CN103556023A - Lanthanum cerium-magnesium intermediate alloy and production method thereof - Google Patents
Lanthanum cerium-magnesium intermediate alloy and production method thereof Download PDFInfo
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- CN103556023A CN103556023A CN201310563389.6A CN201310563389A CN103556023A CN 103556023 A CN103556023 A CN 103556023A CN 201310563389 A CN201310563389 A CN 201310563389A CN 103556023 A CN103556023 A CN 103556023A
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Abstract
The invention discloses a lanthanum cerium-magnesium intermediate alloy and a production method thereof, relating to the technical field of preparation of a rare earth-magnesium intermediate alloy product. According to the production method, a coelectrodeposition method is adopted, a graphite crucible is used as an electrolytic tank and an anode, a molybdenum bar is used as a cathode, a magnesium oxide crucible is used as an alloy supporting device, an electrolyte is formed by mixing KCl, anhydrous MgCl2 and RECl3 together. By adopting the preparation method disclosed by the invention, the lanthanum cerium-magnesium intermediate alloy high in quality and low in cost can be produced through one step by adopting magnesium and rare earth compounds through the coelectrodeposition method. The process indicators of the whole production process are relatively high, wherein the average electric efficiency reaches 65-75% and more than 85% at the maximum, the rare earth direct yield is more than 85%, and the magnesium direct yield is more than 95%. The lanthanum cerium-magnesium intermediate alloy prepared by the invention is lowest in price, and resources can be continuously supplied to promote sustainable development of rare earth-magnesium alloys.
Description
Technical field
The present invention relates to the preparing technical field of a kind of rare-earth magnesium intermediate alloy product.
Background technology
Both at home and abroad generally acknowledged rare earth be promote magnesium alloy over-all properties the most effectively, the most potential alloy element, but many scientific and technical personnel worry too expensive can not afford of rare earth valency, also worry that can rare earth continue supply.
For many years, the bottleneck problem of Rare-earth Industry is that rare earth element production and marketing is uneven, that is: the praseodymium in light rare earths, neodymium are in short supply, price is high, approximately 250,000 yuan, metal per ton, and produce one ton of neodymium metal or praseodymium, just there are about 4 tons of lanthanum cerium residuums to produce, about 30,000 yuan of lanthanum cerium metal price per ton, causes lanthanum cerium to overstock in a large number, urgently Application and Development thus.The high-quality lanthanum cerium-magnesium of magnesium alloy market demand master alloy, existing market can be bought to obtain the foreign matter content higher (< 0.5%) such as Fe in lanthanum cerium metal, to mixing method gained master alloy foreign matter content, is not inconsistent requirement; And to the method for mixing, be first will make rare earth metal and MAGNESIUM METAL, then by the two consolute, production process material and energy expenditure are more.
Summary of the invention
The present invention seeks to the lanthanum cerium-magnesium master alloy that proposes a kind of low price, can promote magnesium-rare earth sustainable development.
Each composition and mass ratio in alloy of the present invention are respectively: La:40%; Ce:55%; Pr is less than 0.5%; Nd is less than 0.01%; Fe is less than 0.05%; Cu is less than 0.01%; Ni is less than 0.01%; Si is less than 0.02%; Other elements are magnesium.
The lanthanum cerium mixed chlorinated rare earth that the present invention uses is not containing expensive praseodymium and neodymium, and in lanthanum cerium-magnesium master alloy, Re total content is 95%, and in the alloy of output, the content of impurity F e, Cu, Ni and Si is low, and purity is high.Particularly lanthanum cerium-magnesium master alloy price of the present invention is the most cheap, and resource can continue supply, can promote magnesium-rare earth sustainable development.
Another object of the present invention is the production method that proposes above lanthanum cerium-magnesium master alloy.
Production method is: adopt coelectrodeposition method, take plumbago crucible as electrolyzer and anode, molybdenum bar is negative electrode, and magnesia crucible is alloy susceptor, by KCl, anhydrous MgCl
2and RECl
3mix and form ionogen, in ionogen, each constituent mass ratio is respectively KCl:40～80%, MgCl
2: 2～10%, ReCl
3: 10～58%, described RECl
3for the lanthanum cerium mixed chlorinated rare earth containing 1～2 crystal water; During deposition, anodic current density is 0.1～2A/cm
2, cathode current density is 1～10A/cm
2, voltage is 10～18V, and electric current is 1200～1800A, and electrolysis temperature is 750～950 ℃.
