CN105803484B - The preparation method of rare earth metal - Google Patents
The preparation method of rare earth metal Download PDFInfo
- Publication number
- CN105803484B CN105803484B CN201410854711.5A CN201410854711A CN105803484B CN 105803484 B CN105803484 B CN 105803484B CN 201410854711 A CN201410854711 A CN 201410854711A CN 105803484 B CN105803484 B CN 105803484B
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- preparation
- ionic liquid
- rare earth
- rare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention provides a kind of preparation methods of rare earth metal.The preparation method is the following steps are included: be mixed to form electrolyte for rare-earth salts, ionic liquid and hydroxyl ether solvent, and electrolyte is placed in electrolytic cell；Electrolyte is electrolysed to form rare earth metal；Wherein, the structural formula of hydroxyl ether solvent are as follows:Wherein, R1 is any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group and tert-butyl；R2 is any one of methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group and tert-butyl；N=1-10.This method is using hydroxyl ether solvent as additive, using hydroxyl hydrotropy rare-earth salts therein, while only one of which hydroxyl, discharge quantity is greatly reduced, makes electric current be unlikely to decline rapidly, and be greatly reduced the porosity in product.And this method alleviates dissolution difficulty, complex steps problem not using solid matter as additive.
Description
Technical field
The present invention relates to rare-earth technique fields, in particular to a kind of preparation method of rare earth metal.
Background technique
The traditional preparation methods of rare earth metal mainly have vacuum-thermal method and fused salt electrolysis process, and these preparation methods exist
Energy consumption is high, seriously polluted, corrosivity is strong and equipment and relevant configuration require high characteristic, to limit it to prepare rare earth golden
The application in category field.
Ionic liquid is used as extensively due to the excellent property such as low with fusing point, difficult volatilization and electrochemical properties stabilization
Electrolyte in electrochemical process.It has been carried out extensively currently, being directed to both at home and abroad by the method for ionic liquid deposition of rare-earth metal
General research.Domestic aspect, for example, application No. is the Chinese patents of ZL201110435737.2 to disclose one kind in ionic liquid
The method of electrodepositing metal lanthanum, this method pass through in two (trimethyl fluoride sulfonyl) imines of ionic liquid 1- methyl -3- ethyl imidazol(e)
Middle deposition has obtained lanthanoid metal, but such ionic liquid is expensive, while the deposition process must be in the gloves of argon atmosphere
It is carried out in case.
For another example Zhai Yuchun team, Northeastern University in 2012 sends the documents for the first time reports La on Pt electrode at room temperature3+And Dy3+
In 1- ethyl -3- methyl-imidazoles tetrafluoroborate ([EMIM] BF4) electrochemical behavior (Jin Ping Xun, Xie Hong in ionic liquid
It is big, dysprosium electro-deposition behavior [J] rare metal material in the .1- ethyl -3- methyl-imidazoles tetrafluoroborate ion liquid such as Zhai Yuchun
Material and engineering .2012,41 (5): 881-884；The .La such as Jin Ping Xun, Xie Hongwei, Zhai Yuchun3+Ion is in EMIMBF4In ionic liquid
Electrochemical behavior research [J] Rare Metals Materials and engineering .2012,41 (4): 599-602), and on this electrode successfully
The sedimentary of lanthanum and dysprosium is arrived.But in this deposition process, lithium chloride solid need to be added as supporting electrolyte, and the solid exists
It needs to be dried in adition process, simultaneously because what is be added is solid, easily causes the dissolution of raw material and additive difficult.
