CN106220691A - The preparation method of sucrose manganese complex - Google Patents
The preparation method of sucrose manganese complex Download PDFInfo
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- CN106220691A CN106220691A CN201610614772.3A CN201610614772A CN106220691A CN 106220691 A CN106220691 A CN 106220691A CN 201610614772 A CN201610614772 A CN 201610614772A CN 106220691 A CN106220691 A CN 106220691A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/04—Disaccharides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
The invention discloses the preparation method of a kind of sucrose manganese complex, it is by sucrose and manganese sulfate complex reaction, obtain sucrose manganese solution, filter the most after cooling, obtaining filtering residue and filtrate, filtrate adds ethanol water and is settled out complex, by pelleting centrifugation sucking filtration, vacuum drying is dried, and obtains purer sucrose complexation manganese product;The manganese ion concentration of detection filtering residue, is 1:4 according to the mol ratio of sucrose Yu manganese ion, continuously adds sucrose and manganese sulfate, and the waste water after centrifugal sucking filtration returns to the mother solution as dissolving saccharose in reactor, and circular response continues to generate sucrose manganese.The present invention prepares the process of sucrose manganese, does not waste resource, reduces production cost, improves production efficiency.Obtain sucrose manganese and there is safe efficient, the advantage of high performance-price ratio, can be applicable to the animal feed being suitable for producing comprehensive nutrition.
Description
Technical field
The present invention relates to a kind of complex, particularly sucrose manganese complex and preparation method thereof, and disclose its purposes.
Background technology
Manganese is arginase, prolinase, RNA polymerase, superoxide dismutase, pyruvate carboxylase in body
Constituent.Manganese ion has the function activating multiple enzyme, as to aldolase, phosphorylase, phosphoglucomutase, different
Citric dehydrogenase and cholinesterase all have activation.Manganese be the effect by animal body endoenzyme and participate in carbohydrate,
The important substance such as fat, protein metabolic, and the synthesis of vitamin B, C, E can be strengthened, manganese is in choline generation
Lipotropic effect is had during thanking.Glutamic oxaloacetic transaminase, GOT, glutamate pyruvate transaminase, lactic acid dehydrogenase, creatine phosphokinase activity with
Manganese in diet is relevant.
Manganese is one of trace element closely-related with poultry bone growth, and the growth promoter of skeleton is had by manganese element
Important function.Before more than 60 year, Wilgus just studies confirmation, and manganese deficiency can cause the generation of chickling " sliding tendon disease ".Manganese element affects bone
The growth promoter of bone, participates in constituting the formation of bone matrix chondroitin sulfate mainly due to manganese.Chondroitin sulfate is organic
The constituent of mucopolysaccharide.Manganese is the special activity factor of polysaccharide polymerase and galactosyl transferase.So in the conjunction of mucopolysaccharide
Cheng Zhong, manganese is necessary to polysaccharide polymerase and galactosyl transferase.Galactose-gala is formed by UDP-galactose and xylose
Sugar-xylose.This trisaccharide and serine connect, and then form mucopolysaccharide with aminohexose polymerization.Manganese deficiency can cause polysaccharide to be polymerized
Enzyme and, core galactosyltransferase both enzymatic activitys reduce, the synthesis of chondroitin sulfate substantially reduces, thus just affects skeleton
It is commonly formed.Morphologic it has been observed that the growth that manganese deficiency affects bone essentially consists in bone sacrum pathological changes from ill domestic animal, this be also manganese deficiency with
Other materials (choline, biotin) lack the difference affecting bone growth and development.During chickling manganese deficiency, occur " sliding tendon disease " or
Claim " the short and thick disease of bone ".Typical case's condition of illness in " 0 " shape or " x " shape, shortens thicker when being to stand.Chicken manganese deficiency the most specifically affects
Chest muscle growth promoter, shows as chest muscle fibre diameter less.Cardinal symptom during domestic animal manganese deficiency shows as forelimb arch, and lower limb is thick
Short and bend, attached arthroncus, walk lamely.
