CN111876793A - Method for purifying dysprosium-copper alloy by liquid cathode in molten salt system - Google Patents
Method for purifying dysprosium-copper alloy by liquid cathode in molten salt system Download PDFInfo
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- CN111876793A CN111876793A CN202010685709.5A CN202010685709A CN111876793A CN 111876793 A CN111876793 A CN 111876793A CN 202010685709 A CN202010685709 A CN 202010685709A CN 111876793 A CN111876793 A CN 111876793A
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- dysprosium
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
Abstract
The invention relates to an electrochemical purification technology of dysprosium copper alloy, in particular to a method for purifying dysprosium copper alloy by a liquid cathode in a molten salt system. The invention comprises the following steps: (1) preparing raw materials; (2) blowing argon for purification; (3) removing impurities at constant voltage; (4) and protecting and collecting products. The purity of the dysprosium copper alloy product obtained by the invention is more than 99.9 wt%, the total content of non-metallic impurities (N, H, O) is not more than 0.3 wt%, the rare earth is free from burning loss in the purification process, no toxic or harmful gas is generated, and the dysprosium copper alloy product meets the requirement of environmental protection.
Description
Technical Field
The invention relates to an electrochemical purification technology of dysprosium copper alloy, in particular to a method for purifying dysprosium copper alloy by a liquid cathode in a molten salt system.
Background
The dysprosium-copper alloy is widely applied to the fields of neodymium iron boron magnets, magnetostrictive materials, magnetic refrigeration materials, high-strength alloys, special alloys and the like, and for example, the coercive force, anisotropy, corrosion resistance and high-temperature stability of the magnets can be obviously improved by adding a small amount of dysprosium-copper intermediate alloy into neodymium iron boron. Dysprosium copper alloy materials are widely applied to the manufacturing field of precise instruments such as aerospace, ultrasonic transducers, sonar and satellite positioning systems as magnetostrictive materials.
At present, the dysprosium copper alloy is industrially prepared mainly by a counter doping method and a metallothermic reduction method, and the two methods have the main problems that the non-metallic impurity (N, H, O) of an alloy product is high and the application of the alloy product is seriously influenced, so that the development of a green rare earth alloy purification process which has uniform components, no burning loss of rare earth, low production cost and energy consumption, simple process and short production period is urgent.
Disclosure of Invention
The invention aims to provide a method for purifying dysprosium copper alloy by a liquid cathode in a molten salt system, which comprises the steps of purifying the dysprosium copper alloy by the liquid dysprosium copper alloy cathode-molten chloride-CaO-ZrO2The ceramic anode system removes the non-metallic impurities of the dysprosium copper alloy.
The technical scheme of the invention is as follows: a method for purifying dysprosium copper alloy by using a liquid cathode in a molten salt system comprises the following steps:
(1) raw material preparation
Anhydrous CaCl is added2NaCl according to CaCl2NaCl in the molar ratio of 1 to 1 is fully mixed into mixed molten salt to be used as a supporting electrolyte raw material; taking crude dysprosium copper alloy with the purity of 95-97 percent by mass as a liquid cathode raw material, CaO & ZrO2Ceramic is used as an anode material;
(2) argon blowing purification
Adding CaCl in the step (1)2Heating the NaCl mixed molten salt in a glass carbon purifying tank protected by argon to 1000-1050 ℃ for full melting, and then adding 95-97 wt% of crude dysprosium copper alloy into the glass carbon purifying tank for full melting; introducing argon gas, stirring for 20-30 min, standing for 30min, and removing N, H, O zero-valent non-metallic impurities in the dysprosium-copper alloy system;
(3) constant voltage impurity removal
Mixing the liquid dysprosium copper alloy and CaCl in the step (2)2Under the protection of argon, taking liquid crude dysprosium copper alloy as a cathode at 1050-1100 ℃ and CaO & ZrO2The ceramic is used as an anode, and the power is supplied for 6-8 hours under the condition of constant voltage of 2.0-2.5V;
(4) product protection collection
Carrying out vacuum siphoning on the purified liquid dysprosium copper alloy to a boron nitride crucible under the protection of argon, cooling the liquid dysprosium copper alloy to the normal temperature in a temperature control furnace under the atmosphere of argon for 5-7 h, and storing the liquid dysprosium copper alloy in a vacuum sealed storage tank; the purity of the obtained dysprosium copper alloy product is more than 99.9 wt%, and the total content of non-metallic impurity N, H, O is not more than 0.3 wt%.
Adding CaCl in the step (1)2Dehydration of the NaCl-mixed molten salt at 150 ℃ under argon for 12 h.
The purity of the dysprosium copper alloy product obtained by the invention is more than 99.9 wt%, the total content of non-metallic impurities (N, H, O) is not more than 0.3 wt%, the rare earth is free from burning loss in the purification process, no toxic or harmful gas is generated, and the dysprosium copper alloy product meets the requirement of environmental protection.
