CN107032410A - The preparation method and applications of alkali formula manganese sulfate - Google Patents
The preparation method and applications of alkali formula manganese sulfate Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of alkali formula manganese sulfate available for animal feed additive, and it comprises the following steps：(1) take manganese sulfate soluble in water, regulation pH value to 6.0~7.5 adds simple substance manganese, and question response is filtered afterwards completely, prepares filtrate A；(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, solution B is obtained after question response is complete；(3) solution B for preparing step (2) is filtered, washing, dry, obtained alkali formula manganese sulfate.The present invention also provides a kind of application of alkali formula manganese sulfate on animal additive is prepared.The alkali formula manganese sulfate that the preparation method provided using the present invention is prepared has the advantages that manganese content is high, prevented from caking, biological value is high, thermally-stabilised good.
Description
Technical field
The invention belongs to field of feed additive technology, more particularly to a kind of alkali formula manganese sulfate preparation method and its should
With.
Background technology
Manganese is as the enzyme activation factor or part in carbohydrate, lipid, protein and cholesterol metabolic.Manganese
The transmission of nervus centralis media and the energy supply of axoneure can be participated in, is to maintain brain eubolism function must can not
Few material, if animal manganese deficiency can cause food ration decline, decreased growth, bone exception, incoordination, slow in reacting and breeding
The phenomenons such as dysfunction.In addition, the enzymatic that thyroid synthesis must have activation manganese could be completed.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 current feed is divided into two kinds of inorganic manganese and Organic Manganese.Inorganic manganese feed addictive include MnO,
MnSO4、MnCl2Deng, but the utilization rate of these compound manganese has difference.MnSO4Middle Mn bioavailability is better than MnO
And MnCO3, with MnCl2It is close.Mn utilization rate 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 are combined, utilization rate, the absorptivity of manganese element are improved.Organic such as Met-Mn is directly entered animal and bird intestines quilt
Absorb and participate 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.
Current inorganic manganese uses manganese sulfate mostly, but because easy deliquescence caking, the scope of application is restricted.Manganese sulfate is because of life
Potassium permanganate or hydrogen peroxide oxidation removal of impurities are used during production, product can remain small amounts thing manganese dioxide, potassium permanganate.This
With the nutritional ingredient of other in feed, such as vitamin, ferrous iron, grease etc. redox reaction, influence can occur for a little oxides
The quality of feed and shelf-life.Meanwhile, the sulfate radical content in manganese sulfate is higher, and animal can be given off after absorbing 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 relatively more on the market at present.The amino acid
Manganese using effect very well, is difficult to sense with the other compositions in feed, shadow of the exhaust emission after animal edible to environment
Sound is also smaller.But the part of manganese amino acid is amino acid, expensive, manganese content is relatively low, and addition is larger, is produced using such
The cost pressure of product feed factory is larger.
Therefore, it is necessary to existing feed addictive containing manganese and preparation method do progress further exploitation there is provided one kind into
This low, utilization rate is high, easy transport is stored feed addictive containing manganese and preparation method.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention with defect that there is provided one in background above technology
The preparation method and applications of alkali formula manganese sulfate are planted, it has the advantages that, and cost is low, utilization rate is high, easy transport storage.
In order to solve the above technical problems, technical scheme proposed by the present invention is：The present invention provides a kind of alkali formula manganese sulfate
Preparation method, comprises the following steps：
(1) take manganese sulfate soluble in water, add simple substance manganese, then adjust pH value to 6.0~7.5, question response is filtered afterwards completely,
Prepare filtrate A；It is preferred that simple substance manganese can several times be added, will the filtrate of gained repeat foregoing addition simple substance manganese, adjust
Save pH value and the operation filtered at least one times,
(2) under nitrogen or inert gas shielding, the filtrate A prepared in step (1) is taken, alkaline solution progress is slowly added to
Reaction, solution B is obtained after question response is complete；
(3) solution B for preparing step (2) is filtered, washing, dry, obtained alkali formula manganese sulfate.
