CN116395695A - Method for preparing phosphate from red mud - Google Patents
Method for preparing phosphate from red mud Download PDFInfo
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- CN116395695A CN116395695A CN202310522350.3A CN202310522350A CN116395695A CN 116395695 A CN116395695 A CN 116395695A CN 202310522350 A CN202310522350 A CN 202310522350A CN 116395695 A CN116395695 A CN 116395695A
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- red mud
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- phosphate
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 22
- 239000010452 phosphate Substances 0.000 title claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 22
- 239000007791 liquid phase Substances 0.000 claims abstract description 72
- 239000007790 solid phase Substances 0.000 claims abstract description 56
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000002386 leaching Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 24
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 17
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 17
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 13
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011575 calcium Substances 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 150000004683 dihydrates Chemical class 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 18
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000002411 adverse Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 description 4
- 229910000398 iron phosphate Inorganic materials 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052663 cancrinite Inorganic materials 0.000 description 3
- 229910052595 hematite Inorganic materials 0.000 description 3
- 239000011019 hematite Substances 0.000 description 3
- -1 hydrocalumite Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 2
- 239000000429 sodium aluminium silicate Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001678 gehlenite Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
-
- 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
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a method for preparing phosphate by utilizing red mud, which specifically comprises the following steps: (1) Firstly ball-milling and sieving red mud, mixing the red mud with water, stirring the mixture, and adding dilute nitric acid solution; (2) Suction filtering, and adding a phosphoric acid solution into the liquid phase A for hydrothermal reaction; (3) Centrifugal separation is carried out, and the solid phase B is dried and roasted to obtain silicon phosphate; (4) Adding ammonia water into the liquid phase B for precipitation reaction to generate white precipitate, stirring, carrying out suction filtration, and drying the solid phase C to obtain calcium hydrophosphate dihydrate; (5) Adding dilute nitric acid solution into the solid phase A for re-leaching, stirring and fully dissolving; (6) Filtering, adding phosphoric acid solution and water into the liquid phase D for hydrothermal reaction; (7) Centrifugal separation, drying and roasting the solid phase E to obtain ferric phosphate; (8) continuing to use the liquid phase E with the next batch of leaching liquid B. The invention realizes the high-value utilization of the red mud and reduces the adverse effect of the red mud on the environment.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of industrial solid wastes, in particular to a method for preparing phosphate by utilizing red mud.
Background
Red mud is a strong alkaline solid waste discharged in the industrial production process of alumina, and is called red mud because of high iron oxide content and similar appearance to red mud. Due to the different ore grade, production method and technical level, about 1.0-1.8 tons of red mud is discharged per 1 ton of alumina produced. In recent years, more than 1 hundred million tons of red mud is discharged from an alumina plant every year in China, and the generated red mud is complex in composition and extremely large in difference due to the difference of bauxite compositions in various places, so that the red mud is difficult to comprehensively utilize. At present, a disposal mode of red mud is mainly to establish a storage yard for storage, but the red mud capable of realizing green application is less than 10%, valuable metals in the red mud can not realize resource utilization, and meanwhile, the ecological and environmental damage is caused to a certain extent.
The mineral phases in the red mud are quite complex, and the red mud in different production places has obvious differences, mainly because of the differences of bauxite components in each place and the differences of extraction processes. According to the analysis of the collected samples, the iron oxide content of the Guangxi red mud is above 60%, and the phase composition comprises hematite, ferrotitanium oxide, boehmite and sodium aluminosilicate; the iron oxide content of Henan red mud and Yunnan red mud is about 30%, and the phases are hematite, gehlenite, calcite, hydrocalumite, cancrinite, hematite, nepheline, quartz and cancrinite respectively. Obvious phase differences in red mud prevent the application of the red mud in various fields.
The red mud usually contains 30% -60% of ferric oxide, and the direct magnetic separation recovery or acid-base leaching method has little benefit. If the components in the red mud are utilized to synthesize the high-purity phosphate, the problems of environment and ecology caused by the red mud can be solved, and meanwhile, the method can create benefits for the aluminum industry.