For another example the Liu Ruiquan of Xinjiang University teaches et al. and to have studied Ce (III) in [BMIM] PF6-EG-CeCl3In electricity
Chemical behavior (Yushan Jiang Hasi wood [BMIM] PF6Electro-deposition behavioral study [D] crow of chromium, cerium, cobalt and ruthenium in ionic liquid
Lu Muqi: Xinjiang University, 2013；Yushan Jiang Hasi is wooden, Liu Ruiquan, and the electro-deposition behavior of cerium, dilute in silver pink space ionic liquid
Have metal, 2014,38 (3): 432-440), and the deposition of cerium is realized on copper surface.In the research of author, [BMIM] PF6-
EG-CeCl3Electrolyte is prepared in glove box, and electrodeposition process also will be in an easy groove body for being similar to glove box
Middle realization, while after adding ethylene glycol, it can largely deflate in electrodeposition process, will cause electric current and sharply decline, in sedimentation products
Have a large amount of stomatas.
External aspect has studied rare earth metal electro-deposition since the nineties in last century, in ionic liquid and uses AlCl mostly3Type
Ionic liquid (Tsuda T., Nohira T., Ito Y..Electrodeposition of Lanthanum in
Lanthanum Chloride Saturated A1C13-1-ethyl-3-methylimidazolium Chloride
Molten Salts [J] .Electrochimica Acta, 2001,46 (12): 1891-1897), due to AlCl3Type ionic liquid
Body is extremely sensitive to the moisture in air, and there is a continuing need for vacuum or noble gas to protect for electrodeposition process, and this substance is to many
Substance all has corrosivity, therefore uses simultaneously inconvenience, while being also unfavorable for large-scale production.
For another example Univ Manchester UK Bhatt etc. reports a series of [R4X][N(SO2CF3)2] (X=N, P, As)
Ionic liquid is used for the higher metal of electro-deposition electro-chemical activity, and such as Li, Eu etc., they are investigated rare earth ion La3+、Sm3+
And Eu3+In [R4X][N(SO2CF3)2] electrochemical behavior (Bhatt A.I., May I., Volkovich in ionic liquid
V.A.,et al.Structural Characterization of a Lanthanum Bistriflimide Complex,
La(N(SO2CF3)2)3(H2O)3,and an Investigation of La,Sm,and Eu Electrochemistry in
a Room-Temperature Ionic Liquid,[Me3NnBu][N(SO2CF3)2][J].Inorganic Chemistry,
2005,44(14):4934-4940).To La3+、Sm3+And Eu3+Electrochemical behavior research process in, observed rare earth
Ion reduction is the peak of metal.But such ionic liquid is expensive, and deposition process is also complete in the glove box of argon gas protection
At.
For another example the H.Kondo etc. of Japanese Yokohama national university in 2012 has studied in the double fluoroforms of 3- ethyl-pentyl phosphine
Base sulfonyl amidic-salt is Nd in [P2225] [TFSA] ionic liquid3+Electrochemical behavior (Kondo H., Matsumiya M.,
Tsunashima K.,et al.Attempts to the electrodeposition of Nd from ionic
Liquids at elevated temperatures [J], Electrochimica Acta, 2012, (66): 313-319), and
The neodymium metal that partial size is 0.5~3 μm is obtained on copper electrode, content is about 48%, remaining ingredient is neodymia.But such from
Sub- liquid is expensive, and deposition process will carry out at 150 DEG C.
In conclusion the existing method for preparing rare earth metal using ionic liquid has, at high cost, energy consumption is high, due to using
Solid additives are cumbersome, while the disadvantages of to operate in glove box, to limit its industrial application.
Summary of the invention
The main purpose of the present invention is to provide a kind of preparation methods of rare earth metal, to improve the industry of the preparation method
Change application.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of preparation method of rare earth metal, is somebody's turn to do
Preparation method is the following steps are included: be mixed to form electrolyte for rare-earth salts, ionic liquid and hydroxyl ether solvent, and by electrolyte
It is placed in electrolytic cell；Electrolyte is electrolysed to form rare earth metal；Wherein, the structural formula of hydroxyl ether solvent are as follows:
Wherein, R1For any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group and tert-butyl；R2
For any one of methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group and tert-butyl；N=1-10.