Manganese element and reproduction manganese are one of key factors promoting animal gonad development and endocrine function.Manganese is dicarboxylic acids enzyme
The catalysis indispensable factor of cholesterol biosynthesis, so Biosynthesis of cholesterol reduces during manganese deficiency, cholesterol is sex hormone precursor,
Therefore manganese deficiency can cause hormonoprivia.The convoluted seminiferous tubule generation degeneration change of buck testis, atrophy of testis, essence during manganese deficiency
Liquid quality is bad or quantity reduces, hyposexuality or lose breeding capacity;Sexual cycle disorder, non-estrus or weak of jenny
Feelings, ovarian atrophy, ovulation stagnation, conception rate reduce or be acyesis, fetus absorb, stillborn fetus.
Trace element has important function to growth maintenance and the production activity of animal.Under the conditions of modern production, along with
Improving constantly of animal productiong level, the requirement of trace element is also continuously increased by animal, the main compensation process of current manganese
It is to ignore the content of manganese in feedstuff, adds by animal requirement, and wherein bioavailability with Chelated Manganese is the highest, trace element
The bioavailability of the chelate of manganese is higher than the utilization rate of inorganic ions, and using microelement chelate is also to solve excess to add
Inorganic salt causes the effective ways of this difficult problem of environmental pollution, also prevent the harmful effect of inorganic salt generation and to dimension simultaneously
The antagonism of raw element.It is reported, the metal ion in chelate presents after combining with covalent bond with aminoacid or little peptide does not live
Sprinkling property, it can effectively utilize aminoacid and the absorbing path of little peptide, intactly enters blood plasma by small intestinal mucosa, and by fully
Target organ it is transported to after absorption.
But, with amino-acid complex (chelating) trace element of the synthesis such as the higher lysine of price, methionine, glycine
Although biological value is higher, but its use cost is the most of a relatively high, especially under current feed market environment with keen competition, and fall
The demand of low use cost highlights day by day.
Therefore, in order to reduce use cost, the present inventor makes full use of the locality that Guangxi cane planting is wide, sugar industry is flourishing
Affluent resources, with sucrose as primary raw material, by the complex reaction of sucrose Yu manganese salt, obtain sucrose manganese, greatly reduce enterprise
Production cost, improve the competitiveness of enterprise.
Summary of the invention
It is an object of the invention to for deficiencies of the prior art, it is provided that one has sexual valence safe efficient, high
The advantage of ratio, develops the even animal husbandry of organic trace element industry and will play the sucrose manganese of positive guiding and impetus
Complex.
The present invention is achieved in that
The preparation method of sucrose manganese complex of the present invention comprises the steps:
Step one, by sucrose and water according to the ratio mix homogeneously of weight fraction 30-35:50-60, according to sucrose and manganese sulfate
Weight fraction is that 30-35:50-60 adds manganese sulfate, adds sodium hydrate aqueous solution regulation pH 11-12 and obtains reactant liquor;
Step 2, by step one gained reactant liquor temperature 60-75 DEG C, be stirred continuously under the conditions of be incubated 1-2 hour, cold filtration
Separate, obtain filtering residue and filtrate;
Step 3, take step 2 gained filtrate, be to add 75% ethanol water at 1: 2 by the weight ratio of filtrate and the ethanol water of 75%
Solution room temperature precipitates 1.5-3 hour, and precipitate is through centrifugal sucking filtration, the waste water obtained and precipitate, and precipitate is vacuum dried,
Detection i.e. obtains sucrose manganese product;
Step 4, take in step 2 filtering residue and detect calcium ion concentration therein, being 1:4 according to the mol ratio of sucrose Yu manganese ion
In filtering residue, add sucrose and manganese sulfate, take the waste water after step 3 is centrifuged sucking filtration and dissolve addition sucrose and the filter of manganese sulfate
Slag, the pH 11-12 of hydro-oxidation sodium water solution regulation solution obtains reactant liquor;
Step 5, taking in step 4 reactant liquor and repeat step 2, step 3 and step 4 and react, circular response generates sucrose
Manganese.
The solubility of described sodium hydrate aqueous solution is 0.1-2mol/L.
Described sucrose manganese complex is as feed additive, and for feeding of pig, chicken, duck, cattle and sheep, addition is
200g/ ton feedstuff.
