CN108163826B - Feed-grade calcium phosphate salt and preparation method thereof - Google Patents
Feed-grade calcium phosphate salt and preparation method thereof Download PDFInfo
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- CN108163826B CN108163826B CN201810030566.7A CN201810030566A CN108163826B CN 108163826 B CN108163826 B CN 108163826B CN 201810030566 A CN201810030566 A CN 201810030566A CN 108163826 B CN108163826 B CN 108163826B
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- calcium phosphate
- phosphate salt
- grade calcium
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011574 phosphorus Substances 0.000 claims abstract description 43
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 43
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 38
- 239000007787 solid Substances 0.000 claims abstract description 30
- 239000000047 product Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 24
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010457 zeolite Substances 0.000 claims abstract description 23
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004140 cleaning Methods 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 abstract description 15
- 239000012535 impurity Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000003674 animal food additive Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 238000006115 defluorination reaction Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000012263 liquid product Substances 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 235000019700 dicalcium phosphate Nutrition 0.000 description 4
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 3
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fodder In General (AREA)
Abstract
Feed-grade calcium phosphate salt provided by the invention and preparation method thereof, is related to field of feed additive technology.A kind of preparation method of feed-grade calcium phosphate salt, including will be filtered after phosphorus ore and phosphoric acid, defluorinating agent, zeolite molecular sieve hybrid reaction, obtain synthos solid powder after obtained filtrate is dried.Synthos solid powder is mixed with organic solvent, is washed, synthos product and cleaning solution are obtained after separation of solid and liquid；Synthos product and cleaning solution are distilled respectively, obtain feed-grade calcium phosphate salt and purifying phosphoric acid.This method is easy to operate, simplifies defluorinate step, reduces production requirement, and controllability is strong, is suitble to large-scale production.A kind of feed-grade calcium phosphate salt is made by the preparation method of above-mentioned feed-grade calcium phosphate salt.Fluorine and impurity content are few, and quality is high.
Description
Technical field
The present invention relates to field of feed additive technology, and more particularly to feed-grade calcium phosphate salt and preparation method thereof.
Background technology
Calcium hydrogen phosphate fodder is the important composition of feed industry, and a certain proportion of feed phosphoric acid hydrogen is coordinated in feed
Calcium, phosphorus therein are the important elements of metabolism and maintenance physiological function in animal body, are known as the title of " element of life ", calcium
It is the important component for constituting bone, tooth, it can promote blood circulation, and maintain nerve under the activation of certain enzymes in vivo
Conductive performance plays important work adjusting the retractility of muscle, the normal osmotic pressure of capillary, internal acid-base balance etc.
With.In the world, calcium hydrogen phosphate fodder is widely promoted and applied, and annual output and consumption figure are at 5,000,000 tons or more.
The traditional handicraft of China's calcium hydrophosphate fodder is to use wet phosphoric acid i.e. H2SO4Or HCI decomposing phosphate rock stones, warp
Slag-liquid separation obtains the phosphoric acid extraction of low concentration, by defluorination process, goes out calcium monohydrogen phosphate with milk of lime neutralization precipitation, through removal of impurities
Drying, pulverization process.But in recent years, H2SO4Spurt in prices, cause production cost significantly to rise, many feeds made to give birth to
Production producer is difficult to bear.In the abundant area of phosphate resources then calcium monohydrogen phosphate, matter are directly generated with industrial phosphoric acid and agstone
Amount is preferable, but total production cost also remains high, and is almost difficult to maintain simple reproduction.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of feed-grade calcium phosphate salt, and this method is easy to operate, simplify
Defluorinate step reduces production requirement, and controllability is strong, is suitble to large-scale production.
Another object of the present invention is to provide a kind of feed-grade calcium phosphate salt, and fluorine and impurity content are few, and quality is high.
The present invention solves its technical problem using following technical scheme to realize：
A kind of preparation method of feed-grade calcium phosphate salt, including：
It will be filtered after phosphorus ore and phosphoric acid, defluorinating agent, zeolite molecular sieve hybrid reaction, phosphorus obtained after obtained filtrate is dried
Acid calcium salt solid powder.
Synthos solid powder is mixed with organic solvent, is washed, synthos product is obtained after separation of solid and liquid and is washed
Wash liquid；Synthos product and cleaning solution are distilled respectively, obtain feed-grade calcium phosphate salt and purifying phosphoric acid.
Further, in the present invention preferably embodiment, including：Phosphorus ore is reacted with phosphoric acid under conditions of 90~99 DEG C
After being 4~6 to pH value, defluorinating agent the reaction was continued 1~2h is added, adds zeolite molecular sieve and reacts 3~4h.