The present invention, with coelectrodeposition method, adopts magnesium and rare earth compound one step just can produce lanthanum cerium-magnesium master alloy that quality is high, cost is low.Coelectrodeposition ratio juris is that following reaction, negative electrode: RE occur on electrode
3++ 3e → RE, standard deposition potential is-3.37V, Mg
2++ 2e → Mg, standard deposition potential is-2.34V, anode: 2Cl
--2e → Cl
2.For 2 kinds of ion energy common-batteries are separated out, need to reduce Mg
2+ion(ic)activity, its current potential is moved to negative direction, correspondingly make RE
3+ion(ic)activity increase, its current potential is moved to positive dirction, thereby on negative electrode, makes the deposition potential of 2 kinds of ions equate, produce common-battery evolution reaction, produce rare-earth and Mg master alloy.It is raw material that the present invention utilizes the separation of mixed light rare earth raw material to remove remaining lanthanum cerium mixed chlorinated rare earth after expensive praseodymium and neodymium, can greatly reduce production costs.Whole production technique index is higher, and wherein average electrical effect reaches 65～75%, and high energy reaches more than 85%, straight yield of rare earth > 85%, magnesium direct yield > 95%.
In a word, the overstocked lanthanum cerium rare earth chloride raw material that the present invention has adopted the most cheaply, urgently utilized, has obtained coelectrodeposition and has produced lanthanum cerium-magnesium master alloy and manufacturing condition thereof, and in gained alloy, impurity F e content is low, and alloy Rare-Earth Content wide ranges is controlled; And production cost is not high, for researching and developing novel lanthanum cerium-magnesium alloy, cheap applicable lanthanum cerium-magnesium master alloy product innovation and production technique thereof are provided, again for a large amount of overstocked lanthanum cerium mischmetals provide a large user-magnesium-rare earth alloy, contribute to alleviate the uneven contradiction of rare earth element production and marketing, promote that Rare-earth Industry is steady, Sustainable development.
In described ionogen, each constituent mass ratio is respectively KCl:55～65%, MgCl
2: 2～7%, ReCl
3: 28～43%.ReCl
3concentration in fused salt is the very important factor that affects current efficiency, ReCl
3concentration when too high, fusant thickness too in molten bath, poor fluidity, fused salt volatilization is also very large; When concentration is too low, electricity effect is also very low, selects ReCl
3concentration is 28～43% to be an applicable concentration electrolysis, has effectively improved current efficiency.
Further, the present invention's anodic current density when deposition is 0.6～0.9A/cm
2.
Further, the present invention's cathode current density when deposition is 3～6A/cm
2.In electrolytic process, the speed of separating out of rare earth metal depends primarily on cathode current density.When cathode current density is large, cathodic metal surface easily forms containing high rare earth and props up shape thing, and this shape thing increases with fused salt secondary action, and easy crust, and the rare earth metal that electrolysis goes out is difficult for and cathodic metal alloying, makes current efficiency reduction.When cathode current density is too small, the speed that metal is separated out is very slow, metal secondary is dissolved and increase, and also can make current efficiency reduce.Therefore, in electrolytic process, selecting suitable current density is to improve the principal element of electricity effect, and getting cathode current density is 3～6A/cm
2time, current efficiency is the highest.
Embodiment
Embodiment 1:
Take respectively the anhydrous MgCl of 65g KCl, 7g
2with the lanthanum cerium mixed chlorinated rare earth of 28g containing 1～2 crystal water, after mixing, form electrolyte system.
Take plumbago crucible as electrolyzer and anode, and molybdenum bar is negative electrode, and magnesia crucible is alloy susceptor.
Adopt coelectrodeposition method, the anodic current density of controlling electrolytic process is 0.6～0.7A/cm
2, cathode current density is 3～4A/cm
2, voltage is 10～12V, and electric current is 1200～1400A, and temperature is 750～800 ℃, and electrolysis obtains RE content in alloy susceptor after 2 hours be lanthanum cerium-magnesium master alloy 2.5kg of 30～40%.
La:40% in alloy by analysis; Ce:55%; Pr is less than 0.5%; Nd is less than 0.01%.Foreign matter content is low, and wherein Fe% < 0.05%, Cu < 0.01%, Ni < 0.01%, Si < 0.02%; All the other are magnesium.
