CN105603461A - Method of preparing praseodymium-neodymium-dysprosium-terbium quaternary alloy by molten salt electrolysis - Google Patents
Method of preparing praseodymium-neodymium-dysprosium-terbium quaternary alloy by molten salt electrolysis Download PDFInfo
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- CN105603461A CN105603461A CN201511015197.7A CN201511015197A CN105603461A CN 105603461 A CN105603461 A CN 105603461A CN 201511015197 A CN201511015197 A CN 201511015197A CN 105603461 A CN105603461 A CN 105603461A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25C3/36—Alloys obtained by cathodic reduction of all their ions
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Abstract
The invention relates to a method of preparing a praseodymium-neodymium-dysprosium-terbium quaternary alloy by molten salt electrolysis. The method is characterized by comprising the following steps: taking a graphite block as an anode, a molybdenum rod as an inert cathode, and a molybdenum crucible as a rare earth alloy receiver; in a fluoride molten salt electrolyte system consisting of rare earth fluoride, dysprosium fluoride and terbium fluoride, lithium fluoride with the mass ratio of (3 to 9):(1 to 6):1, adding a mixture of electrolysis raw materials of rare earth oxide, dysprosium oxide and terbium oxide, wherein the mass percentage composition of dosages of the rare earth oxide to the dysprosium oxide and terbium oxide equals to (99 to 40):(1 to 60); introducing direct current electricity, wherein the anodic current density is 0.5 to 2.0A per square centimeters, and the cathodic current density is 5 to 25A per square centimeters; performing electrolysis at the electrolysis temperature of 1050 to 1200 DEG C, and obtaining the praseodymium-neodymium-dysprosium-terbium quaternary alloy. The method has the following advantages: the praseodymium-neodymium-dysprosium-terbium quaternary alloy is prepared by electrolyzing the mixed oxide by the simple fluoride electrolyte system; the process flow is simple; the cost is low; the product is stable in components; only CO2 and a small amount of CO are produced in the technical process; the environmental pollution is small; the method belongs to a green and environmental protection technology, and is suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of Preparation through Fluoride System in Fused-salt Electrolysis codeposition and prepare the method for praseodymium neodymium dysprosium terbium quaternary alloy, belong to rare earth pyrometallurgy field.
Background technology
Preparation method containing rare earth dysprosium (terbium) alloys such as high-melting-point dysprosiums (terbium) mainly contains two kinds: metal pair is mixed high temperature molten method and fluoride hot reduction of vacuum Ca method mutually.
To mix high temperature mutually molten method refer to the middle heavy rare earth metal dysprosium (terbium) of producing etc. moltenly mutually with one or more high temperature under vacuum environment in other light rare earth metal lanthanums, cerium, praseodymium, neodymium, there is the simple feature of production method. Higher by the alloy product impurity content that the method for mixing is produced, energy consumption is larger, and cost is high.
Fluoride hot reduction of vacuum Ca method refer to adopt calcium metal under vacuum environment taking dysprosium fluoride (terbium) etc. and light rare earth metal and alloy as raw material, be produced into rare earth dysprosium (terbium) alloy. Owing to adopting vacuum reduction method to produce, its energy consumption is still higher, need to use expensive vacuum reduction equipment and tungsten, molybdenum crucible etc., and production cost is high, and production capacity is low.
Summary of the invention
The object of the invention is for above-mentioned the deficiencies in the prior art, provide a kind of oxide and salt melt electrolyzing codeposition to prepare the method for praseodymium neodymium dysprosium terbium rare earth alloy. The method production cost is low, and current efficiency and yield are high, and product quality is high, and environmental friendliness belongs to environmental protection technique.
For achieving the above object, the present invention by the following technical solutions:
Make anode with graphite block, molybdenum bar is inert cathode, molybdenum crucible is as rare earth alloy recipient, in quality than rare earth fluoride: dysprosium fluoride and terbium: lithium fluoride=(3-9): (1-6): in the fluoride molten salt electrolyte system of 1 composition, add the mixture of electrolysis raw material rare earth oxide and dysprosia and terbium, the quality percentage composition of its consumption is rare earth oxide: dysprosia and terbium=(99-40): (1-60), pass to direct current, anodic current density 0.5-2.0A/cm2, cathode-current density is 5-25A/cm2; Electrolysis temperature is 1050-1200 DEG C of electrolysis, obtains praseodymium neodymium dysprosium terbium quaternary alloy.
In described fluoride molten salt electrolyte system, rare earth fluoride is praseodymium fluoride neodymium;
Rare earth oxide in described electrolysis raw material is praseodymium oxide neodymium;
The quality percentage composition RE:Dy+Tb=(99-40 of the rare earth dysprosium of described preparation and terbium alloy middle rare earth and dysprosium and terbium): (1-60).
