CN109399686A - The application of a kind of preparation method and hydroxy carbonate calcium of hydroxy carbonate calcium in field of animal feed - Google Patents
The application of a kind of preparation method and hydroxy carbonate calcium of hydroxy carbonate calcium in field of animal feed Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/24—Compounds of alkaline earth metals, e.g. magnesium
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K40/00—Shaping or working-up of animal feeding-stuffs
- A23K40/10—Shaping or working-up of animal feeding-stuffs by agglomeration; by granulation, e.g. making powders
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/10—Feeding-stuffs specially adapted for particular animals for ruminants
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/30—Feeding-stuffs specially adapted for particular animals for swines
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/70—Feeding-stuffs specially adapted for particular animals for birds
- A23K50/75—Feeding-stuffs specially adapted for particular animals for birds for poultry
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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Abstract
The invention discloses a kind of preparation methods of hydroxy carbonate calcium that can be used for animal feed, comprising the following steps: calcium source is added to the water heating, bicarbonate is added under stiring, isothermal reaction, decrease temperature crystalline after reaction, filtration drying to get arrive hydroxy carbonate calcium.The reaction rate milder of the preparation method, process control, more evenly, by-product generates few, the bioavailability height of product hydroxy calcium carbonate to obtained product particle, and processing cost is low.The invention also discloses hydroxy carbonate calcium in the application of field of animal feed, and when being used for pannage, additive amount is 1-12kg/t mixed feed；When for poultry feed, additive amount is 1-23kg/t mixed feed；When for ruminant animals feed, additive amount is 0.1-4kg/t fully-mixed daily feed.The application can neutralize the acidic materials in feed, prevent or delay feed spoilage.
Description
Technical field
The invention belongs to the preparation methods and hydroxy carbonate calcium of field of animal feed more particularly to a kind of hydroxy carbonate calcium to exist
Application in field of animal feed.
Background technique
Calcium (calcium) is the most abundant mineral element of biological in-vivo content, and enough calcium intakes are normal to maintenance animal
It is most important to reach high bone mass peak value for bone mineral content, bone density.In addition, calcium ion also participates in a variety of physiology function in organism
Can, such as blood clotting maintains heart, muscle, neural normal excitability, signal transduction and the permeability of film etc..
Sense is insufficient compared with the requirement of various animals for calcium content in usual natural plant feed, especially lays eggs
Poultry, cow in milk and growth cub become apparent.Therefore, it should be noted that the supplement of calcium in animal diet.It is applied on the market at present
The calcium source of feed addictive is broadly divided into inorganic calcium and organic calcium.
Common calcium mineral matter feed is inorganic calcium, there is agstone, conch meal etc..Agstone is also known as mountain flour, is
Natural whiting (CaCO3).In natural lime stone, because of mineral deposit concomitant problem, lead, mercury, arsenic, fluorine content be easy it is exceeded,
And mountain flour encounters gastric acid can produce carbon dioxide, easily causes hiccup gastric disorder causing nausea etc..Conch meal is that various shellfish shells are (clam shell, male
Oyster shell, clam shell, snail shell etc.) powdery or pelletized product made of processed crushing are in canescence, grey, taupe more.Shellfish
The impurity such as sandstone and soil are often adulterated in shell powder, are not easy to thoroughly remove, and influence feed nutritive value, and the sandstone and soil adulterated
Equal impurity eat the digestive system function that will affect animal in animal body.If in addition shellfish meat does not eliminate, it is improper to store in addition, accumulation
With the passing of time easily there is situations such as mouldy, rancid, this can be such that its feed value significantly reduces.And conch meal is influenced by the place of production, is transported to interior
The expense on ground is not low, crushes again in addition needing to clear up, and processing request is higher, and cost is not easy to control, compares mountain flour, conch meal it is main at
Dividing equally is CaCO3Cost wants many on height.
Although organic calcium bioavailability is higher than inorganic calcium, expensive, in field of fodder using less.Because organic
Calcium content is lower, and additive amount is larger, larger using the feed factory production cost pressure of such product.
The bioavailability size of microelement is related to its existing morphology.The biology of traditional inorganic microelement
Utilization rate is generally lower, is mostly used in chemical field, rather than special production is in feed, it is therefore desirable to pay special attention to it
Lead, arsenic, cadmium, dioxin, Polychlorinated biphenyls for containing etc. must be strictly controlled in the range of country's license.
