CN105480959A - Method for producing monopotassium phosphate by fluoride salt purification process - Google Patents
Method for producing monopotassium phosphate by fluoride salt purification process Download PDFInfo
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- CN105480959A CN105480959A CN201610046088.XA CN201610046088A CN105480959A CN 105480959 A CN105480959 A CN 105480959A CN 201610046088 A CN201610046088 A CN 201610046088A CN 105480959 A CN105480959 A CN 105480959A
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- phosphoric acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
- C01B25/301—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates
- C01B25/303—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates with elimination of impurities
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
- C01B25/301—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/80—Compositional purity
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Abstract
The invention relates to a method for producing monopotassium phosphate by fluoride salt purification process. The method comprises the following steps: taking wet process phosphoric acid as the raw material; adding phosphate rock powder for desulfuration; re-adding monopotassium phosphate to enable water-bath reaction for defluorination; adding ammonia water into potassium fluosilicate prepared in the defluorination process for reaction so as to prepare a fluoride salt edulcoration agent; neutralizing desulphurized and defluorinated phosphoric acid by ammonia gas, and then adding the prepared fluoride salt edulcoration agent; adjusting the pH; performing immediate filtration after reaction; diluting and adjusting the pH of an ammonium solution; then adding potassium chloride; adding a complexing agent into the filtrate after reaction; after complete dissolution, reducing the temperature, crystallizing and filtering to prepare monopotassium phosphate crystals. The method adopts multiple purification steps, and particularly, the purifying agent (fluoride salt) is extracted in the phosphoric acid defluorinating and purifying process and applied to the purification process in the monopotassium phosphate production process, so that defluorinated by-products are fully utilized, meanwhile, the purity of monopotassium phosphate products is improved, introduction of other impurities is reduced, and the social and economic benefits are achieved.
Description
Technical field
The present invention relates to a kind of method that fluoride salt method of purification produces potassium primary phosphate, belong to chemical production technical field.
Background technology
Water-soluble fertilizer, in the extensive utilization of agricultural planting and flowers ornamental plantation industry, facilitates the development of China's water soluble fertilizer greatly.But in the research work starting evening of domestic Water soluble fertilizer, standard is still unsound, and the market concentration is low, causes quality product on market uneven.For potassium primary phosphate Water soluble fertilizer, because China is vast in territory, the Rock Phosphate (72Min BPL) impurity composition in different province is significantly different with the content of each composition, as higher in impurity such as magnesium in the phosphoric acid of Guizhou, larger on the impact of production potassium primary phosphate.Therefore, how removing the impurity in phosphoric acid according to the composition of raw material thus to produce potassium primary phosphate is more efficiently current problem demanding prompt solution.
Because in phosphoric acid by wet process, the impurity such as calcium, magnesium is higher, larger on the impact of production potassium primary phosphate.For the good product of obtained purity will carry out purifying treatment to phosphoric acid, but the purification in N-process is only adopted not reach production requirement.Current is all adopt neutralisation, electrolytic process, crystallization process, extraction process etc. to the purification of phosphoric acid by wet process, and these method production costs comparatively high pollution are serious, bring very large shrink to the profit of manufacturing enterprise.As Chinese patent document CN200610010782.2 discloses a kind of method of producing potassium primary phosphate, this method completely in a wet process phosphoric acid and Repone K is raw material, phosphoric acid by wet process is mixed with homogeneous mixed solution with Repone K after Chemical Pretreatment, be main composite and obtained extraction agent in order to tertiary amine, chlorion in extraction mixing solutions, form Amine from Tertiary Amine Hydrochloride organic phase, potassium ion free in mixing solutions and phosphoric acid are combined into potassium primary phosphate, and Amine from Tertiary Amine Hydrochloride organic phase is regenerated by washing, back extraction and recycled; The method is, in extraction tower, washing tower, back extraction tower, inorganic aqueous phase solution and organic phase solution are carried out countercurrent reaction, by extraction, washing, back extraction.Although the obtained potassium primary phosphate purity of the method is higher, with organic solvent as extraction agent, production cost is higher, has certain pollution to environment.
And Chinese patent document CN85102377 discloses a kind of method of phosphorus ore, sylvite method of fractional steps potassium dihydrogen phosphate making, take phosphorus ore as raw material, through acidolysis, defluorinate, after preparing mono-calcium phosphate salt, phosphorus is obtained with potassium sulfate metathesis--potassium mixed solution, then through potassium hydroxide or ammonia neutralization, remove impurity with Potassium monofluoride further, potassium dihydrogen phosphate making or ammonium potassium dihydrogen phosphate simultaneously.The method first prepares mono-calcium phosphate, then replacement(metathesis)reaction removes calcium sulfate, and potassium primary phosphate is produced in then neutralization, decon.Obviously the calcium sulfate removed takes away impurity in a part of phosphoric acid by wet process, not only wastes the calcium resource of introducing, and calcium sulfate has taken away a part of phosphoric, causes the loss of nutrient.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method that fluoride salt method of purification produces potassium primary phosphate.The present invention adopts desulfurization, defluorinate rough purification to calcium, iron, phosphoric acid by wet process that magnesium, aluminium foreign matter content are higher, the further purifying treatment of fluoride salt through producing can remove partial impurities again, to reach the object producing qualified potassium primary phosphate.
