CN110904469A - Method for producing rare earth intermediate alloy by continuous suspension electrolysis and application thereof - Google Patents
Method for producing rare earth intermediate alloy by continuous suspension electrolysis and application thereof Download PDFInfo
- Publication number
- CN110904469A CN110904469A CN201911158186.2A CN201911158186A CN110904469A CN 110904469 A CN110904469 A CN 110904469A CN 201911158186 A CN201911158186 A CN 201911158186A CN 110904469 A CN110904469 A CN 110904469A
- Authority
- CN
- China
- Prior art keywords
- electrolysis
- rare earth
- metal
- electrolytic
- fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a method for producing rare earth intermediate alloy by continuous suspension electrolysis, which comprises the following steps: forming a fluoride molten salt system in an electrolytic cell with an anode to form a uniform electrolytic system; adding a metal supplement material into an electrolytic system to form a molten metal in the electrolytic system, wherein the molten metal and a cathode together form a liquid cathode; the control system obtains real-time electrolysis process parameters in the process flow, and controls any one of the supplement speed at least comprising metal supplement materials, the supplement speed of rare earth oxides or the extraction speed of qualified molten metal prepared by electrolysis according to the real-time electrolysis process parameters: at least in the electrolysis process after the electrification, the control system also monitors the monitoring amount in the liquid cathode, and qualified molten metal can be extracted to be continuously electrolyzed after the preset standard is met. The method has the advantages of simple process operation, continuous and stable electrolysis, uniform and stable product components, small environmental pollution, green and environment-friendly process and suitability for large-scale continuous production.
Description
Technical Field
The invention relates to a production method and application of rare earth intermediate alloy, in particular to a method for producing rare earth intermediate alloy by continuous suspension electrolysis and application thereof.
Background
In the prior production of the metallurgical industry, the alloy mixed by metal with lower density and metal with higher density can be used, and the prior production modes mainly comprise two modes, namely, firstly, the metal with lower density and the metal with higher density are produced, then the metal with lower density and the metal with higher density are added into a furnace according to a certain proportion to be melted, stirred and uniformly cast into ingots for reuse. The other is electrolysis production by a suspension method, namely, in a square or round graphite groove, firstly melting a molten salt system, then adding a metal with lighter density into the molten salt system to be melted and suspended on the molten salt system, then contacting a cathode with a suspended metal liquid to form a liquid cathode, simultaneously adding an oxide of the other metal into the graphite groove, electrifying and electrolyzing, after the required proportion of the method is achieved, lifting the cathode, scooping out the alloy to cast into an ingot, and then repeating the operation for electrolysis production again.
Disclosure of Invention
In order to solve the problems, the method for producing the rare earth intermediate alloy by continuous suspension electrolysis and the application thereof disclosed by the invention have the advantages that the process operation is simple, the metal does not need to be scooped out from each furnace, the electrolysis can be continuously and stably carried out, the components of the product are uniform and stable, and only CO is generated in the process2And CO, has little pollution to the environment, belongs to a green and environment-friendly process, and is suitable for large-scale production.
The invention discloses a method for producing rare earth intermediate alloy by continuous suspension electrolysis, which comprises the following steps:
A. forming a fluoride molten salt system in an electrolytic cell with an anode to form a uniform electrolytic system; preferably, the fluoride molten salt system can be further added with a proper amount of rare earth oxide to obtain an electrolytic system. Preferably, the rare earth oxide is added in an amount of 0.5-5% by weight of the total weight of the electrolytic system.
B. Adding a metal supplement material into an electrolytic system to form a metal liquid in the electrolytic system, wherein the metal liquid and a cathode together form a liquid cathode for electrolysis; note that, here, it is preferable that the molten metal is formed on the liquid surface of the electrolytic system.
C. The control system obtains real-time electrolysis process parameters in the process flow, and controls any one of the supplement speed at least comprising metal supplement materials, the supplement speed of rare earth oxides or the extraction speed of qualified molten metal prepared by electrolysis according to the real-time electrolysis process parameters: at least in the electrolysis process after the electrification, the control system also monitors the monitoring amount of the liquid cathode, and qualified molten metal can be extracted to be continuously electrolyzed after the preset standard is met. Preferably, the monitored quantity at least comprises the resistance of the liquid cathode or the conductivity of the liquid cathode or the content of rare earth elements and the like which can directly or indirectly reflect the index of the molten metal component in the liquid cathode.
