CN102639729B - Method for extracting rare earth elements from phosphogypsum - Google Patents
Method for extracting rare earth elements from phosphogypsum Download PDFInfo
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- CN102639729B CN102639729B CN2010800392652A CN201080039265A CN102639729B CN 102639729 B CN102639729 B CN 102639729B CN 2010800392652 A CN2010800392652 A CN 2010800392652A CN 201080039265 A CN201080039265 A CN 201080039265A CN 102639729 B CN102639729 B CN 102639729B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 42
- 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 27
- 238000000605 extraction Methods 0.000 claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000010440 gypsum Substances 0.000 claims abstract description 12
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000005341 cation exchange Methods 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims abstract description 3
- 238000005342 ion exchange Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 7
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 4
- 239000001117 sulphuric acid Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 26
- 238000011084 recovery Methods 0.000 description 14
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011435 rock Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012445 acidic reagent Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- -1 phosphorus compound Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QUEAJVXWJZWZHH-UHFFFAOYSA-L [OH3+].P(=O)([O-])([O-])[O-].[Ti+2] Chemical compound [OH3+].P(=O)([O-])([O-])[O-].[Ti+2] QUEAJVXWJZWZHH-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
-
- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/065—Nitric acids or salts thereof
-
- 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
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention relates to methods for extracting rare earth elements, in particular from phosphogypsum. The proposed method involves the acid extraction of rare earth element compounds from phosphogypsum using a solution consisting of a mixture of sulphuric acid and nitric acid in a ratio of 3.2:1.2 with a concentration of 1-3 wt% and a liquid to solid ratio of 4:5 over a period of 8-12 minutes, while the extraction suspension is agitated and subjected to a hydroacoustic effect. The insoluble gypsum residue is then separated from the extraction suspension and the rare earth element compounds are recovered from the extraction solution by cation exchange sorption with the extraction solution being passed through a cation exchange filter.; The method makes it possible to raise the level of extraction of rare earth elements and halve the time taken to carry out the process, while using smaller concentrations and volumes of acid reagents.
Description
The present invention relates to for rare earth element, particularly reclaim from phosphogypsum the method for the compound of rare earth element.
In current rare-earth industry, the expense greater than 60% is relevant with mining and preparation of ore.Therefore, it is prefitable that the primary products that industry is produced are used, and wherein rare earth element is the accessory constituent that goes out from the subsurface mineral resource exploitation.For these purposes, can use the phosphatic rock phosphogypsum as primary products.During the phosphatic rock concentrate is in order to the vitriolization of making mineral manure, produce phosphogypsum.With by CaSO
4* 2H
2What the plaster of paris stone that O constitutes formed contrast is that phosphogypsum is the technology original prod.Here it is, and why the latter has the reason of quite a large amount of impurity, and described impurity is the compound of rare earth and other element (8-19%).The composition that depends on the phosphatic rock concentrate, the content of rare earth element are 0.5-1.1%.
Exist to relate to from phosphogypsum and reclaim rare earth element (referring to RF patent N 2225892 MPK C22B 59/00) and relate to the currently known methods that uses 25% sulphuric acid soln to handle phosphogypsum.The rate of recovery of rare earth element is 50.0-60.2%.The time of this vitriolization is 3 hours; Sulfuric acid concentration is 20-25 weight %, and liquid-solid ratio equals 2-3.By making the sulphite of rare earth element breed crystal seed (inoculate) to carry out the crystallization of rare earth element to surpass 100 liquid-solid ratio.Such technical requirements production relates to a large amount for the treatment of facilities.In addition, the shortcoming of this method comprises the processing operation of the low rate of recovery of rare earth element, quite big quantity, recycle sulfuric acid solution and the time loss of large volume.
There is another kind of currently known methods, this method relates to the compound that used the 22-30% sulphuric acid soln to handle rare earth element and phosphorus and is extracted in the solution in 20-25 minute, formation contains the insoluble gypsum resistates (RF patent N 2337897, MPK C 01F11/46) of a large amount of sulfuric acid and phosphoric acid.Extraction solution also contains the double sulfate of rare earth element and sodium or potassium.With Ca (OH)
2, CaO or CaCO
3The gained crystal gypsum is handled so that the resistates depickling of sulfuric acid and phosphoric acid, unless their pH value surpasses 5.Need to control the content of phosphorus impurities in the waste liquid simultaneously, this depends on their content and the ratio of remaining gypsum humidity, uses TiOSO
4H
2O this waste liquid is extracted or purification process up to obtaining admissible P
2O
5Content.