Further, hydroxyl ether solvent is 2- hydroxypropyl methyl ether.
Further, in electrolyte, the volume ratio of ionic liquid and hydroxyl ether solvent is 0.1~20:1.
Further, in electrolyte, the volume ratio of ionic liquid and hydroxyl ether solvent is 1~4:1.
Further, the content of rare-earth salts in the electrolytic solution is 5~85g/L.
Further, the anion of ionic liquid is BF4 -Or PF6 -, the cation of ionic liquid is alkyl imidazole or alkyl
Pyridine.
Further, rare-earth salts is that rare earth chloride, sulfuric acid rare earth and nitric acid rare earth are any one or more of.
Further, it is electrolysed using constant current electro-deposition mode, and current density is 10~150A/ in electrolysis step
m2, electrodeposition time is 5~120min.
Further, before the step of electrolysis, the preparation method further include: preelectrolysis is carried out to remove electrolysis to electrolyte
Water in liquid.
Further, preelectrolysis is carried out using constant current electro-deposition mode, and in preelectrolysis step current density be 10~
50A/m2, the time of preelectrolysis is 5~30min.
Further, before the step of electrolysis, preparation method further include: inert gas is passed through into electrolytic cell, to electricity
It solves liquid and carries out pneumatic stirring.
It applies the technical scheme of the present invention, the present invention is by mixing shape for rare-earth salts, ionic liquid and hydroxyl ether solvent
It is electrolysed at electrolyte, and to electrolyte to form rare earth metal.This method utilizes it using hydroxyl ether solvent as additive
In hydroxyl hydrotropy rare-earth salts, while only one of which hydroxyl greatly reduces discharge quantity, under being unlikely to electric current rapidly
Drop, and it is greatly reduced the porosity in product.This method alleviates dissolution difficulty, step not using solid matter as additive
Rapid cumbersome problem, and this method is using ethylene glycol as additive, alleviate largely deflate in deposition process and electric current sharply under
The problem of drop.Moreover, the method not only a large amount of save the costs, energy saving, while the discharge of pollutant can also be substantially reduced, more
Importantly, due to not needing to operate in glove box, while solid phase additive is not added, so that rare earth metal in ionic liquid
Electro-deposition strided forward major step to industrialization.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows the SEM figure for the rare earth metal that embodiment 5 obtains；And
Fig. 2 shows the SEM figures for the rare earth metal that comparative example 1 obtains.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The application is described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
It can be seen from background technology that, it is existing using ionic liquid prepare rare earth metal method have it is at high cost, energy consumption is high, by
In cumbersome using solid additives, while the disadvantages of to be operated in glove box, to limit its industrial application.This
The inventor of invention studies regarding to the issue above, provides a kind of preparation method of rare earth metal, which includes
Following steps: rare-earth salts, ionic liquid and hydroxyl ether solvent are mixed to form electrolyte, and electrolyte is placed in electrolytic cell
In；Electrolyte is electrolysed to form rare earth metal；Wherein, the structural formula of hydroxyl ether solvent are as follows:
Wherein, R1For any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group and tert-butyl；R2
For any one of methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group and tert-butyl；N=1-10.
Above-mentioned preparation method is using hydroxyl ether solvent as additive, using hydroxyl hydrotropy rare-earth salts therein, while wherein
An only hydroxyl, greatly reduces discharge quantity, and electric current is made to be unlikely to decline rapidly, and drops the porosity in product also significantly
It is low.This method alleviates dissolution difficulty, complex steps problem not using solid matter as additive, and this method is not with ethylene glycol
For additive, alleviates in deposition process and largely deflate, the problem of electric current sharply declines.Moreover, the method is not only largely saved into
Originally, energy saving, while the discharge of pollutant can also be substantially reduced, it is often more important that due to not needing to grasp in glove box
Make, while not adding solid phase additive, so that the electro-deposition of rare earth metal has strided forward major step to industrialization in ionic liquid.
