CN107032410B - The preparation method and applications of alkali formula manganese sulfate - Google Patents
The preparation method and applications of alkali formula manganese sulfate Download PDFInfo
- Publication number
- CN107032410B CN107032410B CN201710274854.2A CN201710274854A CN107032410B CN 107032410 B CN107032410 B CN 107032410B CN 201710274854 A CN201710274854 A CN 201710274854A CN 107032410 B CN107032410 B CN 107032410B
- Authority
- CN
- China
- Prior art keywords
- manganese
- manganese sulfate
- alkali formula
- sulfate
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fodder In General (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention provides a kind of preparation method of alkali formula manganese sulfate that can be used for animal feed additive,, the following steps are included: (1) takes manganese sulfate soluble in water, simple substance manganese is added in adjusting pH value to 6.0~7.5 for it, it filters after complete reaction, filtrate A is prepared；(2) under nitrogen or inert gas shielding, the filtrate A prepared in step (1) is taken, alkaline solution is slowly added to and is reacted, obtain solution B after complete reaction；(3) solution B by step (2) preparation filters, washing, dry, obtained alkali formula manganese sulfate.The present invention also provides a kind of application of alkali formula manganese sulfate on preparation animal additive.The alkali formula manganese sulfate being prepared using preparation method provided by the invention has the advantages that manganese content is high, prevented from caking, biological value is high, thermostabilization is good.
Description
Technical field
The invention belongs to the preparation method of field of feed additive technology more particularly to a kind of alkali formula manganese sulfate and its answer
With.
Background technique
Manganese is in carbohydrate, lipid, protein and cholesterol metabolic as the enzyme activation factor or component part.Manganese
The transmitting of nervus centralis media and the energy supply of axoneure can be participated in, is to maintain brain eubolism function must can not
Few substance, if animal manganese deficiency can lead to food ration decline, decreased growth, bone exception, incoordination, slow in reacting and breeding
Phenomena such as dysfunction.In addition, thyroid synthesis must have the enzymatic of activation manganese that could complete.Manganese ion also with hair color
There are much relations in pool, and chroma of hair light may then contain manganese abundance, and the intensely dark pool of hair then may manganese deficiency.
The manganese source added in feed at present is divided into inorganic manganese and two kinds of Organic Manganese.Inorganic manganese feed addictive include MnO,
MnSO4、MnCl2Deng, however there is differences for the utilization rate of these compound manganese.MnSO4The bioavailability of middle Mn is better than MnO
And MnCO3, with MnCl2It is close.The utilization rate of Mn is only MnSO in MnO466%, and MnCO3Only 40%.In fact, single
Manganese element it is most of synthesize phytic acid manganese under one's belt, form insoluble compound, it is difficult to digestibility and utilization.And Mn and organic matter such as egg ammonia
After the complexing agents such as acid combine, utilization rate, the absorptivity of manganese element are improved.As the organic of Met-Mn is directly entered animal and bird intestines quilt
It absorbs and participates in metabolism.When selecting the feed addictive containing manganese, on the one hand it is considered as it and adds cost, be on the other hand also considered as it
Bioavailability.
Inorganic manganese uses manganese sulfate mostly at present, but because solution easy to damp is agglomerated, the scope of application is restricted.Manganese sulfate is because of life
It is cleaned during producing using potassium permanganate or hydrogen peroxide oxidation, product can remain small amounts object manganese dioxide, potassium permanganate.This
A little oxides can be with the nutritional ingredient of other in feed, such as vitamin, ferrous iron, the generation redox reaction such as grease, influence
The quality of feed and shelf-life.Meanwhile the sulfate radical content in manganese sulfate is higher, animal can be given off after being absorbed and utilized containing big
The sulfate excrement of amount causes soil hardening salinization and alkalization to accelerate.
It is Mn-Gly, manganese methionine, methionine hydroxy manganese etc. that Organic Manganese is more on the market at present.The amino acid
Manganese using effect is fine, is not easy to incude with the other compositions in feed, shadow of the exhaust emission after animal edible to environment
Sound is also smaller.But the ligand of manganese amino acid is amino acid, price is more expensive, and manganese content is lower, and additive amount is larger, uses such production
The cost pressure of product feed factory is larger.
