CN1101476C - Process for producing high-purity lutetium oxide by extracting separation method - Google Patents
Process for producing high-purity lutetium oxide by extracting separation method Download PDFInfo
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- CN1101476C CN1101476C CN98100226A CN98100226A CN1101476C CN 1101476 C CN1101476 C CN 1101476C CN 98100226 A CN98100226 A CN 98100226A CN 98100226 A CN98100226 A CN 98100226A CN 1101476 C CN1101476 C CN 1101476C
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- organic phase
- concentration
- rare earth
- ethylhexyl
- lutetium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The present invention relates to a technique in which mono 2-ethylhexyl 2-ethyl hexyl phosphonate is used as extractant, amine extractant is used as an additive, and thulium, ytterbium and lutetium enriched substances or coarse lutetium oxide are continuously separated in a hydrochloric acid medium in one step to produce high-purity lutetium oxide products. The disadvantages of long equilibration time and difficult back extraction and regeneration of organic phases in the production system of the mono 2-ethylhexyl 2-ethyl hexyl phosphonate are overcome, and simultaneously, the advantages of large separation coefficient, high extracting capacity, low requirements for feed solutions, etc. of the system are kept. The present invention has the advantages of simple equipment, continuous production, large treating capacity, easy operation, little unit consumption of reagents and convenient connection with the existing rare earth process flow.
Description
The invention provides a kind of solvent extraction and separation thulium, ytterbium, lutetium enriched substance or thick lutecium oxide, the novel method of continuous production pure zirconia lutetium.Belong to the hydrometallurgy field.
At present, high-purity lutecium oxide is a raw material with thulium, ytterbium, lutetium enriched substance or thick lutecium oxide all, adopts chromes or solvent extration production.The main deficiency of chromes is: the required equipment complexity, the reagent costliness, and need thermostat, requirement to power house environment is also higher, so facility investment is big, difficult in maintenance, and production process is discontinuous, one time charging capacity is little, production cycle is long, and reagent such as the acid of unit output product, alkali consume high, and product yield is low; This method is had relatively high expectations to peopleware and production management level simultaneously.Use solvent extration production, the extraction agent that is adopted has two (2-ethylhexyl phosphonic acid (Cyanwx272) and 2-ethylhexyl phosphonic acid single 2-ethyl hexyl fat (P507).Wherein Cyanex272 system extraction agent costs an arm and a leg, and loading capacity is low, average separation factor little (1.3), and reagent, facility investment are big, feed liquid specification of quality height, the easy emulsification of separation system, the difficult control of production process; And the P507 system is when producing, though separation factor is bigger, but require starting time very long (about 30 minutes), be 5 times of general extracting and separating starting time, make reagent, usage ratio of equipment reduce greatly, and extraction equilibrium acidity height, organic phase is difficult to back extraction regeneration, product yield is low, even can not continuous production.
At above-mentioned deficiency, the present invention adopts a kind of method that adds additive in the P507 system, overcome shortcomings such as starting time length in the P507 production system, organic phase back extraction regeneration difficulty, kept advantages such as this system separation factor is big, loading capacity is high, the feed liquid specification of quality is low simultaneously.The equipment that is characterized in is simple, produce continuously, treatment capacity is big, easy handling, reagent unit consumption are little, be convenient to existing rare-earth process Connection between Processes.
The technology that solvent extraction and separation of the present invention is produced lutecium oxide comprises:
(1). raw material to be separated: wherein containing the lutetium amount is 5-99%, and remaining rare earth component is any, each constituent content
Sum should be 1-95% mutually;
(2). the organic phase of extraction system: for di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, amine extractant add
The mixture that adds agent and kerosene, amine extracted agent addition agent wherein be selected from as shown in the formula compound:
+-
R
1R
2R
3N or R
1R
2R
3R
4NX, the R in the formula
1, R
2, R
3, R
4Can be identical or different, and can each
Hydrogen atom or C do for oneself
6-10The alkyl of straight or branched, X is negative univalent chlorion or nitrate radical.
