CN108950251A - The recovery method of rare earth element - Google Patents
The recovery method of rare earth element Download PDFInfo
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- CN108950251A CN108950251A CN201810866629.2A CN201810866629A CN108950251A CN 108950251 A CN108950251 A CN 108950251A CN 201810866629 A CN201810866629 A CN 201810866629A CN 108950251 A CN108950251 A CN 108950251A
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- rare earth
- earth element
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- oxide
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 104
- 238000011084 recovery Methods 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000007788 liquid Substances 0.000 claims abstract description 66
- 238000000605 extraction Methods 0.000 claims abstract description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- -1 rare-earth chloride Chemical class 0.000 claims abstract description 24
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 21
- 238000005345 coagulation Methods 0.000 claims abstract description 20
- 230000015271 coagulation Effects 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002893 slag Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001940 europium oxide Inorganic materials 0.000 claims abstract description 8
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910003451 terbium oxide Inorganic materials 0.000 claims abstract description 8
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims abstract description 7
- 229940075624 ytterbium oxide Drugs 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 30
- 239000012535 impurity Substances 0.000 claims description 26
- 238000005498 polishing Methods 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 238000012216 screening Methods 0.000 claims description 15
- 239000002699 waste material Substances 0.000 claims description 15
- 239000003350 kerosene Substances 0.000 claims description 11
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 238000007127 saponification reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical class CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 25
- 239000012071 phase Substances 0.000 description 15
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 12
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 8
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 7
- 239000000284 extract Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 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
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/262—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds using alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/32—Carboxylic acids
- C22B3/324—Naphthenic acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides a kind of recovery methods of rare earth element.Sample to be processed includes one of cerium oxide and/or terbium oxide, lanthana, praseodymium oxide, ytterbium oxide and europium oxide or a variety of, the recovery method includes: to be handled using hydrochloric acid sample to be processed, so that sour solvable rare earth component dissolves, coagulation liquid and the first solid slag are obtained；So that coagulation liquid and the first organic extractant is carried out the first extraction process, obtains two stage treatment liquid and organic extraction phase；The pH of two stage treatment liquid is adjusted to 2~5, obtains tertiary treatment liquid and the second solid slag；Second extraction process is carried out to tertiary treatment liquid using the second organic extractant, back extraction processing is then carried out to the extraction phase that the second extraction process obtains using stripping agent, obtains at least one single rare-earth chloride solution；Single rare-earth chloride solution is set successively to carry out precipitation reaction and calcination processing, with recovering rare earth element.This method has many advantages, such as easily operated, and processing cost is low and the rare earth element rate of recovery is high.
Description
Technical field
The present invention relates to the recycling fields of rare earth element, in particular to a kind of recovery method of rare earth element.
Background technique
Rare-earth products are widely used to computer communication, automobile, space flight and aviation, Medical Devices and colour TV saving energy of screen lamp
Etc. multiple industries, and obtain significant progress.China's energy conservation lamp phosphor market scale in 2013 is more than 1200 tons, compared with 2009
Year market demand increase by 97.34%, annual growth is up to 18.52%.Since (about 12000 is small for the restricted lifetime of energy saving lamp source
When), a large amount of fluorescent powder scraps can be accordingly generated during energy-saving lamp is discarded, colour TV polishing powder is also such.Due to polishing powder
The promotion of quality, colour TV screen also thin down, and old television set is also largely eliminated, and can thus generate a large amount of throwing
Light powder waste material.Rare earth element is non-renewable precious resources, thus is recycled from above-mentioned fluorescent powder scrap and polishing powder waste material
Rare earth element just becomes extremely important.However there is a problem of that the rate of recovery is lower when using existing method recovering rare earth element, this
The economic value of fluorescent powder scrap and polishing powder waste material is significantly reduced, while also resulting in the waste of resource.
Summary of the invention
The main purpose of the present invention is to provide a kind of recovery methods of rare earth element, to solve to use existing method pair
There is a problem of that the rate of recovery is lower when rare earth element is recycled.