Further, in the present invention preferably embodiment, the reaction temperature being added after zeolite molecular sieve is 70~80 DEG C.
Further, in the present invention preferably embodiment, phosphorus ore is crushed to 100~120 before mixing, by phosphorus ore
Mesh.
Further, in the present invention preferably embodiment, the amount ratio of the substance of phosphoric acid and phosphorus ore is 1~2:1.
Further, in the present invention preferably embodiment, filtrate is dried under conditions of 80~100 DEG C.
Further, in the present invention preferably embodiment, the mass concentration of phosphoric acid is 50~100%.
Further, in the present invention preferably embodiment, the volume ratio of synthos solid powder and organic solvent is
1:2~3.
Further, in the present invention preferably embodiment, organic solvent includes at least one in methanol, ethyl alcohol, acetone
Kind.
A kind of feed-grade calcium phosphate salt is made by the preparation method of above-mentioned feed-grade calcium phosphate salt.
The advantageous effect of the feed-grade calcium phosphate salt of the embodiment of the present invention and preparation method thereof is：
Defluorinating agent and zeolite molecular sieve is added during phosphorus ore and phosphatase reaction in the present invention, utilizes defluorinating agent and zeolite
Molecular sieve synergistic effect adsorbing contaminant and fluorine have preferable defluorination effect, easy to operate, simplify defluorinate step, reduce life
Production demand.Defluorinating agent and zeolite molecular sieve have the function of catalysis reaction simultaneously, accelerate reaction rate, shorten the production cycle.It is logical
It is few to cross feed-grade calcium phosphate salt impurity made from this method, quality is high.
Specific implementation mode
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Feed-grade calcium phosphate salt of the embodiment of the present invention and preparation method thereof is specifically described below.
A kind of preparation method of feed-grade calcium phosphate salt provided in an embodiment of the present invention, including：
Choose phosphorus ore, in the present invention it is possible to which low-quality phosphorus ore raw ore is raw material in selection, and phosphorus ore is removed by flotation
In the impurity such as magnesium, iron, aluminium, substantially increase the quality of feed-grade calcium phosphate salt.Before the reaction, phosphorus ore is crushed to 100~
120 mesh keep phosphorus ore abundant with phosphatase reaction, accelerate reaction rate.And be conducive to subsequent removal of impurities after crushing phosphorus ore.
After mixing by phosphorus ore and phosphoric acid, reaction to pH value is 4~6 under conditions of 90~99 DEG C.Under this condition,
Most phosphoric acid participates in reaction in reaction system.Preferably, the amount ratio of the substance of phosphoric acid and phosphorus ore is 1~2:1, ensure reaction
Object fully reacts, while helping to improve reaction rate.
Contain fluoride in phosphorus ore, in the reaction process with phosphoric acid, more fluorine element is contained in system, in order to be promoted
Defluorinating agent is added when the pH value of reaction system is 4~6 in the quality of synthos, continues under this condition after mixing anti-
Answer 1~2h.Defluorinating agent has many capillary channels, and surface area is big, big to the selectivity of fluorine ion, and the present invention is inhaled using defluorinating agent
Fluorine in attached system.Defluorinating agent is added under this condition, is added after being reacted completely with phosphoric acid compared to phosphorus ore, defluorination effect is more preferable,
Defluorinating agent also acts the effect that reaction rate is accelerated in catalysis reaction simultaneously, further increases defluorination effect, shortens the reaction time.
After defluorinating agent reaction is added, adds zeolite molecular sieve and react 3~4h under conditions of 70~80 DEG C.Zeolite molecules
Large specific surface area is sieved, surface polarity is high, and stability is good.Zeolite molecular sieve has synergistic function with defluorinating agent, it will be apparent that carries
The type of high adsorbing contaminant and adsorbance to fluorine and other impurities, while zeolite molecular sieve has the function of catalysis reaction,
Accelerate reaction rate, ensures reaction cmpletely.
It is filtered after reaction, obtained filtrate is dry under conditions of 70~80 DEG C, obtain synthos solid powder.By
In impurity and fluorine in front the step of removed, therefore dry temperature is relatively low, does not need high temperature drying, reduces to life
Production and the requirement of equipment, reduce production difficulty.