The volume ratio of di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and kerosene or sulfonated kerosene is 1 than 1-2, adds
The concentration that adds agent is 0.5-20% (weight), and this organic phase is used after sodium hydroxid or ammoniacal liquor saponification,
Saponification deg is 25-40%; (3). implement parameter: the saponification organic phase becomes the rare earth soap form to advance groove, feed concentration with rare earth and after flowing the 3-5 level
0.5-2.0 mole, acidity 0.01-1.5 mole, hydrochloric acid lotion concentration 3.0-6.0 mole, extraction section progression
(n) be 30-60, washing section progression (m) is 20-60, and each flows mutually than being: organic phase (Vs): feed liquid (Vf):
Washing lotion (Vw)=(6.0-20.0): 1: (0.3-1.8);
Under these conditions, can obtain concentration from water outlet is the 0.1-1.5 mole, and acidity is the non-lutetium element of 0.1-2.5 mole, obtain purity from organic phase and be equal to or greater than 99.99% lutecium oxide, again through conventional aftertreatment, get final product high-purity lutecium oxide product.Outstanding advantage of the present invention is:
＜1 〉. compare with chromes, but several times reduce equipment and reagent investment;
＜2 〉. compare with the Cyanex272 system, reagent, facility investment are little, and production process is controlled easily, production cost
Low;
＜3 〉. compare with the P507 system, starting time is short, and about 6 minutes, reagent, usage ratio of equipment greatly improved, and have
Machine is regenerated thoroughly mutually, and the product yield height also can be realized continuous production to the raw material that lutetium content is low.
In order to be illustrated more clearly in the present invention, be listed below example, but this there is not any restriction to scope of the present invention.
Embodiment:
Adopting fractionation extraction process to carry out Yb/Lu separates, the volume percentage composition of extracted organic phase is: P507: the quaternary ammonium salt additive: kerosene=33: 3: 64, the concentration 1.0mol of P507 wherein, the saponification deg of extracted organic phase is 30%, saponification organic phase and rare earth and flow 4 grades after enter the extraction section first step; Rare earth feed liquid concentration is 1.5mol, and the about pH=1 of acidity wherein contains lutetium 7-10%, all the other elements (Ho-Tm)
2O
3Contain 7-10%, Yb
2O
3Contain 80-86%; The washing lotion concentration of hydrochloric acid is 5.0mol, and extraction section progression is 40, and washing section progression is 40, and stream is than being: organic phase: feed liquid: wash acid=20: 1: 1.5.Obtain mixture before the lutetium of concentration 1.0mol, the about 1.0mol of acidity from the water raffinate under the described conditions; Can obtain pure lutetium product (＞99.99%) from the organic phase outlet.Wherein main rare earth impurities is: Ho
2O
3＜3 μ g/g, Er
2O
3＜3 μ g/g, Tm
2O
3＜3 μ g/g, Yb
2O
3＜20 μ g/g, Y
2O
3＜3 μ g/g.
Claims (2)
1. a solvent extraction and separation is produced the technology of lutecium oxide, it is characterized in that described technology comprises:
(1). raw material to be separated: wherein containing the lutetium amount is 5-99%, and remaining rare earth component is any, and each constituent content sum should be 1-95% mutually;
(2). the organic phase of extraction system: be the mixture of di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, amine extracted agent addition agent and kerosene, amine extracted agent addition agent wherein be selected from as shown in the formula compound:
+-
R
1R
2R
3N or R
1R
2R
3R
4NX, the R in the formula
1, R
2, R
3, R
4Can be identical or different, and can respectively do for oneself hydrogen atom or C
6-10The alkyl of straight or branched, X is negative univalent chlorion or nitrate radical; The volume ratio of di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and kerosene or sulfonated kerosene is 1 than 1-2, and the concentration of additive is 0.5-20% (weight), and this organic phase is used after sodium hydroxid or ammoniacal liquor saponification, and saponification deg is 25-40%;
(3). implement parameter: the saponification organic phase becomes the rare earth soap form to advance groove with rare earth and after flowing the 3-5 level, feed concentration 0.5-2.0 mole, acidity 0.01-1.5 mole, hydrochloric acid lotion concentration 3.0-6.0 mole, extraction section progression is 30-60, washing section progression is 20-60, and each flows mutually than being: organic phase: feed liquid: washing lotion=(6.0-20.0): 1: (0.3-1.8);
Under these conditions, can obtain concentration from the water outlet is the 0.1-1.5 mole, and acidity is the non-lutetium element of 0.1-2.5 mole, obtains purity from organic phase and is equal to or greater than 99.99% lutecium oxide, again through conventional aftertreatment, gets the lutecium oxide product.
