CN108033434A - A kind of method of triple method of purification production high-quality industrial phosphoric acid diammoniums - Google Patents
A kind of method of triple method of purification production high-quality industrial phosphoric acid diammoniums Download PDFInfo
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- CN108033434A CN108033434A CN201711072225.8A CN201711072225A CN108033434A CN 108033434 A CN108033434 A CN 108033434A CN 201711072225 A CN201711072225 A CN 201711072225A CN 108033434 A CN108033434 A CN 108033434A
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- 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
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- C01B25/28—Ammonium phosphates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
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Abstract
The present invention relates to a kind of method of triple method of purification production high-quality industrial phosphoric acid diammoniums.This method is before a neutralization reaction, first phosphoric acid by wet process raw material is concentrated, cool down ageing, the liquid that centrifuges out of ageing liquid is passed through ammonia and is once neutralized, and addition complex salt is reacted in obtained ammonium phosphate slip, then separation of solid and liquid, obtains ammonium phosphate solution and filter residue；Gained ammonium phosphate solution is subjected to secondary neutralization, gained Diammonium phosphate (DAP) solution decrease temperature crystalline, obtains industrial phosphoric acid diammonium crystal.The measure that the present invention passes through centrifugation, neutralization, the triple methods of purification purifications of complex salt after phosphoric acid by wet process raw material is concentrated, more thoroughly remove impurity in phosphoric acid by wet process, the waste residue and crystallization liquid all reusable edibles that triple purification separations go out, avoid producing a large amount of waste material waste residue and liquid exhaust gas.Realize yield height, stable quality, the target of high-quality industrial phosphoric acid diammonium under conditions of low cost, low energy consumption.
Description
Technical field
The present invention relates to a kind of method of triple method of purification production high-quality industrial phosphoric acid diammoniums, belong to chemical production technical
Field.
Background technology
Industrial phosphoric acid diammonium (DAP) is mainly used for the fire retardant as heat-barrier material, is widely used in timber, paper, fabric
It is fire-retardant, while be used for the manufacture of plate making, electron tube, ceramics, enamel etc..In addition, in the food industry be used as leavening agent,
Dough conditioner, yeast nutriment, brewing fermentation assistant and feed additive for ruminant, medicine and printing industry etc. also have and make
With.At the same time or a kind of instant capacity high efficiency composition drip irrigation fertilizer.High-grade fertilizer is also served as, is to prepare Liquid Fertilizer, foliar fertilizer, water
The high-quality basic material of the high-end fertilizer such as molten fertilizer.The fast development of domestic and international fine phosphorus chemical industry, market is to industrial phosphoric acid diammonium
Demand it is growing day by day.
The production of current industrial level monoammonium phosphate and Diammonium phosphate (DAP) is typically all to use thermal phosphoric acid or purifying phosphoric acid technique,
Shortcoming is that production cost is high, technique is more complicated, high energy consumption, pollution are big.Some producers also use wet method phosphoric acid manufacture process, but
Dedoping step, such as tenor height in product, can change with phosphoric acid quality there are some problems, make product quality be difficult to protect
Card.
Chinese patent literature CN1872669A is disclosed using the acidic slurry concentration production method of Diammonium phosphate (DAP) and secondary
Ammoniation reactor.Be the phosphoric acid,diluted using two water wet productions as raw material, DAP is produced using ammonification twice, in an ammonification
It is 0.5~1.0 with degree, secondary ammoniation and preparation DAP are produced using Traditional Method DAP techniques.The method is using acidity
The concentration and save steam so as to cost-effective that slurry concentrates to improve slurry concentration, but the impurity in phosphoric acid by wet process is not carried out
Effective purified treatment, and the degree of neutralization of DAP products is not relatively low so as to cause nitrogen content inclined caused by solution diluting phosphate rock
The problem of low.Chinese patent literature CN101337664A discloses a kind of slurry concentrated process co-producing diammonium phosphate and monoammonium phosphate
Technique, is the sedimentation separation after an ammonification, and bottom thick slurry is used for producing monoammonium phosphate after concentrating together with neutralize slip；Upper strata
Secondary ammoniation production diammonium phosphate product after clear liquid is concentrated.Main problem existing for the method is that supernatant liquor is concentrated,
Since supernatant liquor is phosphor ammonium slurry, in order to ensure that concentration process does not crystallize, its concentration concentration is relatively low, meanwhile, to enriching slurry
Secondary ammoniation is carried out, since the process reaction heat of neutralization is smaller, reaction slurry moisture is high, is sent directly into slurry-spraying pelletizing machine,
Its granulation is difficult to complete, and very big to Influence of production, system moisture is difficult to balance, and slurry is directly whitewashed so that miscellaneous in product
Matter and water-insoluble are more.
Chinese patent literature CN101857210A discloses a kind of method for producing industrial phosphoric acid diammonium, is by phosphoric acid by wet process
Neutralization reaction twice is carried out with ammonia, PHOSPHORIC ACID TECH.GRADE diammonium is made, and uses pickling process, the gas raw material recycling of volatilization is made
With crystalline mother solution recycles or concentrated recycling PHOSPHORIC ACID TECH.GRADE diammonium product, improves product yield.The program was producing
The quality of product can be have impact on because impurity is not removed effectively in journey, and carries out concentration at a high ph and adds ammonia
Overflow, though production cost can also be increased to a certain extent by having carried out the recycling of ammonia.
