CN103005166B - Microelement additive and preparation method thereof - Google Patents
Microelement additive and preparation method thereof Download PDFInfo
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- CN103005166B CN103005166B CN2013100239747A CN201310023974A CN103005166B CN 103005166 B CN103005166 B CN 103005166B CN 2013100239747 A CN2013100239747 A CN 2013100239747A CN 201310023974 A CN201310023974 A CN 201310023974A CN 103005166 B CN103005166 B CN 103005166B
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Abstract
The invention discloses microelement additive and a preparation method thereof. The microelement additive is chelated by microelements and small peptides and has a structure of four chelate rings. Stability of product structure is guaranteed by metal small peptide chelates. After ingestion, assimilating portions from an oral cavity to small intestine are kept jointed, original assimilation habits of animals are more accordant, utilization efficiency of the microelements can be improved greatly, the defects that inorganic microelements cannot meet nutrition demands of special physiological period of animals, safety potential hazards are caused by food accumulated in the animals, and ecological environmental pollution is caused by excessive discharge are overcome, damage to microscale active components such as vitamin and drugs during fodder processing and storage is avoided, and unique chemical structure of the microelement additive comes into a play.
Description
Technical field
The present invention relates to a kind of trace mineral supplement, particularly a kind of trace mineral supplement for feed.
Background technology
Trace element is the essential nutrient of animal survival, though it is few to reach in animal body in feed content, for livestock and poultry, aquatic biological grow and health counts for much.Up to the present, micro-element nutrition has experienced inorganic salts, simple organic compound and microelements aminophenol chelated and four developing stage of slowly releasing trace element.Wherein, microelements aminophenol chelated is easier to be absorbed by body, has higher bioavailability, and disease preventing and treating, anti-stress, improve plant recovery of nutrient and improve aspect the reproductive performances of livestock and poultry special role is arranged.
Microelements aminophenol chelated, refer to iron, zinc, manganese etc. and amino acids formed chelate.Existing studies confirm that complete L-Glycylglycine can be absorbed by transhipment, a large amount of metals can be directly be absorbed and enter body and circulate with the form of peptide.Dipeptides, as Gly-Gly, Gly-Ala, Gly-Met, Gly-Trp, Leu-Tyr, Val-Tyr etc.; Tripeptides,, as Gly-Gly-Gly, Gly-Leu-Tyr etc., compare with amino acid whose absorption, have absorb fast, be difficult for saturated, power consumption is low, and with the characteristics such as the absorption of free amino acid is uncontested.
But also there is following shortcoming in present microelements aminophenol chelated: the one, and, existing microelements aminophenol chelated generally only has two chelate rings, makes the stability of chelate still lower; The 2nd, existing microelements aminophenol chelated, its structural form is generally complex cation, acid groups in amino acid still exists, the shortcoming of this structure is that stability constant is on the low side, easily by the phytic acid in animal body, is robbed metal ion and form phytic acid class chelate and be difficult to be absorbed by animal in the animal absorption process; The 3rd, the purity of existing microelements aminophenol chelated is lower, be unfavorable for absorbing, the 4th, existing microelements aminophenol chelated, generally only adopt single amino acid or kilnitamin, still there is larger gap in the physiological structure of its structure and absorption, and utilization rate is low.
Summary of the invention
One of goal of the invention of the present invention is:, for the problem of above-mentioned existence, provide a kind of Stability Analysis of Structures, novel micro element additive that the animal absorption rate is high.
The technical solution used in the present invention is such: a kind of trace mineral supplement, and the structure of described trace mineral supplement is:
, wherein M is divalent metal element.
As preferably: described divalent metal element is Zn
2+
As preferably: described divalent metal is Fe
2+
Two of purpose of the present invention is, a kind of preparation method of above-mentioned trace mineral supplement is provided, and comprises the following steps:
(1) prepare precursor: add sulfate and NaOH, and add water, carry out precipitation reaction, filter, make precipitation of hydroxide;
(2) chelatropic reaction: change the precipitation of hydroxide of step (1) gained over to reactor, and add L-Glycylglycine, carry out chelatropic reaction, wherein, chelatropic reaction temperature 70-78 ℃, control endpoint pH 3.5-4.0;
(3) filtration, drying: products therefrom is filtered, and dry, obtain.
As preferably: the solubility product constant K that controls precipitation of hydroxide in (1) step
sp10
-15～10
-18
As preferably: adopt filter-pressing method to filter in (1) step.
