CN85101885B - Separation of mixed rare-earth elements by extraction - Google Patents
Separation of mixed rare-earth elements by extraction Download PDFInfo
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- CN85101885B CN85101885B CN85101885A CN85101885A CN85101885B CN 85101885 B CN85101885 B CN 85101885B CN 85101885 A CN85101885 A CN 85101885A CN 85101885 A CN85101885 A CN 85101885A CN 85101885 B CN85101885 B CN 85101885B
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Abstract
The present invention relates to a process which can be used for production and the treatment of a mixture containing a large amount of heavy rare earth. Phosphonic acid (2-ethylhexyl)-mono (2-ethylhexyl)ester is used as an extraction agent, grouping is carried out firstly from erbium to tm in a multi-stage solvent extraction method, and then, tm, yttrium and lutetium separation is carried out. The rare earth of groups from La to Er containing smaller than 0.06% of Tm and Yb is obtained, and grades are bigger than 94% of TM, 97% of Yb and 99% of Lu.
Description
The invention belongs to the Rare Earth Separation hydrometallurgical processes, with di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (being designated as HEH(EHP)) be that extraction agent, multistage fractional-distillation extraction carry out Er-Tm grouping and Tm from contain a large amount of heavy rare earths materials, Yb, Lu separates.
HEH(EHP) compare with the extraction agent di-(2-ethylhexyl)phosphoric acid of using always (D2EHPA), it is low to have acidity, and back extraction is easy, is difficult for characteristics such as emulsification, is more suitable for handling the heavy rare earths material.268 pages of organic chemistry 4 phases of nineteen eighty-two are report HEH(EHP once) reflux extraction separation lutetium.Use monazite and brown yttrium columbium ore deposit rare earth to be raw material through the Tm-Tb-Lu enriched substance that ion-exchange obtains, do not relate to the extraction grouping and separate with Tm, Yb, the similar work of using same raw mineral materials to divide into groups with the present invention is the work that we are published in " rare earth chemistry collection of thesis " (Science Press publishes P20-291982).But its order of packets is from Nd-Sm, carries out Gd-Tb, Er-Tm grouping then.So input concentration is low, treatment capacity is little, and the extraction agent consumption is big, unsuitable industrial-scale production, and organic phase Tm-Lu group rare-earth concentration＜0.2 grams per liter after the Er-Tm grouping especially further separates Tm, Yb, Lu is actually can not.
The clear 54-93672 of Japanese Patent, clear 57-198227, clear 58-84118 also use HEH(EHP) extracting and separating rear earth, but all do not relate to Er-Tm grouping and Tm, Yb, Lu separating technology.Clear 58-84118 proposes multistage plus-minus method in proportion, in and the acidity of extraction section, improve separating effect.The present invention adopts and introduces ammonium salt or more simpler than it from the way adjustment acidity of charging level adding dilution water in the extraction agent.Clear 57-198227 proposes to quote the part strip liquor and replaces washing acid after the alkali neutralizing treatment, the present invention separate that Lu partly also adopts in the same way but strip liquor without any processing.
The objective of the invention is at taking heavy rare earths as the mishmetal in main ion type absorption ore deposit, research is suitable for industrial technical process.Carry out the Er-Tm grouping a large amount of heavy rare earths materials earlier and separate with Tm, Yb, Lu from this containing, as this material overall separation process first part, raw material is based on gained mishmetal after the ionic absorption ore deposit separating yttrium of heavy rare earths.
Technical process of the present invention was divided into for three steps shown in figure (1):
1.Er-Tm grouping
2. separate Tm
3.Yb-Lu separate
Earlier be based on following 2 points from the Er-Tm grouping: (1) heavy rare earths between (Tb-Lu) per two adjacent elements separating factor with Er-Tm maximum (2) HEH(EHP) loading capacity little and in the raw material Tm-Lu content low, over-burden to have avoided organic phase from the Er-Tm grouping earlier.So technology of the present invention can be taked high concentration rare earth feed liquid charging (250～300 grams per liter) and obtain the higher outlet raffinate of concentration (140-160 grams per liter) and outlet extraction liquid (14～24 grams per liter), to the step separates very favourable down, the consumption of extraction agent and acid also has obvious reduction simultaneously, so be one of characteristics of the present invention from the Er-Tm grouping earlier.