Technical solution of the present invention is as follows:
The fluoride salt method of purification produces a method for potassium primary phosphate, comprises the steps:
(1) desulfurization process
First phosphoric acid by wet process is carried out desulfurization, after solid-liquid separation, obtain desulfurization phosphoric acid and phosphogypsum;
(2) defluorinate operation
To in obtained desulfurization phosphoric acid, add sylvite and carry out defluorinate, room temperature ageing after reaction, filtration obtain desulfurization phosphoric acid defluorination and potassium silicofluoride;
(3) cleaner operation is prepared
Obtained potassium silicofluoride and ammoniacal liquor are reacted, react terminate rear ageing, solid-liquid separation obtains fluoride salt cleaner and silicon-dioxide;
(4) an ammonium operation is prepared
Get obtained desulfurization phosphoric acid defluorination, with in ammonia and after, add obtained fluoride salt cleaner, regulate pH, solid-liquid separation while hot after reaction terminates, obtains an ammonium solution and colloid;
(5) metathesis operation
One ammonium solution to be diluted and after regulating pH, add Repone K and carry out replacement(metathesis)reaction, replacement(metathesis)reaction terminates rear solid-liquid separation, obtains filter residue and filtrate;
(6) crystal separates out operation
Filtrate adds complexing agent after vacuumizing and concentrating, and dissolves completely, cooling, crystallization, solid-liquid separation, obtained potassium dihydrogen phosphate crystal.
Preferred according to the present invention, in step (1), the method for desulfurization is: in phosphoric acid by wet process, add ground phosphate rock carry out desulphurization reaction, the add-on of ground phosphate rock is according to SO in phosphoric acid by wet process
4 2-content is determined, controls SO in phosphoric acid by wet process
4 2-be 1.2 ~ 1.6:1 with CaO mol ratio in ground phosphate rock; Preferred further, in ground phosphate rock, the content of CaO is 44 ~ 48wt%;
Preferably, the temperature of desulphurization reaction is 50 ~ 70 DEG C, and the reaction times is 1 ~ 2h.
Preferred according to the present invention, in step (2), in defluorinate operation, sylvite is potassium primary phosphate, and in sylvite and phosphoric acid, the mol ratio of fluorine is 1.1 ~ 1.4:1;
Preferably, defluorination reaction reacts 1 ~ 2h in 50 ~ 70 DEG C of water-baths, room temperature ageing 2 ~ 5h after reaction.
Preferred according to the present invention, in step (3), potassium silicofluoride and ammoniacal liquor ratio are: every 100g butt potassium silicofluoride adds 15 ~ 20wt% ammoniacal liquor of 4 ~ 8 times of mass ratioes;
Preferably, potassium silicofluoride and ammoniacal liquor are at 30 ~ 60 DEG C of reactions 0.5 ~ 1.5h, subsequently ageing 0.5 ~ 2h.
According to the present invention, the fluoride salt cleaner described in step (3) is the mix reagent containing Neutral ammonium fluoride, Potassium monofluoride.
Preferred according to the present invention, with ammonia, desulfurization phosphoric acid defluorination being neutralized to pH in step (4) is 2.5 ~ 4.5, after adding fluoride salt cleaner, regulates pH to be 4.0 ~ 6.0, continues reaction 0.5 ~ 1h.
Preferred according to the present invention, in step (5) dilution one ammonium solution degree will according in an ammonium solution with P
2o
5the content of meter phosphorus is determined; Preferably, add water to be diluted in an ammonium solution with P
2o
5the mass percent of meter phosphorus is 16 ~ 18%, then regulates pH to 4.2 ~ 4.6 with hydrochloric acid or ammoniacal liquor;
Preferably, the addition controlling Repone K makes in an ammonium solution with P
2o
5meter phosphorus and Repone K mol ratio 1:1.3 ~ 2.0; The temperature of replacement(metathesis)reaction is 80 ~ 90 DEG C, and the time is 0.5-2h.
Preferred according to the present invention, the degree that filtrate is concentrated in step (6) is: by vacuumizing mode controls that steam pumping amount is total amount of filtrate 1 ~ 3%, the quality adding complexing agent be in step (5) after dilution an ammonium solution quality 0.1% ~ 0.5%; After complexing agent dissolves completely, be cooled to 20 DEG C of crystallization 2 ~ 5h.
