CN102898338A - Alpha-amino acid chromium (III) chelate and preparation method thereof - Google Patents
Alpha-amino acid chromium (III) chelate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an alpha-amino acid chromium (III) chelate. The invention also discloses a method for preparing the chelate. The method comprises the following steps of: reducing hexavalent chromium into trivalent chromium in an acid medium by using an inorganic trivalent chromium salt as a raw material and ethanol as a reducer; and reacting the trivalent chromium with alpha-amino acid under normal pressure at 30 to 90 DEG C for 1 to 5 hours to obtain the alpha-amino acid chromium (III) chelate. The chelate and the method have the advantages of readily available raw materials, low production cost, mild reaction conditions, simplicity in operation, and the like. The industrial application prospects of the chelate and the method are great.
Description
Technical field
The present invention relates to Chelates of Amino Acids And Trace Elements and preparation method thereof, relate in particular to a kind of a-amino acid chromium (III) inner complex and preparation method thereof.
Background technology
The main chromic salts product of China comprises sodium dichromate 99, chromic trioxide, potassium bichromate, chromium sesquioxide, basic chromium sulfate, chromium chloride etc. at present.The Application Areas of chromic salts product is very extensive, relates to the aspects such as tanning, pigment, dyestuff, plating, anticorrosion, organic synthesis, chemicals, pottery, glass, oil production, plate making, magneticsubstance.Its product is relevant with 15% range of goods, is the indispensable important materials of national economy.
But these products mainly are inorganic products, and high value added product is few, so be necessary high added value chromic salts product is studied.The high-valued direction of chromic salts product has medicine, health care, food, fodder additives etc., and high-valued product has organic chromium, pigment-level chromic oxide etc.
Although sexavalent chrome is poisonous, trivalent chromium Cr (III) but is that human body and animal are kept one of essential trace element of normal carbohydrate metabolism and lipid metabolism.From nineteen fifty-nine Schwarz and Mertz(Schwarz K, Mertz W.Chromium (III) and the glucose tolerance factor.Archs Biochem.Biophys.1959,86:292) proposing trivalent chromium is the activeconstituents of glucose tolerance factor (GTF), there is not Cr (III), GTF does not just have after the bioactive hypothesis, studies show that in a large number trivalent chromium is to muroid, the poultry such as chicken, duck, pig, ox, the mammiferous carbohydrate metabolism such as the domestic animal such as sheep and people and lipid metabolism have very important effect.Since the nineties in 20th century, trivalent chromium becomes one of the focus in analysis on trace field.
The main biological function of Cr (III) comprises: as the metabolism of toughener involved in sugar and the lipid metabolism of Regular Insulin, keep the Blood Cholesterol balance; Participate in the synthetic of protein and nucleic acid, promote that amino acid enters cell, improve protein synthesis capacity, participate in the stable of nucleic acid and improve process; Trivalent chromium also has very important effect to mineral metabolism in the animal body.
After recognizing chromic effect, people just begin to develop various energy and replenish chromic product.First-generation chromium product is the inorganic chromium product.This type of chromium product category is more, mainly contains chromium chloride, chromium sulphate etc.Usage mainly is that chromium chloride etc. is mixed with milk powder, or mixes such as iodine, zinc, selenium etc. with other trace elements and the product that makes.These products had both brought facility for people mend chromium, and also have the problem that much can't restrain: (1) specific absorption is low, only is 1 ~ 3%; (2) lifeless matter is active, and need to change into bioactive GTF chromium just has the effect of regulating metabolism, but the body of diabetes and patients with coronary heart disease does not have this conversion capability substantially; (3) deleterious effect of inorganic chromium.
People have developed again the organic chromium product subsequently, and wherein pyridine acid chromic formate, nicotinic acid chromium, chromium propionate etc. are s-generation chromium product.They easily are absorbed in human body, and bioavailability is higher.Modal in the chromium complex by the commercial sources acquisition at present is exactly chromium picolinate, yet some current research results have proposed query to its security, as at (J K Speetkens, et al.The Nutritional Supplement Chromium (III) Tris (picolinate) Cleaves DNA Chem.Res.Tpxocpl.1999,12:483) with (D M Stearns.Chromium (III) picolinate produces chromosome damage in Chinese hamster ovary cells, J.1995, FASEB 9:1643) reports to some extent.
