CN101935756A - Method for reclaiming rare-earth and organic phase from third phase of rare-earth extraction - Google Patents
Method for reclaiming rare-earth and organic phase from third phase of rare-earth extraction Download PDFInfo
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- CN101935756A CN101935756A CN2010102734124A CN201010273412A CN101935756A CN 101935756 A CN101935756 A CN 101935756A CN 2010102734124 A CN2010102734124 A CN 2010102734124A CN 201010273412 A CN201010273412 A CN 201010273412A CN 101935756 A CN101935756 A CN 101935756A
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Abstract
The invention relates to a method for reclaiming rare-earth and an organic phase from a third phase of rare-earth extraction. The method comprises an infiltration part, a demulsification part, a back-extraction part and a cleaning part, wherein third extracting phase is subject to natural infiltration and vibration infiltration, entrained rare-earth solution and the organic phase are reclaimed for recycling; the solid phase after liquid phase is separated and 3 to 5 weight percent of soluble bicarbonate (or carbonate) solution are mixed according to the volume ratio of V third phase to V carbonate equals of 1:1-5:1, are heated at the temperature of between 50 and 80 DEG C and stirred for 0.5 to 3 hours in a stirring tank for demulsification; the water phase and the organic phase are separated after phase separation is stilled for 1 to 3 hours; the organic phase is mixed with 3-6N acid according to the volume ratio of V organic phase to V acid equals of 1-5:1 and stirred for 1 to 3 hours for back-extraction; and the organic phase is cleaned with water and recycled until pH of cleaning water is 2 to 3. The method has the characteristics of simple operation and high reclamation rate of rare-earth and organic phase; and the original property of the reclaimed rare-earth and organic phase can be maintained.
Description
Technical field
The present invention relates to reclaim in the rare earth extraction third phase method of rare earth and organic phase, belong to the hydrometallurgy field.
Background technology
The enrichment of inorganic impurity is the major cause that causes producing in the rare earth extraction process third phase.Owing to contain facile hydrolysis impurity cationic Fe in the rare earth feed liquid
3+, Al
3+Deng, producing oxyhydroxide after the hydrolysis mixes back formation third phase with organic phase; Also contain sedimentable Ca in the rare earth feed liquid
2+, Mg
2+Deng, the throw out of formation with also form third phase after organic phase is mixed; Solid suspended particle with also can generate third phase after organic phase is mixed; The not pure and mild degraded of organic phase also forms third phase in addition.Therefore the generation of third phase is inevitable in the rare earth extraction process.Third phase produces not only influences extraction efficiency, wastes rare earth and organic phase simultaneously; In airtight extraction system, the loss of organic phase more than 80% because due to third phase forms.
Though carry a large amount of liquid in the third phase secretly, because mutual package action is difficult to by standing sedimentation parting liquid solid phase; Because its viscosity is big, also can't filter, so be difficult to reclaim.Now common treating method is mainly long-term placement, relies on natural separation slowly to reclaim small part rare earth and organic phase, leaves standstill usually and has only a small amount of phase-splitting more than half a year, and rare earth yield is about 20%, the organic phase rate of recovery about 10%.
Patent application " to the processing recovery method of the emulsification phase that produces in the rare earths material extracting and separating " (publication number CN1218113) directly behind the hydrochloric acid or sulfuric acid, nitric acid and emulsion splitter breakdown of emulsion with 1-10 times of emulsification phase (being third phase described in the present invention) volume, is reclaimed rare earth and organic phase.This method acid consumption is bigger, and needs repeatedly to handle the recovery that just can finish rare earth and organic phase, a large amount of excessive sour follow-up need processing.
" Study on processing method of emulsification in the rare earth extraction sepn process " that Yang Junhai etc. deliver (" rare earth " 2003 the 24th volumes the 6th phase 25-29 page or leaf) adopts the emulsification (being third phase described in the present invention) that produces in the sepn process of hydrofluoric acid treatment rare earth extraction, the article conclusion is for " adopting hydrofluoric acid to handle; effect is fine; organic phase and rare earth can all reclaim, and the organic phase of handling out is returned cell body and cell body do not had any impact." because the corrodibility and the toxicity of hydrofluoric acid is big, and rare earth fluoride separation difficulty, fluoride waste difficult treatment that hydrofluoric acid generates in the aqueous solution easily cause characteristics such as environmental pollution, the widespread use difficulty is very big in industrial production.