The present invention uses the extraction agent effective ingredient to be HEH(EHP).Molecular formula is
R is the 2-ethylhexyl, extraction agent constitutes HEH(EHP)-kerosene or HEH(EHP)-HEH(EHP) ammonium salt one kerosene, the introducing of ammonium salt is to improve rare earth partition ratio and separating factor in order to reduce the extraction section aqueous phase acidity, obtains the lower outlet raffinate of acidity, is beneficial to further separation.
The feed liquid that the present invention uses: the first step Er-Tm grouping feed liquid can be rare earth HCl solution or HNO from the separating yttrium operation
3Solution, rare earth concentration 250-300 grams per liter, free acid 0.0001～0.2N, the feed liquid in second step is to contain the organic feed liquid of Tm-Lu, be Er-Tm grouping outlet extraction liquid, rare earth concentration 13～24 grams per liters, the 3rd step feed liquid can directly be walked out of a mouthful extraction liquid with second, also can obtain ytterbium lutetium enriched substance hydrochloric acid soln, rare earth concentration 80-130 grams per liter pH=1-4 through handling (molten or ion-exchange membrane dialysis acid) after the back extraction as alkali precipitation-acid.
The present invention uses and to wash acid to be concentration 2～6N nitric acid or hydrochloric acid or to wash acid with the replacement of part strip liquor, and wherein Er-Tm grouping technology is 2.3-2.5NHCl or HNO
3, separating Tm technology is 3.4-3.5NHCl, it is to replace (sour regurgitation concentration is 5.3NHCl) with the part strip liquor that separation Yb-Lu technology is washed acid.It is in order to improve product purity and to reduce the acid consumption that strip liquor replaces washing acid.
Extraction section aqueous phase acidity inflation method of the present invention comprises that following three kinds (1) do not do any adjustment.(2) add a certain amount of dilution water from the charging level.(3) add ammonium salt in the extraction agent.
Each step process of the present invention and his like is than (volume ratio):
Er-Tm grouping: HNO＜`; ; 3`〉the system extraction agent: feed liquid: washing acid is 2.52: 1.40-1.44: 0.6; The HCl system is 3: 1.2: 0.5.
Separate Tm technology extraction agent: organic feed liquid: dilution water: washing acid is 9: 30: 5: 7.
Separate Yb-Lu technology extraction agent: feed liquid: wash acid: sour regurgitation is 31-33: 5: 6: 12.
The per step extracting and separating of the present invention is to carry out in mixer-settler, perhaps simulates with separating funnel.Extraction agent is washed acid and is added from last step from the 1st grade of adding, and rare earth feed liquid to be separated adds from middle certain level.Extraction agent flows to last step from the 1st grade and contacts with water step by step, and the rare earth component that easily comes together preferentially comes together to organic phase, contains easy collection component organic phase and flows out from last step.Desire will from organic phase easily come together the component rare earth must be the back extraction groove with higher concentration mineral acid (sour regurgitation) back extraction to water.Feed liquid and to wash sour flow direction opposite with extraction agent, the difficult component that comes together stay aqueous phase as raffinate from the 1st grade of outflow.
By dividing three step extracting and separating, obtain rare earth oxide (RE
xO
y) concentration is 140-160 grams per liter La-Er group salpeter solution or hydrochloric acid soln, Tm and Yb content all＜0.06% are used for separating Er.Obtain grade 93-94%Tm enriched substance, yield 95-97% extracts high-purity Tm usefulness for chromatograph, obtains grade 97%Yb, and yield＞95% extracts high-purity Yb for chromatograph and uses.Obtain＞99% lutecium oxide (Lu
2O
3) yield 85～90%, as the product or the usefulness of purifying.This technology has characteristics such as input concentration height, treatment capacity is big, the extraction agent consumption is few, is suitable for industrial-scale production.
The flow process that the three steps series connection of this technology constitutes, can be used as the ionic absorption ore deposit overall separation process first part of processing based on heavy rare earths, certainly be applicable to also that handling other contains a large amount of heavy rare earths materials, as the close heavy rare earths enriched substance of composition that obtains from monazite, brown yttrium columbium ore deposit, xenotime.
But three steps that this technology comprises are Individual existence all, and heavy rare earths enriched substance Tm, the Yb, Lu enriched substance, the Yb-Lu enriched substance that are got by additive method in conjunction with constituting independent process, are handled in twos in perhaps (1)-(2), (2)-(3).