Above-mentioned L-Glycylglycine, the preferred L-Glycylglycine that adopts biological enzymolysis to obtain, replace acid, basic hydrolysis albumen waste material, zymolysis technique has been controlled the degree of decomposition of peptide bond, make the protein major part be decomposed into little peptide but not single amino acid, other nutritional labeling in little peptide is not destroyed, and is purer, green when guaranteeing product quality, meets the original pattern of digesting and assimilating of animal.
Utilize amido (amino group), carboxyl (carboxyl group) and the amide groups (amide group) of the little peptide molecule of biological enzymolysis and the characteristics that contain the elements such as N, S, O, as amino acid, the lone pair electrons that the elements such as the N of little peptide molecule, S, O have are certain coordination sites (tooth), and carboxyl both can be used as ligand, also can be used as the central metal ion positive charge of anion balance complex.Different from amino acid, little peptide molecule also has amide groups,
Wherein three center conjugated systems of O, C, N three atomic buildings are also potential parts, can complexing proton and metal ion, thus, little peptide (being L-Glycylglycine) can provide three coordination sites at least as part, and namely tridentate ligand, can form chelate with metal ion, and adopt above-mentioned suitable reaction temperature and pH terminal to control, can form the chelate of four higher chelate rings of Stability Analysis of Structures and absorption rate.
Adopt the amino acid of this molecular weight of L-Glycylglycine to form little peptide, micronutrient levels in conveniently adjusted product, solved the too low shortcoming of micronutrient levels in existing trace mineral supplement.
For precipitation of hydroxide, if K
spToo little, be difficult to carry out with the reaction of metal and little peptide; If K
spToo large, be unfavorable for the utilization fully of metal ion, through great many of experiments, the present invention determines the solubility product constant K of the formed precipitation of hydroxide of these several metal trace elements that animal body needs
spApproximately 10
-15～10
-18In scope, relatively be fit to and metal and little reactive polypeptide, form stable huge legendary turtle compound.
When producing iron chelate, can also add sodium thiosulfate in (1) step.
Add sodium thiosulfate can stop ferrous iron to be oxidized to ferric iron, utilize the reproducibility of sodium thiosulfate and can not introduce other impurity, the sodium sulphate that generates is removed in the filtration washing process, thereby guaranteed that the trace mineral supplement purity that obtains is high, the amount that adds sodium thiosulfate is the 1-2% of weight of iron content.
After realizing Separation of Solid and Liquid and wash away sodium sulphate, the method for use press filtration enters immediately in the chelatropic reaction tank that is watered in advance, isolated with air, to be difficult for being oxidized to ferric iron after precursor and metal and the stable chelate of small-peptide chelated formation, adopt the spray-drying mode when dry, make the product wink-dry, in case chelated iron dries out, will be difficult to by ferric iron that airborne oxygen is oxidized to.
the little peptide huge legendary turtle of metal of the present invention compound has been guaranteed the stable of product quality, keep bonding state after searching for food to the intestinal absorption position from oral cavity, more meet the original pattern of digesting and assimilating of animal, can greatly improve the utilization ratio of trace element, overcome inorganic microelement and can't fully meet the animal special physiological nutritional need in period, and accumulate in a large number in animal body the ecological environmental pollution that the food security hidden danger brought and excessive emissions cause, avoided processing at feed, in storage process to the destruction of the trace active compositions such as vitamin and medicine, and with its unique chemical constitution, play a role.
In sum,, owing to having adopted technique scheme, the invention has the beneficial effects as follows:
1, the reaction of the carboxylic acid metal's hydroxide in amino acid neutralizes acid to form inner complex salt but not complex cation; 2, a plurality of amino acid in little peptide and metal center ion chelating form four chelate rings, and structure is more stable; 3, the trace mineral supplement tenor that makes is high, purity is high; 4, in this structure, metal ion exists form very approaching in organism, is easier to the absorption of organism, thereby in the ight soil of excretion, tenor reduces greatly, and pollution on the environment is little, environmental protection.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in detail.
, in order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1:
A kind of trace mineral supplement, its structure is:
, wherein M is Zn
2+, prepare the method for this trace mineral supplement:
A. prepare the hydroxide precursor: add quantitative zinc sulfate and NaOH, and add water, carry out precipitation reaction, control K
sp=8.0 * 10
-16, make hydroxide zinc precipitation;
(2) chelatropic reaction: change the zinc hydroxide precipitation over to the chelatropic reaction device, and add the L-Glycylglycine (available from the true Bioisystech Co., Ltd in Shanghai) that is obtained by enzyme digestion reaction, carry out chelatropic reaction, wherein, zinc hydroxide and L-Glycylglycine ratio are mol ratio 1:2,75 ℃ of chelatropic reaction temperature, control terminal pH value 3.5;
(3) filtration, drying: products therefrom is filtered, and adopt spray-dired method to carry out drying, obtain,
Based on chemical reaction:
In reaction equation (2), M is configuration metal ions Zn
2+ Fourth Ring chelate for L-Glycylglycine and zinc ion formation;
Fe
2+Deng chelate also available the method is synthetic.