Preferred according to the present invention, step (6) complexing agent is one in EDTA, EDETATE SODIUM, citric acid, Trisodium Citrate or combination; Mother liquor in Crystallization Process after solid-liquid separation can return the dilution operation of an ammonium solution.
Preferred according to the present invention, in step (1), washing and recycling available phosphorus (P wherein wanted by phosphogypsum
2o
5), then phosphogypsum is sent to and produce soil conditioner workshop; In step (4), colloid sends to phosphate fertilizer workshop, as citric soluble phosphate fertilizer; In step (5), filter residue is sent to and is produced soil conditioner workshop.
Principle of the present invention:
Phosphoric acid by wet process of the present invention carries out defluorinate process again after desulfurization, obtains silicofluoride, silicofluoride and ammoniacal liquor is hydrolyzed after reacting, obtained fluoride salt cleaner after filtering out silicon-dioxide.Phosphoric acid adds fluoride salt cleaner after being neutralized to certain pH again, generate the precipitations such as Calcium Fluoride (Fluorspan), magnesium fluoride, ferric fluoride to remove after filtering, phosphoric acid is purified further and together filters out the impurity such as magnesium ammonium phosphate, one ammonium solution adds Repone K and carries out replacement(metathesis)reaction, and low temperature crystallization obtains potassium dihydrogen phosphate crystal.Phosphoric acid by wet process is through the further remove portion calcium of fluorion, magnesium, iron, and the growth being conducive to crystal can obtain the higher product of purity.
The present invention has following beneficial effect:
1. the present invention adopts five heavily to purify: by desulfurization, defluorinate, ammonia neutralization, fluoride salt removal of impurities, add complexing agent, make phosphoric acid by wet process after the neutralization can with Repone K generation replacement(metathesis)reaction, produce qualified water-soluble phosphoric acid potassium dihydrogen product, product purity reaches the standard of the agricultural first grade required in HG-2321-92.
2. the present invention's extraction and cleaning agent fluoride salt purification process it be applied in potassium primary phosphate production process in phosphoric acid defluorinate purification process, makes full use of defluorinate by product, achieves the recycle of material.
3. the present invention utilizes potassium primary phosphate defluorinate, decreases the introducing of other impurity, is conducive to improving product purity and the service requirements reducing raw material.
4. the present invention's water-soluble phosphoric acid potassium dihydrogen technique of producing, product purity is high, and impurity is few, the advantage that raw material sources are general, production cost is low etc.And production process is without waste sludge discharge, and prepared using degree is high, environmental friendliness, has good Social and economic benef@.
Specific implementation method:
Below in conjunction with embodiment, technical scheme of the present invention is further illustrated, but institute of the present invention protection domain is not limited thereto.
Ground phosphate rock in embodiment 1-5 and comparative example adopts the ground phosphate rock purchasing Guizhou Hong Fu company processed, and major ingredient is P
2o
5%32.50; MgO%1.64; Al
2o
3%0.85; CaO%48.0; Fe
2o
3%0.84; SiO
2%5.77;
Phosphoric acid by wet process in embodiment 1-5 and comparative example is that the middle-low grade phosphate adopting Guizhou to open phosphorus obtains through sulfuric acid process phosphoric acid by wet process.Gained phosphoric acid by wet process after testing major ingredient is as follows: P
2o
5%21.19; MgO%1.423; Al
2o
3%0.5208; CaO%0.2855; Fe
2o
3%0.1268; SiO
2%0.8624; F
-%1.92.
Embodiment 1-5 and the technical grade Repone K described in comparative example are purchased from Canadian industrial goods;
Embodiment 1-5 and the ammonia described in comparative example are technical purity, purchased from moral ocean special gas.
" % " in embodiment 1-5 and comparative example is mass percentage.