To achieve the goals above, the present invention provides a kind of recovery method of rare earth element, the recovery method wait locate
Reason sample includes sour solvable component and the insoluble component of acid, and the insoluble component of acid includes cerium oxide and/or terbium oxide, sour solvable group
Dividing includes one of lanthana, praseodymium oxide, ytterbium oxide and europium oxide or a variety of, and recovery method includes: to treat place using hydrochloric acid
Reason sample is handled, so that sour solvable rare earth component dissolves, obtains coagulation liquid and the first solid slag；Make coagulation liquid with
First organic extractant carries out the first extraction process, obtains two stage treatment liquid and organic extraction phase；By the pH tune of two stage treatment liquid
To 2~5, tertiary treatment liquid and the second solid slag are obtained；Second is carried out to tertiary treatment liquid using the second organic extractant to extract
Then journey carries out back extraction processing to the extraction phase that the second extraction process obtains using stripping agent, obtain at least one single dilute
Native chloride solution；Single rare-earth chloride solution is set successively to carry out precipitation reaction and calcination processing, with recovering rare earth element.
Further, using hydrochloric acid to sample to be processed in the process of processing, reaction temperature be 80~90 DEG C.
Further, it is C that the first organic extractant, which includes carbon atom number,7~C9Aphthenic acids；Preferably, first organic extraction
Taking agent further includes isooctanol and kerosene；It is highly preferred that in the first organic extractant, the volume ratio of aphthenic acids, isooctanol and kerosene
For 25:10:65.
Further, the second organic extractant is selected from the soap that two (2- ethyl hexyl) phosphates and/or saponification degree are 30%
Change P507.
Further, stripping agent is selected from water or the weak acid solution of pH=2.
Further, preparation method further includes that the pH of two stage treatment liquid is adjusted to 3.5~4.0, obtains tertiary treatment liquid.
Further, precipitating reagent used in precipitation reaction process is selected from ammonium hydrogen carbonate and/or oxalic acid.
Further, before being dissolved using hydrochloric acid to sample to be processed, recovery method further include: by sample to be processed
Product carry out screening process, obtain screening product, wherein screening aperture is 20~30 mesh；Screening product is subjected to neutralization reaction, is obtained
To coagulation liquid and the first solid slag.
Further, sample to be processed is selected from polishing powder waste material and/or fluorescent powder scrap；Preferably, useless to account for polishing powder
The weight of material, polishing powder waste material include 55~95% rare earth element and the impurity of surplus；Wherein, by accounting for rare earth
The weight of element, rare earth element include 65% cerium oxide, 34% lanthana and 1% praseodymium oxide.
Further, to account for the weight of the useless element material of fluorescent powder, fluorescent powder scrap include 65~90% it is dilute
The impurity of earth elements and surplus；Wherein, by the weight for accounting for rare earth element, rare earth element include 3% praseodymium oxide,
20% cerium oxide, 35% terbium oxide, 22% ytterbium oxide and 20% europium oxide
It applies the technical scheme of the present invention, the rare earth element in sample to be processed mostly exists in the form of the oxide, is divided into
Sour solvable component and the insoluble component of acid.When being handled using hydrochloric acid sample to be processed, sour solvable component is dissolved, and sour
Insoluble component is precipitated in the form precipitated, obtains coagulation liquid.Since there are non-rare earth impurity in coagulation liquid
Ion is extracted using the first organic extractant and coagulation liquid, by the part non-rare earth in coagulation liquid
Foreign ion (such as silica, calcium ion, aluminium ion, phosphate anion) removal, obtain two stage treatment liquid (rare earth chloride it is molten
Liquid).It, will due to still containing a small amount of non-rare earth foreign ion (such as iron ion, aluminium ion) in above-mentioned two stage treatment liquid
The pH of above-mentioned two stage treatment liquid is adjusted to 2~5, so that it is removed in the form of precipitating, obtains tertiary treatment liquid.It is organic using second
Extractant extracts the rare earth element in above-mentioned three-level extract liquor, is then stripped using stripping agent, respectively obtains and contain
There is the single rare earth chloride solution of high-purity rare-earth.Above-mentioned single rare-earth chloride solution is finally set to carry out precipitation reaction respectively
