CN85101885A - Mixed rare-earth elements by extraction separates - Google Patents
Mixed rare-earth elements by extraction separates Download PDFInfo
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- CN85101885A CN85101885A CN 85101885 CN85101885A CN85101885A CN 85101885 A CN85101885 A CN 85101885A CN 85101885 CN85101885 CN 85101885 CN 85101885 A CN85101885 A CN 85101885A CN 85101885 A CN85101885 A CN 85101885A
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Abstract
Invented a kind of technology that can be used for producing, handled and contain a large amount of heavy rare earth mixtures.With di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester is extraction agent, and the multiple-stage solvent extraction process carries out thulium, ytterbium, lutetium separation then earlier from erbium-thulium grouping.Obtain containing Tm, Yb each＜0.06%La-Er group rare-earth, grade＞94%Tm,＞97%Yb,＞99%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 extraction agent, multistage fractional-distillation extraction carries out E from contain a large amount of heavy rare earths materials
r-T
mGrouping and T
m, y
b, L
uSeparate.
HEH(EHP) with extraction agent di-(2-ethylhexyl)phosphoric acid (D commonly used
2EHPA) relatively, have that acidity is low, back extraction easily, be difficult for characteristics such as emulsification, be 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.Tm, yb, the Lu enriched substance of using monazite and brown yttrium columbium ore deposit rare earth to obtain through ion-exchange are raw material, 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 P20-29 1982).But its order of packets is from Nd-Sm, carries out Gd-Tb, Er-Tm grouping then.So the input concentration low processing capacity is little, the extraction agent consumption is big, unsuitable industrial-scale production, and organic phase Tm-Lu group rare-earth concentration＜0.2g/L 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 alkali adding 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 from this containing, as this material overall separation process first part with Tm, yb, Lu.
Raw material is based on gained mishmetal after the ionic absorption ore deposit separating yttrium of heavy rare earths, forms to see Table 1.
Table 1 mishmetal is formed
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 the Er-Tm maximum.(2) HEH(EHP) loading capacity little and in the raw material Tm-Lu content low, over-burden earlier to have avoided organic phase from the Er-Tm grouping.So technology of the present invention can take the charging of high concentration rare earth feed liquid (250～300g/L) and obtain the higher outlet raffinate (140/160g/L) of concentration and the outlet extraction liquid (14～24g/L), 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-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%, 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 13～24g/L, 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 80-130g/L 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 replace washing acid with the part strip liquor, and the latter is in order to improve product purity and to reduce acid and consume.
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 (3) extraction agent from the charging level and add ammonium salt.
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 (m+n level) from the 1st grade of adding, and rare earth feed liquid to be separated adds from middle m level.The 1-m level is an extraction section, and m-(m+n) level is a washing section.Extraction agent flows to (m+n) level 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, washes acid and will come together altogether under the difficulty collection component washing of organic phase at washing section, contains easy collection component organic phase at last and flows out from (m+n) level.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 RE
2O
3Concentration is organized salpeter solution or hydrochloric acid soln Tm and yb content all＜0.06% for 140-160g/L La-Er, uses for separating Er.Obtain grade 93-94%Tm enriched substance, yield 95-97% extracts high-purity T for chromatograph
mWith, obtaining grade 97%yb, yield＞95% extracts high-purity yb for chromatograph and uses.Obtain＞99%Lu yield 85～90% is as product or purify to use.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 this technical process three steps series connection 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 or (1)-(2) 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 (2)-(3).
Description of drawings
Figure: Er-Tm grouping 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
Example one
Er-Tm (the HNO that divides into groups
3System)
Obtain low yttrium mischmetal salpeter solution RE concentration 1.39-1.45M/L from the separating yttrium operation, free acid 0.1-0.2N, the material 1 of rare earth composition such as table 1, extraction agent are HEH(EHP)-kerosene, effective ingredient 1.48-1.52M/L; Wash sour 2.3-2.5N HNO
3, using mixing section is 3 * 3 * 6Cm mixer-settler.Feed liquid adds inbound traffics 1.40-1.44mL/ branch from the 20th grade, and extraction agent adds inbound traffics 2.52mL/ branch from 2 grades, washes acid and adds inbound traffics 0.6mL/ branch from the 39th grade.The raffinate water 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～150g/L, 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.