This method allows to realize and will be extracted into up to 82.1% rare earth element in the extraction solution, wherein with the rate of recovery up to 68.5% they further is separated into enriched material by crystallization.
The shortcoming of this method is that the pH value of gained crystal gypsum does not meet admissible building standard and high P
2O
5Concentration.Lanthanon is suitable time-consuming procedure (2 hours) from the separation of supersaturation extraction solution.Should control the residual humidity of content and the gypsum resistates of phosphorus impurities in the acid extraction agent.For removing excessive phosphorus, need specific installation to make the phosphorus compound depickling in order to use dry titanium compound or the mixture of titanium and the vitriol oil, and further separate the titanium phosphate oxonium salt simultaneously and use the vitriol oil to force to handle.If the concentration of sulfuric acid is reduced to and is lower than 22% in the extraction solution, then should the reclaim(ed) sulfuric acid enriched material so that it can be used for this process again.This will need a large amount of reactors, be used for the storage of the extraction of rare earth element, different extraction solutions and make housing apparatus and the filter plant of phosphorus compound depickling.
Exist and a kind ofly with 85% separation rate (separation) rare earth element is recovered to known nitric acid technology the solution from phosphatic rock, described solution also contains phosphorus and fluorine (V.D.Kosynkin etc., " State of the Art and Development Perspectives of Rare-Earth Industry in Russia "-" Metals ", N 1,2001).
The most similarly be followingly to reclaim the method for rare earth element (referring to RF patent N 2293781 from phosphogypsum with the method for advocating, MPK C 22B 59/00), this method relates to uses the vitriolization phosphogypsum, further be extracted into rare earth element in the solution, isolate insoluble gypsum resistates, improve the content of supersaturated solution middle-weight rare earths element so that the enriched material crystallization of rare earth element, this enriched material is separated with waste liquid and it is handled.Before the separatin non-soluble resistates, use the sulfuric acid of 22-30% (by weight) concentration in 20-30 minute, to handle phosphogypsum to avoid rare earth element from the spontaneous crystallization of solution with the liquid-solid ratio of 1.8-2.2.Because the sodium content of 0.4-1.2g/l obtains the supersaturation of this solution.
The shortcoming of this currently known methods is to need the acid of other reagent, high density and their sizable volumes, much have the basic fundamental operation of inadequate rare earth element rate of recovery and an overall complexity of this method.
The objective of the invention is to obtain to improve the technique effect that reclaims the efficient of rare earth element from the phosphogypsum extraction, it is owing to the minimizing of auxiliary reagent, the reduction of the concentration of acid reagent and in addition by reducing the basic fundamental operation and improving the rate of recovery and the simplified method that rare earth element enters extraction solution.
This technique effect is by obtaining for the method that reclaims rare earth element from phosphogypsum according to the present invention, when this method is included in hybrid extraction suspension from phosphogypsum acid extract rare earth element, the insoluble residue of crystallization phosphogypsum is isolated and reclaimed rare earth element from this extraction solution from extraction solution, use has 1-3 weight % concentration, ratio is that sulfuric acid-nitrate mixture of 3.2-1.2 carried out acid extract with the liquid-solid ratio of 4-5 in 8-12 minute, and simultaneously the extraction suspension that mixes is carried out the underwater sound (hydroacoustic) effect, and use cation exch ange adsorption to carry out rare earth element from the recovery of this extraction solution by making extraction solution through positively charged ion-exchange strainer.
The extraction solution that does not contain rare earth element can be regenerated and isolate in order to the rare earth element that further uses in the stage of phosphogypsum acid extract and will be fettered by the sorbent material from positively charged ion-exchange strainer, this moment, strainer obtained regeneration.
As proving by experiment, formed acidic waste can be used as sulfuric acid-nitrate mixture when producing nitrocotton.
The principal character of advocating of the present invention that can obtain technique effect is as follows.
When using sulfuric acid-nitrate mixture to handle phosphogypsum, rare earth element and sulfuric acid and nitric acid interact.As with the sulfuric acid results of interaction, rare earth element dissolved in 10 minutes, entered in the solution from the sodium of phosphogypsum and potassium cationic simultaneously and formed double sulfate with therein rare earth element.The solubleness of the double sulfate of sodium and rare earth element and potassium and rare earth element in sulphuric acid soln all is low (referring to E.P.Lokshin etc., " Recovery Issues of Rare Earth Metals During Sulfuric Processing of Khibin Apatite Concentrate "-" Metals ", N 1,2001) and be good in nitric acid.
Prove that by experiment the concrete ratio of the mixture of above-mentioned acid and concentration and underwater sound effect simultaneously provide the condition that is used for reclaiming comparatively fully from phosphogypsum rare earth element.