The illustrative embodiments of the preparation method of the rare earth metal provided according to the present invention are provided.
However, these illustrative embodiments can be implemented by many different forms, and it should not be construed to be limited solely to this
In the embodiment that is illustrated.It should be understood that these embodiments are provided so that disclosure herein thoroughly and
Completely, and by the design of these illustrative embodiments those of ordinary skill in the art are fully conveyed to.
Firstly, rare-earth salts, ionic liquid and hydroxyl ether solvent are mixed to form electrolyte, and electrolyte is placed in electrolysis
In slot.In the step, electrolyte quota is carried out under air atmosphere, can also be aided with ultrasonic treatment.And the step does not need
It is operated in glove box, while not adding solid phase additive, so that the electro-deposition of rare earth metal is stepped to industrialization in ionic liquid
Into major step.
In above-mentioned electrolyte, the volume ratio of ionic liquid and hydroxyl ether solvent can be set according to actual needs.
Preferably, the volume ratio of ionic liquid and hydroxyl ether solvent is 0.1~20:1.It is further preferable that further, electrolyte
In, the volume ratio of ionic liquid and hydroxyl ether solvent is 1~4:1.Electrolyte with above-mentioned composition can preferably dissolve
Rare-earth salts.Similarly, the content of rare-earth salts can also be set according to actual needs.In a preferred embodiment,
The content of rare-earth salts in the electrolytic solution is 5~85g/L.At this point, subsequent electrolytic process can more thoroughly.
Ionic liquid employed in the step can be ionic liquid commonly used in the art.In a kind of preferred embodiment party
In formula, further, the anion of ionic liquid is BF4 -Or PF6 -, the cation of ionic liquid is alkyl imidazole or alkylated pyrazole
Pyridine.Certainly, the type of ionic liquid is not limited to above-mentioned preference.
Rare-earth salts in the step can be rare-earth salts common in the user of this field, for example, rare-earth salts be rare earth chloride,
Sulfuric acid rare earth and nitric acid rare earth are any one or more of.Rare earth in rare-earth salts is rare earth ion common in this field, example
Such as La3+、Ce3+And Dy3+Deng, and two or more rare earth ion can also be contained in rare-earth salts.
It completes rare-earth salts, ionic liquid and hydroxyl ether solvent being mixed to form electrolyte, and electrolyte is placed in electrolysis
After step in slot, electrolyte is electrolysed to form rare earth metal.There are many kinds of the modes of electrolysis, such as constant current is heavy
Long-pending or potentiostatic electrodeposition etc..In a preferred embodiment, inert electrode is working electrode, is to electricity with inert electrode
Pole is electrolysed using constant current electro-deposition mode, and current density is 10~150A/m in electrolysis step2, electrodeposition time
For 5~120min, and electro-deposition obtains rare earth metal at room temperature；
Before the step of being electrolysed, it is preferable that the preparation method further include: carry out preelectrolysis to electrolyte to remove electrolysis
Water in liquid.Preelectrolysis step can be pre- when being carried out using constant current electro-deposition mode using modes such as constant current or constant potentials
Electrolysis, and current density is preferably 10~50A/m in preelectrolysis step2, the time of preelectrolysis is preferably 5~30min.
Before the step of being electrolysed, which can also include: that inert gas is passed through into electrolytic cell, to electrolysis
Liquid carries out pneumatic stirring.Specifically, can bottom of electrolytic tank place coiled pipe, and by coiled pipe be passed through into electrolytic cell it is lazy
Property gas, such as nitrogen, argon gas etc..
The present invention also provides a kind of rare earth metal, the rare earth metal above-mentioned preparation method provided by the present invention is made.
The porosity in rare earth metal is greatly reduced, and then improves the surface property of rare earth metal.
