CN105803229B - A kind of extraction and separation technology for directly preparing 5N level europiums - Google Patents
A kind of extraction and separation technology for directly preparing 5N level europiums Download PDFInfo
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- 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
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- 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
- C22B3/28—Amines
- C22B3/282—Aliphatic amines
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- 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
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
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Abstract
A kind of extraction and separation technology for directly preparing 5N level europiums of the present invention, it is feed liquid using P229 as extractant, relative purity 2N~3N level Europium chloride solution, including 8 steps, wherein 3 separating steps and 5 additional steps；3 separating steps are respectively NdSmEu/EuGdTb centrifugal stations, NdSm/Eu centrifugal stations and Eu/GdTb centrifugal stations, and 5 additional steps are respectively concentration section, Cui Suan workshop sections, rare-earth sodium saponification workshop section I, stripping section and rare-earth sodium saponification workshop section II.NdSm/Eu separation separates series connection with Eu/GdTb.The present invention can obtain the 5N level high purity europium products that relative purity is 99.9990%~99.9995%, and yield is 87.40%~96.94%.It is of the invention that there is the advantages such as europium product purity is high, europium product yield is high, production scale is big, chemical reagent consumes less, easy to operate, production cost is low.
Description
Technical field
The present invention relates to a kind of extraction and separation technology for directly preparing 5N level europiums, more particularly to acid phosphonate reagent P229
For rare-earth extractant, using relative purity 2N~3N level Europium chloride solution as feed liquid, prepare relative purity be 5N level europium products extraction
Take separating process.The invention belongs to the technical field of rare-earth separation in solvent extraction.
Background technology
Europium is widely used in the high-tech areas such as fluorescent material, magnetic bubble material, optical glass material.Relative purity (i.e. rare earth
Relative purity, when be often simply called purity) for 99.999% (abbreviation 5N) europium product be the important thing for preparing high-performance europium material
Matter basis.
There is product to be below 5N levels prepared by traditional solvent extraction.In May, 1985, Application No. 85104034
Chinese patent uses is prepared for the europium product that purity reaches 3N5 (99.95%) level by solvent extraction.At present, purity is prepared to reach
Method to 5N level europium products mainly has cation exchange resin, extration resin method and reduction europium method (including electroreduction, zinc powder
Reduction etc.).
Relative to cation exchange resin, extration resin method and reduction europium method, solvent extraction have product yield it is high,
The advantages such as production scale is big, chemical reagent consumes less, automaticity is high, easy to operate, production cost is low.Therefore, solvent extracts
It ought to be the prefered method for preparing 5N europium products to follow the example of.Chlorination of the present invention using relative purity as 2N~3N (99%~99.9%)
Europium solution is feed liquid, using new rare-earth sodium saponification technology, the optimization for being fully loaded with abstraction technique, concentration technique and separation process etc.
To improve the purity of europium product, so as to establish the separation work for preparing 5N level high purity europium products using fractional extraction as core technology
Skill.
In separating technology, the important technology index for evaluating ion exchange resin is effective exchange capacity.Effectively exchange and hold
Measure abbreviation exchange capacity sometimes.Effective exchange capacity of anionic ion-exchange resins refers to that every kg dried resins effectively exchange monovalence
The molal quantity of anion.By the way, total exchange capacity of the dried resin of certain mass is calculated by below equation：
N=m × Q (1)
In formula (1), m is the quality of dried resin, and its unit is kg；Q is effective exchange capacity of resin, and its unit is mol/
kg；N is total exchange capacity, and its unit is mol.From formula (1), maximum when total exchange capacity refers to give resin quality m is effectively
Exchange capacity.In fact, maximum exchange molal quantity when total exchange capacity is exactly given resin quality m, therefore total exchange capacity is also referred to as
It is total to exchange molal quantity.
The content of the invention
The purpose of the present invention be for not there is the technique that solvent extraction prepares 5N level europium products so far, establish one kind with
P229 is the direct extraction and separation technology for preparing 5N level europiums of extractant.
A kind of extraction and separation technology for directly preparing 5N level europiums of the present invention, using P229 as extractant, relative purity 2N~3N
Level Europium chloride solution is feed liquid, including 8 steps, wherein 3 separating steps and 5 additional steps；3 separating steps are respectively
NdSmEu/EuGdTb centrifugal stations, NdSm/Eu centrifugal stations and Eu/GdTb centrifugal stations, 5 additional steps are respectively to concentrate
Workshop section, Cui Suan workshop sections, rare-earth sodium saponification workshop section I, stripping section and rare-earth sodium saponification workshop section II.Cui Suan workshop sections often referred to simply as extract acid
Section；Concentration section is often referred to simply as enriching section；Stripping section is often referred to simply as stripping section；Saponification workshop section is often referred to simply as saponification
Section.NdSm/Eu separation separates series connection with Eu/GdTb.Step is specific as follows：
1) NdSmEu/EuGdTb centrifugal stations
The first step is that NdSmEu/EuGdTb is fully loaded with fractional extraction centrifugal station, realizes that NdSmEu/EuGdTb is separated.Come from
4th step rare-earth sodium saponification workshop section I rare-earth sodium saponification P229 organic phases I is fully loaded with the fractional extraction system first order from NdSmEu/EuGdTb
Into relative purity 2N~3N level Europium chloride solution is fully loaded with fractional extraction system charging level from NdSmEu/EuGdTb and entered, and comes from
The raffinate aqueous phase Europium chloride gadolinium terbium solution of 3rd Bu Cuisuan workshop sections is expired as detergent from afterbody into NdSmEu/EuGdTb
Carry fractional extraction system；Fractional extraction system first order raffinate aqueous phase, which is fully loaded with, from NdSmEu/EuGdTb obtains NdSmEu feed liquids, with
Rare earth molal quantity meter, wherein 84.4995%~84.5411% is used for the 4th step rare-earth sodium saponification workshop section I, remaining 15.5005%~
15.4589% is used as the feed liquid of the 5th step NdSm/Eu centrifugal stations；Fractional extraction system is fully loaded with from NdSmEu/EuGdTb most
Rear stage obtains load EuGdTb organic phases, in terms of rare earth molal quantity, wherein 94.6938%~94.7062% is directly entered the
Two step concentration sections, remaining 5.3062%~5.2938% raw material as the 6th step Eu/GdTb centrifugal stations.
The rare earth concentration of described Europium chloride feed liquid is 0.5mol/L~1.5mol/L, and wherein the relative purity of europium is 99%
~99.9%, pH value range is 2~4.
2) concentration section
Second step is concentration section, realizes the concentration of the load EuGdTb organic phases of the first step.Load EuGdTb organic phases
Concentration use concentration as 2.8mol/L~3.0mol/L hydrochloric acid, countercurrent reextraction load EuGdTb organic phases in rare earth
EuGdTb；It is the ︰ 1 of 3.5 ︰ 1~3.7 to control the ratio between rare earth molal quantity in the molal quantity and load EuGdTb organic phases of hydrochloric acid；From
What aqueous phase obtained more than the back extraction of concentration section contains sour Europium chloride gadolinium terbium solution, is all transferred to the 3rd Bu Cuisuan workshop sections.