Chinese patent literature CN103011113A discloses preparing industrial grade monoammonium phosphate from wet-process phosphoric acid coproduction technical grade phosphorus
The method of sour diammonium, is in being carried out with the filtrate that calcium monohydrogen phosphate and phosphoric acid by wet process obtained after desulphurization reaction with ammonia or ammonium hydroxide
And reaction, obtain phosphor ammonium slurry, then concentrated, crystallized with ammonium sulfide and phosphor ammonium slurry reaction and by gained filtrate, is dry
To industrial grade monoammonium phosphate product, the mother liquor that crystallization and filtration obtains and ammonia or ammonium hydroxide are then subjected to secondary neutralize instead
Should, finally obtained concentrating filter liquor is neutralized, crystallize by secondary, be dried to obtain PHOSPHORIC ACID TECH.GRADE diammonium product, crystallization and filtration
Obtained secondary mother liquid returns to be continued to concentrate in thickener.The invention is not in process of production because metal impurities are gone effectively
Remove, a large amount of metal impurities are contained in monoammonium phosphate mother liquor, and Diammonium phosphate (DAP) mother liquor concentrates repeatedly, crystallization, and metal ion is easily enriched with,
These will all have impact on the quality of diammonium phosphate product.
Chinese patent literature CN104401953A discloses a kind of features of DAP production method, by leading in phosphoric acid by wet process
Enter ammonia, and control the molar ratio of ammonia and total phosphoric acid, it is 0.5-0.8 to maintain relatively low degree of neutralization, and the impurity in phosphoric acid by wet process will be with
Phosphoric acid, fluorine etc. generate sediment, so that phosphoric acid by wet process has obtained a degree of purification, avoid the phosphoric acid prepared
Containing the phenomenon that impurity is relatively low with the available phosphorus content caused by phosphoric acid and the sediment of fluorine generation in diammonium, and then improve
The quality of Diammonium phosphate (DAP), can be reduced to 0.4-0.71% by the Oil repellent in Diammonium phosphate (DAP).The invention is used in process of production
Liquefied ammonia is unmanageable to sprinkling in the Diammonium phosphate (DAP) (its nitrogen content is low) of low degree of neutralization, can influence diammonium phosphate product quality, especially
It is that nitrogen content is difficult to control.Chinese patent literature CN103058157A discloses a kind of side for producing PHOSPHORIC ACID TECH.GRADE diammonium
Method, purifies it with ammonium sulfide during obtained PHOSPHORIC ACID TECH.GRADE diammonium, then carries out desulfurization to it with calcium monohydrogen phosphate,
Then pH value is adjusted, is concentrated, crystallized, dried, packed.The invention concentrates overflowing for ammonia under high degree of neutralization in process of production
Extracting rate is high；Diammonium phosphate (DAP) mother liquor concentrates crystallization and be easy to cause metal ion enrichment repeatedly, can influence the quality of diammonium phosphate product.
In conclusion existing use Wet-process Phosphoric Acid Production Diammonium phosphate (DAP) technique, still have in dedoping step and necessarily ask
Topic, under different pH value of the impurity in phosphoric acid by wet process in N-process, can generate various compounds, can reduce in diammonium
Water-soluble P2O5With effective P2O5Content, influences the viscosity of neutralize slip, and the mobility and solid-liquor separation to neutralization reaction slurry are not
Profit, so that impurity is not easy to remove in technique, is difficult to ensure that product quality.It would therefore be highly desirable to research and develop with the low wet method phosphorus of cost
The excellent features of DAP production technique of the sour quality of production, specifically how the impurity effectively removed in phosphoric acid by wet process is that the industry is long-term
Since existing technical barrier.
The content of the invention
In view of the deficiencies of the prior art, the present invention provide it is a kind of brand-new, efficiently, low cost, removal of impurities it is more thoroughly triple
The method that the method for purification produces industrial phosphoric acid diammonium.Industrial phosphoric acid diammonium industrial production for high-quality.
The technical problem to be solved in the present invention mainly includes：Existing phosphoric acid by wet process prepares industrial phosphoric acid diammonium production technology stream
Cheng Zhong, because fluorine, silicon, calcium, iron, magnesium, aluminium impurity content are more high-leveled and difficult all to remove in process of production in phosphoric acid by wet process, serious shadow
Ring diammonium phosphate product quality, and exhaust gas cannot efficiently use in production technology, high energy consumption, of high cost, pollution is big, product quality
The problems such as unstable.
Term explanation：
Phosphoric acid by wet process, is a kind of raw phosphoric acid obtained by sulfuric acid decomposition phosphorus ore.
Solubility in citric acid：Citric acid is also known as citric acid, and the property of rock phosphate in powder dissolution in citric acid is solubility in citric acid.
