CN103864043B - Defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate - Google Patents
Defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate Download PDFInfo
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Abstract
The present invention relates to defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate, belong to chemical products preparation field.The technical problem to be solved is to provide a kind of defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate.Defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt of the present invention and the method for potassium dihydrogen phosphate, comprise the steps: that taking nertralizer I carries out reaction generation phosphate slip with phosphoric acid defluorination, slip obtains solid phase I and filtrate I after filtering, wherein, described nertralizer I is at least one in calcium oxide, calcium carbonate and calcium hydroxide；Filtrate I is neutralized reaction with nertralizer II again, solid-liquid separation after reaction, obtains solid phase II and filtrate II, is sufficiently mixed and is feed-grade calcium phosphate salt after solid phase I and solid phase II being dried, and filtrate II obtains highly purified potassium dihydrogen phosphate after crystallization.
Description
Technical field
The present invention relates to defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate, belong to chemical products and prepare
Field.
Background technology
Calcium hydrogen phosphate is divided into four kinds of ranks by purposes: toothpaste grade calcium hydrophosphate, is mainly used in toothpaste and produces as abrasivus, food
Calcium hydrophosphate, does raising agent for food industry, and fertilizer grade calcium hydrogen phosphate, as phosphate fertilizer；Calcium hydrophosphate fodder, is one
Planting the large phosphorus chemical product having bright prospects, it is a kind of containing phosphorus, the poultry of two kinds of elements of calcium, domestic animal feed additive,
Due to phosphorus calcium therein than with the phosphorus calcium in animal skeleton than closest to, can all be dissolved in again in animal gastric acid, so holding simultaneously
Easily entrance animal body is interior and participates in metabolism, and hormone, enzyme and the vitamin required for composition body keeps the phosphorus in skeleton
Calcium ratio, thus prevent animal because of the various diseases caused by phosphorus deficiency calcium, simultaneously facilitate animal body fast-growth.
Potassium dihydrogen phosphate is as the colourless or rhomboidal crystal of white band gloss, and it is the phosphorus potash fertilizer of a kind of high concentration, and it has nutrition
Composition is high, soluble in water, the feature of stable chemical nature, and potassium dihydrogen phosphate is in modern medicine, chemical industry chemistry, food work simultaneously
Industry also has a wide range of applications, and the production method of potassium dihydrogen phosphate is a lot, is substantially summarised as neutralisation, extraction, ion exchange
Method, double decomposition, direct method, crystallization process and electrolysis etc., in China, its production technology many employings neutralisation, secondly also have
Organic extraction, double decomposition and ion exchange.
In traditional handicraft, phosphoric acid by wet process and lime cream produce calcium hydrogen phosphate and all use two sections of neutralisations, one section of phosphoric acid hydrogen neutralized out
Calcium, owing to processing only as thick fertilizer is cheap containing substantial amounts of fluorine, this considerably increases production cost.And producing potassium dihydrogen phosphate
Process in, it is expensive to there is organic solvent in organic extraction, and the toxic bad process of organic solvent, phosphorous recovery are low etc.
Problem.It is low to there is resolution ratio in double decomposition, and unstable product quality is serious to equipment corrosion, and what neutralisation utilized is full-boiled process
Phosphoric acid produces, and this adds production cost virtually.
Summary of the invention
The technical problem to be solved is to provide a kind of defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and potassium dihydrogen phosphate
Method.
Defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt of the present invention and the method for potassium dihydrogen phosphate, comprise the steps:
(a) one section of neutralization: take nertralizer I and be neutralized reaction with phosphoric acid defluorination, react complete, solid-liquid separation, obtain solid phase
I and filtrate I, wherein, calcium constituent in nertralizer I in molar ratio: P in phosphoric acid defluorination2O5=0.4～2:1；
Wherein, described nertralizer I is at least one in calcium oxide, calcium carbonate and calcium hydroxide；
B () two-stage nitration neutralizes: take nertralizer II and be neutralized reaction with filtrate I, until reaction system pH=4～5, react complete,
Solid-liquid separation, obtains solid phase II and filtrate II, and solid phase II i.e. obtains feed-grade calcium phosphate salt with mixing after solid phase I drying, filtrate II
After crystallized, solid-liquid separation, obtain solid phase III, solid phase III is potassium dihydrogen phosphate after drying；
Wherein, described nertralizer II is at least one in potassium hydroxide, potassium carbonate and potassium bicarbonate.
In order to react fully, be conducive to stirring, do not produce parcel phenomenon, nertralizer I described in preferred steps (a) can be by stone
Ash breast substitutes；The more preferably preparation method of lime cream is as follows: water in molar ratio: quick lime=1.6～12:1 water intaking and quick lime,
It is uniformly mixed so as to obtain lime cream.
Further, it is preferable to the most described water: quick lime=6.5～10:1.
