CN116443829A - Method, product and system for co-producing phosphoric acid through nitric phosphate fertilizer device - Google Patents
Method, product and system for co-producing phosphoric acid through nitric phosphate fertilizer device Download PDFInfo
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- CN116443829A CN116443829A CN202210005872.1A CN202210005872A CN116443829A CN 116443829 A CN116443829 A CN 116443829A CN 202210005872 A CN202210005872 A CN 202210005872A CN 116443829 A CN116443829 A CN 116443829A
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000002686 phosphate fertilizer Substances 0.000 title description 3
- 238000000605 extraction Methods 0.000 claims abstract description 133
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 48
- 239000002904 solvent Substances 0.000 claims abstract description 48
- 238000000926 separation method Methods 0.000 claims abstract description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 24
- 239000010452 phosphate Substances 0.000 claims abstract description 24
- 239000003337 fertilizer Substances 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 23
- 239000002367 phosphate rock Substances 0.000 claims abstract description 18
- 239000012141 concentrate Substances 0.000 claims abstract description 17
- 230000008014 freezing Effects 0.000 claims abstract description 17
- 238000007710 freezing Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 30
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 24
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000001704 evaporation Methods 0.000 claims description 20
- 229910021645 metal ion Inorganic materials 0.000 claims description 19
- 239000012535 impurity Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- 239000011573 trace mineral Substances 0.000 claims description 6
- 235000013619 trace mineral Nutrition 0.000 claims description 6
- 238000005695 dehalogenation reaction Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 24
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 135
- 239000012071 phase Substances 0.000 description 28
- 238000001914 filtration Methods 0.000 description 18
- 239000011575 calcium Substances 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 8
- 239000007790 solid phase Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000002198 insoluble material Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- -1 nitrate ions Chemical class 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 2
- FGZBFIYFJUAETR-UHFFFAOYSA-N calcium;magnesium;silicate Chemical class [Mg+2].[Ca+2].[O-][Si]([O-])([O-])[O-] FGZBFIYFJUAETR-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000003516 soil conditioner Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- NGLMYMJASOJOJY-UHFFFAOYSA-O azanium;calcium;nitrate Chemical compound [NH4+].[Ca].[O-][N+]([O-])=O NGLMYMJASOJOJY-UHFFFAOYSA-O 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- C01B25/2343—Concentration concomitant with purification, e.g. elimination of fluorine
- C01B25/2346—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
- 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
- C01F11/36—Nitrates
- C01F11/38—Preparation with nitric acid or nitrogen oxides
-
- 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
- C05F7/005—Waste water from industrial processing material neither of agricultural nor of animal origin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/06—Calcium compounds, e.g. lime
-
- 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
Abstract
The invention discloses a method, a product and a system for co-producing phosphoric acid through a nitrophosphate fertilizer device; wherein, the method for co-producing phosphoric acid by the nitrophosphate fertilizer device 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 sulfuric acid solution for decalcification to obtain a second solution; performing denitration treatment on the second solution to obtain a third solution; extracting the third solution by an extraction solvent to obtain an extraction phase; and carrying out back extraction on the extract phase to obtain a phosphoric acid solution. According to the method, the phosphate ore or the phosphate concentrate raw material is produced and prepared to obtain the high-purity phosphoric acid, byproducts in the production process can be directly used for preparing fertilizer or used as independent products, nitric acid and the extractant can be recycled, and the production cost is reduced.
Description
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 phosphoric acid through a nitrophosphate fertilizer device.
Background
In the production of phosphoric acid, the method used is generally wet phosphoric acid, and the wet phosphoric acid has problems that a large amount of phosphogypsum is mainly generated, and the silicon component contained in phosphogypsum is difficult to separate, and the phosphorus component which is not completely decomposed is also contained in phosphogypsum, so that the phosphogypsum is difficult to use. And the phosphoric acid of the wet phosphoric acid needs to be desulfurized, the process is complex, the utilization rate of byproducts is low, and the quality of the phosphoric acid is difficult to improve.
The invention solves a plurality of problems existing in the wet phosphoric acid production by improving the process and equipment of the nitrophosphate fertilizer, greatly improves the yield, the yield and the quality of the phosphoric acid, and can recycle byproducts or be used as a high-quality raw material for fertilizer production.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for co-producing phosphoric acid by a nitrophosphate fertilizer 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 and calcium nitrate crystals;
adding the first solution into sulfuric acid solution for decalcification to obtain second solution and calcium sulfate;
performing denitration treatment on the second solution to obtain a third solution;
extracting the third solution by an extraction solvent to obtain an extraction phase;
and carrying out back extraction on the extract phase to obtain 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 other embodiments, the acidolysis solution comprises a solution obtained by directly filtering and separating liquid phase components in acidolysis slurry and combining washing solutions obtained by washing solid phase components decomposed by acidolysis with process water one or more times.