Therefore, it is necessary to further developed to existing feed addictive containing manganese and preparation method, provide it is a kind of at
This is low, utilization rate is high, the feed addictive containing manganese and preparation method of easy transport storage.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
The preparation method and applications of kind alkali formula manganese sulfate have the advantages that at low cost, utilization rate is high, easy transport storage.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows: the present invention provides a kind of alkali formula manganese sulfate
Preparation method, comprising the following steps:
(1) it takes manganese sulfate soluble in water, simple substance manganese is added, then adjust pH value to 6.0~7.5, filter after complete reaction,
Filtrate A is prepared；Simple substance manganese can be preferably added several times, i.e., resulting filtrate be repeated into aforementioned addition simple substance manganese, adjusted
Save the operation of pH value and filtering at least once,
(2) under nitrogen or inert gas shielding, the filtrate A prepared in step (1) is taken, is slowly added to alkaline solution progress
Reaction, obtains solution B after complete reaction；
(3) solution B by step (2) preparation filters, washing, dry, obtained alkali formula manganese sulfate.
By the way that the study found that manganese ion concentration is higher, it is lower to start the pH hydrolyzed for the easier hydrolysis of manganese ion；Manganese ion
Concentration is lower, then manganese ion more not facile hydrolysis, and the pH for starting hydrolysis is also higher.And the oxidation rate of manganese ion also with manganese from
Sub- concentration is related with pH value, and manganese ion concentration is lower, and pH is smaller, and the oxidation rate of manganese ion is smaller.So in order to keep away as far as possible
Exempt from manganese ion hydrolysis and oxidation, pH value should be acid or neutral.When pH value is greater than 8.0, the calcium and magnesium ion in solution can start
Precipitating.By the way that pH value is adjusted to 6.0~7.5 in the step (1), on the one hand it can hydrolyze and aoxidize to avoid manganese ion；?
The precipitating of the calcium and magnesium ion in solution can be reduced: while increasing the precipitating of the copper in solution, lead, antimony, cadmium, iron, arsenic ion.
A small amount of manganous hydroxide can be generated when manganese sulfate and sodium hydroxide/potassium hydroxide reaction.Manganous hydroxide is heated easily to be divided
Solution, is insoluble in water and alkali, is soluble in the ammonium salt of acid and strong acid.Exposure is oxidized to the compound of brown quickly in air:
2Mn(OH)2+O2=2MnO (OH)2
The micro amount of oxygen even dissolved in water can also aoxidize manganous hydroxide.In the step (2) by setting nitrogen or
Inert gas shielding can prevent a small amount of manganous hydroxide generated and oxidant reaction from generating MnO (OH)2。
The preparation method of above-mentioned alkali formula manganese sulfate, it is preferred that the simple substance manganese is manganese powder, manganese piece or manganese grain, and institute is added
The gross mass for stating simple substance manganese is 1.05~1.6 times of the gross mass of impure copper, lead, antimony, cadmium, iron, arsenic in the manganese sulfate.By
Displacement can occur with harmful heavy metals such as copper, lead, antimony, cadmiums in simple substance manganese to react, it can also be with oxidant potassium permanganate, dioxygen
The reaction such as water, perchloric acid, it is all by be added the simple substance manganese not only can remove the copper contained in the manganese sulfate, lead, antimony,
The harmful heavy metals such as cadmium can also remove oxidant therein.
The preparation method of above-mentioned alkali formula manganese sulfate, it is preferred that in the step (2), the alkaline solution is hydroxide
The molar ratio of sodium or potassium hydroxide solution, the filtrate A and alkaline solution is set as 4.5~5.5: 8.When manganese sulfate and sodium hydroxide
Or the molar ratio of potassium hydroxide is too low can generate Mn (OH)2；When the molar ratio of manganese sulfate and sodium hydroxide or potassium hydroxide is too high
Mn can be generated2(OH)2SO4Or Mn3(OH)2(SO4)2(H2O)2Etc. the low manganese content of forms alkali formula manganese sulfate.So manganese sulfate with
The molar ratio of sodium hydroxide or potassium hydroxide is 4.5~5.5: 8 more appropriate.
The preparation method of above-mentioned alkali formula manganese sulfate, it is preferred that in the step (2), the temperature reacted is 42 DEG C
~78 DEG C, the time for continuing isothermal reaction is 0.5h~2.5h.Precipitation reaction is exothermic reaction, is conducive to react when temperature is lower
It is carried out to forward direction, the precipitating particle of generation is more, and efficiency of the dispersant adsorption on precipitating particle reduces, the mutual making contact of particle
Chance increase, be conducive to reunions, be unfavorable for dispersing agent anti-agglomeration act on；When reaction temperature is higher, the precipitating of generation
Particle warm-up movement aggravation, collision opportunity to each other increases, to enhance as caused by molecular force between particle and Coulomb force
Agglomeration.So 42 DEG C~78 DEG C of setting is conducive to the generation of product, simultaneous reactions rate is suitable for.