Detailed Description
In the following examples, CaCl was added2Dehydrating the NaCl mixed molten salt for 12 hours in argon at the temperature of 150 ℃; the cooling was carried out in a temperature-controlled furnace under an argon atmosphere.
Example 1: CaCl without crystal water in a molar ratio of 1:12Heating NaCl mixed molten salt (supporting electrolyte) in a glass carbon purifying tank protected by argon to 1030 ℃ for fully melting, then adding crude dysprosium copper alloy (96 wt%) into the glass carbon purifying tank for fully melting, introducing argon, stirring for 25min, and then standing for 30 min; taking liquid crude dysprosium copper alloy as a cathode, CaO & ZrO2The ceramic is used as an anode, and the ceramic is electrified and purified for 7 hours under the conditions of the temperature of 1080 ℃ and the constant voltage of 2.3V; carrying out vacuum siphoning on the purified liquid dysprosium copper alloy to a boron nitride crucible under the protection of argon, and cooling for 6h to normal temperature; the purity of the alloy can reach 99.95% by analysis, and the total content of the non-metallic impurities (N, H, O) is not higher than 0.05 wt%.
Example 2: CaCl without crystal water in a molar ratio of 1:12Heating the NaCl mixed molten salt to 1000 ℃ in a glass carbon purifying tank protected by argon to fully melt, then adding the crude dysprosium copper alloy (95 wt%) into the purifying tank to fully melt, introducing argon, stirring for 20min, and then standing for 30 min; taking liquid crude dysprosium copper alloy as a cathode, CaO & ZrO2The ceramic is used as an anode, and the ceramic is electrified and purified for 6 hours under the conditions of 1050 ℃ and constant voltage of 2.0V; carrying out vacuum siphoning on the purified liquid dysprosium copper alloy to a boron nitride crucible under the protection of argon, and cooling for 5h to normal temperature; the purity of the alloy can reach 99.9 by analysis5% and the total content of non-metallic impurities (N, H, O) is not higher than 0.05 wt%.
Example 3: CaCl without crystal water in a molar ratio of 1:12Heating the NaCl mixed molten salt to 1050 ℃ in a glass carbon purifying tank protected by argon to fully melt, then adding a crude dysprosium copper alloy (97 wt%) into the purifying tank to fully melt, introducing argon, stirring for 30min, and then standing for 30 min; taking liquid crude dysprosium copper alloy as a cathode, CaO & ZrO2The ceramic is used as an anode, and the ceramic is electrified and purified for 8 hours under the conditions of 1100 ℃ and constant voltage of 2.5V; carrying out vacuum siphoning on the purified liquid dysprosium copper alloy to a boron nitride crucible under the protection of argon, and cooling for 7h to normal temperature; the purity of the alloy can reach 99.95% by analysis, and the total content of the non-metallic impurities (N, H, O) is not higher than 0.05 wt%.
Example 4: CaCl without crystal water in a molar ratio of 1:12Heating the NaCl mixed molten salt to 1010 ℃ in a glass carbon purifying tank protected by argon to fully melt, then adding a crude dysprosium copper alloy (95.5 wt%) into the purifying tank to fully melt, introducing argon, stirring for 25min, and then standing for 30 min; taking liquid crude dysprosium copper alloy as a cathode, CaO & ZrO2The ceramic is used as an anode, and the ceramic is electrified and purified for 6.5 hours under the conditions of 1060 ℃ and constant voltage of 2.1V; carrying out vacuum siphoning on the purified liquid dysprosium copper alloy to a boron nitride crucible under the protection of argon, and cooling to normal temperature after 5.5 h; the purity of the alloy can reach 99.95% by analysis, and the total content of the non-metallic impurities (N, H, O) is not higher than 0.05 wt%.
Example 5: CaCl without crystal water in a molar ratio of 1:12Heating the NaCl mixed molten salt to 1020 ℃ in a glass carbon purifying tank protected by argon to fully melt, then adding crude dysprosium copper alloy (96 wt%) into the purifying tank to fully melt, introducing argon, stirring for 25min, and then standing for 30 min; taking liquid crude dysprosium copper alloy as a cathode, CaO & ZrO2The ceramic is used as an anode, and the ceramic is electrified and purified for 7 hours under the conditions of 1070 ℃ and constant voltage of 2.2V; carrying out vacuum siphoning on the purified liquid dysprosium copper alloy to a boron nitride crucible under the protection of argon, and cooling for 6h to normal temperature; the purity of the alloy can reach 99.95% by analysis, and the total content of the non-metallic impurities (N, H, O) is not higher than 0.05 wt%.
