CN114436229A - Preparation method for preparing phosphoric acid and byproduct nitrophosphate fertilizer from phosphorite - Google Patents
Preparation method for preparing phosphoric acid and byproduct nitrophosphate fertilizer from phosphorite Download PDFInfo
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- CN114436229A CN114436229A CN202210111828.9A CN202210111828A CN114436229A CN 114436229 A CN114436229 A CN 114436229A CN 202210111828 A CN202210111828 A CN 202210111828A CN 114436229 A CN114436229 A CN 114436229A
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000002367 phosphate rock Substances 0.000 title claims abstract description 39
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 36
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000003337 fertilizer Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000006227 byproduct Substances 0.000 title claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000605 extraction Methods 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 238000001704 evaporation Methods 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 19
- 239000012141 concentrate Substances 0.000 claims abstract description 19
- 239000010452 phosphate Substances 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 230000008014 freezing Effects 0.000 claims abstract description 13
- 238000007710 freezing Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 81
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 29
- 229910017604 nitric acid Inorganic materials 0.000 claims description 29
- 230000008020 evaporation Effects 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229910001424 calcium ion Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 4
- NGLMYMJASOJOJY-UHFFFAOYSA-O azanium;calcium;nitrate Chemical compound [NH4+].[Ca].[O-][N+]([O-])=O NGLMYMJASOJOJY-UHFFFAOYSA-O 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000003516 soil conditioner Substances 0.000 claims description 4
- 239000012045 crude solution Substances 0.000 claims description 2
- VXAPDXVBDZRZKP-UHFFFAOYSA-N nitric acid phosphoric acid Chemical compound O[N+]([O-])=O.OP(O)(O)=O VXAPDXVBDZRZKP-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 9
- 238000003825 pressing Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910021655 trace metal ion Inorganic materials 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/2208—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with an acid or a mixture of acids other than sulfuric acid
- C01B25/2216—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with an acid or a mixture of acids other than sulfuric acid with nitric acid or nitrous vapours in aqueous medium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/238—Cationic impurities, e.g. arsenic compounds
-
- 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
- C01B25/46—Preparation involving solvent-solvent extraction
-
- 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
- C05C—NITROGENOUS FERTILISERS
- C05C1/00—Ammonium nitrate fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
- C05G5/23—Solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Fertilizers (AREA)
Abstract
The invention relates to the technical field of processing of phosphorite or phosphate concentrate, in particular to a preparation method for preparing phosphoric acid and by-producing nitrophosphate fertilizer by phosphorite, which comprises the following steps: s1, carrying out acidolysis reaction on phosphorite or phosphate concentrate, and filtering to obtain acidolysis solution; s2, freezing and crystallizing the acidolysis solution, and filtering at low temperature to obtain a first solid and a first solution; s3, adding a sulfuric acid solution into the first solution for reaction, and filtering to obtain a second solid and a second solution; s4, evaporating and condensing the second solution to obtain a third solution and a fourth solution at the same time; s5, extracting the fourth solution by an extracting agent to obtain an extraction liquid and a raffinate; s6, back extraction: carrying out back extraction after the extractant containing phosphoric acid is finally extracted, and concentrating the extracted solution to obtain phosphoric acid; the method realizes the balance of materials in each link, and the generated byproducts can be recycled or can be used as raw materials of fertilizers for preparing the fertilizers and meet the requirements of industrial products.
Description
Technical Field
The invention relates to the technical field of processing of phosphorite or phosphate concentrate, in particular to a preparation method for preparing phosphoric acid and by-producing nitrophosphate fertilizer from phosphorite.
Background
In the known phosphate rock processing technology, phosphate rock is decomposed by nitric acid or mixed acid, impurities in the phosphate rock are removed by freezing and crystallizing treatment, and then the phosphate rock is prepared.
