CN106894056B - 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 PDF

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CN106894056B
CN106894056B CN201510964913.XA CN201510964913A CN106894056B CN 106894056 B CN106894056 B CN 106894056B CN 201510964913 A CN201510964913 A CN 201510964913A CN 106894056 B CN106894056 B CN 106894056B
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rare earth
purity
earth metal
mischmetal
electrolyte
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CN106894056A (en
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傅排先
刘宏伟
栾义坤
李殿中
夏立军
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Zhongke Xiwang Special Steel Co ltd
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Institute of Metal Research of CAS
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/36Alloys obtained by cathodic reduction of all their ions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24CABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C1/00Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
    • B24C1/08Methods 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
    • B24C1/086Descaling; Removing coating films

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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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 electrolysed by electrolytic cell, and rare earth metal is precipitated in cathode deposition after electrolysis, and then rare earth metal that surface is covered with to electrolyte is positioned in air;After its cooling and demolding, fine Shot Blasting is carried out, so as to eliminate surface oxide layer to greatest extent, rare earth metal surface exposes metallic luster;Rare earth metal after polishing need to carry out vacuum packaging processing, to prevent its surface from aoxidizing, so as to influence its purity.Easy to operate, rare earth high purity of the invention, and it is simple for process, and securely and reliably, obtained alloying component is uniform, reduces segregation.

