CN101786961A - Chromium threonine, preparation method and application thereof - Google Patents
Chromium threonine, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to feed additives and the field of preparation thereof and in particular discloses a threonine chelate named chromium threonine of which the molecular formula is Cr(C4H8NO3)3 and the molecular structural formula is represented below. The preparation method for the chromium threonine comprises the following steps: mixing trivalent inorganic chromium and aqueous solution of threonine, wherein the molar ratio of chromium element in the trivalent inorganic chromium to the threonine is (0.9-1.1):3, adding sodium hydroxide to control the pH value of the mixed solution to be between 6.5 and 7.5, controlling a reaction temperature to be between 60 and 100 DEG C and fully reacting the mixed solution to obtain a reaction product; and cooling, filtering and pumping the reaction product, adding ethanol into a filter cake, filtering the mixture, washing the mixture with the ethanol, and pumping and drying the mixture to obtain the finished product. The chromium threonine of the invention can be used as an animal feed additive, and can promote synchrotron absorption of the threonine and a trace element, namely the chromium, of animals, effectively promote growth of the animals, enhance immunity of the animals and increase utilization rate of the feed.
Description
Technical field
The present invention relates to a kind of fodder additives and preparation method thereof, relate in particular to a kind of amino acid chelate thing and its production and application.
Background technology
Threonine is a kind of important nutrition-fortifying agent, can play the nutritional fortification effect to cereal, cake, milk-product etc.Threonine is the same with tryptophane, also has to recover human-body fatigue, promote the function of growing.Pharmaceutically,, human body skin is had the water holding effect, after oligonucleotide chain combines, can play an important role the protection cytolemma owing to contain hydroxyl in the structure of Threonine; Threonine can also promote the synthetic and Fatty Acid Oxidation of phosphatide in vivo, and its preparation has medicinal efficacies such as the human development of promotion, anti-fatty liveranti-fatty liver, is commonly used for a moiety in the aminoacids complex transfusion.Simultaneously, Threonine is still made efficient low microbiotic hypersensitive---the basic raw material of monobactam.Along with the raising of people's living standard and the continuous development of aquaculture, Threonine has been widely used in and has added pig starter feed, kind pig feed, broiler fodder, prawn feed and eel feed etc. as feed amino acid.Threonine has following characteristics as animal feedstuff additive: can adjust amino acid whose balance in the feed, promote growth of animal; Can improve meat; Can improve the nutritive value of the low animal-feed raw material of amino acid digestibility; Can be used for producing low proteic feed, help to save protein resource; Can reduce the animal-feed raw materials cost; Can reduce ammonia concentration and release rate in nitrogen content in feces of livestock and poultry and the urine, the livestock and poultry house.Threonine is as the common a kind of limiting amino acid of animal, and its content and proportioning directly affect the nutritive value of daily ration and the production performance of livestock and poultry, adds limiting amino acid and can improve efficiency of feed utilization to greatest extent in the animal daily ration.
Chromic salts is divided into inorganic chromium and organic chromium two big classes, and the branch of trivalent, sexavalence is arranged.Sexavalent chrome (Cr
6+) poisonous, with what the sexavalent chrome form existed chromium trioxide, potassiumchromate and potassium bichromate arranged; Inorganic trivalent chromium (Cr
3+) chromium trichloride etc. arranged; Organic trivalent chromium has chromium methionine, nicotinic acid chromium, yeast chromium, chromium picolinate etc.Wherein, inorganic chromium does not allow to add in feed.
Chromium (Cr
3+) be essential micronutrient element in the humans and animals body.Chromium can improve the bonding force of Regular Insulin and special acceptor, promotes the synthetic of glucose transport and liver glycogen; Regulate lipid metabolism, improve the blood fat situation; Keep nucleic acid construct integrity and stability, help the storages of amino acid in tissue such as glycine, Serine, methionine(Met), and strengthen proteic Synthesis; Enhancing body immunologic function and anti-stress ability, and can stimulate the hemopoietic function of body; Can improve the production performance of stressed animal, endocrine regulation.In addition, it all has good effect at aspects such as improving carcass quality and raising reproductive performance.