Disclosure of Invention
In order to solve the problems, the invention aims to disclose the technical field of processing of phosphorite or phosphate concentrate, in particular to a preparation method for preparing phosphoric acid and by-producing nitrophosphate fertilizer by phosphorite.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method for preparing phosphoric acid and a byproduct of nitrophosphate fertilizer from phosphorite is characterized by comprising the following steps:
s1, adding the phosphorite or the phosphate concentrate into nitric acid, carrying out acidolysis reaction, filtering, and filtering acid insoluble substances to obtain acidolysis solution, wherein the mass ratio of the nitric acid to the phosphorite or the phosphate concentrate is 1-5:1, and the mass concentration of the nitric acid is 45-70%;
s2, freezing and crystallizing the acidolysis solution to obtain a first solid-liquid mixture, filtering at low temperature to obtain a first solid and a first solution, wherein the temperature of freezing and crystallizing is-8 ℃ to-5 ℃ for 5-6h, the temperature of filtering at low temperature is-4 ℃ to-3 ℃, filtering at low temperature, washing, and returning the washing solution to the acidolysis solution, preferably, filtering at low temperature under vacuum;
s3, decalcification with sulfuric acid: adding a sulfuric acid solution into the first solution to obtain a second solid-liquid mixture, and then filtering to obtain a second solid and a second solution, wherein the addition amount of the sulfuric acid solution is calculated according to the calcium ion content in the first solution, and the molar weight of sulfate radicals in the sulfuric acid solution is 80-99% of the molar weight of calcium ions in the first solution;
s4, evaporation and condensation: evaporating and condensing the second solution, condensing the evaporated nitric acid to obtain a third solution, wherein the remaining solution after evaporation is a fourth solution, the evaporation pressure is-7 KPa to-4 KPa, the temperature is 120-160-;
s5, extraction reaction: extracting the fourth solution with an extractant to obtain an extract and a raffinate; wherein the extraction agent is recovered from the raffinate, the extraction agent is recycled, and the mass ratio of the extraction agent to the fourth solution is 1-3: 1;
s6, back extraction: and (3) carrying out back extraction on the final extract with water to obtain a phosphoric acid aqueous solution and raffinate, wherein the mass ratio of the water to the extract is 1:2-4, the raffinate is circularly used in the extraction stage of S5, and the phosphoric acid aqueous solution is concentrated to obtain phosphoric acid.
Preferably, in the above preparation method, the acid-insoluble substance obtained by the reaction in step S1 is used for preparing a soil conditioner.
Preferably, in the preparation method, the concentration of the nitric acid solution added in the step S1 is 55-65%, and the mass ratio of the addition amount of the nitric acid solution to the phosphorite or the phosphate concentrate is 1-3: 1.
Preferably, in the above production method, ammonium nitrate is added to the first solid to produce a calcium ammonium nitrate fertilizer.
Preferably, in the preparation method, when the evaporation and condensation are performed in the step S4, the evaporation temperature is 130-150 ℃, the pressure is-6 KPa to-6 KPa, and the time is 3-4h, the third solution is recycled to be used as the acid hydrolysis liquid for acid hydrolysis of phosphorite or phosphate concentrate in the step S1, and the fourth solution is a phosphoric acid crude solution with low-concentration nitrate.
Preferably, in the above preparation method, in the step S5, the extraction solution is recovered to obtain a solution containing metal ions, the solution is used for preparing a nitrophosphate fertilizer, and the recovered extraction agent is recycled.
Preferably, in the preparation method, in the step S5, the extractant includes tributyl phosphate, n-butanol, and isoamyl alcohol, and the mass ratio of the tributyl phosphate, the n-butanol, and the isoamyl alcohol is 1-10:1-10: 1-10.
Preferably, in the preparation method, the phosphorite or the phosphate concentrate of the step S1 is a calcined ore or a non-calcined ore, preferably, the phosphorite is a high-quality phosphorite or a low-quality phosphorite, and the phosphate concentrate is a phosphate concentrate subjected to calcination to remove calcium and magnesium.
Preferably, in the above preparation method, the fourth solution is decolorized to remove organic substances carbonized therein.
Preferably, in the above preparation method, a decolorizing agent is applied to the back-extracted fifth solution for decolorizing, and carbonized organic matters are removed therefrom. Preferably, the content of the decoloring agent by mass relative to the volume of the fifth solution is 10 to 30 g/L.
The invention has the following beneficial effects: the phosphoric acid preparation method provided by the invention realizes high efficiency and high quality of phosphoric acid preparation, simultaneously fully utilizes the process flow and equipment of the nitrophosphate fertilizer, can efficiently utilize byproducts, and the byproducts generated in each link can be recycled or can be used as a raw material of the fertilizer to prepare the fertilizer, and meet the requirements of fertilizer products; in the process, nitric acid can be recycled, high-quality calcium sulfate is produced as a byproduct, and the extracting agent can be recycled. The invention strictly controls the material proportion and the treatment condition of each link, thereby obtaining excellent phosphoric acid, and the whole process of phosphoric acid production can recycle by-products, or the by-products can be used as raw materials of fertilizers, and no waste is generated.