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 ore or phosphate concentrate feed.
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 acid is hydrolyzedThe liquid freezing crystallization temperature is-10 ℃ to-5 ℃, and 60-85% 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 acid hydrolysis solution is frozen to a temperature of-8 ℃ to-5 ℃, and then directly sent into a vacuum filter for filtration and separation, and the first solution is obtained after filtration.
Or in the specific preferred embodiment, the solid phase component obtained after filtration and separation is filtered to obtain a filter cake in a filter pressing mode, the filter cake is washed by frozen nitric acid and frozen water, part of the generated washing liquid is circularly combined into acidolysis liquid for refreezing and crystallizing separation, and the other part of the washing liquid is added into an acidolysis tank for acidolysis.
In some embodiments, a solution of sulfuric acid is added to the first solution.
In a more preferred embodiment, the sulfate in the sulfuric acid solution added is excessive to avoid introducing sulfate impurities; i.e. the molar amount of sulfate in the added sulfuric acid does not exceed the molar amount of calcium ions in the first solution, in order to prevent sulfate affecting the quality of phosphoric acid from being contained in the second solution after decalcification.
In a preferred embodiment, the molar amount of sulfate in the sulfuric acid solution is not excessive relative to the molar amount of calcium ions, it being advantageous for the subsequent removal of impurities to keep the concentration of sulfate in the second solution below 0.5% after decalcification; 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 is subjected to a dehalogenation 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 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 of nitrate in the system is less than 0.5% by evaporation; 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 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 above method further comprises the steps of:
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, and preferably, the extraction solvent comprises n-butanol and isoamyl alcohol. And, the extraction solvent comprises tributyl phosphate.
In a preferred embodiment, the third solution is removed by extraction with an extraction solvent, wherein the volume ratio of the extraction solvent to the third solution is 0.5-5:1.
And, in some specific embodiments, the organic extraction solvent used in the above extraction step may include normal butanol, isoamyl alcohol, sulfonated kerosene, no. 260 solvent oil, 406# environmental solvent oil, and other common metal ion extraction solvents. 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 volume ratio of the addition amount of the extraction solvent to the third solution is 0.5-5:1; preferably, the volume ratio of the addition amount of the extraction solvent to the third solution is 1-2: 1.
in a preferred embodiment, the stripping solvent used in the stripping process is pure water.
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 metal ions to obtain medium trace elements serving as raw materials for producing fertilizer products.
In a preferred embodiment, the above method further comprises the steps of:
the solution containing the metal ions is used for preparing the medium trace element fertilizer.
In a preferred embodiment, the method further comprises:
the nitric acid used for acidolysis of the phosphate ore or phosphate concentrate is at least partly derived from nitric acid obtained by evaporation of the second solution.
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, fe2O3 and Al2O3 in the medium-low grade phosphate rock powder are completely reacted with nitric acid to obtain 110-115% of theoretical amount of nitric acid, and after acidolysis reaction, filter pressing is performed to remove acid insoluble substances and impurities, and the 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 removal tank, controlling the temperature to be 60-75 ℃, adding concentrated sulfuric acid, reacting for 60-120 minutes under stirring, and filtering the reaction liquid after the reaction time expires to obtain 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.
The invention also provides a phosphoric acid product prepared according to the method for co-producing phosphoric acid through the nitrophosphate fertilizer device.
The invention also provides a system for co-producing phosphoric acid by the nitrophosphate fertilizer device, which comprises:
the acidolysis tank is used for carrying out acidolysis reaction on phosphorite or phosphate concentrate;
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 sulfuric 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;
the denitration device is used for evaporating the second solution to remove nitric acid 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;
and the back extraction device is used for carrying out back extraction on the extraction phase to obtain phosphoric acid.
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 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, and the third solid-liquid separation device are the same solid-liquid separation device that is recycled.
In a preferred embodiment, the system 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 system 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 medium and trace elements for preparing fertilizer products.
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 system further comprises:
and the second concentration device is used for concentrating the extraction phase of the back extraction device.
According to the preparation method and the phosphoric acid preparation system, the phosphoric acid with high purity is prepared by producing and preparing the phosphorite or phosphate concentrate raw material, byproducts in the production process can be directly used for preparing the fertilizer or used as independent products, the phosphoric acid and the extracting agent can be recycled, and the produced calcium sulfate is high in quality and can meet various industrial application requirements, so that the process for co-producing the phosphoric acid by the nitrophosphate fertilizer device does not have any waste, nitric acid can be removed by evaporation due to acidolysis of nitric acid and calcium removal of sulfuric acid in the phosphoric acid preparation process, the sulfuric acid consumption does not lead to the need of a desulfurization process, and the phosphoric acid purification process is simpler.
