CN116443832A - Method, product and system for co-producing ferric phosphate through nitrophosphate device - Google Patents

Method, product and system for co-producing ferric phosphate through nitrophosphate device Download PDF

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Publication number
CN116443832A
CN116443832A CN202210006335.9A CN202210006335A CN116443832A CN 116443832 A CN116443832 A CN 116443832A CN 202210006335 A CN202210006335 A CN 202210006335A CN 116443832 A CN116443832 A CN 116443832A
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Prior art keywords
solution
phosphate
acidolysis
solid
liquid separation
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Inventor
黄德明
赵国军
方进
黄仕英
刘法安
程静
张凌云
冯军强
华建青
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Shenzhen Batian Ecotypic Engineering Co Ltd
Guizhou Batian Ecotypic Engineering Co Ltd
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Shenzhen Batian Ecotypic Engineering Co Ltd
Guizhou Batian Ecotypic Engineering Co Ltd
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Priority to CN202210006335.9A priority Critical patent/CN116443832A/en
Publication of CN116443832A publication Critical patent/CN116443832A/en
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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
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B11/00—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes
    • C05B11/04—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid
    • C05B11/06—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid using nitric acid (nitrophosphates)
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D3/00—Calcareous fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D5/00—Fertilisers containing magnesium
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Fertilizers (AREA)

Abstract

The invention discloses a method, a product and a system for co-producing ferric phosphate by a nitrophosphate device; the method comprises the following steps: acidolysis is carried out on phosphorite or phosphate concentrate by nitric acid, and acid insoluble matters are separated to obtain acidolysis solution; freezing and crystallizing acidolysis solution, and carrying out solid-liquid separation to obtain a first solution; adding the first solution into a solution containing sulfate radicals to react to obtain a second solution; performing nitrite removal treatment on the second solution to obtain a third solution; and adding ammonia into the third solution for neutralization, carrying out solid separation on the neutralized solution to obtain ammonium phosphate solution, and adding an iron source into the ammonium phosphate solution for reaction to obtain the ferric phosphate. According to the method, the high-purity ferric phosphate is obtained by producing and preparing the phosphorite raw material, and byproducts in the production process can be directly used for preparing fertilizer or used as independent products, so that no waste is generated.

Description

Method, product and system for co-producing ferric phosphate through nitrophosphate device
Technical Field
The invention relates to the technical field of phosphorite processing, in particular to a method, a product and a system for co-producing ferric phosphate by a nitrophosphate fertilizer device.
Background
The iron phosphate is generally prepared by adopting an iron source and a phosphorus source through reaction, and the prepared iron source and phosphoric acid are adopted for preparing the iron phosphate, but the invention can realize the preparation of the iron phosphate through two routes through a nitrophosphate fertilizer device, wherein one route is the preparation of ammonium phosphate salt for preparing the iron phosphate, the other route is the preparation of the iron phosphate through phosphoric acid, and the two routes fully utilize a nitrophosphate fertilizer device for producing the iron phosphate.
Disclosure of Invention
One embodiment of the invention provides a method for co-producing ferric phosphate by a nitrophosphate device, which comprises the following steps:
acidolysis is carried out on phosphorite or phosphate concentrate by nitric acid, and acid insoluble matters are separated to obtain acidolysis solution;
freezing and crystallizing the acidolysis solution, and carrying out solid-liquid separation to obtain a first solution;
adding the first solution into a solution containing sulfate radicals to decalcify to obtain a second solution A, and/or adding sulfuric acid into the first solution to react, and carrying out solid-liquid separation to obtain a second solution B;
performing nitrite removal treatment on the second solution A and/or the second solution B to obtain a third solution A or a third solution B;
adding ammonia into the third solution A for neutralization, carrying out solid separation on the neutralized solution to obtain ammonium phosphate solution, and adding an iron source into the ammonium phosphate solution for reaction to obtain ferric phosphate;
and/or extracting the third solution B by an extraction solvent to obtain an extraction phase; back-extracting the extract phase to obtain phosphoric acid solution; and (3) obtaining ferric phosphate by reacting an iron source with the phosphoric acid solution.
And extracting the third solution B to remove metal ions, thereby obtaining a phosphoric acid solution.
In some embodiments, the acidolysis solution is obtained by directly filtering and separating the liquid phase component in acidolysis solution; or in still other cases, the acidolysis solution comprises a solution obtained by directly filtering and separating the liquid phase component in acidolysis slurry and combining the solid phase component decomposed by acidolysis with a washing solution obtained by washing one or more times with process water.
In some embodiments, the acidolysis solution of the phosphate concentrate mainly contains phosphate obtained by acidolysis of nitric acid, and the impurity metals include calcium ions and the like, nitrate, and the like, for example. In a preferred embodiment, the nitric acid added during acidolysis may be in a relative excess to complete the reaction of the phosphate rock feedstock.
In some embodiments, the acid insoluble material obtained by solid-liquid separation mainly contains acid insoluble salts of calcium magnesium silicate; in a preferred embodiment, the acid insoluble material obtained by acidolysis can be prepared as a soil conditioner product for soil improvement based on effective use of the elements contained in the acid insoluble material.
In some embodiments, the acidolysis solution is frozen to crystallize at a temperature of-10 ℃ to-5 ℃ and 60 to 85 percent of calcium nitrate is mixed with Ca (NO 3 ) 2 ·4H 2 Separating out O crystal forms; and then carrying out vacuum filtration on the frozen solution to promote coagulation and precipitation of crystal grains, and obtaining a first solution for removing impurity calcium for the first time.
In a more preferred embodiment, the temperature of the acidolysis solution is frozen to be between-8 ℃ and-5 ℃, and then the acidolysis solution is directly sent into a vacuum filter for filtration and separation, and the liquid phase component obtained after filtration is the first solution.
Or in specific preferred implementation details, filtering the solid phase component obtained after filtration and separation, such as a filter cake obtained by filtering in a filter pressing mode, washing the filter cake by using frozen nitric acid and frozen water, and circularly combining part of the generated washing liquid into acidolysis liquid for re-freezing, crystallizing and separating, and adding the other part of the washing liquid into an acidolysis tank for acidolysis.