Amino acid chromium is third generation chromium product, and specific absorption is 10 ~ 25%, and bioavailability is high, can replenish simultaneously the required amino acid of organism and trivalent chromium.Be mainly used in feed, food and the pharmaceutical industries in market at present.Be used in the feed as its additive, can effectively improve the price of deed, improve the growth of animals or poultry performance, reduce trunk fat and back-fat thickness, can reduce the stress reaction of animal, promote growth, add to significantly improve farrowing rate in the daily ration, improve breeding rate, improve the breeding body condition of animal.In the food and medicine industry, be mainly used in the assisting therapy type ii diabetes, also be used as the ancillary component of slimming health food.
At present the synthetic method of a-amino acid chromium (III) inner complex of report generally all is after mixing a-amino acid and solubility chromic salt such as chromium chloride etc. fully in water, under agitation dripping strong caustic regulator solution pH makes a-amino acid chromium (III) the inner complex precipitation of generation and separates out, leave standstill cooled and filtered, abundant drying obtains a-amino acid chromium product after filter cake water and the washing with alcohol.This method operation is more loaded down with trivial details, and regulates method that pH makes the product precipitation and do not have a utility value industrial by dripping sodium hydroxide solution, can't realize continuous production.
Summary of the invention
One of purpose of the present invention is to provide a kind of a-amino acid chromium (III) inner complex, and described inner complex color even, crystal formation and granularity are good.
A kind of a-amino acid chromium (III) inner complex, general formula is as follows:
In the formula, R be natural a-amino acid normal with organic group.
Preferably, choose R so that a-amino acid is any one the amino acid that is selected from Histidine, L-Ala, arginine, leucine, tryptophane, L-glutamic acid, glycine, Threonine, Isoleucine, methionine(Met), Methionin, phenylalanine, aspartic acid or the halfcystine, be preferably any one the amino acid in methionine(Met), glycine, Threonine, phenylalanine and the halfcystine.
Two of purpose of the present invention provides a kind of raw material resources of basing on our country as for being, prepares the method for a-amino acid chromium (III) inner complex in the pure system.Described method production cost is low, and reaction conditions is gentle, and product separation is easy after the reaction, thereby sets up a kind of method for preparing a-amino acid chromium (III) inner complex that realizes suitability for industrialized production.
For realizing the object of the invention, the present invention is take inorganic sexavalence chromic salts as main raw material, and reduction of hexavalent chromium is trivalent chromium, and then prepares a-amino acid chromium (III) inner complex with the a-amino acid reaction.The preparation method of described inner complex comprises the steps:
(1) inorganic sexavalence chromic salts is reduced to chromic salt;
(2) solution of preparation alpha-amino group bronsted lowry acids and bases bronsted lowry/basic salt;
(3) solution that step (2) is obtained mixes with chromic salt, and under normal pressure, under 30 ~ 90 ℃ of temperature, behind reaction 1 ~ 5h, cooling is filtered, and washing and dry obtains a-amino acid chromium (III) inner complex.
The method that described inorganic sexavalence chromic salts is reduced to chromic salt is prior art, those skilled in the art can carry out chromic reduction with reference to prior art or the disclosed content of new technology, as preferred version, the method of the described hexavalent chrome reduction of step (1) is: in acidic medium, under the effect of reductive agent, inorganic sexavalence chromic salts is reduced to chromic salt.Can prepare the aqueous solution of sexavalence chromic salts, under acidic medium, add reductive agent, carry out chromic reduction.
Preferably, the mol ratio of described a-amino acid and sexavalence chromic salts is n:1, and n is between 3 ~ 9.Preferably, the mol ratio of alkali/basic salt and sexavalence chromic salts is n:1, and n is between 3 ~ 9.
The solution of step (2) preparation alpha-amino group bronsted lowry acids and bases bronsted lowry/basic salt is namely: the solution of preparation alpha-amino group bronsted lowry acids and bases bronsted lowry or the solution of preparation a-amino acid and basic salt, described alkali/basic salt be or relation.
