CN1073170C - Preparation of battery grade mixed rareearth metal by rareearth chloride molten-salt electrolysis and its equipment - Google Patents
Preparation of battery grade mixed rareearth metal by rareearth chloride molten-salt electrolysis and its equipment Download PDFInfo
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- CN1073170C CN1073170C CN97103269A CN97103269A CN1073170C CN 1073170 C CN1073170 C CN 1073170C CN 97103269 A CN97103269 A CN 97103269A CN 97103269 A CN97103269 A CN 97103269A CN 1073170 C CN1073170 C CN 1073170C
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Abstract
The present invention relates to a method for preparing battery grade mixed rare earth (RE) metal by electrolyzing RE chloride molten salt and a device thereof. The present invention is characterized in that an electrolysis temperature is increased from 850 to 890 DEG C to 940 to 980 DEG C, electrolysis time is shortened from 2 hours to 1.5 hours for every boiler; the ratio of the inside diameter to the tank depth of an electrolyte tank of a circular graphite crucible is less than 0.8, and the electrolyte tank is matched with proper tungsten or molybdenum cathodes. The electrolyte tank of the present invention has the advantages of reasonable design, long service life, low direct power consumption and high current efficiency; the present invention also has the advantages of small depth loss of RE chloride, and great production capacity and high yield of the RE metal. The electrolyte tank of the present invention can also be suitable for producing common mixed RE metal.
Description
The present invention relates to a kind of rare earth chloride fused salt electrolysis and prepare the norium method, be particularly suitable for the preparation of battery grade mischmetal and the adapted of anode and cathode structure.Belong to the rare earth molten-salt electrolysis technical field.
Rare earth molten-salt electrolysis can be divided into electrolysis of fused chloride salt and oxide and salt melt electrolyzing.Electrolysis of fused chloride salt equipment is simple, easy to operate, be easy to grasp, and the structured material of electrolyzer solves easily, so be the basic skills of producing rare earth metal at present.It is to be raw material with the rare earth chloride that norium is produced in the rare earth chloride fused salt electrolysis, and Repone K is main fused salt component.Electrolyzer generally adopts circular plumbago crucible electrolyzer, and under 850～890 ℃ electrolysis temperature, Repone K is the fusion state, and anhydrous chlorides of rase earth elements is fused to and wherein forms the fused ionogen.The plumbago crucible electrolyzer is to make cathode with plumbago crucible itself, is connected with dc power anode; Last extension molybdenum bar is made negative electrode, is connected with dc power cathode and inserts to be used as in the porcelain dish of metal susceptor.During electrolysis, rare earth chloride is decomposed, and constantly separates out rare earth metal on negative electrode, constantly emits chlorine on anode.Carry out along with electrolytic, rare earth chloride is consumed gradually, needs to add rare earth chloride continuously in electrolyzer, and regularly takes out rare earth metal, to keep normally carrying out of electrolysis production.
Some produce the producer of common or battery grade mischmetal now, adopt circular plumbago crucible electrolyzer mostly, 200 millimeters of its anode graphite crucible internal diameters, 250 millimeters of groove depths; 25 millimeters of negative electrode molybdenum bar or tungsten bar diameters.This kind electrolyzer is because anode and cathode structure adapted is unreasonable, and groove internal diameter and groove depth are than excessive, and the apolegamy of negative electrode diameter is improper; Electrolytic some processing condition such as temperature and time are not adjusted with the change of rare earth chloride raw material middle-weight rare earths element (lanthanum, cerium, praseodymium, neodymium) partition, so electrolyzer power is less, productive rate is lower, and current efficiency only is about 64%, and the rare earth metal yield is less than 90%.
The objective of the invention is low for the productive rate that solves existing circular plumbago crucible electrolyzer, as to reduce precipitating metal solution loss and secondary action, improve current efficiency and rare earth metal yield, suitably adjusting process condition and electrolyzer anode and cathode structure adapted are designed the novel electrolytic bath and the negative electrode adapted of a kind of superpower, high yield, high current efficiency and high rare earth yield.