It is handled with calcination, to recycle required rare earth element.The recovery method of rare earth element provided by the present application has processing method letter
It is single, easily operated, the advantages that processing cost is low and the rare earth element rate of recovery is high.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows the technique of the recovery method for the rare earth element that a kind of typical embodiment according to the present invention provides
Flow chart.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As described in background technique, it is lower that there are the rate of recovery when being recycled using existing method to rare earth element
The problem of.In order to solve the above-mentioned technical problem, this application provides a kind of recovery method of rare earth element, the recovery method to
Processing sample includes sour solvable component and the insoluble component of acid, and the insoluble rare earth component of acid includes cerium oxide and/or terbium oxide, acid
Soluble constituent includes one of lanthana, praseodymium oxide, ytterbium oxide and europium oxide or a variety of.Above-mentioned recovery method includes: to use
Hydrochloric acid handles above-mentioned sample to be processed, so that sour solvable component dissolves, obtains coagulation liquid and the first solid slag；Make one
Grade treatment fluid and the first organic extractant carry out the first extraction process, obtain two stage treatment liquid and organic extraction phase；At second level
The pH of reason liquid is adjusted to 2~5, obtains tertiary treatment liquid and the second solid slag；Tertiary treatment liquid is carried out using the second organic extractant
Then second extraction process carries out back extraction processing using the extraction phase that the second extraction process of stripping agent obtains, obtains at least one
Single earth solution；Above-mentioned single earth solution is set successively to carry out precipitation reaction and calcination processing, with recovering rare earth element.
Rare earth element in sample to be processed mostly exists in the form of the oxide, is divided into sour solvable component and insoluble group of acid
Point.When being handled using hydrochloric acid sample to be processed, sour solvable component is dissolved, and form of the insoluble component of acid to precipitate
It is precipitated, obtains coagulation liquid.Since there are non-rare earth foreign ions in coagulation liquid, using the first organic extractant
Extracted with coagulation liquid, by coagulation liquid part non-rare earth foreign ion (such as silica, calcium from
Son, aluminium ion, phosphate anion etc.) removal, obtain two stage treatment liquid (solution of rare earth chloride).Due to above-mentioned two stage treatment liquid
In still there are also a small amount of non-rare earth foreign ion (such as iron ion, aluminium ion), the pH of above-mentioned two stage treatment liquid is adjusted to 2
~5, so that it is removed in the form of precipitating, obtain tertiary treatment liquid.Using the second organic extractant to above-mentioned three-level extract liquor
In rare earth element extracted, be then stripped using stripping agent, respectively obtain the single rare earth chlorine containing high-purity rare-earth
Compound solution.Above-mentioned single rare-earth chloride solution is finally set to carry out precipitation reaction and calcination processing respectively, needed for recycling
Rare earth element.The recovery method of rare earth element provided by the present application has processing method simple, and easily operated, processing cost is low
And the rare earth element rate of recovery it is high the advantages that.
The application in order to better understand, it should be noted that being extracted using the second organic extractant to tertiary treatment liquid
The process taken includes: that the second organic extractant and tertiary treatment liquid carry out extraction process, obtain the extraction phase containing ytterbium chloride and
Raffinate containing lanthanum chloride, praseodymium chloride and Europium chloride；Using the second organic extractant to contain lanthanum chloride, praseodymium chloride and chlorination
The raffinate of europium is extracted, and the extraction phase containing Europium chloride and the raffinate containing lanthanum chloride and praseodymium chloride are obtained；Using
Two organic extractants extract the raffinate containing lanthanum chloride and praseodymium chloride, obtain the extraction phase containing praseodymium chloride and contain
Lanthanum chloride raffinate (single lanthanum chloride solution)；Above-mentioned extraction phase is stripped respectively using stripping agent (hydrochloric acid), it can
To respectively obtain single ytterbium chloride solution, single Europium chloride solution and single praseodymium chloride solution.
