CN1014976B - High-purity terbium oxide preparation by use of fractional extraction method - Google Patents
High-purity terbium oxide preparation by use of fractional extraction methodInfo
- Publication number
- CN1014976B CN1014976B CN89108954A CN89108954A CN1014976B CN 1014976 B CN1014976 B CN 1014976B CN 89108954 A CN89108954 A CN 89108954A CN 89108954 A CN89108954 A CN 89108954A CN 1014976 B CN1014976 B CN 1014976B
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- China
- Prior art keywords
- terbium
- organic phase
- concentration
- extraction
- mishmetal
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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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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a method using rich terbium rare earth mixture or pure terbium oxide with 10 to 99.5 percent of terbium oxide as raw materials, P507 (HEH (EHP)) or P204 (D2EHPA) as an extractive agent, coal oil as a diluting agent, and water phase as hydrochloric acid media to obtain high-purity terbium oxide which is more than or equal to 99.95 percent by two-stage fractionation and extraction technology. The present invention breaks through the existing method that the high-purity terbium oxide is produced by using an extraction color layer method, etc., and has the characteristics of less investment, simple device, large handling capacity, continuous production process, convenience for connecting with the other technology, and low product cost.
Description
The invention belongs to the rare earth metal field, a kind of method of separating terbium-riched rare earth oxide compound or thick pure zirconia terbium acquisition high purity terbium oxide is provided.
At present, high purity terbium oxide is a raw material with terbium-riched rare earth oxide compound or thick pure zirconia terbium all, adopts chromes production.The main deficiency of this method is: required equipment complexity, reagent costliness, and need thermostat, and also higher to the requirement of power house environment, so equipment, reagent investment are high, difficult in maintenance; Production process is discontinuous, and one time charging capacity is little, and the production cycle is long, and reagent such as the acid of unit product output, alkali consume high, and product yield is lower; Simultaneously, this method is had relatively high expectations to peopleware and production management level.
Adopt fractional-distillation extraction to replace chromes at above-mentioned not enough the present invention and produce high purity terbium oxide, the equipment that is characterized in is simple, produce continuously, treatment capacity is big, easy handling management, unit product output reagent consume low etc.Use the inventive method to obtain high purity terbium oxide (〉=99.95%) by terbium-riched rare earth oxide compound or thick pure zirconia terbium (containing terbium sesquioxide 10-99.5%).
The inventive method comprises: with HEHEHP or HDEHP is extraction agent, in hydrochloric acid medium, adopt two sections fractionation extraction process, terbium/dysprosium of finishing earlier in terbium-riched rare earth mixture or the thick pure zirconia terbium separates, and makes terbium and other Rare Earth Separation again, thereby obtains high purity terbium oxide.The present invention has broken the circle of producing the habitual extraction chromatography method of high purity terbium oxide, has overcome with chromes and has produced the major defect that exists in the high purity terbium oxide technology, has simplified Production Flow Chart; Under the condition of same turnout, but the present invention reduces equipment and reagent investment than the chromes several times, reduce production cost, and production process is continuous, easy and simple to handle, is easy to other Rare Earth Production line supportingly, has remarkable economic efficiency; Because extraction agent that the present invention is included and extraction equipment also can be widely used in the industrial production of other rare earth both at home and abroad, and the raw material compositing range that is suitable for is very big, thereby suitability is wide, simple.
The organic phase of above-mentioned extraction system is the mixture of HEHEHP or HDEHP and kerosene, and wherein the ratio of each component is: HEHEHP(or HDEHP): kerosene=1: the 1-2(volume), and HEHEHP(or HDEHP) concentration 1.0-1.5M; This organic phase is used after sodium hydroxide or ammoniacal liquor saponification, saponification deg 25-40%; Terbium content 10-99.5% in the raw material to be separated, all the other rare earths are formed arbitrarily, and each constituent content sum should be 90-0.5% mutually.
Adopt described extraction system, the significant parameter of first segment process is: the saponification organic phase becomes the rare earth soap form to advance groove with rare earth and after flowing the 3-8 level, feed concentration 0.5-1.5M, acidity 0.2-1.5N, salt pickling acid concentration 3.0-5.5N, extraction section progression n=30-45, washing section progression m=15-30, respectively stream compares V mutually
S: V
F: V
W=(6.0-20.0): 1: (0.3-1.8).Under the described conditions, can obtain mishmetal before the terbium of concentration 0.5-1.5M, acidity 0.1-1.2N from water outlet.(V
S, V
F, V
WBe respectively extraction agent, feed liquid and wash sour volumetric flow rate).Perhaps under these conditions, the saponification organic phase is directly advanced groove.
Second segment process further separates above-mentioned water outlet thing.At salt pickling acid concentration 3.0-5.5N, extraction section progression n=10-20, washing section progression m=20-35, respectively stream compares V mutually
S: V
F: V
W=(6.5-18.0): 1: under the processing condition (0.35-2.0), obtain purity through conventional postprocessing working procedures and be greater than or equal to 99.95% terbium sesquioxide product.