Found by studying, manganese ion concentration is higher, the easier hydrolysis of manganese ion, the pH for starting hydrolysis is lower；Manganese ion
Concentration is lower, then manganese ion more not facile hydrolysis, and it is also higher to start the pH of hydrolysis.And the oxidation rate of manganese ion also with manganese from
Sub- concentration is relevant 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 aoxidize, pH value should be acid or neutral.When pH value is more than 8.0, calcium, magnesium ion in solution can start
Precipitation.By the way that pH value is adjusted to 6.0~7.5 in the step (1), manganese ion on the one hand can be avoided to hydrolyze and aoxidize；
Calcium in solution, the precipitation of magnesium ion can be reduced：Copper simultaneously in increase solution, lead, antimony, cadmium, iron, the precipitation of 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 atmosphere：
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 set nitrogen or
Inert gas shielding, can prevent a small amount of manganous hydroxide and oxidant reaction generation MnO (OH) of generation2。
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, adds institute
State simple substance manganese gross mass be the manganese sulfate in impure copper, lead, antimony, cadmium, iron, 1.05~1.6 times of the gross mass of arsenic.By
Displacement reaction can occur with the harmful heavy metal such as copper, lead, antimony, cadmium in simple substance manganese, can also be with oxidant potassium permanganate, dioxygen
Water, perchloric acid etc. react, it is all by add the simple substance manganese can not only 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
Sodium or potassium hydroxide solution, the mol ratio of the filtrate A and alkaline solution are set to 4.5~5.5: 8.When manganese sulfate and sodium hydroxide
Or the mol ratio of potassium hydroxide is too low can generate Mn (OH)2；When the mol 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 alkali formula manganese sulfate of the low manganese content of form.So manganese sulfate with
The mol ratio of sodium hydroxide or potassium hydroxide is 4.5~5.5: 8 more suitable.
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 reaction when temperature is relatively low
To forward direction progress, the precipitation particle of generation is more, efficiency reduction of the dispersant adsorption on precipitation particle, the mutual making contact of particle
Chance increase, be conducive to reunions, be unfavorable for dispersant anti-agglomeration act on；When reaction temperature is higher, the precipitation of generation
Particle warm-up movement aggravates, collision opportunity increase to each other, so as to enhance what molecular force and Coulomb force between particle were caused
Agglomeration.So setting 42 DEG C~78 DEG C generations for being conducive to product, simultaneous reactions speed is suitable.
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 be 20%~50%, control during reaction manganese sulfate in filtrate A mass fraction be 15%~
30%.By the mass fraction for limiting manganese sulfate and alkaline solution so that reactant can be dissolved completely in water, while subtract 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 alkaline solution is slowly added to,
Anion surfactant is first added into the filtrate A, the anion surfactant is lauryl sodium sulfate, fat
One or more in alcohol sodium sulphate, fatty alcohol-ether sodium sulfate, it is 0.5~1.4g/L in the concentration of reaction system.Pass through step
Suddenly (2) add anion surfactant in the reaction solution, and the anion surfactant is in the reaction solution
Concentration is 0.5~1.4g/L so that precipitation particle agglomeration phenomenon is improved, and grain diameter is more uniform.
The preparation method of above-mentioned alkali formula manganese sulfate, it is preferred that in the step (2), before alkaline solution is slowly added to,
Organic solvent is first added into the filtrate A, the organic solvent is methanol, ethanol, acetone, ethylene glycol, glycerine, acetic acid second
One or more in ester, butanone, the addition of the organic solvent and the mass percent of reaction system are 1%~10%.
Scattered effect is played by adding organic solvent so that the alkali formula manganese sulfate crystalline form of acquisition is more preferable, 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 kind in water manganese sulfate and four water manganese sulfates.
The present invention also provides a kind of application of alkali formula manganese sulfate on animal feed additive is prepared, the alkali formula manganese sulfate
Molecular formula be Mn5(OH)8SO4。
Application of the above-mentioned alkali formula manganese sulfate on animal feed additive is prepared, it is preferred that the alkali formula manganese sulfate by
The preparation method of above-mentioned alkali formula manganese sulfate is prepared from.