Technical solution of the present invention is as follows：
A kind of method of triple methods of purification production high-quality industrial phosphoric acid diammonium, uses phosphoric acid by wet process as raw material, with ammonia into
PHOSPHORIC ACID TECH.GRADE diammonium is made in row neutralization reaction twice, it is characterised in that
A. before a neutralization reaction, first phosphoric acid by wet process raw material is concentrated, cool down ageing after concentration, and gained is aged
Liquid centrifuges, and the liquid centrifuged out is passed through ammonia and is once neutralized, and is 3.0~3.6 to pH, obtains ammonium phosphate slip；
B. complex salt is added in the ammonium phosphate slip obtained into step a to be reacted, and reactant is subjected to separation of solid and liquid,
Obtain ammonium phosphate solution and filter residue；The complex salt is the combination of ammonium fluoride and metal salt, and the metal salt is potassium hydroxide
With the combination of potassium carbonate；
C. the ammonium phosphate solution of step b is passed through ammonia and carries out secondary neutralization, obtain Diammonium phosphate (DAP) solution；Gained di(2-ethylhexyl)phosphate
After ammonium salt solution decrease temperature crystalline, separation of solid and liquid is carried out, the drying of gained crystal, obtains high-quality industrial phosphoric acid diammonium product.
Preferable according to the present invention, in step a, the phosphoric acid by wet process raw material concentration condition is：In 80~100 DEG C of vacuum bars
Under part, P is concentrated into2O5Mass fraction is 40%~43%, mass percent.
Preferable according to the present invention, in step a, the cooling aging condition is：Temperature is down to 25~40 DEG C, and ageing 5~
8h；Preferable according to the present invention, in step a, the speed of the centrifugation is 200-5000r/min.Further preferably, the centrifugation
Speed be 2000-3500r/min.Centrifuge is with regular industrial centrifuge.
In order to reduce cost, be conducive to industrialized production, phosphoric acid by wet process of the present invention is non-desulfurization phosphoric acid by wet process.This
Invention removes magnesium, aluminium, silicon, calcium, iron, fluorine, the sulfate radical in phosphoric acid by wet process by being concentrated in vacuo, being aged, centrifuging by phosphoric acid by wet process
Deng impurity.
Preferable according to the present invention, in step b, the ammonium fluoride is made into ammonium fluoride aqueous solution use；Further preferably, institute
Ammonium fluoride aqueous solution mass fraction is stated as 5~20%.The metal salt is that potassium hydroxide and potassium carbonate are 1~3 in mass ratio:1
Combination；It is further preferred that in the complex salt, the mass ratio of ammonium fluoride aqueous solution and metal salt is 2-4:0.2-0.8；Institute
It is 0.2%-1.6% to state complex salt and account for the mass percent of ammonium phosphate slip, and wherein fluorinion concentration is 2.5%~10.5%.
Preferable according to the present invention, in step b, the reaction condition of the ammonium phosphate slip and the complex salt is：70
DEG C~90 DEG C of 0.5~1h of reaction；It is further preferred that continue to stand insulation 1 at temperature 70 C~90 DEG C after completion of the reaction
~2h.So that complex salt purification of wet process phosphoric acid impurity is more thorough, make that the foreign metal salt crystal grain of generation is big, and slurry is easy
Filtering.
Preferable according to the present invention, in step c, the degree of neutralization of the secondary neutralization is 1.60~1.70；The di(2-ethylhexyl)phosphate
The condition of ammonium salt solution decrease temperature crystalline is：It is cooled to 25 DEG C~40 DEG C crystallizations, 3~5h of crystallization time.
Preferable according to the present invention, in step a, the solid centrifuged out is used as phosphate fertilizer raw material；Mainly for the production of multiple
Hefei；The filter residue that separation of solid and liquid obtains in step b is used as citrate acid soluble phosphatic fertilizer raw material；It is mainly used for composite heat transfer.In step c,
Crystallization liquid reusable edible obtained by separation of solid and liquid, for the once neutralization；For example, during the importing of crystallization liquid is once neutralized
In groove.It is mainly Diammonium phosphate (DAP) aqueous solution in crystallization liquid.Therefore, in features of DAP production method of the invention, triple purifications
The component isolated can recycle, and avoid producing a large amount of waste material waste residue and liquids.
In product prepared by the method for the present invention, the Oil repellent in Diammonium phosphate (DAP) is reduced to 0.01~0.05%.This explanation
" Oil repellent " described in book, " fluorinion concentration " are mass percent.
The technical characterstic of the present invention：
Contain a large amount of impurity, such as Mg in phosphoric acid by wet process2+、Ca2+、Fe3+、Al3+、SO4 2-And F-Deng these impurity contents are not only
Depending on phosphorus ore material composition, work flow is additionally depended on, under the different pH value in N-process, various chemical combination can be generated
Thing, these compounds have plenty of solubility, have plenty of insoluble, the water-soluble P in these compounds reduction diammonium2O5With
Effective P2O5Content, while the viscosity of neutralize slip is influenced, it is totally unfavorable to the mobility and solid-liquor separation of neutralization reaction slurry,
Seriously affect diammonium phosphate product quality.The present invention by phosphoric acid by wet process be concentrated in vacuo, being aged, centrifuge, remove wherein magnesium,
The impurity such as aluminium, silicon, calcium, iron, fluorine, sulfate radical, are passed through ammonia and neutralize to certain pH value, add the thorough purifying phosphoric acid slurry of complex salt
Impurity, removes impurity after separation of solid and liquid, and filtrate is carried out secondary neutralization, is neutralized to the degree of neutralization for producing Diammonium phosphate (DAP), then into
Row crystallization separates out industrial phosphoric acid diammonium crystal.