A pair lone pair electrons, simultaneously transition metal ions (M=Cu is had on the glycosidic bond of sucrose (few disaccharide)2+、Zn2+、Mn2+、
Fe2+、Ca2+) there is suitable unoccupied orbital, can be formed " coordination effect " with sucrose under suitable temperature environment, after chemical reaction network
Close formation complex state metal, beneficially animal body to absorb.It is as follows that it forms molecular structural formula:
Above-mentioned for sucrose trace element molecular structural formula, wherein M=Cu2+、Zn2+、Mn2+、Fe2+、Ca2+。
Because the reaction of sucrose trace-element complex is complicated, product is different from general amino-acid chelate, belongs to more
In macromolecular structure, the molecular weight not determined.
The above-mentioned mechanism preparing sucrose manganese is by sucrose and Mn2+After reacting forming complex, utilize sucrose manganese complex
Insoluble in ethanol, then Precipitation is dried and i.e. can get solid sucrose complexation manganese.
Inventor refilters once after first sucrose manganese solution being cooled down before adding ethanol, its object is to excess
Trace element remains with filtering residue form, as one of sucrose circulation complex reaction thing, by filtrate: the weight of 75% ethanol solution
Amount carries out room temperature precipitation than=1: 2 addition 75% ethanol solution, and its principle is: the trace element of excess is insoluble in ethanol, therefore wants
First filtered this out before adding ethanol.The polarity of ethanol is more weak again, and sucrose manganese this be polyhydroxy salt, polarity is relatively big,
According to the principle of similar intermiscibility, sucrose manganese is slightly soluble in ethanol, therefore both is separated, it is possible to obtains purer sucrose manganese and produces
Product.
Compared with prior art, the positive effect of the present invention is:
1, sucrose manganese complex of the present invention, by the complex reaction of sucrose Yu manganese salt, obtains sucrose manganese solution, add ethanol it
Front by sucrose manganese solution cool down after refilter once, obtain filtering residue and filtrate, by filtrate: weight ratio=1 of 75% ethanol water:
After 2 addition 75% ethanol waters carry out room temperature precipitation, by pelleting centrifugation sucking filtration, vacuum drying is dried, is sieved, detects, obtain relatively
Pure sucrose manganese product;The manganese ion concentration of detecting step two filtering residue, is 1:4 according to the mol ratio of sucrose Yu manganese ion, continues
Continuous add sucrose and manganese salt, step 3 is centrifuged the waste water after sucking filtration and returns in reactor the mother solution as dissolving saccharose, with
Identical reaction condition is circulated reaction to be continued to generate sucrose manganese.The present invention prepares the process of sucrose manganese, is that a circulation is anti-
The chemical process answered, it is achieved that the recycling of the energy, meets the requirement of Green Chemistry, reduces production cost, improve life
Produce efficiency.
2, sucrose manganese complex of the present invention, has fine good palatability due to the addition of sucrose, and slight sugar sweet fragrance makes
Obtain poultry to like taking food.
3, the present invention is with sucrose as primary raw material, the sucrose manganese obtained, with simple amino-acid complex (chelating)
The cost that trace element is used is compared, and present invention reduces the use cost of 20-30%.
4, the complex of sucrose manganese of the present invention, dissolubility absorption good, easy, good stability, as feed additive, can be substantially
Reduce the excrement excretion of feedstuff source trace element, reduce the aquaculture pollution to environment, moreover it is possible to improve meat yellowish pink, enhancing body
Anti-oxidation function, significantly improve the vigor of GSH-Px in liver, muscle, improve serum T-AOC and T-SOD, reduce UN, aobvious
Work improves the Nutrient Apparent Digestibilities such as feedstuff CP, EE, calcium, phosphorus, increases the deposition of nitrogen, moreover it is possible to significantly improve serum levels of iron regulating liver-QI ferrum and contain
Amount.After sucrose manganese enters in animal stomach, generate absorbable Organic Manganese with gastric acid slow reaction, the numerous of pig can be improved
Grow performance, promote oestrusing smoothly of sow, increase the lactation amount of sow, improve the Birth weight of piglet;The life of fowl can also be improved
Produce performance, improve laying rate, fertility rate and hatchability.