The technological conditions of each section of the invention are fully matched, thereby realizing high yield and high quality of phosphoric acid, fully utilizing the by-products and realizing the recycling of nitric acid and extractant.
Detailed Description
Example 1:
a preparation method for preparing phosphoric acid and a byproduct of nitrophosphate fertilizer from phosphorite comprises the following steps:
s1, acidolysis filtration: adding nitric acid into the calcined phosphate concentrate to perform acidolysis reaction, then filtering, namely filter pressing, wherein solid acid insoluble substances are obtained by filter pressing, the acid insoluble substances are used for producing a soil conditioner, the liquid obtained by filter pressing is acidolysis liquid, the mass ratio of the phosphate concentrate to the nitric acid is 1:1.2, and the mass concentration of the nitric acid is 65%.
S2, freezing and crystallizing: freezing and crystallizing the acidolysis solution generated in the step S1 at the temperature of minus 5 ℃, filtering a solid-liquid mixture obtained by freezing and crystallizing at the low temperature of minus 3 ℃ to obtain solid calcium nitrate crystals, washing the calcium nitrate crystals with dilute nitric acid at the low temperature, and returning the obtained washing liquid to the nitric acid in the step S1. Adding ammonium nitrate into calcium nitrate crystals, and preparing calcium ammonium nitrate granular fertilizer by high tower granulation;
s3, adding sulfuric acid: s2, adding a sulfuric acid solution with the mass concentration of 80% into the filtrate, measuring the molar weight of calcium ions in the filtrate before adding the sulfuric acid solution, adding the sulfuric acid solution according to the molar weight of the calcium ions to enable the molar weight of sulfate radicals of the added sulfuric acid solution to be 98% of the molar weight of the calcium ions, reacting after adding the sulfuric acid to obtain a solid-liquid mixture, carrying out filter pressing on the solid-liquid mixture to obtain solid calcium sulfate and filtrate, washing the solid calcium sulfate with water, and using a washing liquid to dilute concentrated sulfuric acid.
S4, evaporation and condensation: evaporating and condensing the filtrate of the step S3 at 140 ℃, the pressure of-5 KPa and the evaporation time of 4 hours, condensing the evaporated nitric acid, circularly sleeving the condensed nitric acid in the step S1 for acidolysis of phosphate concentrate, and evaporating the residual solution for next step treatment.
S5, extraction reaction: adding an extracting agent into the solution left after evaporation in the step S4, wherein the extracting agent is a mixture of tributyl phosphate, n-butyl alcohol and isoamyl alcohol in a mass ratio of 1:1:1, the mass ratio of the extracting agent to the solution left after evaporation is 2:1, performing multistage cross-flow extraction in an extraction tower, using an extracted phase obtained in the next step, recovering the extracting agent from an extracted raffinate through evaporation and condensation, circularly sleeving the recovered extracting agent for extraction reaction, and using the solution obtained after evaporation of the extracting agent as an aqueous solution containing metal ions which is used as a raw material of a medium-trace element fertilizer and is a high-quality fertilizer raw material because the aqueous solution contains rich medium-trace metal ions.
S6, back extraction: and adding water into the extract phase of the S5 for back extraction, wherein the mass ratio of the solution of the extract phase to the water is 2:1, the back extraction is also carried out multistage cross-flow extraction in an extraction tower, the extract phase of the back extraction is an aqueous solution containing phosphoric acid, raffinate is a solvent containing an extracting agent, the solution is used for the step S5, the extracting agent is recycled, and the aqueous solution containing phosphoric acid is concentrated to obtain high-purity phosphoric acid.
Example 2:
a preparation method for preparing phosphoric acid and a byproduct of nitrophosphate fertilizer from phosphorite mainly comprises the following steps:
s1, acidolysis and filtration: adding nitric acid into high-quality phosphorite for acidolysis reaction, then filtering, namely filter pressing, obtaining solid acid insoluble substances by filter pressing, wherein the acid insoluble substances are used for producing a soil conditioner, and obtaining liquid by filter pressing, namely acidolysis liquid. The mass ratio of the phosphorite to the nitric acid is 1:1.3, and the mass concentration of the nitric acid is 65%.