In order to ensure reaction mass, cost-effective, step (a) neutralizes reaction, preferable reaction temperature T1=40～100 DEG C, excellent
Select response time t1=0.5～2h.The most described reaction temperature T1=70～80 DEG C；The most described response time t1=1h。
Further, it is preferable to phosphoric acid defluorination P described in step (a)2O5Concentration is 20～55wt%, preferably phosphoric acid defluorination P2O5Dense
Degree is 42～46wt%.
In order to ensure that the Oil repellent in product does not exceeds standard, P in mass ratio in phosphoric acid defluorination in preferred steps (a)2O5The ratio of/F is big
In 250；Preferably P in mass ratio in phosphoric acid defluorination2O5/ F=350～500.
In order to not introduce new impurity, it is ensured that product quality, in preferred steps (a), the purity of nertralizer I is more than 95wt%.
Further, it is preferable to calcium constituent in nertralizer I in molar ratio in step (a): P in phosphoric acid defluorination2O5=0.8～1.2:1.
In order to make reaction carry out the most thorough, pH described in preferred steps (b) is 4.4～4.7.
In order to ensure reaction mass, cost-effective, neutralize reaction, preferable reaction temperature T described in step (b)2≤ 100 DEG C,
Preferably response time t2=0.5～2h, the most described reaction temperature T2=80～95 DEG C；The most described response time t2=1～
1.5h。
Improve the purity of potassium dihydrogen phosphate in order to remove the impurity in potassium dihydrogen phosphate, after concentrating described in preferred steps (b), adopt
With crystallisation by cooling or spray drying, the temperature of crystallisation by cooling is 20～55 DEG C, and the more preferably temperature of crystallisation by cooling is 25～35 DEG C.
The reaction equation of the method for defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt of the present invention and potassium dihydrogen phosphate is as follows:
Ca(OH)2+2H3PO4=Ca(H2PO4)2+2H2O
Ca(H2PO4)2+Ca(OH)2+2H2O=2CaHPO4·2H2O
H3PO4+KOH=KH2PO4+H2O
There is advantages that
1, compared with traditional wet method processed with acid calcium hydrogen phosphate, a step neutralize to calcium hydrophosphate fodder, centre does not produce slightly
Fertilizer, which greatly enhances the utilization rate of phosphorus, saves production cost.
2, during nertralizer II solid is added directly into phosphoric acid (filtrate), reaction, compared with traditional addition potassium hydroxide solution, subtracts
Lack evaporation of water amount, at T2After under the conditions of≤100 DEG C, reaction terminates, the concentration of potassium dihydrogen phosphate is the highest, permissible
Directly crystallisation by cooling, this eliminates the step of evaporation and concentration, the process route of simplification, has saved the energy, has reduced production cost.
3, phosphoric acid by wet process replaces phosphorous acid production by BEP synthos and potassium dihydrogen phosphate, reduces production cost.Strict control calcium is first
The addition of element, tool ensure that the quality of calcium hydrogen phosphate, also reduces the impurity impact on potassium dihydrogen phosphate, improve di(2-ethylhexyl)phosphate
The quality of hydrogen potassium.
Detailed description of the invention
The technical problem to be solved is to provide a kind of defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and potassium dihydrogen phosphate
Method.
Defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt of the present invention and the method for potassium dihydrogen phosphate, comprise the steps:
(a) one section of neutralization: take nertralizer I and be neutralized reaction with phosphoric acid defluorination, react complete, solid-liquid separation, obtain solid phase
I and filtrate I, wherein, calcium constituent in nertralizer I in molar ratio: P in phosphoric acid defluorination2O5=0.4～2:1；
Wherein, described nertralizer I is at least one in calcium oxide, calcium carbonate and calcium hydroxide；
B () two-stage nitration neutralizes: take nertralizer II and be neutralized reaction with filtrate I, until reaction system pH=4～5, react complete,
Solid-liquid separation, obtains solid phase II and filtrate II, and solid phase II i.e. obtains feed-grade calcium phosphate salt with mixing after solid phase I drying, filtrate II
After crystallized, solid-liquid separation, obtain solid phase III, solid phase III is potassium dihydrogen phosphate after drying；
Wherein, described nertralizer II is at least one in potassium hydroxide, potassium carbonate and potassium bicarbonate.
In order to react fully, be conducive to stirring, do not produce parcel phenomenon, nertralizer I described in preferred steps (a) can be by stone
Ash breast substitutes；The more preferably preparation method of lime cream is as follows: water in molar ratio: quick lime=1.6～12:1 water intaking and quick lime,
It is uniformly mixed so as to obtain lime cream.
Further, it is preferable to the most described water: quick lime=6.5～10:1.
In order to ensure reaction mass, cost-effective, step (a) neutralizes reaction, preferable reaction temperature T1=40～100 DEG C, excellent
Select response time t1=0.5～2h.The most described reaction temperature T1=70～80 DEG C；The most described response time t1=1h。
Further, it is preferable to phosphoric acid defluorination P described in step (a)2O5Concentration is 20～55wt%, preferably phosphoric acid defluorination P2O5Dense
Degree is 42～46wt%.