5, the complex of sucrose manganese of the present invention, organic trace element amount ratio inorganic ions is few, and absorption rate is high
Going out 3-4 times, do not result in waste, problem of environmental pollution is improved simultaneously, and the safety to people is improved.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of description, and in order to allow the above and other objects, features and advantages of the present invention can
Become apparent, below in conjunction with preferred embodiment, describe in detail as follows.
Detailed description of the invention
The following detailed description of the detailed description of the invention of the present invention, it, as the part of this specification, is come by embodiment
The principle of the present invention is described, other aspects of the present invention, feature and advantage thereof will be become apparent from by this detailed description.
Embodiment 1
The preparation method of sucrose manganese complex comprises the steps:
Step one, the sucrose of 35 weight portions and 60 weight parts waters are added reactor mix homogeneously, add 60 parts sulfuric acid
Manganese, adds sodium hydrate aqueous solution regulation pH 12 and obtains reactant liquor;
Step 2, reacting by heating still, keep temperature in the kettle at 75 DEG C, and adding 60 parts sulfuric acid manganese, to carry out complex reaction 2 little
Time, course of reaction is stirred continuously, and generates sucrose manganese solution, and cold filtration separates, and obtains filtering residue and filtrate;
Step 3, by filtrate: weight ratio=1 of 75% ethanol water: 2 add 75% ethanol waters carries out room temperature precipitation, precipitation
Time is 3 hours, and precipitate utilizes through centrifugal sucking filtration, the waste water reclamation obtained, and precipitate is vacuum dried, and detection i.e. obtains
Sucrose manganese product;
Step 4, take in step 2 filtering residue and detect manganese ion concentration therein, being 1 according to the mol ratio of sucrose Yu manganese ion:
4, continuously add 35 parts by weight of sucrose and 56 parts sulfuric acid manganese (manganese ion concentration 4 weight portion here), step 3 is centrifuged
Waste water after sucking filtration returns to the mother solution in reactor as dissolving saccharose, and hydro-oxidation sodium water solution alkalizes, regulation solution
PH 12 obtains reactant liquor;
Step 5, take reactant liquor reacting by heating still in step 4, keep temperature in the kettle to carry out complex reaction at 75 DEG C, repeat step
Two, step 3 and step 4 are reacted, and circular response generates sucrose manganese.
Embodiment 2
The preparation method of sucrose manganese complex comprises the steps:
Step one, toward reactor adds the sucrose of 33 weight portions, after adding the water dissolution sucrose of 55 weight portions, hydro-oxidation sodium is water-soluble
Basified, the pH 11 of regulation solution obtains reactant liquor;
Step 2, reacting by heating still, keep temperature in the kettle at 70 DEG C, add 58 parts sulfuric acid manganese and carry out complex reaction 1.5
Hour, course of reaction is stirred continuously, and generates sucrose manganese solution, and cold filtration separates, and obtains filtering residue and filtrate;
Step 3, by filtrate: weight ratio=1 of 75% ethanol water: 2 add 75% ethanol waters carries out room temperature precipitation, precipitation
Time is 2 hours, and precipitate utilizes through centrifugal sucking filtration, the waste water reclamation obtained, and precipitate is vacuum dried, and detection i.e. obtains
Sucrose manganese product;
Step 4, take in step 2 filtering residue and detect manganese ion concentration therein, being 1 according to the mol ratio of sucrose Yu manganese ion:
4, continuously add 33 parts by weight of sucrose and 55 parts sulfuric acid manganese (manganese ion concentration 3 weight portion here), step 3 is centrifuged
Waste water after sucking filtration returns to the mother solution in reactor as dissolving saccharose, and hydro-oxidation sodium water solution alkalizes, regulation solution
PH 11, obtains reactant liquor;
Step 5, take reactant liquor in step 4, reacting by heating still, keep temperature in the kettle to carry out complex reaction at 70 DEG C, repeat step
Rapid two, step 3 and step 4 are reacted, and circular response generates sucrose manganese.