The preparation method of above-mentioned alkali formula manganese sulfate, it is preferred that in the step (2), the sodium hydroxide solution or hydrogen
The mass fraction of potassium oxide solution is 20%~50%, when reaction in control filtrate A the mass fraction of manganese sulfate be 15%~
30%.By limiting the mass fraction of manganese sulfate and alkaline solution, reactant is completely dissolved in water, while subtracting as far as possible
Small agglomeration.
The preparation method of above-mentioned alkali formula manganese sulfate, it is preferred that in the step (2), before being slowly added to alkaline solution,
Anionic surfactant is first added into the filtrate A, the anionic surfactant is lauryl sodium sulfate, fat
One or more of alcohol sodium sulphate, fatty alcohol-ether sodium sulfate are 0.5~1.4g/L in the concentration of reaction system.Pass through step
Suddenly (2) are added anionic surfactant in the reaction solution, and the anionic surfactant is in the reaction solution
Concentration is 0.5~1.4g/L, so that precipitating particle agglomeration phenomenon is improved, grain diameter is more uniform.
The preparation method of above-mentioned alkali formula manganese sulfate, it is preferred that in the step (2), before being slowly added to alkaline solution,
Organic solvent is first added into the filtrate A, the organic solvent is methanol, ethyl alcohol, acetone, ethylene glycol, glycerine, acetic acid second
One of ester, butanone are a variety of, and the additional amount of the organic solvent and the mass percent of reaction system are 1%~10%.
By be added organic solvent play the role of dispersion so that obtain alkali formula manganese sulfate crystalline form it is more preferable, it is more dispersed, be easier
Filter.
The preparation method of above-mentioned alkali formula manganese sulfate, it is preferred that in the step (2), manganese sulfate is anhydrous manganous sulfate, one
One of water manganese sulfate and four water manganese sulfates.
The present invention also provides a kind of alkali formula manganese sulfates to prepare the application on animal feed additive, the alkali formula manganese sulfate
Molecular formula be Mn5(OH)8SO4。
Above-mentioned alkali formula manganese sulfate is preparing the application on animal feed additive, it is preferred that the alkali formula manganese sulfate by
The preparation method of above-mentioned alkali formula manganese sulfate is prepared.
The dosage of above-mentioned alkali formula manganese sulfate are as follows: the additive amount in pig feed is calculated as 25~135ppm with manganese element；In fowl material
In additive amount 25~135ppm is calculated as with manganese element；30~135ppm is calculated as with manganese element in the additive amount ruminated in material；?
Additive amount is calculated as 5~90ppm with manganese element in aquatic products material.
Compared with the prior art, the advantages of the present invention are as follows:
1. the manganese sulphur molar ratio of alkali formula manganese sulfate prepared by the present invention reach 5: 1, manganese content 54.2%, with a water sulphur
The 32.5% of sour manganese compared to height, under same level of manganese content, alkali formula manganese sulfate additive amount is smaller, can add it is more other
Functional additive, reserve bigger addition leeway for Feeding Prescription Design.
2. the layer structure of basic sulfate manganese prepared by the present invention, good fluidity is not easy to harden in the storage of long-term weight,
The crystallization water is free of simultaneously, it is prevented from caking in prolonged storage.
3. basic sulfate manganese prepared by the present invention as animal feed additive at 280 DEG C hereinafter, thermal stability is good, can hold
Higher temperature when being pelletized by feed processing.
4. sulfate radical content is lower than sulfate radical content in traditional manganese sulfate in basic sulfate manganese prepared by the present invention, as dynamic
Object feed additive animal is reduced using the discharge of rear sulfate, reduces environmental pressure.
5. in application of the invention, with basic sulfate manganese feeding animals prepared by the present invention, stable product quality, the benefit of manganese
With rate height, biological value is high, can be used as the novel manganese source additive of one of animal feed.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with preferred embodiment and more comprehensively, is meticulously retouched
It states, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Unless otherwise specified, the manganese sulfate used in the present invention can be anhydrous manganous sulfate or crystallize containing any number
The aqueous sulfuric acid manganese of water.