In order to ensure that the Oil repellent in product does not exceeds standard, P in mass ratio in phosphoric acid defluorination in preferred steps (a)2O5The ratio of/F is big
In 250；Preferably P in mass ratio in phosphoric acid defluorination2O5/ F=350～500.
In order to not introduce new impurity, it is ensured that product quality, in preferred steps (a), the purity of nertralizer I is more than 95wt%.
Further, it is preferable to calcium constituent in nertralizer I in molar ratio in step (a): P in phosphoric acid defluorination2O5=0.8～1.2:1.
In order to make reaction carry out the most thorough, pH described in preferred steps (b) is 4.4～4.7.
In order to ensure reaction mass, cost-effective, neutralize reaction, preferable reaction temperature T described in step (b)2≤ 100 DEG C,
Preferably response time t2=0.5～2h, the most described reaction temperature T2=80～95 DEG C；The most described response time t2=1～
1.5h。
Improve the purity of potassium dihydrogen phosphate in order to remove the impurity in potassium dihydrogen phosphate, after concentrating described in preferred steps (b), adopt
With crystallisation by cooling or spray drying, the temperature of crystallisation by cooling is 20～55 DEG C, and the more preferably temperature of crystallisation by cooling is 25～35 DEG C.
The reaction equation of the method for defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt of the present invention and potassium dihydrogen phosphate is as follows:
Ca(OH)2+2H3PO4=Ca(H2PO4)2+2H2O
Ca(H2PO4)2+Ca(OH)2+2H2O=2CaHPO4·2H2O
H3PO4+KOH=KH2PO4+H2O
Below in conjunction with embodiment, the detailed description of the invention of the present invention is further described, the most therefore limits the present invention to institute
Among the scope of embodiments stated.
Embodiment 1 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate
A () takes the lime cream and phosphoric acid defluorination prepared, phosphoric acid defluorination P2O5Concentration is 20wt%, by calcium constituent in lime cream with de-
P in fluorophosphoric acid2O5Molar ratio be that 0.4:1 is added slowly to neutralize in reactive tank I, under conditions of reaction temperature is 40 DEG C,
Stirring reaction 0.5h, reacts complete, and reaction slurry is after solid-liquid separation, and (washable three times of filtering residue, the washing liquid of washing can for the first time
Proceed to neutralize in reactive tank II together with filtrate), obtain solid phase I and filtrate I, solid phase I is synthos after drying, filter
Liquid I proceeds to neutralize in reactive tank II；
Wherein, the preparation method of lime cream is as follows: water in molar ratio: quick lime=2:1 water intaking and quick lime, is uniformly mixed so as to obtain lime cream；
(b) second step neutralisation potassium dihydrogen phosphate making: take potassium hydroxide and be neutralized reaction with the filtrate I neutralized in reactive tank II.
Under conditions of temperature 50 C, stirring reaction 2h, now reaction system pH=4, after reaction terminates, carry out solid-liquid separation while hot,
Obtain solid phase II and filtrate II.Solid phase II dry after with dry after solid phase I carry out being sufficiently mixed and i.e. can obtain feed grade phosphoric acid
Calcium salt, filtrate II after concentrating, 20 DEG C of crystallisation by cooling, after carrying out solid-liquor separation, obtain solid phase III, solid phase III dry after i.e.
For highly purified potassium dihydrogen phosphate.
In the middle part of embodiment 1, divided data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P2O521.92%, F0.098%, Fe2O30.57%, Al2O30.45%,
MgO0.63%, SO31.32%；
The each component of synthos is as follows, is all weight percentage: P2O548.79%, Ca15.21%, F0.16%, SO32.32%；
The each component of potassium dihydrogen phosphate is as follows, is all weight percentage: KH2PO498.42%, K28.11%, F0.008%.
From GB/T22549-2008, mixed phosphate calcium salt has reached the standard of calcium hydrophosphate fodder, is entered by whole technique
After row mass balance, P in phosphoric acid defluorination2O5Yield is 97.1%.
Embodiment 2 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate
A () takes the lime cream and phosphoric acid defluorination prepared, phosphoric acid defluorination P2O5Concentration is 55wt%, by calcium constituent in lime cream with de-
P in fluorophosphoric acid2O5Molar ratio be that 2:1 is added slowly to neutralize in reactive tank I, under conditions of reaction temperature is 100 DEG C,
Stirring reaction 2h, reacts complete, reaction paste after solid-liquid separation, (washable three times of filtering residue, for the first time washing liquid of washing
Can proceed to together with filtrate in neutralization chamber II), obtain solid phase I and filtrate I, be synthos after solid phase I drying, filtrate I
Proceed in neutralization chamber II；
Wherein, the preparation method of lime cream is as follows: water in molar ratio: lime cream=12:1 water intaking and quick lime, is uniformly mixed so as to obtain lime cream；
(b) second step neutralisation potassium dihydrogen phosphate making: take potassium hydroxide and be neutralized reaction with the filtrate I neutralized in reactive tank II.