3) Cui Suan workshop sections
3rd step is Cui Suan workshop sections, and N235 extractions remove containing in sour Europium chloride gadolinium terbium solution obtained by second step concentration section
Remaining hydrochloric acid.Extract sour organic phase as N235 and the sulfonated kerosene solution of tributyl phosphate, wherein N235 concentration is 0.6mol/
L, the concentration of tributyl phosphate is 0.4mol/L.Control extracts N235 molal quantity in sour organic phase and contains sour Europium chloride gadolinium terbium solution
In the ratio between remaining hydrochloric acid molal quantity be 2:The extraction of 1,8 stage countercurrent is removed containing the remaining hydrochloric acid in sour Europium chloride gadolinium terbium solution.Extraction
Sour workshop section's outlet organic phase is load hydrochloric acid N235 organic phases；Cui Suan workshop sections outlet raffinate aqueous phase Europium chloride gadolinium terbium solution is all used
Make the detergent of first step NdSmEu/EuGdTb centrifugal stations.
4) rare-earth sodium saponification workshop section I
4th step is rare-earth sodium saponification workshop section I, realizes the rare-earth sodium saponification of P229 extraction organic phases.Control comes from the first step
The NdSmEu feed liquids middle rare earth of NdSmEu/EuGdTb centrifugal stations and the mol ratio of P229 extractants are 0.12 ︰ 1, hydroxyl type
Strong-basicity styrene anion exchange resin with respect to chlorion total exchange molal quantity and NdSmEu feed liquid middle rare earth molal quantity it
Than for 8 ︰ 1；P229 extraction organic phases are sequentially added in saponification device, from first step NdSmEu/EuGdTb centrifugal stations
NdSmEu feed liquids, effective exchange capacity with respect to chlorion be 4mol/kg~6mol/kg and average grain diameter be 0.4mm~
0.6mm hydroxyl type strong-basicity styrene anion exchange resin.After being sufficiently stirred 60min at room temperature, stratification.Upper strata
For rare-earth sodium saponification P229 organic phases, middle level is aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state；Release
Aqueous phase and strong-basicity styrene anion exchange resin phase, obtain rare-earth sodium saponification P229 organic phase I, and its saponification rate is 36%.It is dilute
Rare-earth sodium saponification P229 organic phases I obtained by native saponification workshop section I is completely used for first step NdSmEu/EuGdTb centrifugal stations.
The sulfonated kerosene solution that described P229 extractions organic phase is P229, wherein P229 concentration be 0.5mol/L~
1.5mol/L。
5) NdSm/Eu centrifugal stations
5th step is NdSm/Eu fractional extraction centrifugal stations, realizes that NdSm/Eu is separated.From the 8th step rare earth soap chemical industry
Section II rare-earth sodium saponification P229 organic phases II enters from the NdSm/Eu fractional extraction systems first order, from first step NdSmEu/
The NdSmEu feed liquids of EuGdTb centrifugal stations enter from NdSm/Eu fractional extractions system charging level, divide from the 6th step Eu/GdTb
First order raffinate aqueous phase from workshop section enters NdSm/Eu fractional extraction systems as detergent from afterbody；From NdSm/Eu points
Evaporate extraction system first order raffinate aqueous phase and obtain separation product richness neodymium samarium feed liquid；From last of NdSm/Eu fractional extraction systems
Level obtains load Eu organic phases, and load Eu organic phases are used as the rare-earth sodium saponification organic phase of the 6th step Eu/GdTb centrifugal stations, entirely
Portion enters the first order of the 6th step Eu/GdTb centrifugal stations.
6) Eu/GdTb centrifugal stations
6th step is organic charging Eu/GdTb fractional extraction centrifugal stations, realizes that Eu/GdTb is separated.From the 5th step
The load Eu organic phases of NdSm/Eu centrifugal stations enter from the Eu/GdTb fractional extraction systems first order, from the first step
The load EuGdTb organic phases of NdSmEu/EuGdTb centrifugal stations enter from Eu/GdTb fractional extractions system charging level, washing acid
Enter Eu/GdTb fractional extraction systems from afterbody；Separated from Eu/GdTb fractional extraction system first order raffinate aqueous phases
Product 5N level high purity europiums；The rich GdTb organic phases of load are obtained from the afterbody of Eu/GdTb fractional extraction systems, the load is rich
GdTb organic phases fully enter the 7th step stripping section.
Described washing acid is 1.6mol/L~1.8mol/L hydrochloric acid；
In described separation product 5N level high purity europiums the ratio between the molal quantity of europium and rare earth molal quantity be 0.999990~
0.999995, relative purity is 99.9990%~99.9995%, and yield is 87.40%~96.94%.
7) stripping section
7th step is stripping section, realizes the back extraction for loading rich GdTb organic phases.Use concentration for 3.0mol/L~
3.2mol/L hydrochloric acid is back extraction acid, and countercurrent reextraction loads the rare earth element in rich GdTb organic phases；Mole of control back extraction hydrochloric acid
Number is the ︰ 1 of 3.6 ︰ 1~3.8 with loading the ratio between rare earth molal quantity in rich GdTb organic phases；Aqueous phase obtains more than the back extraction of stripping section
Product richness gadolinium terbium must be separated.
8) rare-earth sodium saponification workshop section II
8th step is rare-earth sodium saponification workshop section II, realizes the rare-earth sodium saponification of P229 extraction organic phases.Control comes from the 5th step
The rich neodymium samarium feed liquid middle rare earth of NdSm/Eu centrifugal stations is 0.12 with the mol ratio of P229 extractants:1, hydroxyl type strong basicity
Styrenic anion exchanger resin is 8 ︰ with respect to the ratio between total exchange molal quantity of chlorion and rich neodymium samarium feed liquid middle rare earth molal quantity
1；Sequentially added in saponification device P229 extraction organic phase, the rich neodymium samarium feed liquid from the 5th step NdSm/Eu centrifugal stations,
The hydroxyl type that effective exchange capacity with respect to chlorion is 4mol/kg~6mol/kg and average grain diameter is 0.4mm~0.6mm
Strong-basicity styrene anion exchange resin.After being sufficiently stirred 60min at room temperature, stratification.Upper strata is rare-earth sodium saponification P229
Organic phase, middle level are aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state；Release aqueous phase and strong basicity benzene
Ethene anion exchange resin phase, obtains rare-earth sodium saponification P229 organic phase II, and its saponification rate is 36%.II institutes of rare-earth sodium saponification workshop section
The rare-earth sodium saponification P229 organic phases II obtained is completely used for the 5th step NdSm/Eu centrifugal stations.
The sulfonated kerosene solution that described P229 extractions organic phase is P229, wherein P229 concentration be 0.5mol/L~
1.5mol/L。
Described NdSm/Eu separation separates series connection with Eu/GdTb.
Advantages of the present invention：The advantages of fractional extraction has not only been fully retained in the present invention, and separating technology is carried out
Optimization.Therefore, it is of the invention with europium product purity is high, europium product yield is high, production scale is big, chemical reagent consumes less, operates
The easy, advantage such as production cost is low.
Brief description of the drawings
Fig. 1 is the extraction and separation technology flow chart of the present invention；
In Fig. 1, saponification section is the abbreviation of saponification workshop section；Extract the abbreviation that sour section is Cui Suan workshop sections；Enriching section is concentration section
Abbreviation；Stripping section is the abbreviation of stripping section.
