CN101824537B - Ultra-pure gadolinium oxide and electrochemical reduction fully-closed type extracting production process thereof - Google Patents
Ultra-pure gadolinium oxide and electrochemical reduction fully-closed type extracting production process thereof Download PDFInfo
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Abstract
The invention discloses a full extracting process for preparing ultra-pure gadolinium oxide and a product thereof. Compared with the traditional ion exchange and chromatography extraction method, the process has the characteristics of large yield and low cost. The primary-pure gadolinium oxide (Gd2O3 at the grade of 99.99 percent) is obtained in advance by adopting a rough gadolinium enriching substance (Gd3O3 at the grade of 10-90 percent) as a raw material and adopting a mixed extracting agent of P507 and P204 through optimized control of factors, such as material liquid concentration, grade, phase ratio, acidity, and the like and classical extraction and separation in two steps; then the electrochemical reduction and the fully-closed type extraction and separation are performed for carrying out deep purification, and trace rare-earth element impurities are removed; and finally, the ultra-pure gadolinium oxide product with the rare-earth impurity content below 0.5ppm is obtained.
Description
Technical field
The present invention relates to ultra-pure gadolinium oxide and extraction preparation method thereof.
Background technology
Gadolinium sesquioxide is the important source material of novel rare-earth functional materials, and it is widely used in fields such as fluorescent material, monocrystal material, opticglass and magneticsubstance, like intensifying screen powder, gadolinium gallium garnet type monocrystalline, electronic memory element and fluorescent material substrate material etc.In some high-end applications fields, require gadolinium sesquioxide to have very high purity, reach ultra-pure (＞99.999%), present conventional gadolinium sesquioxide product can only reach high-purity (＞99.99%).
Publication number is that the one Chinese patent application (calling document 1 in the following text) of CN 101633984A discloses the production technique that a kind of acidic organophosphorus extractant is produced high-purity gadolinium oxide.Publication number is that the Chinese patent of CN 1041115C discloses a kind of method of from high-purity gadolinium oxide, removing europium sesquioxide.The prepared gadolinium sesquioxide of these prior aries can only reach high-purity (＞99.99%), can not get ultra-pure (＞99.999%) gadolinium sesquioxide, can not satisfy high-end demand.And high-purity gadolinium oxide (＞99.99%) only is difficult to be further purified with classical extracting process, and like 1 introduction of document, its finished product REE impurities content generally is＜2ppm, particularly its adjacent impurity element Tb
4O
7And Dy
2O
3Can reach 10ppm.
Some Application Areass need ultra-pure (＞99.999%) gadolinium sesquioxide, require rare earth impurities≤0.5ppm, require 0.05-0.3ppm individually, must carry out deeply to common high-purity (＞99.99%) gadolinium sesquioxide and purify.In addition, existing gadolinium sesquioxide production technique also exists: the production cycle grow, yields poorly, rare earth impurity instability defectives such as (particularly the REE of variable valence directly influence the application product performance).Thereby seek new production technique and prepare ultra-pure gadolinium oxide, be very necessary to adapt to and to satisfy application demand.
Summary of the invention
The purpose of this invention is to provide a kind of ultra-pure gadolinium oxide, satisfy following technical indicator: by weight, REO＞99%, Gd
2O
3/ REO=99.999%-99.9999%, rare earth impurities all≤0.5ppm, Fe
2O
3＜1ppm, CaO＜4ppm, SiO
2＜10ppm, Al
2O
3＜30ppm, Cl
-＜50ppm, other all non-rare earth impurities are all less than 2ppm.
