CN115784238A - Method for recovering soluble fluorine in phosphogypsum - Google Patents
Method for recovering soluble fluorine in phosphogypsum Download PDFInfo
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- CN115784238A CN115784238A CN202211275262.XA CN202211275262A CN115784238A CN 115784238 A CN115784238 A CN 115784238A CN 202211275262 A CN202211275262 A CN 202211275262A CN 115784238 A CN115784238 A CN 115784238A
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- phosphogypsum
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 64
- 239000011737 fluorine Substances 0.000 title claims abstract description 64
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 29
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000000706 filtrate Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000010440 gypsum Substances 0.000 claims abstract description 15
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 15
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000007664 blowing Methods 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 8
- 229960003540 oxyquinoline Drugs 0.000 claims description 8
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 5
- 239000001433 sodium tartrate Substances 0.000 claims description 5
- 229960002167 sodium tartrate Drugs 0.000 claims description 5
- 235000011004 sodium tartrates Nutrition 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- XOJITQHBMRQMRX-UHFFFAOYSA-M sodium;ethane-1,2-diamine;2-oxido-1,3,2$l^{5}-dioxaphosphepane 2-oxide Chemical compound [Na+].NCCN.[O-]P1(=O)OCCCCO1 XOJITQHBMRQMRX-UHFFFAOYSA-M 0.000 claims 1
- 230000001131 transforming effect Effects 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 28
- 238000001704 evaporation Methods 0.000 abstract description 8
- 238000007599 discharging Methods 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000002440 industrial waste Substances 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for recovering soluble fluorine in phosphogypsum, which comprises the steps of heating a phosphogypsum decomposer, adding solid phosphogypsum and a phosphogypsum decomposition accelerator, stirring at constant temperature for reaction, filtering while the reaction is hot, transferring filtrate into a container, adding a metal ion stabilizer, adding a fluorine conversion agent, continuously blowing air into the filtrate, discharging gas phase escaped from a flask into the atmosphere after passing through a washing bottle filled with clear water, evaporating and crystallizing liquid in the flask after the reaction, washing the escaped gas phase with the same washing bottle, filtering after the crystallization is finished to obtain filtrate and gypsum crystals with low impurity content, returning the filtrate as a circulating liquid, and obtaining the liquid in the washing bottle as a fluosilicic acid solution. The method is simple to operate, the reaction conditions are mild, purification and impurity removal are realized in the process of recovering the fluorine in the phosphogypsum, and the method is favorable for recycling solid wastes.
Description
Technical Field
The invention belongs to the field of wet-process phosphoric acid solid waste purification, and particularly relates to a method for recovering soluble fluorine in phosphogypsum.
Background
The phosphogypsum is industrial waste residue discharged in the process of producing phosphoric acid by decomposing phosphate ore by using sulfuric acid, and 5 t phosphogypsum is produced when l t phosphoric acid is produced. It is particularly important to find an efficient recycling method.
Soluble fluorine in phosphogypsum exists mainly in the forms of NaF and KF, and insoluble fluorine exists mainly in the forms of NasAlF6, caSiF6 and CaF. Fluorine has great influence on the application properties of the ardealite product such as strength and setting time of a hardened body, so that research on the removal and recycling of fluorine in ardealite has important practical significance on the comprehensive utilization of ardealite. At present, the removal of fluorine in the phosphogypsum mainly comprises the processes of washing purification, lime neutralization, acid leaching, calcination and the like. The water washing method can effectively remove soluble phosphorus and soluble fluorine in the phosphogypsum, but needs to solve the problem of secondary pollution caused by washing liquid in the water washing process. The calcining method can effectively remove the eutectic phosphorus, but has higher energy consumption and cost. In the research aspect of removing phosphorus and fluorine by a lime neutralization method, wang Ying and the like perform phosphorus and fluorine removal research on certain phosphogypsum under the conditions that the doping amount of quick lime is 8% and the aging time is 24 hours, the removal rate of soluble phosphorus in the phosphogypsum is close to 100%, but the removal rate of soluble fluorine is lower, namely 70.45%, and the using amount of lime is higher; in the research aspect of removing phosphorus and fluorine by an acid leaching method, zhao Gongtao and the like leach phosphogypsum by using 30% sulfuric acid, and the phosphorus and fluorine removal rates are 97.47% and 68.97% respectively.
Although the prior art has a certain effect on removing fluorine, the removed fluorine element often exists in wastewater or solid mixture and is still difficult to recycle, and in view of the reasons and the problems in the prior art, the invention not only realizes the purification of the phosphogypsum, but also can separate the fluorine in the phosphogypsum in the treatment process of the phosphogypsum, thereby achieving the purpose of recycling.