Therefore, how to develop a method for preparing high-purity phosphate by using red mud is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing phosphate by using red mud, so as to solve the defects in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the method for preparing the phosphate by using the red mud specifically comprises the following steps:
(1) Firstly ball-milling and sieving red mud, and mixing the red mud with water to obtain red mud slurry; stirring the red mud slurry under the condition of heating in a water bath, and adding a dilute nitric acid solution for preliminary leaching to obtain a leaching solution A;
(2) Filtering the leaching solution A to obtain a solid phase A and a liquid phase A respectively; then adding phosphoric acid solution into the liquid phase A for hydrothermal reaction and separating out crystals to obtain crystal solution A;
(3) Firstly, centrifugally separating the crystal solution A to obtain a solid phase B and a liquid phase B respectively; drying and roasting the solid phase B to obtain silicon phosphate;
(4) Adding ammonia water into the liquid phase B for precipitation reaction to generate white precipitate, stirring, and performing suction filtration to obtain a solid phase C and a liquid phase C respectively; drying the solid phase C to obtain calcium hydrophosphate dihydrate;
(5) Adding dilute nitric acid solution into the solid phase A for re-leaching, stirring under the condition of heating in a water bath, and fully dissolving to obtain leaching liquid B;
(6) Filtering the leaching solution B to obtain a solid phase D and a liquid phase D respectively; then adding phosphoric acid solution and water into the liquid phase D to perform hydrothermal reaction and separate out crystals to obtain a crystal solution B;
(7) Firstly, centrifugally separating the crystal solution B to obtain a solid phase E and a liquid phase E respectively; drying the solid phase E to obtain hydrated ferric phosphate, and roasting to obtain ferric phosphate;
(8) The liquid phase E is continued to be used with the next batch of leaching liquid B.
Further, in the step (1), the number of the sieved meshes is 300 mesh; the mass volume ratio of the red mud to the water is 1g to 10mL; the temperature of water bath heating is 60-80 ℃; the molar concentration of the dilute nitric acid solution is 1mol/L, and the pH value added into the red mud slurry is 1-2.
The further technical scheme has the beneficial effects that sodium aluminosilicate, cadherite, cancrinite and other composite salts in the red mud enter the liquid phase A after being decomposed by fully reacting the red mud with dilute nitric acid, and meanwhile, the solid phase A enriched with ferric oxide is obtained.
Further, in the step (2), the molar concentration of the phosphoric acid solution is 1-5 mol/L; the volume ratio of the liquid phase A to the phosphoric acid solution is (5-10): 1; the temperature of the hydrothermal reaction is 120-150 ℃ and the time is 3-12 h.
The technical proposal has the beneficial effect that ions in the liquid phase A can fully react with phosphoric acid to generate phosphate under the hydrothermal condition.
Further, in the step (3), the rotational speed of centrifugal separation is 6000r/min, and the time is 5min; the drying temperature is 60-100 ℃ and the drying time is 12 hours; the temperature rising rate of the roasting is 5 ℃/min, the temperature rises to 550 ℃, and the temperature is kept constant for 2 hours.
The technical proposal has the advantages that the crystal precipitated in the crystal solution A is subjected to solid-liquid separation, and is further dried and roasted to obtain the silicon phosphate with stable phase.
Further, in the step (4), the mass percentage of the ammonia water is 10%, and the pH value of the ammonia water added to the liquid phase B is 7-9; stirring for 30min; the drying temperature is 60-100 ℃ and the drying time is 12h.
The further technical proposal has the advantages that ammonia water is used for adjusting the pH value of the solution, so that the calcium hydrophosphate dihydrate is completely precipitated, and the calcium hydrophosphate dihydrate is dried for further dehydration treatment after solid-liquid separation.
Further, in the step (5), the molar concentration of the dilute nitric acid solution is 2-5 mol/L; the mass volume ratio of the solid phase A to the dilute nitric acid solution is 1g to 5mL; the temperature of water bath heating is 80-90 ℃; the stirring time was 2h.
The technical proposal has the beneficial effects that the iron in the iron-rich solid phase A is further leached into the liquid phase by using the nitric acid with higher concentration under the heating condition.
Further, in the step (6), the molar concentration of the phosphoric acid solution is 1 to 5mol/L; the volume ratio of the liquid phase D to the phosphoric acid solution is (5-10): 1; adding water to the pH value of 0.5-1.5; the temperature of the hydrothermal reaction is 120-150 ℃ and the time is 3-12 h.