Embodiment
With reference to specific embodiment to it is of the present invention it is a kind of directly prepare 5N level europiums extraction and separation technology make into
One step describes.
Embodiment 1
1) NdSmEu/EuGdTb centrifugal stations
The first step is that NdSmEu/EuGdTb is fully loaded with fractional extraction centrifugal station, realizes that NdSmEu/EuGdTb is separated.Come from
The P229 rare-earth sodium saponifications organic phase that the saponification rate of 4th step is 0.36 is fully loaded with the 1st grade of fractional extraction system from NdSmEu/EuGdTb
Into, the Europium chloride feed liquid that pH value 3, rare earth concentration 1.0mol/L, the relative purity of europium are 99.5% from NdSmEu/
EuGdTb is fully loaded with the 49th grade of entrance of fractional extraction system, and the raffinate aqueous phase Europium chloride gadolinium terbium solution from the 3rd Bu Cuisuan workshop sections is made
Enter NdSmEu/EuGdTb from the 62nd grade for detergent and be fully loaded with fractional extraction system.Fractional extraction is fully loaded with from NdSmEu/EuGdTb
The 1st grade of raffinate aqueous phase of system obtains NdSmEu feed liquids, in terms of rare earth molal quantity, wherein 84.5227% is used for the 4th step rare earth soap
Chemical industry section I, remaining 15.4773% feed liquid as the 5th step NdSm/Eu centrifugal stations；From the fully loaded fractionation of NdSmEu/EuGdTb
The 62nd grade of extraction system obtains load EuGdTb organic phases, in terms of rare earth molal quantity, wherein 94.6993% is directly entered second
The concentration section of step, remaining 5.3007% raw material as the 6th step Eu/GdTb centrifugal stations.
NdSmEu/EuGdTb is fully loaded with fractional extraction centrifugal station：Normalize extraction quantity S=4.235112, normalization washing
Measure W=4.010623.The Cui Qu Liang ︰ Europium chloride Liao Ye ︰ washing amounts=︰ 4.010623 (rare earth ion mol ratio) of 4.235112 ︰ 1.
Extraction section extraction is than being 0.845227, and washing section extraction is than being 1.055974.
2) concentration section
Second step is concentration section, realizes the concentration of the load EuGdTb organic phases of the first step.Load EuGdTb organic phases
Concentration use hydrochloric acid of the concentration for 2.9mol/L, the rare earth EuGdTb in 12 stage countercurrents back extraction load EuGdTb organic phases；Control
The molal quantity of salt manufacturing acid is 3.6 ︰ 1 with loading the ratio between rare earth molal quantity in EuGdTb organic phases.More than the back extraction of concentration section
What aqueous phase obtained contains sour Europium chloride gadolinium terbium solution, is all transferred to the 3rd Bu Cuisuan workshop sections.
3) Cui Suan workshop sections
3rd step is Cui Suan workshop sections, and N235 extractions remove containing in sour Europium chloride gadolinium terbium solution obtained by second step concentration section
Remaining hydrochloric acid.Extract sour organic phase as N235 and the sulfonated kerosene solution of tributyl phosphate, wherein N235 concentration is 0.6mol/
L, the concentration of tributyl phosphate is 0.4mol/L.Control extracts N235 molal quantity in sour organic phase and contains sour Europium chloride gadolinium terbium solution
In the ratio between remaining hydrochloric acid molal quantity be 2:The extraction of 1,8 stage countercurrent is removed containing the remaining hydrochloric acid in sour Europium chloride gadolinium terbium solution.Extraction
Sour workshop section's outlet organic phase is load hydrochloric acid N235 organic phases；Cui Suan workshop sections outlet raffinate aqueous phase Europium chloride gadolinium terbium solution is all used
Make the detergent of first step NdSmEu/EuGdTb centrifugal stations.
4) rare-earth sodium saponification workshop section I
4th step is rare-earth sodium saponification workshop section I, realizes the rare-earth sodium saponification of P229 extraction organic phases.Control is from the first step
The mol ratio of NdSmEu feed liquids middle rare earth and P229 extractants is 0.12:1, hydroxyl type strong-basicity styrene anion exchange tree
Lipid phase is 8 ︰ 1 to the ratio between total exchange molal quantity (i.e. total exchange capacity) of chlorion and NdSmEu feed liquid middle rare earth molal quantitys；In soap
Change the P229 sulfonated kerosene solution for sequentially adding that concentration is 1.0mol/L in reactor, the NdSmEu feed liquids from the first step, phase
The hydroxyl type strong-basicity styrene anion that effective exchange capacity to chlorion is 5mol/kg and average grain diameter is 0.5mm
Exchanger resin.After being sufficiently stirred 60min at room temperature, stratification.Upper strata is rare-earth sodium saponification P229 organic phases, and middle level is aqueous phase,
Lower floor is the strong-basicity styrene anion exchange resin phase of solid-state；Release aqueous phase and strong-basicity styrene anion exchange resin
Phase, obtains rare-earth sodium saponification P229 organic phases, and its saponification rate is 36%.Rare-earth sodium saponification P229 obtained by rare-earth sodium saponification workshop section I is organic
Mutually it is completely used for first step NdSmEu/EuGdTb centrifugal stations.
5) NdSm/Eu centrifugal stations
5th step is NdSm/Eu fractional extraction centrifugal stations, realizes that NdSm/Eu is separated.Rare-earth sodium saponification from the 8th step
From the 1st grade of entrance of NdSm/Eu fractional extractions system, the NdSmEu feed liquids from the first step are fractionated P229 organic phases from NdSm/Eu
The 13rd grade of entrance of extraction system, the 1st grade of raffinate aqueous phase from the 6th step Eu/GdTb centrifugal stations is as detergent from the 38th grade
Into NdSm/Eu fractional extraction systems.Separation product richness neodymium samarium is obtained from the 1st grade of raffinate aqueous phase of NdSm/Eu fractional extractions system,
The relative purity of neodymium is 2.50% in the rich neodymium samarium, and the relative purity of samarium is 7.50% in the rich neodymium samarium；It is fractionated and extracts from NdSm/Eu
The 38th grade of system is taken to obtain load Eu organic phases, load Eu organic phases are used as the rare earth soap of the 6th step Eu/GdTb centrifugal stations
Change organic phase, fully enter the 1st grade of the 6th step Eu/GdTb centrifugal stations.
NdSm/Eu fractional extraction centrifugal stations：Normalize extraction quantity S=3.094912, normalization washing amount W=
2.120689.The Cui Qu Liang ︰ NdSmEu Liao Ye ︰ washing amounts=rare earth ion mol ratios of 3.094912 ︰, 1 ︰ 2.120689).Extraction section
Extraction is than being 0.991740, and washing section extraction is than being 1.459390.
6) Eu/GdTb centrifugal stations
6th step is organic charging Eu/GdTb fractional extraction centrifugal stations, realizes that Eu/GdTb is separated.From the 5th step
Eu organic phases are loaded from the entrance of the 1st grade of Eu/GdTb fractional extractions system, the load EuGdTb organic phases from the first step are from Eu/
The 40th grade of entrance of GdTb fractional extractions system, the washing acid that concentration of hydrochloric acid is 1.7mol/L enter Eu/GdTb from the 48th grade and are fractionated
Extraction system.Separation product 5N level high purity europiums are obtained from the 1st grade of raffinate aqueous phase of Eu/GdTb fractional extractions system；From Eu/GdTb points
Evaporate extraction system the 48th grade obtains the rich GdTb organic phases of load, and the load richness GdTb organic phases fully enter the 7th step back extraction work
Section.