Embodiment 1:
A kind of preparation method of alkali formula manganese sulfate of the invention, comprising the following steps:
Step (1): taking purity is 98% 388.0Kg manganese sulfate monohydrate, glimmering with atomic absorption spectrophotometer and atom
Light spectrophotometer detection, wherein being 2.1Kg there are also impurity copper, lead, antimony, cadmium, iron, arsenic content summation.By manganese sulfate monohydrate plus
Enter to the 2m that 0.81t water is housed3After in reaction kettle, manganese powder 1.1Kg is added, adjusting solution ph is 6.0, it is filtered after stirring 1h,
Aforementioned manganese powder is added, adjusts pH value, stirring and filtering operation 1 time is repeated, filtrate A is made.
Step (2): the filtrate A prepared in step (1) is again placed in reaction kettle, and 42Kg wine is added in a kettle
Essence and 790g lauryl sodium sulfate are filled with nitrogen protection and entire reaction kettle are made to form the nitrogen environment sealed.Not
It is slowly added to the sodium hydroxide solution 898Kg that concentration is 20%, purity is 99% in the filtrate A of disconnected stirring, after being warming up to 50 DEG C
Isothermal reaction 2.5h, obtains solution B.
Step (3): the solution B prepared in step (2) is subjected to filters pressing, washing, drying, obtains alkali formula manganese sulfate
244.5Kg, with manganese collecting rate for 95%.
The alkali formula manganese sulfate of step (3) preparation is detected using conventional method, wherein sulfate radical content in alkali formula manganese sulfate
It is 18.6%, manganese content 53.4%, volatile substances content is 0.8% at 105 DEG C.
After the excessive diluted hydrochloric acid dissolution of the alkali formula manganese sulfate of step (3) preparation, with sodium hydroxide titration to neutrality, first is used
Base orange is given instruction agent, and the hydrochloric acid content for calculating consumption carrys out the anti-hydroxyl content pushed away in product, similarly hereinafter.Measuring hydroxyl content is
26.4%.
Measured with atomic absorption spectrophotometer: lead content 1.0ppm, arsenic content 0.01ppm, cadmium content are
0.02ppm, antimony content 0.02ppm, total iron content 5.0ppm.The testing result and molecular formula Mn5(OH)8SO4It is consistent, product
Purity are as follows: 98%.The alkali formula manganese sulfate of step (3) preparation is placed under 280 DEG C of environment, its stability, non-recurring structure are detected
Variation, suitable for processing feed under higher temperature environment.
To the alkali formula manganese sulfate of step (3) preparation with 25Kg/ packet, multilayer complex films bag packaging bag packaging, PVC inner bag are used
Tying, waterproof and dampproof pearl film tyre press strip seam packet.
It needs according to practical storage, is stacked on Forklift plate, each frame plate stacks 5 layers, and 2 frame plates overlay same vertical
Position, totally 10 layers.Lowest level one is extracted after 7 days, 14 days, 1 month, 2 months, 3 months, 6 months respectively to contract for fixed output quotas product mistake
Spin vibration sieve does not find that there are unsifted caking materials on sieve, it was demonstrated that deposit for a long time using alkali formula manganese sulfate prepared by the above method
It puts also not easy to harden under weight.
Embodiment 2:
The present invention provides a kind of preparation method of alkali formula manganese sulfate, comprising the following steps:
Step (1): taking purity is 99% tetra- water manganese sulfate of 563.1Kg, glimmering with atomic absorption spectrophotometer and atom
Light spectrophotometer detection, wherein being 0.56Kg there are also impurity copper, lead, antimony, cadmium, iron, arsenic content summation.Four water manganese sulfates are added
Enter to the 5m that 2.2t water is housed3After in reaction kettle, manganese powder 0.37Kg is added, adjusting solution ph is 7.0, stirs mistake after 0.5h
Filter repeats aforementioned manganese powder is added, adjusts pH value, stirring and filtering operation 1 time, filtrate A is made.
Step (2): the filtrate A prepared in step (1) is placed in reaction kettle, and 308Kg alcohol is added in a kettle
With 4.1Kg sodium alkyl sulfate, it is filled with nitrogen protection and entire reaction kettle is made to form the nitrogen environment sealed.Constantly stirring
The sodium hydroxide solution 323Kg that concentration is 50%, purity is 99%, constant temperature after being warming up to 78 DEG C are slowly added in the filtrate A mixed
0.5h is reacted, solution B is obtained.
Step (3): the solution B prepared in step (2) is subjected to filters pressing, washing, drying, obtains alkali formula manganese sulfate
248.3Kg, with manganese collecting rate for 96%.
The alkali formula manganese sulfate of step (3) preparation is detected using conventional method, wherein sulfate radical content in alkali formula manganese sulfate
It is 18.6%, manganese content 53.1%, hydroxyl content 26.2%, volatile substances content is 1.6% at 105 DEG C.