Synthos solid powder is mixed with organic solvent, is washed, synthos product is obtained after separation of solid and liquid and is washed
Wash liquid.In order to avoid the volatilization of organic solvent, cause to wash insufficient, the process of washing carries out in confined conditions.When washing
Between be 15~25 minutes, avoid wash time is too short from causing local supersaturation, generating precipitation influences the effect of filtering.To phosphorus
Acid calcium salt product carries out distillation recovery organic solvent, obtains feed-grade calcium phosphate salt product, and distillation cleaning solution recycles organic solvent,
It is purified phosphoric acid.This method makes full use of phosphorus and calcium in phosphorus ore, produces the feed-grade calcium phosphate product salt of highly-water-soluble,
The higher purifying phosphoric acid of purity can also be obtained simultaneously.
Further, in the present invention preferably embodiment, the volume ratio of synthos solid powder and organic solvent is
1:2~3.Organic solvent includes at least one of methanol, ethyl alcohol, acetone.
The present invention provides a kind of feed-grade calcium phosphate salt, by the preparation method preparation of above-mentioned feed-grade calcium phosphate salt
At.The impurity content of the feed-grade calcium phosphate salt is few, and fluorine content is few, and calcium and phosphorus content are more, and quality is high.
With reference to embodiments to this, the feature and performance of invention are described in further detail.
Embodiment 1
A kind of feed-grade calcium phosphate salt is present embodiments provided, is mainly made by following steps：
Phosphorus ore is chosen, 100 mesh are crushed to.
The amount ratio that phosphoric acid and phosphorus ore are pressed to substance is 1:1 mixing, reaction to pH value is 4 under conditions of 90 DEG C.It is added de-
Fluorine agent, the reaction was continued under this condition after mixing 1h.It adds zeolite molecular sieve and reacts 3h under conditions of 70 DEG C.Reaction
After filter, obtained filtrate is dry under conditions of 70 DEG C, obtain synthos solid powder.
It is 1 by volume by synthos solid powder and methanol:2 mixing are washed, and synthos are obtained after separation of solid and liquid
Product and cleaning solution.Distillation recovery methanol is carried out to synthos product, obtains feed-grade calcium phosphate salt product, distills cleaning solution
Methanol is recycled, phosphoric acid is purified.
Embodiment 2
A kind of feed-grade calcium phosphate salt is present embodiments provided, is mainly made by following steps：
Phosphorus ore is chosen, 90 mesh are crushed to.
The amount ratio that phosphoric acid and phosphorus ore are pressed to substance is 2:1 mixing, reaction to pH value is 6 under conditions of 99 DEG C.It is added de-
Fluorine agent, the reaction was continued under this condition after mixing 2h.It adds zeolite molecular sieve and reacts 4h under conditions of 80 DEG C.Reaction
After filter, obtained filtrate is dry under conditions of 80 DEG C, obtain synthos solid powder.
It is 1 by volume by synthos solid powder and acetone:3 mixing are washed, and synthos are obtained after separation of solid and liquid
Product and cleaning solution.Distillation recovery acetone is carried out to synthos product, obtains feed-grade calcium phosphate salt product, distills cleaning solution
Acetone is recycled, phosphoric acid is purified.
Embodiment 3
A kind of feed-grade calcium phosphate salt is present embodiments provided, is mainly made by following steps：
Phosphorus ore is chosen, 110 mesh are crushed to.
The amount ratio that phosphoric acid and phosphorus ore are pressed to substance is 1:1 mixing, reaction to pH value is 5 under conditions of 95 DEG C.It is added de-
Fluorine agent, the reaction was continued under this condition after mixing 2h.It adds zeolite molecular sieve and reacts 4h under conditions of 80 DEG C.Reaction
After filter, obtained filtrate is dry under conditions of 70 DEG C, obtain synthos solid powder.
It is 1 by volume by synthos solid powder and ethyl alcohol:2 mixing are washed, and synthos are obtained after separation of solid and liquid
Product and cleaning solution.Distillation recovery ethyl alcohol is carried out to synthos product, obtains feed-grade calcium phosphate salt product, distills cleaning solution
Ethyl alcohol is recycled, phosphoric acid is purified.
Embodiment 4
A kind of feed-grade calcium phosphate salt is present embodiments provided, is mainly made by following steps：
Phosphorus ore is chosen, 120 mesh are crushed to.
The amount ratio that phosphoric acid and phosphorus ore are pressed to substance is 2:1 mixing, reaction to pH value is 6 under conditions of 95 DEG C.It is added de-
Fluorine agent, the reaction was continued under this condition after mixing 2h.It adds zeolite molecular sieve and reacts 3h under conditions of 70 DEG C.Reaction
After filter, obtained filtrate is dry under conditions of 60 DEG C, obtain synthos solid powder.