Beneficial effects of the present invention：
1. the present invention is using phosphoric acid by wet process as raw material, by using centrifugation, neutralization, the triple methods of purification of complex salt after vacuum concentration
The measure of purification, more thoroughly removes impurity in phosphoric acid by wet process, realizes the yield under conditions of low cost, low energy consumption
The optimization of height, stable quality, high-quality industrial phosphoric acid diammonium technological parameter；Cleaner complex salt is assisted using ammonium fluoride and metal salt
Acted on removal of impurities is played, significant effect, and component is indispensable in complex salt, lacks any type, impurity-eliminating effect substantially reduces；
2. the present invention directly concentrates phosphoric acid by wet process raw material, magnesium, aluminium, silicon, calcium, iron, fluorine, sulphur in phosphoric acid are not only removed
The impurity such as acid group, and overcome the loss that phosphoric acid by wet process is led to ammonia caused by concentration after ammonia by traditional mode of production Diammonium phosphate (DAP) technique；
3. the technological process of production of the present invention is simple, not only impurity-eliminating effect is notable, and the crystallization by will be produced in technique
Liquid is recycled, and not only ensures the quality of product, but also greatly reduces production cost, realizes the comprehensive utilization of resource；
The advantages of purity is high 4. diammonium phosphate product produced by the invention has, and impurity is few, good water solubility, is significantly better than existing
There is the diammonium phosphate product of Wet-process Phosphoric Acid Production in technology；Oil repellent in the product of the present invention is reduced to 0.01~0.05%；
5. the filter residue produced in present invention process production process can be used as the phosphate fertilizer raw material of composite fertilizer, in whole technical process
Without waste residue, exhaust gas, waste water " three wastes " pollutant discharge, be truly realized economic benefit, social benefit and environmental benefit
General Promotion.
Embodiment
Technical solution of the present invention is further illustrated with reference to embodiment, but institute's protection domain of the present invention is not limited to
This.
Phosphoric acid by wet process in embodiment and comparative example is that Guizhou Nuo Taier companies utilize sulphur by raw material of middle-low grade phosphate
Phosphoric acid by wet process made from acid system, main ingredient is as follows after testing for gained phosphoric acid by wet process：
P2O5%21.25；SO4%3.21；F-%2.38；MgO%1.4513；Al2O3%0.6435；SiO2%0.8510；
CaO%0.593；Fe2O3%0.5321.
Ammonia is passed through described in embodiment and comparative example to refer both to be passed through ammonia.The ammonia is technical purity, purchased from moral ocean
Special gas；Potassium hydroxide is technical purity, purchased from Jiangsu You Lide Chemical Co., Ltd.s；Potassium carbonate is technical purity, is purchased from
Hebei Xinji Chemical Group.
Ammonium fluoride described in embodiment and comparative example is technical purity, purchase Jining of Shandong Province ternary Chemical Co., Ltd..It is described
Ammonium fluoride aqueous solution mass percent is 5~20%." % " in embodiment and comparative example is mass percent；There is special theory
Except bright.
Embodiment 1
A kind of method of triple method of purification production high-quality industrial phosphoric acid diammoniums, includes the following steps：
(1) non-1000 kilograms of desulfurization phosphoric acid by wet process is pumped into vacuum concentrating apparatus and is concentrated into P at 85 DEG C2O5Mass fraction
For 40%；35 DEG C, precipitation 6h are cooled to again, liquid after being aged；
(2) liquid after step (1) is aged is centrifuged with centrifuge, centrifugal speed 2200-2500r/
min；480.78 kilograms of the liquid isolated is pumped into a neutralization chamber, is passed through ammonia and is neutralized to pH3.51, obtains ammonium phosphate slip；
50.47 kilograms of the solid centrifuged out sends to composite heat transfer workshop, the raw material as phosphate fertilizer；
The fluid analysis result isolated is as follows, is mass percent：
P2O5%40.10；SO42-%4.65；F-%1.21；MgO%1.01；Al2O3%2.13；SiO2%0.24；CaO%
0.0026；Fe2O3%0.99.
(3) ammonium phosphate slip obtained in step (2) is pumped into reactive tank, adds 12 kilograms of ammonium fluoride aqueous solution (matter
Measure fraction 10%) and 2.42 kilograms of metal salt (1.61 kilograms of potassium hydroxide, 0.81 kilogram of potassium carbonate), reaction is stirred at 75 DEG C
0.5h, insulation ageing 1h, then separation of solid and liquid, obtains 201.92 kilograms of 292.85 kilograms of ammonium phosphate solution and filter residue, filter residue is sent
Composite heat transfer workshop is gone to, can be used as the phosphate fertilizer of solubility in citric acid；
(4) 292.85 kilograms of ammonium phosphate solution in step (3) is pumped into secondary neutralization chamber, is passed through ammonia and is neutralized to degree of neutralization
1.65, obtain 293.1 kilograms of Diammonium phosphate (DAP) solution；
(5) the Diammonium phosphate (DAP) solution that step (4) obtains is pumped into crystallization tank through slow cooling, 3h, solid-liquid is crystallized at 28 DEG C
After separation, crystal is dried through 50 DEG C~80 DEG C drum dryers, obtains 168.9 kilograms of industrial phosphoric acid diammonium product, crystallization liquid 124.2
Recycled in kilogram (2) neutralization chambers of steps for importing.