Extraction mechanism are as follows:
In tertiary treatment liquid containing there are many rare earth ion (such as lanthanum ion, praseodymium ion, ytterbium ion and europium ion), by
It is different in extracting power of first organic extractant to different rare earth ions, and extracting power is with the increase of the number of nuclear charges
And enhance.Thus by repeating extraction process, one of rare earth ion can be extracted to organic phase, and it is remaining
Rare earth ion remain in water phase, then by extraction organic phase carry out back extraction processing, obtain single rare earth
Chloride solution, and then realize and separate the rare earth-iron-boron in tertiary treatment liquid, obtain single rare earth-iron-boron
Solution.
The recovery method of rare earth element provided by the present application is conducive to improve the rate of recovery of rare earth element.A kind of preferred
In embodiment, using hydrochloric acid to sample to be processed in the process of processing, sample middle rare earth and hydrochloric acid to be processed
The ratio between molal quantity be 1:1.5~2.0.The amount ratio of sample and hydrochloric acid to be processed includes but is not limited to above range, and by its
The content for being conducive to further increase rare earth element in coagulation liquid within the above range is limited, to be conducive to further mention
The rate of recovery of high rare earth element.
In a preferred embodiment, using hydrochloric acid to sample to be processed in the process of processing, reaction temperature
It is 80~90 DEG C.In the process of processing using hydrochloric acid, the temperature of reaction includes but is not limited to above range, and is limited
Be conducive to further increase the solubility of rare earth element within the above range, and then be conducive to improve the recycling of subsequent rare earth element
Rate.
In first extraction process, the first organic extractant can use extractant commonly used in the art.A kind of preferred
In embodiment, the first organic extractant includes but is not limited to that carbon atom number is C7~C9Aphthenic acids.
The principle that aphthenic acids is extracted are as follows: in extraction process, by the H in aphthenic acids+It is replaced with impurity, thus will
Impurity is transferred in organic phase, and then by stripping process, impurity is removed.The characteristics of being cleaned using aphthenic acids are as follows: (1) extracting
During taking, aphthenic acids only extracting impurities, and other extractants extracting rare-earth element and impurity simultaneously, separating effect is not achieved；
(2) less expensive of aphthenic acids.And when the carbochain of aphthenic acids is longer, the viscosity of extractant is too big, when carbochain is shorter,
The water solubility of extractant is larger, thus the C that the application uses7~C9Aphthenic acids as the first organic extractant, this is not only advantageous
In the water solubility and viscosity of control aphthenic acids, the separative efficiency of rare earth element and foreign ion is also advantageously improved, and then advantageous
In the rate of recovery for improving final rare earth element, the economic benefit of the recovery method is improved.
Preferably, above-mentioned first organic extractant further includes isooctanol and kerosene.Using isooctanol and kerosene and carbon atom
Number is C7~C9Aphthenic acids mixture as extractant, this is conducive to improve the first organic extractant to the extraction of foreign ion
Ability is taken, and then is conducive to improve the separative efficiency of impurity and rare earth element.It is highly preferred that carbon atom in the first organic extractant
Number is C7~C9Aphthenic acids, isooctanol and kerosene volume ratio be 25:10:65.
In second extraction process, the second organic extractant can use extractant commonly used in the art.A kind of preferred
In embodiment, the second organic extractant includes but is not limited to two (2- ethyl hexyl) phosphates (P204) and/or saponification degree is
30% saponification P507.Second organic extractant includes but is not limited to above two extractant, and selects above two extractant
Be conducive to improve the separative efficiency and purity of rare earth-iron-boron.In order to further increase the separative efficiency between each rare earth element,
The purity for improving rare-earth chloride solution, it is highly preferred that above-mentioned second organic extractant is the saponification P507 that saponification degree is 30%.