Description

A kind of method of high-purity La, Ce mischmetal of electrolytic preparation
Technical field
The invention belongs to rare earth preparation field, the method for specially a kind of high-purity La, Ce mischmetal of electrolytic preparation.
Background technology
Oxygen is the harmful element in steel, and high oxygen content can cause to occur more bulk oxide in material to be mingled with, from And the continuity of steel matrix is destroyed, it results even in material and serious brittle fracture occurs.Have when smelting molten steel to oxygen content bright True requirement, it is desirable that oxygen content is generally in 20ppm hereinafter, high-end product requirement oxygen content is less than below 10ppm.For in steel-making For needing pure rare earth to be added, require its own that secondary oxidation cannot occur with high degree of purity before adding in molten steel, Otherwise rare earth will be added in the form of rare earth oxide in molten steel, so that molten steel can be polluted, do not have due cleaning molten steel, The effects that rotten field trash and crystal grain thinning.It is typically only capable to choose relatively low high-purity dilute of oxygen content prepared using specific process Soil can lead to the increase of manufacturing cost, while the competitiveness of product in market can also substantially reduce in this way.
In recent years, with the development of science and technology, in terms of high pure rare earth metals are prepared, developed many technology and methods, According to the difference of impurity in the difference of each single rare earth metalline and raw material, the five kinds of Purification of Rare Earth Metals of having grown up Method:Vacuum remelting, distillation/distillation, zone refining, Solid State Electrotransport and electrorefining, zone refining and Solid State Electrotransport are only The magazine " redistribution " for making to be purified in metal, can not from be purified in metal " removal " and " purifying ", though these methods Can so achieve the purpose that purify rare earth metal, but due to the difference of application field, often only Si in Purification of Rare Earth Metals, The impurity alloying element such as Ca, Al, Mg.For the rare earth for being applied to field of steel-making, the method that does not need to spend high cost And the impurity such as Si, Ca, Al, Mg are removed, because these elements can be as strong deoxidier, in addition, utilizing these in steel Method prepares high-purity rare-earth total oxygen content in more than 300ppm.It to be gone in conclusion there is an urgent need to a kind of simple and practical Except the complete preparation method of oxygen content in rare earth metal.
Invention content
The purpose of the present invention is to provide a kind of methods of high-purity La, Ce mischmetal of electrolytic preparation, effectively prepare hypoxemia High pure rare earth metals, improve the degree of purity of alloy, the total oxygen content in steel alloy reduced, so as to reduce the folder in rare earth metal Sundries will not generate it pollution, and then solve pure sex chromosome mosaicism in steel after adding in molten steel.
The technical scheme is that:
A kind of method of high-purity La, Ce mischmetal of electrolytic preparation, by weight percentage, in La, Ce mischmetal, La Ranging from the 60~70% of ranging from 30~35%, the Ce elements of element, this method includes the following steps:
(1) it is electrolysed using electrolytic cell, is passed through direct current, control cathode-current density is 3~9A/cm2, anode current Density is 1~3A/cm2, slot pressure is 6~11V, is electrolysed, and electrolyte is the oxide rare earth and rare earth fluoride of mixing, is powered Later, pure La, Ce rare earth metal is precipitated in cathode deposition;
(2) rare earth metal is come out of the stove using canister, surface is completely covered with electrolyte, tapping temperature for 1000~ 1200 DEG C, canister preheats 200~400 DEG C, and rare earth stirs evenly when coming out of the stove, to prevent causing segregation;
(3) it after the electrolyte of rare earth metal surface covering is fully cured, is dipped in cooling circulating water, water temperature is 25~50 DEG C, after 1~3min of circulating water, rare earth metal is taken out in the complete cooled and solidified of rare earth metal, demoulding;
(4) rare earth metal is put into fine shot-blasting machine and is polished, and polishing time is 10~20min, fully handles rare earth Oxidation on metal surface layer makes it expose metallic luster;
(5) since rare earth metal is extremely active, it is aoxidized in order to prevent, and the high pure rare earth metals after polishing are carried out Vacuum packaging handle, packed weight be 0.5~1.5 kilogram/block, convenient for subsequently being added into molten steel, be finally reached prepare it is high-purity The purpose of La, Ce mixing pure rare earth, the purity of rare earth reach total oxygen content less than 80ppm, complete to prepare.
The method of high-purity La, Ce mischmetal of the electrolytic preparation, electrolyte are the cerium lanthanum oxide and lanthanum fluoride of mixing Cerium, and lanthanum cerium weight ratio is 1 ︰ 2.
The method of high-purity La, Ce mischmetal of the electrolytic preparation, canister are the back taper with 2~10 ° of tapers Shape inner wall, in order to the demoulding of rare earth metal, and surface electrolyte thickness is 1~3mm, rare earth metal to be effectively prevent to come out of the stove It aoxidizes in the process.
The method of high-purity La, Ce mischmetal of the electrolytic preparation, when shot-blasting machine is polished, the granularity of stainless steel pellet In 0.5~3mm, application pressure is 100~300MPa, reaches and was not damaged while eliminating rare earth metal surface oxide layer purpose More rare earth metals.
Rare earth metal after polishing is carried out Vacuum Package by the method for high-purity La, Ce mischmetal of the electrolytic preparation When, using the vacuum packaging bag of 0.5~2mm, vacuum degree is 5~20Pa.
The method of high-purity La, Ce mischmetal of the electrolytic preparation after preparing high-purity La, Ce mixing pure rare earth, carries out Gas oxygen content is examined in sampling.
The invention has the advantages that and advantageous effect:
1. present invention process reasonable design is a kind of method of the removal rare earth metal oxygen content of highly effective, main logical Suitable rare earth metal is crossed to come out of the stove a series of technologies such as mode, rational release method, appropriate follow-up shot-blasting machine vacuum processing Measure, the oxygen content that can be effectively removed in rare earth metal, to be promoted inside the steel-casting of production and the big strand of steel Quality provides a kind of simple and practical method for preparing high-purity rare-earth.
2. the method for high-purity La, Ce mixing pure rare earth of electrolytic preparation of the present invention, can be by final rare earth metal In Control for Oxygen Content within 80ppm, DNA vaccine reaches more than 73%, for development prepare high-purity rare-earth provide it is 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 is reasonable, flow letter Single, safe, operability is strong, and industry is easy to implement.
4. the use of high-purity La, Ce mixing pure rare earth of electrolytic preparation of the present invention can play refining, desulfurization, neutralize low melting point The effect of objectionable impurities, and the processing performance of steel can be improved, the physical and chemical performance of alloy can be improved, and improve alloy 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 mainly passes through electricity Solution slot is electrolysed, and rare earth metal is precipitated in cathode deposition after electrolysis, and then rare earth metal that surface is covered with to electrolyte is placed In air;After its cooling and demolding, fine Shot Blasting is carried out, so as to eliminate surface oxide layer, rare earth to greatest extent Expose metallic luster in metal surface;Rare earth metal after polishing need to carry out vacuum packaging processing, to prevent its surface from aoxidizing, So as to influence its purity.High-purity La, Ce mischmetal of electrolytic preparation of the present invention, by weight percentage, the weight hundred of La elements Divide ratio ranging from 30~35%, the weight percentage ranges of Ce elements are 60~70%, and the weight ratio of La and Ce is about 1 ︰ 2.This method is easy to operate, rare earth high purity, and simple for process, and securely and reliably, obtained alloying component 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 chemical composition of high-purity rare-earth such as Shown in table 1.Electrolyte is put into electrolytic cell, high-purity La, Ce mischmetal is precipitated in cathode after the fusing that is powered, and is fallen using inner wall for 8 ° The canister of taper comes out of the stove rare earth metal, and surface is completely covered with electrolyte, and tapping temperature is 1200 DEG C, canister 200 DEG C of preheating, rare earth stirs evenly before coming out of the stove, to prevent causing segregation;Treat that the electrolyte of rare earth metal surface covering is fully cured Afterwards, it is dipped in cooling circulating water, water temperature is 25 DEG C, and after circulating water 1min, the complete cooled and solidified of rare earth metal takes off Mould takes out rare earth metal;Rare earth metal is put into fine shot-blasting machine and is polished, and polishing time 10min fully handles rare earth Oxidation on metal surface layer makes it expose metallic luster;High pure rare earth metals after polishing are subjected to vacuum packaging processing, packaging weight It measures as 1 kilogram/block, convenient for subsequently being added into molten steel, vacuum packaging before processing takes that finished product sample carries out chemistry and gas content is surveyed Fixed, chemical composition and gas content are as shown in table 2, and most the DNA vaccine of high-purity La, Ce mischmetal reaches more than 67% at last.
1 traditional electrolyte of table 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 chemical composition of high-purity rare-earth such as Shown in table 1.Electrolyte is put into electrolytic cell, high-purity La, Ce mischmetal is precipitated in cathode after the fusing that is powered, and is fallen using inner wall for 6 ° The canister of taper comes out of the stove rare earth metal, and surface is completely covered with electrolyte, and tapping temperature is 1150 DEG C, canister 250 DEG C of preheating, rare earth stirs evenly before coming out of the stove, to prevent causing segregation;Treat that the electrolyte of rare earth metal surface covering is fully cured Afterwards, it is dipped in cooling circulating water, water temperature is 30 DEG C, and after circulating water 2min, the complete cooled and solidified of rare earth metal takes off Mould takes out rare earth metal;Rare earth metal is put into fine shot-blasting machine and is polished, and polishing time 15min fully handles rare earth Oxidation on metal surface layer makes it expose metallic luster;High pure rare earth metals after polishing are subjected to vacuum packaging processing, packaging weight It measures as 1 kilogram/block, convenient for subsequently being added into molten steel, vacuum packaging before processing takes that finished product sample carries out chemistry and gas content is surveyed Fixed, chemical composition and gas content are as shown in table 3, and most the DNA vaccine of high-purity La, Ce mischmetal reaches more than 73% at last.
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
Embodiment the result shows that, high-purity La, Ce mischmetal for preparing of the present invention, rare earth high purity, and technique Simply, securely and reliably, the alloying component obtained is uniform.The total oxygen content in rare earth metal can be substantially reduced, most rare earth at last The DNA vaccine of metal reaches more than 73%, and a kind of approach of high-efficient simple is provided for production super clean rare earth metal.