S2, freezing and crystallizing: freezing and crystallizing the acidolysis solution generated in the step S1 at the temperature of minus 5 ℃, filtering a solid-liquid mixture obtained by freezing and crystallizing at the low temperature of minus 3 ℃ to obtain solid calcium nitrate crystals, washing the calcium nitrate crystals with dilute nitric acid at the low temperature, and returning the obtained washing liquid to the nitric acid in the step S1. Adding ammonium nitrate into calcium nitrate crystals, and preparing calcium ammonium nitrate granular fertilizer by high tower granulation;
s3, adding sulfuric acid: s2, adding a sulfuric acid solution with a mass concentration of 80% into the filtrate, measuring the molar weight of calcium ions in the filtrate before adding the sulfuric acid solution, adding the sulfuric acid solution according to the molar weight of the calcium ions to enable the molar weight of sulfate radicals of the added sulfuric acid solution to be 98% of the molar weight of the calcium ions, reacting after adding sulfuric acid to obtain a solid-liquid mixture, carrying out filter pressing on the solid-liquid mixture to obtain solid calcium sulfate and filtrate, washing the solid calcium sulfate with water, and using the washing liquid to dilute concentrated sulfuric acid.
S4, evaporation and condensation: evaporating and condensing the filtrate of the S3 at the temperature of 150 ℃, the pressure of-6 KPa and the evaporation time of 3 hours, condensing the evaporated nitric acid, circularly using the condensed nitric acid for acidolysis of phosphorite in the step S1, and evaporating the residual solution for next treatment.
S5, extraction reaction: adding an extracting agent into the solution left after evaporation in the step S4, wherein the extracting agent is a mixture of tributyl phosphate, n-butyl alcohol and isoamyl alcohol in a mass ratio of 1:1:1, the mass ratio of the extracting agent to the solution left after evaporation is 2:1, performing multistage cross-flow extraction in an extraction tower, using an extraction phase (extraction liquid) obtained by extraction in the next step, recovering the extracting agent from the extracted raffinate through evaporation and condensation, circularly sleeving the recovered extracting agent for extraction reaction, and using the solution obtained by evaporation of the extracting agent as an aqueous solution containing metal ions which is used as a raw material of a medium-trace element fertilizer and is a high-quality fertilizer raw material because the aqueous solution contains rich medium-trace metal ions.
S6, back extraction: adding water into an extract phase (extract liquid) of S5 for back extraction, wherein the mass ratio of the extract liquid to the water is 2:1, the back extraction is also carried out multistage cross-flow extraction in an extraction tower, the extract phase of the back extraction is a water phase, the water phase is a phosphoric acid-containing water solution, raffinate is a solvent containing an extracting agent, the solution is used in the step S5, the extracting agent is recycled, the phosphoric acid-containing water solution is decolorized, the decolorizing agent is a mixture of active carbon, diatomite, sepiolite fibers and sodium sulfide, the mass ratio of the decolorizing agent to the volume of the phosphoric acid water solution is 10:10:1:3, the content of the decolorizing agent relative to the volume of the phosphoric acid water solution is 20g/L, the decolorizing agent is filtered after 30 minutes of decolorization, and filtrate is concentrated to obtain the high-purity phosphoric acid.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, and those skilled in the art may make modifications and variations within the spirit of the present invention, and all modifications, equivalents and modifications of the above embodiments according to the technical spirit of the present invention are within the scope of the present invention.