In some embodiments, a sulfate-containing solution, such as at least one of sulfuric acid, ammonium sulfate, is added to the first solution.
In a further embodiment, the sulfate-containing solution is not excessive to avoid introducing sulfate impurities; i.e. the molar amount of sulphate added does not exceed the molar amount of calcium ions in the first solution, in order to prevent sulphate affecting the quality of phosphoric acid from being contained in the second solution a after decalcification.
In another embodiment, the sulfate-containing solution is not excessive, maintaining the sulfate concentration in the second solution below 0.5% after decalcification is advantageous for subsequent removal of impurities; in a more preferred embodiment, the concentration of sulfate in the second solution is kept below 0.1% after decalcification; more preferably, the concentration of sulfate in the second solution is kept below 0.01% after decalcification.
In a preferred embodiment, the second solution a or second solution B is subjected to a nitrite removal treatment by evaporating and concentrating the second solution to remove nitric acid.
And in a preferred embodiment, the evaporation temperature for removing nitric acid by evaporating and concentrating the second solution A or B is adjustable between 120 and 180 ℃; in a more preferred embodiment, the temperature at which the nitric acid is removed by evaporation concentration is maintained between 160 and 177 ℃. When evaporated to a nitrate concentration of less than 1% in the system, it is advantageous for the subsequent removal of metallic impurities and the formation of phosphoric acid; further, in a more preferred embodiment, the concentration by evaporation is such that the concentration of nitrate in the system is less than 0.5%; more preferably, the concentration of nitrate in the system is less than 0.1% by evaporation.
And in a preferred embodiment, the third solution after removal of nitric acid by evaporation concentration of the second solution contains nitrate ions at a concentration of less than 0.5%. More preferably, the nitrate ion concentration contained in the third solution is less than 0.1%.
In a preferred embodiment, the above extraction is a multistage cross-flow extraction; so that the extraction efficiency is more sufficient.
The term "multistage cross-flow extraction" is a chemical term and refers to a process in which multistage cross-flow extraction is performed in multistage series-connected equipment. Each stage comprises an extraction chamber and a re-extraction chamber. In the extraction chamber the donor phase is contacted with an extraction solvent which is reextracted upon in the reextraction chamber by contact with the recipient phase, the extraction solvent flowing in the same stage in a suitable manner crosswise to the donor and recipient phases, while the donor and recipient phases flow in countercurrent through some or all of the stages.
In a preferred embodiment, the method further comprises:
and back-extracting the extracted phase obtained by extraction, and separating to obtain phosphoric acid and an extraction solvent which can be recycled for extraction.
In a preferred embodiment, the extraction solvent comprises at least one of n-butanol and isoamyl alcohol.
In a preferred embodiment, the third solution B is removed by extraction with an extraction solvent, and the volume ratio of the extraction solvent to the third solution B is 0.5-5:1.
And, in some specific embodiments, the organic extraction solvent used in the above extraction step may include a common metal ion extraction solvent such as n-butanol, isoamyl alcohol, tributyl phosphate, sulfonated kerosene, no. 260 solvent oil, 406# environmental solvent oil, and the like. In a particularly preferred embodiment, the extraction solvent used in step S50 is a mixture of n-butanol and isoamyl alcohol, the ratio of n-butanol to isoamyl alcohol in the mixed extraction solvent being 1:0.5 to 2, preferably 1:1. In the extraction, the volume ratio of the addition amount of the extraction solvent to the third solution B is 0.5-5:1; preferably, the volume ratio of the addition amount of the extraction solvent to the third solution B is 1-2: 1.
in a preferred embodiment, before the step of back-extracting the extract phase, the method further comprises:
washing the extraction phase to obtain a solution containing metal ions;
and concentrating the solution containing the metal ions to obtain a medium trace element fertilizer product or a raw material for fertilizer production.
In a preferred embodiment, the method further comprises:
the solution containing the metal ions is used for preparing the medium trace element fertilizer.
In a preferred embodiment, the method further comprises:
the acid in acidolysis of the phosphorite is at least partially derived from nitric acid obtained by evaporation and nitrate removal of the second solution A or the second solution B.
In a preferred embodiment, the iron source includes at least one of an iron salt, a ferrous salt, or an elemental iron, and the sulfate-containing solution is at least one of a sulfuric acid solution and an ammonium sulfate solution.
In a preferred embodiment, the pH value of the reaction system is controlled between 4 and 6 in the reaction of the iron source and the phosphoric acid solution.
In a preferred embodiment, the ammonia comprises at least one of ammonia gas, liquid ammonia or aqueous ammonia.
In a specific embodiment, acidolysis of the phosphate ore or phosphate concentrate comprises: the nitric acid with the mass concentration of 65 percent and the dilute nitric acid with the mass concentration of 35 to 45 percent generated in the calcium nitrate filtering process are added into an acidolysis tank together with the medium-low grade phosphate rock powder for acidolysis reaction. The acidolysis reaction process comprises the following steps:
the main reaction:
side reaction:
the nitric acid dosage is as follows: caO, mgO, fe in medium-low grade phosphate rock powder 2 O 3 And Al 2 O 3 And (3) when the acid is completely reacted with nitric acid, the theoretical amount of the nitric acid is 110% -115%, after acidolysis reaction is finished, filter pressing is carried out, acid insoluble substances and impurities are removed, and filtrate is acidolysis solution.
In a specific embodiment, the freeze crystallization of the acidolysis solution comprises: adding acidolysis solution obtained by acidolysis into a crystallizer, performing indirect heat exchange with a coolant to perform crystallization and cooling to form calcium nitrate crystal suspension, wherein the operation is as follows: adding acidolysis solution into a crystallizer with a coil under normal pressure under stirring, indirectly exchanging heat between ammonia water with the mass concentration of 20% and the acidolysis solution in the coil, cooling the acidolysis solution to the temperature of-5 ℃ to-8 ℃ to precipitate calcium nitrate crystals, vacuum filtering the crystal suspension to separate calcium nitrate and filtrate, adding frozen nitric acid and frozen water to wash a calcium nitrate filter cake, returning the washing solution to acidolysis, and ammonifying the obtained calcium nitrate to obtain an ammonium calcium nitrate product.