Drawings
FIG. 1 is a schematic diagram of a process for co-producing phosphoric acid by a nitrophosphate device in one embodiment;
FIG. 2 is a schematic diagram of multistage cross-flow extraction, washing and stripping to obtain phosphoric acid in one embodiment;
FIG. 3 is a schematic diagram of a system for co-producing phosphoric acid by a nitrophosphate device in one 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 phosphoric acid by a nitrophosphate fertilizer device; the method takes phosphorite or phosphate concentrate as raw material to prepare and obtain phosphoric acid.
In some embodiments, the phosphorite raw material used for preparing phosphoric acid is high-grade phosphorite obtained by natural mining, and the phosphate concentrate is obtained by removing impurities or purifying medium-low-grade phosphorite.
Further, fig. 1 shows a schematic diagram of a method for co-producing phosphoric acid in one embodiment, 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 sulfuric acid solution into the first solution to obtain a second solution for further removing calcium;
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 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; and back-extracting the washed extraction phase to enable the phosphoric acid to return to the aqueous phase from the organic extraction solvent, thereby obtaining the phosphoric acid.
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 other embodiments, 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 phosphorite mainly contains phosphate radical obtained by acidolysis of nitric acid, and impurity metals such as calcium ion, nitrate radical and the like. 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 freezing and crystallizing the acidolysis solution, a large amount of calcium ions and part of metal ions are separated out in the form of nitrate crystals during the freezing and crystallizing process; 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.
In the step S30, sulfuric acid solution is added into the first solution, so that the residual calcium ions in the first solution are separated out as slightly soluble or indissoluble calcium sulfate, and solid-liquid separation is carried out; 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 sulfuric acid solution is excessive to avoid introducing sulfate impurities; i.e. the molar amount of sulfuric acid added does not exceed the molar amount of calcium ions in the first solution, in order to prevent sulfate groups affecting the quality of phosphoric acid from being contained in the second solution after decalcification.
In an embodiment, the sulfuric acid solution is not excessive, and the concentration of sulfate in the second solution is kept below 0.5% after decalcification, which 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 the step S40, concentrating the second solution to volatilize and escape 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 step 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; and back-extracting the washed extraction phase to enable the phosphoric acid to return to the aqueous phase from the organic extraction solvent, thereby obtaining the phosphoric acid.
The terms extraction and stripping are fundamental technical terms in the chemical industry. Wherein the term "extraction" is a process whereby a solute material is transferred from one solvent to another by virtue of 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, 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 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 according to the preferred implementation shown in fig. 1, after the extraction step, the extracted phosphoric acid is further decolorized or concentrated, etc., so that on one hand, organic matters or fluorine elements in the solution are further removed, and on the other hand, the appearance, color, concentration, etc. of the product are improved, and the high-purity phosphoric acid of the standardized product is obtained. In a specific embodiment, the final high purity phosphoric acid obtained by decolorization and concentration contains P 2 O 5 The mass percentage of (2) is 61.58%.
On the other hand, besides phosphoric acid obtained after 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. 2; 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 the solution containing the metal ion impurities to be used as a raw material for preparing the fertilizer, or preparing the fertilizer into independent medium trace element fertilizer products.
Yet another embodiment of the present invention also provides a system for co-producing phosphoric acid by a nitrophosphate device. In this preferred embodiment, the system for co-producing phosphoric acid is shown in fig. 3, and comprises:
acidolysis reaction device, which is used for acidolysis of phosphorite or phosphate concentrate raw material with 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 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 sulfuric 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 liquid and the raffinate phase to obtain a phosphoric acid product;
and the back extraction device is used for back extracting the organic extraction solvent containing metal ions, namely an extraction phase.
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.
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.
Further in a more preferred embodiment, the method can further comprise a post-treatment device for post-treating the phosphoric acid product obtained after extraction to prepare a high-purity phosphoric acid product meeting the standards of appearance, color, concentration and the like; for example, the post-processing device includes:
the decoloring device is used for decoloring;
and the second concentration device is used for concentrating the obtained phosphoric acid.
The system of the invention is used for producing and preparing phosphoric acid with high purity by partially utilizing and improving the existing nitrophosphate fertilizer system; the byproducts in the production process can be directly used for preparing fertilizer or used as independent products, and no waste is generated.