Embodiment 1
A method for Wet-process Phosphoric Acid Production potassium primary phosphate, comprises the steps:
(1) get phosphoric acid by wet process 1000 kilograms, first add 32.81 kilograms, ground phosphate rock, at 60 DEG C, stirring reaction 1 hour, obtains desulfurization phosphoric acid and phosphogypsum after filtration, phosphogypsum washing and recycling P wherein
2o
5, phosphogypsum is sent to and produces soil-grown amendment workshop;
(2) desulfurization phosphoric acid liquid is added potassium primary phosphate 52.2 kilograms and react solid-liquor separation after 2 hours, obtain 956 kilograms of desulfurization phosphoric acid defluorinations, 26.25 kilograms of potassium silicofluorides.The phosphoric acid obtained by analysis result is as follows, is mass percent;
P
2O
5％24.53；MgO％1.4811；Al
2O
3％0.5119；CaO％0.2295；Fe
2O
3％0.1268；SO
4 2－％0.79，SiO
2％0.0257；F
-％0.52；
(3) potassium silicofluoride that step (2) is obtained is added the ammoniacal liquor 162.8 kilograms of 10%, 40 DEG C of reactions 1 hour, obtain fluoride salt cleaner 165.33 kilograms, obtain silicon-dioxide 9.06 kilograms;
(4) in the obtained desulfurization phosphoric acid defluorination of step (2), pass into ammonia is neutralized to after pH is stabilized in 3.3, the fluoride salt cleaner adding step (3) more obtained carries out being neutralized to pH4.5, solid-liquor separation obtains an ammonium liquid 775 kilograms, composition is as follows by analysis, is mass percent;
P
2O
5％20.27；MgO％0.6001；Al
2O
3％0.0000；CaO％0.0045；Fe
2O
3％0.0077；SO
4 2－％0.70；SiO
2％0.0209；F
-％0.022；
The phosphoric acid salt totally 137 kilograms of the CI that neutralization obtains, magnesium, aluminium, can be used as citric soluble phosphate fertilizer;
(5) add water in the ammonium liquid obtained to step (4) and be diluted to concentration 16%, regulate pH to 4.2 with hydrochloric acid or ammoniacal liquor, then add the Repone K of 305 kilograms, react 1 hour at temperature 85 DEG C;
(6) reaction is being incubated suction filtration after terminating, filter out filter residue, by vacuumizing mode, to control suction filtration amount be 2% to filtrate in a water bath, suction filtration adds EDTA complexing agent (EDTA, EDETATE SODIUM, citric acid, Trisodium Citrate etc.) the complexing trace element wherein of the rear ammonium quality 0.3% of dilution after going out moisture, until completely dissolved, temperature is down to the obtained potassium primary phosphate 236 kilograms of 25 DEG C of crystallizatioies more than 2 hours.N%1.38, P in product
2o
5%50.84, K
2o%33.22%, SO
4 2-%0.30%, Cl2.06%.
Embodiment 2
A method for Wet-process Phosphoric Acid Production potassium primary phosphate, comprises the steps:
(1) get phosphoric acid by wet process 1000 kilograms, first add 32.81 kilograms, ground phosphate rock, at 50 DEG C, stir 1 reaction 1 hour, obtain desulfurization phosphoric acid and phosphogypsum after filtration, phosphogypsum washing and recycling P wherein
2o
5, phosphogypsum is sent to and produces soil-grown amendment workshop;
(2) desulfurization phosphoric acid liquid is added potassium primary phosphate 53.7 kilograms and react solid-liquor separation after 2 hours, obtain 948 kilograms of desulfurization phosphoric acid defluorinations, 27.83 kilograms of potassium silicofluorides.The phosphoric acid obtained by analysis result is as follows, is mass percent;
P
2O
5％24.85；MgO％1.4871；Al
2O
3％0.4769；CaO％0.3297；Fe
2O
3％0.1362；SO
4 2－％0.82，SiO
2％0.023；F
-％0.48；
(3) potassium silicofluoride that step (2) is obtained is added the ammoniacal liquor 172.6 kilograms of 10%, 40 DEG C of reactions 1 hour, obtain fluoride salt cleaner 175.30 kilograms, obtain silicon-dioxide 9.6 kilograms;
(4) in the obtained desulfurization phosphoric acid defluorination of step (2), pass into ammonia is neutralized to after pH is stabilized in 3.5, the fluoride salt cleaner adding step (3) more obtained carries out being neutralized to pH4.5, solid-liquor separation obtains an ammonium liquid 770 kilograms, composition is as follows by analysis, is mass percent;
P
2O
5％20.95；MgO％0.5081；Al
2O
3％0.0000；CaO％0.0032；Fe
2O
3％0.0057；SO
4 2－％0.70；SiO
2％0.0113；F
-％0.020；
The phosphoric acid salt totally 145 kilograms of the CI that neutralization obtains, magnesium, aluminium, can be used as citric soluble phosphate fertilizer;
(5) add water in the ammonium liquid obtained to step (3) and be diluted to concentration 17%, regulate pH to 4.3 with hydrochloric acid or ammoniacal liquor, then add the Repone K of 310 kilograms, react 1 hour at temperature 85 DEG C;
(6) reaction is being incubated suction filtration after terminating, filter out filter residue, by vacuumizing mode, to control suction filtration amount be 2% to filtrate in a water bath, suction filtration adds EDETATE SODIUM complexing agent (EDTA, EDETATE SODIUM, citric acid, Trisodium Citrate etc.) the complexing trace element wherein of the rear ammonium quality 0.3% of dilution after going out moisture, until completely dissolved, temperature is down to the obtained potassium primary phosphate 240 kilograms of 25 DEG C of crystallizatioies more than 2 hours.N%1.27, P in product
2o
5%51.80, K
2o%33.40%, SO
4 2-%0.33%, Cl2.59%.