Another object of the present invention is low cost, the high yield preparation method of above-mentioned ultra-pure gadolinium oxide to be provided, with thick gadolinium enriched substance (Gd
2O
3Grade 10%-90%) is raw material, obtains elementary pure gadolinium (Gd through classical extracting and separating approach of two steps earlier
2O
3Grade 99.99%), removes residual rare earth impurities through methods such as electrochemical reduction and airtight extractions again, obtain at last＞99.999% ultra-pure gadolinium oxide product.Comprise the following steps:
One, thick gadolinium enriched substance is made into re chloride, regulates the pH value, remove mechanical inclusion through secondary filter, again through N
235Extraction agent removes Fe, supplies extraction for use as liquid stock;
Two, the preparation mixed extractant is and for use with its suitable saponification, the preparation hydrochloric acid soln as washing, back extraction wash acid and sour regurgitation is for use;
Three, the first step extraction with step 1 gained liquid stock, is used the mixed extractant of step 2 preparation; Carry out the RE/Gd extracting and separating,, separate through multi-stage solvent extraction with the water feeding manner; Remove the preceding component of gadolinium in the thick gadolinium enriched substance, use the hydrochloric acid soln washing of step 2 preparation, make gadolinium obtain enrichment;
Four, second step extraction with step 3 gained gadolinium enriched substance, is used the mixed extractant of step 2 preparation; Carry out the Gd/RE extracting and separating; With the organic phase feeding manner, separate through multi-stage solvent extraction, remove component behind the gadolinium; Use hydrochloric acid soln washing, the back extraction of step 2 preparation, obtain the Gadolinium trichloride liquid of elementary purity;
Five, with the Gadolinium trichloride feed liquid of the elementary purity of step 4 gained, certain flow input electrochemical reduction equipment utilizes electrochemical reaction, realizes micro-changeable valence rare earth RE in the feed liquid
3+To RE
2+Conversion process;
Six, with step 5 gained Gadolinium trichloride and substate rare earth mixed liquor, under protective atmosphere, get into the fully-closed type extracting groove, use the mixed extractant of step 2 preparation, carry out RE
2+/ Gd
3+Extracting and separating obtains＞99.0% Gadolinium trichloride solution and ultra-pure Gadolinium trichloride (＞99.999%) solution;
Seven, with the ultra-pure Gadolinium trichloride solution of step 6 gained, through N
235Extraction removing heavy metals impurity;
Eight, with the ultra-pure Gadolinium trichloride solution of step 7 gained, change into gadolinium oxalate with refining oxalic acid precipitation, gadolinium oxalate decomposes in the high temperature sintering stove, finally prepares the ultra-pure gadolinium oxide product.
The preferred 0.3-1.5mol/L of the said re chloride concentration of step 1, the preferred 1.5-2.5 of pH value.
The said mixed extractant of step 2 is preferably by volume ratio 30-35%P
507Extraction agent, 15-20%P
204Extraction agent and 45-55% sulfonated kerosene are formulated, and with alkali with its suitable saponification, saponification supported rare earth concentration is not less than 0.12mol/L.Preferred saponification deg is preferably 10%-20%, adopts organic phase interlock mode simultaneously, and it is about 30% that the chemical raw material usage quantity of washing back extraction reduces, and the generation of corresponding minimizing waste water and quantity discharged are about 30%, have both reduced cost, help environment protection again.
The preferred 2mol/L of step 3 used salt acid solutions; The step 4 washing is with the preferred 5mol/L of concentration of hydrochloric acid solution, and back extraction is with the preferred 4mol/L of concentration of hydrochloric acid solution.
The preferred argon gas of the said protection gas of step 6.
The preferred six grades of extraction tanks of the said extraction tank of step 7.
The whole process technical process of preparation ultra-pure gadolinium oxide is shown in accompanying drawing 4, and details are as follows:
To contain thick gadolinium enriched substance (Gd
2O
3Grade 10%-90%) is raw material, gadolinium come together into organic phase, realize that the separation of europium gadolinium makes gadolinium obtain enrichment simultaneously with the water feeding manner; And then, gadolinium is rotated back into water with the mode of organic phase charging, realize that the gadolinium terbium separates; Through progression, compare, the control of acidity, can obtain purity greater than 99.99% pure gadolinium; Be raw material with this material again, further separate with fully-closed type extracting through electrochemical reduction and remove trace rare-earth element impurity,, finally obtain the ultra-pure gadolinium oxide product of purity＞99.999% through aftertreatment.
In above-mentioned flow process, obtain purity and belong to classical extraction process greater than 99.99% pure gadolinium, below the pure gadolinium introduced with 99.99% in detail be raw material, through the technology of electrochemical reduction with the ultra-pure gadolinium oxide of fully-closed type extracting acquisition purity＞99.999%.
1, electrochemical reduction Processes and apparatus
(1) its principle is according to Eu
3+→ Eu
2+The character of appraising at the current rate, when the standard potential difference of two kinds of materials during, can use the method for electrochemical reduction to make one of them that electrochemical reaction take place greater than 0.35V.Electrochemical reducting reaction is to occur on the negative electrode, can carry out in circulation, the mobile electrolytic vessel continuously, for the basic demand of negative electrode be easy and simple to handle, be difficult for stopping up, wear-resisting, the life-span is long etc., the preferable alloy titanium is as cathode material.In order not make on the negative electrode reductive metals ion oxidized at anode; Preferably between the male-female tank room, it is separated with the carbonaceous barrier film; Stop the two poles of the earth indoor ion phase mutual interference, flow, the redox reaction that makes different substances is carried out in that different electrolysis are indoor respectively without interfering with each other.