Product analysis authentication method: atomic emission spectrum.
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.
Example 1
As shown in drawings, 1. adopt two outlet fractionation extraction process to carry out terbium/dysprosium and separate, the consisting of of extracted organic phase: HEHEHP: kerosene=1: the 1.5(volume), HEHEHP concentration 1.23M, saponification deg 40%, saponification organic phase and rare earth and flow 4 grades after enter extraction section; Rare earth feed liquid concentration 0.7M, acidity 1.3N wherein contains terbium sesquioxide 14%, and all the other elementary composition and percentage compositions are: La
2O
3＜0.1, CeO
2＜0.1, Pr
6O
11＜0.1, Nd
2O
3＜0.1, Sm
2O
3=3.7, Eu
2O
3=0.5, Gd
2O
3=21.4, Dy
2O
3=31.1, Ho
2O
3=2.6, Er
2O
3=3.2, Tm
2O
3=0.6, Yb
2O
3=2.1, Lu
2O
3=0.3, Y
2O
3=20.4; Washing lotion concentration of hydrochloric acid 5.0N, extraction section progression n=34, washing section progression m=23; Extract stream compares V
S: V
F: V
W=6.4: 1: 0.47.Under the described conditions, obtain light, middle-weight rare earths mixture before the terbium of concentration 0.7-0.8M, acidity 0.6N and the terbium from water, wherein heavy rare earths content is less than or equal to 100ppm behind the terbium.
2. be feed liquid with light before 1. water outlet terbium and the terbium, middle-weight rare earths mixture, adopt and 1. identical organic phase and washing lotion, extraction section progression n=15, washing section progression m=30, stream compares V
S: V
F: V
W=6.85: 1: 0.56, the outlet organic phase was through back extraction, and aftertreatment obtains high purity terbium oxide, and wherein main rare earth impurities is: Sm
2O
3＜30ppm, Eu
2O
3＜10ppm, Gd
2O
3＜40ppm, Dy
2O
3＜80ppm, Ho
2O
3＜10ppm, Er
2O
3＜10ppm, Yb
2O
3＜10ppm, Y
2O
3＜50ppm.
Example 2
As shown in drawings, 1. adopt two outlet technologies to separate terbium/dysprosiums, the consisting of of extracted organic phase: HDEHP: kerosene=1: 1.0, HDEHP concentration 1.5M, saponification deg 30%, saponification organic phase and rare earth also flow 7 grades and enter extraction section; Rare earth feed liquid concentration 1.46M, acidity 0.7N wherein contains terbium sesquioxide 55.1%, and all the other elementary composition and percentage compositions are: La
2O
3≤ 1, CeO
2≤ 0.5, Pr
6O
11≤ 1, Nd
2O
3=3.6.Sm
2O
3=11.4, Eu
2O
3=3.1, Gd
2O
3=18.7, Dy
2O
3=3.2, Y
2O
3=2.3, other heavy rare earths sum is less than 0.5; Washing lotion concentration of hydrochloric acid 5.5N, extraction section progression n=44, washing section progression m=30, respectively stream compares V mutually
S: V
F: V
W=15.5: 1: 1.76.Under the described conditions, obtain concentration 1.1-1.2M from water, light, middle-weight rare earths mixture before the terbium of acidity 1.1N and the terbium, wherein behind the terbium heavy rare earths content sum less than 100ppm.
2. be feed liquid with 1. water outlet thing, adopt with 1. identical organic phase with wash acid, extraction section progression n=20, washing section progression m=35, stream compares V
S: V
F: V
W=11.5: 1: 0.80, can get high purity terbium oxide by the outlet organic phase, wherein main rare earth impurities is: La
2O
3＜10ppm, CeO
2＜10ppm, Pr
6O
11＜10ppm, Nd
2O
3＜10ppm, Sm
2O
3＜40ppm, Eu
2O
3＜10ppm, Gd
2O
3＜80ppm, Dy
2O
3＜60ppm, Y
2O
3＜50ppm.
Example 3
As shown in drawings, 1. at first adopt one section fractionation extraction process to separate terbium/dysprosium, extracted organic phase consists of: HEHEHP: kerosene=1: 1.8, HEHEHP concentration 1.07M, saponification deg 25%, saponification organic phase and rare earth and flow 5 grades after enter extraction section; Rare earth feed liquid concentration 1.0M, acidity 0.9N wherein contains terbium sesquioxide 98.0%, and all the other elements and percentage composition are: Sm
2O
3=0.042, Eu
2O
3=0.01, Gd
2O
3=0.83, Dy
2O
3=0.61, Ho
2O
3=0.01, Y
2O
3=0.45, all the other are light, the heavy rare earths sum is less than 0.05; Wash acid concentration 4.0N, extraction section and washing section progression are respectively n=35, m=15, and stream compares V
S: V
F: V
W=18.5: 1: 1.3.Under the described conditions, obtain concentration 0.9-1.0M from water, light, middle-weight rare earths mixture before the terbium of acidity 0.9N and the terbium, wherein behind the terbium heavy rare earths total content less than 80ppm.