What use was more at present is chromium picolinate, nicotinic acid chromium, chromium methionine, yeast chromium etc., although wherein the chromium picolinate specific absorption is much higher than inorganic chromium, but after chromium picolinate enters in the animal body, chromium element and pyridine ring are combined closely, keeping original form for a long time, chromium ion is difficult to be utilized, and life-time service also can cause dna break, and mutagenesis is arranged.Simultaneously, pyridine ring also has certain detrimental effect to animal body, poisons liver; The effective constituent less stable of yeast chromium, bad quantification.
How better in conjunction with the advantage of above-mentioned nutritive ingredient and trace element, the complementarity of two kinds of materials can be found full expression in feed, and better promote the synchronous absorption of animal body to above-mentioned two kinds of materials, just become the technical problem that those skilled in the art need to be resolved hurrily.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, a kind of fodder additives chromium threonine that can promote that animal absorbs synchronously to Threonine and trace element chromium is provided, and provide the preparation method of a kind of technology chromium threonine simple, with low cost at this novel substance chromium threonine, also provide a kind of chromium threonine to be applied to method in the animal feedstuff additive simultaneously, to reach effective promotion growth of animal, strengthen the animal resistibility and to improve the purpose of food utilization efficiency.
For solving the problems of the technologies described above, the present invention proposes a kind of Threonine huge legendary turtle compound, it is characterized in that: the name of described Threonine huge legendary turtle compound is called chromium threonine (III), and its molecular formula is Cr (C
4H
8NO
3)
3, molecular structural formula is
Chromium threonine of the present invention is the light violet magenta powder, is slightly soluble in water, is insoluble to alcohols.As the important composition composition of glucose tolerance factor, the glucose normal level plays an important role with the trans-utilization that promotes body to sugar in the animal blood to keeping; Can impel Regular Insulin to activate and, quicken amino acid and enter in the cell and receptors bind, thereby promote protein synthesis, improve the fattening pig lean ratio, reduce fryer abdomen fat rate, improve carcass quality attached on the cell; Increase the avidity of tissue, regulate the secretion and the release of gonad-stimulating hormone, improve sow reproductive performance, increase sow ovulation and litter size Regular Insulin; Animal stress, be activated and promotion function of immune system aspect plays an important role to alleviating.
The present invention also provides a kind of preparation method of above-mentioned chromium threonine, may further comprise the steps:
(1) with trivalent inorganic chromium (the perhaps crystalline hydrate of inorganic chromium) and mass concentration is 10%～60% Threonine aqueous solution, the mol ratio of chromium element and Threonine is (0.9～1.1) in the described trivalent inorganic chromium: 3, the pH value of adding sodium hydroxide control mixed solution again is 6.5～7.5 (the general mass concentration of sodium hydroxide in reaction solution is 5%～45%), temperature of reaction is controlled at 60 ℃～100 ℃, fully obtains reaction product after the reaction;
(2) with described reaction product cooling, suction filtration, drain, in filter cake, add ethanol then, suction filtration again, at last with washing with alcohol, drain, obtain finished product after the drying.
Use the hydrogen peroxide oxidation trivalent chromium, add potassiumiodide again and be oxidized into iodine, the iodimetry,iodometry of Sulfothiorine titration iodine is surveyed trivalent chromium, measures threonine content with the method for deciding nitrogen; Can determine finally that by XRD and infrared spectra finished product is a chromium threonine.
Above-mentioned preparation method's main reaction formula is:
CrCl
3·6H
2O+3C
4H
9NO
3+3NaOH＝Cr(C
4H
8NO
3)
3+3NaCl+9H
2O。
Among the above-mentioned preparation method, described trivalent inorganic chromium preferably includes chromium chloride (CrCl
3), water miscible trivalent inorganic chromate salt such as chromium nitrate or chromium sulphate.
Among the above-mentioned preparation method, described exsiccant method is preferably and at room temperature is dried to earlier no ethanol smell, thorough drying under 80 ℃～150 ℃ temperature again.This preferred drying mode mainly is for security consideration, and the too high meeting of temperature makes product decompose.
The present invention also provides the application of above-mentioned chromium threonine in the preparation animal feedstuff additive.Described chromium threonine is preferred for preparing the fodder additives of pig feed, poultry feed, and described pig feed comprises brood sow feed, pig starter feed or grow-finish pig feed, and described poultry feed comprises poultry feed or egg fowl feed.
With the additive of above-mentioned chromium threonine as the brood sow feed, in feed per ton, add under the optimum condition of 150～250g, can obviously shorten the breeding cycle of sow, increase to produce and live young number and produce parity per year, reduce the equal death toll of nest.