Anode: 2Cl
--2e=Cl
2↑;
H
2O-2e＝1/2O
2↑+2H
+；
Negative electrode: Eu
3++ e=Eu
2+
(2) the electrochemical reduction system schematic is seen accompanying drawing 1;
The electrochemical reduction process schematic representation is seen accompanying drawing 2.
2, closed extraction process and equipment
(1) the gadolinium liquid behind the electrochemical reduction, changeable valence rare earth foreign matter contents such as the europium in the gadolinium seldom and basically all have been reduced to RE
2+, the separation factor between it is adjacent is very big, mainly prevents RE this moment
2+Oxidized once again, just can be with the bivalent rare earth delamination in the gadolinium liquid.Therefore this extraction and stripping apparatus must charge into protection gas and totally-enclosed, the preferred argon gas of protection gas.With greater than 99.99% elementary pure gadolinium feed liquid (water) charging, adopt electrochemical reduction fully-closed type extracting further to separate trace rare-earth element impurity, finally obtain ultra-pure gadolinium material of purity＞99.999%.
(2) electrochemical reduction and fully-closed type extracting separation process synoptic diagram are seen accompanying drawing 3.
Advantage of the present invention:
1. the present invention is to adopt electrochemical reduction technology and device for the method for rare earth impurities such as deeply purifying and removing europium; The production technique of more existing metallic reducing, it has clean environment firendly and treatment capacity is big, reduction effect is good, can remove effectively minimal residue europium and rare earth impurities, do not introduce other impurity metal ions;
2. behind the electrochemical reduction of the present invention, the last extracting and separating that adopts is fully closed, and the substate rare earth that it can be stopped after reduction is oxidized once again, the europium isoreactivity rare earth impurities degree of depth is purified to below the 0.5ppm, and makes other rare earth impurities obtain purifying simultaneously;
3. mixed extractant (the P that the present invention adopted
507And P
204), under the situation that does not influence separating effect, suitably control saponification deg (10%-20%), its extracting and separating effect is not less than single P
507Extraction agent adopts organic phase interlock mode simultaneously, to the chemical raw material usage quantity reduction by 30% of washing back extraction, the generation of corresponding minimizing waste water and quantity discharged 30%.
4. the prepared ultra-pure gadolinium oxide product (Gd of the present invention
2O
3Grade 99.999-99.9999%), reached leading domestic level, its more present high-purity gadolinium oxide has the extremely low advantage of rare earth impurity, has reached the requirement of special purpose.
Description of drawings
Fig. 1 is the electrolytic reduction system schematic.
Fig. 2 is the electrochemical reduction process schematic representation.
Fig. 3 is electrochemical reduction and fully-closed type extracting separation process synoptic diagram.
Fig. 4 is a preparation ultra-pure gadolinium oxide whole process process flow sheet.
Embodiment
Embodiment 1
(1) reagent parameter
(1) raw material is formed:
(2) feed concentration 0.3mol/L acidity PH=1.5
(3) extraction agent volume ratio 30%P
507Extraction agent, 15%P
204Extraction agent and 55% sulfonated kerosene
(4) caustic soda 8mol/L
(5) hydrochloric acid 2mol/L, 5mol/L, 4mol/L
(6) wash water deionized water
(2) RE/Gd extracting and separating:
Input:
Stream compares V
Organic phase: V
Feed liquid: V
Wash acid=1: 0.2: 0.05
The multistage composition of progression extraction section+washing section
Output:
Extracting and separating obtains the rich gadolinium material (organic phase) of low samarium
(3) Gd/RE extracting and separating:
With the low rich gadolinium material of samarium of RE/Gd extracting and separating gained (organic phase) is raw material, adopts the further extracting and separating of organic feeding manner.
