CN106894056A - A kind of method of high-purity La, Ce mischmetal of electrolytic preparation - Google Patents
A kind of method of high-purity La, Ce mischmetal of electrolytic preparation Download PDFInfo
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- CN106894056A CN106894056A CN201510964913.XA CN201510964913A CN106894056A CN 106894056 A CN106894056 A CN 106894056A CN 201510964913 A CN201510964913 A CN 201510964913A CN 106894056 A CN106894056 A CN 106894056A
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- rare earth
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- earth metal
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
- B24C1/08—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods for polishing surfaces, e.g. smoothing a surface by making use of liquid-borne abrasives
- B24C1/086—Descaling; Removing coating films
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Abstract
The invention belongs to rare earth preparation field, the method for specially a kind of high-purity La, Ce mischmetal of electrolytic preparation.The method of high-purity La, Ce mixing pure rare earth of electrolytic preparation is mainly and is electrolysed by electrolytic cell, and cathode deposition separates out rare earth metal after electrolysis, and then the rare earth metal that surface is covered with electrolyte is positioned in air；After after its cooling and demolding, fine Shot Blasting is carried out, so as to surface oxide layer can be eliminated to greatest extent, rare earth metal surface exposes metallic luster；Rare earth metal after polishing need to carry out vacuum packaging treatment, to prevent its surface from aoxidizing, so as to influence its purity.Easy to operate, rare earth high purity of the invention, and process is simple, safe and reliable, the alloying component for obtaining is uniform, reduces segregation.
Description
Technical field
The invention belongs to rare earth preparation field, the side of specially a kind of high-purity La, Ce mischmetal of electrolytic preparation
Method.
Background technology
Oxygen is the harmful element in steel, and oxygen content high can cause more bulk oxide occur in material to be mingled with,
So as to destroy the continuity of steel matrix, result even in material and serious brittle fracture occurs.Smelt molten steel when pair
Oxygen content is clearly required, it is desirable to which typically in below 20ppm, high-end product requirement oxygen content is less than oxygen content
Below 10ppm.For the pure rare earth of addition is needed in steel-making, to add and require that its own has before molten steel
Degree of purity high, i.e., can not occur secondary oxidation, and otherwise rare earth will add molten steel in the form of rare earth oxide
In, so as to molten steel can be polluted, do not have the effects such as due cleaning molten steel, rotten field trash and crystal grain thinning.
It is typically only capable to choose using the relatively low high-purity rare-earth of the oxygen content of specific process preparation, can so causes manufacturing cost
Increase, while the competitiveness of product in market can also be substantially reduced.
In recent years, with the development of science and technology, in terms of high pure rare earth metals are prepared, developed many technologies and
Method, according to the difference of impurity in the difference and raw material of each single rare earth metalline, has grown up five kinds
The method of Purification of Rare Earth Metals：Vacuum remelting, distillation/distillation, zone refining, Solid State Electrotransport and electrorefining,
Zone refining and Solid State Electrotransport are to make the magazine " redistribution " being purified in metal, can not be from being purified gold
" removal " and " purifying " in category, although these methods can reach the purpose to rare earth metal purification, due to should
With the difference in field, the often simply impurity alloying element such as Si, Ca, Al, Mg in Purification of Rare Earth Metals.It is right
For the rare earth for being applied to field of steel-making, and need not spend high cost method and remove such as Si, Ca,
The impurity such as Al, Mg, because these elements can be as strong deoxidier, additionally, using these methods in steel
High-purity rare-earth total oxygen content is prepared in more than 300ppm.In sum, in the urgent need to one kind is simple and real
The complete preparation method of oxygen content in removal rare earth metal.
The content of the invention
It is an object of the invention to provide a kind of method of high-purity La, Ce mischmetal of electrolytic preparation, effectively make
The high pure rare earth metals of standby hypoxemia, improve the degree of purity of alloy, the total oxygen content in steel alloy are reduced, so as to subtract
Field trash in few rare earth metal, pure property is asked in will not producing pollution, and then solution steel after addition molten steel to it
Topic.