The present invention realizes by following steps: it comprises the anhydrous chlorides of rase earth elements feedstock production, the fusion electrolysis vent gas treatment.With the required anhydrous chlorides of rase earth elements raw material of preparation battery grade mischmetal, pulverize the back and add gradually in the plumbago crucible electrolyzer by proportioning with Repone K, energising intensification fusion is by the rising of temperature and electrolyte levels, electrolyte concentration increases, when ionogen middle-weight rare earths concentration reaches 22%, when temperature rises to more than 940 ℃, mention negative electrode, put into and give the good metal reception porcelain dish of heat, insert negative electrode again, adjust bath voltage, electric current, make electrolysis temperature be controlled at 940-980 ℃.Rare earth chloride feed rate: 100-105g/min, through normally carrying out of electrolytic process, rare earth metal constantly folds on negative electrode, falls into negative electrode lower end metal receptor porcelain dish, electrolysis time: 1.5 hours/stove.
The present invention produces the partition of contained four kinds of light rare earths lanthanums, cerium, praseodymium, neodymium in the common norium and changes to some extent according to producing battery grade mischmetal, and its fluxing point raises, so be 940～980 ℃ with electrolysis temperature by 850～890 ℃ of risings.
The present invention has done change to electrolyzer and cathode construction.Negative electrode is tungsten bar or molybdenum bar, the ratio of groove internal diameter and groove depth is reduced to below 0.8, because the ratio of groove internal diameter and groove depth descends the corresponding increase of the pole distance of anode and cathode.Metal turns to the process of positive column difficult from the cathodic area, so just can reduce the solution loss of precipitating metal.Simultaneously, also the electrolysis time of every stove was shortened to 1.5 hours by 2 hours; So also can reduce the secondary action and the solution loss of precipitating metal, again because of the electrolyzer appropriate depth, in the electrolytic process, the gas that anode produces is still overflowed easily, and ionogen is by stirring to central all around, and cyclicity is good, electrolysis temperature and rare earth concentration are more even, electrolysis is carried out normally, and feed rate is brought up to per minute 100～105 grams by per minute 60～70 grams, and corresponding output also improves.
The present invention compared with prior art has the following advantages:
1, improves the power rectifier usage ratio of equipment, solved the problem that heavy body equipment carries the low power load substantially.Under the constant situation of original rectifying installation capacity, can improve rare earth metal output about 40%.According to technology condition of the present invention, the power rectifier equipment that can be various capacity is matched cell construction and negative electrode efficiently.
2, main economic and technical indices of the present invention and processing condition all are better than the cell construction of similar and other type, meet cell construction and power to maximize, high-power direction demand for development.
3, design of electrolysis cells of the present invention is reasonable, and directly power consumption is low, the current efficiency height, and the rare earth unit consumption is few, output is big, yield is high, long service life.
Below in conjunction with drawings and Examples the present invention is further described:
Accompanying drawing is a cell construction synoptic diagram of the present invention.
As shown in the figure, the groove internal diameter is that a, groove depth are that the circular plumbago crucible (anode) [2] of b is embedded in the iron shell [3], and the ratio of a and b is less than 0.8.Tungsten bar negative electrode [1] vertically inserts metal susceptor porcelain dish [5] top of plumbago crucible bottom centre, and ionogen [4] is melted in the plumbago crucible, and electrolysis gained rare earth metal [6] is contained in metal susceptor porcelain dish [5], regularly takes out.
Embodiment 1:
1800 amperes of three of circular graphitic cell series connection are a series, and internal diameter a is that 220 millimeters, groove depth b are 300 millimeters, and a: b=0.733, adapted diameter are respectively three kinds of specification tungsten bar negative electrodes of 35,30 and 25 millimeters.Rare earth concentration: 22～26%, 940～980 ℃ of electrolysis temperatures, the every stove of electrolysis time 1.5 hours.Output was lower in first day, between 7.6～8.0 kilograms/stove, just began to enter the high yield state behind 35 millimeters negative electrodes of second day adapted.
Embodiment 2:
Selecting internal diameter a for use is that 240 millimeters, groove depth b are 300 millimeters three of electrolyzer series connection, a: b=0.8, other conditions are with embodiment 1, just entered higher occurrence attitude in first day, during 35 millimeters negative electrodes of adapted diameter, 9.0～9.3 kilograms of average every furnace outputs, other two kinds of small dimension negative electrode output of adapted are all lower.But this electrolyzer is shorter work-ing life, average out to 5 days, and strength of current when entering the 6th day, output all descends, and the rare earth chloride unit consumption increases, and directly power consumption raises.