The adoption of the further technical scheme has the beneficial effects that under the hydrothermal condition, the iron ions in the liquid phase D can fully react with phosphoric acid to generate hydrated ferric phosphate; under the condition of fixed pH, the generated hydrated ferric phosphate is precipitated at the bottom of the reaction kettle.
Further, in the step (7), the rotational speed of centrifugal separation is 6000r/min, and the time is 5min; the drying temperature is 60-100 ℃ and the drying time is 12 hours; the temperature rising rate of the roasting is 5 ℃/min, the temperature rises to 500 ℃, and the temperature is kept constant for 2 hours.
The method has the beneficial effects that the hydrated ferric phosphate generated by the reaction is subjected to solid-liquid separation, and the combined water is removed by further drying and roasting, so that the ferric phosphate with stable phase is obtained.
Compared with the prior art, the invention has the following beneficial effects:
1. firstly, preliminarily leaching part of components in red mud through a low-concentration dilute nitric acid solution, filtering the leaching solution A to obtain a solid phase A enriched with ferric oxide, reacting the liquid phase A with a phosphoric acid solution to separate out silicon phosphate crystals, centrifugally separating, and adding ammonia water into the liquid phase B to generate calcium hydrophosphate dihydrate precipitate; and (3) carrying out secondary acid leaching on the solid phase A enriched with ferric oxide, reacting the filtered liquid phase D with a phosphoric acid solution, adding water to adjust the pH value, controlling the reaction temperature and the reaction time, carrying out solid-liquid separation after the reaction is finished, and roasting the solid phase E to obtain the high-purity ferric phosphate.
2. The invention converts main substances in the red mud into phosphate products such as high-purity ferric phosphate, silicon phosphate, calcium hydrophosphate dihydrate and the like with economic value, and reduces the adverse effect of the red mud on the environment while realizing the high-value utilization of the red mud.
3. The process for treating the red mud is simple and convenient, has low cost and operability, and can be popularized to the application of large-batch red mud, thereby reducing the adverse effect of the aluminum industry on the environment.
Drawings
FIG. 1 is a process flow diagram of a method for preparing phosphate from red mud according to the present invention;
FIG. 2 is an XRD pattern of silicon phosphate in step (3) of example 2;
FIG. 3 is an XRD pattern of dibasic calcium phosphate dihydrate of step (4) of example 2;
fig. 4 is an XRD pattern of iron phosphate in step (7) of example 2.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The method for preparing phosphate by using red mud, as shown in fig. 1, specifically comprises the following steps:
(1) Firstly ball milling red mud, sieving with a 300-mesh sieve, and mixing with water according to the mass-volume ratio of 1g to 10mL to obtain red mud slurry; adding the red mud slurry into a water bath kettle, stirring under the water bath heating condition of 60 ℃, slowly adding a dilute nitric acid solution with the molar concentration of 1mol/L into the red mud slurry by using a separating funnel, stopping adding the dilute nitric acid solution when the pH value of the red mud slurry is detected to be 1 by using an electronic pH meter, sealing by using a preservative film, continuing stirring for 1h, performing primary leaching, taking out, and standing for 15min to obtain a leaching solution A;
(2) Filtering the leaching solution A to obtain a solid phase A and a liquid phase A respectively; then transferring the liquid phase A into a reaction kettle, adding a phosphoric acid solution with the molar concentration of 1mol/L into the liquid phase A according to the volume ratio of 5:1, putting into an oven, carrying out hydrothermal reaction for 12 hours at the constant temperature of 120 ℃, and observing that a large amount of light blue crystals are precipitated in the liquid after natural cooling to obtain a crystal solution A;
(3) Firstly, centrifugally separating the crystal solution A for 5min at a rotating speed of 6000r/min to obtain a solid phase B and a liquid phase B respectively; then placing the solid phase B into an oven, drying for 12 hours at 60 ℃, then placing into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2 hours for roasting to obtain silicon phosphate;
(4) Adding 10 mass percent of ammonia water into the liquid phase B until the pH value of the liquid phase B is 7, carrying out precipitation reaction, generating a large amount of white precipitates, continuously stirring for 30min, and carrying out suction filtration to obtain a solid phase C and a liquid phase C respectively; then putting the solid phase C into a baking oven, and drying for 12 hours at 60 ℃ to obtain calcium hydrophosphate dihydrate;
(5) Adding a dilute nitric acid solution with the molar concentration of 2mol/L into the solid phase A according to the mass-volume ratio of 1g to 5mL, leaching again, adding into a water bath kettle, stirring for 2 hours under the water bath heating condition of 80 ℃, fully dissolving, taking out, and standing for 15min to obtain a leaching solution B;
(6) Filtering the leaching solution B to obtain a solid phase D and a liquid phase D respectively; adding 1-5 mol/L phosphoric acid solution into the liquid phase D according to the volume ratio of 5:1, adding water until the pH value of the liquid phase D is 0.5, transferring into a reaction kettle, putting into a baking oven, carrying out hydrothermal reaction for 12 hours under the constant temperature condition of 120 ℃, and observing that a large amount of white crystals are precipitated in the liquid after natural cooling to obtain a crystal solution B;
(7) Firstly, centrifugally separating the crystal solution B for 5min at the rotating speed of 6000r/min to obtain a solid phase E and a liquid phase E respectively; then placing the solid phase E into a baking oven, drying for 12 hours at 60 ℃ to obtain hydrated ferric phosphate, then placing into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2 hours for roasting to obtain the ferric phosphate;
(8) The liquid phase E is continued to be used with the next batch of leaching liquid B.