Hydroxy carbonate calcium, molecular formula Ca3(CO3)2(OH)2And Ca6(CO3)5(OH)2, bioavailability height, processing cost
It is low, so there is very wide application prospect in animal feed addition field.However hydroxy carbonate calcium is more common in cement at present
Industry, the concrete application in animal have not been reported.Mostly use calcium oxide or calcium hydroxide and carbon dioxide gas anti-at present
Hydroxy carbonate calcium should be prepared under room temperature and temperatures above environment, calcium hydroxide and carbon dioxide start to generate hydroxy carbonate
Calcium, but hydroxy carbonate calcium will continue to continue to generate calcium carbonate with carbon dioxide reaction, it is seen that carbon dioxide reacts system with calcium
The process of standby hydroxy carbonate calcium is uncontrollable.Carbon dioxide is gas, and density is small, solubility very little in water, can be rapid
Float on liquid level, be unfavorable for accurately control carbon dioxide reacting dose be easy to cause generation if carbon dioxide is excessive
Product is calcium carbonate.Therefore, find that a kind of reaction process is easy to control, by-product generates less, the lower hydroxy carbonate of cost
The preparation method of calcium, has a very important significance field of animal feed.
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
Reaction process is easy to control kind, the preparation method that by-product generates less hydroxy carbonate calcium and hydroxy carbonate calcium are in animal feed
Application in field.
In order to solve the above technical problems, technical solution proposed by the present invention is a kind of hydroxy carbonate that can be used for animal feed
The preparation method of calcium, comprising the following steps: calcium source is added to the water, is cooled down, bicarbonate is added under stiring and is reacted,
After reaction, filtration drying to get arrive hydroxy carbonate calcium.
The bicarbonate that the present invention uses is soluble easily in water, reacts with calcium, reaction rate milder, process control；And carbon
Sour hydrogen salt is weaker than the alkalinity of carbonate, reacts milder, obtained product particle is more evenly；Especially selection calcium bicarbonate with
When calcium source reaction prepares hydroxy carbonate calcium, almost no coupling product is generated.
It is preferred in above-mentioned preparation method:
When bicarbonate is sodium bicarbonate and/or saleratus, calcium source includes calcium salt and alkaline calcic object, in calcium source
The molar ratio of calcium and bicarbonate control be (1.1~1.6): 1, calcium salt is calcium chloride, alkaline calcic object be calcium hydroxide and/or
Calcium oxide.Calcium source can be not only provided, while reaction system can also be adjusted by the way that calcium chloride, calcium hydroxide, calcium oxide is added
PH value be alkalinity.Wherein, calcium oxide meets water and generates calcium hydroxide, and solubility is not high, is disappeared constantly reacting with bicarbonate
Consumption, undissolved part are also gradually dissolved in water, are maintained a metastable dynamic equilibrium, are made reaction rate in a small range wave
Dynamic, the product particle of generation is in the same size, good dispersion.It is obtained by test of many times, by rubbing for calcium in calcium source and bicarbonate
You are (1.1~1.6) than control: when 1, reaction system is just maintained in an alkaline environment, is conducive to target product
It generates, if calcium source additive amount is excessive or very few, will lead to yield decline, product purity is not high.
Specific reaction equation is as follows:
2NaHCO3+CaCl2+2Ca(OH)2=Ca3(CO3)2(OH)2+2NaCl+2H2O；
2NaHCO3+CaCl2+ 2CaO=Ca3(CO3)2(OH)2+2NaCl；
Or
2KHCO3+CaCl2+2Ca(OH)2=Ca3(CO3)2(OH)2+2KCl+2H2O；
2KHCO3+CaCl2+ 2CaO=Ca3(CO3)2(OH)2+2KCl；
Or
10NaHCO3+5CaCl2+7Ca(OH)2=2Ca6(CO3)5(OH)2+10NaCl+10H2O；
10NaHCO3+5CaCl2+ 7CaO=2Ca6(CO3)5(OH)2+10NaCl+3H2O；
Or
10KHCO3+5CaCl2+7Ca(OH)2=2Ca6(CO3)5(OH)2+10KCl+10H2O；
10KHCO3+5CaCl2+ 7CaO=2Ca6(CO3)5(OH)2+10KCl+3H2O。
When bicarbonate is calcium bicarbonate, calcium source is calcium hydroxide and/or calcium oxide, calcium and calcium bicarbonate in calcium source
Molar ratio control be (1.3~2.2): 1.Calcium source can be not only provided by being added in calcium hydroxide and/or calcium oxide, simultaneously
The pH value of reaction system can also be adjusted as alkalinity.It is obtained by test of many times, by the molar ratio of calcium in calcium source and bicarbonate
Control is (1.3~2.2): when 1, reaction system is just maintained in an alkaline environment, is conducive to the generation of target product,
If calcium source additive amount is excessive or very few, yield decline will lead to, product purity is not high.Selection calcium bicarbonate system of reacting with calcium source
When standby hydroxy carbonate calcium, no coupling product is generated.