In a specific embodiment, adding a sulfate-containing solution to the first solution to decalcify comprises: adding the filtrate into a calcium removing tank, controlling the temperature to be 60-75 ℃, adding concentrated sulfuric acid, and stirringStirring and reacting for 60-120 minutes, filtering the reaction liquid after the reaction time expires, and obtaining white phosphogypsum (calcium sulfate) and a calcium removal mother solution; the reaction formula is: SO (SO) 4 2- +Ca 2+ =CaSO 4 The method comprises the steps of carrying out a first treatment on the surface of the The addition amount of the concentrated sulfuric acid is Ca in the filtrate 2+ With SO 4 2- 80 to 90 percent of the theoretical dosage of sulfuric acid required in the complete reaction.
In a preferred embodiment, the process of adding ammonia to the third solution a for the neutralization reaction comprises two-stage neutralization;
first stage neutralization:
second stage neutralization:
NH 4 H 2 PO 4 +NH 3 =(NH 4 ) 2 HPO 4
the preferred control range for pH of the ammonia-passing neutralization reaction slurry is as follows: 4.2 to 4.8.
The invention also provides an iron phosphate product prepared according to the method for co-producing iron phosphate by the nitrophosphate fertilizer device.
The invention also provides a system for co-producing ferric phosphate by the nitrophosphate device, which comprises:
the acidolysis tank is used for carrying out acidolysis reaction on phosphorite;
the first solid-liquid separation device is used for carrying out solid-liquid separation on acidolysis slurry after acidolysis so as to obtain acidolysis solution;
the freezing and crystallizing device is used for freezing and crystallizing the acidolysis solution;
the second solid-liquid separation device is used for carrying out solid-liquid separation on the acidolysis solution of the frozen crystals so as to obtain a first solution;
the decalcification reaction device is used for carrying out decalcification reaction on the first solution and the solution containing sulfate radicals;
the third solid-liquid separation device is also used for carrying out solid-liquid separation on the product of the decalcification reaction so as to obtain a second solution;
the denitration device is used for evaporating the second solution to remove nitrate radical so as to obtain a concentrated denitration third solution and nitric acid;
the extraction device is used for extracting the third solution by using an extraction solvent to obtain an extraction phase;
the back extraction device is used for back extracting the extraction phase to obtain phosphoric acid;
an iron phosphate reaction device for preparing iron phosphate by reacting an iron source with the phosphoric acid or ammonium phosphate salt solution,
a fifth solid-liquid separation device for performing solid separation on the solution obtained by reacting the iron source with the phosphoric acid or ammonium phosphate solution to obtain a solid product of ferric phosphate;
and/or the system is provided with a neutralization device and a fourth solid-liquid separation device, wherein the neutralization device is used for carrying out neutralization reaction on the third solution and ammonium to obtain a neutralization reaction solution, and the fourth solid-liquid separation device is used for carrying out solid-liquid separation on the neutralization reaction solution to obtain an ammonium phosphate solution.
In a preferred embodiment, the denitration device is connected with an acidolysis tank, so that nitric acid removed by the denitration device enters the acidolysis tank.
In a preferred embodiment, the first and/or second and/or third and/or fourth and/or fifth solid-liquid separation device is one of a settling tank, a filter press or a suction filter.
In a preferred embodiment, the first solid-liquid separation device, the second solid-liquid separation device, the third solid-liquid separation device, the fourth solid-liquid separation device, and the fifth solid-liquid separation device are the same solid-liquid separation device that is recycled.
In a preferred embodiment, the method further comprises:
and the back extraction device is used for carrying out back extraction on the extraction phase of the extraction device.
In a preferred embodiment, the method further comprises:
the washing device is positioned between the extraction device and the back extraction device and is used for washing the extraction phase of the extraction device to obtain washing liquid containing metal ions.
And the first concentrating device is used for concentrating the washing liquid containing the metal ions to obtain a medium trace element fertilizer product.
In a preferred embodiment, the extraction device comprises one of a rotating disk extraction column, a multistage centrifugal extraction column, a vibrating screen plate column or a screen plate extraction column.
In a preferred embodiment, the method further comprises:
and the second concentration device is used for concentrating the extraction phase of the back extraction device.
According to the preparation method, the iron phosphate is prepared by using equipment of the nitrophosphate fertilizer, the high-purity iron phosphate is obtained by producing and preparing the phosphorite raw material, byproducts in the production process can be directly used for preparing the fertilizer or used as independent products, no waste is generated, the nitrophosphate fertilizer equipment is used for preparing the iron phosphate through two paths, namely an ammonium phosphate path and a phosphoric acid path, the two paths are respectively prepared by producing and preparing the nitrophosphate fertilizer by using the nitrophosphate fertilizer equipment, the two paths can be respectively carried out, the two paths can be simultaneously carried out, the byproduct products have high calcium sulfate quality, the application of industrial calcium sulfate can be met, the trace metal ions and the neutralized precipitate metal phosphate in the byproduct extract can be used as raw materials for preparing the fertilizer, the byproduct nitric acid can be directly used for producing the fertilizer, and the byproduct nitric acid can be recycled for decomposing the phosphorite and can also be used for preparing iron sources, such as ferric nitrate or ferrous nitrate.
Drawings
FIG. 1 is a schematic diagram of a method of co-producing ferric phosphate by a nitrophosphate device in one embodiment;
FIG. 2 is a schematic illustration of the preparation of an iron source in one embodiment;
FIG. 3 is a schematic diagram of multistage cross-flow extraction, washing and stripping to obtain phosphoric acid in one embodiment;
FIG. 4 is a schematic diagram of a system for co-producing ferric phosphate by a nitrophosphate device in one embodiment;
FIG. 5 is a schematic diagram of a method for co-producing ferric phosphate in a nitrophosphate device in yet another embodiment;
fig. 6 is a schematic diagram of a system for co-producing iron phosphate by a nitrophosphate device in yet another embodiment.