Disclosure of Invention
In order to achieve the purpose, the technical scheme of the invention is as follows: a method for recovering soluble fluorine in phosphogypsum comprises the steps of heating a phosphogypsum decomposing agent to 70-90 ℃, adding a certain amount of solid phosphogypsum and a proper amount of phosphogypsum decomposition accelerator, stirring at a constant temperature for reaction for 1-3 hours, filtering while the reaction is hot after the reaction is finished, keeping the temperature of a filtrate constant at 80-90 ℃, adding a metal ion stabilizer into the filtrate, adding a fluorine converting agent into the filtrate after 30-60 minutes, blowing air into the filtrate continuously, discharging gas phase escaping from a flask into the atmosphere after the gas phase passes through a bottle washing filled with water, reacting for 2-3 hours, washing with water and collecting to obtain a fluosilicic acid solution.
In another technical scheme, the liquid after the reaction is evaporated and crystallized, the escaped gas phase is washed and collected by the same washing bottle, filtrate and gypsum crystals with low impurity content are obtained by filtering after the crystallization is finished, the filtrate is used as phosphogypsum decomposer to be returned for use, and the liquid obtained in the washing bottle is fluosilicic acid solution.
In the scheme, the phosphogypsum decomposer is industrial waste sulfuric acid or a mixture of by-product sulfuric acid and any one of phosphoric acid and hydrochloric acid, and the mass concentration of the phosphogypsum decomposer is 10-40%.
In the scheme, the decomposition accelerator is one or a mixture of two of sodium citrate, sodium tartrate, phthalic acid and oxalic acid. The addition amount of the decomposition accelerator is 0.2 to 1 percent of the mass of the solid phosphogypsum.
In the scheme, the metal ion stabilizer is one or a mixture of 8-hydroxyquinoline, triethanolamine, ethylene diamine tetra methylene sodium phosphate and the like. The metal ion stabilizer accounts for 0.5 to 1 percent of the mass of the filtrate.
In the scheme, the fluorine converting agent is a mixture of any one of industrial waste residue, wollastonite and diatomite. The fluorine conversion agent accounts for 0.4-0.7% of the mass of the filtrate.
In the scheme, the metal ion curing agent and the fluorine conversion agent are added in sequence, wherein the metal ion curing agent is added at an interval of 30-60 minutes, and then the fluorine conversion agent is added.
In the scheme, the fluosilicic acid solution is a colorless and transparent strong acid liquid and is a main raw material for preparing fluosilicate and hydrofluoric acid.
The technical scheme of the invention dissolves phosphogypsum in an acid environment, most of soluble fluorine and a small part of indissolvable fluorine in the phosphogypsum are dissolved, the phosphogypsum exists in a fluorine ion form in the solution, and the introduced decomposition accelerator can dissolve the phosphogypsum to the maximum extent, so that the fluorine element wrapped in the gypsum is released. The metal ion stabilizer can perform a complexing reaction with metal ions in the solution to prevent the metal ions from performing a precipitation reaction with dissolved free fluorine, the fluorine conversion agent is high-purity and high-activity silicon dioxide, the free fluorine ions are converted into silicon tetrafluoride in the solution, the silicon tetrafluoride escapes from the solution system in a gas form under certain temperature and aeration conditions, and the fluorosilicic acid solution is obtained through water absorption.
Detailed Description
The invention is further described below with reference to specific examples.
Example 1
Preparing 30% by mass of dilute solution from industrial waste sulfuric acid, heating 1000 parts of the solution to 90 ℃, adding 500 parts of raw materials of phosphogypsum (with the fluorine content of 0.8%) and 0.5 part of sodium tartrate, stirring at constant temperature for reaction for 3 hours, filtering when the solution is hot after the reaction is finished, transferring the filtrate to a closed container, keeping the constant temperature at 85 ℃, adding 1.5 parts of 8-hydroxyquinoline into the filtrate, reacting for 30 minutes, then adding 1.5 parts of industrial waste residues, continuously blowing air into the reaction system, discharging gas phase escaped from the flask into the atmosphere after passing through a washing bottle filled with deionized water, evaporating and crystallizing liquid in the flask after reacting for 3 hours, washing the escaped gas phase with the same washing bottle until crystals appear in the flask, stopping evaporation, filtering evaporated slurry to obtain filtrate and gypsum crystals, and obtaining low-concentration fluorosilicic acid solution in the washing bottle. Through analysis and determination, the fluorine content of the gypsum crystal is 0.3%, the obtained solution only contains fluorine and silicon elements, and the fluosilicic acid content is 2%.
