CN102373490A - Method for separating Gd and Eu through fused salt electrolysis - Google Patents
Method for separating Gd and Eu through fused salt electrolysis Download PDFInfo
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- CN102373490A CN102373490A CN2011103365850A CN201110336585A CN102373490A CN 102373490 A CN102373490 A CN 102373490A CN 2011103365850 A CN2011103365850 A CN 2011103365850A CN 201110336585 A CN201110336585 A CN 201110336585A CN 102373490 A CN102373490 A CN 102373490A
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- gadolinium
- sesquioxide
- fused salt
- electrolysis
- europium
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Abstract
The invention provides a method for separating Gd and Eu through fused salt electrolysis, which comprises the following steps of: using inert metal molybdenum as a cathode in an electrolytic furnace, placing the cathode at the bottom of an electrolytic tank, using graphite as an anode, adding10-16% of MgCl2, 42-45% of LiCl and 42-45% of KCl in percentage by weight, adding a mixture of gadolinium oxide and europium oxide accounting for 13-20% of MgCl2 by weight, controlling the temperature at 690-780 DEG C, introducing a direct current to electrolyze after materials in a crucible are fused, controlling the current density of the cathode at 9-12 A/cm2 and the current density of the anode at 0.4-0.5 A/cm2, controlling the voltage of the tank at 6.6-7.7 V, and depositing magnesium alloy near the cathode of the electrolytic tank after 3-5 h of electrolysis. Gadolinium is mainly transferred to magnesium alloy, and europium is mainly remained in fused salt. In the invention, the processing equipment becomes more miniaturized. The alloy material can also be directly recovered after separation through electrolysis.
Description
Technical field
What the present invention relates to is the isolating method of a kind of dry method, specifically separates the method for Gd, Eu through fused salt electrolysis, belongs to the pyrometallurgy technical field.
Background technology
REE is widespread in nature, and rare-earth mineral has kind more than 250, and wherein kind has commercial value more than 50.Because REE character is quite similar, one of the most difficult problem of inorganic chemistry that is separated between the REE.The isolating basic skills of REE has fractionation crystallization and precipitation classification, ion exchange method and solvent extration, the transmission of pyrogenic process chemical gas phase etc.
Fused salt electrolysis process because can work continuously, equipment is simple, economical convenient, not limited by reductive agent, be widely used for producing macro-mixing rare earth metal and part single rare earth metal and rare earth alloy.Fused salt electrolysis process can be divided into electrolysis of fused chloride salt and fluorochemical-oxide and salt melt electrolyzing again.Two kinds of methods respectively have relative merits:
(1) to have fused salt corrosion property less for the electrolysis of fused chloride salt method, easy master, and the structured material of large scale electrolytic cell solves easily, therefore is the basic skills that modern rare earth electrolytic industry is produced rare earth metal.But the preparation cost of rare earth chloride is high, dehydration difficulty and reactive behavior are high, the accumulating difficulty.
(2) fluorochemical-oxide electrolysis method has the advantage of the good accumulating of oxide compound, but with respect to the molten chloride system, the fusing point of fluorochemical-oxide compound fused salt is higher, and electrolysis temperature is high, and fused salt corrosion property is strong.
The maximum characteristics of two kinds of electrolysis process are: can handle dystectic rare earth metal, and as long as constantly replenish rare earth oxide, electrolysis just can be carried out continuously.
In the prior art relevant for the report of Rare Earth Separation; Adopting solvent extration mostly secondly is the gentle phase transmission method of ion exchange method etc.; For example; For example number of patent application is 89100200.6; Name is called and discloses the method that a kind of usefulness is dissolved the continuous separation of rare earth elements of Ji extraction in the patent document of " separation method of REE ", through five operations therefrom, in the less REE material solution of heavy rare-earth element content continuously and isolate highly purified light rare earths, middle-weight rare earths element, heavy rare earth element and yttrium.Number of patent application is 95117489.4 for another example, name be called disclose in the patent document of " technology of preparing high purity neodymia with ion exchange method " a kind of to contain NdCl
31-10%, pH are that the solution of 2-5 is feed liquid with the ammonium acetate solution (II) of the ammonium acetate solution (I) of 0.3-0.8 mol and 0.9-1.2 mol as leacheate, carry out drip washing successively, and the pH of ammonium acetate solution (I), (II) is 5.8-6.5.Collect product solution, precipitate, burn into neodymium sesquioxide with oxalic acid.Number of patent application is 200910012454.X for another example, and name is called " a kind of method of utilizing ammonium chloride-potassium chloride gas phase transmission rare-earth separating oxide compound from rare-earth mineral " and opens up a new way again for the separation of rare earth.The method that the character rare-earth separating that appraises at the current rate that utilizes rare earth is also arranged in addition; For example the patent No. is 96205784.3; Name is called scheme of record in " electrolytic extraction rare-earth separating device ", is to use high efficiency separation is carried out in electrolysis, electrophoresis, electrodialysis, abstraction technique to rare earth a kind of method.