Example 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 260～275g/L, and PH=2-4 forms as 1 material 2; Extraction agent is HEH(EHP)-kerosene, effective ingredient concentration, is washed sour feed liquor position with example one at 1.48-1.52M/L extraction agent, feed liquid, and flow is respectively 3mL/ branch, 0.5mL/ branch.The outlet raffinate gets (La-Er) group rare-earth after reaching balance, concentration 150～154g/L, and Tm and yb content＜0.06%, the outlet extraction liquid is (Tm-Lu) group rare-earth concentration 13～16g/L, 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, obtains from example one or two any methods, and this example is 0.084～0.085M/L with organic feed liquid rare earth concentration, adds each 30mL from the 18th grade; Extraction agent is HEH(EHP)-kerosene, effective ingredient concentration 1.48-1.52M/L adds each 9ml from the 1st grade; Washing acid is 3.4～3.5NHC, adds each 7mL from 36 grades; Add dilution waters in order to adjust aqueous phase acidity from 18 grades, shake Swing 10 minutes of each 5mL, 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/L, and 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 obtains RECl from example three
3Concentration 0.60M/L PH2-4 adds each 5ml from the 20th grade; Extraction agent is HEH(HEP)-HEH(EHP) ammonium salt-kerosene, effective ingredient concentration 1.48～1.52M/L, ammonium salt concentration 0.5-0.54M/L 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/ branches with 53NHCl 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 (5)
1, a kind of is extraction agent grouping separation of mixed rare-earth technology with HEH (EHP), it is characterized in that the mishmetal based on the ionic of heavy rare earths absorption ore deposit is carried out the Er-Tm grouping earlier to be separated with Tm, yb, Lu, obtain Tm, yb content＜0.06%La-Er group rare-earth, grade＞99%Lu, the enriched substance of grade＞95%Tm and the enriched substance of grade＞97%yb.
2, technology as claimed in claim 1 wherein Er-Tm grouping comprise HNO
3System and HCl system, its separation condition: feed liquid rare earth concentration 1.40～1.45M/L, free acid 0.0001～0.2N; Extraction agent HEH(EHP)-kerosene or HEH(EHP)-HEH(EHP) ammonium salt-kerosene (effective ingredient concentration 1.48～1.50M/L ammonium salt concentration 0.5-0.53M/L); Wash sour HNO
3System 2.3-2.5N, HCl system 2.8-3.1N; 40 grades of progression, stream ratio: extraction agent: feed liquid: wash acid (volume ratio) HNO
3System 2.52: 1.44: 0.6HCl system 3: 1.2: 0.5.
3, technology as claimed in claim 1 is separated the Tm condition: organic feed concentration 0.08～0.085M/L; Extraction agent HEH(EHP)-kerosene effective ingredient concentration 1.48～1.52M/L; Wash acid 3.4～3.5NHCl and add entry adjusting extraction section acidity from the charging level; 36 grades of progression; Stream ratio: extraction agent: feed liquid: water: wash acid=9: 30: 5: 7.
4, technology as claimed in claim 1, wherein yb-Lu separating technology condition: feed liquid rare earth concentration 0.6MPH2-4; Extraction agent HEH(EHP)-HEH(EHP) ammonium salt-kerosene effective ingredient concentration 1.48-1.5M/L ammonium salt concentration 0.5-0.53M/L; Sour regurgitation 5.3NHCl; Wash acid and replace 48 grades of progression, 7 grades of back extractions with the anti-liquid of part; The stream ratio: extraction agent: feed liquid: wash acid: sour regurgitation is 32: 5: 6: 12.
5, separation and the yb-Lu as claim the 1,2,3,4 described technology Er-Tm groupings, Tm both can contact technical process of formation as the fore portion that contains a large amount of heavy rare earths material overall separation process, also can independently separately exist, also can be by the former two and the latter two 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 true CN85101885A (en) | 1986-09-24 |
| CN85101885B CN85101885B (en) | 1986-11-26 |
Family
ID=4792119
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85101885A Expired CN85101885B (en) | 1985-04-01 | 1985-04-01 | Separation of mixed rare-earth elements by extraction |
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| Country | Link |
|---|---|
| CN (1) | CN85101885B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106148696A (en) * | 2016-07-08 | 2016-11-23 | 广东省稀有金属研究所 | One removes radioactive method from lanthanum chloride solution |
| CN106536010A (en) * | 2014-07-14 | 2017-03-22 | 株式会社神户制钢所 | Extraction method |
| CN107099666A (en) * | 2017-05-16 | 2017-08-29 | 广东富远稀土新材料股份有限公司 | A kind of extract and separate thulium, ytterbium, the method for lutetium |
-
1985
- 1985-04-01 CN CN85101885A patent/CN85101885B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106536010A (en) * | 2014-07-14 | 2017-03-22 | 株式会社神户制钢所 | Extraction method |
| CN106536010B (en) * | 2014-07-14 | 2019-03-29 | 株式会社神户制钢所 | Extracting process |
| 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 |
| CN106148696A (en) * | 2016-07-08 | 2016-11-23 | 广东省稀有金属研究所 | One removes radioactive method from lanthanum chloride solution |
| CN107099666A (en) * | 2017-05-16 | 2017-08-29 | 广东富远稀土新材料股份有限公司 | A kind of extract and separate thulium, ytterbium, the method for lutetium |
| 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 |
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| Publication number | Publication date |
|---|---|
| CN85101885B (en) | 1986-11-26 |
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