The possibility of rare earth element crystallization has been got rid of in the acid extraction of using sulfuric acid-nitrate mixture to carry out with the liquid-solid ratio of 4-5 before gypsum separates, and can make suspension best in extractor and the stable mixing of acquisition when this suspension is passed through rotation-oscillation device.The use of the mixture of sulfuric acid and nitric acid helps other impurity separating fully from gypsum crystal.
Because the constant underwater sound effect to phosphogypsum extraction suspension can obtain the compound of rare earth element and other impurity and the needed Best Times of interaction (8-12 minute) of sulfuric acid and nitric acid.The pass through working element (element) of rotation-oscillation device of suspension, and gypsum stands intense mechanical and grinds and become the particle (participle) with 10-15 μ m and carry out cavitation under corresponding to the parameter of ultrasonic frequency.This is that 150-250mm diameter and spinner velocity are that the operator scheme of rotation-oscillation device of 50Hz is guaranteed by its working element especially.Described parameter in the rotation-oscillation device produces strong influence to the suspension in the labyrinth type between its rotor and stator (labyrinth) space (10-15 μ m), thereby and the Mechanical Crushing that the crystal cavitation occurs make mass transfer process quite fast.Known this supersound process is used for making physics and chemical process violent (referring to L.D.Rosenberg " Ultrasonics ", M., 1956) more.
After finishing extraction process, with suspension impouring separating unit, for example centrifuge separator or strainer go out crystal gypsum in this from solution separating.
Described solution is supplied to the positively charged ion-exchange strainer of the compound that contains absorption rare earth element and phosphorus.The solution that leaves this positively charged ion-exchange strainer is the aqueous solution of sulfuric acid and nitric acid and is recovering can be used for this process again after the sour ratio.The resistates of rare earth element is separated with the working-surface of positively charged ion-exchange strainer, and this strainer can be used for the other absorption of rare earth element.
Experimental results show that the purposes of the mixture of the so-called acidic waste that when using different methods to produce soluble cotton, forms.The rate of recovery that experimental result shows rare earth element is close to the rate of recovery that obtains when using 3 weight % concentration sour.
Above-mentioned feature of the present invention has been guaranteed the realization of this method and allow have been reduced the quantity of reagent and time that consumption and this technological process are required and the load of base unit.They also help to improve the rate of recovery of rare earth element and make the technological process optimization on the whole.
The essence of the method for advocating can be understood by following examples.
Embodiment:
Embodiment 1
Slag material (dump) phosphogypsum (phosphatic rock) that 100kg is contained 0.45% rare earth element is handled when using sulfuric acid-nitrate mixture solution of 1 weight % to mix in big capacity pot type extractor with 5 liquid-solid ratio in 10 minutes.Accordingly, sulfuric acid and nitric acid are included in the described mixture with the ratio of 3: 1 (weight part).During extraction process, mix when suspension flowed through rotation-oscillation device in 10 minutes and it is carried out the underwater sound handle.These parameters have been guaranteed the required stability of suspension and to the underwater sound effect of its generation.The rotor diameter of rotation-oscillation device is 150mm, and its rotational frequency is 50Hz, and feeding rate is 5m
3/ h.For solution is separated with the crystallization phosphogypsum, in separating centrifuge, handle gained suspension.
The sample analysis of use ICPMS (inductively coupled plasma mass spectrometry) demonstrates and equals 86.1% the rare earth element rate of recovery.
Make the solution that contains rare earth element through positively charged ion-exchange strainer.The enriched material of rare earth element is the products obtained therefrom of this method on positively charged ion-exchange strainer.The rate of recovery is 86.1%.Reuse acidic extractant (after making its process positively charged ion-exchange strainer and regenerating).
In following table, shown the rare earth element rate of recovery based on the experiment of carrying out.
As finding out from above-described embodiment and table, the method of advocating makes the raising rare earth element reach 85-86.1% and the time of extraction process is reduced by half from the rate of recovery of phosphogypsum, allows to use the less reagent of low concentration and acid reagent and the permission of smaller size smaller to reduce many technological operations.
The method of advocating can be used for industrial application, and condition is to use and rotates-standard equipment of vibrating device and positively charged ion-exchange combination of filters.