Further preferably, the monitoring of the monitoring amount of the liquid cathode by the monitoring system may be real-time monitoring, or may be timed monitoring, for example, sampling monitoring is performed at certain intervals, such as 0.5min, 2min, 5min, 10min, or 30 min.
Further preferably, the metallic patch is provided in the form of a wire. Further, the metal supplement should be preheated before being added to the electrolysis system. Furthermore, the preheating temperature of the metal repairing material is 300-400 ℃.
Further preferably, when the extraction pipe is used for extracting the qualified molten metal, the extraction pipe should be preheated. Further, the preheating temperature of the extraction pipeline is 800-.
More preferably, the electrolysis is direct current electrolysis, and the electrolysis voltage is 8-12V.
The invention discloses an improvement of a method for producing rare earth intermediate alloy by continuous suspension electrolysis, wherein in the electrolysis process after electrification, a control system monitors the content of rare earth elements in a liquid cathode in real time, and the content of the total rare earth elements in molten metal of a liquid electrode meets a preset standard of 1-20 wt% when qualified molten metal is extracted.
The invention discloses an improvement of a method for producing rare earth intermediate alloy by continuous suspension electrolysis, wherein in the step C, the control system obtains real-time electrolysis process parameters in the process flow and at least comprises any one of the following parameters: the temperature of a fluoride molten salt system, the temperature of a metal supplement material, the temperature of a pipeline used for extracting qualified molten metal, the voltage between a cathode and an anode of an electrolytic system, the voltage between the cathode and a liquid cathode, the voltage between an electrolytic bath and an anode, the voltage between the liquid cathode and the electrolytic bath, and the voltage between the cathode and the electrolytic bath. The voltage here can be the interface voltage or the direct voltage at a particular location in the electrolysis process, selected according to the process requirements.
The invention discloses an improvement of a method for producing rare earth intermediate alloy by continuous suspension electrolysis, wherein the thickness of molten metal in step B is 10-25 mm.
The invention discloses an improvement of a method for producing rare earth intermediate alloy by continuous suspension electrolysis, wherein the supplement speed of rare earth oxide is calculated according to the equivalent of 80-100% of current efficiency during electrolysis.
The invention discloses an improvement of a method for producing rare earth intermediate alloy by continuous suspension electrolysis, wherein the replenishing speed of rare earth oxide is 1.1-25 wt% of the quality of immediately extracted qualified molten metal. That is, the replenishing speed of the rare earth oxide is 1.1 wt.% to 25.39 wt.% of the extraction speed of qualified metal in mass fraction in the continuous production process of the process.
The invention discloses an improvement of a method for producing rare earth intermediate alloy by continuous suspension electrolysis, wherein the replenishing speed of a metal replenishing material is 80-99 wt% of the quality of immediately extracted qualified molten metal. That is, in the continuous production process of the process, the replenishing speed of the metal supplement material is 80-99 wt.% of the extraction speed of qualified metal in terms of mass fraction.
The metal supplement material is corresponding metal wire, metal wire or metal bar, such as aluminum metal wire with diameter of 1mm or directly aluminum magnesium alloy metal wire with diameter of 2mm or directly aluminum alloy metal bar with diameter of 5 mm.
The invention discloses an improvement of a method for producing rare earth intermediate alloy by continuous suspension electrolysis, wherein a fluoride molten salt electrolysis system is obtained by mixing and melting fluorides.
The invention discloses an improvement of a method for producing rare earth intermediate alloy by continuous suspension electrolysis, wherein the fluoride comprises the following components in percentage by mass: rare earth fluoride: barium fluoride: lithium fluoride (60-70): (15-25): 10-20).
The invention discloses an improvement of a method for producing rare earth intermediate alloy by continuous suspension electrolysis, wherein a fluoride molten salt electrolysis system is obtained at the temperature of 810-.
The invention discloses an application of a method for producing rare earth intermediate alloy by continuous suspension electrolysis in aluminum alloy, magnesium alloy, aluminum-zirconium alloy, aluminum-beryllium alloy, magnesium-zirconium alloy and magnesium-beryllium alloy.
The following is a brief introduction to one possible approach:
the method for producing the rare earth intermediate alloy by continuous suspension electrolysis comprises the following steps of:
the first step is as follows: preparing a fluoride fused salt electrolysis system, wherein the components in mass ratio are as follows: rare earth fluoride: barium fluoride: and (5) lithium fluoride (60-70), 15-25 and 10-20) in percentage by mass.