Summary of the invention
The recovery method that the purpose of this invention is to provide a kind of simple to operate and effective thired extracting phase improves the rare earth and the organic phase rate of recovery, and chemical constitution and character do not change, and can return to produce and use.
The technical solution used in the present invention may further comprise the steps:
A) the rare earth extraction third phase reclaims the rare earth feed liquid and the load organic phases of carrying secretly and returns use through diafiltration;
B) solid phase after the diafiltration is with solubility carbonic acid hydrogen salt or carbonate solution mixing post-heating and stir breakdown of emulsion;
C) leave standstill water phase separated behind the breakdown of emulsion;
D) load organic phases reclaims rare earth after use is returned in washing with sour back extraction.
The natural filtration after vibration diafiltration in 1～4 hour 0.5～4 hour in diafiltration equipment of described step a), rare earth extraction third phase.
Described step b), the solid phase after the diafiltration is V with 3～5wt% solubility carbonic acid hydrogen salt or carbonate solution mixed volume ratio
Gu: V
Liquid=1: 1～5: 1.
Described step b), it is 50～80 ℃ that the solid phase after the diafiltration stirs the breakdown of emulsion temperature.
Described step b), it is 0.5～3 hour that the solid phase after the diafiltration stirs the breakdown of emulsion time.
Described step c) leaves standstill phase-splitting water phase separated after 1～3 hour behind the breakdown of emulsion.
Described step d), load organic phases is with 3～6N HCl or HNO
3Or H
2SO
4Or rare earth was reclaimed in the HAC back extraction in 1～2 hour.
Described step d), load organic oppositing back-extraction volume ratio are V
Organic phase: V
Acid=1: 1～1: 2.
Described step d), organic phase becomes blank organic phase and returns use after the back extraction after being washed to wash water PH=2～3.
Described vibration diafiltration is to vibrate with 30-300Hz, amplitude 2-5mm.
The present invention is simple to operate, the rate of recovery height of rare earth and organic phase, and the rare earth of recovery and organic phase keep original character, can directly return use.
Description of drawings:
Fig. 1 reclaims rare earth and organic phase process schematic flow sheet in the rare earth extraction third phase.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment one
Referring to Fig. 1, get the Dy/Ho grouping groove P507 rare earth extraction third phase 1000kg (the about 1000L of volume) that contains REO 2wt%, organic phase 22wt%, add in the 1500L diafiltration equipment, natural filtration vibrated diafiltration 0.5 hour with 300Hz, amplitude 2mm after 1 hour, reclaim rare earth feed liquid 186L, reclaim rare earth after measured and amount to REO=14.6kg; Reclaiming the load organic phases that reclaims behind load organic phases 15kg and the breakdown of emulsion together handles.Solid phase after the diafiltration is mixed with the solution of potassium carbonate 780L of 3wt% in reactor, stirs breakdown of emulsion 0.5 hour after being heated to 80 ℃, leave standstill again phase-splitting after 1 hour from reactor bottom drainage water phase; All load organic phases are mixed stirring back extraction in 1 hour with 6mol/L acetic acid 400L, leave standstill phase-splitting 2 hours, from reactor bottom drainage water phase, reclaim rare earth behind the water filtering insolubles and amount to REO=4.4kg; Organic phase washes with water 2 times, to the whole PH=3 of wash water.Add up to and reclaim blank organic phase 195kg, the organic phase rate of recovery 88.6%; Add up to and reclaim rare earth REO=19kg, rare earth yield 95%.