Organic charging Eu/GdTb fractional extraction centrifugal stations：Extraction quantity S=10.747719 is normalized, normalizes washing amount
W=11.480530.The ︰ 11.480530 of Cui Qu Liang ︰ loads EuGdTb organic phase Liao Ye ︰ washing amounts=10.747719 ︰ 1 (rare earth from
Sub- mol ratio).Extraction section extraction is than being 0.936169, and washing section extraction is than being 1.023273.
The ratio between the molal quantity of europium and rare earth molal quantity are in separation product 5N level high purity europiums described in 6th step
0.999993, yield 93.73%.
7) stripping section
7th step is stripping section, realizes the back extraction for loading rich GdTb organic phases.Use salt of the concentration for 3.1mol/L
Acid is back extraction acid, and the back extraction of 12 stage countercurrents loads the rare earth element in rich GdTb organic phases；The molal quantity of control back extraction hydrochloric acid is with bearing
It is 3.7 ︰ 1 to carry the ratio between rare earth molal quantity in rich GdTb organic phases；It is rich to obtain separation product for aqueous phase more than the back extraction of stripping section
Gadolinium terbium, the relative purity of gadolinium is 5.27% in the rich gadolinium terbium product, and the relative purity of terbium is 1.06% in the rich gadolinium terbium product.
8) rare-earth sodium saponification workshop section II
8th step is rare-earth sodium saponification workshop section II, realizes the rare-earth sodium saponification of P229 extraction organic phases.Control is from the 5th step
The mol ratio of NdSmEu feed liquids middle rare earth and P229 extractants is 0.12:1, hydroxyl type strong-basicity styrene anion exchange tree
Lipid phase is 8 ︰ 1 to the ratio between total exchange molal quantity (i.e. total exchange capacity) of chlorion and rich neodymium samarium feed liquid middle rare earth molal quantity；In soap
Change the P229 sulfonated kerosene solution for sequentially adding that concentration is 1.0mol/L in reactor, the rich neodymium samarium feed liquid from the 5th step, phase
The hydroxyl type strong-basicity styrene anion that effective exchange capacity to chlorion is 5mol/kg and average grain diameter is 0.5mm
Exchanger resin.After being sufficiently stirred 60min at room temperature, stratification.Upper strata is rare-earth sodium saponification P229 organic phases, and middle level is aqueous phase,
Lower floor is the strong-basicity styrene anion exchange resin phase of solid-state.Release aqueous phase and strong-basicity styrene anion exchange resin
Phase, obtains rare-earth sodium saponification P229 organic phases, and its saponification rate is 36%.Rare-earth sodium saponification P229 obtained by rare-earth sodium saponification workshop section II is organic
Mutually it is completely used for the 5th step NdSm/Eu centrifugal stations.
By above step, final three kinds of separation products of acquisition are respectively：Relative purity is 99.9993%, yield is
93.73% europium product, obtained by the organic charging Eu/GdTb fractional extractions centrifugal station of the 6th step；Neodymium samarium relative purity is
10.00% rich neodymium samarium product, obtained by the 5th step NdSm/Eu fractional extractions centrifugal station；Gadolinium terbium relative purity is 6.33%
Rich gadolinium terbium product, by the 7th step back extraction workshop section obtain.
Embodiment 2
1) NdSmEu/EuGdTb centrifugal stations
The first step is that NdSmEu/EuGdTb is fully loaded with fractional extraction centrifugal station, realizes that NdSmEu/EuGdTb is separated.Come from
The P229 rare-earth sodium saponifications organic phase that the saponification rate of 4th step is 0.36 is fully loaded with the 1st grade of fractional extraction system from NdSmEu/EuGdTb
Into, the Europium chloride feed liquid that pH value 4, rare earth concentration 0.5mol/L, the relative purity of europium are 99.9% from NdSmEu/
EuGdTb is fully loaded with the 43rd grade of entrance of fractional extraction system, and the raffinate aqueous phase Europium chloride gadolinium terbium solution from the 3rd Bu Cuisuan workshop sections is made
Enter NdSmEu/EuGdTb from the 53rd grade for detergent and be fully loaded with fractional extraction system.Fractional extraction is fully loaded with from NdSmEu/EuGdTb
The 1st grade of raffinate aqueous phase of system obtains NdSmEu feed liquids, in terms of rare earth molal quantity, wherein 84.5411% is used for the 4th step rare earth soap
Chemical industry section I, remaining 15.4589% feed liquid as the 5th step NdSm/Eu centrifugal stations；From the fully loaded fractionation of NdSmEu/EuGdTb
The 53rd grade of extraction system obtains load EuGdTb organic phases, in terms of rare earth molal quantity, wherein 94.6938% is directly entered second
The concentration section of step, remaining 5.3062% raw material as the 6th step Eu/GdTb centrifugal stations.
NdSmEu/EuGdTb is fully loaded with fractional extraction centrifugal station：Normalize extraction quantity S=4.238755, normalization washing
Measure W=4.013840.The Cui Qu Liang ︰ Europium chloride Liao Ye ︰ washing amounts=︰ 4.013840 (rare earth ion mol ratio) of 4.238755 ︰ 1.
Extraction section extraction is than being 0.845411, and washing section extraction is than being 1.056035.
2) concentration section
Second step is concentration section, realizes the concentration of the load EuGdTb organic phases of the first step.Load EuGdTb organic phases
Concentration use hydrochloric acid of the concentration for 2.8mol/L, the rare earth EuGdTb in 13 stage countercurrents back extraction load EuGdTb organic phases；Control
The molal quantity of salt manufacturing acid is 3.7 ︰ 1 with loading the ratio between rare earth molal quantity in EuGdTb organic phases.More than the back extraction of concentration section
What aqueous phase obtained contains sour Europium chloride gadolinium terbium solution, is all transferred to the 3rd Bu Cuisuan workshop sections.
3) Cui Suan workshop sections
3rd step is Cui Suan workshop sections, and N235 extractions remove containing in sour Europium chloride gadolinium terbium solution obtained by second step concentration section
Remaining hydrochloric acid.Extract sour organic phase as N235 and the sulfonated kerosene solution of tributyl phosphate, wherein N235 concentration is 0.6mol/
L, the concentration of tributyl phosphate is 0.4mol/L.Control extracts N235 molal quantity in sour organic phase and contains sour Europium chloride gadolinium terbium solution
In the ratio between remaining hydrochloric acid molal quantity be 2:The extraction of 1,8 stage countercurrent is removed containing the remaining hydrochloric acid in sour Europium chloride gadolinium terbium solution.Extraction
Sour workshop section's outlet organic phase is load hydrochloric acid N235 organic phases；Cui Suan workshop sections outlet raffinate aqueous phase Europium chloride gadolinium terbium solution is all used
Make the detergent of first step NdSmEu/EuGdTb centrifugal stations.