Preferably, the described temperature of reaction of step (3) is 40 ~ 88 ℃, for example 41 ℃, 43 ℃, 47 ℃, 51 ℃, 55 ℃, 60 ℃, 64 ℃, 68 ℃, 72 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 87 ℃, preferred 45 ~ 85 ℃, further preferred 55 ~ 85 ℃.
Preferably, the time of the described reaction of step (3) is 1.5 ~ 5h, for example 1.8h, 2.1h, 2.4h, 2.7h, 3h, 3.3h, 3.6h, 3.9h, 4.2h, 4.5h, 4.8h, 4.9h, preferred 2 ~ 5h.
Described normal pressure refers to standard atmospheric pressure, i.e. a 101325Pa.
The described reaction of step (3) can be carried out under agitation condition, and described washing can be adopted washing.
Preferably, described sexavalence chromic salts is selected from the mixture of any one or at least two kinds in potassium bichromate, sodium dichromate 99, chromic trioxide or the Sodium chromate.Described mixture is the mixture of Sodium chromate and potassiumchromate for example, the mixture of chromic trioxide and sodium dichromate 99, the mixture of potassium bichromate and Sodium chromate, the mixture of potassiumchromate and chromic trioxide, the mixture of sodium dichromate 99 and potassium bichromate, the mixture of Sodium chromate, potassiumchromate and chromic trioxide, the mixture of sodium dichromate 99, potassium bichromate and chromic trioxide, the mixture of Sodium chromate, potassiumchromate, chromic trioxide and sodium dichromate 99.
Preferably, used alkali/basic salt is selected the mixture of any one or at least two kinds in sodium hydroxide, potassium hydroxide, yellow soda ash or the salt of wormwood.
Preferably, described reductive agent is selected from the monobasic low-carbon alcohol, the monohydroxy-alcohol of preferred 1 ~ 12 carbon atom, the straight-chain monohydric alcohol of further preferred 1 ~ 5 carbon atom, for example methyl alcohol, ethanol, propyl alcohol, butanols or amylalcohol, the mixture of any one in particular methanol, ethanol or the propyl alcohol or at least two kinds further, more further preferred alcohol, most preferably dehydrated alcohol.
Preferably, the solvent of the described solution of step (2) is selected from the monobasic low-carbon alcohol, the straight-chain monohydric alcohol of preferred 1 ~ 5 carbon atom, for example methyl alcohol, ethanol, propyl alcohol, butanols or amylalcohol, the further mixture of any one in particular methanol, ethanol or the propyl alcohol or at least two kinds, further preferred alcohol again, more preferably volume fraction is 10 ~ 100% ethanol, most preferably volume fraction is 50 ~ 75% ethanol, and for example volume fraction is respectively 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% ethanol.When volume fraction was 100%, described ethanol was dehydrated alcohol.The solvent of the described solution of step (2) can recycle and reuse after reaction finish to be filtered, and reenters the preparation of carrying out solution in the step (2).
Preferably, described a-amino acid is any one in pharmaceutical grade, food grade or the feed grade a-amino acid, can select in the purposes medical, that the food and feeds industry is different according to described inner complex product application.
A-amino acid chromium of the present invention (III) inner complex can be used for feed, food and pharmaceutical industries.For example a-amino acid chromium (III) inner complex can be used in the feed as additive, can effectively improve the price of deed, improve the growth of animals or poultry performance, reduce trunk fat and back-fat thickness, can reduce the stress reaction of animal, promote growth, add to significantly improve farrowing rate in the daily ration, improve breeding rate, improve the breeding body condition of animal.In the food and medicine industry, can be used for the assisting therapy type ii diabetes, also be used as the ancillary component of slimming health food.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention has set up the novel process that normal temperature and pressure prepares a-amino acid chromium (III) inner complex, compare with synthetic method in traditional preparation technology and the up-to-date aqueous solution: synthetic method of the present invention is to carry out in alcoholic solution, do not adopt and use water as reaction medium, avoided the protonation in the reaction process, temperature of reaction is low, the operating time is short, react 1 ~ 5h under normal pressure, yield reaches more than 80%;
(2) method of the present invention has avoided regulating with aqueous sodium hydroxide solution the loaded down with trivial details step of pH, has simplified operation;
(3) method that proposes of the present invention is compared with present preparation technology and has been realized that normal temperature and pressure reacts efficiently, can under stirring, the slow speed of revolution prepare good a-amino acid chromium (III) inner complex of color even, crystal formation and granularity, product drying need not to pulverize later, and key equipment industrialization reliability is strong;
(4) the method for the invention is under the prerequisite that guarantees high yield, and reaction medium can reclaim cycling and reutilization under certain condition, and because solvent boiling point is low, therefore energy consumption is low in the recovery working cycle of solvent.