Industrial phosphoric acid diammonium product analysis result is as follows, is mass percent：
N%20.66；P2O5%51.24；SO42-%1.33；MgO%0.1172；Al2O3%0.0056；SiO2%0.035；
CaO%0.0027；Fe2O3%0.016；F-%0.01；H20%0.2；Water-insoluble %0.
Embodiment 2
A kind of method of triple method of purification production high-quality industrial phosphoric acid diammoniums, includes the following steps：
(1) non-1000 kilograms of desulfurization phosphoric acid by wet process is pumped into vacuum concentrating apparatus and is concentrated into P at 90 DEG C2O5Mass fraction
For 41%；35 DEG C are cooled to again, are aged 8h, liquid after being aged；
(2) liquid after step (1) is aged is centrifuged with centrifuge, and centrifugal speed is about 3000r/min；Point
124.2 kilograms of 466.46 kilograms of the liquid separated out and 1 crystallization liquid of example are pumped into a neutralization chamber, are passed through ammonia and are neutralized to
PH3.15, obtains ammonium phosphate slip；51.83 kilograms of the solid centrifuged out sends to composite heat transfer workshop, as phosphate fertilizer
Raw material；
The fluid analysis result isolated is as follows, is mass percent：
P2O5%40.90；SO42-%4.95；F-%1.20；MgO%1.10；Al2O3%2.03；SiO2%0.21；CaO%
0.0020；Fe2O3%1.01.
(3) ammonium phosphate slip obtained in step (2) is pumped into reactive tank, adds 17.68 kilograms of ammonium fluoride aqueous solutions
4.71 kilograms of (mass fraction 20%) and metal salt (3.53 kilograms of potassium hydroxide, 1.18 kilograms of potassium carbonate), is stirred at 80 DEG C
0.5h is reacted, insulation ageing 2h, then separation of solid and liquid, obtains 212.5 kilograms of 401.12 kilograms of ammonium phosphate solution and filter residue, filter residue
Composite heat transfer workshop is sent to, can be used as the phosphate fertilizer of solubility in citric acid；
(4) 401.12 kilograms of ammonium phosphate solution in step (3) is pumped into secondary neutralization chamber, is passed through ammonia and is neutralized to degree of neutralization
1.67 obtain 401.9 kilograms of Diammonium phosphate (DAP) solution；
(5) the Diammonium phosphate (DAP) solution that step (4) obtains is pumped into crystallization tank through slow cooling, 4h, solid-liquid is crystallized at 25 DEG C
After separation, crystal is dried through 50 DEG C~80 DEG C drum dryers, obtains 191.42 kilograms of industrial phosphoric acid diammonium product, crystallization liquid 210
Kilogram.Crystallization liquid can be imported in a neutralization chamber and recycled, as described in Example 3.
Industrial phosphoric acid diammonium product analysis result is as follows, is mass percent：
N%20.94；P2O5%50.83；SO42-%1.36；MgO%0.1399；Al2O3%0.0051；SiO2%0.028；
CaO%0.012；Fe2O3%0.014；F-%0.01；H20%0.2；Water-insoluble %0.
Embodiment 3
A kind of method of triple method of purification production high-quality industrial phosphoric acid diammoniums, includes the following steps：
(1) non-1000 kilograms of desulfurization phosphoric acid by wet process is pumped into vacuum concentrating apparatus, P is concentrated at 90 DEG C2O5Mass fraction
For 43%；38 DEG C are cooled to again, are aged 8h, liquid after being aged；
(2) liquid after step (1) precipitation is centrifuged with centrifuge, centrifugal speed is about 2500r/min；Point
210 kilograms of 439.46 kilograms of the liquid separated out and 2 crystallization liquid of embodiment are pumped into a neutralization chamber, are passed through ammonia and are neutralized to
PH3.32, obtains ammonium phosphate slip；54.13 kilograms of the solid centrifuged out sends to composite heat transfer workshop, as phosphate fertilizer
Raw material；
The fluid analysis result isolated is as follows, is mass percent：
P2O5%42.90；SO42-%5.05；F-%1.11；MgO%1.19；Al2O3%2.13；SiO2%0.20；CaO%
0.0020；Fe2O3%1.11.