4) rare-earth sodium saponification workshop section I
4th step is rare-earth sodium saponification workshop section I, realizes the rare-earth sodium saponification of P229 extraction organic phases.Control is from the first step
The mol ratio of NdSmEu feed liquids middle rare earth and P229 extractants is 0.12:1, hydroxyl type strong-basicity styrene anion exchange tree
Lipid phase is 8 ︰ 1 to the ratio between total exchange molal quantity (i.e. total exchange capacity) of chlorion and NdSmEu feed liquid middle rare earth molal quantitys；In soap
Change the P229 sulfonated kerosene solution for sequentially adding that concentration is 0.5mol/L in reactor, the NdSmEu feed liquids from the first step, phase
The hydroxyl type strong-basicity styrene anion that effective exchange capacity to chlorion is 4mol/kg and average grain diameter is 0.4mm
Exchanger resin.After being sufficiently stirred 60min at room temperature, stratification.Upper strata is rare-earth sodium saponification P229 organic phases, and middle level is aqueous phase,
Lower floor is the strong-basicity styrene anion exchange resin phase of solid-state；Release aqueous phase and strong-basicity styrene anion exchange resin
Phase, obtains rare-earth sodium saponification P229 organic phases, and its saponification rate is 36%.Rare-earth sodium saponification P229 obtained by rare-earth sodium saponification workshop section I is organic
Mutually it is completely used for first step NdSmEu/EuGdTb centrifugal stations.
5) NdSm/Eu centrifugal stations
5th step is NdSm/Eu fractional extraction centrifugal stations, realizes that NdSm/Eu is separated.Rare-earth sodium saponification from the 8th step
From the 1st grade of entrance of NdSm/Eu fractional extractions system, the NdSmEu feed liquids from the first step are fractionated P229 organic phases from NdSm/Eu
The 15th grade of entrance of extraction system, the 1st grade of raffinate aqueous phase from the 6th step Eu/GdTb centrifugal stations is as detergent from the 37th grade
Into NdSm/Eu fractional extraction systems.Separation product richness neodymium samarium is obtained from the 1st grade of raffinate aqueous phase of NdSm/Eu fractional extractions system,
The relative purity of neodymium is 1.25% in the rich neodymium samarium, and the relative purity of samarium is 3.76% in the rich neodymium samarium；It is fractionated and extracts from NdSm/Eu
The 37th grade of system is taken to obtain load Eu organic phases, load Eu organic phases are used as the rare earth soap of the 6th step Eu/GdTb centrifugal stations
Change organic phase, fully enter the 1st grade of the 6th step Eu/GdTb centrifugal stations.
NdSm/Eu fractional extraction centrifugal stations：Normalize extraction quantity S=3.110393, normalization washing amount W=
2.120689.The Cui Qu Liang ︰ NdSmEu Liao Ye ︰ washing amounts=︰ 2.120689 (rare earth ion mol ratio) of 3.110393 ︰ 1.Extraction section
Extraction is than being 0.996701, and washing section extraction is than being 1.466690.
6) Eu/GdTb centrifugal stations
6th step is organic charging Eu/GdTb fractional extraction centrifugal stations, realizes that Eu/GdTb is separated.From the 5th step
Eu organic phases are loaded from the entrance of the 1st grade of Eu/GdTb fractional extractions system, the load EuGdTb organic phases from the first step are from Eu/
The 35th grade of entrance of GdTb fractional extractions system, the washing acid that concentration of hydrochloric acid is 1.6mol/L enter Eu/GdTb from the 45th grade and are fractionated
Extraction system.Separation product high purity europium is obtained from the 1st grade of raffinate aqueous phase of Eu/GdTb fractional extractions system；It is fractionated and extracts from Eu/GdTb
Take the 45th grade of system to obtain and load rich GdTb organic phases, the load richness GdTb organic phases fully enter the 7th step stripping section.
Organic charging Eu/GdTb fractional extraction centrifugal stations：Extraction quantity S=10.747719 is normalized, normalizes washing amount
W=11.614551.The ︰ 11.614551 of Cui Qu Liang ︰ loads EuGdTb organic phase Liao Ye ︰ washing amounts=10.747719 ︰ 1 (rare earth from
Sub- mol ratio).Extraction section extraction is than being 0.925367, and washing section extraction is than being 1.011466.
The ratio between the molal quantity of europium and rare earth molal quantity are 0.999995 in separation product high purity europium described in 6th step, production
Rate is 96.94%.
7) stripping section
7th step is stripping section, realizes the back extraction for loading rich GdTb organic phases.Use salt of the concentration for 3.0mol/L
Acid is back extraction acid, and the back extraction of 13 stage countercurrents loads the rare earth element in rich GdTb organic phases；The molal quantity of control washing hydrochloric acid is with bearing
It is 3.8 ︰ 1 to carry the ratio between rare earth molal quantity in rich GdTb organic phases.It is rich to obtain separation product for aqueous phase more than the back extraction of stripping section
Gadolinium terbium, the relative purity of gadolinium is 2.12% in the rich gadolinium terbium product, and the relative purity of terbium is 0.43% in the rich gadolinium terbium product.
8) rare-earth sodium saponification workshop section II
8th step is rare-earth sodium saponification workshop section II, realizes the rare-earth sodium saponification of P229 extraction organic phases.Control is from the 5th step
The mol ratio of rich neodymium samarium feed liquid middle rare earth and P229 extractants is 0.12:1, hydroxyl type strong-basicity styrene anion exchange tree
Lipid phase is 8 ︰ 1 to the ratio between total exchange molal quantity (i.e. total exchange capacity) of chlorion and rich neodymium samarium feed liquid middle rare earth molal quantity；In soap
Change the P229 sulfonated kerosene solution for sequentially adding that concentration is 0.5mol/L in reactor, the rich neodymium samarium feed liquid from the 5th step, phase
The hydroxyl type strong-basicity styrene anion that effective exchange capacity to chlorion is 4mol/kg and average grain diameter is 0.4mm
Exchanger resin.After being sufficiently stirred 60min at room temperature, stratification.Upper strata is rare-earth sodium saponification P229 organic phases, and middle level is aqueous phase,
Lower floor is the strong-basicity styrene anion exchange resin phase of solid-state.Release aqueous phase and strong-basicity styrene anion exchange resin
Phase, obtains rare-earth sodium saponification P229 organic phases, and its saponification rate is 36%.Rare-earth sodium saponification P229 obtained by rare-earth sodium saponification workshop section II is organic
Mutually it is completely used for the 5th step NdSm/Eu centrifugal stations.
By above step, final three kinds of separation products of acquisition are respectively：Relative purity is 99.9995%, yield is
96.94% europium product, obtained by the organic charging Eu/GdTb fractional extractions centrifugal station of the 6th step；Neodymium samarium relative purity is
5.01% rich neodymium samarium product, obtained by the 5th step NdSm/Eu fractional extractions centrifugal station；Gadolinium terbium relative purity is 2.55%
Rich gadolinium terbium product, by the back extraction of the 7th step, workshop section obtains.