Detailed Description
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
One embodiment of the invention provides a method for co-producing ferric phosphate by a nitrophosphate fertilizer device; the method takes phosphorite and an iron source as raw materials to prepare and obtain ferric phosphate.
In some embodiments, the phosphate ore or phosphate concentrate raw material used for preparing the ferric phosphate is high-grade phosphate ore obtained by natural mining, and the phosphate concentrate is obtained by removing impurities or purifying medium-low-grade phosphate ore.
Further FIG. 1 shows a schematic diagram of a method of co-producing ferric phosphate in one embodiment, the method comprising:
s10, acidolysis is carried out on phosphorite or phosphate concentrate raw materials by nitric acid or mixed acid containing nitric acid, and acid insoluble substances are separated and removed to obtain acidolysis solution;
s20, freezing and crystallizing calcium nitrate from acidolysis solution, and filtering out the crystallized calcium nitrate to obtain a first solution;
s30, adding sulfuric acid solution into the first solution, and further removing calcium to obtain a second solution;
s40, concentrating the second solution to volatilize excessive nitric acid from the second solution, so as to obtain a concentrated and denitrated third solution;
s50, extracting the third solution obtained in the step S40 to separate phosphoric acid and part of metal ions from the third solution into an extraction phase; then washing to remove metal ions from the extraction phase by washing; back-extracting the washed extraction phase to enable phosphoric acid to return to the water phase from the organic extraction solvent, thereby obtaining a phosphoric acid solution;
s60, preparing and obtaining ferric phosphate by reacting a phosphoric acid solution with an iron source.
In step S60, the obtained iron phosphate is prepared by reacting an iron source with the phosphoric acid solution obtained in step S50. Wherein in some embodiments the iron source comprises at least one of an iron salt, such as ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, ferric chloride, or elemental iron, such as iron powder, and the like.
For example, in one embodiment of fig. 2, the iron source is a ferric salt solution obtained by dissolving and filtering a raw material of 85% by mass of ferrous sulfate heptahydrate, adding 25% ammonia water, and further filtering and removing impurities.
In a specific embodiment, the pH of the reaction system is preferably controlled to be in the range of 4 to 6 during the reaction by adding an iron source to the phosphoric acid solution obtained in step S50. On the one hand, the large precipitation of other metal impurities and indissolvable ferrous phosphate is avoided when the pH value of the reaction system is higher than 6, and on the other hand, the difficult precipitation of the ferric phosphate is avoided when the pH value of the reaction system is lower than 4.
And in a specific embodiment, carrying out solid-liquid separation on the reaction product of the iron source and the phosphoric acid solution in the step S60, wherein the solid phase component is the ferric phosphate containing crystal water, and further drying to remove the crystal water to obtain an anhydrous ferric phosphate product with higher purity. And the liquid phase component of the solid-liquid separation of the reaction product in the step S60 also contains phosphate, nitrate and other non-precipitated metal ions. Further in a more preferred embodiment, the method further comprises:
and (3) preparing the nitrophosphate fertilizer by taking the liquid phase component obtained in the solid-liquid separation in the step S60 as a nitrophosphate fertilizer raw material.
In some embodiments, the acidolysis solution in step S10 is obtained by directly filtering and separating the liquid phase component in the acidolysis solution; or in still other cases, the acidolysis solution comprises a washing solution obtained by directly filtering and separating liquid phase components in acidolysis slurry and washing solid phase components decomposed by acidolysis with process water for one or more times;
the acidolysis solution of phosphate concentrate mainly contains phosphate obtained by acidolysis of nitric acid, and impurity metals such as calcium ion, nitrate, etc. In a preferred embodiment, the nitric acid added during acidolysis may be in a relative excess to complete the reaction of the phosphate rock feedstock.
In this embodiment, the acid-insoluble substance obtained by solid-liquid separation mainly contains an acid-insoluble salt of calcium magnesium silicate; in a preferred embodiment, the acid insoluble material obtained by acidolysis can be prepared as a soil conditioner product for soil improvement based on effective use of the elements contained in the acid insoluble material.
In the step S20, freezing and crystallizing calcium nitrate from acidolysis solution, and filtering out the crystallized calcium nitrate to obtain a first solution; specifically, in step S20, by first freeze-crystallizing the acidolysis solution, a large amount of calcium ions and a part of metal ions such as magnesium are precipitated in the form of nitrate crystals during the freeze-crystallization; for example, the calcium nitrate is frozen to a temperature of-10 ℃ to-5 ℃ and preferably-8 ℃ to-5 ℃ in the acidolysis solution, and 60 to 85% of the calcium nitrate is added with Ca (NO 3 ) 2 ·4H 2 Separating out O crystal forms; then directly sending the solution into a vacuum filter for filtering and separating, and obtaining a liquid phase component after filtering to obtain a first solution.
Or in specific preferred implementation details, filtering the solid phase component obtained after filtration and separation, such as a filter cake obtained by filtering in a filter pressing mode, washing the filter cake by using frozen nitric acid and frozen water, and adding part of the generated washing liquid into acidolysis liquid for freezing and crystallizing separation again in a system circulation way, wherein the other part of the washing liquid is added into an acidolysis tank for acidolysis.
And in step S30, adding sulfuric acid solution into the first solution to precipitate the residual calcium ions in the first solution as slightly or poorly soluble calcium sulfate, and performing solid-liquid separation; the solid phase component obtained is a second solution containing a certain amount of calcium sulfate such as calcium sulfate hemihydrate, and further removing calcium.
In embodiments, the sulfate-containing solution is not excessive to avoid introducing sulfate impurities; i.e. the molar amount of sulphate in the added sulphuric acid solution does not exceed the molar amount of calcium ions in the first solution, in order to prevent sulphate affecting the quality of phosphoric acid from being contained in the second solution after decalcification.
In embodiments, the sulfate-containing solution is not excessive, maintaining the sulfate concentration in the second solution below 0.5% after decalcification is advantageous for subsequent removal of impurities; in a more preferred embodiment, the concentration of sulfate in the second solution is kept below 0.1% after decalcification; more preferably, the concentration of sulfate in the second solution is kept below 0.01% after decalcification.