Summary of the invention
The object of the present invention is to provide a kind of good separating effect, can make the processing unit miniaturized, and after separating can also directly reclaim the fused salt electrolysis separation Gd of alloy material, the method for Eu.
The objective of the invention is to realize like this:
In electrolytic furnace, be negative electrode and place the electrolyzer lower curtate that graphite is anode with the inert metal molybdenum, the ratio that is respectively 10-16%, 42-45%, 42-45% according to mass percent adds MgCl
2, LiCl, KCl, press MgCl again
2The 13-20% of quality adds the mixture of gadolinium sesquioxide and europium sesquioxide, and controlled temperature is treated in the crucible after the material fusion electrolysis of feeding direct current, control cathode current density 9-12A/cm under 690-780 ℃ condition
2, anodic current density is 0.4-0.5A/cm
2, bath voltage 6.6-7.7V was through 3-5 hour electrolysis; Near negative electrode, deposit magnesiumalloy at electrolyzer, gadolinium is mainly transferred in the magnesiumalloy, and the content of gadolinium in magnesiumalloy is more, account for 6.9～10.7%; Europium is mainly stayed in the fused salt, and the content of europium in magnesiumalloy is very little, account for 4.4 * 10
-3～1.0 * 10
-2%, the recovery of gadolinium is 74.5-89.7%, and the partition ratio of gadolinium sesquioxide in alloy and fused salt is 2.55-4.01, and the partition ratio of europium sesquioxide in alloy and fused salt is 1.7 * 10
-3-3.2 * 10
-2, the separation factor of gadolinium sesquioxide and europium sesquioxide is 112-2330.
Said LiCl and KCl are earlier respectively 300 ℃, 600 ℃ drying treatment 24 hours.
The mixture of said gadolinium sesquioxide and europium sesquioxide is the quality mixture of gadolinium sesquioxide and europium sesquioxide.
The present invention is to provide mixture directly electrolysis in fused salt, in resultant alloy, carry out the ICP test analysis through the element in the alloy that goes out for electrolysis with gadolinium sesquioxide and europium sesquioxide; According to people such as M.Kurata its article " Distribution behavior of uranium, neptunium, rare-earth elements (Y; La, Ce, Nd; Sm; Eu, Gd) and alkaline-earth metals (Sr, Ba) between molten LiCl-KCI eutectic salt and liquid cadmium or bismuth " in formula:
β＝D
Gd/D
Eu (3)
(wherein: D
GdAnd D
EuBe respectively Gd
2O
3And Eu
2O
3Partition ratio;
With
Be respectively Gd and the Eu molar content in alloy and fused salt; β is a separation factor.) calculate Gd respectively
2O
3And Eu
2O
3Partition ratio D in alloy and fused salt
Gd, D
EuWith separation factor β.
It is the isolating method of a kind of dry method that fused salt electrolysis of the present invention separates, and separates with respect to water law, and the volume of the isolating operation material of dry method is less, can make more miniaturized of processing unit like this.And can also directly reclaim alloy material after the electrolytic separation.
Gadolinium sesquioxide provided by the present invention and europium sesquioxide separation method, the recovery of gadolinium are 74.5-89.7%, and the partition ratio of gadolinium sesquioxide in alloy and fused salt is 2.55-4.01, and the partition ratio of europium sesquioxide in alloy and fused salt is 1.7 * 10
-3-3.2 * 10
-2, the separation factor of gadolinium sesquioxide and europium sesquioxide is 112-2330.Gadolinium, europium in the oxide compound of one step of fused salt electrolysis direct separation rare earth, and prepared master alloy; Method through adding raw material continuously can realize the serialization electrolytic separation.