Embodiment 3
A method for Wet-process Phosphoric Acid Production potassium primary phosphate, comprises the steps:
(1) get phosphoric acid by wet process 1000 kilograms, first add 32.81 kilograms, ground phosphate rock, at 70 DEG C, stirring reaction 1 hour, obtains desulfurization phosphoric acid and phosphogypsum after filtration, phosphogypsum washing and recycling P wherein
2o
5, phosphogypsum is sent to and produces soil-grown amendment workshop;
(2) desulfurization phosphoric acid liquid is added potassium primary phosphate 53.7 kilograms and react solid-liquor separation after 2 hours, obtain 948 kilograms of desulfurization phosphoric acid defluorinations, 28.10 kilograms of potassium silicofluorides.The phosphoric acid obtained by analysis result is as follows, is mass percent;
P
2O
5％24.85；MgO％1.4811；Al
2O
3％0.4769；CaO％0.3297；Fe
2O
3％0.1362；SO
4 2－％0.82，SiO
2％0.023；F
-％0.48；
(3) potassium silicofluoride that step (2) is obtained is added the ammoniacal liquor 174.27 kilograms of 10%, 40 DEG C of reactions 1 hour, obtain fluoride salt cleaner 178.30 kilograms, obtain silicon-dioxide 9.7 kilograms;
(4) in the obtained desulfurization phosphoric acid defluorination of step (2), pass into ammonia is neutralized to after pH is stabilized in 3.8, add obtained fluoride salt cleaner again to carry out being neutralized to pH4.1, solid-liquor separation obtains an ammonium liquid 765 kilograms, and composition is as follows by analysis, is mass percent;
P
2O
5％21.0；MgO％0.4880；Al
2O
3％0.0000；CaO％0.0046；Fe
2O
3％0.0046；SO
4 2－％0.67；SiO
2％0.0121；F
-％0.026；
The phosphoric acid salt totally 150 kilograms of the CI that neutralization obtains, magnesium, aluminium, can be used as citric soluble phosphate fertilizer;
(5) add water in the ammonium liquid obtained to step (4) and be diluted to concentration 16%, regulate pH to 4.4 with hydrochloric acid or ammoniacal liquor, then add the Repone K of 320 kilograms, react 1 hour at temperature 80 DEG C;
(6) reaction is being incubated suction filtration after terminating, filter out filter residue, by vacuumizing mode, to control suction filtration amount be 2% to filtrate in a water bath, suction filtration adds citric acid complexing agent (EDTA, EDETATE SODIUM, citric acid, Trisodium Citrate etc.) the complexing trace element wherein of the rear ammonium quality 0.3% of dilution after going out moisture, until completely dissolved, temperature is down to the obtained potassium primary phosphate 235 kilograms of 25 DEG C of crystallizatioies more than 2 hours.N%1.38, P in product
2o
5%50.84, K
2o%33.22%, SO
4 2-%0.32%, Cl%2.09.
Embodiment 4
A method for Wet-process Phosphoric Acid Production potassium primary phosphate, comprises the steps:
(1) get phosphoric acid by wet process 1000 kilograms, first add 34 kilograms, ground phosphate rock, at 50 DEG C, stirring reaction 1 hour, obtains desulfurization phosphoric acid and phosphogypsum after filtration, phosphogypsum washing and recycling P wherein
2o
5, phosphogypsum is sent to and produces soil-grown amendment workshop;
(2) desulfurization phosphoric acid liquid is added potassium primary phosphate 54.2 kilograms and react solid-liquor separation after 2 hours, obtain 952 kilograms of desulfurization phosphoric acid defluorinations, 28.29 kilograms of potassium silicofluorides.The phosphoric acid obtained by analysis result is as follows, is mass percent;
P
2O
5％24.99；MgO％01.4919；Al
2O
3％0.4467；CaO％0.4337；Fe
2O
3％0.1431；SO
4 2－％0.79，SiO
2％0.033；F
-％0.50；
(3) potassium silicofluoride that step (2) is obtained is added the ammoniacal liquor 175.5 kilograms of 10%, 40 DEG C of reactions 1 hour, obtain fluoride salt cleaner 179.30 kilograms, obtain silicon-dioxide 9.8 kilograms;
(4) in the obtained desulfurization phosphoric acid defluorination of step (2), pass into ammonia is neutralized to after pH is stabilized in 3.6, add obtained fluoride salt cleaner again to carry out being neutralized to pH4.3, solid-liquor separation obtains an ammonium liquid 770 kilograms, and composition is as follows by analysis, is mass percent;
P
2O
5％21.10；MgO％0.6390；Al
2O
3％0.0000；CaO％0.0053；Fe
2O
3％0.0040；SO
4 2－％0.70；SiO
2％0.0201；F
-％0.030；
The phosphoric acid salt totally 153 kilograms of the CI that neutralization obtains, magnesium, aluminium, can be used as citric soluble phosphate fertilizer;
(5) add water in the ammonium liquid obtained to step (4) and be diluted to concentration 18%, regulate pH to 4.3 with hydrochloric acid or ammoniacal liquor, then add the Repone K of 315 kilograms, react 1 hour at temperature 80 DEG C;
(6) reaction is being incubated suction filtration after terminating, filter out filter residue, by vacuumizing mode, to control suction filtration amount be 2% to filtrate in a water bath, suction filtration adds sodium citrate complexing agent (EDTA, EDETATE SODIUM, citric acid, Trisodium Citrate etc.) the complexing trace element wherein of the rear ammonium quality 0.3% of dilution after going out moisture, until completely dissolved, temperature is down to the obtained potassium primary phosphate 230 kilograms of 25 DEG C of crystallizatioies more than 2 hours.N%1.33, P in product
2o
5%50.77, K
2o%33.62%, SO
4 2-%0.37%, Cl%2.36.