In a preferred embodiment, in the second extraction process, stripping agent includes but is not limited to water or PH=2
Weak acid solution.
It, can be molten to single rare earth chloride using precipitating reagent commonly used in the art in the precipitation process of above-mentioned recovery method
Rare earth element in liquid is precipitated.In a preferred embodiment, precipitating reagent used in precipitation reaction process includes
But it is not limited to ammonium hydrogen carbonate and/or oxalic acid.
It can include the impurity of some bulky grains in usual sample to be processed, this is unfavorable for subsequent removal process.In order to drop
Influence of the low large granular impurity to removal process and the rate of recovery for improving rare earth element, in a preferred embodiment,
Before being dissolved using hydrochloric acid to sample to be processed, above-mentioned recovery method further include: sample to be processed is subjected to screening process,
Screening product is obtained, aperture≤20~30 mesh are sieved；Screening product is subjected to neutralization reaction, coagulation liquid and first is obtained and consolidates
Slag.
In recovery method provided by the present application, sample to be processed can be fluorescent powder scrap and/or polishing powder waste material.One
In kind of preferred embodiment, to account for the weight of polishing powder waste material, polishing powder waste material include 55~95% it is dilute
The impurity of earth elements and surplus；Wherein, by the weight for accounting for rare earth element, rare earth element includes 65% oxidation
Cerium, 34% lanthana and 1% praseodymium oxide.In a preferred embodiment, to account for the weight percent of fluorescent powder scrap
Content meter, fluorescent powder scrap include 65~90% rare earth element and the impurity of surplus；Wherein, by the weight hundred for accounting for rare earth element
Divide content meter, rare earth element includes 3% praseodymium oxide, 20% cerium oxide, 35% terbium oxide, 22% ytterbium oxide and 20%
Europium oxide.Fluorescent powder scrap and polishing powder waste material content of rare earth with higher with above-mentioned composition, but ingredient is more
Complexity, the rate of recovery of rare earth is low when being recycled using conventional recovery method to rare earth element.And it uses provided by the present application
Recovery method can greatly improve the rate of recovery of rare earth element.
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally
Apply for range claimed.
Embodiment 1
Sample to be processed includes: polishing powder waste material and fluorescent powder scrap.Wherein, polishing powder waste material includes the rare earth of 70wt%
Other impurity (such as Fe of element, the silica of 29wt% and 1wt%2O3、Al2O3, phosphate anion, fluorine ion, calcium oxide
And glass dregs etc.).Wherein, the group of rare earth element becomes the cerium oxide of 65wt%, the oxidation of the lanthana and 1wt% of 34wt%
Praseodymium, impurity are mainly silica；Praseodymium oxide of the group of fluorescent powder scrap as 3wt%, the cerium oxide of 20wt%, 35wt%'s
Terbium oxide, the ytterbium oxide of 22wt%, the europium oxide of 20wt%.
It is handled using process flow chart shown in FIG. 1, the specific steps are as follows:
By powdered solid waste by screening (sieve pore is 20 mesh), to remove large granular impurity (such as glass dregs),
Obtain screening materials carrying.
Under conditions of temperature is 80 DEG C, by the dissolving with hydrochloric acid (and a small amount of water) of above-mentioned screening materials carrying 30wt%, and
It is separated by solid-liquid separation, obtains coagulation liquid and the first solid slag, wherein the ratio between screening materials carrying middle rare earth and the molal quantity of hydrochloric acid
For 1:1.5.
Use the first organic extractant (cycloheptyl acid, isooctanol and kerosene are made by volume for 25:10:65) to above-mentioned one
Grade treatment fluid carries out the first extraction process, two stage treatment liquid and organic extraction phase is obtained, wherein the first organic extractant and level-one
The volume ratio for the treatment of fluid is 1:1.