Example 2
The method for preparing phosphate by using red mud, as shown in fig. 1, specifically comprises the following steps:
(1) Firstly ball milling red mud, sieving with a 300-mesh sieve, and mixing with water according to the mass-volume ratio of 1g to 10mL to obtain red mud slurry; adding the red mud slurry into a water bath kettle, stirring under the water bath heating condition of 70 ℃, slowly adding a dilute nitric acid solution with the molar concentration of 1mol/L into the red mud slurry by using a separating funnel, stopping adding the dilute nitric acid solution when the pH value of the red mud slurry is detected to be 1.5 by using an electronic pH meter, sealing by using a preservative film, continuously stirring for 1h, performing primary leaching, taking out, and standing for 15min to obtain a leaching solution A;
(2) Filtering the leaching solution A to obtain a solid phase A and a liquid phase A respectively; then transferring the liquid phase A into a reaction kettle, adding a phosphoric acid solution with the molar concentration of 2mol/L into the liquid phase A according to the volume ratio of 7:1, putting into an oven, carrying out hydrothermal reaction for 6 hours at the constant temperature of 130 ℃, and observing that a large amount of light blue crystals are precipitated in the liquid after natural cooling to obtain a crystal solution A;
(3) Firstly, centrifugally separating the crystal solution A for 5min at a rotating speed of 6000r/min to obtain a solid phase B and a liquid phase B respectively; then placing the solid phase B into a baking oven, drying for 12 hours at 80 ℃, then placing into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2 hours for baking to obtain silicon phosphate;
(4) Adding 10 mass percent of ammonia water into the liquid phase B until the pH value of the liquid phase B is 8 to carry out precipitation reaction and generate a large amount of white precipitates, continuously stirring for 30min, and carrying out suction filtration to obtain a solid phase C and a liquid phase C respectively; then putting the solid phase C into a baking oven, and drying for 12 hours at 80 ℃ to obtain calcium hydrophosphate dihydrate;
(5) Adding a dilute nitric acid solution with the molar concentration of 3mol/L into the solid phase A according to the mass-volume ratio of 1g to 5mL, leaching again, adding into a water bath kettle, stirring for 2 hours under the water bath heating condition of 85 ℃, fully dissolving, taking out, and standing for 15min to obtain a leaching solution B;
(6) Filtering the leaching solution B to obtain a solid phase D and a liquid phase D respectively; adding phosphoric acid solution with the molar concentration of 2mol/L into the liquid phase D according to the volume ratio of 7:1, adding water until the pH value of the liquid phase D is 1, transferring into a reaction kettle, putting into an oven, performing hydrothermal reaction for 6 hours under the constant temperature condition of 130 ℃, and observing that a large amount of white crystals are precipitated in the liquid after natural cooling to obtain a crystal solution B;
(7) Firstly, centrifugally separating the crystal solution B for 5min at the rotating speed of 6000r/min to obtain a solid phase E and a liquid phase E respectively; then placing the solid phase E into a baking oven, drying for 12 hours at 80 ℃ to obtain hydrated ferric phosphate, then placing into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2 hours for roasting to obtain the ferric phosphate;
(8) The liquid phase E is continued to be used with the next batch of leaching liquid B.