Measured with atomic absorption spectrophotometer: lead content 0.9ppm, arsenic content 0.02ppm, cadmium content are
0.01ppm, antimony content 0.02ppm, total iron content 4.2ppm.The testing result and molecular formula Mn5(OH)8SO4It is consistent, product
Purity are as follows: 98%.The alkali formula manganese sulfate of step (3) preparation is placed under 280 DEG C of environment, its stability, non-recurring structure are detected
Variation, suitable for processing feed under higher temperature environment.
To the alkali formula manganese sulfate of step (3) preparation with 50Kg/ packet, multilayer complex films bag packaging bag packaging, PVC inner bag are used
Tying, waterproof and dampproof pearl film tyre press strip seam packet.
It needs according to practical storage, is stacked on Forklift plate, each frame plate stacks 5 layers, and 2 frame plates overlay same vertical
Position, totally 10 layers.Lowest level one is extracted after 7 days, 14 days, 1 month, 2 months, 3 months, 6 months respectively to contract for fixed output quotas product mistake
Spin vibration sieve does not find that there are unsifted caking materials on sieve, it was demonstrated that deposit for a long time using alkali formula manganese sulfate prepared by the above method
It puts also not easy to harden under weight.
Embodiment 3:
The present invention provides a kind of preparation method of alkali formula manganese sulfate, comprising the following steps:
Step (1): taking purity is 97% 428.1Kg anhydrous manganous sulfate, glimmering with atomic absorption spectrophotometer and atom
Light spectrophotometer detection, wherein being 109g there are also impurity copper, lead, antimony, cadmium, iron, arsenic content summation.Anhydrous manganous sulfate is added
To the 5m that 1.7t water is housed3After in reaction kettle, manganese powder 87.2g is added, adjusting solution ph is 7.5, is filtered after stirring 0.2h, weight
Multiple aforementioned manganese powder is added, adjusts pH value, stirring and filtering operation 1 time, is made filtrate A.
Step (2): the filtrate A prepared in step (1) is placed in reaction kettle, and 32.6Kg alcohol is added in a kettle
With 2.8Kg fatty alcohol-ether sodium sulfate, it is filled with nitrogen protection and entire reaction kettle is made to form the nitrogen environment sealed.Continuous
The potassium hydroxide solution 1133Kg that concentration is 40%, purity is 99% is slowly added in the filtrate A of stirring, it is permanent after being warming up to 42 DEG C
Temperature reaction 1h, obtains solution B.
Step (3): the solution B prepared in step (2) is subjected to filters pressing, washing, drying, obtains alkali formula manganese sulfate
226.5Kg, with manganese collecting rate for 88%.
The alkali formula manganese sulfate of step (3) preparation is detected using conventional method, wherein sulfate radical content in alkali formula manganese sulfate
It is 18.6%, manganese content 53.4%, hydroxyl content 26.4%, volatile substances content is 0.7% at 105 DEG C.
Measured with atomic absorption spectrophotometer: lead content 1.1ppm, arsenic content 0.01ppm, cadmium content are
0.02ppm, antimony content 0.02ppm, total iron content 2.8ppm.The testing result and molecular formula Mn5(OH)8SO4It is consistent, product
Purity are as follows: 98%.The alkali formula manganese sulfate of step (3) preparation is placed under 280 DEG C of environment, its stability, non-recurring structure are detected
Variation, suitable for processing feed under higher temperature environment.
To the alkali formula manganese sulfate of step (3) preparation with 25Kg/ packet, multilayer complex films bag packaging bag packaging, PVC inner bag are used
Tying, waterproof and dampproof pearl film tyre press strip seam packet.
It needs according to practical storage, is stacked on Forklift plate, each frame plate stacks 5 layers, and 2 frame plates overlay same vertical
Position, totally 10 layers.Lowest level one is extracted respectively after 7 days, 14 days, 1 month, 2 months, 3 months, 6 months, 12 months the to wrap
Product crosses spin vibration sieve, does not find that there are unsifted caking materials on sieve, it was demonstrated that the alkali formula manganese sulfate prepared using the above method
It is also not easy to harden under long-term storage weight.
Embodiment 4: application of the alkali formula manganese sulfate as sow feed additive.
The feeding experiment of brood sow is used for using the alkali formula manganese sulfate prepared in embodiment 1 as animal feed additive.