The consumption of above-mentioned alkali formula manganese sulfate is：Addition in pig feed is calculated as 25~135ppm with manganese element；In fowl material
In addition 25~135ppm is calculated as with manganese element；Addition in material is ruminated is calculated as 30~135ppm with manganese element；
Addition is calculated as 5~90ppm with manganese element in aquatic products material.
Compared with prior art, the advantage of the invention is that：
1. the manganese sulphur mol ratio of alkali formula manganese sulfate prepared by the present invention reach 5: 1, manganese content is 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 addition is smaller, can add it is more other
Functional additive, be that Feeding Prescription Design reserves bigger addition leeway.
2. the layer structure of basic sulfate manganese prepared by the present invention, good fluidity, be difficult in the storage of long-term weight it is hardened,
It is prevented from caking in prolonged storage simultaneously without the crystallization water.
3. basic sulfate manganese prepared by the present invention is as animal feed additive below 280 DEG C, heat endurance is good, can hold
Higher temperature when being pelletized by feed manufacturing.
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
Thing feed additive animal is discharged using rear sulfate and reduced, and reduces environmental pressure.
5. in the application of the present invention, the basic sulfate manganese feeding animals prepared with the present invention, product quality is stable, the profit of manganese
High with rate, biological value is high, can be used as a kind of new manganese source additive in animal feed.
Embodiment
For the ease of understanding the present invention, more comprehensively, meticulously retouched below in conjunction with preferred embodiment to inventing to do herein
State, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical terms used hereinafter are generally understood that implication phase with those skilled in the art
Together.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention's
Protection domain.
Unless otherwise specified, various raw material, reagent, instrument and equipment used in the present invention etc. can be by city
Field is commercially available or can prepared by existing method.
Unless otherwise specified, the manganese sulfate used in the present invention can be anhydrous manganous sulfate or be crystallized containing any number
The aqueous sulfuric acid manganese of water.
Embodiment 1：
A kind of preparation method of alkali formula manganese sulfate of the present invention, comprises the following steps：
Step (1)：The 388.0Kg manganese sulfate monohydrates that purity is 98% are taken, it is glimmering with atomic absorption spectrophotometer and atom
Light spectrophotometer is detected, wherein also impurity copper, lead, antimony, cadmium, iron, arsenic content summation are 2.1Kg.By manganese sulfate monohydrate plus
Enter to the 2m equipped with 0.81t water3After in reactor, manganese powder 1.1Kg is added, regulation solution ph is 6.0, is filtered after stirring 1h,
Foregoing addition manganese powder, regulation pH value, the operation stirred and filtered 1 time is repeated, filtrate A is made.
Step (2)：The filtrate A prepared in step (1) is again placed in reactor, and adds 42Kg wine in a kettle.
Essence and 790g lauryl sodium sulfate, are filled with nitrogen and protect and make one sealed nitrogen environment of whole reactor formation.Not
It is the sodium hydroxide solution 898Kg that 20%, purity is 99% to be slowly added to concentration in the filtrate A of disconnected stirring, is warming up to after 50 DEG C
Isothermal reaction 2.5h, obtains solution B.
Step (3)：The solution B prepared in step (2) is subjected to press filtration, washing, dried, alkali formula manganese sulfate is obtained
244.5Kg, using manganese rate of collecting as 95%.
Alkali formula manganese sulfate prepared by step (3) is detected using conventional method, wherein sulfate radical content in alkali formula manganese sulfate
For 18.6%, manganese content is that volatile substances content is 0.8% at 53.4%, 105 DEG C.
Alkali formula manganese sulfate prepared by step (3), with sodium hydroxide titration to neutrality, uses first with after excessive diluted hydrochloric acid dissolution
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%.