(3) ammonium phosphate slip obtained in step (2) is pumped into reactive tank, adds 12.56 kilograms of ammonium fluoride aqueous solutions
5.02 kilograms of (mass fraction 15%) and metal salt (2.51 kilograms of potassium hydroxide, 2.51 kilograms of potassium carbonate), is stirred at 85 DEG C
0.5h is reacted, insulation ageing 2h, then separation of solid and liquid, obtains 232.5 kilograms of 434.54 kilograms of ammonium phosphate solution and filter residue, filter residue
Composite heat transfer workshop is sent to, can be used as the phosphate fertilizer of solubility in citric acid；
(4) 434.54 kilograms of ammonium phosphate solution in step (3) is pumped into secondary neutralization chamber, is passed through ammonia and is neutralized to degree of neutralization
1.70, obtain 435.10 kilograms of Diammonium phosphate (DAP) solution；
(5) the Diammonium phosphate (DAP) solution that step (4) obtains is pumped into crystallization tank through slow cooling, 4h, solid-liquid is crystallized at 25 DEG C
After separation, crystal is dried through 50 DEG C~80 DEG C drum dryers, obtains 206.7 kilograms of industrial phosphoric acid diammonium product, crystallization liquid 228.4
Kilogram.Crystallization liquid can be imported in a neutralization chamber and recycled, as described in Example 4.
Industrial phosphoric acid diammonium product analysis result is as follows, is mass percent：
N%20.81；P2O5%51.01；SO42-%1.56；MgO%0.0742；Al2O3%0.0046；SiO2%0.022；
CaO%0.014；Fe2O3%0.010；F-%0.01；H20%0.21；Water-insoluble %0.
Embodiment 4
A kind of method of triple method of purification production high-quality industrial phosphoric acid diammoniums, includes the following steps：
(1) non-1000 kilograms of desulfurization phosphoric acid by wet process is pumped into vacuum concentrating apparatus, P is concentrated at 90 DEG C2O5Mass fraction
For 42%；35 DEG C are cooled to again, are aged 7h, liquid after being aged；
(2) liquid after step (1) precipitation is centrifuged with centrifuge, centrifugal speed is about 3500r/min；Point
228.4 kilograms of 453.46 kilograms of the liquid separated out and 3 crystallization liquid of embodiment are pumped into a neutralization chamber, are passed through ammonia and are neutralized to
PH3.45, obtains ammonium phosphate slip；52.13 kilograms of the solid centrifuged out sends to composite heat transfer workshop, as phosphate fertilizer
Raw material；
The fluid analysis result isolated is as follows, is mass percent：
P2O5%41.90；SO42-%5.00；F-%1.08；MgO%1.21；Al2O3%2.23；SiO2%0.20；CaO%
0.0020；Fe2O3%1.16.
(3) ammonium phosphate slip obtained in step (2) is pumped into reactive tank, adds 19.79 kilograms of ammonium fluoride aqueous solutions
1.98 kilograms of (mass fraction 8%) and metal salt (1.32 kilograms of potassium hydroxide, 0.66 kilogram of potassium carbonate), is stirred anti-at 85 DEG C
0.5h is answered, insulation ageing 2h, then separation of solid and liquid, obtains 241.88 kilograms of 461.2 kilograms of ammonium phosphate solution and filter residue, filter residue is sent
Composite heat transfer workshop is gone to, can be used as the phosphate fertilizer of solubility in citric acid；
(4) 461.2 kilograms of ammonium phosphate solution in step (3) is pumped into secondary neutralization chamber, is passed through ammonia and is neutralized to degree of neutralization
1.68, obtain 461.8 kilograms of Diammonium phosphate (DAP) solution；
(5) the Diammonium phosphate (DAP) solution that step (4) obtains is pumped into crystallization tank through slow cooling, 4h, solid-liquid is crystallized at 30 DEG C
After separation, crystal is dried through 50 DEG C~80 DEG C drum dryers, obtains 225.2 kilograms of industrial phosphoric acid diammonium product, crystallization liquid 236.6
Kilogram.Crystallization liquid can be imported in a neutralization chamber and recycled, as described in Example 5.
Industrial phosphoric acid diammonium product analysis result is as follows, is mass percent：
N%20.51；P2O5%52.04；SO42-%1.68；MgO%0.0462；Al2O3%0.0042；SiO2%0.022；
CaO%0.0092；Fe2O3%0.010；F-%0.01；H20%0.20；Water-insoluble %0.
Embodiment 5
A kind of method of triple method of purification production high-quality industrial phosphoric acid diammoniums, includes the following steps：
(1) non-1000 kilograms of desulfurization phosphoric acid by wet process is pumped into vacuum concentrating apparatus, P is concentrated at 90 DEG C2O5Mass fraction
For 40%；35 DEG C are cooled to again, are aged 7h, liquid after being aged；
(2) liquid after step (1) precipitation is centrifuged with centrifuge, centrifugal speed is about 2800r/min；Point
236.6 kilograms of 480.78 kilograms of the liquid separated out and 4 crystallization liquid of embodiment are pumped into a neutralization chamber, are passed through ammonia and are neutralized to
PH3.60, obtains ammonium phosphate slip；50.47 kilograms of the solid centrifuged out sends to composite heat transfer workshop, as phosphate fertilizer
Raw material；
The fluid analysis result isolated is as follows, is mass percent：
P2O5%40.03；SO4 2-%4.80；F-%1.18；MgO%1.20；Al2O3%2.13；SiO2%0.20；CaO%
0.0020；Fe2O3%1.10.