The second step is that: and connecting a data line for detecting the temperature of a molten salt system, a data line for detecting the preheating temperature of the metal wire, a data line for detecting the temperature of a pipeline for extracting the alloy, a data line for detecting the voltage between the cathode and the anode, a data line for detecting the voltage between the liquid cathode and the cathode, and a lead for detecting the resistance of the liquid cathode to a PLC control system.
The third step: adding molten salt into a graphite groove with a long waist-shaped hole section, heating and melting to form a molten salt system, and controlling the temperature at 810-980 ℃.
The fourth step: adding 0.5-5% of rare earth oxide into the molten salt system, fully dissolving, and uniformly stirring.
The fifth step: and in the third step, starting the PLC control system to control the preheating temperature of the metal wire to be 400 ℃ at 300 ℃ and the temperature of the pipeline for extracting the alloy to be 980 ℃ at 800 ℃.
And a sixth step: and (3) feeding the metal wire into a molten salt system by using a wire feeder, melting the metal wire into metal liquid with the thickness of 10-25mm, and stopping feeding the wire.
The seventh step: the cathode, which is long kidney-shaped at the end, is inserted into the liquid metal.
Eighth step: starting an electrolysis direct current power supply, controlling the voltage to be 8-12V, starting electrolysis under the action of direct current, and starting a feeder to add rare earth oxide according to the current efficiency of 80-100%.
The ninth step: sampling once every 0.5-2 minutes, analyzing the components, and inputting all parameters into a PLC control system to form process control parameters.
The tenth step: when the rare earth content in the liquid cathode reaches 1-20%, starting a liquid pump and a wire feeder, pumping out qualified metal liquid by the liquid pump and cooling the metal liquid into ingots, and adding 80-99 parts of metal wires into the wire feeder and 1.1-25 parts of rare earth oxide into the feeder when one part of metal liquid is pumped out.
In the method for producing the rare earth intermediate alloy by continuous suspension electrolysis, a fluoride molten salt electrolysis system comprises the following components in percentage by mass: rare earth fluoride: barium fluoride: and (5) lithium fluoride (60-70), 15-25 and 10-20) in percentage by mass.
In the method for producing the rare earth intermediate alloy by continuous suspension electrolysis, the metal wire is an aluminum metal wire and/or a magnesium metal wire and/or an aluminum magnesium metal wire.
In the method for producing the rare earth intermediate alloy by continuous suspension electrolysis, 0.5-5% of rare earth oxide is added into a molten salt system.
In the method for producing the rare earth intermediate alloy by continuous suspension electrolysis, a PLC control system acquires data such as the temperature of a molten salt system, the temperature of a preheating pipe, the temperature of a heat preservation pipe, the voltage difference between a cathode and a liquid cathode, the voltage difference between the liquid cathode and a graphite groove and a graphite anode, the resistance of the liquid cathode and the like through a control line, a data acquisition line and a detection probe, compares the data with a preset method, and controls the temperature of a heating pipe, the heat preservation pipe and the molten salt system, the feeding speed of an oxide feeder, the wire feeding speed of a wire feeder and the alloy drawing speed of a liquid pump to reach the requirement, thereby achieving the aim of continuous electrolysis production.
In the method for producing the rare earth intermediate alloy by continuous suspension electrolysis, the electrolysis temperature is as follows: the temperature of the metal wire is controlled to be 300-400 ℃ in 810-980 ℃, the temperature of the pipeline for extracting the alloy is controlled to be 800-980 ℃, and the electrolytic voltage is controlled to be 8-12V.
In the method for producing the rare earth intermediate alloy by continuous suspension electrolysis, the thickness of molten metal formed by the metal wire is 10-25 mm.
The method for producing the rare earth intermediate alloy by continuous suspension electrolysis can be used for producing rare earth aluminum and/or magnesium alloy by electrolysis, and can also be used for producing aluminum zirconium, aluminum beryllium, magnesium zirconium and magnesium beryllium alloy by electrolysis.
Drawings
FIG. 1 is a schematic structural diagram of a method for producing a rare earth intermediate alloy by continuous suspension electrolysis according to the present invention.
FIG. 2 is a schematic view of an apparatus for use in a continuous suspension electrolysis process for producing a rare earth master alloy according to the present invention.
Detailed Description
The present invention is further illustrated by the following specific embodiments, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
It should be noted that the examples including, but not limited to, the embodiments set forth below focus on the core solution examples, wherein processes or steps that are not explicitly defined are supplemented by the existing conventional techniques in the art to form a complete solution, and the conventional techniques are not described herein, but may be adjusted by those skilled in the art according to the actual production requirements, and thus should not be considered as being insufficiently disclosed.
