CN1091158C - La, Pr and Ce mixed rare-earth metal and its making technology - Google Patents
La, Pr and Ce mixed rare-earth metal and its making technology Download PDFInfo
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- CN1091158C CN1091158C CN99115002A CN99115002A CN1091158C CN 1091158 C CN1091158 C CN 1091158C CN 99115002 A CN99115002 A CN 99115002A CN 99115002 A CN99115002 A CN 99115002A CN 1091158 C CN1091158 C CN 1091158C
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- rare earth
- cerium
- reo
- praseodymium
- lanthanum
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Abstract
The present invention provides a new lanthanum, praseodymium and cerium mixed rare earth metal and production technology thereof, wherein the new lanthanum, praseodymium and cerium mixed rare earth metal comprises 78 to 86% of lanthanum, 4 to 12% of praseodymium, 5 to 15% of cerium and less than 1% of neodymium; the total amount of the rare earth metal is from 99 to 99.5%; and the total amount of impurities is from 0.5 to 1%. The production technology adopts a salt melting electrolysis method and electrolyte is RECI3-KCl mixed melting salts, wherein the raw materials RECI3 are the residual hydrous lanthanum, praseodymium and cerium mixed rare earth chloride after neodymium and cerium are extracted and Sm, Eu and Gd are separated; the electrolysed products are prepared into the finished product of the new lanthanum, praseodymium and cerium mixed rare earth metal by ingot casting and packaging after being taken out of a furnace, and slag and chlorine gas are recovered. The production technology has the advantages of low cost of the raw materials and high economic and technical indexes, and the products are widely used for new materials in the fields of metallurgy, hydrogen storage alloys, etc.
Description
The present invention relates to the rare earth metal field, particularly relate to a kind of New Rare Earth Mixture and production technique thereof.
Rare earth metal is divided into two big classes, first norium, and it two is single rare earth metals.Production China of norium almost all adopts the rare earth chloride electrolytic process, common norium is generally made raw material with the rare earth chloride of raw ore ree distribution pattern, adopt fused salt electrolysis process, ionogen consists of KCI-RECI3, does anode with graphite, molybdenum bar or tungsten bar are done negative electrode, electrolyzer for 1000A adopts plumbago crucible double as anode, and porcelain crucible is made the metal susceptor, and electrolysis temperature is generally 870～920 ℃, current efficiency is 40～50%, and direct yield is 80～85%.And along with the development of rare earth metal Application Areas, the consumption city field boundary of Neodymium trioxide and cerium oxide constantly enlarges, the demand sharp increase, their price is more much higher than common mishmetal, the leading product of rare earth oxide have been become, and carry neodymium, carry a large amount of lpc rare-earth mixtures remaining behind the cerium and become neodymium, the cerium by product in producing, this " tankage " of bulk deposition have become the restraining factors that have a strong impact on the balanced growth of rare earth industry.
The object of the present invention is to provide a kind of neodymium, cerium by product in producing that utilizes, remaining a large amount of lanthanum praseodymium cerium mixed chlorinated rare earths of promptly carry neodymium, carrying behind the cerium are raw material, New Rare Earth Mixture that production performance is good and production technique thereof.
% meter by weight in the New Rare Earth Mixture of the present invention, the total amount of norium is 99～99.5, and total impurities is 0.5～1, and its ree distribution pattern is:
Lanthanum 78～86%
Praseodymium 4～12%
Cerium 5～15%
Neodymium 0.01＜1% wherein, impurity component comprises iron, silicon, carbon, sulphur and phosphorus.