To demonstrate the efficiency of the present invention in the preparation of phosphoric acid, 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 acidolysis solution to-10 ℃ to-5 ℃ for crystallization, vacuum filtering the frozen solution at-2 to 1 ℃ to obtain 60% crude calcium nitrate liquid crystal 3.54t and 2.186t 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 (mixed by 1:1 volume 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 finally by using pure water, and separating after the back extraction to obtain a phosphoric acid product and a recyclable organic extraction solvent (mixed by 1:1 volume of n-butanol and isoamyl alcohol);
s60, carrying out conventional decolorization and concentration on the phosphoric acid product separated by back extraction to obtain 0.524t of commodity phosphoric acid (P) with the concentration of 85 percent 2 O 5 61.58%、0.323tP 2 O 5 ）。
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 (15)
1. The method for co-producing the phosphoric acid by the nitrophosphate fertilizer 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 and calcium nitrate crystals;
adding the first solution into sulfuric acid solution for reaction, and carrying out solid-liquid separation to obtain second solution and calcium sulfate;
performing denitration treatment on the second solution to obtain a third solution;
extracting the third solution by an extraction solvent to obtain an extraction phase;
and carrying out back extraction on the extract phase to obtain a phosphoric acid solution.
2. The method for co-production of phosphoric acid by means of a nitrophosphate device according to claim 1, characterized in that the second solution is subjected to a dehalogenation treatment by evaporating the second solution to remove nitric acid, the removed nitric acid being recycled for acidolysis of phosphoric acid or phosphate concentrate.
3. The method for co-producing phosphoric acid by a nitrophosphate device according to claim 1 or 2, wherein the concentration of nitrate in the third solution is less 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%.
4. The method for co-production of phosphoric acid by a nitrophosphate device as claimed in claim 2, wherein the temperature at which the second solution is evaporated to remove nitric acid is maintained between 120 and 180 ℃.
5. The method for co-producing phosphoric acid by a nitrophosphate device according to claim 1 or 2, wherein the extraction solvent comprises n-butanol and isoamyl alcohol.
6. The method for co-producing phosphoric acid by a nitrophosphate device according to claim 1 or 2, wherein in the extraction of the third solution by an extraction solvent, the volume ratio of the extraction solvent to the third solution is 0.5 to 5:1.
7. The method for co-production of phosphoric acid by a nitrophosphate device according to claim 1 or 2, wherein the extraction is a multistage extraction.
8. The method for co-producing phosphoric acid by a nitrophosphate device according to claim 1 or 2, wherein in the step of decalcifying the first solution by adding sulfuric acid solution, the molar amount of sulfuric acid added is lower than the molar amount of calcium ions in the first solution.
9. The method for co-production of phosphoric acid by a nitrophosphate device according to claim 1 or 2, wherein the concentration of sulfate in the third solution is less than 0.5%.
10. The method for co-producing phosphoric acid by a nitrophosphate device according to claim 1 or 2, further comprising:
the acid in acidolysis of the phosphate ore or phosphate concentrate is at least partly derived from nitric acid obtained by dehalogenation of the second solution.
11. The method for co-producing phosphoric acid by a nitrophosphate device according to claim 1 or 2, further comprising, before subjecting the extracted phase to the stripping step:
washing the extraction phase to obtain a solution containing metal ions;
and concentrating the solution containing metal ions to obtain medium trace elements serving as raw materials for producing fertilizer products.
12. The method for co-production of phosphoric acid by a nitrophosphate plant according to claim 1 or 2, wherein the extraction of the third solution by an extraction solvent is at least partially derived from stripping the extraction phase to obtain a solvent.
13. A phosphoric acid product produced by the method of co-producing phosphoric acid by a nitrophosphate plant according to any one of claims 1 to 7.
14. A system for co-producing phosphoric acid by means of a nitrophosphate device, comprising:
the acidolysis reaction device is used for carrying out acidolysis reaction on phosphorite or phosphate concentrate to obtain acidolysis slurry;
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 sulfuric 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;
the denitration device is used for evaporating the second solution to remove nitric acid 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;
and the back extraction device is used for carrying out back extraction on the extraction phase to obtain phosphoric acid.
15. The system according to claim 14, characterized in that the system further comprises a washing device for washing the product of the extraction device and a decolorizing device for further removal of impurities from phosphoric acid.
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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 |
| CN217350771U (en) * | 2022-01-05 | 2022-09-02 | 贵州芭田生态工程有限公司 | System for coproduction phosphoric acid 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 |
| CN217350771U (en) * | 2022-01-05 | 2022-09-02 | 贵州芭田生态工程有限公司 | System for coproduction phosphoric acid through nitrophosphate fertilizer device |
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