Under conditions of temperature 50 C, stirring reaction 0.5h, now reaction system pH=5, after reaction terminates, carry out solid-liquid while hot and divide
From, obtain solid phase II and filtrate II.Solid phase II dry after with dry after solid phase I carry out being sufficiently mixed and i.e. can obtain feed grade
Synthos, filtrate II through concentration after, 55 DEG C of crystallisation by cooling, after carrying out solid-liquor separation, obtain solid phase III, solid phase III is dried
After be highly purified potassium dihydrogen phosphate.
In the middle part of embodiment 2, divided data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P2O535.01%, F0.089%, Fe2O30.51%, Al2O30.57%,
MgO0.64%, SO31.35%；
The each component of synthos is as follows, is all weight percentage: P2O549.12%, Ca15.51%, F0.18%, SO32.40%；
The each component of potassium dihydrogen phosphate is as follows, is all weight percentage: KH2PO498.69%, K28.36%, F0.012%；
From GB/T22549-2008, mixed phosphate calcium salt has reached the standard of calcium hydrophosphate fodder, is entered by whole technique
After row mass balance, P in phosphoric acid defluorination2O5Yield is 97.28%.
Embodiment 3 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate
A () takes the lime cream and phosphoric acid defluorination prepared, phosphoric acid defluorination P2O5Concentration is 42wt%, by calcium constituent in lime cream with
P in phosphoric acid defluorination2O5Molar ratio be that 0.8:1 is added slowly to neutralize in reactive tank I, in the condition that reaction temperature is 80 DEG C
Under, stirring reaction 1h, react complete, reaction slurry is (washable three times of filtering residue, for the first time washing liquid of washing after solid-liquid separation
Can proceed to neutralize in reactive tank II together with filtrate), obtain solid phase I and filtrate I, solid phase I is synthos after drying,
Filtrate I proceeds to neutralize in reactive tank II；
Wherein, the preparation method of lime cream is as follows: water in molar ratio: quick lime=6.5:1 water intaking and quick lime, is uniformly mixed so as to obtain Calx
Breast；
(b) second step neutralisation potassium dihydrogen phosphate making: take potassium hydroxide and be neutralized reaction with the filtrate I neutralized in reactive tank II.
Under conditions of temperature 80 DEG C, stirring reaction 1.5h, now reaction system pH=4.4, after reaction terminates, carry out solid-liquid while hot
Separate, obtain solid phase II and filtrate II.Solid phase II dry after with dry after solid phase I carry out being sufficiently mixed and i.e. can obtain feedstuff
Grade calcium phosphate salt, filtrate II through concentration after, 35 DEG C of crystallisation by cooling, after carrying out solid-liquor separation, obtain solid phase III, solid phase III is dried
Highly purified potassium dihydrogen phosphate it is after Gan.
In the middle part of embodiment 3, divided data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P2O541.32%, F0.11%, Fe2O30.58%, Al2O30.63%,
MgO0.72%, SO31.45%；
The each component of synthos is as follows, is all weight percentage: P2O549.35%, Ca15.61%, F0.17%, SO32.30%；
The each component of potassium dihydrogen phosphate is as follows, is all weight percentage: KH2PO499.23%, K28.22%, F0.01%；
From GB/T22549-2008, mixed phosphate calcium salt has reached the standard of calcium hydrophosphate fodder, is entered by whole technique
After row mass balance, P2O5Yield is 97.40%.
Embodiment 4 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate
A () takes the lime cream and phosphoric acid defluorination prepared, phosphoric acid defluorination P2O5Concentration is 46wt%, by calcium constituent in lime cream with
P in phosphoric acid defluorination2O5Molar ratio be that 1.2:1 is added slowly to neutralize in reactive tank I, in the condition that reaction temperature is 70 DEG C
Under, stirring reaction 1h, react complete, reaction slurry is (washable three times of filtering residue, for the first time washing liquid of washing after solid-liquid separation
Can proceed to neutralize in reactive tank II together with filtrate), obtain solid phase I and filtrate I, solid phase I is synthos after drying,
Filtrate I proceeds to neutralize in reactive tank II；
Wherein, the preparation method of lime cream is as follows: water in molar ratio: quick lime=10:1 water intaking and quick lime, is uniformly mixed so as to obtain Calx
Breast；
(b) second step neutralisation potassium dihydrogen phosphate making: take potassium hydroxide and be neutralized reaction with the filtrate I neutralized in reactive tank II.
Under conditions of temperature 95 DEG C, stirring reaction 1h, now reaction system pH=4.7, after reaction terminates, carry out solid-liquid while hot and divide
From, obtain solid phase II and filtrate II.Solid phase II dry after with dry after solid phase I carry out being sufficiently mixed and i.e. can obtain feed grade
Synthos, filtrate II through concentration after, 20 DEG C of crystallisation by cooling, after carrying out solid-liquor separation, obtain solid phase III, solid phase III is dried
After be highly purified potassium dihydrogen phosphate.
