2 to 1: 3.
4. The method for preparing metal amino acid chelate according to claim 3, wherein themetal compound is Ca (OH)2、CaO、Mg(OH)2Or the molar ratio of MgO to ligand L-aspartic acid is 1: 2.
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| WO2008034238A1 (en) * | 2006-09-20 | 2008-03-27 | Viva Pharmaceuticals Inc. | Methods for producing pure amino acid chelate complexes, and uses thereof |
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| CN101973899A (en) * | 2010-09-13 | 2011-02-16 | 三亚百泰微纳生物工程有限公司 | Novel production process of nanometer calcium amino acid chelate with high efficiency |
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| CN103626867B (en) * | 2013-06-19 | 2015-08-12 | 中国海洋大学 | A kind of preparation technology of zinc fish-skin collagen polypeptide chelate |
| CN104098518B (en) * | 2014-07-15 | 2017-02-01 | 浙江大学 | Preparation method of 1-alkyl-substituted triazole compound |
| CN106858610B (en) * | 2017-03-01 | 2018-05-22 | 岳智广 | The preparation method of a kind of amino acid chelated calcium and including the chelated calcium calcium-supplementing preparation |
| CN107744136A (en) * | 2017-10-14 | 2018-03-02 | 江西倍得力生物工程有限公司 | A kind of high calcium white fungus nano powder, preparation method and processing and eating method |
| CN109043442A (en) * | 2018-08-26 | 2018-12-21 | 重庆海航农业开发有限公司 | A kind of instant ginger decoction |
| CN110938009A (en) * | 2019-10-25 | 2020-03-31 | 湖北长联杜勒制药有限公司 | Preparation method of amino acid chelated ferrous iron and iron supplement preparation thereof |
| CN112409200B (en) * | 2020-11-27 | 2023-06-20 | 长沙兴嘉生物工程股份有限公司 | Preparation method and application of isoleucine chelate metal |
| CN113277954B (en) * | 2021-06-17 | 2023-04-28 | 英德市匠心新材料股份有限公司 | Amino acid metal chelate micro-nano powder and preparation method thereof |
| CN114369034A (en) * | 2022-01-11 | 2022-04-19 | 西安利君制药有限责任公司 | Preparation method of amino acid nano-chelated calcium |
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| CN1587257A (en) * | 2004-08-05 | 2005-03-02 | 金三元科技（深圳）有限公司 | Process for preparing amino acid chelated calcium and its special device |
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