CN105908218A - High-purity rare earth metal and preparation method and application thereof - Google Patents
High-purity rare earth metal and preparation method and application thereof Download PDFInfo
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- CN105908218A CN105908218A CN201610265575.5A CN201610265575A CN105908218A CN 105908218 A CN105908218 A CN 105908218A CN 201610265575 A CN201610265575 A CN 201610265575A CN 105908218 A CN105908218 A CN 105908218A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
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Abstract
The invention relates to the field of manufacturing of high-quality metal materials, in particular to high-purity rare earth metal and a preparation method and application thereof. The high-purity rare earth metal is characterized in that the total content of rare earth metal is higher than 99.5%, and the oxygen content O is not higher than 0.02% (by weight percentage). The high-purity rare earth metal is obtained by electrolysis of oxide rare earth or rare earth oxide villiaumite and solidified under airtight/protective atmosphere. The main rare earth element of the high-purity rare earth metal is lanthanum and cerium. The high-purity rare earth metal is mainly applied to, but not limited to, the fields of manufacturing of high-quality steel for continuous casting or die casting, high-quality structural steel for equipment manufacturing, special steel, aluminum alloy, magnesium alloy and other metal materials. Additives are provided for equipment manufacturing and high-quality steel materials, molten steel is purified, grains are refined, inclusions are modified, the performance of the steel materials is stably improved, and the negative effects of thick inclusions, water gap blockage, performance deterioration and the like caused by rare earth additives in the steel materials are avoided.
Description
Technical field
The present invention relates to high-test metal material and manufacture field, specifically a kind of high pure rare earth metals and preparation method thereof
And purposes.
Background technology
China starts from the eighties of last century later stage fifties to rare earth element in the research of application of RE in the steel.About rare earth element at steel
The research of middle application, resonable practice of touching upon achieves certain breakthrough, and the application aspect at rare earth steel achieves a lot of achievement.
Substantial amounts of research shows with knowhow, and rare earth element has important impact to the microstructure and mechanical property of steel and alloy.
Such as, rare earth has deep deoxidation, the effect of deep desulfurization, and rare earth can go bad and refine field trash, and rare earth can suppress crystal grain long
Greatly, thus improve the toughness plasticity of metal material, fatigue behaviour, wearability, corrosion resistance and thermostability etc..
But rare earth in steel application maximum has a problem in that what rare earth element can not be continual and steady plays a role, and also
There is many negative effects.Such as, the seventies and eighties in last century, the application process of a large amount of rare earth steels creates Large Inclusions
Assemble, cause the unstable properties of steel even to deteriorate；Production process middle rare earth steel reacts with refractory material, causes nozzle clogging,
Impact produces direct motion, even results in serious production accident etc..
Trace it to its cause, be that current domestic rare earth metal performs standard (such as GB/T 4153-2008 etc.) and produces rare earth metal
The degree of purity of product is less demanding, the most wide in range, it is impossible to meet the equipment manufacturing metal material quality to rare earth metal additive
Requirement, thus cause the problems such as unstable properties, negative effect highlight.Therefore, a kind of ultra-pure cleanliness rare earth metal is invented also
Ensure that its preparation technology's is reliable and stable most important.
Specifically, the national standard of current rare earth metal product mainly emphasizes the impurity elements such as Mg, Zn, Pb, Fe, C
Content, and these trace element are little in the hazardness of steel, host element in the even steel having；Otherwise, to metal material shadow
Ring bigger oxygen element not specify in current rare earth metal standard and commercially produced product, thus cause, rare earth metal
The degree of purity of product focuses on the control of the impurity elements such as Mg, Fe, C the most unilaterally, and have ignored Control for Oxygen Content.Further, at present
Commercialization rare-earth products be entirely open with air contact in the environment of carry out being electrolysed and solidify, therefore in rare earth metal
Oxygen content the highest often as high as more than 0.1%, oxygen is general and rare earth chemical combination formation rare earth oxide, this part rare earth oxygen
Compound, when adding in steel, presented in field trash, thus will deteriorate the performance of steel, especially wearability, heat-resisting
Property, corrosion resistance and low-temperature flexibility.Therefore, for the angle of rare earth metal product, the most more effectively reduce oxygen therein and contain
Amount is most important to the quality promoting rare earth metal product.