It is 1 by volume by synthos solid powder and acetone:2 mixing are washed, and synthos are obtained after separation of solid and liquid
Product and cleaning solution.Distillation recovery acetone is carried out to synthos product, obtains feed-grade calcium phosphate salt product, distills cleaning solution
Acetone is recycled, phosphoric acid is purified.
Comparative example 1
This comparative example provides a kind of feed-grade calcium phosphate salt, is mainly made by following steps：
The amount ratio that phosphoric acid and phosphorus ore are pressed to substance is 1:1 mixing, reacts 5h under conditions of 90 DEG C.Defluorinating agent is added, mixes
The reaction was continued under this condition 1h after closing uniformly.It is filtered after reaction, obtained filtrate is dry under conditions of 70 DEG C, obtain phosphorus
Acid calcium salt solid powder.
It is 1 by volume by synthos solid powder and methanol:2 mixing are washed, and synthos are obtained after separation of solid and liquid
Product and cleaning solution.Distillation recovery methanol is carried out to synthos product, obtains feed-grade calcium phosphate salt product, distills cleaning solution
Methanol is recycled, phosphoric acid is purified.
Comparative example 2
This comparative example provides a kind of feed-grade calcium phosphate salt, is mainly made by following steps：
The amount ratio that phosphoric acid and phosphorus ore are pressed to substance is 2:1 mixing, reacts 6h under conditions of 90 DEG C.Add zeolite molecules
Sieve reacts 4h under conditions of 70 DEG C.It is filtered after reaction, obtained filtrate is dry under conditions of 70 DEG C, obtain synthos
Solid powder.
It is 1 by volume by synthos solid powder and organic solvent:2 mixing are washed, and phosphoric acid is obtained after separation of solid and liquid
Calcium salt product and cleaning solution.Distillation recovery organic solvent is carried out to synthos product, obtains feed-grade calcium phosphate salt product, is steamed
Cleaning solution recycling organic solvent is evaporated, phosphoric acid is purified.
Comparative example 3
This comparative example provides a kind of feed-grade calcium phosphate salt, is mainly made by following steps：
The amount ratio that phosphoric acid and phosphorus ore are pressed to substance is 1:1 mixing, reaction to pH value is 4 under conditions of 90~99 DEG C.Add
Enter defluorinating agent, the reaction was continued under this condition after mixing 1h.It adds zeolite molecular sieve and reacts 3h under conditions of 70 DEG C.
It is filtered after reaction, obtained filtrate is dry under conditions of 75 DEG C, obtain synthos solid powder.
Comparative example 4
This comparative example provides a kind of feed-grade calcium phosphate salt, is mainly made by following steps：
Phosphorus ore is chosen, 100 mesh are crushed to.The amount ratio that phosphoric acid and phosphorus ore are pressed to substance is 1~2:1 mixing, at 90 DEG C
Under conditions of react 6h.Obtained product is sent into spray tower and carries out atomization drying and defluorinate, is 600 DEG C into tower hot blast temperature,
It is 160 DEG C to go out tower hot blast temperature, and the dry materials after defluorinate are obtained synthos solid.
Examples 1 to 4, the product quality indicator such as following table of comparative example 1~4：
1 quality index of table
By GB/T22549-2008 it is found that the feed-grade calcium phosphate salt that Examples 1 to 4 provides has reached standard.And it is real
Apply example 1~4 offer feed-grade calcium phosphate salt in fluorine content it is relatively low, illustrate that the preparation method defluorination effect is preferable, impurity content
It is few.The effect that defluorinating agent is used alone compared with effect when zeolite molecular sieve uses simultaneously is more preferable, illustrates that the two has collaboration
The effect of synergy, defluorination effect are stronger.