The technical scheme is that：
A kind of method of high-purity La, Ce mischmetal of electrolytic preparation, by weight percentage, La, Ce mixing
In rare earth, the scope of La elements is 60~70% for the scope of 30~35%, Ce elements, the method include with
Lower step：
(1) it is electrolysed using electrolytic cell, is passed through direct current, it is 3~9A/cm to control cathode-current density2,
Anodic current density is 1~3A/cm2, groove pressure is 6~11V, is electrolysed, and electrolyte is the oxide of mixing
Rare earth and rare earth fluoride, after energization, cathode deposition separates out pure La, Ce rare earth metal；
(2) rare earth metal is come out of the stove using canister, surface is completely covered with electrolyte, tapping temperature is
1000~1200 DEG C, canister preheats 200~400 DEG C, and rare earth stirs when coming out of the stove, in case causing segregation；
(3) after the electrolyte of rare earth metal surface covering is fully cured, it is dipped in cooling circulating water,
Water temperature is 25~50 DEG C, and after 1~3min of circulating water, the complete cooled and solidified of rare earth metal, the demoulding is taken out dilute
Earth metal；
(4) rare earth metal is put into fine shot-blasting machine and is polished, and polishing time is 10~20min, fully place
Reason rare earth metal surface oxide layer, makes it expose metallic luster；
(5) because rare earth metal is extremely active, in order to prevent it from aoxidizing, by the high-purity rare-earth gold after polishing
Category carries out vacuum packaging treatment, and packed weight is 0.5~1.5 kilogram/block, is easy to subsequently be added in molten steel, most
The purpose for preparing high-purity La, Ce mixing pure rare earth is reached eventually, and the purity of rare earth reaches total oxygen content less than 80ppm,
Complete to prepare.
The method of high-purity La, Ce mischmetal of described electrolytic preparation, electrolyte be mixing cerium lanthanum oxide and
Lanthanum fluoride cerium, and lanthanum cerium part by weight is 1 ︰ 2.
The method of high-purity La, Ce mischmetal of described electrolytic preparation, canister is with 2~10 ° of tapers
Back taper inwall, in order to the demoulding of rare earth metal, and surface electrolyte thickness is 1~3mm, with effective
Prevent rare earth metal from being aoxidized during coming out of the stove.
The method of high-purity La, Ce mischmetal of described electrolytic preparation, when shot-blasting machine is polished, stainless steel
The granularity of ball is 100~300MPa in 0.5~3mm, applying pressure, reaches elimination rare earth metal surface oxidation
Excessive rare earth metal is not damaged while layer purpose.
The method of high-purity La, Ce mischmetal of described electrolytic preparation, the rare earth metal after polishing is carried out very
During sky encapsulation, using the vacuum packaging bag of 0.5~2mm, vacuum is 5~20Pa.
The method of high-purity La, Ce mischmetal of described electrolytic preparation, prepares high-purity La, Ce mixing pure rare earth
Afterwards, it is sampled, checks gas oxygen content.
The invention has the advantages that and beneficial effect：
1. present invention process is reasonable in design, is a kind of method of the removal rare earth metal oxygen content of highly effective, main
To be come out of the stove mode, rational release method, appropriate follow-up shot-blasting machine application of vacuum by suitable rare earth metal
Etc. a series of technical measures, the oxygen content in rare earth metal can be effectively removed, be the casting of lifting production
Steel part and the big Inner Quality of Billet of steel, there is provided a kind of simply method for preparing high-purity rare-earth of practicality.
2. the method for high-purity La, Ce mixing pure rare earth of electrolytic preparation of the present invention, can be final dilute
Within 80ppm, DNA vaccine reaches more than 73% to Control for Oxygen Content in earth metal, for development prepare it is high-purity dilute
Soil provides a kind of simple and efficient method.
3. the method for high-purity La, Ce mixing pure rare earth of electrolytic preparation of the present invention, technological design rationally,
Flow is simple, safe, workable, and industry is easily realized.
4. the use of high-purity La, Ce mixing pure rare earth of electrolytic preparation of the present invention, can play refining, desulfurization, in
With the effect of low melting point objectionable impurities, it is possible to improve the processing characteristics of steel, the physical chemistry of alloy can be improved
Performance, and improve Alloy At Room Temperature and high-temperature mechanical property.
Specific embodiment
In specific implementation process, the method for high-purity La, Ce mixing pure rare earth of electrolytic preparation of the present invention is mainly
It is electrolysed by electrolytic cell, cathode deposition separates out rare earth metal after electrolysis, and surface then is covered with into electrolyte
Rare earth metal be positioned in air；After after its cooling and demolding, fine Shot Blasting is carried out, so that can maximum limit
The elimination surface oxide layer of degree, rare earth metal surface exposes metallic luster；Rare earth metal after polishing need to be carried out very
Empty package treatment, to prevent its surface from aoxidizing, so as to influence its purity.The high-purity La of electrolytic preparation of the present invention,
Ce mischmetals, by weight percentage, the weight percentage ranges of La elements are 30~35%, Ce elements
Weight percentage ranges be 60~70%, and the part by weight of La and Ce is about 1 ︰ 2.The method is grasped
Facilitate, rare earth high purity, and process is simple, safe and reliable, the alloying component for obtaining is uniform, reduces
Segregation.