Example 2
Preparing 30% by mass of dilute solution from industrial waste sulfuric acid, heating 1000 parts of the solution to 90 ℃, adding 500 parts of raw materials of phosphogypsum (with the fluorine content of 0.8%) and 1.0 part of sodium tartrate, stirring at constant temperature for reaction for 3 hours, filtering when the solution is hot after the reaction is finished, transferring the filtrate to a closed container, keeping the constant temperature at 85 ℃, adding 2.5 parts of 8-hydroxyquinoline into the filtrate, adding 2.5 parts of kieselguhr after the reaction is carried out for 30 minutes, continuously blowing air into the reaction system, discharging gas phase escaped from the flask into the atmosphere after passing through a washing bottle filled with deionized water, evaporating and crystallizing the liquid in the flask after the reaction is carried out for 3 hours, washing the escaped gas phase by using the same washing bottle until crystals appear in the flask, stopping evaporation, filtering the evaporation slurry to obtain filtrate and gypsum crystals, and obtaining the liquid in the washing bottle as low-concentration fluorosilicic acid solution. Through analysis and determination, the fluorine content of the gypsum crystal is 0.1%, the obtained solution only contains fluorine and silicon elements, and the fluosilicic acid content of the solution is 2.5%.
Example 2-1
The method and the steps are the same as the example 2, and only the conditions are changed: 2.5 parts of 8-hydroxyquinoline are added to the filtrate, and after 60 minutes of reaction, 2.5 parts of diatomaceous earth are added. Through analysis and determination, the fluorine content of the gypsum crystal is 0.08%, the obtained solution only contains fluorine and silicon elements, and the fluosilicic acid content of the solution is 2.7%.
Examples 2 to 2
The method and the steps are the same as the example 2, and only the conditions are changed: 2.5 parts of 8-hydroxyquinoline are added to the filtrate, and after 90 minutes of reaction, 2.5 parts of diatomaceous earth are added. Through analysis and determination, the fluorine content of the gypsum crystal is 0.12%, the obtained solution only contains fluorine and silicon elements, and the fluosilicic acid content of the solution is 2.1%.
Examples 2 to 3
The method and the steps are the same as the example 2, and only the conditions are changed: 2.5 parts of 8-hydroxyquinoline is added to the filtrate, and after 10 minutes of reaction, 2.5 parts of diatomaceous earth are added. Through analysis and determination, the fluorine content of the gypsum crystal is 0.15%, the obtained solution only contains fluorine and silicon elements, and the fluosilicic acid content of the solution is 1.8%.
Example 3
Preparing 30% by mass of dilute solution from industrial waste sulfuric acid, heating 1000 parts of the solution to 90 ℃, adding 500 parts of raw materials of phosphogypsum (with the fluorine content of 0.8%) and 1.0 part of sodium tartrate, stirring at constant temperature for reaction for 3 hours, filtering while the solution is hot after the reaction is finished, transferring the filtrate to a closed container, keeping the constant temperature at 85 ℃, adding 2.5 parts of diatomite, adding 2.5 parts of 8-hydroxyquinoline after the reaction is carried out for 30 minutes, simultaneously blowing air into the reaction system continuously, discharging gas phase escaped from the flask into the atmosphere after passing through a washing bottle filled with deionized water, carrying out evaporative crystallization on the liquid in the flask after the reaction is carried out for 3 hours, washing the escaped gas phase by using the same washing bottle until crystals appear in the flask, stopping evaporation, filtering the evaporative slurry to obtain filtrate and gypsum crystals, and obtaining low-concentration fluorosilicic acid solution in the washing bottle. Through analysis and determination, the fluorine content of the gypsum crystal is 0.7%, the obtained solution only contains fluorine and silicon elements, and the fluosilicic acid content of the solution is 0.2%.