With the additive of above-mentioned chromium threonine as pig starter feed, in feed per ton, add under the optimum condition of 150～200g, can improve the speed of growth of suckling piglet, strengthen its resistance against diseases.
With the additive of above-mentioned chromium threonine as the grow-finish pig feed, in feed per ton, add under the optimum condition of 100～250g, can improve day weight gain, the reduction material anharmonic ratio of fattening pig, help to improve the bodily form simultaneously, improve carcass quality, reduce the fat thickness degree, reduce fat ratio.
With the additive of above-mentioned chromium threonine as the poultry feed, in feed per ton, add under the condition of 100～250g, the speed of growth, reduction feedstuff-meat ratio, increase trunk protein, the reduction fat ratio of broiler chicken be can improve, and anti-stress ability, reduction mortality ratio improved.
With the additive of above-mentioned chromium threonine as egg fowl feed, in feed per ton, add under the situation of 150～300g, can improve the laying rate of laying hen, improve eggs ' quality, reduce cholesterol level in the yolk, Hough unit increases.
The addition manner of above-mentioned fodder additives preferably adds with solid form, will make other composition in the feed can the oxidation because of the moisture absorption because add with solid form.
Compared with prior art, the invention has the advantages that: chromium threonine of the present invention is to absorb by the amino acid approach in livestock and poultry alimentary tract, and its absorption rate is fast, and specific absorption improves greatly, the biological value height.Chromium threonine of the present invention also has good promoter action to the micro-element nutrition of improving animal.Chromium threonine of the present invention also can provide the nutrition of Threonine except that satisfying the needs of animal to trace element chromium, so can promote growth of animal, significantly improve the utilization ratio of feed.Chromium threonine of the present invention has stable chemical structure as trace mineral supplement, safety non-toxic, nonirritant, and the output of inorganic chromium is little in the animal excrement, therefore can protect environment, reduce and pollute.Trace mineral supplement chromium threonine of the present invention can be widely used in (as pig, fowl etc.) in the various animal-feeds, can significantly improve the growth performance of animal, improves the utilization ratio of feed.The preparation method who the present invention is directed to above-mentioned chromium threonine proposition also has advantages such as technology is simple, easy to operate, reaction is quick, equipment cost is cheap, energy-conserving and environment-protective.
Embodiment
Embodiment 1:
A kind of chromium threonine finished product of the present invention is to prepare by following steps: at first drop into 150g water in reactor, get the 35.8g Threonine then, put in the reaction vessel and fully stir, drop into the CrCl of 26.6g again
36H
2O, heating for dissolving also is warming up to 70 ℃, uses the pH value to 6.8 of 14g sodium hydroxide conditioned reaction mixed solution then, react 0.5h under the condition of normal pressure, postcooling to 30 ℃, suction filtration are finished in reaction, drain, filter cake after draining is placed the ethanol of 50ml, continue suction filtration, drain, use 95% washing with alcohol again, drain, prior to being dried to no ethanol smell under the room temperature,, prepare the finished product of light violet magenta after the pulverizing again 110 ℃ of following thorough dryings.
Finished product hydrogen peroxide oxidation trivalent chromium adds potassiumiodide again and is oxidized into iodine, and the iodimetry,iodometry of Sulfothiorine titration iodine is surveyed trivalent chromium, measures threonine content with the method for deciding nitrogen; According to measurement result, chromium content is 12.5% in the finished product, and threonine content is 85.5%, and moisture content is 1.5%, and surplus is an impurity.With XRD diffracting spectrum and infrared spectra can qualitative product be chromium threonine.
The above-mentioned fodder additives chromium threonine finished product that makes is used for the store pig feeding experiment.Select body weight 75kg, same cross combination, store pig 20 hurdles that body weight is close, every hurdle pig is weighed by head, with excessive pig, cross piggy, cad pig is chosen respectively, 6～12 of every circle pigs according to every group 5 hurdle, are divided into 4 groups at random, be every group of 5 repetitions, every hurdle is a repetition.Control group feed per ton adds chromium trichloride 250g, tests one group of feed per ton and adds chromium threonine 100g, tests two groups of feeds per ton and adds chromium threonine 175g, tests three groups of feeds per ton and adds chromium threonine 250g.Test-results sees Table 1.