For preparation technology angle, existing rare earth metal preparation technology is to make with rare earth oxide or oxide villiaumite
For raw material, prepare liquid rare earth metal by the method for electrolysis, and then rare earth metal is frozen into bulk and moves towards commercialization.
In rare earth metal process of setting from liquid to solid-state, generally use open cast, the technique of unprotect solidification, whole process
All and air contact, thus causing rare earth metal oxidation serious, oxygen content is higher.Therefore, exploitation protectiveness rare earth metal solidification
Preparation technology is to ensure that basis and the guarantee obtaining high-purity rare earth metal product.
Summary of the invention
It is an object of the invention to provide a kind of pure rare earth metal of superelevation and its production and use, for equipment manufacturing
There is provided additive with high-quality ferrous materials, purify molten steel, crystal grain thinning, go bad and be mingled with, stably promote the performance of ferrous materials, keep away
Exempt from rare earth addition in ferrous materials, to produce that field trash is thick, the blocking mouth of a river, deteriorate the negative effect such as performance.
Based on this purpose, the technical scheme is that
A kind of high pure rare earth metals, by weight percentage, rare earth metal total content is more than 99.5%, oxygen content O≤
0.02%.
Described high pure rare earth metals, rare earth metal is the mixture of lanthanum, cerium or lanthanum and cerium.
In the mixture of described high pure rare earth metals, lanthanum and cerium, the mass ratio of lanthanum and cerium is 1:(1～5).
The preparation method of described high pure rare earth metals, comprises the steps of:
1) electrolysis step: use rare earth oxide or rare earth oxide villiaumite as raw material, utilize electrolytic method by dilute
Earth metal is reduced into molten condition；
2) coagulation step: by the rare earth metal of the temperature electrolyzing fused state more than 800 DEG C, in electrolyte guard mode
Descend or under inert gas shielding state, in hermetic container or in Dewar vessel, solidify.
The preparation method of described high pure rare earth metals, rare earth metal solidifies in the environment of isolation air.
The preparation method of described high pure rare earth metals, when rare earth metal degree of purity needs to promote further, uses true
Empty induction melting furnace carries out remelting and purifies further rare earth metal.
The preparation method of described high pure rare earth metals, rare earth metal is the mixture of lanthanum, cerium or lanthanum and cerium.
The purposes of described high pure rare earth metals, this rare earth metal is used as continuous casting or the molding structural steel of high-quality, alloy
The additive of steel, special steel, aluminium alloy or magnesium alloy.
The design philosophy of the present invention is:
First, the present invention proposes a kind of industrial attainable high-purity rare earth metal product, and it is typically characterised by: rare earth
Total metal content be more than 99.5%, oxygen content be less than 0.02% (percentage by weight), rare earth metal be mainly lanthanum, cerium and lanthanum and
The mixture of cerium.This is to ensure that rare earth metal is applied as in additive ferrous materials and almag, is allowed to give full play to
Benefit effect, it is to avoid the premise of its side effect and basis.Secondly, The present invention gives a kind of preparation technology side of high pure rare earth metals
Method, i.e. use rare earth oxide or rare earth oxide villiaumite as raw material, by the method for electrolysis, metal is reduced to simple substance
Molten state.Then, rare earth metal is made to solidify in the environment of isolation air, it is to avoid process of setting to produce oxidation, causes oxygen to contain
Amount increases.The methods of isolation air use the electrolyte such as LiF, KCl to carry out covering protection, use inert gas shielding or incite somebody to action
Molten rare earth metal is placed in airtight or Dewar vessel and solidifies.When rare earth degree of purity needs to promote further, permissible
Select vacuum induction melting furnace that rare earth metal carries out remelting and the degree of depth purifies.The low oxygen content high-purity rare earth gold of final preparation
Belong to be used as continuous casting or molding high-quality structural steel, steel alloy, special steel (have special chemical composition, use special technique
Produce, possess special tissue and performance, disclosure satisfy that the steel class of special requirement), and the metal material such as aluminium alloy, magnesium alloy
Additive.