The preparation method of rare earth metal provided by the invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Present embodiments provide a kind of preparation method of rare earth metal, comprising the following steps:
Firstly, by LaCl3, ionic liquid and 2- hydroxypropyl methyl ether is mixed to form electrolyte, and electrolyte is placed in electricity
It solves in slot, wherein the volume ratio of ionic liquid and 2- hydroxypropyl methyl ether is 10:1, and the content of rare-earth salts in the electrolytic solution is
5g/L, the anion of ionic liquid are BF4 -, the cation of ionic liquid is 1- ethyl-3-methylimidazole cation；
Then, coiled pipe is passed through nitrogen into electrolytic cell to carry out pneumatic stirring to electrolyte, and carries out to electrolyte pre-
Electrolysis, wherein current density is preferably 10A/m2, the time of preelectrolysis is preferably 10min.
Finally, inert electrode is to electrode, using constant current electro-deposition mode to electrolysis using inert electrode as working electrode
Liquid is electrolysed, and wherein, current density 10A/m2, electrodeposition time 20min.
Embodiment 2
Present embodiments provide a kind of preparation method of rare earth metal, comprising the following steps:
Firstly, by LaCl3, ionic liquid and 2- hydroxypropyl ethyl ether is mixed to form electrolyte, and electrolyte is placed in electricity
It solves in slot, wherein the volume ratio of ionic liquid and 2- hydroxypropyl ethyl ether is 5:1, and the content of rare-earth salts in the electrolytic solution is
15g/L, the anion of ionic liquid are BF4 -, the cation of ionic liquid is 1- ethyl-3-methylimidazole cation；
Then, coiled pipe is passed through nitrogen into electrolytic cell to carry out pneumatic stirring to electrolyte, and carries out to electrolyte pre-
Electrolysis, wherein current density is preferably 10A/m2, the time of preelectrolysis is preferably 20min.
Finally, inert electrode is to electrode, using constant current electro-deposition mode to electrolysis using inert electrode as working electrode
Liquid is electrolysed, and wherein, current density 10A/m2, electrodeposition time 30min.
Embodiment 3
Present embodiments provide a kind of preparation method of rare earth metal, comprising the following steps:
Firstly, by LaCl3, ionic liquid and glycol monoethyl ether be mixed to form electrolyte, and electrolyte be placed in electrolysis
In slot, wherein the volume ratio of ionic liquid and glycol monoethyl ether is 0.5:1, and the content of rare-earth salts in the electrolytic solution is 25g/
L, the anion of ionic liquid are BF4 -, the cation of ionic liquid is 1- ethyl-3-methylimidazole cation；
Then, coiled pipe is passed through nitrogen into electrolytic cell to carry out pneumatic stirring to electrolyte, and carries out to electrolyte pre-
Electrolysis, wherein current density is preferably 20A/m2, the time of preelectrolysis is preferably 5min.
Finally, inert electrode is to electrode, using constant current electro-deposition mode to electrolysis using inert electrode as working electrode
Liquid is electrolysed, and wherein, current density 10A/m2, electrodeposition time 50min.
Embodiment 4
Present embodiments provide a kind of preparation method of rare earth metal, comprising the following steps:
Firstly, by LaCl3, ionic liquid and 2- hydroxypropyl methyl ether is mixed to form electrolyte, and electrolyte is placed in electricity
It solves in slot, wherein the volume ratio of ionic liquid and hydroxyl ether solvent 2- hydroxypropyl methyl ether is 1:1, and rare-earth salts is in electrolyte
In content be 55g/L, the anion of ionic liquid is BF4 -, the cation of ionic liquid be 1- ethyl-3-methylimidazole sun from
Son；
Then, coiled pipe is passed through nitrogen into electrolytic cell to carry out pneumatic stirring to electrolyte, and carries out to electrolyte pre-
Electrolysis, wherein current density is preferably 50A/m2, the time of preelectrolysis is preferably 5min.