(3) ammonium phosphate slip obtained in step (2) is pumped into reactive tank, adds 16.49 kilograms of ammonium fluoride aqueous solutions
6.59 kilograms of (mass fraction 17%) and metal salt (4.94 kilograms of potassium hydroxide, 1.65 kilograms of potassium carbonate), is stirred at 85 DEG C
0.5h is reacted, insulation ageing 2h, then separation of solid and liquid, obtains 260.81 kilograms of 479.57 kilograms of ammonium phosphate solution and filter residue, filter
Slag sends to composite heat transfer workshop, can be used as the phosphate fertilizer of solubility in citric acid；
(4) 479.57 kilograms of ammonium phosphate solution in step (3) is pumped into secondary neutralization chamber, is passed through ammonia and is neutralized to degree of neutralization
1.69, obtain 481.3 kilograms of Diammonium phosphate (DAP) solution；
(5) the Diammonium phosphate (DAP) solution that step (4) obtains is pumped into crystallization tank through slow cooling, 4h, solid-liquid is crystallized at 30 DEG C
After separation, crystal is dried through 50 DEG C~80 DEG C drum dryers, obtains 238.7 kilograms of industrial phosphoric acid diammonium product, crystallization liquid 242.6
Recycled in kilogram (2) neutralization chambers of steps for importing.
Industrial phosphoric acid diammonium product analysis result is as follows, is mass percent：
N%20.87；P2O5%52.37；SO42-%1.41；MgO%0.0362；Al2O3%0.0396；SiO2%
0.0028；CaO%0.0032；Fe2O3%0.0058；F-%0.01；H20%0.23；Water-insoluble %0.
Comparative example 1：Do not concentrate, centrifugal cleaning step
Technique productions step is same as Example 5, except that step (1) and step (2) merge into non-desulfurization is wet
000 kilogram of method phosphatase 11, is passed through ammonia and is neutralized to pH3.60, obtain ammonium phosphate slip；
Comparative example 2：Cleaner only uses ammonium fluoride aqueous solution
Technique productions step is same as Example 5, except that the ammonium phosphate that will be obtained in step (3) in step (2)
Slurry is pumped into reactive tank, adds 16.49 kilograms of ammonium fluoride solutions, the stirring reaction 0.5h at 85 DEG C, insulation ageing 2h.
Comparative example 3：Cleaner only uses metal salt
Technique productions step is same as Example 5, except that the ammonium phosphate that will be obtained in step (3) in step (2)
Slurry is pumped into reactive tank, 6.59 kilograms of metal salt (4.94 kilograms of potassium hydroxide, 1.65 kilograms of potassium carbonate) is added, at 85 DEG C
Stirring reaction 0.5h, insulation ageing 2h.
Comparative example 4：Cleaner only uses potassium hydroxide in metal salt
Technique productions step is same as Example 5, except that the ammonium phosphate that will be obtained in step (3) in step (2)
Slurry is pumped into reactive tank, adds 4.94 kilograms of cleaner potassium hydroxide, the stirring reaction 0.5h at 85 DEG C, insulation ageing 2h.
Comparative example 5：Cleaner only uses potassium carbonate in metal salt
Technique productions step is same as Example 5, except that the ammonium phosphate that will be obtained in step (3) in step (2)
Slurry is pumped into reactive tank, adds 1.65 kilograms of cleaner potassium carbonate, the stirring reaction 0.5h at 85 DEG C, insulation ageing 2h.
Obtaining diammonium phosphate product impurity analysis by above example 5 and comparative example 1-5, the results are shown in Table 1：
P2O5%21.25；SO4%3.21；F-%2.38；MgO%1.4513；Al2O3%0.6435；SiO2%0.8510；
CaO%0.0593；Fe2O3%0.5321.
N%20.87；P2O5%52.37；SO42-%1.41；MgO%0.0462；Al2O3%0.0396；SiO2%
0.0032；CaO%0.0032；Fe2O3%0.0082；F-%0.01；H20%0.23；Water-insoluble %0.
1 diammonium phosphate product impurity analysis result of table
| F-% | MgO% | Al2O3% | SiO2% | CaO% | Fe2O3% | Water-insoluble % | |
| Embodiment 5 | 0.01 | 0.0362 | 0.0396 | 0.0028 | 0.0032 | 0.0058 | 0 |
| Comparative example 1 | 0.02 | 0.1307 | 0.0489 | 0.0998 | 0.0156 | 0.0198 | 0.93 |
| Comparative example 2 | 0.06 | 0.1689 | 0.0545 | 0.0989 | 0.0368 | 0.0967 | 1.09 |
| Comparative example 3 | 0.08 | 0.1898 | 0.0789 | 0.0945 | 0.0484 | 0.1008 | 1.10 |
| Comparative example 4 | 0.09 | 0.1886 | 0.0796 | 0.0967 | 0.0489 | 0.1043 | 1.12 |
| Comparative example 5 | 0.10 | 0.2043 | 0.0710 | 0.1045 | 0.0443 | 0.1082 | 1.13 |
As shown in Table 1, the present invention is net by concentration centrifugation, neutralization, the triple methods of purification of complex salt using phosphoric acid by wet process as raw material
Change, more thoroughly remove phosphoric acid by wet process in impurity, in triple purifications, the neutralization method of purification is the traditional coarse method of purification, concentrate from
The heart, complex salt method are verified by production technology, all effectively eliminate impurity in phosphoric acid by wet process, wherein cleaner complex salt uses fluorine
Change ammonium and metal salt collaboration plays removal of impurities effect, significant effect, and component is indispensable in complex salt, lacks any type, removes
Miscellaneous effect substantially reduces.