And in step S40, concentrating the second solution to volatilize and release the excessive nitric acid from the second solution, thereby obtaining a concentrated and denitrated third solution.
And in a preferred embodiment, the evaporation temperature for removing nitric acid by evaporating and concentrating the second solution is adjustable between 120 and 180 ℃; in a more preferred embodiment, the temperature at which the nitric acid is removed by evaporation concentration is maintained between 160 and 177 ℃. When evaporated to a nitrate concentration of less than 0.5% in the system, it is advantageous for the subsequent removal of metallic impurities and the formation of phosphoric acid; further in a more preferred embodiment, the concentration of nitrate in the system is less than 0.1% by evaporation; more preferably, the concentration of nitrate in the system is less than 0.01% by evaporation.
And in an embodiment, the third solution after removing nitric acid by evaporating and concentrating the second solution contains nitrate ions with a concentration of less than 0.5%. More preferably, the nitrate ion concentration contained in the third solution is less than 0.1%.
And in a preferred embodiment, the process further re-absorbs or recovers the nitric acid removed in step S40, and then uses the recovered nitric acid in step S10 to acidolyze the phosphate rock raw material.
And concentrating the third solution after removing the nitric acid, wherein the third solution mainly comprises phosphoric acid and partial impurities and metal ions.
And in step S50, extracting the third solution obtained in step S40 to separate phosphoric acid and a part of metal ions from the third solution into an extraction phase; then washing to remove metal ions from the extraction phase by washing; and back-extracting the washed extraction phase to enable phosphoric acid to return to the aqueous phase from the organic extraction solvent, thereby obtaining a phosphoric acid solution.
The terms extraction and stripping are fundamental technical terms in the chemical industry. Wherein the term "extraction" is a process of transferring a solute material from one solvent to another by utilizing the difference in solubility or partition coefficient of the material in two mutually immiscible (or slightly soluble) solvents. The term "stripping" is a process in which solute material is returned from the extraction solvent, as opposed to "extraction".
And, in some specific embodiments, the organic extraction solvent used in the above extraction step may include a common metal ion extraction solvent such as n-butanol, isoamyl alcohol, sulfonated kerosene, no. 260 solvent oil, 406# environmental solvent oil, and the like. In a particularly preferred embodiment, the extraction solvent used in step S50 is a mixture of n-butanol and isoamyl alcohol, the ratio of n-butanol to isoamyl alcohol in the mixed extraction solvent being 1:0.5-2, preferably the ratio of n-butanol to isoamyl alcohol being 1:1. In the extraction, the addition amount of the extraction solvent is 0.5-5:1 according to the volume ratio of the extraction solvent to the third solution.
Further in more preferred implementation, after the back extraction step, the phosphoric acid solution separated after the back extraction is decolorized or concentrated, and the like, so that on one hand, organic matters or fluorine elements in the solution are further removed, and on the other hand, the appearance, the color, the concentration and the like of the product are improved, and the high-purity industrial phosphoric acid of the standardized product is obtained. In a specific embodiment, the final high purity phosphoric acid solution obtained by decolorization and concentration contains P 2 O 5 The mass percentage of (2) is 61.58%.
On the other hand, besides the phosphoric acid obtained by back extraction, the extraction solvent can be reduced and purified so that the extraction solvent can be recycled.
In a preferred embodiment, the above extraction mode is a multistage cross-flow extraction; so that the extraction efficiency is more sufficient.
The term "multistage cross-flow extraction" is a chemical term and refers to a process in which multistage cross-flow extraction is performed in multistage series-connected equipment. Each stage comprises an extraction chamber and a re-extraction chamber. In the extraction chamber the donor phase is contacted with an extraction solvent which is reextracted upon in the reextraction chamber by contact with the recipient phase, the extraction solvent flowing in the same stage in a suitable manner crosswise to the donor and recipient phases, while the donor and recipient phases flow in countercurrent through some or all of the stages.
For example, a schematic diagram of a multistage cross-flow extraction in one embodiment is shown in FIG. 3; in the embodiment, the separation efficiency of components in each step is improved through multistage extraction, multistage washing and repeated back extraction, so that the purity of the final separated and prepared product is improved as much as possible.
And in some specific embodiments, washing to obtain a solution containing metal ion impurities, wherein the solution contains medium and trace metal elements such as calcium, magnesium, manganese and the like, and then the solution is added into phosphate fertilizer or fertilizer products to supplement medium and trace elements; or concentrating and adding the solution containing the metal ion impurities to prepare the independent medium trace element fertilizer product.
Yet another embodiment of the present invention also provides a system for co-producing industrial phosphoric acid by a nitrophosphate device. In this preferred embodiment, the system for co-producing industrial phosphoric acid is shown in fig. 4, and comprises:
acidolysis reaction device for acidolysis of phosphorite material with nitric acid or mixed acid;
the first solid-liquid separation device is used for carrying out solid-liquid separation on acidolysis slurry after acidolysis so as to obtain acidolysis solution;
the freezing and crystallizing device is used for freezing and crystallizing acidolysis solution;
the second solid-liquid separation device is used for carrying out solid-liquid separation on acidolysis solution of the freezing crystallization device so as to obtain a first solution and solid-phase calcium nitrate crystal hydrate;
the decalcification reaction device is used for reacting the first solution with the nitric acid solution;
the third solid-liquid separation device is also used for carrying out solid-liquid separation on the product of the decalcification reaction so as to obtain a second solution and solid-phase calcium sulfate;
the denitration device is used for concentrating and denitrating the second solution to obtain a concentrated and denitrated third solution and nitric acid;
the extraction device is used for extracting the third solution by using an organic extraction solvent so as to remove metal ions in the third solution;
the washing device is positioned between the extraction device and the back extraction device and is used for washing the extracted phase extracted by the extraction device; combining the washing solution and the raffinate phase to obtain a phosphoric acid solution;
the back extraction device is used for carrying out back extraction on an organic extraction solvent containing metal ions, namely an extraction phase, so as to obtain a phosphoric acid solution;
the ferric phosphate reaction device is used for reacting the phosphoric acid solution with an iron source to generate ferric phosphate;
and a fifth solid-liquid separation device for carrying out solid-liquid separation on the reaction product of the ferric phosphate reaction device, and taking the solid phase component as the ferric phosphate product containing crystal water.