Example 1
The continuous suspension electrolysis production of the rare earth intermediate alloy in the embodiment is as follows: and finishing preparation work, wherein a molten fluoride salt melting system which takes fluoride as a main component and is molten is formed in the electrolytic bath, and the fluoride is rare earth fluoride in mass ratio: barium fluoride: lithium fluoride is a mixture of 61:20:19, and the amount of fluoride added to the cell depends on the size of the cell. An anode for electrolysis is formed in the electrolytic cell. The anode may be a separate member formed inside the electrolytic cell, or may be the electrolytic cell itself. The molten fluoride salt system can be obtained by transferring energy to the fluoride in the electrolytic cell by means of external electric heating, radiant heating, high-frequency electromagnetic heating, etc., so that the fluoride is melted into the molten fluoride salt system. At the moment, rare earth oxide is added into a fluoride molten salt system to form an electrolytic system, the adding mass is 0.5 percent of the total mass of the electrolytic system, and the electrolytic system is kept at 820 ℃ at the electrolytic temperature. Introducing a preheated (preheating temperature of 400 ℃) metal supplement material, namely a metal wire into an electrolytic system, thereby forming molten metal on the liquid level of the electrolytic system, and controlling the thickness of the molten metal to be 20 mm. During electrolysis, the cathode is inserted into the molten metal to jointly form a liquid cathode, and after electrification, the liquid cathode, the melt in the electrolysis system and the anode jointly form an electrolytic cell for electrolysis. Monitoring the content of rare earth substances in the molten metal in the electrolytic process, and when the content meets the requirement, namely the content is 5 wt.%, starting a liquid pump to appropriately pump qualified molten metal from a liquid pumping pipe to form metal alloy, and sampling and monitoring the metal alloy. The PLC system arranged in the electrolysis equipment controls the whole system according to the monitored parameters in the electrolysis process, the monitored parameters comprise the temperature of a fluoride molten salt system, the temperature of a metal supplement material, the temperature of a pipeline used for extracting qualified molten metal, the voltage between a cathode and an anode of an electrolysis system, the voltage between the cathode and a liquid cathode, the voltage between an electrolytic bath and the anode, the voltage between the liquid cathode and the electrolytic bath, the voltage between the cathode and the electrolytic bath and the like, according to the monitoring of the parameters and the comparison with the standard value set according to the process requirements, the control is converted into the control of heating and heat preservation, material supplement and extraction and the like of each part of subsystem, and continuously extracting qualified molten metal under the control of the molten metal, wherein the metal wire and the rare earth oxide are continuously supplemented in the electrolysis process, so that the supplementing speeds of the metal wire and the rare earth oxide are 95 wt.% and 6.35 wt.% of the mass of the molten metal respectively.
Example 2
The continuous suspension electrolysis production of the rare earth intermediate alloy in the embodiment is as follows: and finishing preparation work, wherein a molten fluoride salt melting system which takes fluoride as a main component and is molten is formed in the electrolytic bath, and the fluoride is rare earth fluoride in mass ratio: barium fluoride: lithium fluoride is a mixture of 65:18:17, and the amount of fluoride added to the cell depends on the size of the cell. An anode for electrolysis is formed in the electrolytic cell. The anode may be a separate member formed inside the electrolytic cell, or may be the electrolytic cell itself. The molten fluoride salt system can be obtained by transferring energy to the fluoride in the electrolytic cell by means of external electric heating, radiant heating, high-frequency electromagnetic heating, etc., so that the fluoride is melted into the molten fluoride salt system. At the moment, rare earth oxide is introduced into a fluoride molten salt system to form an electrolytic system, the mass of the introduced electrolytic system is 1.0 percent of the total mass of the electrolytic system, and the electrolytic system is kept at 850 ℃ at the electrolytic temperature. Introducing a preheated (preheating temperature of 340 ℃) metal supplement material, namely a metal wire into an electrolytic system, thereby forming a metal liquid on the liquid level of the electrolytic system, and controlling the thickness of the metal liquid to be 15 mm. During electrolysis, the cathode is inserted into the molten metal to jointly form a liquid cathode, and after electrification, the liquid cathode, the melt in the electrolysis system and the anode jointly form an electrolytic cell for electrolysis. Monitoring the content of rare earth substances in the molten metal in the electrolytic process, and when the content meets the requirement, namely the content is 10 wt.%, starting a liquid pump to appropriately pump qualified molten metal from a liquid pumping pipe to form metal alloy, and sampling and monitoring the metal alloy. The PLC system arranged in the electrolysis equipment controls the whole system according to the monitored parameters in the electrolysis process, the monitored parameters comprise the temperature of a fluoride molten salt system, the temperature of a metal supplement material, the temperature of a pipeline used for extracting qualified molten metal, the voltage between a cathode and an anode of an electrolysis system, the voltage between the cathode and a liquid cathode, the voltage between an electrolytic bath and the anode, the voltage between the liquid cathode and the electrolytic bath, the voltage between the cathode and the electrolytic bath and the like, according to the monitoring of the parameters and the comparison with the standard value set according to the process requirements, the control is converted into the control of heating and heat preservation, material supplement and extraction and the like of each part of subsystem, and continuously extracting qualified molten metal under the control of the molten metal, wherein the metal wire and the rare earth oxide are continuously supplemented in the electrolysis process, and the supplement speeds of the metal wire and the rare earth oxide are respectively 90 wt.% and 12.7 wt.% of the mass of the molten metal.