In the middle part of embodiment 4, divided data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P2O545.76%, F0.093%, Fe2O30.63%, Al2O30.67%,
MgO0.68%, SO31.38%；
The each component of synthos is as follows, is all weight percentage: P2O549.68%, Ca15.71%, F0.16%, SO32.34%；
The each component of potassium dihydrogen phosphate is as follows, is all weight percentage: KH2PO499.18%, K28.32%, F0.0081%；
From GB/T22549-2008, mixing filtering residue has reached the standard of calcium hydrophosphate fodder, has been carried out by whole technique
After mass balance, P in phosphoric acid defluorination2O5Yield is 97.59%.
Embodiment 5 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate
A () takes calcium hydroxide and phosphoric acid defluorination, phosphoric acid defluorination P2O5Concentration is 35wt%, by calcium constituent in calcium hydroxide and defluorinate
P in phosphoric acid2O5Molar ratio be that 1:1 is added slowly to neutralize in reactive tank I, under conditions of reaction temperature is 75 DEG C, stir
Mixing reaction 1h, react complete, (washable three times of filtering residue, the washing liquid of washing can be with filter for the first time after solid-liquid separation for reaction slurry
Liquid proceeds to neutralize in reactive tank II together), obtain solid phase I and filtrate I, solid phase I is synthos after drying, filtrate I
Proceed to neutralize in reactive tank II；
(b) second step neutralisation potassium dihydrogen phosphate making: take potassium carbonate and be neutralized reaction with the filtrate I neutralized in reactive tank II.
Under conditions of temperature 85 DEG C, stirring reaction 1.5h, now reaction systempH=4.8, after reaction terminates, carries out solid-liquid while hot
Separate, obtain solid phase II and filtrate II.Solid phase II dry after with dry after solid phase I carry out being sufficiently mixed and i.e. can obtain feedstuff
Grade calcium phosphate salt, filtrate II through concentration after, 45 DEG C of crystallisation by cooling, after carrying out solid-liquor separation, obtain solid phase III, solid phase III is dried
Highly purified potassium dihydrogen phosphate it is after Gan.
In the middle part of embodiment 5, divided data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P2O546.76%, F0.089%, Fe2O30.63%, Al2O30.61%,
MgO0.7%, SO31.35%；
The each component of synthos is as follows, is all weight percentage: P2O549.89%, Ca15.84%, F0.13%, SO32.36%；
The each component of potassium dihydrogen phosphate is as follows, is all weight percentage: KH2PO499.58%, K28.4%, F0.0054%；
From GB/T22549-2008, mixing filtering residue has reached the standard of calcium hydrophosphate fodder, has been carried out by whole technique
After mass balance, P in phosphoric acid defluorination2O5Yield is 98.59%.
Embodiment 6 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate
A () takes calcium carbonate and phosphoric acid defluorination, phosphoric acid defluorination P2O5Concentration is 52wt%, by calcium constituent in calcium carbonate and phosphoric acid defluorination
Middle P2O5Molar ratio be that 1.6:1 is added slowly to neutralize in reactive tank I, under conditions of reaction temperature is 70 DEG C, stirring
Reaction 1.5h, reacts complete, and (washable three times of filtering residue, the washing liquid of washing can be with filter for the first time after solid-liquid separation for reaction slurry
Liquid proceeds to neutralize in reactive tank II together), obtain solid phase I and filtrate I, solid phase I is synthos after drying, filtrate I
Proceed to neutralize in reactive tank II；
(b) second step neutralisation potassium dihydrogen phosphate making: take potassium carbonate and be neutralized reaction with the filtrate I neutralized in reactive tank II.
Under conditions of temperature 100 DEG C, stirring reaction 1.5h, now reaction system pH=4.8, after reaction terminates, carry out solid-liquid while hot
Separate, obtain solid phase II and filtrate II.Solid phase II dry after with dry after solid phase I carry out being sufficiently mixed and i.e. can obtain feedstuff
Grade calcium phosphate salt, filtrate II through concentration after, 45 DEG C of crystallisation by cooling, after carrying out solid-liquor separation, obtain solid phase III, solid phase III is dried
Highly purified potassium dihydrogen phosphate it is after Gan.
In the middle part of embodiment 6, divided data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P2O546.76%, F0.095%, Fe2O30.62%, Al2O30.63%,
MgO0.64%, SO31.35%；
The each component of synthos is as follows, is all weight percentage: P2O549.71%, Ca15.82%, F0.14%, SO32.3%；
The each component of potassium dihydrogen phosphate is as follows, is all weight percentage: KH2PO499.38%, K28.36%, F0.0079%；
From GB/T22549-2008, mixing filtering residue has reached the standard of calcium hydrophosphate fodder, has been carried out by whole technique
After mass balance, P in phosphoric acid defluorination2O5Yield is 97.69%.