Finally, inert electrode is to electrode, using constant current electro-deposition mode to electrolysis using inert electrode as working electrode
Liquid is electrolysed, and wherein, current density 30A/m2, electrodeposition time 100min.
Embodiment 5
Present embodiments provide a kind of preparation method of rare earth metal, comprising the following steps:
Firstly, by LaCl3, ionic liquid and 2- hydroxypropyl methyl ether is mixed to form electrolyte, and electrolyte is placed in electricity
It solves in slot, wherein the volume ratio of ionic liquid and 2- hydroxypropyl methyl ether is 4:1, and the content of rare-earth salts in the electrolytic solution is
10g/L, the anion of ionic liquid are BF4 -, the cation of ionic liquid is 1- ethyl-3-methylimidazole cation；
Then, coiled pipe is passed through nitrogen into electrolytic cell to carry out pneumatic stirring to electrolyte, and carries out to electrolyte pre-
Electrolysis, wherein current density is preferably 10A/m2, the time of preelectrolysis is preferably 15min.
Finally, inert electrode is to electrode, using constant current electro-deposition mode to electrolysis using inert electrode as working electrode
Liquid is electrolysed, and wherein, current density 50A/m2, electrodeposition time 150min.
Comparative example 1
By LaCl3, ionic liquid and ethylene glycol is mixed to form electrolyte, and electrolyte is placed in electrolytic cell, wherein from
The volume ratio of sub- liquid and ethylene glycol is 4:1, and the content of rare-earth salts in the electrolytic solution is 10g/L, and the anion of ionic liquid is
BF4 -, the cation of ionic liquid is 1- ethyl-3-methylimidazole cation；
Then, coiled pipe is passed through nitrogen into electrolytic cell to carry out pneumatic stirring to electrolyte, and carries out to electrolyte pre-
Electrolysis, wherein current density is preferably 10A/m2, the time of preelectrolysis is preferably 15min.
Finally, inert electrode is to electrode, using constant current electro-deposition mode to electrolysis using inert electrode as working electrode
Liquid is electrolysed, and wherein, current density 50A/m2, electrodeposition time 150min.
Test:
The SEM that the present invention also uses scanning electron microscope to obtain the rare earth metal obtained to embodiment 5 and comparative example 1 schemes,
Middle Fig. 1 is the SEM figure for the rare earth metal that embodiment 5 obtains, and Fig. 2 is the SEM figure for the rare earth metal that comparative example 1 obtains.It can from Fig. 1
To find out, the microstructure for the rare earth metal that embodiment 5 obtains is very fine and close, and the stomata of large scale (several microns) is not present.From Fig. 2
As can be seen that the rare earth metal that comparative example 1 obtains is there are many stomatas (having a size of a few micrometers), the porosity is much larger than embodiment
The porosity of 5 obtained rare earth metals.
The present invention also obtains the SEM figure (present invention of the rare earth metal obtained to embodiment 1 to 4 using scanning electron microscope
In do not provide), and the result shows that the microstructure for the rare earth metal that embodiment 1 to 4 obtains is also very fine and close, there is no large-sized
Stomata.
As can be seen from the above embodiments, the above-mentioned example of the present invention realizes following technical effect: the present invention pass through by
Rare-earth salts, ionic liquid and hydroxyl ether solvent are mixed to form electrolyte, and are electrolysed electrolyte to form rare earth metal.
This method is using hydroxyl ether solvent as additive, using hydroxyl hydrotropy rare-earth salts therein, while only one of which hydroxyl, greatly
Discharge quantity is reduced greatly, makes electric current be unlikely to decline rapidly, and be greatly reduced the porosity in product.This method is not with solid
State substance is additive, alleviates dissolution difficulty, complex steps problem, and this method alleviates not using ethylene glycol as additive
It largely deflates in deposition process, the problem of electric current sharply declines.Moreover, the method not only a large amount of save the costs, energy saving, simultaneously
The discharge of pollutant can also be substantially reduced, it is often more important that due to not needing to operate in glove box, while not adding solid phase
Additive, so that the electro-deposition of rare earth metal has strided forward major step to industrialization in ionic liquid.