Specific reaction equation is as follows:
Ca(HCO3)2+2Ca(OH)2=Ca3(CO3)2(OH)2+2H2O；
Ca(HCO3)2+ 2CaO=Ca3(CO3)2(OH)2；
Or
5Ca(HCO3)2+7Ca(OH)2=2Ca6(CO3)5(OH)2+10H2O；
5Ca(HCO3)2+ 7CaO=2Ca6(CO3)5(OH)2+3H2O。
In above-mentioned preparation method, it is preferred that at -5 DEG C~1 DEG C, the time of reaction is controlled in 1h for the temperature control of reaction
~4h.When hydroxy carbonate calcium reaction temperature is higher, when the reaction time is too long, product purity can be reduced, and generate a small amount of calcium carbonate；
But when product temperature is too low, solution can freeze, and be easy to cause reaction not complete, conversion rate of products is lower.In conjunction with raw material, product,
The characteristic and reaction principle of by-product, by repeatedly testing repeatedly, after the calcium source in reaction raw materials either of the present invention is dissolved in water
The salt water that the sodium chloride (or potassium chloride) obtained after salt water, or reaction is formed is formed, the zero boundary's point temperature to freeze is all lower,
It will not freeze in -5 DEG C~1 DEG C of range of reaction temperature, guarantee the stabilization of reaction system.Reaction temperature be -5 DEG C~1 DEG C,
Reaction, time, when being 1h~4h, it is ensured that reaction system does not freeze in reaction process, fully reacting and has higher yield,
It reduces reaction time inadequate bring wastage of material and reacts bring energy consumption with long-time, improve product purity.
Preferably, the quality of water is 2~3.4 times of calcium source and bicarbonate quality sum.If amount of water is very little, reactant
System is too sticky, contains a large amount of calcium source (such as calcium hydroxide particle) in water, and calcium source may be wrapped up, be caused by the product of generation
Reaction is incomplete；If amount of water is too many, the solubility of calcium hydroxide in water is smaller, and (calcium oxide also will become hydrogen-oxygen after being dissolved in water
Change calcium), the positive of reaction rate is influenced less, makes reaction system be easy to freeze because calcium chloride content is too low instead, and not
Product and wastewater treatment is precipitated conducive to subsequent crystallization；So the additional amount of water be calcium source and bicarbonate quality sum 2~
3.4 times more appropriate.
As a general technical idea, the present invention correspondingly provides a kind of hydroxy carbonate calcium in field of animal feed
Using, comprising the following steps:
1) use above-mentioned preparation method that molecular formula is prepared as Ca3(CO3)2(OH)2Or Ca6(CO3)5(OH)2Hydroxyl
Calcium carbonate；
2) hydroxy carbonate calcium is further pelletized, obtains hydroxy carbonate calcium particle；
3) it is applied using hydroxy carbonate calcium particle as feed addictive.
In above-mentioned application, it is preferred that granulation specifically includes: hydroxy carbonate calcium is obtained mesh after crushing, granulation, sieving
Number is the hydroxy carbonate calcium particle of 8~100 mesh, and the mode of the granulation is disk pelletizing, spraying granulation or fluidized bed granulation.System
The adhesive used in grain is soluble material or insolubility material.The mobility dispersibility of hydroxy carbonate calcium after granulation
Good, different meshes meet the requirement of different feeds specification, if feed for piglet instead of milk product is more likely to fine grain material, and it is big
Pig feed product is more likely to coarse grained material.
In above-mentioned application, it is preferred that when hydroxy carbonate calcium is used for pannage, additive amount is to add in mixed feed per ton
Add 1-12kg hydroxy carbonate calcium；When hydroxy carbonate calcium is used for poultry feed, additive amount is to add in mixed feed per ton
Add 1-23kg hydroxy carbonate calcium；When hydroxy carbonate calcium is used for ruminant animals feed, additive amount is fully mixed diet per ton
0.1-4kg hydroxy carbonate calcium is added in feed.
Compared with the prior art, the advantages of the present invention are as follows:
1, preparation method of the invention is reacted using bicarbonate with calcium, and bicarbonate is soluble easily in water, reacts with calcium
Reaction rate milder, process control, more evenly, by-product generates few obtained product particle；With prior art dioxy
Change carbon is reacted with calcium prepares hydroxy carbonate calcium phase ratio, and preparation method process provided by the invention is easier to control, and by-product generates
Less, cost is lower, and technique is more simple, and yield is higher.
2, preparation method of the invention, bicarbonate is added in the water of calcic, and the process that makes entirely to feed intake is all in alkali
In property environment, it is more advantageous to the generation of target product；Meanwhile calcium oxide meets water and generates calcium hydroxide, solubility is not high, continuous
It reacts and is consumed with bicarbonate, undissolved part is also gradually dissolved in water, maintains a metastable dynamic equilibrium, is made anti-
Rate is answered to fluctuate in a small range, the product particle of generation is in the same size, good dispersion.