Input:
Stream compares V
Organic phase: V
Organic feed liquid: V
Wash acid=1: 1: 0.3
The multistage composition of progression extraction section+washing section
Output:
Extracting and separating obtains greater than 99.99% elementary pure gadolinium feed liquid (water)
(4) electrochemical reduction main raw and parameter:
1. material
Anode: Pt/Ti silk;
Negative electrode: Ti rod;
Barrier film: carbonaceous barrier film;
Electro-chemical equipment: external diameter 200mm, internal diameter 100mm, height 1000mm
2. electrochemical parameter
Feed liquid: be the elementary pure gadolinium liquid after two step extracting and separating,
PH=2
Flow: 1.5-2.5L/min
Voltage: 2-5V
Electric current: 15-20A
Ionogen: 1-2mol/L NaCl
(5) fully closed abstraction purification
Protection gas: Ar gas
Cell body material: PVC material
Mixing section volume: 50L
Limit ratio: clarification: mix=3: 1
Input: stream compares V
Organic phase electroreduction solution: V
Wash acid: V
Sour regurgitation=1: 1: 0.3
The multistage composition of progression extraction section+washing section
Four, result
Ultra-pure gadolinium material is through refining oxalic acid precipitation, and conventional calcination is decomposed, and final ultra-pure gadolinium oxide product quality indicator is following:
TREO＞99%, LOI＜1.0%, Gd
2O
3/ REO=99.999%-99.9999%, each element of its REE impurities all below 0.5ppm, the minimum 0.03ppm that reaches; Non-rare earth impurity Fe
2O
3＜1ppm, CaO＜4ppm, SiO
2＜10ppm,, Al
2O
3＜10ppm, Cl
-＜50ppm, other non-rare earth impurities see table one for details all less than 2ppm.
Embodiment 2
(1) reagent parameter
(1) raw material is formed:
(2) feed concentration 1.5mol/L acidity PH=2.5
(3) extraction agent volume ratio 35%P
507Extraction agent, 20%P
204Extraction agent and 45% sulfonated kerosene
(4) caustic soda 8mol/L
(5) hydrochloric acid 2mol/L, 5mol/L, 4mol/L
(6) wash water deionized water
(2) RE/Gd extracting and separating:
Input:
Stream compares V
Organic phase: V
Feed liquid: V
Wash acid=1: 0.2: 0.05
The multistage composition of progression extraction section+washing section
Output:
Extracting and separating obtains the rich gadolinium material (organic phase) of low samarium
(3) Gd/RE extracting and separating:
With the low rich gadolinium material of samarium of RE/Gd extracting and separating gained (organic phase) is raw material, adopts the further extracting and separating of organic feeding manner.
Input:
Stream compares V
Organic phase: V
Organic feed liquid: V
Wash acid=1: 1: 0.3
The multistage composition of progression extraction section+washing section
Output:
Extracting and separating obtains greater than 99.99% elementary pure gadolinium feed liquid (water)
(4) electrochemical reduction main raw and parameter:
3. material
Anode: Pt/Ti silk;
Negative electrode: Ti rod;
Barrier film: carbonaceous barrier film;
Electro-chemical equipment: external diameter 69mm, internal diameter 59mm, height 320mm
4. electrochemical parameter
Feed liquid: be the elementary pure gadolinium liquid after two step extracting and separating,
PH=3
Flow: 100-200ml/min
Voltage: 2-5V
Electric current: 15-20A
Ionogen: 1-2mol/L NaCl
(5) fully closed abstraction purification
Protection gas: Ar gas
Cell body material: PVC material
Mixing section volume: 50L
Limit ratio: clarification: mix=3: 1
Input: stream compares V
Organic phase electroreduction solution: V
Wash acid: V
Sour regurgitation=1: 1: 0.3
The multistage composition of progression extraction section+washing section
Four, result
Ultra-pure gadolinium material is through refining oxalic acid precipitation, and conventional calcination is decomposed, and final ultra-pure gadolinium oxide product quality indicator is following:
TREO＞99%, LOI＜1.0%, Gd
2O
3/ REO=99.999%-99.9999%, each element of its REE impurities all below 0.5ppm, the minimum 0.03ppm that reaches; Non-rare earth impurity Fe
2O
3＜1ppm, CaO＜4ppm, SiO
2＜10ppm,, Al
2O
3＜10ppm, Cl
-＜50ppm, other non-rare earth impurities see table one for details all less than 2ppm.
Table one: ultra-pure gadolinium oxide product analysis report
Claims (9)
1. a ultra-pure gadolinium oxide is characterized in that, by weight, and REO＞99%, Gd
2O
3/ REO=99.999%-99.9999%; Rare earth impurities is all below 0.5ppm; Fe
2O
3＜1ppm, CaO＜4ppm, SiO
2＜10ppm, Al
2O
3＜30ppm, Cl
-＜50ppm, other all non-rare earth impurities are all less than 2ppm.