Embodiment 7 defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate
A () takes calcium oxide and phosphoric acid defluorination, phosphoric acid defluorination P2O5Concentration is 28wt%, by calcium constituent in calcium oxide and phosphoric acid defluorination
Middle P2O5Molar ratio be that 1.6:1 is added slowly to neutralize in reactive tank I, under conditions of reaction temperature is 70 DEG C, stir
Mixing reaction 1.5h, react complete, (washable three times of filtering residue, for the first time the washing liquid of washing can be with after solid-liquid separation for reaction slurry
Filtrate proceeds to neutralize in reactive tank II together), obtain solid phase I and filtrate I, solid phase I is synthos after drying, filtrate
I proceeds to neutralize in reactive tank II；
Wherein, the preparation method of lime cream is as follows: water in molar ratio: quick lime=12:1 water intaking and quick lime, is uniformly mixed so as to obtain Calx
Breast；
(b) second step neutralisation potassium dihydrogen phosphate making: take potassium bicarbonate and be neutralized reaction with the filtrate I neutralized in reactive tank II.
Under conditions of temperature 100 DEG C, stirring reaction 1.5h, now reaction system pH=4.8, after reaction terminates, carry out solid-liquid while hot
Separate, obtain solid phase II and filtrate II.Solid phase II dry after with dry after solid phase I carry out being sufficiently mixed and i.e. can obtain feedstuff
Grade calcium phosphate salt, filtrate II through concentration after, 45 DEG C of crystallisation by cooling, after carrying out solid-liquor separation, obtain solid phase III, solid phase III is dried
Highly purified potassium dihydrogen phosphate it is after Gan.
In the middle part of embodiment 7, divided data is as follows:
The each component of phosphoric acid defluorination is as follows, is all weight percentage: P2O546.51%, F0.09%, Fe2O30.65%, Al2O30.61%,
MgO0.64%, SO31.32%；
The each component of synthos is as follows, is all weight percentage: P2O549.72%, Ca15.68%, F0.17%, SO32.3%；
The each component of potassium dihydrogen phosphate is as follows, is all weight percentage: KH2PO499.23%, K28.31%, F0.0082%；
From GB/T22549-2008, mixing filtering residue has reached the standard of calcium hydrophosphate fodder, has been carried out by whole technique
After mass balance, P in phosphoric acid defluorination2O5Yield is 97.65%.
Claims (52)
1. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt and the method for potassium dihydrogen phosphate, it is characterised in that: comprise the steps:
(a) one section of neutralization: take nertralizer I and be neutralized reaction with phosphoric acid defluorination, react complete, solid-liquid separation, obtain solid phase
I and filtrate I, wherein, calcium constituent in nertralizer I in molar ratio: P in phosphoric acid defluorination2O5=0.4～2:1；
Wherein, described nertralizer I is at least one in calcium oxide, calcium carbonate and calcium hydroxide；
B () two-stage nitration neutralizes: take nertralizer II and be neutralized reaction with filtrate I, until reaction system pH=4～5, react complete,
Solid-liquid separation, obtains solid phase II and filtrate II, and solid phase II i.e. obtains feed-grade calcium phosphate salt with mixing after solid phase I drying, filtrate II
After crystallized, solid-liquid separation, obtain solid phase III, solid phase III is potassium dihydrogen phosphate after drying；
Wherein, described nertralizer II is at least one in potassium hydroxide, potassium carbonate and potassium bicarbonate；
P in mass ratio in phosphoric acid defluorination in step (a)2O5The ratio of/F is more than 250.
Defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt the most according to claim 1 and the method for potassium dihydrogen phosphate, it is special
Levy and be: nertralizer I described in step (a) can be substituted by lime cream.
Defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt the most according to claim 2 and the method for potassium dihydrogen phosphate, it is special
Levy and be: the preparation method of described lime cream is as follows: water in molar ratio: quick lime=1.6～12:1 water intaking and quick lime, mixing
Obtain lime cream.
Defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt the most according to claim 3 and the method for potassium dihydrogen phosphate, it is special
Levy and be: the most described water: quick lime=6.5～10:1.
5. according to the defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt described in any one of Claims 1 to 4 and potassium dihydrogen phosphate
Method, it is characterised in that: step (a) neutralizes reaction, reaction temperature T1=40～100 DEG C, response time t1=0.5～2h.
Defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt the most according to claim 5 and the method for potassium dihydrogen phosphate, it is special
Levy and be: described reaction temperature T1=70～80 DEG C；Described response time t1=1h.
7. according to the defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt described in any one of Claims 1 to 4 and potassium dihydrogen phosphate
Method, it is characterised in that: phosphoric acid defluorination P described in step (a)2O5Concentration is 20～55wt%.
Defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt the most according to claim 5 and the method for potassium dihydrogen phosphate, it is special
Levy and be: phosphoric acid defluorination P described in step (a)2O5Concentration is 20～55wt%.
Defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt the most according to claim 7 and the method for potassium dihydrogen phosphate, it is special
Levy and be: phosphoric acid defluorination P described in step (a)2O5Concentration is 42～46wt%.
Defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt the most according to claim 8 and the method for potassium dihydrogen phosphate, its
It is characterised by: phosphoric acid defluorination P described in step (a)2O5Concentration is 42～46wt%.
11. according to the defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt described in any one of Claims 1 to 4 and potassium dihydrogen phosphate
Method, it is characterised in that: P in mass ratio in phosphoric acid defluorination in step (a)2O5/ F=350～500.
12. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 5 and the methods of potassium dihydrogen phosphate, its
It is characterised by: P in mass ratio in phosphoric acid defluorination in step (a)2O5/ F=350～500.
13. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 7 and the methods of potassium dihydrogen phosphate, its
It is characterised by: P in mass ratio in phosphoric acid defluorination in step (a)2O5/ F=350～500.
14. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 8 and the methods of potassium dihydrogen phosphate, its
It is characterised by: P in mass ratio in phosphoric acid defluorination in step (a)2O5/ F=350～500.
15. according to the defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt described in any one of Claims 1 to 4 and potassium dihydrogen phosphate
Method, it is characterised in that: in step (a), the purity of nertralizer I is more than 95wt%.
16. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 5 and the methods of potassium dihydrogen phosphate, its
It is characterised by: in step (a), the purity of nertralizer I is more than 95wt%.
17. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 7 and the methods of potassium dihydrogen phosphate, its
It is characterised by: in step (a), the purity of nertralizer I is more than 95wt%.
18. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 8 and the methods of potassium dihydrogen phosphate, its
It is characterised by: in step (a), the purity of nertralizer I is more than 95wt%.
19. according to the defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt described in any one of Claims 1 to 4 and potassium dihydrogen phosphate
Method, it is characterised in that: calcium constituent in nertralizer I in molar ratio in step (a): P in phosphoric acid defluorination2O5=0.8～1.2:1.
20. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 5 and the methods of potassium dihydrogen phosphate, its
It is characterised by: calcium constituent in nertralizer I in molar ratio in step (a): P in phosphoric acid defluorination2O5=0.8～1.2:1.
21. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 7 and the methods of potassium dihydrogen phosphate, its
It is characterised by: calcium constituent in nertralizer I in molar ratio in step (a): P in phosphoric acid defluorination2O5=0.8～1.2:1.
22. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 8 and the methods of potassium dihydrogen phosphate, its
It is characterised by: calcium constituent in nertralizer I in molar ratio in step (a): P in phosphoric acid defluorination2O5=0.8～1.2:1.
23. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 15 and the methods of potassium dihydrogen phosphate, its
It is characterised by: calcium constituent in nertralizer I in molar ratio in step (a): P in phosphoric acid defluorination2O5=0.8～1.2:1.
24. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 16 and the methods of potassium dihydrogen phosphate, its
It is characterised by: calcium constituent in nertralizer I in molar ratio in step (a): P in phosphoric acid defluorination2O5=0.8～1.2:1.
25. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 17 and the methods of potassium dihydrogen phosphate, its
It is characterised by: calcium constituent in nertralizer I in molar ratio in step (a): P in phosphoric acid defluorination2O5=0.8～1.2:1.
26. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 18 and the methods of potassium dihydrogen phosphate, its
It is characterised by: calcium constituent in nertralizer I in molar ratio in step (a): P in phosphoric acid defluorination2O5=0.8～1.2:1.
27. according to the defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt described in any one of Claims 1 to 4 and potassium dihydrogen phosphate
Method, it is characterised in that: neutralize reaction, reaction temperature T described in step (b)2≤ 100 DEG C, response time t2=0.5～2h；
PH described in step (b) is 4.4～4.7.
28. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 5 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, reaction temperature T2≤ 100 DEG C, response time t2=0.5～2h；Step (b)
Described in pH be 4.4～4.7.
29. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 7 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, reaction temperature T2≤ 100 DEG C, response time t2=0.5～2h；Step (b)
Described in pH be 4.4～4.7.
30. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 8 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, reaction temperature T2≤ 100 DEG C, response time t2=0.5～2h；Step (b)
Described in pH be 4.4～4.7.
31. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 15 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, reaction temperature T2≤ 100 DEG C, response time t2=0.5～2h；Step (b)
Described in pH be 4.4～4.7.
32. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 16 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, reaction temperature T2≤ 100 DEG C, response time t2=0.5～2h；Step (b)
Described in pH be 4.4～4.7.
33. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 17 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, reaction temperature T2≤ 100 DEG C, response time t2=0.5～2h；Step (b)
Described in pH be 4.4～4.7.
34. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 18 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, reaction temperature T2≤ 100 DEG C, response time t2=0.5～2h；Step (b)
Described in pH be 4.4～4.7.
35. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 27 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, described reaction temperature T2=80～95 DEG C；Described response time t2=1～1.5h.
36. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 28 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, described reaction temperature T2=80～95 DEG C；Described response time t2=1～1.5h.
37. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 29 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, described reaction temperature T2=80～95 DEG C；Described response time t2=1～1.5h.
38. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 30 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, described reaction temperature T2=80～95 DEG C；Described response time t2=1～1.5h.
39. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 31 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, described reaction temperature T2=80～95 DEG C；Described response time t2=1～1.5h.
40. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 32 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, described reaction temperature T2=80～95 DEG C；Described response time t2=1～1.5h.
41. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 33 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, described reaction temperature T2=80～95 DEG C；Described response time t2=1～1.5h.
42. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 34 and the methods of potassium dihydrogen phosphate, its
It is characterised by: described in step (b), neutralize reaction, described reaction temperature T2=80～95 DEG C；Described response time t2=1～1.5h.
43. according to the defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt described in any one of Claims 1 to 4 and potassium dihydrogen phosphate
Method, it is characterised in that: after step (b) concentrates, use crystallisation by cooling or spray drying, the temperature of crystallisation by cooling be 20～
55℃。
44. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 5 and the methods of potassium dihydrogen phosphate, its
Being characterised by: after concentrating in step (b), using crystallisation by cooling or spray drying, the temperature of crystallisation by cooling is 20～55 DEG C.
45. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 7 and the methods of potassium dihydrogen phosphate, its
Being characterised by: after concentrating in step (b), using crystallisation by cooling or spray drying, the temperature of crystallisation by cooling is 20～55 DEG C.
46. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 8 and the methods of potassium dihydrogen phosphate, its
Being characterised by: after concentrating in step (b), using crystallisation by cooling or spray drying, the temperature of crystallisation by cooling is 20～55 DEG C.
47. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 15 and the methods of potassium dihydrogen phosphate, its
Being characterised by: after concentrating in step (b), using crystallisation by cooling or spray drying, the temperature of crystallisation by cooling is 20～55 DEG C.
48. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 43 and the methods of potassium dihydrogen phosphate, its
It is characterised by: the temperature of crystallisation by cooling is 25～35 DEG C.
49. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 44 and the methods of potassium dihydrogen phosphate, its
It is characterised by: the temperature of crystallisation by cooling is 25～35 DEG C.
50. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 45 and the methods of potassium dihydrogen phosphate, its
It is characterised by: the temperature of crystallisation by cooling is 25～35 DEG C.
51. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 46 and the methods of potassium dihydrogen phosphate, its
It is characterised by: the temperature of crystallisation by cooling is 25～35 DEG C.
52. defluorinate phosphoric acid by wet process coproduction feed-grade calcium phosphate salt according to claim 47 and the methods of potassium dihydrogen phosphate, its
It is characterised by: the temperature of crystallisation by cooling is 25～35 DEG C.
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| CN105417516A (en) * | 2015-12-18 | 2016-03-23 | 瓮福（集团）有限责任公司 | Production method for feed-grade monocalcium phosphate |
| CN110395704B (en) * | 2018-04-24 | 2020-12-22 | 四川大学 | Method for co-producing industrial-grade potassium dihydrogen phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid |
| CN108726498A (en) * | 2018-06-27 | 2018-11-02 | 湖北吉星化工集团有限责任公司 | A kind of toothpaste grade dicalcium phosphate dihydrate mother liquor recycling method |
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|---|---|---|---|---|
| CN1033261A (en) * | 1987-11-25 | 1989-06-07 | 沈阳化工综合利用研究所 | A kind of method of producing ammonium phosphate |
| CN1108055A (en) * | 1994-12-30 | 1995-09-13 | 吴隽 | Feed-stuff grade calcium hydrophosphate prodn. defluorination method circulating |
| CN1174812A (en) * | 1996-08-26 | 1998-03-04 | 四川联合大学 | Industrial monoammonium phosphate and productive method for industrial monoammunium phosphate and calcium hydrogen phosphate fodder |
| CN1463916A (en) * | 2002-06-28 | 2003-12-31 | 李光明 | Process for production of fodder level di-calcium phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033261A (en) * | 1987-11-25 | 1989-06-07 | 沈阳化工综合利用研究所 | A kind of method of producing ammonium phosphate |
| CN1108055A (en) * | 1994-12-30 | 1995-09-13 | 吴隽 | Feed-stuff grade calcium hydrophosphate prodn. defluorination method circulating |
| CN1174812A (en) * | 1996-08-26 | 1998-03-04 | 四川联合大学 | Industrial monoammonium phosphate and productive method for industrial monoammunium phosphate and calcium hydrogen phosphate fodder |
| CN1463916A (en) * | 2002-06-28 | 2003-12-31 | 李光明 | Process for production of fodder level di-calcium phosphate |
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