The pH of above-mentioned two stage treatment liquid is adjusted to 3.5 using ammonium hydroxide, so that partial impurities ion conversion is precipitating, solid-liquid point
From rear, tertiary treatment liquid is obtained.
Using the second organic extractant, (saponification degree is for the concentration of P507 in 30% P507 and the mixed solution of kerosene
The second extraction process 1.5mol/L) is carried out to above-mentioned tertiary treatment liquid.Specifically, the second organic extractant and tertiary treatment liquid into
Row extraction process obtains the extraction phase containing ytterbium chloride and the raffinate containing lanthanum chloride, praseodymium chloride and Europium chloride；Using second
Organic extractant extracts the raffinate containing lanthanum chloride, praseodymium chloride and Europium chloride, obtains the extraction phase containing Europium chloride
With the raffinate containing lanthanum chloride and praseodymium chloride；Using the second organic extractant to the raffinate containing lanthanum chloride and praseodymium chloride into
Row extraction obtains the extraction phase containing praseodymium chloride and contains lanthanum chloride raffinate (single lanthanum chloride solution)；Using stripping agent
(hydrochloric acid of 6mol/L) is respectively stripped above-mentioned extraction phase, can respectively obtain single ytterbium chloride solution, single
Europium chloride solution and single praseodymium chloride solution.
At 70 DEG C, above-mentioned single re chloride is precipitated respectively using precipitating reagent (oxalic acid), is obtained dilute
Native sediment, wherein the weight ratio of rare earth-iron-boron and oxalic acid is 1:1.5. each time in precipitation process.Then by above-mentioned rare earth
Sediment carries out calcination at 800 DEG C, obtains required rare earth oxide.The purity of rare earth oxide obtained is greater than
99wt%, rate of recovery 98wt%, impurities removing efficiency 99wt%.
Embodiment 2
With the difference of embodiment 1 are as follows: the pH of two stage treatment liquid is adjusted to 2, obtains tertiary treatment liquid and the second solid slag.
The purity of rare earth oxide obtained is greater than 98wt%, rate of recovery 95wt%, impurities removing efficiency 98wt%.
Embodiment 3
With the difference of embodiment 1 are as follows: using hydrochloric acid to the sample to be processed in the process of processing, reaction temperature is
70℃。
The purity of rare earth oxide obtained is greater than 98wt%, rate of recovery 95wt%, impurities removing efficiency 98wt%.
Embodiment 4
With the difference of embodiment 1 are as follows: the first organic extractant is that ring valeric acid, isooctanol and kerosene are 25:10 by volume:
Solution made from 65.
The purity of rare earth oxide obtained is greater than 95wt%, rate of recovery 98wt%, impurities removing efficiency 95wt%.
Embodiment 5
With the difference of embodiment 1 are as follows: the first organic extractant is that cycloheptyl acid, isooctanol and kerosene are 15:10 by volume:
Solution made from 75.The purity of rare earth oxide obtained is greater than 94wt%, rate of recovery 97wt%, impurities removing efficiency 94wt%.
Embodiment 6
With the difference of embodiment 1 are as follows: second organic extractant is selected from two (2- ethyl hexyl) phosphate (P204)。
The purity of rare earth oxide obtained is greater than 96wt%, rate of recovery 98wt%, impurities removing efficiency 95wt%.
Comparative example 1
With the difference of embodiment 1 are as follows: the pH of uncomfortable section two stage treatment liquid obtains tertiary treatment liquid and the second solid slag.
The purity of rare earth oxide obtained is greater than 88wt%, rate of recovery 92wt%, impurities removing efficiency 90wt%.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
Comparing embodiment 1 to 6 and comparative example 1 using the preparation method of rare earth element provided by the present application it is found that be conducive to
Improve the rate of recovery and purity of rare earth element.
Comparing embodiment 1 and 2 and comparative example 1 are it is found that the pH of two stage treatment liquid is adjusted to have in the preferred range of the application
Conducive to the rate of recovery and purity for improving rare earth element.