Claims (10)
1. A preparation method for preparing phosphoric acid and a byproduct of nitrophosphate fertilizer from phosphorite is characterized by comprising the following steps:
s1, acidolysis filtration: adding the phosphorite or phosphate concentrate into nitric acid, carrying out acidolysis reaction, filtering to remove acid insoluble substances to obtain acidolysis solution, wherein the mass ratio of the nitric acid to the phosphorite or phosphate concentrate is 1-5:1, and the mass concentration of the nitric acid is 45-70%;
s2, freezing and crystallizing: freezing and crystallizing the acidolysis solution to obtain a first solid-liquid mixture, filtering at low temperature to obtain a first solid and a first solution, wherein the temperature of freezing and crystallizing is-15 ℃ to-5 ℃ for 5-6 hours, the temperature of filtering at low temperature is-5 ℃ to-1 ℃, filtering at low temperature and washing, and returning the washing solution to the acidolysis solution, preferably, filtering at low temperature under vacuum;
s3, decalcification with sulfuric acid: adding a sulfuric acid solution into the first solution to obtain a second solid-liquid mixture, and then filtering to obtain a second solid and a second solution, wherein the addition amount of the sulfuric acid solution is calculated according to the calcium ion content in the first solution, and the molar weight of sulfate radicals in the sulfuric acid solution is 80-99% of the molar weight of calcium ions in the first solution;
s4, evaporation and condensation: evaporating and condensing the second solution, condensing the evaporated nitric acid to obtain a third solution, wherein the solution remained after evaporation is a fourth solution, the evaporation pressure is-7 KPa to-4 KPa, the temperature is 120-160 ℃, and the time is 2-5 h;
s5, extraction reaction: extracting the fourth solution with an extractant to obtain an extract and a raffinate; wherein the extraction agent is recovered from the raffinate, the extraction agent is recycled, and the mass ratio of the extraction agent to the fourth solution is 1-3: 1;
s6, back extraction: and (3) carrying out back extraction on the final extract with water to obtain a phosphoric acid aqueous solution and raffinate, wherein the mass ratio of the water to the extract is 1:2-4, the raffinate is circularly used in the extraction stage of S5 and is used as an extractant of S5, and the phosphoric acid aqueous solution is concentrated to obtain phosphoric acid.
2. The method for preparing phosphoric acid and a nitrophosphate fertilizer byproduct from phosphorite as claimed in claim 1, wherein the acid-insoluble substance obtained from the reaction of step S1 is used for preparing a soil conditioner.
3. The method for preparing phosphoric acid and a byproduct of nitrophosphate fertilizer from phosphorite as claimed in claim 2, wherein the concentration of the nitric acid solution added in the step S1 is 55% -65%, and the mass ratio of the addition amount of the nitric acid solution to the phosphorite or the phosphate concentrate is 1-3: 1.
4. The method for preparing phosphoric acid and a byproduct of nitrophosphate fertilizer from phosphorite as claimed in claim 3, characterized in that ammonium nitrate is added to the first solid to prepare calcium ammonium nitrate fertilizer.
5. The method as claimed in claim 4, wherein the temperature of evaporation is 130-150 ℃ and the pressure is-6 KPa to-6 KPa for 3-4h when the phosphate rock is evaporated and condensed in step S4, the third solution is recycled as the acid hydrolysis solution to perform acid hydrolysis on phosphate rock or phosphate concentrate in step S1, and the fourth solution is a crude solution of low-concentration nitrate phosphoric acid.
6. The method of claim 1, wherein in step S5, the extraction solution is recovered with an extractant to obtain a solution containing metal ions, which is used for preparing nitrophosphate, and the recovered extractant is recycled.
7. The method of claim 1, wherein in the step S5, the extractant comprises tributyl phosphate, n-butanol, and isoamyl alcohol, and the mass ratio of tributyl phosphate, n-butanol, and isoamyl alcohol is 1-10:1-10: 1-10.
8. The method for preparing phosphoric acid and a byproduct of nitrophosphate fertilizer from phosphorite as claimed in claim 1, characterized in that the phosphorite or phosphate concentrate of step S1 is non-calcined ore.
9. The method as claimed in claim 8, wherein the fourth solution is decolorized to remove organic substances carbonized in the fourth solution.
10. The method for preparing phosphoric acid and a byproduct of nitrophosphate fertilizer from phosphorite as claimed in claim 8, wherein a decolorizing agent is applied to the back-extracted fifth solution for decolorizing and removing carbonized organic matters.
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| CN115215309A (en) * | 2022-07-11 | 2022-10-21 | 四川顺应动力电池材料有限公司 | Method for producing industrial-grade phosphoric acid and recycling industrial-grade phosphoric acid by phosphorite-nitric acid method |
| CN116002740A (en) * | 2022-12-30 | 2023-04-25 | 贵州芭田生态工程有限公司 | Method for preparing and purifying calcium sulfate in nitric acid solution |
| CN116902947A (en) * | 2022-06-20 | 2023-10-20 | 贵州芭田生态工程有限公司 | Method for preparing lithium iron phosphate by using high-purity phosphoric acid |
| 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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