(5) a part of a-amino acid chromium (III) inner complex product of taking away in washing process of the method for the invention can reclaim, and has avoided the loss of product;
(6) technical process of preparation a-amino acid chromium (III) inner complex of the present invention's proposition is simple, easily realizes industrialization, process stabilizing, and the industrial reliability of key equipment is strong.
Description of drawings
Further specify technical scheme of the present invention below in conjunction with accompanying drawing and by embodiment.
Fig. 1: a-amino acid chromium (III) inner complex preparation technology general flow chart;
Fig. 2: chromium methionine (III) inner complex infrared spectrogram;
Fig. 3: glycine chromium (III) inner complex infrared spectrogram;
Fig. 4: chromium threonine (III) inner complex infrared spectrogram;
Fig. 5: phenylalanine chromium (III) inner complex infrared spectrogram;
Fig. 6: halfcystine chromium (III) inner complex infrared spectrogram.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
In with the reactor of prolong, add sodium dichromate 99 1.49g(0.005mol) and 10mL water stirring and dissolving, then to the mixed solution that wherein drips 4mL concentrated hydrochloric acid (36%) and 10mL dehydrated alcohol, drip and finish rear insulation reaction 20min, obtain the solution of deep green chromic salt.6.40g D, L-Methionine (0.0425mol), sodium hydroxide 1.70g(0.0425mol) and volume fraction be 50% ethanol, stirring and dissolving obtains solution, it is joined in the solution of above-mentioned chromic salt, after interpolation finishes, under the normal pressure, 80 ℃, reacted 2 hours.After reaction finishes, filter, washing, drying obtains the red-purple crystalline powder, chromium methionine chelate yield 91.9%.Trivalent chromium content adopts the ICP method to measure in the chromium methionine chelate, and methionine content utilizes the column front derivation high performance liquid chromatography to measure, and recording methionine content is 89.56%, and trivalent chromium content is 10.44%.
Embodiment 2
In with the reactor of prolong, add potassium bichromate 1.47g(0.005mol) and 10mL sulphuric acid soln (1+3, i.e. 1 part of sulfuric acid+3 part water), stirring and dissolving, then to the mixed solution that wherein drips the 10mL dehydrated alcohol, drip and finish rear insulation reaction 20min, obtain the solution of deep green chromic salt.2.27g glycine (0.03mol), potassium hydroxide 1.68g(0.03mol) and volume fraction be 75% ethanol, stirring and dissolving obtains solution, and it is joined in the solution of above-mentioned chromic salt, add finish after, under the normal pressure, 75 ℃, reacted 4 hours.After reaction finishes, filter, washing, drying obtains the rose crystalline powder, glycine chromium complex yield 84.8%.Trivalent chromium content adopts the ICP method to measure in the glycine chromium complex, and glycine content utilizes the column front derivation high performance liquid chromatography to measure, and recording glycine content is 80.96%, and trivalent chromium content is 19.04%.
Embodiment 3
In with the reactor of prolong, add chromic trioxide 1.01g(0.01mol) and 10mL water stirring and dissolving, then to the mixed solution that wherein drips 3.5mL concentrated hydrochloric acid (36%) and 10mL dehydrated alcohol, drip and finish rear insulation reaction 20min, obtain the solution of deep green chromic salt, 3.61g Threonine (0.03mol), yellow soda ash 3.18g(0.03mol) and volume fraction be 50% ethanol, stirring and dissolving obtains solution, it is joined in the solution of above-mentioned chromic salt, after adding end, under the normal pressure, 85 ℃, reacted 3 hours.After reaction finishes, filter, washing, drying obtains pink crystalline powder, chromium threonine inner complex yield 91.8%.Trivalent chromium content adopts the ICP method to measure in the chromium threonine inner complex, and threonine content utilizes the column front derivation high performance liquid chromatography to measure, and recording threonine content is 87.21%, and trivalent chromium content is 12.79%.