Claims (3)
1. method that reclaims rare earth element from phosphogypsum, this method comprises: in hybrid extraction suspension, from phosphogypsum acid extract rare earth element, insoluble crystal gypsum resistates is isolated and reclaimed rare earth element from described extraction solution from extraction solution, the method is characterized in that in 8-12 minute sulfuric acid-nitrate mixture of using sulfuric acid with 1-3 weight % concentration and nitric acid 3.2:1-1.2:1 weight ratio and carry out described acid extract with the liquid-solid ratio of 4-5, simultaneously the extraction suspension that mixes is produced underwater sound effect, and use cation exch ange adsorption to reclaim described rare earth element through positively charged ion-exchange strainer from described extraction solution by making described extraction solution.
2. according to the process of claim 1 wherein described rare earth element is regenerated described extraction solution after described extraction solution reclaims, and carrying out acid extract again.
3. use when producing soluble cotton formed acidic waste as described sulfuric acid-nitrate mixture according to the process of claim 1 wherein.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/RU2010/000504 WO2011008137A2 (en) | 2009-07-16 | 2010-09-14 | Method for extracting rare earth elements from phosphogypsum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102639729A CN102639729A (en) | 2012-08-15 |
| CN102639729B true CN102639729B (en) | 2013-09-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2010800392652A Expired - Fee Related CN102639729B (en) | 2010-09-14 | 2010-09-14 | Method for extracting rare earth elements from phosphogypsum |
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| KR (1) | KR101690819B1 (en) |
| CN (1) | CN102639729B (en) |
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| RU2519692C1 (en) * | 2012-11-12 | 2014-06-20 | Закрытое Акционерное Общество "Твин Трейдинг Компани" | Extraction of rare-earth elements from hard materials containing rare-earth metals |
| RU2528573C1 (en) * | 2013-03-05 | 2014-09-20 | Открытое акционерное общество "Объединенная химическая компания "УРАЛХИМ" | Method of extracting rare-earth metals and producing gypsum plaster from phosphogypsum hemihydrate |
| RU2543160C2 (en) * | 2013-03-18 | 2015-02-27 | Открытое акционерное общество "Объединенная химическая компания "УРАЛХИМ" | Method of sulphuric acid decomposition of rem-containing phosphate raw material |
| CN104357663B (en) * | 2014-11-10 | 2016-06-15 | 德阳三汇太阳能发电设备有限公司 | A kind of ardealite Application way |
| CN104724746B (en) * | 2015-02-15 | 2017-01-11 | 潍坊学院 | Method for recycling ardealite |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0265547A1 (en) * | 1986-10-30 | 1988-05-04 | URAPHOS CHEMIE GmbH | Method of recovering rare earths, and in a given case, uranium and thorium from heavy phosphate minerals |
| PL155815B1 (en) * | 1988-05-16 | 1992-01-31 | Politechnika Krakowska | Method of recovering lanthanides from phospogypsum wastes |
| FR2643911B1 (en) * | 1989-03-03 | 1992-06-12 | Rhone Poulenc Chimie | PROCESS FOR TREATING RARE EARTH ORES |
| RU2225892C1 (en) * | 2002-07-23 | 2004-03-20 | Институт химии и технологии редких элементов и минерального сырья им. И.В.Тананаева Кольского научного центра РАН | Method of recovering rare-earth minerals from phosphogypsum |
| RU2293781C1 (en) * | 2005-07-04 | 2007-02-20 | Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук | Method of recovering rare-earth elements from phosphogypsum |
| CN100471963C (en) | 2007-02-05 | 2009-03-25 | 扬州大学 | Ultrasonic leaching-extracting separation method for sulphating roasting rare earth mine |
| CN101451200B (en) * | 2007-11-29 | 2011-04-20 | 北京有色金属研究总院 | Rare-earth enrichment recovery method from phosphorite |
| US8206024B2 (en) | 2007-12-28 | 2012-06-26 | Kimberly-Clark Worldwide, Inc. | Ultrasonic treatment chamber for particle dispersion into formulations |
| CN101597688A (en) * | 2008-06-03 | 2009-12-09 | 贵州光大能源发展有限公司 | From phosphogypsum, reclaim a kind of method of rare earth |
| CN101597687A (en) * | 2008-06-03 | 2009-12-09 | 贵州光大能源发展有限公司 | The sulfuric acid rare earth that goes out from the phosphogypsum leaching solution crystallization is converted into the method for rare earth chloride |
| CN101824536B (en) * | 2009-03-03 | 2011-12-14 | 北京有色金属研究总院 | Process for extracting rare-earth from sulfuric acid treating phosphorite process |
-
2010
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| Publication number | Publication date |
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| CN102639729A (en) | 2012-08-15 |
| KR101690819B1 (en) | 2016-12-28 |
| KR20130040765A (en) | 2013-04-24 |
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