Embodiment 3
1) NdSmEu/EuGdTb centrifugal stations
The first step is that NdSmEu/EuGdTb is fully loaded with fractional extraction centrifugal station, realizes that NdSmEu/EuGdTb is separated.Come from
The P229 rare-earth sodium saponifications organic phase that the saponification rate of 4th step is 0.36 is fully loaded with the 1st grade of fractional extraction system from NdSmEu/EuGdTb
Into, the Europium chloride feed liquid that pH value 2, rare earth concentration 1.5mol/L, the relative purity of europium are 99% from NdSmEu/EuGdTb
Fully loaded the 53rd grade of entrance of fractional extraction system, the raffinate aqueous phase Europium chloride gadolinium terbium solution from the 3rd Bu Cuisuan workshop sections is as washing
Agent enters NdSmEu/EuGdTb from the 67th grade and is fully loaded with fractional extraction system.Fractional extraction system is fully loaded with from NdSmEu/EuGdTb
1 grade of raffinate aqueous phase obtains NdSmEu feed liquids, in terms of rare earth molal quantity, wherein 84.4995% is used for the 4th step rare-earth sodium saponification workshop section
I, remaining 15.5005% feed liquid as the 5th step NdSm/Eu centrifugal stations；Fractional extraction body is fully loaded with from NdSmEu/EuGdTb
The 67th grade of system obtains load EuGdTb organic phases, in terms of rare earth molal quantity, wherein 94.7062% is directly entered the dense of second step
Contracting workshop section, remaining 5.2938% raw material as the 6th step Eu/GdTb centrifugal stations.
NdSmEu/EuGdTb is fully loaded with fractional extraction centrifugal station：Normalize extraction quantity S=4.230533, normalization washing
Measure W=4.006575.The Cui Qu Liang ︰ Europium chloride Liao Ye ︰ washing amounts=︰ 4.006575 (rare earth ion mol ratio) of 4.230533 ︰ 1.
Extraction section extraction is than being 0.844995, and washing section extraction is than being 1.055898.
2) concentration section
Second step is concentration section, realizes the concentration of the load EuGdTb organic phases of the first step.Load EuGdTb organic phases
Concentration use hydrochloric acid of the concentration for 3.0mol/L, the rare earth EuGdTb in 11 stage countercurrents back extraction load EuGdTb organic phases；Control
The molal quantity of salt manufacturing acid is 3.5 ︰ 1 with loading the ratio between rare earth molal quantity in EuGdTb organic phases.More than the back extraction of concentration section
What aqueous phase obtained contains sour Europium chloride gadolinium terbium solution, is all transferred to the 3rd Bu Cuisuan workshop sections.
3) Cui Suan workshop sections
3rd step is Cui Suan workshop sections, and N235 extractions remove containing in sour Europium chloride gadolinium terbium solution obtained by second step concentration section
Remaining hydrochloric acid.Extract sour organic phase as N235 and the sulfonated kerosene solution of tributyl phosphate, wherein N235 concentration is 0.6mol/
L, the concentration of tributyl phosphate is 0.4mol/L.Control extracts N235 molal quantity in sour organic phase and contains sour Europium chloride gadolinium terbium solution
In the ratio between remaining hydrochloric acid molal quantity be 2:The extraction of 1,8 stage countercurrent is removed containing the remaining hydrochloric acid in sour Europium chloride gadolinium terbium solution.Extraction
Sour workshop section's outlet organic phase is load hydrochloric acid N235 organic phases；Cui Suan workshop sections outlet raffinate aqueous phase Europium chloride gadolinium terbium solution is all used
Make the detergent of first step NdSmEu/EuGdTb centrifugal stations.
4) rare-earth sodium saponification workshop section I
4th step is rare-earth sodium saponification workshop section I, realizes the rare-earth sodium saponification of P229 extraction organic phases.Control is from the first step
The mol ratio of NdSmEu feed liquids middle rare earth and P229 extractants is 0.12:1, hydroxyl type strong-basicity styrene anion exchange tree
Lipid phase is 8 ︰ 1 to the ratio between total exchange molal quantity (i.e. total exchange capacity) of chlorion and NdSmEu feed liquid middle rare earth molal quantitys；In soap
Change the P229 sulfonated kerosene solution for sequentially adding that concentration is 1.5mol/L in reactor, the NdSmEu feed liquids from the first step, phase
The hydroxyl type strong-basicity styrene anion that effective exchange capacity to chlorion is 6mol/kg and average grain diameter is 0.6mm
Exchanger resin.After being sufficiently stirred 60min at room temperature, stratification.Upper strata is rare-earth sodium saponification P229 organic phases, and middle level is aqueous phase,
Lower floor is the strong-basicity styrene anion exchange resin phase of solid-state；Release aqueous phase and strong-basicity styrene anion exchange resin
Phase, obtains rare-earth sodium saponification P229 organic phases, and its saponification rate is 36%.Rare-earth sodium saponification P229 obtained by rare-earth sodium saponification workshop section I is organic
Mutually it is completely used for first step NdSmEu/EuGdTb centrifugal stations.
5) NdSm/Eu centrifugal stations
5th step is NdSm/Eu fractional extraction centrifugal stations, realizes that NdSm/Eu is separated.Rare-earth sodium saponification from the 8th step
From the 1st grade of entrance of NdSm/Eu fractional extractions system, the NdSmEu feed liquids from the first step are fractionated P229 organic phases from NdSm/Eu
The 12nd grade of entrance of extraction system, the 1st grade of raffinate aqueous phase from the 6th step Eu/GdTb centrifugal stations are entered as detergent from the 40th
Enter NdSm/Eu fractional extraction systems.Separation product richness neodymium samarium is obtained from the 1st grade of raffinate aqueous phase of NdSm/Eu fractional extractions system, should
The relative purity of neodymium is 3.75% in rich neodymium samarium, and the relative purity of samarium is 11.25% in the rich neodymium samarium；It is fractionated and extracts from NdSm/Eu
The 40th grade of system is taken to obtain load Eu organic phases, load Eu organic phases are used as the rare earth soap of the 6th step Eu/GdTb centrifugal stations
Change organic phase, fully enter the 1st grade of the 6th step Eu/GdTb centrifugal stations.
NdSm/Eu fractional extraction centrifugal stations：Normalize extraction quantity S=3.086335, normalization washing amount W=
2.120689.The Cui Qu Liang ︰ NdSmEu Liao Ye ︰ washing amounts=︰ 2.120689 (rare earth ion mol ratio) of 3.086335 ︰ 1.Extraction section
Extraction is than being 0.988992, and washing section extraction is than being 1.455345.
6) Eu/GdTb centrifugal stations
6th step is organic charging Eu/GdTb fractional extraction centrifugal stations, realizes that Eu/GdTb is separated.From the 5th step
Eu organic phases are loaded from the entrance of the 1st grade of Eu/GdTb fractional extractions system, the load EuGdTb organic phases from the first step are from Eu/
The 40th grade of entrance of GdTb fractional extractions system, the washing acid that concentration of hydrochloric acid is 1.8mol/L enter Eu/GdTb from the 45th grade and are fractionated
Extraction system.Separation product high purity europium is obtained from the 1st grade of raffinate aqueous phase of Eu/GdTb fractional extractions system；It is fractionated and extracts from Eu/GdTb
Take the 45th grade of system to obtain and load rich GdTb organic phases, the load richness GdTb organic phases fully enter the 7th step stripping section.