Embodiment 5
A method for Wet-process Phosphoric Acid Production potassium primary phosphate, comprises the steps:
(1) get phosphoric acid by wet process 1000 kilograms, first add 33 kilograms, ground phosphate rock, at 40 DEG C, stirring reaction 2 hours, obtains desulfurization phosphoric acid and phosphogypsum after filtration, phosphogypsum washing and recycling P wherein
2o
5, phosphogypsum is sent to and produces soil-grown amendment workshop;
(2) desulfurization phosphoric acid liquid is added potassium primary phosphate 55 kilograms and react solid-liquor separation after 1 hour, obtain 950 kilograms of desulfurization phosphoric acid defluorinations, 28 kilograms of potassium silicofluorides.The phosphoric acid obtained by analysis result is as follows, is mass percent;
P
2O
5％24.36；MgO％1.5019；Al
2O
3％0.4467；CaO％0.4337；Fe
2O
3％0.1431；SO
4 2－％0.79，SiO
2％0.033；F
-％0.50；
(3) potassium silicofluoride that step (2) is obtained is added the ammoniacal liquor 173.7 kilograms of 10%, 40 DEG C of reactions 1 hour, obtain fluoride salt cleaner 176.30 kilograms, obtain silicon-dioxide 9.66 kilograms;
(4) in the obtained desulfurization phosphoric acid defluorination of step (2), pass into ammonia is neutralized to after pH is stabilized in 3.5, add obtained fluoride salt cleaner again to carry out being neutralized to pH4.2, solid-liquor separation obtains an ammonium liquid 768 kilograms, and composition is as follows by analysis, is mass percent;
P
2O
5％21.33；MgO％0.4990；Al
2O
3％0.0000；CaO％0.004；Fe
2O
3％0.0036；SO
4 2－％0.68；SiO
2％0.0222；F
-％0.029；
The phosphoric acid salt totally 148 kilograms of the CI that neutralization obtains, magnesium, aluminium, can be used as citric soluble phosphate fertilizer;
(5) add water in the ammonium liquid obtained to step (4) and be diluted to concentration 17%, regulate pH to 4.2 with hydrochloric acid or ammoniacal liquor, then add the Repone K of 319 kilograms, react 1 hour at temperature 80 DEG C;
(6) reaction is being incubated suction filtration after terminating, filter out filter residue, by vacuumizing mode, to control suction filtration amount be 2% to filtrate in a water bath, suction filtration adds EDTA complexing agent (EDTA, EDETATE SODIUM, citric acid, Trisodium Citrate etc.) the complexing trace element wherein of the rear ammonium quality 0.3% of dilution after going out moisture, until completely dissolved, temperature is down to the obtained potassium primary phosphate 232 kilograms of 25 DEG C of crystallizatioies more than 2 hours.N%1.43, P in product
2o
5%50.97, K
2o%33.16%, SO
4 2-%0.31, %, Cl%2.60.