Embodiment 4
In with the reactor of prolong, add potassiumchromate 1.94g(0.01mol) and 10mL water stirring and dissolving, then to the mixed solution that wherein drips 4.0mL concentrated hydrochloric acid (36%) and 10mL dehydrated alcohol, drip and finish rear insulation reaction 20min, obtain the solution of deep green chromic salt, 5.01g phenylalanine (0.03mol), salt of wormwood 8.32g(0.06mol) and volume fraction be 50% ethanol, stirring and dissolving obtains solution, it is joined in the solution of above-mentioned chromic salt, after adding end, under the normal pressure, 80 ℃, reacted 3 hours.After reaction finished, filtration, washing, drying obtained the purple crystal powder, phenylalanine chromium complex yield 82.5%.Trivalent chromium content adopts the ICP method to measure in the phenylalanine chromium complex, and phenylalanine content utilizes the column front derivation high performance liquid chromatography to measure, and recording phenylalanine content is 90.4%, and trivalent chromium content is 9.6%.
Embodiment 5
In with the reactor of prolong, add Sodium chromate 1.62g(0.01mol) and 10mL nitric acid (50%) stirring and dissolving, then to the mixed solution that wherein drips the 10mL dehydrated alcohol, drip and finish rear insulation reaction 20min, obtain the solution of deep green chromic salt, 3.67g halfcystine (0.03mol), sodium hydroxide 2.41g(0.06mol) and volume fraction be 75% ethanol, stirring and dissolving obtains solution, it is joined in the solution of above-mentioned chromic salt, after adding end, under the normal pressure, 70 ℃, reacted 5 hours.After reaction finished, filtration, washing, drying obtained the royalblue crystalline powder, halfcystine chromium complex yield 81.4%.Trivalent chromium content adopts the ICP method to measure in the halfcystine chromium complex, and cysteine content utilizes the column front derivation high performance liquid chromatography to measure, and recording cysteine content is 87.43%, and trivalent chromium content is 12.57%.
Embodiment 6
In with the reactor of prolong, add Sodium chromate 1.62g(0.01mol) and 10mL nitric acid (50%) stirring and dissolving, then to the mixed solution that wherein drips the 10mL dehydrated alcohol, drip and finish rear insulation reaction 20min, obtain the solution of deep green chromic salt, 10.98g halfcystine (0.09mol), sodium hydroxide 3.60g(0.09mol) and volume fraction be 10% ethanol, stirring and dissolving obtains solution, it is joined in the solution of above-mentioned chromic salt, after adding end, under the normal pressure, 30 ℃, reacted 5 hours.After reaction finished, filtration, washing, drying obtained the royalblue crystalline powder, halfcystine chromium complex yield 80.8%.Trivalent chromium content adopts the ICP method to measure in the halfcystine chromium complex, and cysteine content utilizes the column front derivation high performance liquid chromatography to measure, and recording cysteine content is 88.45%, and trivalent chromium content is 11.55%.
Embodiment 7
In with the reactor of prolong, add potassium bichromate 1.49g(0.005mol) and 10mL water stirring and dissolving, then to the mixed solution that wherein drips 4.0mL concentrated hydrochloric acid (36%) and 10mL dehydrated alcohol, drip and finish rear insulation reaction 20min, obtain the solution of deep green chromic salt, 6.72g D, L-Methionine (0.045mol), potassium hydroxide 2.52g(0.045mol) and volume fraction be 10% ethanol, stirring and dissolving obtains solution, it is joined in the solution of above-mentioned chromic salt, after adding end, under the normal pressure, 90 ℃, reacted 1 hour.After reaction finished, filtration, washing, drying obtained the purple crystal powder, chromium methionine chelate yield 84.6%.Trivalent chromium content adopts the ICP method to measure in the phenylalanine chromium complex, and methionine content utilizes the column front derivation high performance liquid chromatography to measure, and recording methionine content is 89.46%, and trivalent chromium content is 10.54%.
Applicant's statement, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not mean that namely the present invention must rely on above-mentioned method detailed and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. an a-amino acid chromium (III) inner complex is characterized in that, described inner complex general formula is as follows:
In the formula, R be natural a-amino acid normal with organic group.