These are only the preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of rare earth metal, which is characterized in that the preparation method comprises the following steps:
Rare-earth salts, ionic liquid and hydroxyl ether solvent are mixed to form electrolyte, and the electrolyte is placed in electrolytic cell；
The electrolyte is electrolysed to form the rare earth metal；Wherein,
The structural formula of the hydroxyl ether solvent are as follows:
Wherein,
R1For any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group and tert-butyl；
R2For any one of methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group and tert-butyl；
N=1-10,
The anion of the ionic liquid is BF4 -Or PF6 -, the cation of the ionic liquid is alkyl imidazole or alkyl pyridine.
2. preparation method according to claim 1, which is characterized in that the hydroxyl ether solvent is 2- hydroxypropyl methyl
Ether.
3. preparation method according to claim 1, which is characterized in that in the electrolyte, the ionic liquid with it is described
The volume ratio of hydroxyl ether solvent is 0.1~20:1.
4. preparation method according to claim 3, which is characterized in that in the electrolyte, the ionic liquid with it is described
The volume ratio of hydroxyl ether solvent is 1~4:1.
5. preparation method according to claim 1, which is characterized in that content of the rare-earth salts in the electrolyte be
5~85g/L.
6. preparation method according to claim 1, which is characterized in that the rare-earth salts be rare earth chloride, sulfuric acid rare earth and
Nitric acid rare earth is any one or more of.
7. preparation method according to any one of claim 1 to 6, which is characterized in that use constant current electro-deposition mode
The electrolysis is carried out, and current density is 10~150A/m in the electrolysis step2, electrodeposition time is 5~120min.
8. preparation method according to any one of claim 1 to 6, which is characterized in that before the step of the electrolysis, institute
State preparation method further include: preelectrolysis is carried out to remove the water in the electrolyte to the electrolyte.
9. preparation method according to claim 8, which is characterized in that carry out the pre- electricity using constant current electro-deposition mode
Solution, and current density is 10~50A/m in the preelectrolysis step2, the time of the preelectrolysis is 5~30min.
10. preparation method according to any one of claim 1 to 6, which is characterized in that before the step of the electrolysis,
The preparation method further include: inert gas is passed through in Xiang Suoshu electrolytic cell, to carry out pneumatic stirring to the electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410854711.5A CN105803484B (en) | 2014-12-31 | 2014-12-31 | The preparation method of rare earth metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410854711.5A CN105803484B (en) | 2014-12-31 | 2014-12-31 | The preparation method of rare earth metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105803484A CN105803484A (en) | 2016-07-27 |
| CN105803484B true CN105803484B (en) | 2019-05-31 |
Family
ID=56465223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410854711.5A Active CN105803484B (en) | 2014-12-31 | 2014-12-31 | The preparation method of rare earth metal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105803484B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102888631A (en) * | 2011-07-20 | 2013-01-23 | 中国科学院过程工程研究所 | Method for preparing Al-Bi alloy or plated Al-Bi alloy by low-temperature electro-deposition of ionic liquid |
| CN103540974A (en) * | 2013-10-14 | 2014-01-29 | 昆明理工大学 | Method for preparing metal lanthanum through dicyandiamide ionic liquid low-temperature electro-deposition |
-
2014
- 2014-12-31 CN CN201410854711.5A patent/CN105803484B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102888631A (en) * | 2011-07-20 | 2013-01-23 | 中国科学院过程工程研究所 | Method for preparing Al-Bi alloy or plated Al-Bi alloy by low-temperature electro-deposition of ionic liquid |