The denitration device is connected with the acidolysis reaction device and is used for enabling nitric acid generated in the evaporation denitration to enter the acidolysis tank for acidolysis.
The system further comprises:
and the calcining device is used for calcining the solid phase component separated by the fifth solid-liquid separation device to obtain an anhydrous ferric phosphate product.
And in some embodiments, the extraction apparatus comprises one of a rotating disk extraction column, a multistage centrifugal extraction column, a vibrating screen tray column, or a screen tray extraction column.
In some embodiments, the first solid-liquid separation device, the second solid-liquid separation device, and the third solid-liquid separation device are separate devices or apparatuses that are independent of each other; or in yet other embodiments the first, second, and third solid-liquid separation devices are common separation devices or apparatuses, and the separation processes of the first, second, and third solid-liquid separation devices are performed in sequence in different steps, respectively. In some specific embodiments, the first, second, and third solid-liquid separation devices may include a settling tank, a filter press, a suction filter, and the like.
The system of the invention is used for producing and preparing the high-purity ferric phosphate by partially utilizing and improving the existing nitrophosphate system; the byproducts in the production process can be directly used for preparing fertilizer or used as independent products, and no waste is generated.
A method of co-producing ferric phosphate in yet another embodiment of the invention is shown in fig. 5, the method comprising:
s10, acidolysis is carried out on phosphorite raw materials by nitric acid or mixed acid containing nitric acid, and acid insoluble substances are separated and removed to obtain acidolysis solution;
s20, freezing and crystallizing calcium nitrate from acidolysis solution, and filtering out the crystallized calcium nitrate to obtain a first solution;
s30, adding a sulfate-containing solution into the first solution, and further removing calcium to obtain a second solution;
s40, concentrating the second solution to volatilize excessive nitric acid from the second solution, so as to obtain a concentrated and denitrated third solution;
s50, adding ammonia such as ammonia gas, liquid ammonia or ammonia water into the third solution obtained in the step S40, performing a neutralization reaction, and filtering to obtain a solution of ammonium phosphate salt;
and S60, adding an iron source into the ammonium phosphate salt solution obtained in the step S50 for reaction, and obtaining an iron phosphate product after solid-liquid separation.
And in step S60, reacting at least one of iron source such as ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, ferric chloride, or elemental iron such as iron powder, with the ammonium phosphate solution obtained in step S50 to obtain ferric phosphate.
In the same manner as in step S60, the pH of the reaction system is preferably controlled to be in the range of 4 to 6.
And in a preferred embodiment, the neutralization reaction by adding ammonia in step S50 can produce the desired target product ammonium phosphate salt by neutralization; on the other hand, the pH value of the system is gradually increased in the neutralization reaction process, partial metal ions such as calcium, magnesium, manganese and the like can form solid phase precipitation, which is favorable for reducing and reducing impurities in ammonium phosphate products, and then the ammonium phosphate with higher purity is obtained after impurity removal and concentration.
Further in a more preferred embodiment, the solid phase component separated by filtration in step S50 is mainly a phosphate containing calcium, magnesium, manganese; and then the elements are used as elements of the nitrophosphate fertilizer to prepare the nitrophosphate fertilizer.
In a more preferred embodiment, ammonia gas is introduced into the third solution in step S50 to perform a neutralization reaction until the pH of the system reaches 6 or more. Preferably, when the pH of the system reaches above 6, the impurity metal ions in the system such as calcium, magnesium, manganese and the like form precipitates in the form of phosphate, which is advantageous for reducing the impurity to raise the purity of ammonium phosphate salt.
Further in still other embodiments, in step S50, ammonia is added to the third solution to neutralize the pH of the reaction system, such that the pH of the neutralization reaction system is adjustable between 4 and 7, depending on the ratio or demand of monoammonium phosphate, diammonium phosphate, and ammonium phosphate in the desired ammonium phosphate product; the proportion of monoammonium phosphate, diammonium phosphate and ammonium phosphate in the prepared product can be adjusted by adjusting the pH range of the neutralization reaction system to different intervals.
Yet another embodiment of the present invention also provides a system for co-producing ferric phosphate, as shown in fig. 5, comprising:
acidolysis reaction device for acidolysis of phosphorite material with nitric acid or mixed acid;
the first solid-liquid separation device is used for carrying out solid-liquid separation on acidolysis slurry after acidolysis so as to obtain acidolysis solution;
the freezing and crystallizing device is used for freezing and crystallizing acidolysis solution;
the second solid-liquid separation device is used for carrying out solid-liquid separation on acidolysis solution of the freezing crystallization device so as to obtain a first solution and solid-phase calcium nitrate crystal hydrate;
decalcification reaction means for reacting the first solution with a sulfate group-containing solution such as sulfuric acid or ammonium sulfate;
the third solid-liquid separation device is also used for carrying out solid-liquid separation on the product of the decalcification reaction so as to obtain a second solution and solid-phase calcium sulfate;
the denitration device is used for concentrating and denitrating the second solution to obtain a concentrated and denitrated third solution and nitric acid;
neutralization means for neutralizing the third solution with ammonia;
the fourth solid-liquid separation device is used for filtering and separating a system after the neutralization reaction, and the liquid phase is ammonium phosphate salt solution;
the ferric phosphate reaction device is used for reacting the ammonium phosphate salt solution with an iron source to generate ferric phosphate;
and a fifth solid-liquid separation device for carrying out solid-liquid separation on the reaction product of the ferric phosphate reaction device to obtain a solid phase component, namely the ferric phosphate product containing crystal water.
The denitration device is connected with the acidolysis reaction device and is used for enabling nitric acid generated in the evaporation denitration to enter the acidolysis tank for acidolysis.