The present invention is described in further detail below by embodiment.
Embodiment 1
Prepared high-purity La, Ce mischmetal of experiment is 50kg.Traditional electrolyte prepares the chemistry of high-purity rare-earth
Composition is as shown in table 1.Electrolyte is put into electrolytic cell, negative electrode separates out high-purity La, Ce mixing after the fusing that is powered
Rare earth, is come out of the stove rare earth metal using the canister that inwall is 8 ° of back tapers, and surface is completely covered with electrolysis
Matter, tapping temperature is 1200 DEG C, and canister preheats 200 DEG C, and rare earth stirs before coming out of the stove, in case causing
Segregation；After the electrolyte of rare earth metal surface covering is fully cured, it is dipped in cooling circulating water, water
Temperature is 25 DEG C, and after circulating water 1min, rare earth metal is taken out in the complete cooled and solidified of rare earth metal, the demoulding；
Rare earth metal is put into fine shot-blasting machine and is polished, and polishing time is 10min, fully treatment rare earth metal table
Face oxide layer, makes it expose metallic luster；High pure rare earth metals after polishing are carried out into vacuum packaging treatment, is wrapped
Dress weight is 1 kilogram/block, is easy to subsequently be added in molten steel, and vacuum packaging before processing takes finished product sample carries out chemistry
And Determination of octafluoropropane content, as shown in table 2, most high-purity La, Ce mix at last for its chemical composition and gas content
The DNA vaccine of rare earth reaches more than 67%.
The traditional electrolyte of table 1 prepares the chemical composition (wt%) of high-purity rare-earth
Table 2 uses the chemical composition (wt%) of electrolytic preparation high-purity rare-earth of the present invention
Embodiment 2
Prepared high-purity La, Ce mischmetal of experiment is 500kg.Traditional electrolyte prepares the chemistry of high-purity rare-earth
Composition is as shown in table 1.Electrolyte is put into electrolytic cell, negative electrode separates out high-purity La, Ce mixing after the fusing that is powered
Rare earth, is come out of the stove rare earth metal using the canister that inwall is 6 ° of back tapers, and surface is completely covered with electrolysis
Matter, tapping temperature is 1150 DEG C, and canister preheats 250 DEG C, and rare earth stirs before coming out of the stove, in case causing
Segregation；After the electrolyte of rare earth metal surface covering is fully cured, it is dipped in cooling circulating water, water
Temperature is 30 DEG C, and after circulating water 2min, rare earth metal is taken out in the complete cooled and solidified of rare earth metal, the demoulding；
Rare earth metal is put into fine shot-blasting machine and is polished, and polishing time is 15min, fully treatment rare earth metal table
Face oxide layer, makes it expose metallic luster；High pure rare earth metals after polishing are carried out into vacuum packaging treatment, is wrapped
Dress weight is 1 kilogram/block, is easy to subsequently be added in molten steel, and vacuum packaging before processing takes finished product sample carries out chemistry
And Determination of octafluoropropane content, as shown in table 3, most high-purity La, Ce mix at last for its chemical composition and gas content
The DNA vaccine of rare earth reaches more than 73%.
Table 3 uses the chemical composition (wt%) of electrolytic preparation high-purity rare-earth of the present invention
| La | Ce | S | P | O | Fe |
| 35 | 64 | <0.02 | <0.02 | 0.008 | Surplus |
The result of embodiment shows, high-purity La, Ce mischmetal prepared by the present invention, rare earth high purity,
And process is simple, safe and reliable, the alloying component for obtaining is uniform.Can substantially reduce complete in rare earth metal
Oxygen content, most the DNA vaccine of rare earth metal reaches more than 73% at last, for production super clean rare earth metal is provided
A kind of approach of high-efficient simple.