Select Duluke's sow 90 of same parity, be divided into three groups (control groups and test one, two group), every group 30, every group with 2~
3 Duroc boars are bred, it is desirable that breeding is completed within an oestrus, wherein control group feeds manganese deficiency daily ration to pig,
One group is tested in pig with alkali formula manganese sulfate of the invention is added in manganese deficiency daily ration, alkali formula sulfuric acid manganese content is in terms of manganese element in daily ration
For 25ppm, two groups are tested in pig with alkali formula manganese sulfate of the present invention is added in manganese deficiency daily ration, alkali formula sulfuric acid manganese content is in daily ration with manganese
Element is calculated as 135ppm.Test result is shown in Table 1.
Table 1: influence of the alkali formula manganese sulfate to brood sow production performance
As it can be seen from table 1 control group and test group have significant difference (p < 0.05) for nascent young number living, but
Do not have a great impact to weigth at birth；With the variation of feeding time, control group and test group in 21 age in days son's number living with
Litter weight starts to show larger difference, and survival rate has the difference (p < 0.05) of conspicuousness；When 42 age in days, live son's number and 21 days
Age is similar, and there were significant differences for incubation rate (p < 0.05), adds the test group of alkali formula manganese sulfate of the present invention, the son living of brood sow
Number, the survival rate in later period, incubation rate have the raising of conspicuousness compared with control group, and later period litter weight also has biggish mention compared with control group
It is high.The above phenomenon shows that alkali formula manganese sulfate prepared by the present invention improves a lot to the reproductive performance of brood sow.
Embodiment 5: application of the alkali formula manganese sulfate as duck feed addictive in terms of improving duckling immunity.
The alkali formula manganese sulfate prepared in embodiment 2 is used for the feeding experiment of duckling.Select 1 age in days without duck viral liver
The Beijing duckling of scorching vaccine inoculation 80 is randomly divided into 4 groups, and every group 20, point circle plane raising, every group one is enclosed, every group of duckling
Constant illumination for 24 hours is freely eaten and drinks water.Experimental period 30d, after the test, with group for unit slaughter duckling, collection blood,
Thymus gland, spleen are simultaneously analyzed.Wherein, control group feeds manganese deficiency basal diet to duckling；One group is tested to add in duckling manganese deficiency daily ration
Alkali formula manganese sulfate, alkali formula manganese sulfate additive amount is calculated as 25ppm with manganese element in daily ration；Two groups are tested to add in duckling manganese deficiency daily ration
Add alkali formula manganese sulfate, alkali formula manganese sulfate additive amount is calculated as 135ppm with manganese element in daily ration, tests three groups in duckling manganese deficiency daily ration
Middle addition manganese sulfate monohydrate, manganese sulfate monohydrate additive amount is calculated as 135ppm with manganese element in daily ration per ton.Test result is shown in Table 2.
Table 2: influence of the alkali formula manganese sulfate to duckling immune parameter
From table 2 it can be seen that control group and the thymus gland of test group, spleen and serum HI spend clearly difference.Test group phase
It increased than the thymus gland and spleen weight in control group, serum HI spends clearly decline；By test one group and test two groups it is found that with
The weight of the increase of manganese additive amount, thymus gland and spleen is in rising trend, and serum HI spends clearly on a declining curve；By testing two groups and test
Three groups it is found that be all the manganese element for adding 135ppm, the data of two groups of test are better than three groups of test.The above phenomenon shows to add
Manganese addition can enhance the immunity of duckling, the raising of alkali formula manganese sulfate additive amount, and the effect that duckling immunity improves becomes apparent from, and this
The alkali formula manganese sulfate for inventing preparation will be substantially better than manganese sulfate monohydrate to the effect for improving duckling immunity.
Embodiment 6: application of the alkali formula manganese sulfate in Russian carp.
The alkali formula manganese sulfate prepared in embodiment 3 is used for the feeding experiment of Russian carp.Selection is healthy, uniform, first
Initial body weight is 1500 tail of Russian carp of (132.0 ± 2.0) g, is equally divided into 5 big group, and each big group is divided into 3 groups,
Each 100 tail of group, fingerling are bought the same day back and are grouped immediately, are splashed disinfection after grouping with anti-bacteria and virus, are then put into each group
Specification is the cement pit of 6m × 9m.The spare fish substitute that dead fish selects specification close in 1st week, is gradually completing examination in 3d after grouping
The replacement expected to former feed is tested, is fed daily under normal circumstances 4 times during test, aerator is started according to weather condition in due course,
Per two weeks is sterilized 1 time with chlorinated product, changes 1/3 water weekly, and dissolved oxygen keeps 6mg/L or more, experimental period 70d.Wherein compare
Group feeds manganese deficiency basal diet, and addition alkali formula manganese sulfate is calculated as 5ppm, test two with manganese in the manganese deficiency basal diet of one group of test
Alkali formula manganese sulfate is added in the manganese deficiency basal diet of group, 90ppm is calculated as with manganese, wherein crude protein 35.00% in basal diet, slightly
Fat 5.40%, available phosphorus 0.60%.Test result is shown in Table 3.