Embodiment 3
The preparation method of sucrose manganese complex comprises the steps:
Step one, toward reactor adds the sucrose of 35 weight portions, after adding the water dissolution sucrose of 60 weight portions, hydro-oxidation sodium is water-soluble
Basified, the pH 12 of regulation solution obtains reactant liquor;
Step 2, reacting by heating still, keep temperature in the kettle at 75 DEG C, and adding 60 parts sulfuric acid manganese, to carry out complex reaction 2 little
Time, course of reaction is stirred continuously, and generates sucrose manganese solution, and cold filtration separates, and obtains filtering residue and filtrate;
Step 3, take step 2 gained filtrate, by filtrate: weight ratio=1 of 75% ethanol water: 2 add 75% ethanol waters
Carrying out room temperature precipitation, the sedimentation time is 3 hours, and precipitate utilizes through centrifugal sucking filtration, the waste water reclamation obtained, and precipitate is through true
Empty dry, detection i.e. obtains sucrose manganese product;
Step 4, take in step 2 filtering residue and detect manganese ion concentration therein, being 1 according to the mol ratio of sucrose Yu manganese ion:
4, continuously add 35 parts by weight of sucrose and 56 parts sulfuric acid manganese (manganese ion concentration 4 weight portion here), step 3 is centrifuged
Waste water after sucking filtration returns to the mother solution in reactor as dissolving saccharose, and hydro-oxidation sodium water solution alkalizes, regulation solution
PH 12, obtains reactant liquor;
Step 5, take reactant liquor in step 4, reacting by heating still, keep temperature in the kettle to carry out complex reaction at 75 DEG C, repeat step
Rapid two, step 3 and step 4 are reacted, and circular response generates sucrose manganese.
Application implementation is tested
1, experimental animal and EXPERIMENTAL DESIGN
108 age in days average body quality are become 2 process, 9 weights of each process in the male broiler chicken random assortment of 49.21g
Multiple, 6 chickens of each repetition.Test 1 group be feed corn-soybean meal basal diet on the basis of add the inorganic sulfur of 60mg/kg
Acid manganese, tests 2 groups of sucrose manganese adding 60mg/kg on basal diet;Test is early stage (0-21 age in days) and (22-42 day
Age).
2, the source of test material
Manganese sulfate is commercial diet level manganese sulfate, and sucrose manganese is that Nanjing Zeweier Feed Co., Ltd. develops.
3, feeding and management
Broiler chicken feeds in 3 layers of chicken coop of 69cm*65cm*38cm, and each stage illumination is all referring to " AA broiler chicken feeding and management hands
Volume ", temperature is temperature automatically controlled, within first week, controls at 35 DEG C, and second week controls at 32 DEG C, within the 3rd week, controls at 29 DEG C, later temperature
Control at 24 DEG C;Freely drink water;Indoor humidity is maintained at 60%-65%, records temperature, humidity in the process every day.
4, method of testing and index
Production performance: respectively at test the 21st, 42d to be repeated as unit 8 hours on an empty stomach, title weight and residual mass, and according to
This calculates the quality that increases day by day of broiler chicken, daily ingestion amount amount and feed conversion rate.
5, test results and analysis
Manganese sulfate group and two groups of result of the test such as following tables of sucrose manganese group:
As can be seen from the above table, on the basis of daily ration basis is identical, the adding weight (0-6 week) of sucrose manganese group is substantially than sulphuric acid
Wanting of manganese group is high, and feed intake (0-6 week) is basically identical, and feedstuff-meat ratio (0-6 week) then sucrose manganese group is then significantly lower than manganese sulfate group.Can
See that adding sucrose manganese in broiler diet can improve efficiency of feed utilization, improves the adding weight of broiler chicken.
Compared with prior art, the positive effect of the present invention is:
1, sucrose manganese complex of the present invention, by the complex reaction of sucrose Yu manganese salt, obtains sucrose manganese solution, add ethanol it
Front by sucrose manganese solution cool down after refilter once, obtain filtering residue and filtrate, by filtrate: weight ratio=1 of 75% ethanol water:
After 2 addition 75% ethanol waters carry out room temperature precipitation, by pelleting centrifugation sucking filtration, vacuum drying is dried, is sieved, detects, obtain relatively
Pure sucrose manganese product;The manganese ion concentration of detecting step two filtering residue, is 1:4 according to the mol ratio of sucrose Yu manganese ion, continues
Continuous add sucrose and manganese salt, step 3 is centrifuged the waste water after sucking filtration and returns in reactor the mother solution as dissolving saccharose, with
Identical reaction condition is circulated reaction to be continued to generate sucrose manganese.The present invention prepares the process of sucrose manganese, is that a circulation is anti-
The chemical process answered, it is achieved that the recycling of the energy, meets the requirement of Green Chemistry, reduces production cost, improve life
Produce efficiency.