Description of drawings
Fig. 1 is the SEM face scanned photograph of embodiment 3 gained alloys;
Fig. 2 is the distribution plan of the Mg element analyzed of the EDS power spectrum of embodiment 3 gained alloys;
Fig. 3 is the distribution plan of the Gd element analyzed of the EDS power spectrum of embodiment 3 gained alloys;
Fig. 4 is the distribution plan of the Eu element analyzed of the EDS power spectrum of embodiment 3 gained alloys.
Embodiment
For example the present invention is done in more detail below and describes:
Basic technical scheme of the present invention is: with MgCl
2+ LiCl+KCl is an electrolyte system, MgCl
2, LiCl, each composition of KCl mass percent be respectively 10-16%, 42-45%, 42-45%, press MgCl again
2The 13-20% of quality adds mixed rare earth oxide (quality of gadolinium sesquioxide and europium sesquioxide equates), and controlled temperature is treated in the crucible after the material fusion electrolysis of feeding direct current, control cathode current density 9-12A/cm under 690-780 ℃ condition
2, anodic current density is 0.4-0.5A/cm
2, bath voltage 6.6-7.7V, the electrolysis through 3-5 hour deposits magnesium-rare earth alloy at electrolyzer near negative electrode.The recovery of gadolinium is 74.5～89.7%.The partition ratio of gadolinium sesquioxide in alloy and fused salt is 2.55～4.01, and the partition ratio of europium sesquioxide in alloy and fused salt is 1.7 * 10
-3～3.2 * 10
-2, the separation factor of gadolinium sesquioxide and europium sesquioxide is 1112～2330.Gadolinium is mainly transferred in the alloy, and the content of gadolinium in alloy is more 6.9～10.7%, however the content of europium in alloy very little 4.4 * 10
-3～1.0 * 10
-2%, europium mainly also stay in fused salt, explain that the effect of separating experiment is quite desirable, reach gadolinium, europium separation purpose.
Embodiment 1: with MgCl
2+ LiCl+KCl is an electrolyte system, and the mass percent of each composition is respectively 16%, 42% and 42%, presses MgCl again
213% of quality adds europium sesquioxide and gadolinium sesquioxide mixed rare earth oxide, is negative electrode with inert metal molybdenum (Mo), and graphite is anode, and under 690 ℃ of the electrolysis temperatures, cathode current density is 9A/cm
2, anodic current density is 0.4A/cm
2, bath voltage 6.6～7.1V through 3 hours electrolysis, deposits the Mg alloy at electrolyzer near negative electrode, and the content of the Mg in the alloy, Li and Gd is respectively 84.9%, 10.6% and 8.5%.The content of gadolinium in alloy is more 8.5%, however the content of europium in alloy very little 7.6 * 10
-3%, the recovery of gadolinium is 78.6%.The partition ratio of gadolinium sesquioxide in alloy and fused salt is 3.53, and the partition ratio of europium sesquioxide in alloy and fused salt is 3.2 * 10
-2, the separation factor of gadolinium sesquioxide and europium sesquioxide is 112.
Embodiment 2: with MgCl
2+ LiCl+KCl is an electrolyte system, and the mass percent of each composition is respectively 16%, 42% and 42%, presses MgCl again
213% of quality adds europium sesquioxide and gadolinium sesquioxide mixed rare earth oxide, is negative electrode with inert metal molybdenum (Mo), and graphite is anode, and under 720 ℃ of the electrolysis temperatures, cathode current density is 9A/cm
2, anodic current density is 0.4A/cm
2, bath voltage 6.5～6.9V through 4 hours electrolysis, deposits the Mg alloy at electrolyzer near negative electrode, and the content of the Mg in the alloy, Li and Gd is respectively 77.2%, 15.9% and 6.9%.The content of gadolinium in alloy is more 6.9%, however the content of europium in alloy very little 1.0 * 10
-2%, the recovery of gadolinium is 74.5%.The partition ratio of gadolinium sesquioxide in alloy and fused salt is 2.55, and the partition ratio of europium sesquioxide in alloy and fused salt is 4.1 * 10
-3, the separation factor of gadolinium sesquioxide and europium sesquioxide is 626.