Organic charging Eu/GdTb fractional extraction centrifugal stations：Extraction quantity S=10.747719 is normalized, normalizes washing amount
W=11.211983.The ︰ 11.211983 of Cui Qu Liang ︰ loads EuGdTb organic phase Liao Ye ︰ washing amounts=10.747719 ︰ 1 (rare earth from
Sub- mol ratio).Extraction section extraction is than being 0.958592, and washing section extraction is than being 1.047782.
The ratio between the molal quantity of europium and rare earth molal quantity are 0.999990 in separation product high purity europium described in 6th step, production
Rate is 87.40%.
7) stripping section
7th step is stripping section, realizes the back extraction for loading rich GdTb organic phases.Use salt of the concentration for 3.2mol/L
Acid is back extraction acid, and the back extraction of 11 stage countercurrents loads the rare earth element in rich GdTb organic phases；The molal quantity of control back extraction hydrochloric acid is with bearing
It is 3.6 ︰ 1 to carry the ratio between rare earth molal quantity in rich GdTb organic phases.It is rich to obtain separation product for aqueous phase more than the back extraction of stripping section
Gadolinium terbium, the relative purity of gadolinium is 4.62% in the rich gadolinium terbium product, and the relative purity of terbium is 0.93% in the rich gadolinium terbium product.
8) rare-earth sodium saponification workshop section II
8th step is rare-earth sodium saponification workshop section II, realizes the rare-earth sodium saponification of P229 extraction organic phases.Control is from the 5th step
The mol ratio of rich neodymium samarium feed liquid middle rare earth and P229 extractants is 0.12:1, hydroxyl type strong-basicity styrene anion exchange tree
Lipid phase is 8 ︰ 1 to the ratio between total exchange molal quantity (i.e. total exchange capacity) of chlorion and rich neodymium samarium feed liquid middle rare earth molal quantity；In soap
Change the P229 sulfonated kerosene solution for sequentially adding that concentration is 1.5mol/L in reactor, the rich neodymium samarium feed liquid from the 5th step, phase
The hydroxyl type strong-basicity styrene anion that effective exchange capacity to chlorion is 6mol/kg and average grain diameter is 0.6mm
Exchanger resin.After being sufficiently stirred 60min at room temperature, stratification.Upper strata is rare-earth sodium saponification P229 organic phases, and middle level is aqueous phase,
Lower floor is the strong-basicity styrene anion exchange resin phase of solid-state.Release aqueous phase and strong-basicity styrene anion exchange resin
Phase, obtains rare-earth sodium saponification P229 organic phases, and its saponification rate is 36%.Rare-earth sodium saponification P229 obtained by rare-earth sodium saponification workshop section II is organic
Mutually it is completely used for the 5th step NdSm/Eu centrifugal stations.
By above step, final three kinds of separation products of acquisition are respectively：Relative purity is 99.9990%, yield is
87.40% europium product, obtained by the organic charging Eu/GdTb fractional extractions centrifugal station of the 6th step；Neodymium samarium relative purity is
15.00% rich neodymium samarium product, obtained by the 5th step NdSm/Eu fractional extractions centrifugal station；Gadolinium terbium relative purity is 5.55%
Rich gadolinium terbium product, by the 7th step back extraction workshop section obtain.
Claims (2)
- A kind of 1. extraction and separation technology for directly preparing 5N level europiums, it is characterised in that：Described extraction and separation technology using P229 as Extractant, relative purity 2N~3N level Europium chlorides solution are feed liquid, including 8 steps, wherein 3 separating steps and 5 auxiliary Step；3 separating steps are respectively NdSmEu/EuGdTb centrifugal stations, NdSm/Eu centrifugal stations and Eu/GdTb centrifugal stations, 5 additional steps are respectively concentration section, Cui Suan workshop sections, rare-earth sodium saponification workshop section I, stripping section and rare-earth sodium saponification workshop section II；Step It is rapid specific as follows：1) NdSmEu/EuGdTb centrifugal stationsRare-earth sodium saponification P229 organic phases I from the 4th step rare-earth sodium saponification workshop section I is fully loaded with fractional extraction body from NdSmEu/EuGdTb It is that the first order enters, relative purity 2N~3N level Europium chloride solution is fully loaded with fractional extraction system charging level from NdSmEu/EuGdTb Into the raffinate aqueous phase Europium chloride gadolinium terbium solution from the 3rd Bu Cuisuan workshop sections enters as detergent from afterbody NdSmEu/EuGdTb is fully loaded with fractional extraction system；Fractional extraction system first order raffinate aqueous phase is fully loaded with from NdSmEu/EuGdTb to obtain NdSmEu feed liquids are obtained, in terms of rare earth molal quantity, wherein 84.4995%~84.5411% is used for the 4th step rare-earth sodium saponification workshop section I, Remaining 15.5005%~15.4589% feed liquid as the 5th step NdSm/Eu centrifugal stations；Divide from NdSmEu/EuGdTb is fully loaded The afterbody for evaporating extraction system obtains load EuGdTb organic phases, in terms of rare earth molal quantity, wherein 94.6938%~ 94.7062% is directly entered second step concentration section, remaining 5.3062%~5.2938% be used as the 6th step Eu/GdTb separation work The raw material of section；The rare earth concentration of described Europium chloride feed liquid is 0.5mol/L~1.5mol/L, wherein the relative purity of europium be 99%~ 99.9%, pH value range is 2~4；2) concentration sectionThe concentration of load EuGdTb organic phases uses concentration as 2.8mol/L~3.0mol/L hydrochloric acid, countercurrent reextraction load EuGdTb Rare earth EuGdTb in organic phase；The molal quantity for controlling hydrochloric acid is with loading the ratio between rare earth molal quantity in EuGdTb organic phases The ︰ 1 of 3.5 ︰ 1~3.7；What aqueous phase obtained more than the back extraction of concentration section contains sour Europium chloride gadolinium terbium solution, is all transferred to the 3rd step extraction Sour workshop section；3) Cui Suan workshop sectionsExtract sulfonated kerosene solution of the sour organic phase for N235 and tributyl phosphate, wherein N235 concentration is 0.6mol/L, phosphoric acid The concentration of tributyl is 0.4mol/L；Control extract in sour organic phase N235 molal quantity with containing residual in sour Europium chloride gadolinium terbium solution The ratio between remaining hydrochloric acid molal quantity is that the extraction of the stage countercurrents of 2 ︰ 1,8 is removed containing the remaining hydrochloric acid in sour Europium chloride gadolinium terbium solution；Cui Suan workshop sections Organic phase is exported as load hydrochloric acid N235 organic phases；Cui Suan workshop sections outlet raffinate aqueous phase Europium chloride gadolinium terbium solution is completely used as first Walk the detergent of NdSmEu/EuGdTb centrifugal stations；4) rare-earth sodium saponification workshop section IControl the mol ratio of NdSmEu feed liquids middle rare earth and P229 extractants from first step NdSmEu/EuGdTb centrifugal stations For 0.12:1, hydroxyl type strong-basicity styrene anion exchange resin is expected with respect to total exchange molal quantity of chlorion with NdSmEu The ratio between liquid middle rare earth molal quantity is 8 ︰ 1；P229 extraction