Embodiment 3:
Selecting internal diameter a for use is that 230 millimeters, groove depth b are three series connection of electrolyzer of 300 millimeters, a: b=0.766, and other processing condition are with embodiment 1.2.Single furnace output was all higher in first day, and on average between 8.8～9.6 kilograms/stove, during 35 millimeters negative electrodes of adapted diameter, electrolyzer is in 7 days the cycle of operation, and the key technical indexes such as output, unit consumption and power consumption are all good.Interior each parameter value contrast of each parameter value and prior art grooved (300 millimeters of internal diameters, 300 millimeters of groove depths, 25 millimeters of negative electrode diameters) lifetime is listed in the subordinate list in this kind grooved lifetime:
Each parameter value contrast table of the present invention and prior art grooved
Claims (3)
1, a kind of rare earth chloride fused salt electrolysis prepares the battery grade mischmetal method, it comprises the anhydrous chlorides of rase earth elements feedstock production, the fusion electrolysis vent gas treatment, it is characterized in that: will prepare the required anhydrous chlorides of rase earth elements raw material of battery grade mischmetal, pulverizing the back adds in the plumbago crucible electrolyzer by proportioning gradually with Repone K, energising intensification fusion, rising by temperature and electrolyte levels, electrolyte concentration increases, when ionogen middle-weight rare earths concentration reaches 22%, when temperature rises to more than 940 ℃, mention negative electrode, put into and give the good metal reception porcelain dish of heat, insert negative electrode again, adjust bath voltage, electric current makes electrolysis temperature be controlled at 940-980 ℃, rare earth chloride feed rate: 100-105g/min, through normally carrying out of electrolytic process, rare earth metal constantly folds on negative electrode, falls into negative electrode lower end metal receptor porcelain dish, electrolysis time: 1.5 hours/stove.
2, rare earth chloride fused salt electrolysis according to claim 1 prepares the battery grade mischmetal method, it is characterized in that: the ratio of electrolyzer internal diameter and electrolysis groove depth is less than 0.8, and negative electrode is tungsten bar or molybdenum bar.
3, rare earth chloride fused salt electrolysis according to claim 1 and 2 prepares the battery grade mischmetal method, it is characterized in that: cathode current density is 4.28-5.36A/cm
2, anodic current density is 0.41-0.67A/cm
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103269A CN1073170C (en) | 1997-05-05 | 1997-05-05 | Preparation of battery grade mixed rareearth metal by rareearth chloride molten-salt electrolysis and its equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103269A CN1073170C (en) | 1997-05-05 | 1997-05-05 | Preparation of battery grade mixed rareearth metal by rareearth chloride molten-salt electrolysis and its equipment |
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| Publication Number | Publication Date |
|---|---|
| CN1198482A CN1198482A (en) | 1998-11-11 |
| CN1073170C true CN1073170C (en) | 2001-10-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN97103269A Expired - Fee Related CN1073170C (en) | 1997-05-05 | 1997-05-05 | Preparation of battery grade mixed rareearth metal by rareearth chloride molten-salt electrolysis and its equipment |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368282B (en) * | 2007-08-14 | 2012-07-11 | 北京有色金属研究总院 | Lower cathode rare earth metal electrolytic tank and electrolysis technique adopting the same |
| CN104328458B (en) * | 2014-11-19 | 2018-05-04 | 赣州三友稀土新材料有限公司 | A kind of high yield and saving energy re metal electrolyzing stove |
| CN111411372B (en) * | 2019-09-10 | 2022-04-29 | 包头稀土研究院 | Preparation method of rare earth iron alloy |
| CN110578156A (en) * | 2019-10-17 | 2019-12-17 | 黄运蕉 | enhanced rare earth electrolysis graphite crucible |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087136A (en) * | 1991-04-17 | 1994-05-25 | 日用电池有限公司 | Make the electrolytic process of the alloy of rare earth metal and other metal |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087136A (en) * | 1991-04-17 | 1994-05-25 | 日用电池有限公司 | Make the electrolytic process of the alloy of rare earth metal and other metal |
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| CN1198482A (en) | 1998-11-11 |
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Applicant after: Neimonggu Baogang High Sciences and Tech. Co., Ltd. Applicant before: No.3 Rare Earth Factory, Baotou Iron & Steel Corp. |
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Free format text: CORRECT: APPLICANT; FROM: NO.3 RARE EARTH FACTORY, BAOTOU IRON + STEEL CO. TO: BAOGANG RARE EARTH HIGH-TECH STOCK CO., LTD., NEIMENGGU |
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