Determined with atomic absorption spectrophotometer：Lead content is 1.0ppm, and arsenic content is 0.01ppm, and cadmium content is
0.02ppm, antimony content is 0.02ppm, total iron content 5.0ppm.The testing result and molecular formula Mn5(OH)8SO4It is consistent, product
Purity is：98%.Alkali formula manganese sulfate prepared by step (3) is placed under 280 DEG C of environment, its stability, non-recurring structure is detected
Change, suitable for processing feed under higher temperature environment.
The alkali formula manganese sulfate prepared to step (3) uses multilayer complex films bag packaging bags, PVC inner bags with 25Kg/ bags
Tying, waterproof and dampproof pearl film tyre press strip seam bag.
Need, stacked on Forklift plate according to actual storage, each frame plate stacks 5 layers, and 2 frame plates overlay same vertical
Position, totally 10 layers.Orlop one was extracted respectively after 7 days, 14 days, 1 month, 2 months, 3 months, 6 months to contract for fixed output quotas product mistake
Spin vibration sieve, does not find there are unsifted caking materials on sieve, it was demonstrated that the alkali formula manganese sulfate prepared using the above method is deposited for a long time
Put be not easy under weight it is hardened.
Embodiment 2：
The present invention provides a kind of preparation method of alkali formula manganese sulfate, comprises the following steps：
Step (1)：The water manganese sulfates of 563.1Kg tetra- that purity is 99% are taken, it is glimmering with atomic absorption spectrophotometer and atom
Light spectrophotometer is detected, wherein also impurity copper, lead, antimony, cadmium, iron, arsenic content summation are 0.56Kg.Four water manganese sulfates are added
Enter to the 5m equipped with 2.2t water3After in reactor, manganese powder 0.37Kg is added, regulation solution ph is 7.0, mistake after stirring 0.5h
Filter, repeat foregoing addition manganese powder, regulation pH value, the operation stirred and filtered 1 time, filtrate A is made.
Step (2)：The filtrate A prepared in step (1) is placed in reactor, and adds 308Kg alcohol in a kettle.
With 4.1Kg sodium alkyl sulfates, it is filled with nitrogen and protects and make one sealed nitrogen environment of whole reactor formation.Constantly stirring
It is the sodium hydroxide solution 323Kg that 50%, purity is 99% that concentration is slowly added in the filtrate A mixed, is warming up to constant temperature after 78 DEG C
0.5h is reacted, solution B is obtained.
Step (3)：The solution B prepared in step (2) is subjected to press filtration, washing, dried, alkali formula manganese sulfate is obtained
248.3Kg, using manganese rate of collecting as 96%.
Alkali formula manganese sulfate prepared by step (3) is detected using conventional method, wherein sulfate radical content in alkali formula manganese sulfate
For 18.6%, manganese content is 53.1%, and hydroxyl content is that volatile substances content is 1.6% at 26.2%, 105 DEG C.
Determined with atomic absorption spectrophotometer：Lead content is 0.9ppm, and arsenic content is 0.02ppm, and cadmium content is
0.01ppm, antimony content is 0.02ppm, total iron content 4.2ppm.The testing result and molecular formula Mn5(OH)8SO4It is consistent, product
Purity is：98%.Alkali formula manganese sulfate prepared by step (3) is placed under 280 DEG C of environment, its stability, non-recurring structure is detected
Change, suitable for processing feed under higher temperature environment.
The alkali formula manganese sulfate prepared to step (3) uses multilayer complex films bag packaging bags, PVC inner bags with 50Kg/ bags
Tying, waterproof and dampproof pearl film tyre press strip seam bag.
Need, stacked on Forklift plate according to actual storage, each frame plate stacks 5 layers, and 2 frame plates overlay same vertical
Position, totally 10 layers.Orlop one was extracted respectively after 7 days, 14 days, 1 month, 2 months, 3 months, 6 months to contract for fixed output quotas product mistake
Spin vibration sieve, does not find there are unsifted caking materials on sieve, it was demonstrated that the alkali formula manganese sulfate prepared using the above method is deposited for a long time
Put be not easy under weight it is hardened.