Advantage of the present invention is: make praseodymium neodymium dysprosium terbium quaternary alloy with simple fluoride electrolyte system electrolysis mixed oxide, technological process is simple, and cost is low, and product composition is stable, and technical process only produces CO2With a small amount of CO, environmental pollution is little, belongs to environmental protection technique, is suitable for large-scale production.
Detailed description of the invention
By rare earth fluoride, dysprosium fluoride, fluoridize terbium, lithium fluoride mixes and adds in electrolytic cell by design proportion, treat electrolyte melting, temperature reaches after electrolysis temperature, insert negative electrode conduction molybdenum bar, make it to be inserted into electrolyte levels desired depth, start rectifier, carry out electrolysis, after electrolysis a period of time, take out alloy, weigh and perform an analysis.
Embodiment one:
Electrolyte ratio is praseodymium fluoride neodymium: dysprosium fluoride: fluoridize terbium: lithium fluoride=6.4:0.9:0.9:1(mass ratio), material rate is praseodymium oxide neodymium: terbium oxide=10.5:1:1(mass ratio). In 300A electrolytic furnace, carry out electrolysis, Faradaic current intensity is 300A, and cathode-current density is 8A/cm2, anodic current density is 1.1A/cm2, electrolysis time 240min, mixed oxide addition is 2.5kg, 1070 DEG C of electrolysis temperatures, electrolysis makes the heavy 1.6kg of praseodymium neodymium dysprosium terbium alloy. Alloy component analysis result is as follows:
(mass fraction, %)
| Pr | Nd | Dy | Tb | C |
| 20.8 | 61.7 | 8.5 | 8.8 | 0.037 |
Embodiment two:
Electrolyte ratio is praseodymium fluoride neodymium: fluoridize terbium: lithium fluoride=6.2:1:2.3:1(mass ratio), material rate is praseodymium oxide neodymium: terbium oxide=3.9::0.3:1(mass ratio). In 300A electrolytic furnace, carry out electrolysis, Faradaic current intensity is 300A, and cathode-current density is 10A/cm2, anodic current density is 1.1A/cm2, electrolysis 400min, mixed oxide addition is 3.1kg, 1100 DEG C of electrolysis temperatures, electrolysis makes the heavy 2.01kg of praseodymium neodymium terbium alloy. Alloy component analysis result is as follows:
(mass fraction, %)
| Pr | Nd | Dy | Tb | C |
| 17.42 | 54.94 | 6.22 | 20.01 | 0.035 |
Claims (3)
1. the method for praseodymium neodymium dysprosium terbium quaternary alloy is prepared in a molten-salt electrolysis, it is characterized in that: make anode with graphite block, molybdenum bar is inert cathode, molybdenum crucible is as rare earth alloy recipient, in quality than rare earth fluoride: dysprosium fluoride and terbium: lithium fluoride=(3-9): (1-6): in the fluoride molten salt electrolyte system of 1 composition, add the mixture of electrolysis raw material rare earth oxide and dysprosia and terbium, the quality percentage composition of its consumption is rare earth oxide: dysprosia and terbium=(99-40): (1-60), pass to direct current, anodic current density 0.5-2.0A/cm2, cathode-current density is 5-25A/cm2; Electrolysis temperature is 1050-1200 DEG C of electrolysis, obtains praseodymium neodymium dysprosium terbium quaternary alloy.
2. the method for praseodymium neodymium dysprosium terbium quaternary alloy is prepared in molten-salt electrolysis according to claim 1, it is characterized in that: in described fluoride molten salt electrolyte system, rare earth fluoride is praseodymium fluoride neodymium.
3. the method for praseodymium neodymium dysprosium terbium quaternary alloy is prepared in molten-salt electrolysis according to claim 1, it is characterized in that: the rare earth oxide in described electrolysis raw material is praseodymium oxide neodymium.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112030193A (en) * | 2020-08-27 | 2020-12-04 | 包头稀土研究院 | Method for reducing segregation of gadolinium-yttrium-magnesium alloy |
| CN112725841A (en) * | 2020-12-24 | 2021-04-30 | 四川省乐山市科百瑞新材料有限公司 | Rare earth alloy material 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 |
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| 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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Patent Citations (4)
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| CN1064510A (en) * | 1992-03-18 | 1992-09-16 | 冶金工业部包头稀土研究院 | The preparation method of neodymium and Nd-Pr base heavy rare-earth alloy |
| 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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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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| CN112030193A (en) * | 2020-08-27 | 2020-12-04 | 包头稀土研究院 | Method for reducing segregation of gadolinium-yttrium-magnesium alloy |
| CN112030193B (en) * | 2020-08-27 | 2021-11-09 | 包头稀土研究院 | Method for reducing segregation of gadolinium-yttrium-magnesium alloy |
| CN112725841A (en) * | 2020-12-24 | 2021-04-30 | 四川省乐山市科百瑞新材料有限公司 | Rare earth alloy material and preparation method thereof |
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