3, preparation method of the invention, the temperature control of isothermal reaction at -5 DEG C~1 DEG C, reaction time control 1h~
4h.It is influenced by hydroxy carbonate calcium physicochemical property itself, reduces reaction temperature, can inhibit side reaction, improve product purity；When anti-
When answering temperature higher, when the reaction time is too long, product purity can be reduced, and generate a small amount of calcium carbonate.But when product temperature is too low,
Solution can freeze, and be easy to cause reaction not complete, conversion rate of products is lower；In conjunction with the characteristic and reaction of raw material, product, by-product
Principle, by repeatedly testing repeatedly, reaction temperature is -5 DEG C~1 DEG C, and the reaction time controls in 1h~4h, it is ensured that reacted
Reaction system does not freeze in journey, fully reacting and has higher yield, reduces reaction time inadequate bring wastage of material and length
Time response bring energy consumption improves product purity；Compared to other reaction temperatures reported in the literature, reaction of the invention
Temperature is lower, inhibits the generation of by-product, and obtained product is purer.
4, preparation method of the invention pelletizes hydroxy carbonate calcium, the mobility dispersibility of the hydroxy carbonate calcium after granulation
Preferably, prevented from caking, different meshes meet the requirement of different feeds specification, as feed for piglet instead of milk product is more likely to buy thin
The material of grain, and big pig feed product is more likely to buy coarse grained material.
5, hydroxy carbonate calcium produced by the present invention, bioavailability is high, and processing cost is low, is applied to animal feed addition neck
Domain can neutralize the acidic materials in feed, prevent or delay feed spoilage；It is applied in bird feed, is not influencing
Meat chicken growth performance can be effectively improved in the case that shin bone is strong, having while reducing and discharging pressure improves Egg Production of Laying Hens
The effect of energy；Be applied in pannage, add low dosage hydroxy carbonate calcium can achieve it is consistent with high dose calcium carbonate
Growth performance, and on other physiological and biochemical indexs without influence；It is applied in ruminant feed, ruminant can be maintained
Plasma calcium phosphorus concentration activity, parathormone, BGP content it is normal, the Metabolism of Normal of calcium, especially having to milk cow improves
The effect of dairy cattle.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, embodiment will be described below
Needed in attached drawing be briefly described, it should be apparent that, the accompanying drawings in the following description is some implementations of the invention
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Obtain other attached drawings.
Fig. 1 is hydroxy carbonate calcium infared spectrum obtained in the embodiment of the present invention 1.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is done below in conjunction with preferred embodiment and more comprehensively, is meticulously described,
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.The measurement of calcium and carbanion is surveyed with EDTA calcon in product
Fixed, hydroxyl is measured with acid base titration.Free water and other volatile substances are that low temperature drying to constant weight is surveyed at 103 DEG C ± 2 DEG C
It is fixed.
Embodiment 1:
A kind of preparation method of hydroxy carbonate calcium, comprising the following steps:
It is that the calcium chloride of 98% 113g and the calcium oxide of 114g are added in 1.3L water by purity, cooling is being stirred
The lower sodium bicarbonate that the 171g that purity is 98% is added and the isothermal reaction 1h at -1 DEG C, crystallize 1h after reaction, were centrifuged
After filter in 105 DEG C of baking ovens after drying and crushing, hydroxy carbonate calcium 258g is obtained.
The target product hydroxy carbonate calcium that the present invention obtains is through detecting, and wherein carbanion content is 43.2%, and calcium contains
Amount is 43.3%, hydroxyl content 12.2%, and volatile substances content is 0.6% at 105 DEG C, the testing result and hydroxyl
Calcium carbonate molecular formula Ca3(CO3)2(OH)2It is consistent.Product yield is 93.2%, product purity 98.7%.
Product infared spectrum is shown in Fig. 1, as shown in Figure 1: 3644cm-1Place sharp band and in 3436cm-1With 3568cm-1Place
Sharp band be respectively free O-H base vibration absorption peak and hydrogen bond displacement.H2The bending vibration of O is in 1795cm-1, CO3 2-Asymmetry
Stretching vibration appears in wide and strong peak 1416cm-1Place, CO3 2-Symmetrical stretching vibration absorption peak appear in 1261cm-1Place, knot
CO in structure3 2-Bonding in the form of an ion.422cm-1With 711cm-1The peak at place is respectively the bending and stretching vibration absworption peak of Ca-O.
Embodiment 2:
A kind of preparation method of hydroxy carbonate calcium, comprising the following steps:
It is that the calcium chloride of 98% 113kg and the calcium oxide of 114kg are added in 1t water by purity, cooling is being stirred
The lower saleratus that the 204kg that purity is 98% is added and the isothermal reaction 1.0h at -3 DEG C, are down to room temperature knot after reaction
Brilliant 50min, rear expansion drying after centrifugal filtration, then add the granulation of 2% converted starch and sieve with 100 mesh sieve, obtain hydroxy carbonate calcium
273kg。
The target product hydroxy carbonate calcium that the present invention obtains is through detecting, and wherein carbanion content is 41.7%, and calcium contains
Amount is 41.7%, hydroxyl content 11.8%, and volatile substances content is 3.6% at 105 DEG C, the testing result and hydroxyl
Calcium carbonate molecular formula Ca3(CO3)2(OH)2It is consistent.Product yield is 94.8%, product purity 95.3%.