2. with second section fractionation extraction process, separate by the water outlet lucium that 1. obtains, adopt and 1. identical organic phase and washing lotion, extraction section and washing section progression are respectively n=15, m=30, and stream compares V
S: V
F: V
W=17.0: 1: 0.40, can get high purity terbium oxide by the outlet organic phase through back extraction, aftertreatment, wherein major impurity is: Gd
2O
3＜20ppm, Dy
2O
3＜30ppm, Ho
2O
3＜10ppm, Y
2O
3＜20ppm.
Description of drawings:
Technological process block-diagram
1 saponification organic phase
2 feed liquids
3 washing lotions
4 saponification organic phases
5 raffinates (rare earth soap feed liquid and feed liquid)
6 washing lotions
Claims (1)
1, a kind of method of separating high purity terbium oxide from rich terbium mishmetal or thick pure zirconia terbium is characterized in that described method comprises:
(1) mishmetal as raw material is rich terbium mishmetal or thick pure zirconia terbium (containing terbium sesquioxide 10-99.5%), and other components except that terbium are any, each element oxide content sum correspondingly is 90-0.5%;
(2) adopt two sections fractionation extraction process, the organic phase of extraction agent consists of: HEHEHP (or HDEHP): kerosene=1: 1-2 (volume), and concentration is 1.0-1.5M, saponification deg is 25-40%;
(3) adopt (1), (2) described raw material, organic phase is carried out terbium/dysprosium earlier in hydrochloric acid medium fractionation extraction separates, the saponification organic phase is directly advanced groove or is become the rare earth soap form to advance groove with rare earth and after flowing the 3-8 level, the concrete optional feed concentration 0.5-1.5M that uses of parameter, acidity 0.2-1.5N, salt pickling acid concentration 3.0-5.5N, extraction section progression n=30-45, washing section progression m=15-30, each flows mutually than being organic phase (V
S): feed liquid (V
F): wash acid (V
W)=(6.0-20.0): 1.0: (0.3-1.8) (volume) gets concentration 0.5-1.5M from water, mishmetal before the terbium of acidity 0.1-1.2N;
(4) adopt (2) described organic phase to carry out another section fractionation extraction process again, in hydrochloric acid medium, separate the preceding mishmetal of the terbium that obtains by (3), obtain high-purity (〉=99.95%) terbium sesquioxide, concrete parameter can select for use hydrochloric acid to wash acid concentration 3.0-5.5N, extraction section progression n=10-20, washing section progression m=20-35, each phase volume stream compares V
S: V
F: V
W=(6.5-18.0): 1: (0.35-2.0).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89108954A CN1014976B (en) | 1989-12-04 | 1989-12-04 | High-purity terbium oxide preparation by use of fractional extraction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89108954A CN1014976B (en) | 1989-12-04 | 1989-12-04 | High-purity terbium oxide preparation by use of fractional extraction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1042570A CN1042570A (en) | 1990-05-30 |
| CN1014976B true CN1014976B (en) | 1991-12-04 |
Family
ID=4857806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89108954A Expired CN1014976B (en) | 1989-12-04 | 1989-12-04 | High-purity terbium oxide preparation by use of fractional extraction method |
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|---|---|
| CN (1) | CN1014976B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936665B (en) * | 2011-08-04 | 2013-11-06 | 陆文光 | Method for extracting rare earth elements |
| CN103482669B (en) * | 2013-09-10 | 2015-01-21 | 中铝稀土（常熟）有限公司 | Method for preparing high-purity terbium oxide |
| CN104087748B (en) * | 2014-07-21 | 2016-08-17 | 赣州湛海工贸有限公司 | A kind of extract and separate Rare earth element and method of terbia. Diterbium trioxide from terbium dysprosium rareearth enriching material |
| US10029920B2 (en) | 2015-06-25 | 2018-07-24 | Iowa State University Research Foundation, Inc. | Separation of terbium(III,IV) oxide |
| CN105112658A (en) * | 2015-08-28 | 2015-12-02 | 昆明理工大学 | Method for extracting rare-earth elements through micro channels |
| CN105063382B (en) * | 2015-09-12 | 2017-06-13 | 北京科技大学 | A kind of separation method of La, Ce, Pr, Nd mixed rare earth ions |
| CN106498193B (en) * | 2016-12-22 | 2019-07-26 | 南昌航空大学 | A kind of extracting process of three kinds of rare earths materials of grouping separation |
-
1989
- 1989-12-04 CN CN89108954A patent/CN1014976B/en not_active Expired
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|---|---|
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