Table 1: chromium threonine is to the influence of store pig production performance
| Group | Average initial weight kg | The heavy kg in average end | Average daily ingestion amount kg | Average daily gain g | Feedstuff-meat ratio |
| Control group | ??75.92±1.57 a | ??99.71±4.68 a | ??2.45±0.11 a | ??665.33±36.72 a | ??3.68±0.021 a |
| Test one group | ??76.03±1.32 a | ??101.67±3.07 b | ??2.48±0.15 a | ??710.11±41.26 b | ??3.49±0.034 b |
| Test two groups | ??75.42±1.49 a | ??103.48±4.17 b | ??2.52±0.09 a | ??728.83±23.26 b | ??3.46±0.019 b |
| Test three groups | ??76.10±1.63 a | ??105.54±3.89 b | ??2.51±0.12 a | ??732.56±39.74 b | ??3.43±0.082 b |
Annotate: same column shoulder marking-up parent phase expression difference together is remarkable (p＞0.05) not; The female expression significant difference (p＜0.05) inequality of same column shoulder marking-up.
As can be seen from Table 1, control group and test group be difference not significantly (p＞0.05) on average initial weight, average daily ingestion amount index, but the difference (p＜0.05) of significance is arranged on, average daily gain heavy at average end and the feedstuff-meat ratio; Along with the raising of chromium threonine addition, day weight gain has the trend of rising, feedstuff-meat ratio to have a declining tendency, but test group differences not significantly (p＞0.05).This test-results shows, chromium threonine has remarkable advantages improving the fattening pig speed of growth and improve on the price of deed.
Embodiment 2:
At first in reactor, drop into 300g water, get the 285g Threonine then, put in the reaction vessel and fully stir, drop into the Cr (NO of 325g again
3)
39H
2O, heating for dissolving also is warming up to 95 ℃, slowly drops into the pH value to 6.9 of the about 106g conditioned reaction of sodium hydroxide mixed solution then, react 2h under the condition of normal pressure, postcooling to 25 ℃, suction filtration are finished in reaction, drain, filter cake after draining is dropped in 95% ethanol of 180ml, stir the back of loosing and continue suction filtration, use 95% washing with alcohol again, drain, prior to being dried to no ethanol smell under the room temperature,, prepare the finished product of light violet magenta after the pulverizing again 95 ℃ of following thorough dryings.Adopt the detection method of embodiment 1 and means can record that chromium content is 12.6% in the finished product, threonine content is 85.0%, and moisture content is 1.9%, and surplus is an impurity.
The fodder additives that present embodiment is made makes an addition in the brood sow daily ration.Select the Du Luoke multiparity sow of same parity, be divided into four groups, 10 every group, breed with 2～3 Du Luoke boars for every group, require in a rutting sedson, to finish breeding.Wherein interpolation chromium nitrate 250g in the feed per ton of control group tests one group of feed per ton and adds chromium threonine 150g, two groups of feeds interpolation chromium threonine 175g per ton of test, three groups of feeds interpolation chromium threonine 250g per ton of test, and test-results sees Table 2.
Table 2: chromium threonine is to the influence of sow reproductive performance
Annotate: same column shoulder marking-up parent phase expression difference together is remarkable (p＞0.05) not; The female expression significant difference (p＜0.05) inequality of same column shoulder marking-up.
As can be seen from Table 2, for young number of nascent work and nascent litter weight, control group and test group difference is remarkable (p＞0.05) not; But along with the variation of feeding time, young number of the work of its 21 age in days and litter weight also change thereupon, and survival rate also shows the difference (p＜0.05) of significance; During 42 ages in days, the performance of the young number of living is similar to 21 ages in days, and incubation rate also reaches significant difference (p＜0.05).Above result shows: add the test group of chromium threonine, though not remarkable at the young number of the work of nascent brood sow and litter weight and control group difference, the survival rate in its later stage and incubation rate all reach significant difference, and litter weight also has raising trend.