The production technique of New Rare Earth Mixture of the present invention adopts fused salt electrolysis process, electrolytic solution is the REC13-KCl fused salt mixt, wherein, raw material REC13 carries neodymium, carries cerium, divides the moisture lanthanum praseodymium cerium mixed chlorinated rare earth that removes behind Sm, Eu, the Gd, moisture content is less than 28%, and chemical ingredients % by weight is expressed as follows:
REO ≥46
NH
4CI 3～5
SO
4 2- ＜0.03
PO
4 3- ＜0.01
Fe
2O
3＜0.07REO middle-weight rare earths partition is:
La
2O
3/REO 78～86
CeO
2/REO 5～15
Pr
6O
11/REO 9～12
Nd
2O
3/REO ＜1
Sm
2O
3Its production process of/REO＜0.03 is, because of the easy moisture absorption of rare earth chloride, easy splash and slag making when electrolysis is reinforced, raw material should be crushed to granularity less than 3mm in humidity under less than 45% environment, and under this humidity environment condition, preserve, fruit carries out electrolysis with traditional fused salt electrolysis mode then, contain electrolytic solution double as anode with plumbago crucible, tungsten bar is made negative electrode, electrolytic solution is RECI3: KCI=60～68: 32～40, control promptly that REO concentration is 21～25% in the electrolytic solution, adjust that electrolysis voltage is 10～18V in the electrolytic process, electric current 1000～1100A, 900～940 ℃ of electrolysis temperatures, and clear up negative electrode at any time, and under the effect of direct current field boundary, RE
3+Get electron reduction at negative electrode and become rare earth metal, come together in the porcelain dish of negative electrode lower end, take out porcelain dish after the electrolysis, with the electrolytic production ingot casting, pack the finished product New Rare Earth Mixture, slag and chlorine adopt traditional way to reclaim.The general single groove of many groups that adopts of electrolysis is connected.The economic and technical norms of this production technique are as shown in table 1.
The advantage of New Rare Earth Mixture of the present invention is that its reductibility is better than common norium the hydrogen in iron and steel and the non-ferrous metal is removed ability greater than common mishmetal, and to compare aluminum silicon alloy modifying-refining ability better with common norium.Main additive as iron and steel and non-ferrous metal is produced rare earth alloy, and produces hydrogen-storage alloy, and as nickel-hydrogen battery negative pole material, its electrochemistry capacitance is than the alloy height made from common norium; The advantage of New Rare Earth Mixture production technique of the present invention is to carry cerium because raw material adopts, carry " tankage " behind the neodymium, its price descends significantly, comparing price with common mixed chlorinated rare earth descends more than 30%, simultaneously because this production technique improves more than 15% than the current efficiency of common norium, the highest at present organic efficiency of ratio improves more than 2%, unit consumption reduces by 0.1～0.3 ton of rare earth chloride crystallization material/metal per ton, so product price is also low, adopting this kind raw material mainly is to have solved to carry cerium, carry by product bulk deposition behind the neodymium and press for the big problem of solution, help the balance sustainable development of rare earth industry, excellent property and cheap New Rare Earth Mixture are provided simultaneously, for creating the more superior novel rare-earth non-ferrous metal of performance, rare earth is handled type materials such as steel and rare earth hydrogen-storage alloy basic substance is provided.
Describe the utility model embodiment below in detail.
Embodiment 1: adopt single groove electrolysis, with Repone K and rare earth chloride is electrolytic solution, consume 7.7 kilograms of lanthanum praseodymium cerium mixed chlorinated rare earth crystallizations, REO concentration is 25% in the electrolytic solution, electrolysis voltage is 16～18V in the adjustment electrolytic process, electric current 1100A, 920～940 ℃ of electrolysis temperatures, electrolysis 2 hours gets 2.8 kilograms of New Rare Earth Mixture products.Current efficiency 73.5%, yield 93%.Mishmetal total amount and ree distribution pattern are as shown in table 2.