In some embodiments, the first solid-liquid separation device, the second solid-liquid separation device, the third solid-liquid separation device, the fourth solid-liquid separation device, the fifth solid-liquid separation device are separate devices or apparatuses independent of each other; or in still other embodiments, the first solid-liquid separation device, the second solid-liquid separation device, the third solid-liquid separation device, the fourth solid-liquid separation device, and the fifth solid-liquid separation device are a common separation device or apparatus, and the separation processes of the first solid-liquid separation device, the second solid-liquid separation device, the third solid-liquid separation device, the fourth solid-liquid separation device, and the fifth solid-liquid separation device are sequentially performed in different steps. In some specific embodiments, the first solid-liquid separation device, the second solid-liquid separation device, the third solid-liquid separation device, the fourth solid-liquid separation device, the fifth solid-liquid separation device may include a settling tank, a filter press, a suction filter, and the like.
In a preferred embodiment, the denitration device includes at least: a receiving chamber for receiving or receiving a second solution; and a heater for heating and evaporating the second solution.
In a more preferred embodiment, the heater is a resistive heater; and is configured in operation to heat the second solution to 120-180 ℃ for evaporation.
The system further comprises:
and the calcining device is used for calcining the solid phase component separated by the fifth solid-liquid separation device to obtain an anhydrous ferric phosphate product.
To demonstrate the efficiency of the present invention in the preparation of iron phosphate products, example 1 below shows the material usage and yield of the preparation process in one embodiment, including:
s10, the mass 2t contains 34% of P 2 O 5 The phosphate concentrate (containing about 45.58% of impurity calcium, about 0.77% of impurity magnesium oxide, and about 1-5% of other impurities such as iron, aluminum, silicon and fluorine) is acidolyzed with 2.4t (0.53 tN) of folded nitric acid, and the acidolyzed slurry is subjected to solid-liquid separation to obtain 0.09t of acid insoluble matters (containing raw materials of calcium and magnesium silicate) and acidolyzed solution; and acid insoluble matter is washed for 2 to 3 times by water, and the washing solution is combined into acidolysis solution;
s20, freezing the acid liquor to a temperature of minus 10 ℃ to minus 5 ℃ for crystallization, vacuum filtering the frozen solution at a temperature of minus 2 ℃ to 1 ℃ to obtain 3.54t of 60 percent crude calcium nitrate liquor crystal and 2.186t of first solution (0.635 tP) 2 O 5 ）；
S30, adding sulfuric acid 0.349t into the first solution, and performing deep solid-liquid separation to obtain calcium sulfate hemihydrate 0.51t and 2.055t of second solution (0.635 tP 2 O 5 ）
S40, evaporating, concentrating and removing nitric acid from the second solution at 160-170 ℃ until nitrate ions in the system are less than 0.1%, stopping the reaction, and recovering to obtain 0.473t of furfurfurhundred nitric acid and a third solution;
s50, carrying out multistage cross-flow extraction on the third solution in an extraction tower by using an organic extraction solvent (1-volume mixing of n-butanol and isoamyl alcohol) with the volume of 1 times of the third solution, washing an extraction phase by using water, carrying out back extraction by using pure water finally, and separating after the back extraction to obtain a phosphoric acid solution;
s60, preparing an iron source: dissolving the purchased 85% ferrous sulfate heptahydrate with the weight of 2.3t with pure water, filtering to remove impurities, neutralizing the solution, adding 25% ammonia water for 0.93t, and filtering to remove impurities again to obtain an iron salt solution;
the ferric salt solution reacts with phosphoric acid solution which is reversely extracted and separated in the step S50, the pH value of a reaction system is controlled to be 4-6, after the reaction is completely and fully precipitated, solid-liquid separation is carried out through pressure filtration, and a solid-phase filter cake containing 0.335t of ferric phosphate with crystal water (containing 0.13t of P therein) is obtained through separation 2 O 5 ）；
Further drying the ferric phosphate containing the crystal water, and removing the crystal water to obtain anhydrous ferric phosphate of 0.27t; p in anhydrous ferric phosphate 2 O 5 At a level of 48%, about 0.13tP 2 O 5 。
And S70, concentrating the liquid phase component obtained by the solid-liquid separation in the step S60 to prepare the nitrophosphate fertilizer.
Example 2 below shows the material usage and throughput of the manufacturing process in one embodiment, including:
s10, the mass 2t contains 34% of P 2 O 5 The phosphate concentrate (containing about 45.58% of impurity calcium, about 0.77% of impurity magnesium oxide, and about 1-5% of other impurities such as iron, aluminum, silicon and fluorine) is acidolyzed with 2.4t (0.53 tN) of folded nitric acid, and the acidolyzed slurry is subjected to solid-liquid separation to obtain 0.09t of acid insoluble matters (containing raw materials of calcium and magnesium silicate) and acidolyzed solution; and acid insoluble matter is washed for 2 to 3 times by water, and the washing solution is combined into acidolysis solution;
s20, freezing the acid liquor to a temperature of between 10 ℃ below zero and 5 ℃ below zero for crystallization, vacuum filtering the cooling solution at a temperature of between 2 ℃ below zero and 1 ℃ below zero, and separating to obtain 60% crude calcium nitrate liquor crystals of 3.54t and 2.186t of a first solution (0.635 tP 2 O 5 ）；
S30, adding sulfuric acid 0.349t into the first solution, and performing deep solid-liquid separation to obtain calcium sulfate hemihydrate 0.51t and 2.055t of second solution (0.635 tP 2 O 5 ）
S40, concentrating and removing nitric acid from the second solution, and recovering to obtain 0.473t of folded hundred nitric acid and a third solution;
s50, gradually adding 0.007t of liquid ammonia into the third solution to perform a neutralization reaction until the pH value of a neutralization reaction system is controlled to be 4.2-4.8 and the reaction is completed, and separating a liquid phase component to be an ammonium phosphate solution;
s60, preparing an iron source: dissolving the purchased 85% ferrous sulfate heptahydrate with the weight of 2.3t with pure water, filtering to remove impurities, neutralizing the solution, adding 25% ammonia water for 0.93t, and filtering to remove impurities again to obtain an iron salt solution;
gradually adding ferric salt solution into the ammonium phosphate salt solution in the step S50, controlling the pH value of a reaction system to be 4-6, and fully precipitating after the reactionFilter-pressing, solid-liquid separation, and obtaining solid phase filter cake of ferric phosphate 1.24t (containing P) containing crystal water 2 O 5 0.48 t); after further calcination to remove crystal water, anhydrous ferric phosphate iron phosphate product 1t (containing P is obtained 2 O 5 48%).