Embodiment two
Referring to Fig. 1, get the La/Nd groove P507 rare earth extraction third phase 1000kg that contains REO 2.3wt%, organic phase 25wt%, add in the 1500L diafiltration equipment, natural filtration vibrated diafiltration 2 hours with 50Hz, amplitude 3mm after 3 hours, reclaim rare earth feed liquid 195L, reclaim rare earth after measured and amount to REO=16.3kg; Reclaiming the load organic phases that reclaims behind load organic phases 26kg and the breakdown of emulsion together handles.Solid phase after the diafiltration with after the sodium hydrogen carbonate solution 160L of 5wt% mixes, is heated to 50 ℃ and stirred breakdowns of emulsion 3 hours in reactor, static phase-splitting after 1.5 hours from reactor bottom drainage water phase; Load organic phases is mixed stirring back extraction in 2 hours with 5N hydrochloric acid 200L, and static phase-splitting 2 hours from reactor bottom drainage water phase, is reclaimed rare earth REO=5.8kg behind the water filtering insolubles; Organic phase washes with water 2 times, and to the whole PH=2 of wash water, washing water discard.Add up to and reclaim organic phase 197kg, the organic phase rate of recovery 89.2%; Add up to and reclaim rare earth REO=22.1kg, rare earth yield 96%.The organic phase and the rare earth element that reclaim all are directly used in production.
Embodiment three
Referring to Fig. 1, get the Ce/Pr groove P507 rare earth extraction third phase 1000kg that contains REO 1.6wt%, organic phase 16wt%, add in the 1500L diafiltration equipment, natural filtration vibrated diafiltration 4 hours with 50Hz, amplitude 5mm after 4 hours, reclaim rare earth feed liquid 173L, reclaim rare earth after measured and amount to REO=11.7kg; Reclaiming the load organic phases that reclaims behind load organic phases 18kg and the breakdown of emulsion together handles.Solid phase after the diafiltration with after the sodium carbonate solution 400L of 4wt% mixes, stirred breakdown of emulsion 2 hours after being heated to 70 ℃ in reactor, water is discharged in static phase-splitting from reactor after 3 hours; All load organic phases are mixed stirring back extraction in 2 hours with 3mol/l nitric acid 300L in reactor, static phase-splitting 2 hours, and from reactor bottom drainage water phase, water filtering insolubles reclaims rare earth REO=3.2kg; Organic phase washes with water 2 times, to the whole PH=2 of wash water; Add up to and reclaim organic phase 138kg, the organic phase rate of recovery 86.25%; Add up to and reclaim rare earth REO=22.1kg, rare earth yield 93.12%; The organic phase and the rare earth element that reclaim all are directly used in production.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (10)
1. reclaim the method for rare earth and organic phase in the rare earth extraction third phase, it is characterized in that may further comprise the steps:
A) the rare earth extraction third phase reclaims the rare earth feed liquid and the load organic phases of carrying secretly and returns use through diafiltration;
B) solid phase after the diafiltration is with solubility carbonic acid hydrogen salt or carbonate solution mixing post-heating and stir breakdown of emulsion;
C) leave standstill water phase separated behind the breakdown of emulsion;
D) load organic phases reclaims rare earth after use is returned in washing with sour back extraction.
2. according to the method that reclaims rare earth and organic phase in the described a kind of rare earth extraction third phase of claim 1, it is characterized in that step a), the natural filtration after vibration diafiltration in 1～4 hour 0.5～4 hour in diafiltration equipment of rare earth extraction third phase.
3. according to the method that reclaims rare earth and organic phase in the described a kind of rare earth extraction third phase of claim 1, it is characterized in that step b), the solid phase after the diafiltration is V with 3～5wt% solubility carbonic acid hydrogen salt or carbonate solution mixed volume ratio
Gu: V
Liquid=1: 1～5: 1.
4. according to the method that reclaims rare earth and organic phase in the described a kind of rare earth extraction third phase of claim 1, it is characterized in that step b), it is 50～80 ℃ that the solid phase after the diafiltration stirs the breakdown of emulsion temperature.
5. according to the method that reclaims rare earth and organic phase in the described a kind of rare earth extraction third phase of claim 1, it is characterized in that step b), it is 0.5～3 hour that the solid phase after the diafiltration stirs the breakdown of emulsion time.
6. according to the method that reclaims rare earth and organic phase in the described a kind of rare earth extraction third phase of claim 1, it is characterized in that step c), leave standstill phase-splitting water phase separated after 1～3 hour behind the breakdown of emulsion.
7. according to the method that reclaims rare earth and organic phase in the described a kind of rare earth extraction third phase of claim 1, it is characterized in that step d), load organic phases is with 3～6N HCl or HNO
3Or H
2SO
4Or rare earth was reclaimed in the HAC back extraction in 1～2 hour.