Embodiment 2: adopt the series connection of 3 grooves, totally 2 groups are carried out electrolysis, are electrolytic solution with Repone K and rare earth chloride, consume 19.7 tons of lanthanum praseodymium cerium mixed chlorinated rare earth crystallizations, REO concentration is 21～25% in the electrolytic solution, and electrolysis voltage is 16～18V in the adjustment electrolytic process, electric current 1030～1070A, 900～940 ℃ of electrolysis temperatures, electrolysis 40 days totally 960 hours, gets 7.063 tons of New Rare Earth Mixture products, current efficiency 67.5%, yield 92%.Mishmetal total amount and ree distribution pattern are as shown in table 2.Table 1: the main economic and technical norms contrast of the present invention and common norium
Table 2: New Rare Earth Mixture total amount and ree distribution pattern
| The norium kind | Unit consumption rare earth chloride crystallization material ton/metal per ton | Rare earth yield % | Current efficiency % |
| The present invention | ＜2.8 | ＞92 | ＞65 |
| Common norium | 2.9～3.1 | 80～90 | 45～50 |
| Mishmetal total amount % | Impurity % | Ree distribution pattern % | ||||
| Lanthanum | Praseodymium | Cerium | Neodymium | |||
| Embodiment 1 | 99.68 | 0.32 | 81.1 | 9.1 | 9.5 | 0.3 |
| Embodiment 2 | 99.59 | 0.41 | 84.2 | 10.1 | 5.6 | 0.41 |
Claims (4)
1, a kind of New Rare Earth Mixture, % counts by weight, and the mishmetal total amount is 99～99.5, and total impurities is 0.5～1, it is characterized in that the ree distribution pattern of norium is expressed as follows:
Lanthanum 78～86%
Praseodymium 4～12%
Cerium 5～15%
Neodymium 0.01～1%
2, a kind of production technique of New Rare Earth Mixture as claimed in claim 1, adopt fused salt electrolysis process, electrolytic solution is the REC13-KCI fused salt mixt, it is characterized in that, raw material RECI3 is the moisture lanthanum praseodymium cerium mixed chlorinated rare earth after carrying neodymium, carry cerium and divide removing Sm, Eu, Gd, moisture content is less than 28%, and granularity is less than 3mm, and chemical ingredients % meter by weight is expressed as follows:
REO ≥46
NH
4CI 3～5
SO
4 2- ＜0.03
PO
4 3- ＜0.01
Fe
2O
3＜0.07REO middle-weight rare earths partition is:
La
2O
3/REO 78～86
CeO
2/REO 5～15
Pr
6O
11/REO 4～12
Nd
2O
3/REO ＜1
Sm
2O
3The control electrolysis voltage is 10～18V in/REO＜0.03 electrolytic process, electric current 1000～1100A, 900～940 ℃ of electrolysis temperatures, and REO concentration is 21～25% in the adjustment electrolytic solution, after the electrolysis products therefrom come out of the stove after ingot casting, pack the finished product La, Pr and Ce mixed rare-earth metal, slag and chlorine reclaim routinely.
3, the production technique of New Rare Earth Mixture as claimed in claim 2 is characterized in that the pulverizing of raw material lanthanum praseodymium cerium mixed chlorinated rare earth and storage condition humidity are less than 45%.
4, the production technique of New Rare Earth Mixture as claimed in claim 2 is characterized in that the SO in raw material lanthanum praseodymium cerium mixed chlorinated rare earth and the Repone K
4 2-Content＜0.03%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99115002A CN1091158C (en) | 1999-07-12 | 1999-07-12 | La, Pr and Ce mixed rare-earth metal and its making technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99115002A CN1091158C (en) | 1999-07-12 | 1999-07-12 | La, Pr and Ce mixed rare-earth metal and its making technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1239152A CN1239152A (en) | 1999-12-22 |
| CN1091158C true CN1091158C (en) | 2002-09-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99115002A Expired - Fee Related CN1091158C (en) | 1999-07-12 | 1999-07-12 | La, Pr and Ce mixed rare-earth metal and its making technology |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8282703B2 (en) * | 2010-12-20 | 2012-10-09 | General Electric Company | Rare earth recovery from phosphor material and associated method |
| CN103352239A (en) * | 2013-07-03 | 2013-10-16 | 哈尔滨工程大学 | Method for directly preparing LaNi5 hydrogen storage alloy by molten salt electrolysis |
| CN106894056B (en) * | 2015-12-18 | 2018-07-10 | 中国科学院金属研究所 | A kind of method of high-purity La, Ce mischmetal of electrolytic preparation |
| CN110669936B (en) * | 2019-11-06 | 2021-08-20 | 包头市金为达稀土材料有限公司 | Rare earth processing device |
| CN112921360B (en) * | 2019-12-05 | 2023-01-03 | 乐山有研稀土新材料有限公司 | Method for preparing rare earth metal by molten salt electrolysis |
| CN114164368A (en) * | 2020-09-10 | 2022-03-11 | 厦门稀土材料研究所 | Rare earth hydrogen storage alloy and preparation method and application thereof |
| CN115354176A (en) * | 2022-08-25 | 2022-11-18 | 萍乡鑫森新材料有限责任公司 | Method for preparing rare earth metal or rare earth alloy |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147568A (en) * | 1995-10-12 | 1997-04-16 | 冶金工业部包头稀土研究院 | Prepn of lanthanum-rich rare-earth metal |
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1999
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147568A (en) * | 1995-10-12 | 1997-04-16 | 冶金工业部包头稀土研究院 | Prepn of lanthanum-rich rare-earth metal |
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