The foregoing embodiments and the specific schemes are not limited to the scope of the invention, and all equivalent structures or equivalent flow changes made by the content of the present disclosure, or direct or indirect application in other related technical fields are included in the scope of the invention.

Claims (8)

1. The method for co-producing the ferric phosphate by the nitrophosphate device is characterized by comprising the following steps of:
acidolysis is carried out on phosphorite or phosphate concentrate by nitric acid, and acid insoluble matters are separated to obtain acidolysis solution;
freezing and crystallizing the acidolysis solution, and carrying out solid-liquid separation to obtain a first solution;
adding the first solution into a solution containing sulfate radicals for reaction, and carrying out solid-liquid separation to obtain a second solution A; and/or adding sulfuric acid into the first solution for reaction, and carrying out solid-liquid separation to obtain a second solution B;
performing nitrite removal treatment on the second solution A and/or the second solution B to obtain a third solution A and/or a third solution B;
adding ammonia into the third solution A for neutralization, carrying out solid separation on the neutralized solution to obtain ammonium phosphate solution, and adding an iron source into the ammonium phosphate solution for reaction to obtain ferric phosphate;
and/or extracting the third solution B by an extraction solvent to obtain an extraction phase; back-extracting the extract phase to obtain phosphoric acid solution; and (3) obtaining ferric phosphate by reacting an iron source with the phosphoric acid solution.
2. The method for co-producing iron phosphate by a nitrophosphate device of claim 1, wherein the iron source comprises at least one of an iron salt, a ferrous salt, or elemental iron, and the sulfate-containing solution is at least one of a sulfuric acid solution and an ammonium sulfate solution.
3. The method for co-producing iron phosphate by means of a nitrophosphate device according to claim 1 or 2, wherein the pH value of the reaction system is controlled to be between 4 and 6 in the reaction of the iron source with the phosphoric acid solution.
4. The method for co-producing iron phosphate by means of a nitrophosphate device according to claim 1 or 2, characterized in that the concentration of nitrate in the third solution a and the third solution B is lower than 1%; more preferably, the concentration of nitrate in the third solution is less than 0.5%; more preferably, the concentration of nitrate in the third solution is less than 0.1%.
5. The method for co-producing iron phosphate by a nitrophosphate device according to claim 1 or 2, wherein in the extraction of the third solution B by an extraction solvent, the volume ratio of the extraction solvent to the third solution B is 0.5-5:1.
6. The method for co-producing iron phosphate by a nitrophosphate device of claim 1, wherein the ammonia comprises at least one of ammonia gas, liquid ammonia, or aqueous ammonia.
7. An iron phosphate product produced by the method of co-producing iron phosphate by a nitrophosphate device according to any one of claims 1 to 6.
8. A system for co-producing iron phosphate by means of a nitrophosphate device, comprising:
the acidolysis reaction device is used for carrying out acidolysis reaction on phosphorite by nitric acid;
the first solid-liquid separation device is used for carrying out solid-liquid separation on acidolysis slurry after acidolysis so as to obtain acidolysis solution;
the freezing and crystallizing device is used for freezing and crystallizing the acidolysis solution;
the second solid-liquid separation device is used for carrying out solid-liquid separation on the acidolysis solution of the frozen crystals so as to obtain a first solution;
decalcification reaction device for reacting the first solution with sulfate-containing solution;
the third solid-liquid separation device is also used for carrying out solid-liquid separation on the product of the decalcification reaction device so as to obtain a second solution;
the denitration device is used for evaporating the second solution to remove nitrate radical so as to obtain a third solution;
the extraction device is used for extracting the third solution by using an extraction solvent to obtain an extraction phase;
the back extraction device is used for back extracting the extraction phase to obtain phosphoric acid;
an iron phosphate reaction device for preparing iron phosphate by reacting an iron source with the phosphoric acid or ammonium phosphate salt solution,
a fifth solid-liquid separation device for performing solid separation on the solution obtained by reacting the iron source with the phosphoric acid or ammonium phosphate solution to obtain a solid product of ferric phosphate;
and/or the system is provided with a neutralization device and a fourth solid-liquid separation device, wherein the neutralization device is used for carrying out neutralization reaction on the third solution and ammonia to obtain a neutralization reaction solution, and the fourth solid-liquid separation device is used for carrying out solid-liquid separation on the neutralization reaction solution to obtain an ammonium phosphate salt solution.
CN202210006335.9A 2022-01-05 2022-01-05 Method, product and system for co-producing ferric phosphate through nitrophosphate device Pending CN116443832A (en)

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WO2023246540A1 (en) * 2022-06-20 2023-12-28 贵州芭田生态工程有限公司 Method for iron phosphate co-production by means of nitrophosphate fertilizer apparatus, product and system

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CN102718200A (en) * 2012-07-10 2012-10-10 中海石油化学股份有限公司 Method for preparing industrial-grade phosphoric acid by decomposing mid-low-grade phosphorite with nitric acid
CN113184819A (en) * 2021-04-12 2021-07-30 深圳市德方纳米科技股份有限公司 Method for preparing iron phosphate by utilizing phosphorite and preparation method of lithium iron phosphate
CN217350773U (en) * 2022-01-05 2022-09-02 贵州芭田生态工程有限公司 System for coproduction iron phosphate through nitrophosphate fertilizer device

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CN102718200A (en) * 2012-07-10 2012-10-10 中海石油化学股份有限公司 Method for preparing industrial-grade phosphoric acid by decomposing mid-low-grade phosphorite with nitric acid
CN113184819A (en) * 2021-04-12 2021-07-30 深圳市德方纳米科技股份有限公司 Method for preparing iron phosphate by utilizing phosphorite and preparation method of lithium iron phosphate
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