Description of drawings
Figure: Er-Tm grouping and Tm, Yb, Lu separation process scheme
The 1-Er-Tm extraction plant that divides into groups
1-1: feeding liquid 1-2: advance extraction agent
1-3: advance to wash sour 1-4: go out raffinate (La-Er group)
1-5: go out extraction liquid (Tm-Lu group)
2-separates the Tm extraction plant
2-1: back extraction device 2-2 feeding liquid
2-3: advance extraction agent 2-4 and advance to wash acid
2-5: advance sour regurgitation 2-6 and go out raffinate (Tm)
2-7: go out extraction liquid 2-8 and go out anti-liquid (Yb, Lu)
2-9: go out organic phase after the back extraction
3-Yb, Lu separating and extracting device
3-1: back extraction device 3-2 feeding liquid
3-3: advance extraction agent 3-4 and advance to wash acid (replacing) with the anti-liquid of part
3-5: advance washing lotion 3-6 and go out raffinate (Yb)
3-7: go out extraction liquid 3-8 and go out anti-liquid (Lu)
3-9: go out organic phase after the back extraction
Embodiment one
Er-Tm (the HNO that divides into groups
3System)
Obtain low gadolinium mishmetal salpeter solution RE concentration 1.39-1.45M from the separating yttrium operation, free acid 0.1-0.2N, rare earth composition such as table 1:
Extraction agent is HEH(EHP)-kerosene, effective ingredient 1.48-152m; Wash sour 2.3-2.5N HNO
3, using mixing section is 3 * 3 * 6cm mixer-settler.Feed liquid adds inbound traffics 1.40-1.44 ml/min from the 20th grade, and extraction agent adds inbound traffics 2.52 ml/min from 2 grades, washes acid and adds inbound traffics 0.6 ml/min from the 39th grade.Aqueous phase extracted is from the 1st grade of outflow, and extraction liquid is from the 39th grade of outflow, reaches that the raffinate water is the La-Er rare earth after the balance, concentration～150 grams per liters, and Tm can be for separating Er usefulness with Yb content＜0.05%, and extraction liquid is the Tm-Lu group rare-earth, concentration～22g/L, Er
2O
3Content＜0.1%Y
2O
3Content＜0.05% separates Tm for second step of this flow process and uses.
Embodiment two
Er-Tm divide into groups (HCL system) obtains the mishmetal hydrochloric acid soln as feed liquid from the separating yttrium operation, rare earth concentration 260～275 grams per liters, and pH=2-4 forms as 1 material 2; Extraction agent is HEH(EHP)-kerosene, effective ingredient concentration 1.48-1.52M.Extraction agent, feed liquid, wash acid, feed liquor position with example one.Flow is respectively 3 ml/min, 1.2 ml/min, 0.5 ml/min.The outlet raffinate gets (La-Er) group rare-earth after reaching balance, concentration 150～154 grams per liters, and Tm and Yb content＜0.06%, the outlet extraction liquid is (Tm-Lu) group rare-earth concentration 13～16 grams per liters, Er content＜1%, Y
2O
3Content＜0.03%.
Example three
Separate Tm
Test is simulated with separating funnel, and each separating funnel replaces the one-level of mixer-settler.
Feed liquid is the organic phase that contains Tm, Yb, Lu, obtain from example one or two any methods, this example is 0.084～0.085M with organic feed liquid rare earth concentration, add each 30ml from the 18th grade, extraction agent is HEH(EHP) kerosene, effective ingredient concentration 1.48-1.52M adds each 9ml from the 1st grade; Washing acid is 3.4～3.5NHCl, adds each 7ml from 36 grades; Add dilution waters in order to adjust aqueous phase acidity from 18 grades, each 5ml vibration 10 minutes, every grade of water moves toward low level number then, and organic phase moves toward high level number, and the raffinate water is emitted from the 1st grade, and extraction liquid is emitted from the 36th grade.So repeatable operation until reaching balance, gets the Tm enriched substance from the raffinate water, and rare earth concentration is 0.021M.Tm grade～94% contains Yb＜0.6%.From extraction liquid get the Yb-Lu enriched substance contain Tm＜0.3% can be directly as separating the organic feed liquid of Yb-La, also can after back extraction and intermediate treatment, obtain down going on foot and separate the Yb-Lu hydrochloric acid soln.
Example four
Yb-Lu separates (water charging)
With separating funnel simulation, to operate identically with example three, feed liquid is for to obtain RECl from example three
3Concentration 0.60mpH2-4 adds each 5ml from the 20th grade; Extraction agent is HEH(HEP)-HEH(EHP) ammonium salt one kerosene, effective ingredient concentration 1.48～1.52M, ammonium salt concentration 0.5-0.54M adds each 31-33ml from the first step, and ammonium salt is to add the strong aqua preparation under stirring state; Wash the strip liquor replacement of acid, add each 6ml from 48 grades with stripping section; Extraction liquid is from the back extraction of the 49th grade of inflow stripping section, and sour regurgitation adds each 12ml with 5.3NHCl from 56 grades.Reaching and get Yb enriched substance grade＞97%(from the outlet raffinate after the balance and contain Lu＜1.7%) the outlet strip liquor gets Lu, purity＞99%.
Claims (2)
1, a kind of with HEH(EHP) or HEH(EHP) ammonium salt be extraction agent grouping separation of mixed rare-earth technology, it is characterized in that to ionic absorption ore deposit mishmetal hydrochloric acid soln or salpeter solution based on heavy rare earth be raw material, rare earth concentration 250-300 grams per liter, free acid 0.0001～0.2N, carry out multistage fractionation extraction Er-Tm grouping, extraction agent effective constituent 1.48-1.52M washes sour 2.3-2.5N HNO
3Or HCl, HNO
3System stream is organic phase than (volume ratio): feed liquid: wash acid-2.52: 14 1.44: the 0.6HCl system is 3: 12: 0.5.Grouping obtains containing Tm, Yb, Lu exports organic phase, as organic feed liquid, carry out multistage fractionation extraction again and separate Tm, feed liquid rare earth concentration 0.08-0.085M, extraction agent effective concentration 1.48-1.52M washes sour 3.4-3.5N HCl, and flow than (volume ratio): extraction agent: feed liquid: water: washing acid is 9: 30: 5: 7: 5, gained Yb-Lu enriched substance is carried out multistage fractionation extraction again and is separated, feed concentration 0.6M, pH2-4, extraction agent effective constituent 1.48-1.52M, its ammonium salt concentration 0.5-0.54M, wash acid and replace with the anti-liquid of part, sour regurgitation 5.3N HCl, flow than (volume ratio) extraction agent: feed liquid: wash acid: sour regurgitation is 31-33: 5: 6: 12.
2, the technology of grouping separation of mixed rare-earth as claimed in claim 1, it is characterized in that the Er-Tm grouping, the separation of Tm and the separating technology of Yb-Lu, both can contact and constitute a technical process, also can independently separately exist as the fore portion that contains a large amount of heavy rare earths material overall separation process, also can by the above two and back both in conjunction with constituting technical process, handle by what other raw mineral materialss (monazite, brown yttrium columbium ore deposit, xenotime) obtained and form similar corresponding enriched substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85101885A CN85101885B (en) | 1985-04-01 | 1985-04-01 | Separation of mixed rare-earth elements by extraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85101885A CN85101885B (en) | 1985-04-01 | 1985-04-01 | Separation of mixed rare-earth elements by extraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101885A CN85101885A (en) | 1986-09-24 |
| CN85101885B true CN85101885B (en) | 1986-11-26 |
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ID=4792119
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|---|---|---|---|
| CN85101885A Expired CN85101885B (en) | 1985-04-01 | 1985-04-01 | Separation of mixed rare-earth elements by extraction |
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| JP6205317B2 (en) * | 2014-07-14 | 2017-09-27 | 株式会社神戸製鋼所 | Extraction method |
| CN104451191A (en) * | 2014-12-03 | 2015-03-25 | 紫金矿业集团股份有限公司 | Dilution extraction process capable of improving copper recovery rate |
| CN106148696B (en) * | 2016-07-08 | 2018-01-05 | 广东省稀有金属研究所 | One kind removes radioactive method from lanthanum chloride solution |
| CN107099666B (en) * | 2017-05-16 | 2018-06-08 | 广东富远稀土新材料股份有限公司 | A kind of extraction and separation thulium, ytterbium, lutetium method |
-
1985
- 1985-04-01 CN CN85101885A patent/CN85101885B/en not_active Expired
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| CN85101885A (en) | 1986-09-24 |
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