Embodiment 3:
A kind of preparation method of hydroxy carbonate calcium, comprising the following steps:
The calcium hydroxide that purity is 98% 156kg is added in 1t water, is cooled down, purity is added under stiring is
The calcium bicarbonate of 99% 164kg and the isothermal reaction 1.0h at 1 DEG C, are down to crystallizing at room temperature 45min after reaction, were centrifuged
It dry, pulverize 30 mesh in 105 DEG C of baking ovens after filter, and obtained hydroxy carbonate calcium 271kg.
The target product hydroxy carbonate calcium that the present invention obtains is through detecting, and wherein carbanion content is 42.7%, and calcium contains
Amount is 42.8%, hydroxyl content 12.1%, and volatile substances content is 1.3% at 105 DEG C, the testing result and hydroxyl
Calcium carbonate molecular formula Ca3(CO3)2(OH)2It is consistent.Product yield is 96.5%, product purity 97.8%.
Embodiment 4:
A kind of preparation method of hydroxy carbonate calcium, comprising the following steps:
It is that the calcium chloride of 98% 566kg and the calcium hydroxide of 529kg are added in 6.5t water by purity, cooling,
It is added with stirring the sodium bicarbonate for the 857kg that purity is 98% and the isothermal reaction 2.0h at -5 DEG C, is down to room after reaction
Temperature crystallization 30min, expansion drying after filters pressing, then add 3.5% dextrin and pelletized 8 meshes, obtain hydroxy carbonate calcium 1.1t.
The target product hydroxy carbonate calcium that the present invention obtains is through detecting, and wherein carbanion content is 49.5%, and calcium contains
Amount is 39.6%, hydroxyl content 5.6%, and volatile substances content is 1.2% at 105 DEG C, the testing result and hydroxyl
Calcium carbonate molecular formula Ca6(CO3)5(OH)2It is consistent.Product yield is 93.8%, product purity 94.7%.
Embodiment 5:
A kind of preparation method of hydroxy carbonate calcium, comprising the following steps:
It is that the calcium chloride of 98% 566kg and the calcium oxide of 400kg are added in 6t water by purity, cooling is being stirred
The lower saleratus that the 1t that purity is 98% is added and the isothermal reaction 1.5h at -3 DEG C, are down to crystallizing at room temperature after reaction
35min, expansion drying after filters pressing, then add 3.5% zein and pelletized 40 meshes, obtain hydroxy carbonate calcium 1.2t.
The target product hydroxy carbonate calcium that the present invention obtains is through detecting, and wherein carbanion content is 49.3%, and calcium contains
Amount is 39.5%, hydroxyl content 5.6%, and volatile substances content is 1.4% at 105 DEG C, the testing result and hydroxyl
Calcium carbonate molecular formula Ca6(CO3)5(OH)2It is consistent.Product yield is 96.7%, product purity 94.4%.
Embodiment 6:
A kind of preparation method of hydroxy carbonate calcium, comprising the following steps:
The calcium hydroxide that purity is 98% 535kg is added in 4.5t water, is cooled down, purity is added under stiring is
The calcium bicarbonate of 98% 830kg and the isothermal reaction 4h at 1 DEG C, are down to crystallizing at room temperature 40min, centrifugal filtration after reaction
Afterwards, 1.5% ethyl cellulose is added in disk drying and granulating, obtains the hydroxy carbonate calcium 1.1t of 60 mesh.
The target product hydroxy carbonate calcium that the present invention obtains is through detecting, and wherein carbanion content is 50.1%, and calcium contains
Amount is 40.1%, hydroxyl content 5.7%, and volatile substances content is 2.9% at 105 DEG C, the testing result and hydroxyl
Calcium carbonate molecular formula Ca6(CO3)5(OH)2It is consistent.Product yield is 93.8%, product purity 95.9%.
It by product obtained in embodiment 6 with 25kg/ packet, is packed using MULTILAYER COMPOSITE film package bag, wherein PVC inner bag
Tying, waterproof and dampproof pearl film outer bag press strip seam packet.It needs, is stacked on Forklift plate, each frame plate stacks 5 according to practical storage
Layer product, 2 frame plates overlay same upright position, totally 10 layers of product.The 7th day, 14 days, 1 month, 2 months, 3 months, 6
One product of contracting for fixed output quotas of lowest level are extracted after a month respectively and cross 60 mesh spin vibration sieves, do not find to sieve in the presence of the caking materials that are not sieved.
Application Example 1:
The hydroxy carbonate calcium being prepared in embodiment 2 is applied to the feeding experiment of broiler chicken.