It is excellent to be limited to the application it is found that during using dissolving with hydrochloric acid sample by comparing embodiment 1 and 3 for solution temperature
The range of choosing is conducive to improve the rate of recovery and purity of rare earth element.
Comparing embodiment 1,4,5 and 6 is it is found that using preferred first organic extractant of the application and the second organic extractant
Be conducive to improve the rate of recovery and purity of rare earth element.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of recovery method of rare earth element, which is characterized in that the sample to be processed of the recovery method includes sour solvable group
Divide and the insoluble component of acid, the insoluble component of acid include cerium oxide and/or terbium oxide, the sour solvable component includes oxidation
One of lanthanum, praseodymium oxide, ytterbium oxide and europium oxide are a variety of, and the recovery method includes:
The sample to be processed is handled using hydrochloric acid, so that the sour solvable rare earth component dissolves, obtains coagulation
Liquid and the first solid slag；
So that the coagulation liquid and the first organic extractant is carried out the first extraction process, obtains two stage treatment liquid and organic extraction
Phase；
The pH of the two stage treatment liquid is adjusted to 2~5, obtains tertiary treatment liquid and the second solid slag；
Second extraction process is carried out to the tertiary treatment liquid using the second organic extractant, then using stripping agent to described the
The extraction phase that two extraction process obtain carries out back extraction processing, obtains at least one single rare-earth chloride solution；
The single rare-earth chloride solution is set successively to carry out precipitation reaction and calcination processing, to recycle the rare earth element.
2. recovery method according to claim 1, which is characterized in that described to be carried out using hydrochloric acid to the sample to be processed
During processing, reaction temperature is 80~90 DEG C.
3. recovery method according to claim 1 or 2, which is characterized in that first organic extractant includes carbon atom
Number is C7~C9Aphthenic acids；Preferably, first organic extractant further includes isooctanol and kerosene；It is highly preferred that described
In one organic extractant, the volume ratio of the aphthenic acids, the isooctanol and the kerosene is 25:10:65.
4. recovery method according to any one of claim 1 to 3, which is characterized in that the second organic extractant choosing
The saponification P507 for being 30% from two (2- ethyl hexyl) phosphates and/or saponification degree.
5. recovery method according to claim 4, which is characterized in that the stripping agent is selected from water or the weak acid of pH=2
Solution.
6. recovery method according to any one of claim 1 to 3, which is characterized in that the preparation method further include by
The pH of the two stage treatment liquid is adjusted to 3.5~4.0, obtains the tertiary treatment liquid.
7. recovery method according to any one of claim 1 to 3, which is characterized in that make during the precipitation reaction
Precipitating reagent is selected from ammonium hydrogen carbonate and/or oxalic acid.
8. recovery method according to any one of claim 1 to 3, which is characterized in that in use hydrochloric acid to sample to be processed
Before product are dissolved, the recovery method further include:
The sample to be processed is subjected to screening process, obtains screening product, wherein screening aperture is 20~30 mesh；
The screening product is subjected to neutralization reaction, obtains the coagulation liquid and first solid slag.
9. recovery method according to claim 1, which is characterized in that the sample to be processed be selected from polishing powder waste material and/
Or fluorescent powder scrap；Preferably, to account for the weight of the polishing powder waste material, the polishing powder waste material includes 55~
95% rare earth element and the impurity of surplus；Wherein, by the weight for accounting for the rare earth element, the rare earth element
Including 65% cerium oxide, 34% lanthana and 1% praseodymium oxide.
10. recovery method according to claim 9, which is characterized in that contained with accounting for the weight percent of the fluorescent powder scrap
Meter, the fluorescent powder scrap include 65~90% rare earth element and the impurity of surplus；Wherein, by accounting for the rare earth element
Weight, the rare earth element include 3% praseodymium oxide, 20% cerium oxide, 35% terbium oxide, 22% oxygen
Change the europium oxide of ytterbium and 20%.
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