2. one kind prepares the method for ultra-pure gadolinium oxide according to claim 1, it is characterized in that, comprises the following steps:
One, thick gadolinium enriched substance is made into re chloride, regulates the pH value, remove mechanical inclusion through secondary filter, again through N
235Extraction agent removes Fe, supplies extraction for use as liquid stock;
Two, by volume ratio 30-35%P
507Extraction agent, 15-20%P
204Extraction agent and 45-55% sulfonated kerosene preparation mixed extractant, and with alkali that its suitable saponification is for use; The preparation hydrochloric acid soln is for use as extracting and washing acid and back extraction acid;
Three, the first step extraction with step 1 gained liquid stock, is used the mixed extractant of step 2 preparation; Carry out the RE/Gd extracting and separating,, separate through multi-stage solvent extraction with the water feeding manner; Remove the preceding component of gadolinium in the thick gadolinium enriched substance, use the hydrochloric acid soln washing of step 2 preparation, make gadolinium obtain enrichment;
Four, second step extraction with step 3 gained gadolinium enriched substance, is used the mixed extractant of step 2 preparation; Carry out the Gd/RE extracting and separating,, separate through multi-stage solvent extraction with the organic phase feeding manner; Remove component behind the gadolinium, use the hydrochloric acid soln washing of step 2 preparation, obtain the Gadolinium trichloride liquid of elementary purity;
Five, with the Gadolinium trichloride feed liquid of the elementary purity of step 4 gained, certain flow input electrochemical reduction equipment utilizes electrochemical reaction, realizes micro-changeable valence rare earth RE in the feed liquid
3+To RE
2+Conversion process;
Six, with step 5 gained Gadolinium trichloride and substate rare earth mixed liquor, under protective atmosphere, get into the fully-closed type extracting groove, use the mixed extractant of step 2 preparation, carry out RE
2+/ Gd
3+Extracting and separating is used hydrochloric acid soln washing, the back extraction of step 2 preparation, obtains＞99.0% Gadolinium trichloride solution and ultra-pure Gadolinium trichloride solution of＞99.999%;
Seven, with the ultra-pure Gadolinium trichloride solution of step 6 gained, through N
235Extraction removing heavy metals impurity;
Eight, with the ultra-pure Gadolinium trichloride solution of step 7 gained, change into gadolinium oxalate with refining oxalic acid precipitation, gadolinium oxalate decomposes in the high temperature sintering stove, finally prepares the ultra-pure gadolinium oxide product.
3. method as claimed in claim 2 is characterized in that, the said re chloride concentration of step 1 is 0.3-1.5mol/L, and the pH value is 1.5-2.5.
4. method as claimed in claim 2 is characterized in that, the said mixed extractant of step 2, and with its suitable saponification, saponification supported rare earth concentration is not less than 0.12mol/L with alkali.
5. method as claimed in claim 4 is characterized in that, uses alkali control saponification deg to be 10%-20%, adopts organic phase interlock mode simultaneously.
6. method as claimed in claim 2 is characterized in that, step 3 used salt acid solutions is 2mol/L; Step 4 used salt acid solutions is 2mol/L, and step 6 used salt acid solutions is 4mol/L.
7. method as claimed in claim 2 is characterized in that, the cathode material of the said electrochemical reduction equipment of step 5 is a titanium.
8. method as claimed in claim 2 is characterized in that, is separated by the carbonaceous barrier film between the said electrochemical reduction equipment of the step 5 negative and positive tank room.
9. method as claimed in claim 2 is characterized in that, protection gas is argon gas in the step 6, feed liquid RE
3+Concentration 50-120g/L, pH value 2-3, voltage 2-5V, electric current 15-20A, ionogen are the NaCl of 1-2mol/L.
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| CN102676853B (en) * | 2012-05-28 | 2013-11-20 | 五矿（北京）稀土研究院有限公司 | Rare earth separation method with material linkage cyclic utilization function |
| CN103482670B (en) * | 2013-09-10 | 2014-09-24 | 中铝稀土（常熟）有限公司 | Method for preparing high-purity dysprosium oxide |
| CN104152965B (en) * | 2014-08-12 | 2016-08-17 | 浙江大学 | A kind of preparation method of divalent europium doping calcium fluoride blue light luminescent film |
| CN104726710B (en) * | 2015-01-26 | 2017-07-18 | 江西理工大学 | A kind of method of separation of rare earth elements |
| CN105861859B (en) * | 2016-05-17 | 2017-12-19 | 南昌航空大学 | A kind of method that technical grade holmium raw material prepares 5N holmiums |
| CN105861858B (en) * | 2016-05-17 | 2017-11-10 | 南昌航空大学 | A kind of extraction separation method prepares the technological process of 5N dysprosiums |
| CN117446851B (en) * | 2023-12-26 | 2024-03-19 | 全南县新资源稀土有限责任公司 | High-purity low-aluminum gadolinium oxide and preparation method thereof |
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