Embodiment 2
Adopt ferrous hydroxide and L-Glycylglycine chelating, 78 ℃ of chelatropic reaction temperature, control terminal pH value 4.0, wherein, controls the K of ferrous hydroxide
sp=8.0 * 10
-18, also adding sodium thiosulfate while preparing precursor, all the other are identical with embodiment 1.
Embodiment 3
The chelate stability test
Adopt respectively the chelate (D1) of glycine and zinc complexing and chelate (S2) that embodiment 2 obtains as experimental subjects, adopting x-ray photoelectron power spectrum (XPS) to detect (respectively takes a sample 8 times, calculate finally mean value), result shows, in S2, the electron binding energy of Fe2p3/2 track is 690.258eV, electron binding energy 690.966 eV far below Fe2p3/2 track in D1, illustrate that biological enzymolysis Metal Phase used has stronger coordination ability than glycine, namely has stronger chelation.
Embodiment 4
Animal absorbs experiment:
Choose the piglet of 80 body weight at 15-15.2kg, be divided at random two groups, 40 every group, one group is contrast groups, and one group is experimental group,
wherein experimental group adopts the little peptide of zinc chelating that embodiment 1 obtains as zinc additive, the zinc that the contrast groups employing is common and glycine chelate (mol ratio of zinc and glycine is 1:2) are as the additive of zinc, and after conversion, zinc content is consistent, experimental group adopts all the other identical trace mineral supplements with contrast groups, adopt the mode of free choice feeding to feed 30 days, and detected the content of zinc in ight soil in every 6 days, result shows: the average proportions that contrast groups detects in ight soil zinc accounts for addition is respectively 21.1%, 18.2%, 15.6%, 16.5% and 11.8%, and accounting for the average proportions of addition, experimental group detects in ight soil zinc is respectively 12.8%, 11.2%, 9.5%, 8.2% and 6.7%, show that the zinc absorptivity of experimental group has substantially exceeded the absorptivity of contrast groups, simultaneously, after 30 days, the important comparison of average body of experimental group is manyed 2.8kg than the average weight of group, and the zinc absorptivity of illustrative experiment group is high, is fully utilized simultaneously.
The foregoing is only preferred embodiment of the present invention,, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. the preparation method of a trace mineral supplement is characterized in that: comprise the following steps:
(1) prepare precursor: add sulfate and NaOH, and add water, carry out precipitation reaction, filter, make precipitation of hydroxide;
(2) chelatropic reaction: change the precipitation of hydroxide of step (1) gained over to reactor, and add L-Glycylglycine, carry out chelatropic reaction, wherein, chelatropic reaction temperature 70-78 ℃, control endpoint pH 3.5-4.0;
(3) filtration, drying: products therefrom is filtered, and dry, obtain.
2. the preparation method of a kind of trace mineral supplement according to claim 1, it is characterized in that: the L-Glycylglycine in (2) step is the L-Glycylglycine that biological enzymolysis obtains.
3. the preparation method of a kind of trace mineral supplement according to claim 1, is characterized in that: the solubility product constant K that controls precipitation of hydroxide in (1) step
sp10
-15～10
-18
4. the preparation method of a kind of trace mineral supplement according to claim 1, is characterized in that: adopt filter-pressing method to filter in (1) step.
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| CN2013100239747A CN103005166B (en) | 2013-01-23 | 2013-01-23 | Microelement additive and preparation method thereof |
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|---|---|---|---|
| CN2013100239747A CN103005166B (en) | 2013-01-23 | 2013-01-23 | Microelement additive and preparation method thereof |
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| CN103005166B true CN103005166B (en) | 2013-11-13 |
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| CN101112222B (en) * | 2007-06-29 | 2012-01-11 | 中国农业大学 | Method for producing composite peptide hydrolysate, the rumen bypass composite peptide chelate complex and the production process thereof and the application |
| WO2009142755A2 (en) * | 2008-05-22 | 2009-11-26 | Marical, Inc. | Methods of nourishing animals |
| CN102550824B (en) * | 2012-01-17 | 2013-09-18 | 罗宪章 | Method for producing small peptide amino acid microelement chelate by way of acid hydrolysis of protein |
| CN102657285A (en) * | 2012-05-30 | 2012-09-12 | 张军民 | Smallpeptide chelate trace element feed additive and production process thereof |
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