Example 6: will not contain crystal waterCaCl with a molar ratio of 1:12Heating the NaCl mixed molten salt to 1030 ℃ in a glass carbon purifying tank protected by argon to fully melt, then adding a crude dysprosium copper alloy (96.5 wt%) into the purifying tank to fully melt, introducing argon, stirring for 30min, and then standing for 30 min; taking liquid crude dysprosium copper alloy as a cathode, CaO & ZrO2The ceramic is used as an anode, and the ceramic is electrified and purified for 7.5 hours under the conditions of 1090 ℃ and 2.4V of constant voltage; carrying out vacuum siphoning on the purified liquid dysprosium copper alloy to a boron nitride crucible under the protection of argon, and cooling to normal temperature after 6.5 h; the purity of the alloy can reach 99.95% by analysis, and the total content of the non-metallic impurities (N, H, O) is not higher than 0.05 wt%.
Claims (3)
1. A method for purifying dysprosium copper alloy by using a liquid cathode in a molten salt system is characterized by comprising the following steps: the method comprises the following steps:
(1) raw material preparation
Anhydrous CaCl is added2NaCl according to CaCl2NaCl in the molar ratio of 1 to 1 is fully mixed into mixed molten salt to be used as a supporting electrolyte raw material; taking crude dysprosium copper alloy with the purity of 95-97 percent by mass as a liquid cathode raw material, CaO & ZrO2Ceramic is used as an anode material;
(2) argon blowing purification
Adding CaCl in the step (1)2Heating the NaCl mixed molten salt in a glass carbon purifying tank protected by argon to 1000-1050 ℃ for full melting, and then adding 95-97 wt% of crude dysprosium copper alloy into the glass carbon purifying tank for full melting; introducing argon gas, stirring for 20-30 min, standing for 30min, and removing N, H, O zero-valent non-metallic impurities in the dysprosium-copper alloy system;
(3) constant voltage impurity removal
Mixing the liquid dysprosium copper alloy and CaCl in the step (2)2Under the protection of argon, taking liquid crude dysprosium copper alloy as a cathode at 1050-1100 ℃ and CaO & ZrO2The ceramic is used as an anode, and the power is supplied for 6-8 hours under the condition of constant voltage of 2.0-2.5V;
(4) product protection collection
Carrying out vacuum siphoning on the purified liquid dysprosium copper alloy to a boron nitride crucible under the protection of argon, cooling the liquid dysprosium copper alloy to the normal temperature in a temperature control furnace under the atmosphere of argon for 5-7 h, and storing the liquid dysprosium copper alloy in a vacuum sealed storage tank; the purity of the obtained dysprosium copper alloy product is more than 99.9 wt%, and the total content of non-metallic impurity N, H, O is not more than 0.3 wt%.
2. The method for purifying dysprosium copper alloy by using a liquid cathode in a molten salt system according to claim 1, wherein the method comprises the following steps: adding CaCl in the step (1)2Dehydration of the NaCl-mixed molten salt at 150 ℃ under argon for 12 h.
3. The method for purifying dysprosium copper alloy by using a liquid cathode in a molten salt system according to claim 1, wherein the method comprises the following steps: CaCl without crystal water in a molar ratio of 1:12Heating the NaCl mixed molten salt to 1030 ℃ in a glass carbon purification tank protected by argon to fully melt, then adding 96 wt% of crude dysprosium copper alloy into the glass carbon purification tank to fully melt, introducing argon, stirring for 25min, and then standing for 30 min; taking liquid crude dysprosium copper alloy as a cathode, CaO & ZrO2The ceramic is used as an anode, and the ceramic is electrified and purified for 7 hours under the conditions of the temperature of 1080 ℃ and the constant voltage of 2.3V; carrying out vacuum siphoning on the purified liquid dysprosium-copper alloy to a boron nitride crucible under the protection of argon, and then cooling the liquid dysprosium-copper alloy to the normal temperature in a temperature control furnace under the atmosphere of argon for 7 hours; the purity of the dysprosium-copper alloy can reach 99.95% through analysis, and the total content of the non-metallic impurity N, H, O is not higher than 0.05 wt%;
the CaCl is2The NaCl mixed molten salt is dehydrated for 12 hours in argon at the temperature of 150 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114807637A (en) * | 2022-05-24 | 2022-07-29 | 江西理工大学 | Method for electrically removing oxide impurities in praseodymium-neodymium alloy |
| CN114934298A (en) * | 2022-05-24 | 2022-08-23 | 江西理工大学 | Method for removing non-metal impurities in praseodymium neodymium dysprosium alloy |
| CN114941079A (en) * | 2022-05-24 | 2022-08-26 | 国瑞科创稀土功能材料(赣州)有限公司 | Method for removing oxide inclusion in Dy-Fe alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114807637A (en) * | 2022-05-24 | 2022-07-29 | 江西理工大学 | Method for electrically removing oxide impurities in praseodymium-neodymium alloy |
| CN114934298A (en) * | 2022-05-24 | 2022-08-23 | 江西理工大学 | Method for removing non-metal impurities in praseodymium neodymium dysprosium alloy |
| CN114941079A (en) * | 2022-05-24 | 2022-08-26 | 国瑞科创稀土功能材料(赣州)有限公司 | Method for removing oxide inclusion in Dy-Fe alloy |
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