Embodiment 3：
The present invention provides a kind of preparation method of alkali formula manganese sulfate, comprises the following steps：
Step (1)：The 428.1Kg anhydrous manganous sulfates that purity is 97% are taken, it is glimmering with atomic absorption spectrophotometer and atom
Light spectrophotometer is detected, wherein also impurity copper, lead, antimony, cadmium, iron, arsenic content summation are 109g.Anhydrous manganous sulfate is added
To the 5m equipped with 1.7t water3After in reactor, manganese powder 87.2g is added, regulation solution ph is 7.5, is filtered after stirring 0.2h, weight
It is foregoing again to add manganese powder, regulation pH value, the operation stirred and filtered 1 time, obtained filtrate A.
Step (2)：The filtrate A prepared in step (1) is placed in reactor, and adds 32.6Kg alcohol in a kettle.
With 2.8Kg fatty alcohol-ether sodium sulfates, it is filled with nitrogen and protects and make one sealed nitrogen environment of whole reactor formation.Continuous
It is the potassium hydroxide solution 1133Kg that 40%, purity is 99% that concentration is slowly added in the filtrate A of stirring, is warming up to after 42 DEG C permanent
Temperature reaction 1h, obtains solution B.
Step (3)：The solution B prepared in step (2) is subjected to press filtration, washing, dried, alkali formula manganese sulfate is obtained
226.5Kg, using manganese rate of collecting as 88%.
Alkali formula manganese sulfate prepared by step (3) is detected using conventional method, wherein sulfate radical content in alkali formula manganese sulfate
For 18.6%, manganese content is 53.4%, and hydroxyl content is that volatile substances content is 0.7% at 26.4%, 105 DEG C.
Determined with atomic absorption spectrophotometer：Lead content is 1.1ppm, and arsenic content is 0.01ppm, and cadmium content is
0.02ppm, antimony content is 0.02ppm, total iron content 2.8ppm.The testing result and molecular formula Mn5(OH)8SO4It is consistent, product
Purity is：98%.Alkali formula manganese sulfate prepared by step (3) is placed under 280 DEG C of environment, its stability, non-recurring structure is detected
Change, suitable for processing feed under higher temperature environment.
The alkali formula manganese sulfate prepared to step (3) uses multilayer complex films bag packaging bags, PVC inner bags with 25Kg/ bags
Tying, waterproof and dampproof pearl film tyre press strip seam bag.
Need, stacked on Forklift plate according to actual storage, each frame plate stacks 5 layers, and 2 frame plates overlay same vertical
Position, totally 10 layers.The bag of orlop one was extracted respectively after 7 days, 14 days, 1 month, 2 months, 3 months, 6 months, 12 months
Product crosses spin vibration sieve, does not find there are unsifted caking materials on sieve, it was demonstrated that the alkali formula manganese sulfate prepared using the above method
It is not easy under long-term storage weight hardened.
Embodiment 4：Alkali formula manganese sulfate as sow feed additive application.
The alkali formula manganese sulfate prepared in embodiment 1 is used for the feeding experiment of brood sow as animal feed additive.
Select the Duluke's sow 90 of same parity, be divided into three groups (control groups and experiment one, two groups), every group 30, every group with 2~
3 Duroc boars are bred, it is desirable to breeding is completed within an oestrus, and wherein control group feeds manganese deficiency daily ration to pig,
One group is tested in pig with the alkali formula manganese sulfate that the present 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 of experiment is in pig with alkali formula sulfuric acid manganese content in addition alkali formula manganese sulfate of the present invention, daily ration in manganese deficiency daily ration with manganese
Element is calculated as 135ppm.Result of the test 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 for nascent young number living, control group has significant difference (p ＜ 0.05) with test group, but
Do not have a great impact to weigth at birth；With the change of feeding time, control group and test group is lived in 21 age in days young number and
Litter weight starts to show larger difference, and survival rate has the difference (p ＜ 0.05) of conspicuousness；During 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 stage, incubation rate have the raising of conspicuousness compared with control group, and later stage litter weight also has larger carry compared with control group
It is high.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 duckling immunity is improved.