Electricity effect reaches 72～75%, and straight yield of rare earth is 85%, and magnesium direct yield is 98%.
Embodiment 2:
Take respectively the anhydrous MgCl of 66g KCl, 5g
2with the lanthanum cerium mixed chlorinated rare earth of 35g containing 1～2 crystal water, after mixing, form electrolyte system.
Adopt coelectrodeposition method, the anodic current density of controlling electrolytic process is 0.7～0.8A/cm
2, cathode current density is 4～5A/cm
2, voltage is 12～15V, and electric current is 1400～1600A, and temperature is 800～850 ℃, and electrolysis obtains RE content in alloy susceptor after 2 hours be lanthanum cerium-magnesium master alloy 3kg of 40～60%.
La:40% in alloy by analysis; Ce:55%; Pr is less than 0.5%; Nd is less than 0.01%.Foreign matter content is low, and wherein Fe% < 0.05%, Cu < 0.01%, Ni < 0.01%, Si < 0.02%; All the other are magnesium.
Electricity effect reaches 70～72%, and straight yield of rare earth is 90%, and magnesium direct yield is 95%.
Embodiment 3:
Take respectively the anhydrous MgCl of 55g KCl, 2g
2with the lanthanum cerium mixed chlorinated rare earth of 43g containing 1～2 crystal water, after mixing, form electrolyte system.
Adopt coelectrodeposition method, the anodic current density of controlling electrolytic process is 0.8～0.9A/cm
2, cathode current density is 5～6A/cm
2, voltage is 15～18V, and electric current is 1600～1800A, and temperature is 850～950 ℃, and electrolysis obtains RE content in alloy susceptor after 2 hours be lanthanum cerium-magnesium master alloy 3.5kg of 60～90%.
La:40% in alloy by analysis; Ce:55%; Pr is less than 0.5%; Nd is less than 0.01%.In alloy, foreign matter content is low, and wherein Fe% < 0.05%, Cu < 0.01%, Ni < 0.01%, Si < 0.02%; All the other are magnesium.
Electricity effect reaches 65～70%, and straight yield of rare earth is 92%, and magnesium direct yield is 95%.
From the result of above three embodiment, in the alloy that the lanthanum cerium mixed chlorinated rare earth that the present invention uses (not containing expensive praseodymium and neodymium) is prepared, the content of impurity F e, Cu, Ni and Si is low, and purity is high.Particularly lanthanum cerium-magnesium master alloy price of the present invention is the most cheap, and resource can continue supply, can promote magnesium-rare earth sustainable development.
Claims (5)
1. lanthanum cerium-magnesium master alloy, is characterized in that each composition and the mass ratio in alloy is respectively: La:40%; Ce:55%; Pr is less than 0.5%; Nd is less than 0.01%; Fe is less than 0.05%; Cu is less than 0.01%; Ni is less than 0.01%; Si is less than 0.02%; Other elements are magnesium.
2. a production method for lanthanum cerium-magnesium master alloy as claimed in claim 1, is characterized in that adopting coelectrodeposition method, take plumbago crucible as electrolyzer and anode, and molybdenum bar is negative electrode, and magnesia crucible is alloy susceptor, by KCl, anhydrous MgCl
2and RECl
3mix and form ionogen, in ionogen, each constituent mass ratio is respectively KCl:40～80%, MgCl
2: 2～10%, ReCl
3: 10～58%, described RECl
3for the lanthanum cerium mixed chlorinated rare earth containing 1～2 crystal water; During deposition, anodic current density is 0.1～2A/cm
2, cathode current density is 1～10A/cm
2, voltage is 10～18V, and electric current is 1200～1800A, and electrolysis temperature is 750～950 ℃.
3. the production method of lanthanum cerium-magnesium master alloy according to claim 2, is characterized in that in described ionogen, each constituent mass ratio is respectively KCl:55～65%, MgCl
2: 2～7%, ReCl
3: 28～43%.
4. according to the production method of lanthanum cerium-magnesium master alloy described in claim 2 or 3, while it is characterized in that depositing, anodic current density is 0.6～0.9A/cm
2.