Claims (6)

  1. A kind of 1. method of high-purity La, Ce mischmetal of electrolytic preparation, which is characterized in that by weight percentage, La, Ce mixing In rare earth, ranging from the 60~70% of ranging from 30~35%, the Ce elements of La elements, this method includes the following steps:
    (1) it is electrolysed using electrolytic cell, is passed through direct current, control cathode-current density is 3~9A/cm2, anodic current density For 1~3A/cm2, slot pressure is 6~11V, is electrolysed, and electrolyte is the oxide rare earth and rare earth fluoride of mixing, is powered it Afterwards, pure La, Ce rare earth metal is precipitated in cathode deposition;
    (2) rare earth metal is come out of the stove using canister, surface is completely covered with electrolyte, and tapping temperature is 1000~1200 DEG C, canister preheats 200~400 DEG C, and rare earth stirs evenly when coming out of the stove;
    (3) after the electrolyte of rare earth metal surface covering is fully cured, be dipped in cooling circulating water, water temperature for 25~ 50 DEG C, after 1~3min of circulating water, rare earth metal is taken out in the complete cooled and solidified of rare earth metal, demoulding;
    (4) rare earth metal is put into fine shot-blasting machine and is polished, and polishing time is 10~20min, fully handles rare earth metal Surface oxide layer makes it expose metallic luster;
    (5) high pure rare earth metals after polishing are subjected to vacuum packaging processing, packed weight is 0.5~1.5 kilogram/block, is convenient for It is subsequently added into molten steel, is finally reached the purpose for preparing high-purity La, Ce mixing pure rare earth, the purity of rare earth reaches total oxygen content Less than 80ppm, complete to prepare.
  2. 2. the method for high-purity La, Ce mischmetal of electrolytic preparation described in accordance with the claim 1, which is characterized in that electrolyte is The cerium lanthanum oxide of mixing and lanthanum fluoride cerium, and lanthanum cerium weight ratio is 1 ︰ 2.
  3. 3. the method for high-purity La, Ce mischmetal of electrolytic preparation described in accordance with the claim 1, which is characterized in that canister To have the back taper inner wall of 2~10 ° of tapers, and surface electrolyte thickness is 1~3mm.
  4. 4. the method for high-purity La, Ce mischmetal of electrolytic preparation described in accordance with the claim 1, which is characterized in that shot-blasting machine into During row polishing, for the granularity of stainless steel pellet in 0.5~3mm, application pressure is 100~300MPa.
  5. 5. the method for high-purity La, Ce mischmetal of electrolytic preparation described in accordance with the claim 1, which is characterized in that after polishing Rare earth metal when carrying out Vacuum Package, using the vacuum packaging bag of 0.5~2mm, vacuum degree is 5~20Pa.
  6. 6. the method for high-purity La, Ce mischmetal of electrolytic preparation described in accordance with the claim 1, which is characterized in that prepare high-purity It after La, Ce mixing pure rare earth, is sampled, examines gas oxygen content.
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Citations (5)

* Cited by examiner, † Cited by third party
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
熔盐电脱氧法制备La0.5Ce0.5Ni5的研究;张庆军 等;《功能材料》;20100731;第41卷(第7期);第1257-1260页 *

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