Advantages of the present invention and providing the benefit that:
1, preparing with conventionally employed electrolytic method compared with the product quality requirement of rare earth metal, the present invention more emphasizes rare earth
Degree of purity, on the basis of GB/T 4153-2008 standard middle rare earth metal first water requires, controls oxygen content further.
2, in process of preparing of the present invention, it is to avoid the rare earth metal casting method that tradition is extensive, it is to avoid liquid rare earth gold
Belong to and air contact, solidify in airtight or protective atmosphere, prevent rare earth metal impurity element from increasing, and avoid oxygen content
Increase.If desired, in vacuum induction melting furnace, high pure rare earth metals is carried out degree of depth purification.
3, the lifting further of rare earth degree of purity of the present invention can improve the credit rating of rare earth application link.Such as, originally
High-purity rare-earth in invention is when battery material is applied, it is possible to improve battery quality stability further；At gold such as aluminum, magnesium, steel
When genus material is applied, it is possible to reduce the generation of bulk non-metallic inclusion, give full play to the performance boost effect of rare earth.
4, when high-purity rare-earth of the present invention is applied to smelting iron and steel with casting process, can be by effectively preventing molten steel with fire-resistant
Material, air reaction and avoid block the mouth of a river, it is ensured that produce stable smooth operation.
In a word, the present invention proposes the high-purity rare earth metal product higher than Standard, and electrolyzing fused by controlling
The curing condition of state rare earth metal and environment realize high pure rare earth metals to be prepared.This kind of high-purity rare-earth as additive application in gold
Belong to material when preparing, can avoid producing that field trash is thick, material property fluctuation, production process blocks the series such as the mouth of a river ask
Topic, it is ensured that the stable lifting of metal material performance.
Accompanying drawing explanation
The high pure rare earth metals that Fig. 1 (a)-Fig. 1 (b) is prepared for using the present invention.Wherein, Fig. 1 (b) is the amplification of Fig. 1 (a)
Figure.
Fig. 2 (a)-Fig. 2 (b) is rare earth metal commercially produced product.Wherein, Fig. 2 (b) is the enlarged drawing of Fig. 2 (a).
Detailed description of the invention
In specific implementation process, the present invention provides a kind of high-purity rare earth metal, provides one to and guiding property and prepares
Process, particular content is as follows:
1, use rare earth oxide or rare earth oxide villiaumite (rare earth oxyfluoride) as raw material.
2, rare earth oxide or rare earth oxide villiaumite are electrolysed in specialty electrolysis installation, separate prepared liquid dilute
Earth metal.
3, liquid rare earth metal is poured under electrolyte or inert gas shielding casting mold, and makes liquid rare earth metal
(specifically cover with electrolyte such as LiF, the KCl in electrolysis bath) under electrolyte guard mode, or inert gas shielding
Under state, or in hermetic container, or solidify in Dewar vessel, create the solidifying of pollution-free, non-oxidation for rare earth metal
Gu environment.For promoting the cleanliness factor of rare earth metal further, the high-purity rare-earth solidified remelting in vaccum sensitive stove can be entered
Row degree of depth purification processes.
4, remove surface scale and carry out ball blast, blasting treatment after high pure rare earth metals solidification, detection encapsulation.
5, high pure rare earth metals can use as additive prepared by the metal materials such as aluminum, magnesium, iron and steel.