5. according to the production method of lanthanum cerium-magnesium master alloy described in claim 2 or 3, while it is characterized in that depositing, cathode current density is 3～6A/cm
2.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757169A (en) * | 2016-12-10 | 2017-05-31 | 包头稀土研究院 | A kind of hydrogen bearing alloy rare earth intermediate alloy and preparation method thereof |
| CN107630233A (en) * | 2017-10-20 | 2018-01-26 | 安吉绿金金属材料有限公司 | A kind of method using rare earth-iron-boron Electrowinning rare earth metal |
| CN109440150A (en) * | 2018-12-10 | 2019-03-08 | 沈阳大学 | A kind of method that room temperature electro-deposition prepares magnalium lanthanum alloy film |
| CN111440978A (en) * | 2020-03-24 | 2020-07-24 | 龙南龙钇重稀土科技股份有限公司 | Lanthanum-cerium-yttrium-magnesium intermediate alloy and preparation method thereof |
| CN113430575A (en) * | 2021-07-07 | 2021-09-24 | 南昌大学 | Preparation method for accurately controlling proportion of rare earth magnesium intermediate alloy |
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| CN1772963A (en) * | 2005-10-21 | 2006-05-17 | 中国科学院长春应用化学研究所 | Common-battery deposition producing method for Mg La Pr Ce intermediate alloy |
| CN102424987A (en) * | 2011-12-19 | 2012-04-25 | 中国科学院长春应用化学研究所 | Preparation method for rare earth-magnesium alloy |
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| CN1772963A (en) * | 2005-10-21 | 2006-05-17 | 中国科学院长春应用化学研究所 | Common-battery deposition producing method for Mg La Pr Ce intermediate alloy |
| CN102424987A (en) * | 2011-12-19 | 2012-04-25 | 中国科学院长春应用化学研究所 | Preparation method for rare earth-magnesium alloy |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757169A (en) * | 2016-12-10 | 2017-05-31 | 包头稀土研究院 | A kind of hydrogen bearing alloy rare earth intermediate alloy and preparation method thereof |
| CN113122884A (en) * | 2016-12-10 | 2021-07-16 | 包头稀土研究院 | Preparation method of rare earth intermediate alloy for hydrogen storage alloy |
| CN113122884B (en) * | 2016-12-10 | 2023-02-17 | 包头稀土研究院 | Preparation method of rare earth intermediate alloy for hydrogen storage alloy |
| CN107630233A (en) * | 2017-10-20 | 2018-01-26 | 安吉绿金金属材料有限公司 | A kind of method using rare earth-iron-boron Electrowinning rare earth metal |
| CN109440150A (en) * | 2018-12-10 | 2019-03-08 | 沈阳大学 | A kind of method that room temperature electro-deposition prepares magnalium lanthanum alloy film |
| CN109440150B (en) * | 2018-12-10 | 2021-01-29 | 沈阳大学 | Method for preparing aluminum-magnesium-lanthanum alloy film by room temperature electrodeposition |
| CN111440978A (en) * | 2020-03-24 | 2020-07-24 | 龙南龙钇重稀土科技股份有限公司 | Lanthanum-cerium-yttrium-magnesium intermediate alloy and preparation method thereof |
| WO2021189511A1 (en) * | 2020-03-24 | 2021-09-30 | 龙南龙钇重稀土科技股份有限公司 | Lanthanum-cerium-yttrium-magnesium intermediate alloy and preparation method therefor |
| CN113430575A (en) * | 2021-07-07 | 2021-09-24 | 南昌大学 | Preparation method for accurately controlling proportion of rare earth magnesium intermediate alloy |
| CN113430575B (en) * | 2021-07-07 | 2022-11-18 | 南昌大学 | Preparation method for accurately controlling proportion of rare earth magnesium intermediate alloy |
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Inventor after: Meng Jian Inventor after: Wang Leigang Inventor after: Liu Xiaojuan Inventor after: Lv Henglin Inventor after: Niu Xiaodong Inventor after: Lu Huayi Inventor after: Hu Dongpo Inventor before: Meng Jian Inventor before: Yin Fei Inventor before: Liu Xiaojuan Inventor before: Lv Henglin Inventor before: Niu Xiaodong Inventor before: Lu Huayi Inventor before: Hu Dongpo |
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Free format text: CORRECT: INVENTOR; FROM: MENG JIAN YIN FEI LIU XIAOJUAN LV HENGLIN NIU XIAODONG LU HUAYI HU DONGPO TO: MENG JIAN WANG LEIGANG LIU XIAOJUAN LV HENGLIN NIU XIAODONG LU HUAYI HU DONGPO |
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Application publication date: 20140205 |