| CN103540974A (en) * | 2013-10-14 | 2014-01-29 | 昆明理工大学 | Method for preparing metal lanthanum through dicyandiamide ionic liquid low-temperature electro-deposition |
Non-Patent Citations (2)
| Title |
|---|
| 1-乙基-3-甲基-咪唑四氟硼酸盐离子液体中镝电沉积行为;金炳勋;《稀有金属材料与工程》;20120531;第41 卷(第5期);全文 |
| 离子液体中铈的电沉积行为;玉山江·哈斯木;《稀有金属》;20140531;第38卷(第3期);全文 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105803484A (en) | 2016-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107904614B (en) | A kind of Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and the preparation method and application thereof | |
| CN103007965B (en) | Titanium-based carbon nanotube supported copper/palladium bimetallic catalyst and preparation method thereof | |
| CN103787311A (en) | Preparation methods of graphene-carbon nanotube composite thin film and electrochemical capacitor | |
| CN102627768A (en) | Preparation method of grapheme/polypyrrole nanocomposite material for super capacitor electrode | |
| Liu et al. | Enhanced methanol oxidation activity of Pt catalyst supported on the phosphorus-doped multiwalled carbon nanotubes in alkaline medium | |
| Kim et al. | A high-temperature tolerance solution for positive electrolyte of vanadium redox flow batteries | |
| CN106783201B (en) | A kind of molybdenum sulfide/ferric oxide composite material and its preparation method and application | |
| CN104492426A (en) | Modified manganese dioxide catalyst, modified manganese dioxide catalyst electrode and preparation method of modified manganese dioxide catalyst and modified manganese dioxide catalyst electrode | |
| CN103252243A (en) | Carbon nano tube film load cuprum and palladium bimetallic catalyst, preparation method and application | |
| CN102247828A (en) | Hydrotreated TiO2 nanotube array and preparation method thereof | |
| CN106362767A (en) | Nanometer platinum-copper alloy catalytic material for electrolysis of water | |
| CN103508442A (en) | Preparation method of graphene | |
| CN102691089B (en) | Electrochemical method for preparing superhydrophobic surface on copper substrates by using aqueous electrolyte | |
| Liu et al. | Low Pt content catalyst supported on nitrogen and phosphorus-codoped carbon nanotubes for electrocatalytic O2 reaction in acidic medium | |
| CN102516575B (en) | Method for preparing bipolar membrane modified by heavy metal ion loaded carbon nao tube | |
| CN105063665A (en) | Method for electrically depositing nanometer platinum powder from ionic liquid | |
| CN110470710B (en) | Preparation and test method of electromagnetic composite material | |
| Liu et al. | A novel method for evaluating the photoelectrocatalytic performance of reduced graphene oxide/protonated g-C3N4 composites | |
| CN106981650A (en) | A kind of preparation method of nanoscale bismuth with elementary | |
| CN103165866A (en) | Nitrogen doped graphene/metal composite electrode and its preparation method | |
| CN107417588B (en) | A kind of novel ion liquid and the method using its electrolytic preparation nano aluminum | |
| CN105803484B (en) | The preparation method of rare earth metal | |
| CN104269552B (en) | A kind of nano nickel cobalt oxide and preparation method thereof | |
| CN103882499B (en) | CNT membrane electrode CNT-Ti electrode as catalyst carrier is prepared and application | |
| CN109665521A (en) | For capacitive deionization electrode N doping self shrinking formula 3D graphene and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100088, 2, Xinjie street, Xicheng District, Beijing Patentee after: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee after: Youyan Technology Group Co.,Ltd. Address before: 100088, 2, Xinjie street, Xicheng District, Beijing Patentee before: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee before: GENERAL Research Institute FOR NONFERROUS METALS Address after: 100088, 2, Xinjie street, Xicheng District, Beijing Patentee after: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee after: China Youyan Technology Group Co.,Ltd. Address before: 100088, 2, Xinjie street, Xicheng District, Beijing Patentee before: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee before: Youyan Technology Group Co.,Ltd. |