Table 3: influence of the alkali formula manganese sulfate to Russian carp growth performance
From table 3 it can be seen that test group and control group do not have a significant change on taking the photograph bait amount, but weight gain, body weight increase rate,
Variant on feed coefficient and the death rate, the growth of experimental group carp and survival benefit are substantially better than control group；By experiment one
Group with test two groups it is found that with alkali formula manganese sulfate additive amount raising, body weight increase rate is improved trend, the death rate and bait
Coefficient has a declining tendency.
Embodiment 7: application of the alkali formula manganese sulfate in calf.
Alkali formula manganese sulfate in embodiment 3 is used for the feeding experiment of calf.Select same head black-and-white flower breeding oxen and just
Producing 28 calves (80-90 age in days) that the hybridization of Qin Chuan cow is given birth to is test ox, is randomly divided into 4 groups, every group 7.Wherein compare
Group feeds manganese deficiency basal diet, and addition alkali formula manganese sulfate is calculated as 30ppm, test two with manganese in the manganese deficiency basal diet of one group of test
Alkali formula manganese sulfate is added in the manganese deficiency basal diet of group, and 135ppm is calculated as with manganese.Experimental period total 37d, wherein preliminary trial period 7d, positive to try
Phase 30d.Test result is shown in Table 7.
Table 7: influence of the alkali formula manganese sulfate packet to calf growth performance
As can be seen from Table 7, under conditions of original body mass is not much different, the calf of test group and control group averagely increases day by day
There were significant differences for weight, and the average daily gain of test group is substantially better than control group；By two groups of one group of experiment and experiment it is found that with alkali
The raising of formula manganese sulfate additive amount, daily gain are improved trend, and alkali formula manganese sulfate prepared by the present invention has calf good
Growth-promoting effect.
Claims (6)
1. a kind of preparation method for the alkali formula manganese sulfate that can be used for animal feed additive, which comprises the following steps:
(1) it takes manganese sulfate soluble in water, adjusts pH value to 6.0~7.5, simple substance manganese is added, filters, is prepared into after complete reaction
To filtrate A；
(2) under nitrogen or inert gas shielding, it is slowly added to alkaline solution into the filtrate A prepared in step (1) and carries out instead
It answers, obtains solution B after complete reaction；Wherein, the alkaline solution is sodium hydroxide or potassium hydroxide solution, the filtrate A
The molar ratio of middle manganese sulfate and sodium hydroxide or potassium hydroxide is 4.5 ~ 5.5:8；The temperature reacted is 42 DEG C~78 DEG C, is held
The time of continuous isothermal reaction is 0.5h~2.5h；
(3) solution B by step (2) preparation filters, washing, dry, obtained alkali formula manganese sulfate Mn5(OH)8SO4。
2. the preparation method of alkali formula manganese sulfate according to claim 1, which is characterized in that the simple substance manganese is manganese powder, manganese
Piece or manganese grain, the gross mass that the simple substance manganese is added is the gross mass of impure copper, lead, antimony, cadmium, iron, arsenic in the manganese sulfate
1.05 ~ 1.6 times.
3. the preparation method of alkali formula manganese sulfate according to claim 1, which is characterized in that in the step (2), the hydrogen
The mass fraction of sodium hydroxide solution or potassium hydroxide solution is 20%~50%, when reaction in control filtrate A manganese sulfate quality point
Number is 15%~30%.
4. the preparation method of alkali formula manganese sulfate according to any one of claim 1-3, which is characterized in that the step
(2) in, before being slowly added to alkaline solution, anionic surfactant, the anionic surface are first added into the filtrate A
Activating agent is one or more of lauryl sodium sulfate, sodium alkyl sulfate, fatty alcohol-ether sodium sulfate, in reaction system
Concentration be 0.5~1.4g/L.
5. the preparation method of alkali formula manganese sulfate according to any one of claim 1-3, which is characterized in that the step
(2) in, before being slowly added to alkaline solution, organic solvent is first added into the filtrate A, the organic solvent is methanol, second
One of alcohol, acetone, ethylene glycol, glycerine, ethyl acetate, butanone are a variety of, and the additional amount of the organic solvent is reaction
The 1% ~ 10% of system quality.