In conclusion the present invention is in phosphorus ore and defluorinating agent and zeolite molecular sieve are added during phosphatase reaction, using de-
Fluorine agent and zeolite molecular sieve synergistic effect adsorbing contaminant and fluorine, have preferable defluorination effect, easy to operate, simplify defluorinate step
Suddenly, production requirement is reduced.Defluorinating agent and zeolite molecular sieve have the function of catalysis reaction simultaneously, accelerate reaction rate, shorten life
Produce the period.Few by feed-grade calcium phosphate salt impurity made from this method, quality is high.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of feed-grade calcium phosphate salt, which is characterized in that including：
It will be filtered after phosphorus ore and phosphoric acid, defluorinating agent, zeolite molecular sieve hybrid reaction, calcium phosphate obtained after obtained filtrate is dried
Salt solid powder；
The phosphorus ore is reacted with the phosphoric acid under conditions of 90 ~ 99 DEG C be 4 ~ 6 to pH value after, be added the defluorinating agent continue it is anti-
1 ~ 2h is answered, the zeolite molecular sieve is added and reacts 3 ~ 4h；It is 70 ~ 80 DEG C that the reaction temperature after the zeolite molecular sieve, which is added,；
The amount ratio of the phosphoric acid and the substance of the phosphorus ore is 1 ~ 2:1；
The synthos solid powder is mixed with organic solvent, is washed, synthos product is obtained after separation of solid and liquid and is washed
Wash liquid；The synthos product and the cleaning solution are distilled respectively, obtain feed-grade calcium phosphate salt and purifying phosphoric acid.
2. the preparation method of feed-grade calcium phosphate salt according to claim 1, which is characterized in that the phosphorus ore is in mixing
Before, the phosphorus ore is crushed to 100 ~ 120 mesh.
3. the preparation method of feed-grade calcium phosphate salt according to claim 1, which is characterized in that the filtrate is 80 ~ 100
It is dried under conditions of DEG C.
4. the preparation method of feed-grade calcium phosphate salt according to claim 1, which is characterized in that the quality of the phosphoric acid is dense
Degree is 50 ~ 100%.
5. the preparation method of feed-grade calcium phosphate salt according to claim 1, which is characterized in that the synthos solid
The volume ratio of powder and the organic solvent is 1:2~3.
6. the preparation method of feed-grade calcium phosphate salt according to claim 5, which is characterized in that the organic solvent includes
At least one of methanol, ethyl alcohol, acetone.
7. a kind of feed-grade calcium phosphate salt, which is characterized in that by such as claim 1 ~ 6 any one of them feed-grade calcium phosphate salt
Preparation method be made.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810030566.7A CN108163826B (en) | 2018-01-12 | 2018-01-12 | Feed-grade calcium phosphate salt and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810030566.7A CN108163826B (en) | 2018-01-12 | 2018-01-12 | Feed-grade calcium phosphate salt and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN108163826A CN108163826A (en) | 2018-06-15 |
| CN108163826B true CN108163826B (en) | 2018-11-13 |
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| CN1178769A (en) * | 1997-11-11 | 1998-04-15 | 浙江大学 | Process for producing fodder grade calcium biphosphate by wet process of ground phosphate rock |
| CN102167301B (en) * | 2011-03-17 | 2013-02-06 | 贵州川恒化工有限责任公司 | Production method for co-production of high-water-solubility feed grade calcium phosphate and purified phosphoric acid |
| CN103771380B (en) * | 2013-11-08 | 2016-06-29 | 昆明川金诺化工股份有限公司 | A kind of method utilizing Wet-process Phosphoric Acid Production industrial phosphoric acid salt |
| CN106853962A (en) * | 2016-12-18 | 2017-06-16 | 贵州越都化工有限公司 | A kind of feed-level calcium biphosphate and preparation method thereof |
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Denomination of invention: Feed-grade calcium orthophosphate and preparation method thereof Effective date of registration: 20181218 Granted publication date: 20181113 Pledgee: Nanjing Bank Co.,Ltd. Nanjing Financial City Branch Pledgor: NANJING POLIFAR BIOTECHNOLOGY Co.,Ltd. Registration number: 2018320000366 |
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Denomination of invention: Feed grade calcium phosphate and its preparation method Effective date of registration: 20220208 Granted publication date: 20181113 Pledgee: Nanjing Bank Co.,Ltd. Nanjing Financial City Branch Pledgor: NANJING POLIFAR BIOTECHNOLOGY Co.,Ltd. Registration number: Y2022320000044 |
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Denomination of invention: Feed grade calcium phosphate and its preparation method Effective date of registration: 20230110 Granted publication date: 20181113 Pledgee: Nanjing Bank Co.,Ltd. Nanjing Financial City Branch Pledgor: NANJING POLIFAR BIOTECHNOLOGY Co.,Ltd. Registration number: Y2022980028924 |
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Denomination of invention: Feed grade calcium phosphate and its preparation method Granted publication date: 20181113 Pledgee: Nanjing Bank Co.,Ltd. Nanjing Financial City Branch Pledgor: NANJING POLIFAR BIOTECHNOLOGY Co.,Ltd. Registration number: Y2024980001370 |