Embodiment 3: with MgCl
2+ LiCl+KCl is an electrolyte system, and the mass percent of each composition is respectively 10%, 45% and 45%, presses MgCl again
220% of quality adds europium sesquioxide and gadolinium sesquioxide mixed rare earth oxide, is negative electrode with inert metal molybdenum (Mo), and graphite is anode, and under 750 ℃ of the electrolysis temperatures, cathode current density is 12A/cm
2, anodic current density is 0.5A/cm
2, bath voltage 7.2～7.7V through 5 hours electrolysis, deposits the Mg alloy at electrolyzer near negative electrode, and the content of the Mg in the alloy, Li and Gd is respectively 71.1%, 18.2% and 10.7%.The content of gadolinium in alloy is more 10.7%, however the content of europium in alloy very little 4.4 * 10
-3%, the recovery of gadolinium is 89.7%.The partition ratio of gadolinium sesquioxide in alloy and fused salt is 4.01, and the partition ratio of europium sesquioxide in alloy and fused salt is 1.7 * 10
-3, the separation factor of gadolinium sesquioxide and europium sesquioxide is 2330.
Embodiment 4: with MgCl
2+ LiCl+KCl is an electrolyte system, and the mass percent of each composition is respectively 10%, 45% and 45%, presses MgCl again
220% of quality adds europium sesquioxide and gadolinium sesquioxide mixed rare earth oxide, is negative electrode with inert metal molybdenum (Mo), and graphite is anode, and under 780 ℃ of the electrolysis temperatures, cathode current density is 12A/cm
2, anodic current density is 0.5A/cm
2, bath voltage 6.8～7.2V through 4 hours electrolysis, deposits the Mg alloy at electrolyzer near negative electrode, and the content of the Mg in the alloy, Li and Gd is respectively 77.5%, 12.8% and 9.7%.The content of gadolinium in alloy is more 9.7%, however the content of europium in alloy very little 7.2 * 10
-3%, the recovery of gadolinium is 85.3%.The partition ratio of gadolinium sesquioxide in alloy and fused salt is 4.00, and the partition ratio of europium sesquioxide in alloy and fused salt is 2.7 * 10
-3, the separation factor of gadolinium sesquioxide and europium sesquioxide is 1509.
Figure of description is the SEM face scanned photograph of embodiment 3 gained alloys and the distribution plan of Mg, Gd and Eu element that the EDS power spectrum is analyzed.The content of gadolinium (10.7%) is far longer than the content (4.4 * 10 of europium in the description of drawings alloy
-3%), the content of europium is very little, and promptly the mixed rare earth oxide of gadolinium sesquioxide and europium sesquioxide can separate through fused salt electrolysis.
Claims (3)
1. the method that fused salt electrolysis separates Gd, Eu is characterized in that: in electrolytic furnace, be negative electrode and place the electrolyzer lower curtate that graphite is anode with the inert metal molybdenum, be respectively the ratio adding MgCl of 10-16%, 42-45%, 42-45% according to mass percent
2, LiCl, KCl, press MgCl again
2The 13-20% of quality adds the mixture of gadolinium sesquioxide and europium sesquioxide, and controlled temperature is treated in the crucible after the material fusion electrolysis of feeding direct current, control cathode current density 9-12A/cm under 690-780 ℃ condition
2, anodic current density is 0.4-0.5A/cm
2, bath voltage 6.6-7.7V, the electrolysis through 3-5 hour deposits magnesiumalloy at electrolyzer near negative electrode, and gadolinium is mainly transferred in the magnesiumalloy, and europium is mainly stayed in the fused salt.
2. a kind of fused salt electrolysis according to claim 1 separates the method for Gd, Eu, it is characterized in that: said LiCl and KCl are first respectively 300 ℃, 600 ℃ drying treatment 24 hours.
3. a kind of fused salt electrolysis according to claim 1 and 2 separates the method for Gd, Eu, and it is characterized in that: the mixture of said gadolinium sesquioxide and europium sesquioxide is the quality mixture of gadolinium sesquioxide and europium sesquioxide.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108277507A (en) * | 2018-02-06 | 2018-07-13 | 北京科技大学 | A kind of method of vanadium and chromium in electrolytic separation containing vanadium and chromium fused salt |
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| JPS60228692A (en) * | 1984-04-24 | 1985-11-13 | Namiki Precision Jewel Co Ltd | Manufacture of r-t alloy |
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|---|
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|---|---|---|---|---|
| CN108277507A (en) * | 2018-02-06 | 2018-07-13 | 北京科技大学 | A kind of method of vanadium and chromium in electrolytic separation containing vanadium and chromium fused salt |
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Application publication date: 20120314 |