2. inner complex as claimed in claim 1, it is characterized in that, choose R so that a-amino acid is any one the amino acid that is selected from Histidine, L-Ala, arginine, leucine, tryptophane, L-glutamic acid, glycine, Threonine, Isoleucine, methionine(Met), Methionin, phenylalanine, aspartic acid or the halfcystine, be preferably any one the amino acid in methionine(Met), glycine, Threonine, phenylalanine and the halfcystine.
3. the preparation method of an inner complex as claimed in claim 1 or 2 is characterized in that, described method comprises the steps:
(1) inorganic sexavalence chromic salts is reduced to chromic salt;
(2) solution of preparation alpha-amino group bronsted lowry acids and bases bronsted lowry/basic salt;
(3) solution that step (2) is obtained mixes with chromic salt, and under normal pressure, under 30 ~ 90 ℃ of temperature, behind reaction 1 ~ 5h, cooling is filtered, and washing and dry obtains a-amino acid chromium (III) inner complex.
4. method as claimed in claim 3 is characterized in that, the described method of step (1) is:
In acidic medium, under the effect of reductive agent, inorganic sexavalence chromic salts is reduced to chromic salt.
5. such as claim 3 or 4 described methods, it is characterized in that, the mol ratio of described a-amino acid and sexavalence chromic salts is n:1, and n is between 3 ~ 9;
Preferably, the mol ratio of alkali/basic salt and sexavalence chromic salts is n:1, and n is between 3 ~ 9.
6. such as the described method of one of claim 3-5, it is characterized in that, the described temperature of reaction of step (3) is 40 ~ 88 ℃, preferred 45 ~ 85 ℃, and further preferred 55 ~ 85 ℃;
Preferably, the time of the described reaction of step (3) is 1.5 ~ 5h, preferred 2 ~ 5h.
7. such as the described method of one of claim 3-6, it is characterized in that, described sexavalence chromic salts is selected from the mixture of any one or at least two kinds in potassium bichromate, sodium dichromate 99, chromic trioxide, potassiumchromate or the Sodium chromate;
Preferably, used alkali/basic salt is selected the mixture of any one or at least two kinds in sodium hydroxide, potassium hydroxide, yellow soda ash or the salt of wormwood.
8. such as the described method of one of claim 4-7, it is characterized in that, described reductive agent is selected from the monobasic low-carbon alcohol, the monohydroxy-alcohol of preferred 1 ~ 12 carbon atom, the straight-chain monohydric alcohol of further preferred 1 ~ 5 carbon atom, the mixture of any one in particular methanol, ethanol or the propyl alcohol or at least two kinds further, more further preferred alcohol, most preferably dehydrated alcohol.
9. such as the described method of one of claim 3-8, it is characterized in that, the solvent of the described solution of step (2) is selected from the monobasic low-carbon alcohol, the straight-chain monohydric alcohol of preferred 1 ~ 5 carbon atom, the further mixture of any one in particular methanol, ethanol or the propyl alcohol or at least two kinds, further preferred alcohol again, more preferably volume fraction is 10 ~ 100% ethanol, most preferably volume fraction is 50 ~ 75% ethanol;
Preferably, can reclaim and enter step (2) recycle behind the solvent filter of the described solution of step (2).
10. such as the described method of one of claim 3-9, it is characterized in that, described a-amino acid is any one in pharmaceutical grade, food grade or the feed grade a-amino acid.
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| CN104569238A (en) * | 2013-10-21 | 2015-04-29 | 中国科学院过程工程研究所 | Method for measuring content of amino acid in amino acid chromium complex |
| CN107950777A (en) * | 2017-11-02 | 2018-04-24 | 中国农业科学院北京畜牧兽医研究所 | The preparation method and application of moderate strength glycine chelate chromium novel fodder additive |
| CN109456239A (en) * | 2018-11-09 | 2019-03-12 | 禄丰天宝磷化工有限公司 | A kind of production technology of a-amino acid chelated chromium (III) |
| CN112209821A (en) * | 2020-11-05 | 2021-01-12 | 建明(中国)科技有限公司 | Preparation method of chromium propionate |
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