The alkali formula manganese sulfate prepared in embodiment 2 is used for the feeding experiment of duckling.From 1 age in days without duck viral liver
The Beijing duckling of scorching vaccine inoculation 80, is randomly divided into 4 groups, every group 20, a point circle plane is raised, and every group one is enclosed, every group of duckling
24h constant illuminations, free choice feeding and drinking-water.Experimental period 30d, after off-test, slaughters duckling in units of group, collect blood,
Thymus gland, spleen are simultaneously analyzed.Wherein, control group feeds manganese deficiency basal diet to duckling；Test one group of addition in duckling manganese deficiency daily ration
Alkali formula manganese sulfate addition is calculated as 25ppm with manganese element in alkali formula manganese sulfate, daily ration；Two groups are tested in duckling manganese deficiency daily ration to add
Plus alkali formula manganese sulfate, alkali formula manganese sulfate addition is calculated as 135ppm with manganese element in daily ration, and three groups of experiment is in duckling manganese deficiency daily ration
Manganese sulfate monohydrate addition is calculated as 135ppm with manganese element in middle addition manganese sulfate monohydrate, daily ration per ton.Result of the test 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 degree clearly difference.Test group phase
It increased than the thymus gland in control group and spleen weight, serum HI spends clearly decline；From testing one group and two groups of experiment, with
The weight of the increase of manganese addition, thymus gland and spleen is in rising trend, and serum HI spends clearly on a declining curve；By testing two groups and experiment
Three groups understand, are all the manganese element for adding 135ppm, and the data of two groups of experiment are better than three groups of experiment.Above phenomenon shows, adds
Manganese addition can strengthen the immunity of duckling, and the raising of alkali formula manganese sulfate addition, the effect that duckling immunity is improved becomes apparent from, and this
Manganese sulfate monohydrate will be substantially better than to the effect for improving duckling immunity by inventing the alkali formula manganese sulfate prepared.
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 (132.0 ± 2.0) g tail of Russian carp 1500, is equally divided into 5 big group, and each big component is 3 groups,
Each tail of group 100, fingerling is bought the same day back and is grouped immediately, is splashed sterilization, is then put into each group with anti-bacteria and virus after packet
Specification is 6m × 9m cement pit.Dead fish is gradually completing examination from specification close standby fish substitute in 1st week in 3d after packet
Replacement of the material to former feed is tested, is fed daily under normal circumstances 4 times during experiment, aerator is started according to weather condition in good time,
Sterilized 1 time with chlorinated product per two weeks, 1/3 water is changed weekly, dissolved oxygen keeps more than 6mg/L, experimental period 70d.Wherein compare
Addition alkali formula manganese sulfate is calculated as 5ppm, experiment two with manganese in group feeding manganese deficiency basal diet, the manganese deficiency basal diet of one group of experiment
Addition alkali formula manganese sulfate is calculated as 90ppm with manganese in the manganese deficiency basal diet of group, crude protein 35.00% wherein in basal diet, slightly
Fat 5.40%, available phosphorus 0.60%.Result of the test 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 significant change taking the photograph in bait amount, but weightening, 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 understands that, with the raising of alkali formula manganese sulfate addition, body weight increase rate is improved trend, the death rate and bait for two groups with experiment
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.From same head black-and-white flower breeding oxen and just
28 calves (80-90 ages in days) that production Qin Chuan cow hybridization is given birth to are test ox, are randomly divided into 4 groups, every group 7.Wherein compare
Addition alkali formula manganese sulfate is calculated as 30ppm, experiment two with manganese in group feeding manganese deficiency basal diet, the manganese deficiency basal diet of one group of experiment
Addition alkali formula manganese sulfate is calculated as 135ppm with manganese in the manganese deficiency basal diet of group.Experimental period common 37d, wherein preliminary trial period 7d, positive examination
Phase 30d.Result of the test is shown in Table 7.