6. the preparation method of alkali formula manganese sulfate according to any one of claim 1-3, which is characterized in that the step
(1) in, manganese sulfate is one of anhydrous manganous sulfate, manganese sulfate monohydrate and four water manganese sulfates or a variety of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710274854.2A CN107032410B (en) | 2017-04-24 | 2017-04-24 | The preparation method and applications of alkali formula manganese sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710274854.2A CN107032410B (en) | 2017-04-24 | 2017-04-24 | The preparation method and applications of alkali formula manganese sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107032410A CN107032410A (en) | 2017-08-11 |
| CN107032410B true CN107032410B (en) | 2019-04-05 |
Family
ID=59535654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710274854.2A Active CN107032410B (en) | 2017-04-24 | 2017-04-24 | The preparation method and applications of alkali formula manganese sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107032410B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807414B (en) * | 2020-06-18 | 2022-06-17 | 贵州金瑞新材料有限责任公司 | Method for producing fluorine-free ultrapure manganese sulfate monohydrate by using basic salt method |
| CN114162871A (en) * | 2021-11-23 | 2022-03-11 | 广西锰华新能源科技发展有限公司 | Preparation method of basic manganese sulfate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843939A (en) * | 2006-05-15 | 2006-10-11 | 北京科技大学 | Method for preparing hybrid oxide of manganese by manganese sulfate solution |
| CN103005165A (en) * | 2013-01-08 | 2013-04-03 | 长沙兴嘉动物营养科技有限公司 | Preparation method of lactobionic acid microelement complex and application of complex as animal feed additive |
-
2017
- 2017-04-24 CN CN201710274854.2A patent/CN107032410B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843939A (en) * | 2006-05-15 | 2006-10-11 | 北京科技大学 | Method for preparing hybrid oxide of manganese by manganese sulfate solution |
| CN103005165A (en) * | 2013-01-08 | 2013-04-03 | 长沙兴嘉动物营养科技有限公司 | Preparation method of lactobionic acid microelement complex and application of complex as animal feed additive |
Non-Patent Citations (1)
| Title |
|---|
| 硫酸锰在氨性介质中制备四氧化三锰的研究;邹兴等;《中国锰业》;20091130;第27卷(第1期);第4-6页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107032410A (en) | 2017-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3874966B1 (en) | Zero-starch no-binder shrimp fry starter compound feed and preparation method therefor | |
| US8518466B2 (en) | Selenium covered basic copper chloride, its preparation method and the use | |
| CN107032410B (en) | The preparation method and applications of alkali formula manganese sulfate | |
| CN106243162B (en) | The preparation method of sucrose complex | |
| US11666071B2 (en) | Compound salt of N,N-dimethylglycine and an organic acid and composition and use thereof | |
| RU2411747C2 (en) | Bioavailable form of microelement additives to fodder mixtures for animals and birds | |
| EP1439160A2 (en) | Solid phase synthesis of salts of organic acids including butyric acid | |
| CN106188200B (en) | The preparation method of sucrose zinc complex | |
| CN101961330A (en) | Anti-stress agent for aquatic livestock | |
| CN109123101B (en) | Preparation method of manganese nicotinate | |
| CN111087318B (en) | Preparation method of zinc serine and application of zinc serine in field of animal feed | |
| JPS5876050A (en) | Feedstuff and additive for promoting weight increase of domestic animal and production thereof | |
| CN102422985B (en) | Iodine, selenium and cobalt composite package for animal feed and preparation method and application method thereof | |
| RU2465783C1 (en) | Preliminarily prepared fodder mixture containing multiple microelements and mixture production method | |
| CN109279632B (en) | Preparation method and application of hydroxyl magnesium chloride | |
| CN102007884A (en) | Method for producing eggs rich in multiple trace elements | |
| JP2024511428A (en) | Copper aspartate complex and its applications | |
| WO2020159398A1 (en) | Complete integrated microelement feed additive based on organic compounds of iron, manganese, zinc, copper, cobalt, iodine, and selenium, and method for application of same | |
| CN103005165A (en) | Preparation method of lactobionic acid microelement complex and application of complex as animal feed additive | |
| CN106234774A (en) | The preparation method of sucrose magnesium complex | |
| JPH0239860A (en) | Animal feed and pelletization thereof | |
| CN112979504B (en) | Preparation method and application of argininyl manganese | |
| CN104605161A (en) | Preparation method and application of glycocyamine complex | |
| RU2790532C1 (en) | Method for preparing a feed additive for bees | |
| KR20030006877A (en) | Feed additive containing methionine-fe chelate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |