CN85102244B - Phosphonates lle separation of rare earth elements - Google Patents
Phosphonates lle separation of rare earth elements Download PDFInfo
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- CN85102244B CN85102244B CN85102244A CN85102244A CN85102244B CN 85102244 B CN85102244 B CN 85102244B CN 85102244 A CN85102244 A CN 85102244A CN 85102244 A CN85102244 A CN 85102244A CN 85102244 B CN85102244 B CN 85102244B
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- rare earth
- heh
- extraction
- ehp
- rare
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Abstract
The present invention relates to a method for separating rare earth elements by the liquid-liquid extraction of aminated P507, which belongs to hydrometallurgical solvent extraction technology. The present invention provides a technological process for separating Er, Dy, La, Ce, Pr and Nd in ionic rare earth ore, mainly heavy rare earth, by the extraction of the aminated P507. Since the capacity and for extracting the rare earth elements and a separating factor are increased and balance time is shortened, the rare earth oxide of the following purity of La2O3 whose purity is more than 99.97%, Dy2O3 whose purity is more than 99%, Pr6O11 whose purity is from 99 to 99.5%, Er2O3 whose purity is more than 95%, Nd2O3 whose purity is more than 97%, CeO2 whose purity is more than 90% and HO enriched substances whose purity is more than 60% can be obtained by the technology.
Description
The invention belongs to hydrometallurgical solvent extraction technology.
The not only contained rare earth great variety of goods of ion type rareearth ore.And be easy to extract.It is development and the resource of crucial importance of opening up emerging rare-earth industry.How easily ionic ore deposit Rare Earth Separation to be come out.Become problem anxious to be solved.Since the mid-1960s.About the isolation technique of rare earth element has had new breakthrough and development.The method that has replaced classical rare-earth separating with the liquid-liquid extraction method of organic solvent gradually.Liquid-liquid extraction method is the efficient height not only, can be applicable to serialization large-scale commercial production.And good separating effect.What representative was arranged most is exactly HDEHP(two-" 2-ethylhexyl " phosphonic acids) the liquid-liquid extraction separation of rare earth elements.But HDEHP exists loading capacity little, and difficult back extraction is particularly big and incomplete to heavy rare earth element back extraction acidity.Shortcomings such as easy emulsification.The present invention is big with loading capacity, the separating factor height, the easy ammonification HEH(EHP of back extraction) (2-ethylhexyl phosphonic acid list " 2-ethylhexyl " ester is represented with HL) is to the extracting and separating based on the ionic ore deposit rare earth element (yttriums have given first separation in a large number) of heavy rare earths.
(clear 54-93672, clear 57-198227 and clear 58-84118) such as bright great, the golden Gu time heros of liana reported and used HEH(EHP) the extracting and separating rear earth element, they have enumerated and separated Nd-Sm in the HCl systems, at HNO
3From Sm-Eu-Gd, separate Gd in the system and from Sm-Gd-Tb-Dy-Y, carry out the Tb-Dy grouping, proposed to adjust aqueous phase acidity with alkali (using NaOH in the example), and compare with mode and the effect of adjusting aqueous phase acidity importing alkali, think to be divided into twoport and to import and import effective than single port importing an alkali number.They think HEH(EHP) people such as extraction process is to be used for monazite, and the Rare Earth Separation Li De of bastnasite and xenotime etc. is modest is once to the mining part ammonification of ionic HEH(EHP) the HCl system carries out Nd-Sm grouping, organic phase charging HNO then
3System is carried out Gd-Tb respectively, Er-Tm grouping (the rare earth chemistry collection of thesis, Science Press 1982, P20) but use ammonification HEH(EHP) the extracting and separating erbium then is not reported.
Erbium has very important purposes in modernization industry and national defense construction, it not only serves as on laserable material, the stupalith, and is the good material of making safety goggles against radiation.Erbium accounts for 5% in the ionic ore deposit based on heavy rare earths (Y account for～6%), it is the valuable source that extracts erbium.
The objective of the invention is at the mishmetal based on the ionic ore deposit of heavy rare earths, research is suitable for the technical process that the industrial production extraction process separates erbium.
The present invention proposes and use ammonification HEH(EHP) extracting and separating is the technical process of the erbium in the main ion type ore deposit with heavy rare earths, obtained purity＞95%Er
2O
3(through the pure Er that makes of EDTA ion-exchange
2O
3＞99.98%).
The present invention is owing to adopt ammonification HEH(EHP) can improve HEH(EHP greatly) capacity and the separating factor of extracting rare-earth element.Because at liquid-liquid extraction process middle-weight rare earths ion and HEH(EHP) in hydrogen ion exchange (this reaction formula is suitable for the HCl system under the low acidity, has nothing to do with rare earth concentration) by reaction formula (1):
RE
3++3（HL）
2（o） 
RE（HL
2）
3（o）+3H
+ （1）
RE
3+Represent trivalent rare earth ions, (o) represent organic phase, therefore, raffinate aqueous phase acidity is improved constantly, influence the further extracting and separating of rare earth element.For maintaining the extracting and separating of rare earth element under certain separating factor condition, just must additionally add alkali to keep the balance acidity of separating required water.Ammonification HEH(EHP of the present invention) be to give by desired ammonification rate strong aqua being added to HEH(EHP equably earlier) in, do not need to import alkali lye in a bite or twoport in addition, so both saved equipment, be easy to handled easily again, play the steady state extraction effect, can reach the separating effect of the phase of giving well.Solubility studies result shows.Ammonification HEH(EHP) solubleness in the substantial sepn system is 10
-4-10
-5M, promptly loss of solubility is very little.
For reaching the separation purpose, must use mineral acid to wash acid, so that the rare earth that many collections are gone in the organic phase washes, reach the purpose of exchange extracting and separating once more, play fractionation.The separating effect of phase is given in acquisition.Adopt any class mineral acid to wash acid, generally should be consistent with rare-earth salts to be separated.The present invention has at length studied HEH(EHP) at HCl and HNO
3Separating factor (the β of system middle-weight rare earths element
Z+1 Z), the result shows that for light rare earths, the separating factor of HCl system is greater than HNO
3System.Centering, heavy rare earths, when rare earth concentration is little, HNO
3The β value of system is a little more than the HCl system, no matter but to Er-y HNO
3Or the HCl system, its β
Er yBe 1.3～1.5.
The present invention uses re chloride to consist of La-Gd～55%, Tb-Er(Y)～45%, wherein Er account for～10%, rare earth concentration is 1.4～2M, pH=1-3 is with the HEH(EHP of 30-40% ammonification rate 1.4-1.6M)-kerosene is extraction agent, carries out multistage fractionation extraction in 60-125 milliliter separating funnel.Add ammonification HEH(EHP respectively in extraction and washing section two ends) and washing acid, the reinforced level between head and the tail adds the rare earths material aqueous solution, and two ends are flowed out the aqueous solution that contains the raffinate rare earth respectively and are contained the organic phase solution that collection is gone into rare earth.This organic phase solution imports an end of stripping section, and the other end adds back extraction acid, and two ends are flowed out isolating rare earth aqueous solution and extraction agent HEH(EHP respectively), this HEH(EHP) with a certain amount of strong aqua uniform mixing after just can continue to use.
The present invention ammonification HEH(EHP) extracts thick Er product, guarantee that yield＞98% of Er makes high-purity Er with the EDTA ion exchange method then
2O
3Product (purity＞99.98%) obtains expected results in order to guarantee extraction process, adopts high concentration rare earth (1.4-2M) solution as feed liquid, strengthen the Hui Cui ratio, temperature is being carried out fractionation extraction more than 15-20 ℃, and it is little to have overcome separating factor, shortcomings such as starting time is long have reached expected results.Be applicable to industrial production.