Comparative example, do not use fluoride salt cleaner
A method for Wet-process Phosphoric Acid Production potassium primary phosphate, comprises the steps:
(1) get phosphoric acid by wet process 1000 kilograms, first add 32.81 kilograms, ground phosphate rock, at 60 DEG C, stirring reaction 1 hour, obtains desulfurization phosphoric acid and phosphogypsum after filtration, and washing and recycling P wherein wanted by phosphogypsum
2o
5, then send to and produce soil-grown amendment workshop;
(2) desulfurization phosphoric acid liquid is added potassium primary phosphate 52.2 kilograms and react solid-liquor separation after 2 hours, obtain 956 kilograms of desulfurization phosphoric acid defluorinations, 26.25 kilograms of potassium silicofluorides.The phosphoric acid obtained by analysis result is as follows, is mass percent;
P
2O
5％24.07；MgO％1.4811；Al
2O
3％0.5119；CaO％0.2295；Fe
2O
3％0.1268；SO
4 2－％0.71，SiO
2％0.0257；F
-％0.42；
(3) phosphoric acid salt totally 163 kilograms of the CI obtained after neutralization, magnesium, aluminium, can be used as citric soluble phosphate fertilizer.Obtain an ammonium liquid 671 kilograms;
(4) add water in the ammonium liquid obtained to step (3) and be diluted to concentration 17%, regulate pH to 4.2 with hydrochloric acid or ammoniacal liquor, then add the Repone K of 313 kilograms, react 1 hour at temperature 85 DEG C;
(5) reaction is being incubated suction filtration after terminating, filter out filter residue, by vacuumizing mode, to control suction filtration amount be 2% to filtrate in a water bath, suction filtration adds the EDTA complexing agent complexes trace element wherein of the rear ammonium quality 0.3% of dilution after going out moisture, until completely dissolved, temperature is down to the obtained potassium primary phosphate 261 kilograms of 25 DEG C of crystallizatioies more than 2 hours.N%1.31, P in product
2o
5%46.73, K
2o%34.60%, SO
4 2-%0.37%, Cl%5.06.
Embodiment 4 contrasts with comparative example crystal analysis result
The phosphorus ore used in the embodiment of the present invention is middle-low grade phosphate, the phosphoric acid by wet process obtained with it is that raw material obtains potassium primary phosphate, by the nutrient contrast in embodiment and comparative example, the product purity that embodiment obtains is high, illustrate and adopt fluoride salt cleaner to purify further phosphoric acid, have significant effect to the purity improving potassium primary phosphate.
Claims (10)
1. produce a method for potassium primary phosphate by the fluoride salt method of purification, comprise the steps:
(1) desulfurization process
First phosphoric acid by wet process is carried out desulfurization, after solid-liquid separation, obtain desulfurization phosphoric acid and phosphogypsum;
(2) defluorinate operation
To in obtained desulfurization phosphoric acid, add sylvite and carry out defluorinate, room temperature ageing after reaction, filtration obtain desulfurization phosphoric acid defluorination and potassium silicofluoride;
(3) cleaner operation is prepared
Obtained potassium silicofluoride and ammoniacal liquor are reacted, react terminate rear ageing, solid-liquid separation obtains fluoride salt cleaner and silicon-dioxide;
(4) an ammonium operation is prepared
Get obtained desulfurization phosphoric acid defluorination, with in ammonia and after, add obtained fluoride salt cleaner, regulate pH, solid-liquid separation while hot after reaction terminates, obtains an ammonium solution and colloid;
(5) metathesis operation
One ammonium solution to be diluted and after regulating pH, add Repone K and carry out replacement(metathesis)reaction, replacement(metathesis)reaction terminates rear solid-liquid separation, obtains filter residue and filtrate;
(6) crystal separates out operation
Filtrate adds complexing agent after vacuumizing and concentrating, and dissolves completely, cooling, crystallization, solid-liquid separation, obtained potassium dihydrogen phosphate crystal.
2. the fluoride salt method of purification according to claim 1 produces the method for potassium primary phosphate, it is characterized in that, in step (1), the method for desulfurization is: in phosphoric acid by wet process, add ground phosphate rock carry out desulphurization reaction, controls SO in phosphoric acid by wet process
4 2-be 1.2 ~ 1.6:1 with CaO mol ratio in ground phosphate rock; Preferably, the temperature of desulphurization reaction is 50 ~ 70 DEG C, and the reaction times is 1 ~ 2h.
3. the fluoride salt method of purification according to claim 1 produces the method for potassium primary phosphate, it is characterized in that, in step (2), in defluorinate operation, sylvite is potassium primary phosphate, and in sylvite and phosphoric acid, the mol ratio of fluorine is 1.1 ~ 1.4:1;
Preferably, defluorination reaction reacts 1 ~ 2h in 50 ~ 70 DEG C of water-baths, room temperature ageing 2 ~ 5h after reaction.
4. the fluoride salt method of purification according to claim 1 produces the method for potassium primary phosphate, it is characterized in that, in step (3), potassium silicofluoride and ammoniacal liquor ratio are: every 100g butt potassium silicofluoride adds 15 ~ 20wt% ammoniacal liquor of 4 ~ 8 times of mass ratioes.
5. the fluoride salt method of purification according to claim 1 produces the method for potassium primary phosphate, it is characterized in that, in step (3), potassium silicofluoride and ammoniacal liquor are at 30 ~ 60 DEG C of reactions 0.5 ~ 1.5h, subsequently ageing 0.5 ~ 2h.