Claims (6)
1. the method for high-purity La, Ce mischmetal of a kind of electrolytic preparation, it is characterised in that by weight percentage
Meter, in La, Ce mischmetal, the scope of La elements is 60~70% for the scope of 30~35%, Ce elements,
The method is comprised the following steps：
(1) it is electrolysed using electrolytic cell, is passed through direct current, it is 3~9A/cm to control cathode-current density2,
Anodic current density is 1~3A/cm2, groove pressure is 6~11V, is electrolysed, and electrolyte is the oxide of mixing
Rare earth and rare earth fluoride, after energization, cathode deposition separates out pure La, Ce rare earth metal；
(2) rare earth metal is come out of the stove using canister, surface is completely covered with electrolyte, tapping temperature is
1000~1200 DEG C, canister preheats 200~400 DEG C, and rare earth stirs when coming out of the stove；
(3) after the electrolyte of rare earth metal surface covering is fully cured, it is dipped in cooling circulating water,
Water temperature is 25~50 DEG C, and after 1~3min of circulating water, the complete cooled and solidified of rare earth metal, the demoulding is taken out dilute
Earth metal；
(4) rare earth metal is put into fine shot-blasting machine and is polished, and polishing time is 10~20min, fully place
Reason rare earth metal surface oxide layer, makes it expose metallic luster；
(5) high pure rare earth metals after polishing are carried out into vacuum packaging treatment, packed weight is 0.5~1.5 kilogram
/ block, is easy to subsequently be added in molten steel, is finally reached the purpose for preparing high-purity La, Ce mixing pure rare earth, dilute
The purity of soil reaches total oxygen content less than 80ppm, completes to prepare.
2., according to the method for high-purity La, Ce mischmetal of electrolytic preparation described in claim 1, its feature exists
In electrolyte is the cerium lanthanum oxide and lanthanum fluoride cerium of mixing, and lanthanum cerium part by weight is 1 ︰ 2.
3., according to the method for high-purity La, Ce mischmetal of electrolytic preparation described in claim 1, its feature exists
It is that, with 2~10 ° of back taper inwalls of taper, and surface electrolyte thickness is 1~3mm in, canister.
4., according to the method for high-purity La, Ce mischmetal of electrolytic preparation described in claim 1, its feature exists
In when shot-blasting machine is polished, in 0.5~3mm, applying pressure is 100~300MPa to the granularity of stainless shot.
5., according to the method for high-purity La, Ce mischmetal of electrolytic preparation described in claim 1, its feature exists
In when the rare earth metal after polishing is carried out into Vacuum Package, using the vacuum packaging bag of 0.5~2mm, vacuum
It is 5~20Pa to spend.
6., according to the method for high-purity La, Ce mischmetal of electrolytic preparation described in claim 1, its feature exists
In, after preparing high-purity La, Ce mixing pure rare earth, it is sampled, check gas oxygen content.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855087A (en) * | 1972-10-11 | 1974-12-17 | Shinetsu Chemical Co | Method for producing rare earth metal-containing alloys |
| CN1239152A (en) * | 1999-07-12 | 1999-12-22 | 唐定骧 | La, Pr and Ce mixed rare-earth metal and its making technology |
| CN1435513A (en) * | 2002-11-08 | 2003-08-13 | 包头市长河稀土材料有限公司 | Lanthanum and cerium composite alloy additive and preparing method thereof |
| CN103484898A (en) * | 2013-10-10 | 2014-01-01 | 宝纳资源控股(集团)有限公司 | Vacuum high-temperature continuous electrolytic furnace system and electrolytic method |
| CN103849900A (en) * | 2014-02-25 | 2014-06-11 | 广东省工业技术研究院(广州有色金属研究院) | Method for preparing rare earth alloy |
-
2015
- 2015-12-18 CN CN201510964913.XA patent/CN106894056B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855087A (en) * | 1972-10-11 | 1974-12-17 | Shinetsu Chemical Co | Method for producing rare earth metal-containing alloys |
| CN1239152A (en) * | 1999-07-12 | 1999-12-22 | 唐定骧 | La, Pr and Ce mixed rare-earth metal and its making technology |
| CN1435513A (en) * | 2002-11-08 | 2003-08-13 | 包头市长河稀土材料有限公司 | Lanthanum and cerium composite alloy additive and preparing method thereof |
| CN103484898A (en) * | 2013-10-10 | 2014-01-01 | 宝纳资源控股(集团)有限公司 | Vacuum high-temperature continuous electrolytic furnace system and electrolytic method |
| CN103849900A (en) * | 2014-02-25 | 2014-06-11 | 广东省工业技术研究院(广州有色金属研究院) | Method for preparing rare earth alloy |
Non-Patent Citations (1)
| Title |
|---|
| 张庆军 等: "熔盐电脱氧法制备La0.5Ce0.5Ni5的研究", 《功能材料》 * |
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Effective date of registration: 20220527 Address after: 256218 west side of middle section of Xiwang Avenue, Xiwang Industrial Park, Zouping City, Binzhou City, Shandong Province Patentee after: Zhongke Xiwang Special Steel Co.,Ltd. Address before: 110016 No. 72, Wenhua Road, Shenhe District, Liaoning, Shenyang Patentee before: INSTITUTE OF METAL RESEARCH CHINESE ACADEMY OF SCIENCES |