In order to make technical scheme and advantage clearer, carry out in detail below in conjunction with specific embodiments and the drawings
Thin description.
Prepared by embodiment 1 high-purity rare-earth
The present embodiment uses rare earth oxide (lanthana and cerium oxide) to be raw material, carries out electricity in graphitic cell
Solve, decomposition voltage 120V, electric current 800A, electrolysis time 2h, rare earth metal is reduced into 900 DEG C of molten conditions.Electrolytic process is tied
Shu Hou, molten state rare earth metal solidifies under villaumite (such as: KCl) covers, the rare earth metal obtained such as Fig. 1 (a)-Fig. 1 (b)
Shown in.
Through analyzing detection, its rare earth element content and major impurity constituent content are as shown in table 1.
High pure rare earth metals main component (surplus is other impurity elements) prepared by table 1 embodiment of the present invention
| Element | La | Ce | Zn | Pb | O |
| Content (wt%) | 33.23 | 66.69 | 0.011 | 0.0095 | 0.0086 |
Comparative example 1 GB contrasts
High pure rare earth metals in the present invention and first water grade (the GB/T 4153-of existing product implementing quality standards
2008 noriums or XB/T 216-1995 battery grade mischmetal) to compare, degree of purity improves further, specifically
Comparative run is as shown in table 2.
Table 2 high pure rare earth metals of the present invention contrasts with GB product quality indicator
Comparative example 2 high pure rare earth product contrasts
Shown in rare earth metal commercially produced product such as Fig. 2 (a)-Fig. 2 (b), the high-purity rare-earth that table 3 is prepared for the embodiment of the present invention
Metal ingredient and the component analysis testing result of existing commercial rare earth metal product, as can be seen from the table, the present embodiment produces
Product degree of purity is far above existing commercial product quality level.
Table 3 high pure rare earth metals of the present invention contrasts (surplus is other impurity elements) with commercialization rare earth metal component
Prepared by embodiment 2 high-purity rare-earth
The present embodiment uses rare earth oxide villiaumite (fluorine lanthana and fluorine cerium oxide) to be raw material, in graphitic cell
It is electrolysed, decomposition voltage 150V, electric current 850A, electrolysis time 3h, rare earth metal is reduced into 1000 DEG C of molten conditions.Electrolysis
After process terminates, molten state rare earth metal solidifies under villiaumite (such as: LiF) covers.
Through analyzing detection, its rare earth element content and major impurity constituent content are as shown in table 4.
High pure rare earth metals main component (surplus is other impurity elements) prepared by table 4 embodiment of the present invention
As can be seen from the table, the present embodiment product degree of purity is far above existing commercial product quality level.
Claims (8)
1. a high pure rare earth metals, it is characterised in that: by weight percentage, rare earth metal total content is more than 99.5%, oxygen
Content O≤0.02%.
2. according to the high pure rare earth metals described in claim 1, it is characterised in that: rare earth metal is the mixed of lanthanum, cerium or lanthanum and cerium
Compound.
3. according to the high pure rare earth metals described in claim 2, it is characterised in that: in the mixture of lanthanum and cerium, lanthanum and the matter of cerium
Amount ratio is 1:(1～5).
4. the preparation method of the high pure rare earth metals described in a claim 1, it is characterised in that comprise the steps of:
1) electrolysis step: use rare earth oxide or rare earth oxide villiaumite as raw material, utilize electrolytic method by rare earth gold
Belong to and be reduced into molten condition；
2) coagulation step: by the rare earth metal of the temperature electrolyzing fused state more than 800 DEG C, under electrolyte guard mode or
Under inert gas shielding state, in hermetic container or in Dewar vessel, solidify.
5. according to the preparation method of the high pure rare earth metals described in claim 4, it is characterised in that: rare earth metal is at isolation air
Environment in solidify.