Embodiment 3:
At first in reactor, drop into 35g water, get the 35.8g Threonine then, put in the reaction vessel and fully stir, drop into the Cr of 25g again
2(SO
4)
36H
2O, heating for dissolving also is warming up to 95 ℃, slowly drops into the pH value to 6.7 of the about 13.5g conditioned reaction of sodium hydroxide mixed solution then, react 2h under the condition of normal pressure, postcooling to 10 ℃, suction filtration are finished in reaction, drain, filter cake after draining is dropped in 95% ethanol of 20ml, stir the back of loosing and continue suction filtration, use 95% washing with alcohol again, drain, prior to being dried to no ethanol smell under the room temperature,, prepare the finished product of light violet magenta after the pulverizing again 95 ℃ of following thorough dryings.Adopt the detection method of embodiment 1 and means can record that chromium content is 12.6% in the finished product, threonine content is 84.9%, and moisture content is 1.7%, and surplus is an impurity.
The above-mentioned fodder additives that makes is used to the feeding experiment of feeding laying hen.Select 360 of the consistent blue commodity eggs in 39 seas in age in week of health, body weight for use, be divided into 4 groups at random, every group of 3 repetitions, each repeats 30.Test one group of interpolation ammonia chromium 150g of Soviet Union per ton, test two groups of interpolation chromium threonine 225g per ton, test three groups of chromium threonine 300g per ton; Control group interpolation chromium sulphate per ton 300g.Test-results sees Table 3.
Table 3: chromium threonine is to the influence of production performance of layer chicken
| Group | Laying rate % | Egg productivity g/ day/only | Food consumption g/ day/only | Feedstuff-egg ratio | Breakage rate % | Death rate % |
| Control group | ??81.27±1.62 a | ??48.69±0.98 a | ??94.92±1.34 a | ??1.95±0.03 a | ??0.50±0.09 a | ??1.32±0.35 a |
| Test one group | ??84.43±0.93 b | ??50.16±0.56 b | ??94.68±1.18 a | ??1.89±0.03 b | ??0.38±0.09 b | ??0.75±0.24 b |
| Test two groups | ??85.01±1.01 b | ??50.71±0.66 b | ??94.40±1.70 a | ??1.86±0.03 b | ??0.31±0.04 bc | ??0.66±0.25 b |
| Test three groups | ??85.76±1.10 b | ??51.44±0.06 b | ??94.59±0.94 a | ??1.84±0.05 b | ??0.28±0.04 c | ??0.35±0.20 c |
Annotate: same column shoulder marking-up parent phase expression difference together is remarkable (p＞0.05) not; The female expression significant difference (p＜0.05) inequality of same column shoulder marking-up.
As can be seen from Table 3, each test group is compared with control group on laying rate, egg productivity, feedstuff-egg ratio index and is improved, difference reaches conspicuous level (p＜0.05), the egg product matter of test group is better than control group, its breakage rate has been compared tangible minimizing with control group, difference reaches conspicuous level (p＜0.05); Test group is compared the death rate fall with control group all bigger, all significantly is lower than control group (p＜0.05); And the difference between the test group on indexs such as breakage rate, death rate has significance.Above test-results shows that chromium threonine can significantly improve the laying rate of laying hen and lay eggs heavily, can effectively improve feedstuff-egg ratio, reduce breakage rate and death rate, and not influence the daily ration palatability.
Embodiment 4:
At first in reactor, drop into 450Kg water, get the 335kg Threonine then, put in the reaction vessel and fully stir, drop into the CrCl of 233kg again
36H
2O, heating for dissolving also is warming up to 80 ℃, slowly drops into the pH value to 7.4 of the about 115kg conditioned reaction of sodium hydroxide mixed solution then, react 1h under the condition of normal pressure, postcooling to 20 ℃, suction filtration are finished in reaction, drain, filter cake after draining is dropped in the ethanol of 200L95%, stir the back of loosing and continue suction filtration, use 95% washing with alcohol again, drain, prior to being dried to no ethanol smell under the room temperature,, prepare the finished product of light violet magenta after the pulverizing again 95 ℃ of following thorough dryings.Adopt the detection method of embodiment 1 and means can record that chromium content is 11.8% in the finished product, threonine content is 86.5%, and moisture content is 1.3%, and surplus is an impurity.