The present invention uses ammonification HEH(EHP) be extraction agent, its general expression is:
(alkyl alkylphosphonate, wherein R
1=R
2During=2-ethylhexyl, promptly be HEH(EHP) HEH(EHP)-kerosin, adding a certain amount of strong aqua, to make the ammonification rate be 30-40%(0.42-0.64M NH
+ 4) ammonification HEH(EHP)-kerosin.
The present invention uses 3.8-4.0N HCl as washing acid, and 4-5N HCl is back extraction acid, is in a ratio of ammonification HEH(HHP): feed liquid: wash acid: sour regurgitation=14: 3: 2: 2-3, temperature is preferably in more than 15-20 ℃.
The present invention obtains Er through the multi-stage countercurrent fractionation extraction
2O
3The thick product of purity＞95% meets the Er that the EDTA ion exchange method obtains purity＞99.98%
2O
3Contain Er0.1-0.2% in the La-HO group.
Realize that example of the present invention is as follows:
The separation of Er:
Extraction agent HEH(EHP) be 1.4-1.6M, the ammonification rate is 34-36%(0.48-0.58M NH
+ 4), rare earth chloride liquid is that 1.45-1.55M(forms La-Gd-55%, Tb-Er(Y)～45%, wherein Er account for～10%), wash acid for 3.8-40N HCl sour regurgitation is 4-5N HCl, be in a ratio of ammonification HEH(EHP): feed liquid: wash acid: sour regurgitation=14: 3: 2: 2-3.Go out among the water La-Ho to contain Er0.1-0.2% Er in the strip liquor through 45 stage countercurrent fractionation extraction results
2O
3Purity＞95%(wherein contains＜0.2%Dy
2O
3,＜0.2%Ho
2O
3, 2%Y
2O
31.8%Tm
2O
3), connect the EDTA ion exchange method and make purity＞99.98%Er
2O
3
The rare earth element that above example is equally applicable to resulting similar composition from other rare-earth mineral separates.
Claims (2)
1, a kind of with ammonification HEH(EHP) technology of liquid-liquid extraction separation of rare earth elements Er, it is characterized in that at ion type rareearth ore based on heavy rare earths, adopting the rare earth element component is La-Gd～55%, Tb-Er(Y)～45%, wherein Er account for～10%, rare earth concentration is 1.4-2M, the re chloride of pH=1-3 is a raw material, the HEH(EHP of 30-40% ammonification rate 1.4-1.6M)-kerosene is extraction agent, as washing acid, 4-5NHCl is in a ratio of ammonification HEH(EHP as back extraction acid with 3.8-4.0N HCl): feed liquid: wash acid: sour regurgitation=14: 3: 2: 2-3, carry out the multi-stage countercurrent fractionation extraction, temperature is preferably in more than 15-20 ℃.
2,, it is characterized in that it is not only applicable to ionic ore deposit based on heavy rare earths, and be applicable to that other rare-earth mineral with similar composition separates single rare earth Er as the technology of the described rare-earth separating of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85102244A CN85102244B (en) | 1985-04-01 | 1985-04-01 | Phosphonates lle separation of rare earth elements |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85102244A CN85102244B (en) | 1985-04-01 | 1985-04-01 | Phosphonates lle separation of rare earth elements |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85102244A CN85102244A (en) | 1987-01-17 |
| CN85102244B true CN85102244B (en) | 1988-02-03 |
Family
ID=4792362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85102244A Expired CN85102244B (en) | 1985-04-01 | 1985-04-01 | Phosphonates lle separation of rare earth elements |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85102244B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618736B (en) | 2012-03-31 | 2013-09-04 | 中国科学院长春应用化学研究所 | Extraction separation method of rare-earth element |
| CN108220596B (en) * | 2018-02-08 | 2020-08-25 | 赣州齐畅新材料有限公司 | Praseodymium-neodymium extraction, enrichment and separation method |
| CN109161683B (en) * | 2018-11-14 | 2019-12-27 | 中国地质大学（北京） | Mineral leaching liquid for ionic rare earth ore and use method thereof |
-
1985
- 1985-04-01 CN CN85102244A patent/CN85102244B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN85102244A (en) | 1987-01-17 |
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