organic phases are sequentially added in saponification device, from the first step The NdSmEu feed liquids of NdSmEu/EuGdTb centrifugal stations, effective exchange capacity with respect to chlorion are 4mol/kg~6mol/kg And the hydroxyl type strong-basicity styrene anion exchange resin that average grain diameter is 0.4mm~0.6mm；It is sufficiently stirred at room temperature After 60min, stratification；Upper strata is rare-earth sodium saponification P229 organic phases, and middle level is aqueous phase, and lower floor is the strong-basicity styrene of solid-state Anion exchange resin phase；Aqueous phase and strong-basicity styrene anion exchange resin phase are released, it is organic to obtain rare-earth sodium saponification P229 Phase I, its saponification rate are 36%；Rare-earth sodium saponification P229 organic phases I obtained by rare-earth sodium saponification workshop section I is completely used for the first step NdSmEu/EuGdTb centrifugal stations；The sulfonated kerosene solution that described P229 extraction organic phases are P229, wherein P229 concentration is 0.5mol/L~1.5mol/ L；5) NdSm/Eu centrifugal stationsRare-earth sodium saponification P229 organic phases II from the 8th step rare-earth sodium saponification workshop section II is from the NdSm/Eu fractional extraction system first order Into the NdSmEu feed liquids from first step NdSmEu/EuGdTb centrifugal stations feed grading from NdSm/Eu fractional extractions system Enter, the first order raffinate aqueous phase from the 6th step Eu/GdTb centrifugal stations is as detergent from afterbody into NdSm/Eu points Evaporate extraction system；Separation product neodymium samarium feed liquid is obtained from NdSm/Eu fractional extraction system first order raffinate aqueous phases；From NdSm/Eu The afterbody of fractional extraction system obtains load Eu organic phases, and load Eu organic phases are used as the 6th step Eu/GdTb separation works The rare-earth sodium saponification organic phase of section, fully enter the first order of the 6th step Eu/GdTb centrifugal stations；6) Eu/GdTb centrifugal stationsLoad Eu organic phases from the 5th step NdSm/Eu centrifugal stations enter from the Eu/GdTb fractional extraction systems first order, come Fed from the load EuGdTb organic phases of first step NdSmEu/EuGdTb centrifugal stations from Eu/GdTb fractional extractions system grading Enter, washing acid enters Eu/GdTb fractional extraction systems from afterbody；From Eu/GdTb fractional extraction system first order raffinate water Mutually obtain separation product 5N level high purity europiums；Load GdTb organic phases are obtained from the afterbody of Eu/GdTb fractional extraction systems, should Load GdTb organic phases fully enter the 7th step stripping section；Described washing acid is 1.6mol/L~1.8mol/L hydrochloric acid；The ratio between the molal quantity of europium and rare earth molal quantity are 0.999990~0.999995 in described separation product 5N level high purity europiums, Relative purity is 99.9990%~99.9995%, and yield is 87.40%~96.94%；7) stripping sectionUse concentration for 3.0mol/L~3.2mol/L hydrochloric acid be back extraction acid, countercurrent reextraction load GdTb organic phases in rare earth member Element；The molal quantity of control back extraction hydrochloric acid is the ︰ 1 of 3.6 ︰ 1~3.8 with loading the ratio between rare earth molal quantity in GdTb organic phases；From anti- Aqueous phase obtains separation product gadolinium terbium more than the back extraction of extraction workshop section；8) rare-earth sodium saponification workshop section II8th step is rare-earth sodium saponification workshop section II, realizes the rare-earth sodium saponification of P229 extraction organic phases；Control comes from the 5th step NdSm/Eu The neodymium samarium feed liquid middle rare earth of centrifugal station is 0.12 with the mol ratio of P229 extractants:1, hydroxyl type strong-basicity styrene the moon from Sub-exchange resin is 8 ︰ 1 with respect to the ratio between total exchange molal quantity of chlorion and neodymium samarium feed liquid middle rare earth molal quantity；In saponification P229 extraction organic phases, the neodymium samarium feed liquid from the 5th step NdSm/Eu centrifugal stations, with respect to having for chlorion are sequentially added in device It is cloudy to imitate the hydroxyl type strong-basicity styrene that exchange capacity is 4mol/kg~6mol/kg and average grain diameter is 0.4mm~0.6mm Ion exchange resin；After being sufficiently stirred 60min at room temperature, stratification；Upper strata is rare-earth sodium saponification P229 organic phases, and middle level is water Phase, lower floor are the strong-basicity styrene anion exchange resin phase of solid-state；Release aqueous phase and strong-basicity styrene anion exchange Resin phase, obtains rare-earth sodium saponification P229 organic phase II, and its saponification rate is 36%；Rare-earth sodium saponification obtained by rare-earth sodium saponification workshop section II P229 organic phases II is completely used for the 5th step NdSm/Eu centrifugal stations；The sulfonated kerosene solution that described P229 extraction organic phases are P229, wherein P229 concentration is 0.5mol/L~1.5mol/ L。
- A kind of 2. extraction and separation technology for directly preparing 5N level europiums according to claim 1, it is characterised in that：Described NdSm/Eu separation separates series connection with Eu/GdTb.
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| CN107098373A (en) * | 2017-05-17 | 2017-08-29 | 中铝稀土（江苏）有限公司 | A kind of method of Isolating chlorinated europium |
| CN108893625B (en) * | 2018-07-05 | 2020-08-18 | 南昌航空大学 | Process for preparing high-purity lanthanum by extraction method |
| CN108996536B (en) * | 2018-08-08 | 2020-07-21 | 南昌航空大学 | Extraction separation method for co-production of pure praseodymium and pure gadolinium |
| CN108950252B (en) * | 2018-08-12 | 2020-07-28 | 南昌航空大学 | Separation method for co-production of pure samarium and pure terbium by fractional extraction |
| CN110284002B (en) * | 2019-08-12 | 2021-01-01 | 南昌航空大学 | Method for extracting and separating samarium-europium-gadolinium enriched substance |
| CN110627096B (en) * | 2019-11-11 | 2022-01-25 | 南昌航空大学 | Method for preparing 5N-grade magnesium chloride solution |
| CN110787485B (en) * | 2019-11-14 | 2021-05-14 | 南昌航空大学 | Method for preparing 6N-grade calcium chloride solution |
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| CN85104034A (en) * | 1985-05-21 | 1986-11-19 | 冶金工业部包头稀土研究院 | Direx process prepares fluorescence europium oxide |
| CN1706972A (en) * | 2004-06-12 | 2005-12-14 | 包头市京瑞新材料有限公司 | Improvent of RE extracting and separating process and circular waste liquid utilizing method |
| CN100435899C (en) * | 2006-01-24 | 2008-11-26 | 北京有色金属研究总院 | Saponification of organic extractant |
| 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 |
| JP5867727B2 (en) * | 2012-12-17 | 2016-02-24 | 住友金属鉱山株式会社 | Separation method of rare earth elements |
| CN103526058B (en) * | 2013-10-21 | 2014-10-08 | 南昌航空大学 | Technique for preparing high-purity praseodymium from industrial praseodymium raw material |
| CN104532022B (en) * | 2014-12-29 | 2016-08-24 | 南昌航空大学 | The process of fully loaded fractional extraction rare-earth separating |
| CN104561613B (en) * | 2015-01-13 | 2016-06-15 | 南昌航空大学 | The process in yttrium richness europium ore deposit in a kind of Nd/Sm～Dy/Ho packet separation |
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