The 1 age in days health love for selecting 540 plumages to hatch from same hatchery pulls out increasingly Broiler chicks.Broiler chicks are placed in the feeding of broiler chicken cage
It supports, whole process is freely eaten and free water, and according to routine immunization program immunity.It is randomly divided into 3 processing groups, each processing group
6 repetitions, each 30 plumage of repetition.Wherein, control group adds 15kg mountain flour (Ca content 36.5%)/t cooperation in basal diet
Feed tests 1 group and adds 8kg hydroxy carbonate calcium (Ca content 41.7%)/t mixed feed in basal diet, tests 2 groups in base
11kg hydroxy carbonate calcium/t mixed feed is added in plinth daily ration.Each group basal diet is consistent, and calcium monohydrogen phosphate additive amount is 17kg/
T mixed feed does not add other calcium sources.Test period totally 42 days.
Testing index, growth performance: 1 age and 42 ages all chickens claim quality, count feed intake, calculate feedstuff-meat ratio.As a result such as
Shown in the following table 1.
Table 1: influence of the hydroxy carbonate calcium to meat chicken growth performance
As can be seen from Table 1: testing 1 group and test 2 groups of broiler chicken daily gains higher than control group 4.15%, 6.41% respectively.
Daily ingestion amount slightly improves.In terms of feed conversion rate, tests 1 group and test 2 groups of higher than control group 2.31%, 4.61% respectively.
Each group survival rate indifference.The above results explanation, adds the hydroxy carbonate calcium of low dosage, compares mountain flour, can effectively reduce calcium
Pitch-based sphere reduces discharge, and can improve meat chicken growth performance.
Application Example 2:
The hydroxy carbonate calcium prepared in embodiment 2 is used for the feeding experiment of laying hen.
Select the blue brown laying hen in 59 week old sea, 600 plumages.It is randomly divided into 4 groups, every group of 5 repetitions, each 30 plumage of repetition.Respectively
Group basal diet is consistent, middling flour 75kg/t mixed feed is only added in basal diet, without other calcium sources.Wherein, control group exists
30kg microlith powder (Ca content 36.5%)/t mixed feed is added in basal diet, and (total calcium level is 3.9%, and digestion phosphorus is
0.25%) it, tests 1 group and adds hydroxy carbonate calcium (Ca content 41.7%) 12kg+10kg microlith powder/t cooperation in basal diet
Feed tests 2 groups and adds hydroxy carbonate calcium 15kg+10kg microlith powder/t mixed feed in basal diet, tests 3 groups on basis
Hydroxy carbonate calcium 23kg/t mixed feed is added in daily ration.During test, laying hen is placed in the raising of ladder cage, and whole process is freely eaten
And free water, and according to routine immunization program immunity.Test period totally 28 days.
Testing index, egg laying performance: statistics feed intake, egg number, egg size, broken egg number calculate laying rate, feedstuff-egg ratio, break
Egg rate.Eggshell quality: detection shell thickness, eggshell strength.As a result as shown in table 2 below.
Table 2: influence of the hydroxy carbonate calcium to Layer Production Performance and eggshell quality
As can be seen from Table 2: 3 groups of 1 group of test, 2 groups of test, test laying rate of laying hen respectively higher than control group 1.50%,
2.37%, 1.99%；Feedstuff-egg ratio reduces by 3.5%, 5.39%, 4.14% than control group respectively；Test 2 groups of shell thicknesses and eggshell
Intensity highest, respectively higher than control group 3.60%, 4.03%.The above results explanation, is added low in Egg Production of Laying Hens later period feed
Dosage hydroxy carbonate calcium partly or entirely substitutes microlith powder, can effectively reduce calcium source additive amount, while reducing discharge, has and changes
Kind Layer Production Performance and quality of egg, the effect for reducing rate of broken eggs.
Application Example 3:
The hydroxy carbonate calcium that embodiment 2 is prepared is applied in growing-finishing pig feeding experiment.
Test uses the random packet design of single-factor, selects the Ternary Pig that 90 genetic backgrounds are identical, are in a good state of health
Growing-finishing pig 144 is randomly divided into 3 processing, and 6 repetitions of each processing, each repetition 8, average weight is consistent.Wherein, right
12.0kg mountain flour (Ca content 35.5%)/t mixed feed (total calcium content 0.62%, available phosphorus is added in basal diet according to group
Content 0.22%), it tests 1 group and adds hydroxy carbonate calcium (Ca content 41.7%) 10kg/t mixed feed, examination in basal diet
It tests 2 groups and adds hydroxy carbonate calcium 8kg/t mixed feed in basal diet.Each group basal diet consistent (other calcium sources and phosphorus source
It is calcium monohydrogen phosphate, additive amount is 4kg/t mixed feed).It is placed in the raising of cement flooring column home, be freely eaten and is drunk water.Test
Period totally 35 days.Test data sheet and sample acquisition: (1) feeding amount, the pig health status recorded daily；(2) before on-test
With at the end of, test pig empty stomach 12h (free water) weighs afterwards, record weight and calculate the feed intake of test pig, daily gain with
And feed-weight ratio；(3) blood serum sample acquires: test 9:00 in morning last day weighs on an empty stomach, randomly selects counterpoise in every processing group
The test pig of ± 2kg each 3, vena cava anterior is taken a blood sample at 4 DEG C, and 1800rpm centrifugation 10-15min prepares serum, -20 DEG C of conditions
Under save backup.