Example 4
Preparing 30% by mass of dilute solution from industrial waste sulfuric acid, heating 1000 parts of the solution to 90 ℃, adding 500 parts of raw materials of phosphogypsum (with the fluorine content of 0.8%) and 1.0 part of oxalic acid, stirring at constant temperature for reaction for 3 hours, filtering when the solution is hot after the reaction is finished, transferring the filtrate to a closed container, keeping the constant temperature at 85 ℃, adding 2.5 parts of ethylene diamine tetramethylene sodium phosphate, adding 2.5 parts of kieselguhr after the reaction is carried out for 30 minutes, blowing no air into a reaction system, discharging gas phase escaped from a flask into the atmosphere after a bottle washing bottle filled with deionized water, carrying out evaporative crystallization on liquid in the flask after the reaction is carried out for 3 hours, washing the escaped gas phase by using the same bottle washing bottle until crystals appear in the flask, stopping evaporation, filtering evaporative slurry to obtain filtrate and gypsum crystals, and obtaining low-concentration fluorosilicic acid solution in the bottle washing bottle. Through analysis and determination, the fluorine content of the gypsum crystal is 0.6%, the obtained solution only contains fluorine and silicon elements, and the fluosilicic acid content of the solution is 0.8%.
Claims (10)
1. A method for recovering soluble fluorine in phosphogypsum is characterized by comprising the following steps:
(1) Adding solid phosphogypsum and a decomposition accelerator into the phosphogypsum decomposition agent, stirring for reaction, and filtering;
(2) And (2) adding a metal ion stabilizer into the filtrate obtained in the step (1), stirring, adding a fluorine conversion agent, continuously blowing air into the filtrate for reaction, and collecting gas phase escaped in the reaction process by adopting water to obtain a fluosilicic acid solution.
2. The method for recovering soluble fluorine in phosphogypsum according to claim 1, wherein the phosphogypsum decomposer in the step (1) is any one or a mixture of sulfuric acid, phosphoric acid and hydrochloric acid, and the mass concentration of the phosphogypsum decomposer is 10-40%.
3. The method for recovering soluble fluorine in phosphogypsum according to claim 2, wherein the decomposition accelerator in step (1) is one or two of sodium citrate, sodium tartrate, phthalic acid and oxalic acid; the addition amount of the decomposition accelerator is 0.2-1% of the mass of the solid phosphogypsum.
4. The method for recovering soluble fluorine in phosphogypsum according to claim 3, characterized in that the stirring reaction condition in the step (1) is 70-90 ℃ and the reaction time is 1-3h.
5. The method of recovering soluble fluorine in phosphogypsum according to claim 4, wherein in step (2) the filtrate is heated to 80-90 ℃ and then added with metal ion stabilizer.
6. The method for recovering soluble fluorine in phosphogypsum according to claim 5, wherein the metal ion stabilizer in step (2) is one or two of 8-hydroxyquinoline, triethanolamine, and sodium ethylenediamine tetramethylene phosphate; the metal ion stabilizer accounts for 0.5-1% of the mass of the filtrate.
7. The method for recovering soluble fluorine in phosphogypsum according to claim 6, characterized in that the fluorine transforming agent in step (2) is wollastonite or diatomite; the fluorine converting agent accounts for 0.4-0.7% of the mass of the filtrate.
8. The method of recovering soluble fluorine from phosphogypsum according to claim 7, wherein the metal ion stabilizer and the fluorine converting agent are added in sequence by adding the metal ion stabilizer first and adding the fluorine converting agent after 30-60 minutes.
9. The method for recovering soluble fluorine in phosphogypsum according to claim 7, wherein the liquid obtained after the reaction in step (2) is completely evaporated and crystallized, the escaped gas phase is collected by water to obtain a fluosilicic acid solution, the solution is filtered after the crystallization is completed to obtain a filtrate and gypsum crystals, and the filtrate is returned to step (1) to be used as a circulating liquid.