8. according to the method that reclaims rare earth and organic phase in the described a kind of rare earth extraction third phase of claim 1, it is characterized in that step d), the load organic oppositing back-extraction volume ratio is V
Organic phase: V
Acid=1: 1～1: 2.
9. according to the method that reclaims rare earth and organic phase in the described a kind of rare earth extraction third phase of claim 1, it is characterized in that step d), organic phase becomes blank organic phase and returns use after the back extraction after being washed to wash water pH=2～3.
10. according to the natural filtration after vibration diafiltration in 1～4 hour 0.5～4 hour in diafiltration equipment of the described rare earth extraction third phase of claim 2, it is characterized in that vibrating diafiltration, vibrate with 30-300Hz, amplitude 2-5mm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862505A (en) * | 2015-06-05 | 2015-08-26 | 乐山盛和稀土股份有限公司 | Method for recycling organic phase from rare earth extract dregs |
| CN109112308A (en) * | 2018-08-21 | 2019-01-01 | 广西银亿新材料有限公司 | A kind of processing method of third phase in hydrometallurgical extraction system |
| CN109306403A (en) * | 2018-10-27 | 2019-02-05 | 湖南懋天世纪新材料有限公司 | The processing method of quaternary ammonium salt alkaline extraction three-phase flocculate in tungsten hydrometallurgy |
| CN111647744A (en) * | 2020-07-01 | 2020-09-11 | 四川省冕宁县方兴稀土有限公司 | Method for recovering organic and rare earth from bastnaesite extraction three phases |
| CN113584329A (en) * | 2021-07-29 | 2021-11-02 | 赣州稀土友力科技开发有限公司 | Recovery method for extracting three-phase substances from neodymium iron boron waste |
| CN115418504A (en) * | 2022-08-25 | 2022-12-02 | 萍乡鑫森新材料有限责任公司 | Method for extracting rare earth from rare earth organic slag |
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| JPH04147929A (en) * | 1990-10-11 | 1992-05-21 | Mitsubishi Materials Corp | Separation of rare earth element |
| CN1074487A (en) * | 1992-01-16 | 1993-07-21 | 北京有色金属研究总院 | Emulsive removing method in the extraction process |
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2010
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| JPH04147929A (en) * | 1990-10-11 | 1992-05-21 | Mitsubishi Materials Corp | Separation of rare earth element |
| CN1074487A (en) * | 1992-01-16 | 1993-07-21 | 北京有色金属研究总院 | Emulsive removing method in the extraction process |
| CN101602519A (en) * | 2008-06-12 | 2009-12-16 | 北京有色金属研究总院 | A kind of technology of directly preparing rare-earth compound from extraction separation load organic phase |
Non-Patent Citations (1)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862505A (en) * | 2015-06-05 | 2015-08-26 | 乐山盛和稀土股份有限公司 | Method for recycling organic phase from rare earth extract dregs |
| CN104862505B (en) * | 2015-06-05 | 2016-08-17 | 乐山盛和稀土股份有限公司 | A kind of method reclaiming organic phase in rare earth extraction slag |
| CN109112308A (en) * | 2018-08-21 | 2019-01-01 | 广西银亿新材料有限公司 | A kind of processing method of third phase in hydrometallurgical extraction system |
| CN109306403A (en) * | 2018-10-27 | 2019-02-05 | 湖南懋天世纪新材料有限公司 | The processing method of quaternary ammonium salt alkaline extraction three-phase flocculate in tungsten hydrometallurgy |
| CN111647744A (en) * | 2020-07-01 | 2020-09-11 | 四川省冕宁县方兴稀土有限公司 | Method for recovering organic and rare earth from bastnaesite extraction three phases |
| CN111647744B (en) * | 2020-07-01 | 2021-09-21 | 四川省冕宁县方兴稀土有限公司 | Method for recovering organic and rare earth from bastnaesite extraction three phases |
| CN113584329A (en) * | 2021-07-29 | 2021-11-02 | 赣州稀土友力科技开发有限公司 | Recovery method for extracting three-phase substances from neodymium iron boron waste |
| CN115418504A (en) * | 2022-08-25 | 2022-12-02 | 萍乡鑫森新材料有限责任公司 | Method for extracting rare earth from rare earth organic slag |
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