2, sucrose manganese complex of the present invention, has fine good palatability due to the addition of sucrose, and slight sugar sweet fragrance makes
Obtain poultry to like taking food.
3, the present invention is with sucrose as primary raw material, the sucrose manganese obtained, with simple amino-acid complex (chelating)
The cost that trace element is used is compared, and present invention reduces the use cost of 20-30%.
4, the complex of sucrose manganese of the present invention, dissolubility absorption good, easy, good stability, as feed additive, can be substantially
Reduce the excrement excretion of feedstuff source trace element, reduce the aquaculture pollution to environment, moreover it is possible to improve meat yellowish pink, enhancing body
Anti-oxidation function, significantly improve the vigor of GSH-Px in liver, muscle, improve serum T-AOC and T-SOD, reduce UN, aobvious
Work improves the Nutrient Apparent Digestibilities such as feedstuff CP, EE, calcium, phosphorus, increases the deposition of nitrogen, moreover it is possible to significantly improve serum levels of iron regulating liver-QI ferrum and contain
Amount.After sucrose manganese enters in animal stomach, generate absorbable Organic Manganese with gastric acid slow reaction, the numerous of pig can be improved
Grow performance, promote oestrusing smoothly of sow, increase the lactation amount of sow, improve the Birth weight of piglet;The life of fowl can also be improved
Produce performance, improve laying rate, fertility rate and hatchability.
5, the complex of sucrose manganese of the present invention, organic trace element amount ratio inorganic ions is few, and absorption rate is high
Going out 3-4 times, do not result in waste, problem of environmental pollution is improved simultaneously, and the safety to people is improved.
The above is the preferred embodiment of the present invention, certainly can not limit the right model of the present invention with this
Enclose, it is noted that for those skilled in the art, under the premise without departing from the principles of the invention, also may be used
To make some improvement and variation, these improve and variation is also considered as protection scope of the present invention.
Claims (3)
1. the preparation method of a sucrose manganese complex, it is characterised in that comprise the steps:
Step one, by sucrose and water according to the ratio mix homogeneously of weight fraction 30-35:50-60, according to sucrose and manganese sulfate
Weight fraction is that 30-35:50-60 adds manganese sulfate, adds sodium hydrate aqueous solution regulation pH 11-12 and obtains reactant liquor;
Step 2, by step one gained reactant liquor temperature 60-75 DEG C, be stirred continuously under the conditions of be incubated 1-2 hour, cold filtration
Separate, obtain filtering residue and filtrate;
Step 3, take step 2 gained filtrate, be to add 75% ethanol water at 1: 2 by the weight ratio of filtrate and the ethanol water of 75%
Solution room temperature precipitates 1.5-3 hour, and precipitate is through centrifugal sucking filtration, the waste water obtained and precipitate, and precipitate is vacuum dried,
Detection i.e. obtains sucrose manganese product;
Step 4, take in step 2 filtering residue and detect calcium ion concentration therein, being 1:4 according to the mol ratio of sucrose Yu manganese ion
In filtering residue, add sucrose and manganese sulfate, take the waste water after step 3 is centrifuged sucking filtration and dissolve addition sucrose and the filter of manganese sulfate
Slag, the pH 11-12 of hydro-oxidation sodium water solution regulation solution obtains reactant liquor;
Step 5, taking in step 4 reactant liquor and repeat step 2, step 3 and step 4 and react, circular response generates sucrose
Manganese.
2. the preparation method of sucrose manganese complex as claimed in claim 1, it is characterised in that: described sodium hydrate aqueous solution
Solubility is 0.1-2mol/L.
3. the preparation method of sucrose manganese complex as claimed in claim 1, it is characterised in that: described sucrose manganese complex conduct
Feed additive, for feeding of pig, chicken, duck, cattle and sheep, addition is 200g/ ton feedstuff.
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CN107805263A (en) * | 2017-11-21 | 2018-03-16 | 天峨县宏昌农机专业合作社 | A kind of manganese complex and its production and use |
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