10. The fluorosilicic acid solution prepared according to any one of claims 1 to 9, wherein the fluorosilicic acid solution contains 1% to 3% by mass of fluorosilicic acid.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1507542A (en) * | 1967-01-05 | 1967-12-29 | Coswig Chemiewerk Veb | Process for removing fluorine from gypsum waste from the manufacture of phosphoric acid by wet process |
| BE779982A (en) * | 1971-03-02 | 1972-06-16 | Knauf Westdeutsche Gips | PROCESS FOR MANUFACTURING PHOSPHORIC ACID AND A GYPSUM SUITABLE FOR A SUBSEQUENT TECHNICAL TREATMENT |
| GB1303190A (en) * | 1969-06-06 | 1973-01-17 | ||
| US3969485A (en) * | 1971-10-28 | 1976-07-13 | Flemmert Goesta Lennart | Process for converting silicon-and-fluorine-containing waste gases into silicon dioxide and hydrogen fluoride |
| US4171342A (en) * | 1974-04-03 | 1979-10-16 | Occidental Chemical Company | Recovery of calcium fluoride from phosphate operation waste water |
| GB2094282A (en) * | 1981-02-27 | 1982-09-15 | Dharamsi Morarji Chemical The | Phosphoric acid manufacture |
| JP2006290703A (en) * | 2005-04-14 | 2006-10-26 | Cabot Supermetal Kk | Method of recovering fluorine |
| CN102502551A (en) * | 2011-10-20 | 2012-06-20 | 瓮福（集团）有限责任公司 | Method for recycling phosphorus and fluorine in defluorination residues |
| CN102887535A (en) * | 2012-10-09 | 2013-01-23 | 湖北富邦科技股份有限公司 | Method for recycling high-purity fluorine and phosphorus from wastewater of phosphogypsum residue field |
| CN105442047A (en) * | 2015-12-25 | 2016-03-30 | 华东理工大学 | Method for extracting fluorine element from industrial gypsum |
| CN107473775A (en) * | 2017-09-07 | 2017-12-15 | 中化化肥有限公司成都研发中心 | Reclaim phosphorus and the molten fertile method of fluorine co-production low fluorine water in Phosphoric Acid Concentration slag acid |
| CN111498940A (en) * | 2020-05-11 | 2020-08-07 | 江苏一夫科技股份有限公司 | Separation treatment method of phosphorus-containing and fluorine-containing phosphogypsum washing waste liquid |
| CN111943156A (en) * | 2020-08-12 | 2020-11-17 | 福建瓮福蓝天氟化工有限公司 | Process for optimizing phosphoric acid reaction and separation by using active silicon dioxide |
-
2022
- 2022-10-18 CN CN202211275262.XA patent/CN115784238B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1507542A (en) * | 1967-01-05 | 1967-12-29 | Coswig Chemiewerk Veb | Process for removing fluorine from gypsum waste from the manufacture of phosphoric acid by wet process |
| GB1303190A (en) * | 1969-06-06 | 1973-01-17 | ||
| BE779982A (en) * | 1971-03-02 | 1972-06-16 | Knauf Westdeutsche Gips | PROCESS FOR MANUFACTURING PHOSPHORIC ACID AND A GYPSUM SUITABLE FOR A SUBSEQUENT TECHNICAL TREATMENT |
| US3969485A (en) * | 1971-10-28 | 1976-07-13 | Flemmert Goesta Lennart | Process for converting silicon-and-fluorine-containing waste gases into silicon dioxide and hydrogen fluoride |
| US4171342A (en) * | 1974-04-03 | 1979-10-16 | Occidental Chemical Company | Recovery of calcium fluoride from phosphate operation waste water |
| GB2094282A (en) * | 1981-02-27 | 1982-09-15 | Dharamsi Morarji Chemical The | Phosphoric acid manufacture |
| JP2006290703A (en) * | 2005-04-14 | 2006-10-26 | Cabot Supermetal Kk | Method of recovering fluorine |
| CN102502551A (en) * | 2011-10-20 | 2012-06-20 | 瓮福（集团）有限责任公司 | Method for recycling phosphorus and fluorine in defluorination residues |
| CN102887535A (en) * | 2012-10-09 | 2013-01-23 | 湖北富邦科技股份有限公司 | Method for recycling high-purity fluorine and phosphorus from wastewater of phosphogypsum residue field |
| CN105442047A (en) * | 2015-12-25 | 2016-03-30 | 华东理工大学 | Method for extracting fluorine element from industrial gypsum |
| CN107473775A (en) * | 2017-09-07 | 2017-12-15 | 中化化肥有限公司成都研发中心 | Reclaim phosphorus and the molten fertile method of fluorine co-production low fluorine water in Phosphoric Acid Concentration slag acid |
| CN111498940A (en) * | 2020-05-11 | 2020-08-07 | 江苏一夫科技股份有限公司 | Separation treatment method of phosphorus-containing and fluorine-containing phosphogypsum washing waste liquid |
| CN111943156A (en) * | 2020-08-12 | 2020-11-17 | 福建瓮福蓝天氟化工有限公司 | Process for optimizing phosphoric acid reaction and separation by using active silicon dioxide |
Non-Patent Citations (2)
| Title |
|---|
| KAZAK, V. G.等: ""Improvement of the technology for recovery of fluorine and strontium in nitric acid processing of apatite"", 《SOVIET CHEMICAL INDUSTRY》, vol. 20, no. 02, pages 43 - 48 * |
| 付云枫等: ""从熔盐电解废渣中回收钪和氟"", 《过程工程学报》, vol. 20, no. 08, pages 929 - 937 * |
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