Example 3
The method for preparing phosphate by using red mud, as shown in fig. 1, specifically comprises the following steps:
(1) Firstly ball milling red mud, sieving with a 300-mesh sieve, and mixing with water according to the mass-volume ratio of 1g to 10mL to obtain red mud slurry; adding the red mud slurry into a water bath kettle, stirring under the water bath heating condition of 80 ℃, slowly adding a dilute nitric acid solution with the molar concentration of 1mol/L into the red mud slurry by using a separating funnel, stopping adding the dilute nitric acid solution when the pH value of the red mud slurry is detected to be 2 by using an electronic pH meter, sealing by using a preservative film, continuing stirring for 1h, performing primary leaching, taking out, and standing for 15min to obtain a leaching solution A;
(2) Filtering the leaching solution A to obtain a solid phase A and a liquid phase A respectively; then transferring the liquid phase A into a reaction kettle, adding a phosphoric acid solution with the molar concentration of 5mol/L into the liquid phase A according to the volume ratio of 10:1, putting into an oven, carrying out hydrothermal reaction for 3 hours at the constant temperature of 150 ℃, and observing that a large amount of light blue crystals are precipitated in the liquid after natural cooling to obtain a crystal solution A;
(3) Firstly, centrifugally separating the crystal solution A for 5min at a rotating speed of 6000r/min to obtain a solid phase B and a liquid phase B respectively; then placing the solid phase B into a baking oven, drying for 12 hours at the temperature of 100 ℃, then placing into a muffle furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 2 hours for baking to obtain silicon phosphate;
(4) Adding 10 mass percent of ammonia water into the liquid phase B until the pH value of the liquid phase B is 9 to carry out precipitation reaction and generate a large amount of white precipitates, continuously stirring for 30min, and carrying out suction filtration to obtain a solid phase C and a liquid phase C respectively; then putting the solid phase C into a baking oven, and drying for 12 hours at the temperature of 100 ℃ to obtain calcium hydrophosphate dihydrate;
(5) Adding a dilute nitric acid solution with the molar concentration of 5mol/L into the solid phase A according to the mass-volume ratio of 1g to 5ml, leaching again, adding into a water bath kettle, stirring for 2 hours under the water bath heating condition of 90 ℃, fully dissolving, taking out, and standing for 15min to obtain a leaching solution B;
(6) Filtering the leaching solution B to obtain a solid phase D and a liquid phase D respectively; adding phosphoric acid solution with the molar concentration of 5mol/L into the liquid phase D according to the volume ratio of 10:1, adding water until the pH value of the liquid phase D is 1.5, transferring into a reaction kettle, putting into a baking oven, carrying out hydrothermal reaction for 3 hours under the constant temperature condition of 150 ℃, and observing that a large amount of white crystals are precipitated in the liquid after natural cooling to obtain a crystal solution B;
(7) Firstly, centrifugally separating the crystal solution B for 5min at the rotating speed of 6000r/min to obtain a solid phase E and a liquid phase E respectively; then placing the solid phase E into a baking oven, drying for 12 hours at the temperature of 100 ℃ to obtain hydrated ferric phosphate, then placing into a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 2 hours for roasting to obtain the ferric phosphate;
(8) The liquid phase E is continued to be used with the next batch of leaching liquid B.
Performance testing
The silicon phosphate prepared in step (3) of example 2, the dibasic calcium phosphate dihydrate prepared in step (4) of example 2 and the iron phosphate prepared in step (7) of example 2 were each subjected to X-ray diffraction, and the corresponding XRD patterns were shown in FIGS. 2 to 4 in order.
Results:
1. EXAMPLE 2 XRD patterns of the silicon phosphate in step (3) are shown in FIG. 2, and the resulting silicon phosphate phase is combined with Si 5 O(PO 4 ) 6 The standard cards are basically consistent, which indicates that the crystallinity of the substance is good.
2. Example 2 XRD pattern of dibasic calcium phosphate dihydrate in step (4) is shown in FIG. 3, and the characteristic peaks of the calcium phosphate dihydrate phase produced are sharp and comparable to CaPO 3 (OH)·2H 2 The O standard card corresponds completely, which indicates that the crystallinity of the substance is good.