Table 7：Influence of the alkali formula manganese sulfate bag to calf growth performance
As can be seen from Table 7, under conditions of original body mass is more or less the same, 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；From two groups of one group of experiment and experiment, with alkali
The raising of formula manganese sulfate addition, its daily gain is improved trend, and alkali formula manganese sulfate prepared by the present invention has good to calf
Growth-promoting effect.
Claims (10)
1. the preparation method of a kind of alkali formula manganese sulfate available for animal feed additive, it is characterised in that comprise the following steps：
(1) take manganese sulfate soluble in water, regulation pH value to 6.0~7.5 adds simple substance manganese, and question response is filtered, is prepared into afterwards completely
To filtrate A；
(2) under nitrogen or inert gas shielding, the filtrate A prepared in step (1) is taken, alkaline solution is slowly added to and carries out instead
Should, obtain solution B after question response is complete；
(3) solution B for preparing step (2) is filtered, washing, dry, obtained alkali formula manganese sulfate.
2. the preparation method of alkali formula manganese sulfate according to claim 1, it is characterised in that the simple substance manganese is manganese powder, manganese
Piece or manganese grain, the gross mass for adding the simple substance manganese is impure copper, lead, antimony, cadmium, iron, the gross mass of arsenic in the manganese sulfate
1.05~1.6 times.
3. the preparation method of alkali formula manganese sulfate according to claim 1, it is characterised in that in the step (2), the alkali
Property solution be sodium hydroxide or potassium hydroxide solution, the mol ratio of manganese sulfate and sodium hydroxide or potassium hydroxide in the filtrate A
For 4.5~5.5: 8.
4. the preparation method of alkali formula manganese sulfate according to claim 1, it is characterised in that in the step (2), is carried out anti-
The temperature answered is 42 DEG C~78 DEG C, and the time for continuing isothermal reaction is 0.5h~2.5h.
5. the preparation method of alkali formula manganese sulfate according to claim 3, it is characterised in that in the step (2), the hydrogen
The mass fraction of sodium hydroxide solution or potassium hydroxide solution is 20%~50%, and the quality of manganese sulfate in filtrate A is controlled during reaction
Fraction is 15%~30%.
6. the preparation method of the alkali formula manganese sulfate according to any one of claim 1-5, it is characterised in that the step
(2) in, before alkaline solution is slowly added to, anion surfactant, the anionic surface are first added into the filtrate A
Activating agent is the one or more in lauryl sodium sulfate, sodium alkyl sulfate, fatty alcohol-ether sodium sulfate, and it is in reaction system
Concentration be 0.5~1.4g/L.
7. the preparation method of the alkali formula manganese sulfate according to any one of claim 1-5, it is characterised in that the step
(2) in, before alkaline solution is slowly added to, organic solvent is first added into the filtrate A, the organic solvent is methanol, second
One or more in alcohol, acetone, ethylene glycol, glycerine, ethyl acetate, butanone, the addition of the organic solvent is reaction
The 1%~10% of system quality.
8. the preparation method of the alkali formula manganese sulfate according to any one of claim 1-5, it is characterised in that the step
(1) in, manganese sulfate is the one or more in anhydrous manganous sulfate, manganese sulfate monohydrate and four water manganese sulfates.
9. the alkali formula manganese sulfate that any one of claim 1-8 is prepared answering on animal feed additive is prepared a kind of such as
With the molecular formula of the alkali formula manganese sulfate is Mn5(OH)8SO4。
10. application according to claim 9, it is characterised in that the alkali formula manganese sulfate any institute in claim 1-8
The preparation method for stating alkali formula manganese sulfate is prepared from, and consumption is：Addition of the alkali formula manganese sulfate in pig feed is with manganese element
It is calculated as additions of the 25~135ppm in fowl material and additions of the 25~135ppm in material is ruminated is calculated as with manganese member with manganese element
Element is calculated as 30~135ppm；Addition is calculated as 5~90ppm with manganese element in aquatic products material.
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| CN111807414A (en) * | 2020-06-18 | 2020-10-23 | 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 |
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| 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 |
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