The measurement of test index: (1) calculating of growth performance index.Average daily gain=feeding gross weight/(raising number of days
× head number)；Average daily gain=total augment weight/(raising number of days × head number)；Feed-weight ratio=feeding gross weight/total augment weight × 100%.
(2) measurement of physiochemical indice: Swine serum calcium content pours a libation phthalein complexon colorimetric method for determining using adjacent first, and phosphorus measures serum with ultraviolet method
Content, Serum alkaline phosphatase activity are measured using performance rate method.Determining instrument is to use Roche automatic clinical chemistry analyzer.Detection
As a result as shown in table 3 below.
Table 3: Different Calcium Sources and calcium level are added in feed to the shadow of growth of growing-finishing pigs performance and blood parameters
It rings
From upper table 3 as it can be seen that the test group of addition various dose hydroxy carbonate calcium, daily gain and feed conversion rate be superior to
Mountain flour is the control group of main calcium source, and 1 group of growing and fattening daily gain in pigs of test and feed conversion rate are optimal.Refer to from serum biochemistry
Mark sees, each group calcium level and the horizontal no significant difference of phosphorus.The above results explanation, hydroxy carbonate calcium can be used as a kind of good
Calcium source is applied in fattening pannage, and after the mountain flour of substitution high dose, while maintaining normal calcium, phosphorus Absorption And Metabolism,
It has some improvement effect to growth performance.When equal calcium levels addition, growth-promoting effect is more excellent.
Application Example 4:
The hydroxy carbonate calcium prepared in embodiment 2 is added in china holstein cows material.
Parity (3-4), the output of milk (20.35 ± 0.96kg/d), China similar in lactation period (95 ± 3.7d) are chosen in test
Holstein cow (613 ± 19kg) 4.This test daily ration is prepared (total calcareous amount according to Chinese raising dairy cattle standard
0.78%, total phosphorus quality 0.41%), 4 kinds of test daily rations are designed altogether, and daily ration is in addition to total calcium content is horizontal, other trophic level phases
Together, meet the nutritional need of china holstein cows, the supply amount of Dietary Calcium presses Chinese raising dairy cattle standard recommendation needs respectively
The 100% of amount, i.e., add in fully-mixed daily feed per ton 0.40% (quality) hydroxy carbonate calcium (Ca content 41.7%) A group,
Add 0.30% (quality) hydroxy carbonate calcium B group, 0.2% (quality) hydroxy carbonate calcium C group of addition, 0.10% (quality) hydroxyl of addition
Base calcium carbonate D group.Test daily ration belongs to fully mixed diet (TMR).Using 4 × 4 Latin―Square designs, test arrangement is shown in Table 4.Each issue
17d is tested, wherein preliminary trial period 14d, it is positive to try phase 3d.Subfield ties drylot feeding in entire experimental period, and daily sports ground move freely 5-
6h, whole free water.
The measurement of test index: (1) daily dry matter intake and the output of milk performance test: are recorded；(2) excrement calcium
Content, urinary calcium assay: urine sample is in the daily 06:30 acquisition of just examination phase, and excrement sample is in the daily 08:30 acquisition of just examination phase.(3)
Blood specimen collection: in the positive examination phase daily 08:00 (before feeding) from the jugular vein blood collection 20mL of test milk cow, be placed in plus heparin sodium from
In heart pipe, it is centrifuged 15min under 3000rpm on constant temperature centrifuge immediately, blood plasma is taken out in separation.Blood plasma is divided into 2 parts, is put into -80
DEG C ultra low temperature freezer in it is spare.1 part refers to for measuring the blood biochemicals such as plasma calcium phosphorus concentration and alkaline phosphatase (ALP) activity
Mark, 1 part for measuring the hormones such as serum parathyroid plain (PHT), calcitonin (CT), osteocalcin (BGP), aldosterone (ALD)
Concentration.Testing result is shown in Table 5.