2. according to the described technology of claim 1, it is characterized in that described technology comprises:
(1 '). raw material to be separated: wherein containing the lutetium amount is 7-10%, all the other elements (Ho-Tm)
2O
3Contain 7-10%, Yb
2O
3Contain 80-86%;
(2 '). the organic phase of extraction system: be the mixture of di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, tertiary amine extraction agent additive and kerosene, wherein the volume ratio of di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and additive and kerosene equals 33: 3: 64, the concentration of di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester is 1 mole, and the saponification deg of this organic phase is 30%;
(3 '). implement parameter: saponification organic phase and rare earth and flow 4 grades after enter the extraction section first step, 1.5 moles of rare earth feed liquid concentration, acidity is Ph=1, hydrochloric acid lotion concentration is 5.0 moles, extraction section progression is 40, washing section progression is 40, and each flows mutually than being: organic phase: feed liquid: washing lotion=20: 1: 1.5;
In the above conditions, can obtain concentration from the water outlet is 1.0 moles, and acidity is mixture before 1.0 moles of lutetiums, obtains pure lutetium product from the organic phase outlet, and purity is greater than 99.99%, and wherein main rare earth impurities is: Ho
2O
3＜3 μ g/g, Er
2O
3＜3 μ g/g, Tm
2O
3＜3 μ g/g, Yb
2O
3＜20 μ g/g, Y
2O
3＜3 μ g/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98100226A CN1101476C (en) | 1998-01-13 | 1998-01-13 | Process for producing high-purity lutetium oxide by extracting separation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98100226A CN1101476C (en) | 1998-01-13 | 1998-01-13 | Process for producing high-purity lutetium oxide by extracting separation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1192479A CN1192479A (en) | 1998-09-09 |
| CN1101476C true CN1101476C (en) | 2003-02-12 |
Family
ID=5215886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98100226A Expired - Lifetime CN1101476C (en) | 1998-01-13 | 1998-01-13 | Process for producing high-purity lutetium oxide by extracting separation method |
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| Country | Link |
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| CN (1) | CN1101476C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748275B (en) * | 2009-12-22 | 2011-02-02 | 江阴加华新材料资源有限公司 | Preparation method of low-thorium lutetium oxide |
| 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 |
| CN105950891B (en) * | 2016-05-19 | 2018-01-02 | 南昌航空大学 | A kind of solvent extraction prepares the technological process of 5N ytterbiums |
| CN105950890B (en) * | 2016-05-19 | 2017-12-12 | 南昌航空大学 | A kind of technical grade thulium raw material prepares 5N thulium methods |
| CN105950892B (en) * | 2016-05-20 | 2017-12-12 | 南昌航空大学 | The method that the separation of technical grade lutetium raw material abstraction prepares 5N lutetiums |
| CN110386618B (en) * | 2019-08-20 | 2020-05-01 | 福建省长汀金龙稀土有限公司 | Preparation method of low-thorium and low-uranium lutetium oxide for PET (polyethylene terephthalate) |
| CN112028106A (en) * | 2020-08-17 | 2020-12-04 | 广西国盛稀土新材料有限公司 | Preparation method of lutetium nitrate feed liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101874A (en) * | 1985-04-01 | 1986-07-30 | 中国科学院长春应用化学研究所 | P507 extration resin chromatography is separated and extraction HIGH PURITY THULIUM OXIDE and lutecium oxide |
| CN1131200A (en) * | 1995-11-08 | 1996-09-18 | 北京大学 | Solvent extraction and separation new system of thulium, ytterbium and lutetium |
-
1998
- 1998-01-13 CN CN98100226A patent/CN1101476C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101874A (en) * | 1985-04-01 | 1986-07-30 | 中国科学院长春应用化学研究所 | P507 extration resin chromatography is separated and extraction HIGH PURITY THULIUM OXIDE and lutecium oxide |
| CN1131200A (en) * | 1995-11-08 | 1996-09-18 | 北京大学 | Solvent extraction and separation new system of thulium, ytterbium and lutetium |
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| Publication number | Publication date |
|---|---|
| CN1192479A (en) | 1998-09-09 |
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