3. The XRD pattern of the iron phosphate in example 2, step (7) is shown in FIG. 4, and the characteristic peaks of the generated iron phosphate phase are narrow and sharp, and are similar to FePO 4 The standard card basically corresponds to the standard card, which indicates that the crystallinity of the substance is good.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The method for preparing the phosphate by using the red mud is characterized by comprising the following steps of:
(1) Firstly ball-milling and sieving red mud, and mixing the red mud with water to obtain red mud slurry; stirring the red mud slurry under the condition of heating in a water bath, and adding a dilute nitric acid solution for preliminary leaching to obtain a leaching solution A;
(2) Filtering the leaching solution A to obtain a solid phase A and a liquid phase A respectively; then adding phosphoric acid solution into the liquid phase A for hydrothermal reaction and separating out crystals to obtain crystal solution A;
(3) Firstly, centrifugally separating the crystal solution A to obtain a solid phase B and a liquid phase B respectively; drying and roasting the solid phase B to obtain silicon phosphate;
(4) Adding ammonia water into the liquid phase B for precipitation reaction to generate white precipitate, stirring, and performing suction filtration to obtain a solid phase C and a liquid phase C respectively; drying the solid phase C to obtain calcium hydrophosphate dihydrate;
(5) Adding dilute nitric acid solution into the solid phase A for re-leaching, stirring under the condition of heating in a water bath, and fully dissolving to obtain leaching liquid B;
(6) Filtering the leaching solution B to obtain a solid phase D and a liquid phase D respectively; then adding phosphoric acid solution and water into the liquid phase D to perform hydrothermal reaction and separate out crystals to obtain a crystal solution B;
(7) Firstly, centrifugally separating the crystal solution B to obtain a solid phase E and a liquid phase E respectively; drying the solid phase E to obtain hydrated ferric phosphate, and roasting to obtain ferric phosphate;
(8) The liquid phase E is continued to be used with the next batch of leaching liquid B.
2. A method for preparing phosphate from red mud according to claim 1, wherein in step (1), the number of the sieved mesh is 300 mesh; the mass volume ratio of the red mud to the water is 1g to 10mL; the temperature of the water bath heating is 60-80 ℃; the molar concentration of the dilute nitric acid solution is 1mol/L, and the pH value added into the red mud slurry is 1-2.
3. A method for preparing phosphate by using red mud according to claim 1, wherein in the step (2), the molar concentration of the phosphoric acid solution is 1-5 mol/L; the volume ratio of the liquid phase A to the phosphoric acid solution is (5-10): 1; the temperature of the hydrothermal reaction is 120-150 ℃ and the time is 3-12 h.
4. A method for preparing phosphate from red mud according to claim 1, wherein in step (3), the centrifugal separation is performed at a rotation speed of 6000r/min for 5min; the drying temperature is 60-100 ℃ and the drying time is 12 hours; the temperature rising rate of the roasting is 5 ℃/min, the temperature rises to 550 ℃, and the temperature is kept constant for 2 hours.
5. The method for preparing phosphate by utilizing red mud according to claim 1, wherein in the step (4), the mass percentage of the ammonia water is 10%, and the pH value added to the liquid phase B is 7-9; the stirring time is 30min; the drying temperature is 60-100 ℃ and the drying time is 12 hours.
6. A method for preparing phosphate from red mud according to claim 1, wherein in step (5), the molar concentration of the dilute nitric acid solution is 2-5 mol/L; the mass volume ratio of the solid phase A to the dilute nitric acid solution is 1g to 5mL; the temperature of the water bath heating is 80-90 ℃; the stirring time is 2h.
7. A method for preparing phosphate from red mud according to claim 1, wherein in step (6), the molar concentration of the phosphoric acid solution is 1-5 mol/L; the volume ratio of the liquid phase D to the phosphoric acid solution is (5-10): 1; the pH value of the water added to the liquid phase D is 0.5-1.5; the temperature of the hydrothermal reaction is 120-150 ℃ and the time is 3-12 h.
8. A method for preparing phosphate from red mud according to claim 1, wherein in step (7), the centrifugal separation is performed at a rotation speed of 6000r/min for 5min; the drying temperature is 60-100 ℃ and the drying time is 12 hours; the temperature rising rate of the roasting is 5 ℃/min, the temperature rises to 500 ℃, and the temperature is kept constant for 2 hours.
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