Table 4: 4 × 4 Latin―Square designs of test
| Project | Ox 1 | Ox 2 | Ox 3 | Ox 4 |
| 1st phase | Diet A | Diet B | Diet C | Diet D |
| 2nd phase | Diet B | Diet C | Diet D | Diet A |
| 3rd phase | Diet C | Diet D | Diet A | Diet B |
| 4th phase | Diet D | Diet A | Diet B | Diet C |
Table 5: influence of the diet hydroxy carbonate calcium level to dairy cattle and calcium metabolism
From upper table 5 as it can be seen that 0.30% hydroxy carbonate calcium level diet dairy cattle of addition is optimal.Lower than raising mark
In the case where quasi- calcium level, with the raising of hydroxy carbonate calcium additive amount, milk performance is in raising trend.Excrement, urine are calcium
Discharge approach, with the raising of diet calcium level, the digestibility of calcium is reduced.Normocalcemic physiological range (7.24-7.54), this
Test is in the normal range.Parathormone is a kind of important hormone for adjusting bone metabolism, and effect is when blood calcium reduces
Promote the mobilization of bone calcium, to maintain the normal level of blood calcium.Osteocalcin can be used to measure the turnaround speed of bone calcium.This test is aobvious
Show that parathormone is increased as the additive amount of calcium reduces, osteocalcin is increased as hydroxy carbonate calcium additive amount increases.With
Normal calcium metabolism rule is similar.Illustrate, hydroxy carbonate calcium can maintain the eubolism of calcium, can be used as a kind of effective calcium source
It is applied in lactating cow diet, wherein 0.30% hydroxy carbonate calcium pitch-based sphere, which has, preferably improves dairy cattle
Effect.
Claims (10)
1. a kind of preparation method for the hydroxy carbonate calcium that can be used for animal feed, which comprises the following steps: by calcium source
Be added to the water, cool down, under stiring be added bicarbonate reacted, after reaction, filtration drying to get arrive hydroxyl carbon
Sour calcium.
2. preparation method according to claim 1, which is characterized in that the bicarbonate is sodium bicarbonate and/or carbonic acid
Hydrogen potassium；The calcium source includes calcium salt and alkaline calcic object.
3. preparation method according to claim 2, which is characterized in that calcium in the calcium source rubs with the bicarbonate
You are (1.1~1.6) than control: 1, the calcium salt is calcium chloride, and the alkalinity calcic object is calcium hydroxide and/or calcium oxide.
4. preparation method according to claim 1, which is characterized in that the bicarbonate is calcium bicarbonate；The calcium source
For calcium hydroxide and/or calcium oxide.
5. the preparation method according to claim 4, which is characterized in that calcium in the calcium source rubs with the calcium bicarbonate
You are (1.3~2.2) than control: 1.
6. preparation method according to any one of claims 1 to 5, which is characterized in that the control of the temperature of the reaction-
5 DEG C~1 DEG C, the time of the reaction controls in 1h~4h.
7. preparation method according to any one of claims 1 to 5, which is characterized in that the quality of the water is the calcium
2~3.4 times of source and the bicarbonate quality sum.
8. a kind of application of hydroxy carbonate calcium in field of animal feed, which comprises the following steps:
1) use preparation method according to any one of claims 1 to 7 such as that molecular formula is prepared as Ca3(CO3)2(OH)2Or
Ca6(CO3)5(OH)2Hydroxy carbonate calcium；
2) the hydroxy carbonate calcium is further pelletized, obtains hydroxy carbonate calcium particle；
3) it is applied using the hydroxy carbonate calcium particle as feed addictive.
9. application according to claim 8, which is characterized in that the granulation specifically includes: the hydroxy carbonate calcium is passed through
Mesh number is obtained as hydroxy carbonate calcium particle described in 8~100 purposes after crossing crushing, granulation, sieving, and the mode of the granulation is disk
Granulation, spraying granulation or fluidized bed granulation.
10. application according to claim 9, which is characterized in that when the hydroxy carbonate calcium is used for pannage, addition
Amount is that 1-12kg hydroxy carbonate calcium is added in mixed feed per ton；When the hydroxy carbonate calcium is used for poultry feed,
Additive amount is that 1-23kg hydroxy carbonate calcium is added in mixed feed per ton；The hydroxy carbonate calcium is used for ruminant animals feed
When, additive amount is that 0.1-4kg hydroxy carbonate calcium is added in fully-mixed daily feed per ton.
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| CN109198191A (en) * | 2018-10-30 | 2019-01-15 | 长沙兴嘉生物工程股份有限公司 | A kind of preparation method and applications of hydroxy chloride calcium |
| CN112408450A (en) * | 2020-11-27 | 2021-02-26 | 广西华纳新材料科技有限公司 | Preparation method of cubic-like nano calcium carbonate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109198191A (en) * | 2018-10-30 | 2019-01-15 | 长沙兴嘉生物工程股份有限公司 | A kind of preparation method and applications of hydroxy chloride calcium |
| CN112408450A (en) * | 2020-11-27 | 2021-02-26 | 广西华纳新材料科技有限公司 | Preparation method of cubic-like nano calcium carbonate |
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