Claims (10)
1. a kind of method of triple method of purification production high-quality industrial phosphoric acid diammoniums, uses phosphoric acid by wet process as raw material, is carried out with ammonia
PHOSPHORIC ACID TECH.GRADE diammonium is made in neutralization reaction twice, it is characterised in that
A. before a neutralization reaction, first phosphoric acid by wet process raw material is concentrated, after concentration cool down ageing, by gained ageing liquid from
The heart, the liquid centrifuged out are passed through ammonia and are once neutralized, and are 3.0~3.6 to pH, obtain ammonium phosphate slip；
B. complex salt is added in the ammonium phosphate slip obtained into step a to be reacted, and reactant is subjected to separation of solid and liquid, is obtained
Ammonium phosphate solution and filter residue；The complex salt is the combination of ammonium fluoride and metal salt, and the metal salt is potassium hydroxide and carbon
The combination of sour potassium；
C. the ammonium phosphate solution of step b is passed through ammonia and carries out secondary neutralization, obtain Diammonium phosphate (DAP) solution；Gained Diammonium phosphate (DAP) is molten
After liquid decrease temperature crystalline, separation of solid and liquid is carried out, the drying of gained crystal, obtains industrial phosphoric acid diammonium product.
2. the method for triple method of purification production high-quality industrial phosphoric acid diammoniums as claimed in claim 1, it is characterised in that step a
In, the phosphoric acid by wet process raw material concentration condition is：Under 80~100 DEG C of vacuum conditions, P is concentrated into2O5Mass fraction for 40%~
43%.
3. the method for triple method of purification production high-quality industrial phosphoric acid diammoniums as claimed in claim 1, it is characterised in that step a
In, the cooling aging condition is：Temperature is down to 25~40 DEG C, is aged 5~8h；Preferably, in step a, the speed of the centrifugation
Spend for 200-5000r/min.
4. the method for triple method of purification production high-quality industrial phosphoric acid diammoniums as claimed in claim 1, it is characterised in that step b
In, the ammonium fluoride is made into ammonium fluoride aqueous solution use；Further preferably, the ammonium fluoride aqueous solution mass fraction for 5~
20%.
5. the method for triple method of purification production high-quality industrial phosphoric acid diammoniums as claimed in claim 1, it is characterised in that described
Metal salt is that potassium hydroxide and potassium carbonate are 1~3 in mass ratio:1 combination.
6. the method for triple method of purification production high-quality industrial phosphoric acid diammoniums as claimed in claim 1, it is characterised in that described
The mass percent that complex salt accounts for ammonium phosphate slip is 0.2%-1.6%, and wherein fluorinion concentration is 2.5%~10.5%.
7. the method for triple method of purification production high-quality industrial phosphoric acid diammoniums as claimed in claim 4, it is characterised in that described
In complex salt, the mass ratio of ammonium fluoride aqueous solution and metal salt is 2-4:0.2-0.8.
8. the method for triple method of purification production high-quality industrial phosphoric acid diammoniums as claimed in claim 1, it is characterised in that step b
In, the reaction condition of the ammonium phosphate slip and the complex salt is：0.5~1h is reacted at 70 DEG C~90 DEG C；Preferably, anti-
Continue to stand 1~2h of insulation at temperature 70 C~90 DEG C after the completion of answering.
9. the method for triple method of purification production high-quality industrial phosphoric acid diammoniums as claimed in claim 1, it is characterised in that step c
In, the degree of neutralization of the secondary neutralization is 1.60~1.70；Preferably, the condition of the Diammonium phosphate (DAP) solution decrease temperature crystalline is：
It is cooled to 25 DEG C~40 DEG C crystallizations, 3~5h of crystallization time.
10. the method for triple method of purification production high-quality industrial phosphoric acid diammoniums as claimed in claim 1, it is characterised in that step
In a, the solid centrifuged out is used as phosphate fertilizer raw material；
The filter residue that separation of solid and liquid obtains in step b is used as citrate acid soluble phosphatic fertilizer raw material；
In step c, crystallization liquid reusable edible obtained by separation of solid and liquid, for the once neutralization.
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| CN115092898A (en) * | 2022-06-21 | 2022-09-23 | 云南磷化集团有限公司 | Method for removing sulfate radical in wet-process phosphoric acid by using yellow phosphorus slag |
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| JP2000189927A (en) * | 1998-12-28 | 2000-07-11 | Mie Prefecture | Process for separately recovering aluminum and phosphate from material containing incineration ash or aluminum phosphate |
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| CN115092898A (en) * | 2022-06-21 | 2022-09-23 | 云南磷化集团有限公司 | Method for removing sulfate radical in wet-process phosphoric acid by using yellow phosphorus slag |
| CN115092898B (en) * | 2022-06-21 | 2023-09-19 | 云南磷化集团有限公司 | Method for removing sulfate radical in wet-process phosphoric acid by utilizing yellow phosphorus slag |
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