6. according to the preparation method of the high pure rare earth metals described in claim 4, it is characterised in that: when rare earth metal degree of purity needs
When promoting further, vacuum induction melting furnace is used rare earth metal to carry out remelting and purifies further.
7. according to the preparation method of the high pure rare earth metals described in claim 4, it is characterised in that: rare earth metal be lanthanum, cerium or
Lanthanum and the mixture of cerium.
8. the purposes of the high pure rare earth metals described in a claim 1, it is characterised in that: this rare earth metal be used as continuous casting or
The molding structural steel of high-quality, steel alloy, special steel, aluminium alloy or the additive of magnesium alloy.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106609314A (en) * | 2017-01-24 | 2017-05-03 | 中国科学院金属研究所 | Method for preparing high-quality steel H13 |
| CN106609313A (en) * | 2017-01-24 | 2017-05-03 | 中国科学院金属研究所 | High-purity rare earth steel treatment method |
| CN106636880A (en) * | 2016-12-13 | 2017-05-10 | 中国科学院金属研究所 | Extra-low oxygen rare earth alloy and use |
| CN109371429A (en) * | 2018-11-30 | 2019-02-22 | 乐山有研稀土新材料有限公司 | A method of improving rare earth metal product quality |
| CN111621815A (en) * | 2020-05-27 | 2020-09-04 | 赣州市华新金属材料有限公司 | Short-process method for preparing low-oxygen high-purity rare earth metal |
| CN113088791A (en) * | 2021-03-24 | 2021-07-09 | 钢铁研究总院 | Method for preparing rare earth steel by reducing rare earth oxide step by step in refining process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789991A (en) * | 2015-05-13 | 2015-07-22 | 江西理工大学 | Method and device for preparing high-purity rare earth metal through electrolytic refining and in-situ directional solidification |
-
2016
- 2016-04-26 CN CN201610265575.5A patent/CN105908218B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789991A (en) * | 2015-05-13 | 2015-07-22 | 江西理工大学 | Method and device for preparing high-purity rare earth metal through electrolytic refining and in-situ directional solidification |
Non-Patent Citations (2)
| Title |
|---|
| TORU H.OKABE ET AL.: "Thermodynamic Properties of Ln-O(Ln=La,Pr,Nd)Solid Solutions and Their Deoxidation by Molten Salt Electrolysis", 《SHIGEN-TO-SOZAI》 * |
| 武淑珍等: "高纯稀土金属制备工艺的研究现状", 《稀有金属与硬质合金》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106636880A (en) * | 2016-12-13 | 2017-05-10 | 中国科学院金属研究所 | Extra-low oxygen rare earth alloy and use |
| CN106609314A (en) * | 2017-01-24 | 2017-05-03 | 中国科学院金属研究所 | Method for preparing high-quality steel H13 |
| CN106609313A (en) * | 2017-01-24 | 2017-05-03 | 中国科学院金属研究所 | High-purity rare earth steel treatment method |
| CN106609313B (en) * | 2017-01-24 | 2019-03-26 | 中国科学院金属研究所 | A kind of high-purity rare earth steel processing method |
| CN109371429A (en) * | 2018-11-30 | 2019-02-22 | 乐山有研稀土新材料有限公司 | A method of improving rare earth metal product quality |
| CN109371429B (en) * | 2018-11-30 | 2020-05-19 | 乐山有研稀土新材料有限公司 | Method for improving quality of rare earth metal product |
| CN111621815A (en) * | 2020-05-27 | 2020-09-04 | 赣州市华新金属材料有限公司 | Short-process method for preparing low-oxygen high-purity rare earth metal |
| CN111621815B (en) * | 2020-05-27 | 2022-05-13 | 赣州市华新金属材料有限公司 | Short-process method for preparing low-oxygen high-purity rare earth metal |
| CN113088791A (en) * | 2021-03-24 | 2021-07-09 | 钢铁研究总院 | Method for preparing rare earth steel by reducing rare earth oxide step by step in refining process |
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