Claims (7)
1. a name is called the Threonine huge legendary turtle compound of chromium threonine, and it is characterized in that: the molecular formula of described chromium threonine is Cr (C
4H
8NO
3)
3, molecular structural formula is as follows:
2. the preparation method of a chromium threonine as claimed in claim 1 may further comprise the steps:
(1) with trivalent inorganic chromium and mass concentration is 10%～60% Threonine aqueous solution, the mol ratio of chromium element and Threonine is (0.9～1.1) in the described trivalent inorganic chromium: 3, the pH value of adding sodium hydroxide control mixed solution again is 6.5～7.5, temperature of reaction is controlled at 60 ℃～100 ℃, fully obtains reaction product after the reaction;
(2) with described reaction product cooling, suction filtration, drain, in filter cake, add ethanol then, suction filtration again, at last with washing with alcohol, drain, obtain finished product after the drying.
3. preparation method according to claim 2 is characterized in that: described trivalent inorganic chromium comprises chromium chloride, chromium nitrate or chromium sulphate.
4. according to claim 2 or 3 described preparation methods, it is characterized in that: described exsiccant method is at room temperature being dried to earlier no ethanol smell, thorough drying under 80 ℃～150 ℃ temperature again.
One kind as claimed in claim 1 or as the application in the preparation animal feedstuff additive of each prepares in the claim 2～4 chromium threonine.
6. application according to claim 5 is characterized in that: described chromium threonine is the fodder additives that is used to prepare pig feed, and described pig feed comprises brood sow feed, pig starter feed or grow-finish pig feed; Wherein, brood sow feed per ton adds described chromium threonine 150～250g; Pig starter feed per ton adds described chromium threonine 150～200g; Grow-finish pig feed per ton adds described chromium threonine 100～250g.
7. application according to claim 5 is characterized in that: described chromium threonine is the fodder additives that is used to prepare poultry feed, and described poultry feed comprises poultry feed or egg fowl feed; Wherein, poultry feed per ton adds described chromium threonine 100～250g; Egg fowl feed per ton adds described chromium threonine 150～300g.
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| CN102550830A (en) * | 2012-02-17 | 2012-07-11 | 长沙兴嘉动物营养科技有限公司 | Method for applying and preparing gamma-aminobutyric acid complex compound |
| CN102718803A (en) * | 2012-06-01 | 2012-10-10 | 广州九益生物技术有限公司 | Preparation method and application of N-carbamoyl-L-chromium glutamate complex |
| CN103030584A (en) * | 2012-12-04 | 2013-04-10 | 山东省化工研究院 | Method for preparing feed additive tryptophan chromium complex |
| CN103739509A (en) * | 2014-01-09 | 2014-04-23 | 山东祥维斯生物科技有限公司 | Industrial production and preparation process of glycine chelated manganese |
| CN109362997A (en) * | 2018-10-15 | 2019-02-22 | 浙江省海洋水产研究所 | A kind of feed addictive and preparation method thereof improving marine fish quality |
| CN112209821A (en) * | 2020-11-05 | 2021-01-12 | 建明(中国)科技有限公司 | Preparation method of chromium propionate |
| CN115053937A (en) * | 2022-06-20 | 2022-09-16 | 浙江惠嘉生物科技股份有限公司 | Preparation method of chromium nicotinate nano dispersion preparation |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102550830A (en) * | 2012-02-17 | 2012-07-11 | 长沙兴嘉动物营养科技有限公司 | Method for applying and preparing gamma-aminobutyric acid complex compound |
| CN102550830B (en) * | 2012-02-17 | 2015-01-14 | 长沙兴嘉生物工程股份有限公司 | Method for applying and preparing gamma-aminobutyric acid complex compound |
| CN102718803A (en) * | 2012-06-01 | 2012-10-10 | 广州九益生物技术有限公司 | Preparation method and application of N-carbamoyl-L-chromium glutamate complex |
| CN103030584A (en) * | 2012-12-04 | 2013-04-10 | 山东省化工研究院 | Method for preparing feed additive tryptophan chromium complex |
| CN103739509A (en) * | 2014-01-09 | 2014-04-23 | 山东祥维斯生物科技有限公司 | Industrial production and preparation process of glycine chelated manganese |
| CN109362997A (en) * | 2018-10-15 | 2019-02-22 | 浙江省海洋水产研究所 | A kind of feed addictive and preparation method thereof improving marine fish quality |
| CN112209821A (en) * | 2020-11-05 | 2021-01-12 | 建明(中国)科技有限公司 | Preparation method of chromium propionate |
| CN115053937A (en) * | 2022-06-20 | 2022-09-16 | 浙江惠嘉生物科技股份有限公司 | Preparation method of chromium nicotinate nano dispersion preparation |
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