6. the fluoride salt method of purification according to claim 1 produces the method for potassium primary phosphate, it is characterized in that, with ammonia, desulfurization phosphoric acid defluorination being neutralized to pH in step (4) is 2.5 ~ 4.5, after adding fluoride salt cleaner, regulate pH to be 4.0 ~ 6.0, continue reaction 0.5 ~ 1h.
7. the fluoride salt method of purification according to claim 1 produces the method for potassium primary phosphate, it is characterized in that, adds water and be diluted in an ammonium solution with P in step (5)
2o
5the mass percent of meter phosphorus is 16 ~ 18%, then regulates pH to 4.2 ~ 4.6 with hydrochloric acid or ammoniacal liquor.
8. the fluoride salt method of purification according to claim 1 produces the method for potassium primary phosphate, it is characterized in that, the addition controlling Repone K in step (5) makes in an ammonium solution with P
2o
5meter phosphorus and Repone K mol ratio 1:1.3 ~ 2.0;
Preferably, the temperature of replacement(metathesis)reaction is 80 ~ 90 DEG C, and the time is 0.5-2h.
9. the fluoride salt method of purification according to claim 1 produces the method for potassium primary phosphate, it is characterized in that, the degree that in step (6), filtrate is concentrated is: by vacuumizing mode controls that steam pumping amount is total amount of filtrate 1 ~ 3%;
Preferably, the quality adding complexing agent is 0.1% ~ 0.5% of the rear ammonium solution quality of dilution in step (5);
Preferably, after complexing agent dissolves completely, be cooled to 20 DEG C of crystallization 2 ~ 5h.
10. the fluoride salt method of purification according to claim 1 produces the method for potassium primary phosphate, it is characterized in that, step (6) complexing agent is one in EDTA, EDETATE SODIUM, citric acid, Trisodium Citrate or combination.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107434245A (en) * | 2017-06-26 | 2017-12-05 | 湖北祥云(集团)化工股份有限公司 | A kind of method and system of industrial grade monoammonium phosphate mother liquor production potassium dihydrogen phosphate |
| CN110395707A (en) * | 2019-08-13 | 2019-11-01 | 广州怡和生物科技有限公司 | A kind of preparation method of potassium dihydrogen phosphate |
| CN110482507A (en) * | 2019-08-08 | 2019-11-22 | 宜都兴发化工有限公司 | A kind of method of metal ion in reduction raffinate |
| CN115285955A (en) * | 2022-09-01 | 2022-11-04 | 四川大学 | Method for preparing food-grade phosphoric acid by deep defluorination of industrial-grade phosphoric acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4639359A (en) * | 1985-12-16 | 1987-01-27 | International Minerals & Chemical Corp. | Process of removing cationic impurities from wet process phosphoric acid |
| CN103072963A (en) * | 2012-12-28 | 2013-05-01 | 山东金正大生态工程股份有限公司 | Method for producing potassium dihydrogen phosphate through wet-process phosphoric acid |
| CN103523764A (en) * | 2013-06-27 | 2014-01-22 | 云南云天化国际化工股份有限公司 | Method for reducing magnesium and aluminum impurities in wet-process phosphoric acid |
-
2016
- 2016-01-22 CN CN201610046088.XA patent/CN105480959B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4639359A (en) * | 1985-12-16 | 1987-01-27 | International Minerals & Chemical Corp. | Process of removing cationic impurities from wet process phosphoric acid |
| CN103072963A (en) * | 2012-12-28 | 2013-05-01 | 山东金正大生态工程股份有限公司 | Method for producing potassium dihydrogen phosphate through wet-process phosphoric acid |
| CN103523764A (en) * | 2013-06-27 | 2014-01-22 | 云南云天化国际化工股份有限公司 | Method for reducing magnesium and aluminum impurities in wet-process phosphoric acid |
Non-Patent Citations (1)
| Title |
|---|
| 王娜等: "湿法磷酸净化生产磷酸二氢钾的研究", 《磷肥与复肥》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107434245A (en) * | 2017-06-26 | 2017-12-05 | 湖北祥云(集团)化工股份有限公司 | A kind of method and system of industrial grade monoammonium phosphate mother liquor production potassium dihydrogen phosphate |
| CN107434245B (en) * | 2017-06-26 | 2019-11-08 | 湖北祥云(集团)化工股份有限公司 | A kind of method and system of industrial grade monoammonium phosphate mother liquor production potassium dihydrogen phosphate |
| CN110482507A (en) * | 2019-08-08 | 2019-11-22 | 宜都兴发化工有限公司 | A kind of method of metal ion in reduction raffinate |
| CN110395707A (en) * | 2019-08-13 | 2019-11-01 | 广州怡和生物科技有限公司 | A kind of preparation method of potassium dihydrogen phosphate |
| CN115285955A (en) * | 2022-09-01 | 2022-11-04 | 四川大学 | Method for preparing food-grade phosphoric acid by deep defluorination of industrial-grade phosphoric acid |
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