Example 3
The continuous suspension electrolysis production of the rare earth intermediate alloy in the embodiment is as follows: and finishing preparation work, wherein a molten fluoride salt melting system which takes fluoride as a main component and is molten is formed in the electrolytic bath, and the fluoride is rare earth fluoride in mass ratio: barium fluoride: lithium fluoride is a mixture of 70:25:15, and the amount of fluoride added to the cell depends on the size of the cell. An anode for electrolysis is formed in the electrolytic cell. The anode may be a separate member formed inside the electrolytic cell, or may be the electrolytic cell itself. The molten fluoride salt system can be obtained by transferring energy to the fluoride in the electrolytic cell by means of external electric heating, radiant heating, high-frequency electromagnetic heating, etc., so that the fluoride is melted into the molten fluoride salt system. At the moment, rare earth oxide is introduced into a fluoride molten salt system to form an electrolytic system, the introduced mass is 4 percent of the total mass of the electrolytic system, and the electrolytic system is kept at 980 ℃ at the electrolytic temperature. Introducing a preheated (preheating temperature of 330 ℃) metal supplement material, namely a metal wire into an electrolytic system, thereby forming a metal liquid on the liquid surface of the electrolytic system, and controlling the thickness of the metal liquid to be 12 mm. During electrolysis, the cathode is inserted into the molten metal to jointly form a liquid cathode, and after electrification, the liquid cathode, the melt in the electrolysis system and the anode jointly form an electrolytic cell for electrolysis. Monitoring the content of rare earth substances in the molten metal in the electrolytic process, and when the content meets the requirement, namely the content is 20 wt.%, starting a liquid pump to appropriately pump qualified molten metal from a liquid pumping pipe to form metal alloy, and sampling and monitoring the metal alloy. The PLC system arranged in the electrolysis equipment controls the whole system according to the monitored parameters in the electrolysis process, the monitored parameters comprise the temperature of a fluoride molten salt system, the temperature of a metal supplement material, the temperature of a pipeline used for extracting qualified molten metal, the voltage between a cathode and an anode of an electrolysis system, the voltage between the cathode and a liquid cathode, the voltage between an electrolytic bath and the anode, the voltage between the liquid cathode and the electrolytic bath, the voltage between the cathode and the electrolytic bath and the like, according to the monitoring of the parameters and the comparison with the standard value set according to the process requirements, the control is converted into the control of heating and heat preservation, material supplement and extraction and the like of each part of subsystem, and continuously extracting qualified molten metal under the control of the molten metal, wherein the metal wire and the rare earth oxide are continuously supplemented in the electrolysis process, and the supplement speeds of the metal wire and the rare earth oxide are respectively 80 wt.% and 25.39 wt.%.
Example 4
The continuous suspension electrolysis production of the rare earth intermediate alloy in the embodiment is as follows: and finishing preparation work, wherein a molten fluoride salt melting system which takes fluoride as a main component and is molten is formed in the electrolytic bath, and the fluoride is rare earth fluoride in mass ratio: barium fluoride: lithium fluoride 67:22:17, the amount of fluoride added to the cell depending on the size of the cell. An anode for electrolysis is formed in the electrolytic cell. The anode may be a separate member formed inside the electrolytic cell, or may be the electrolytic cell itself. The molten fluoride salt system can be obtained by transferring energy to the fluoride in the electrolytic cell by means of external electric heating, radiant heating, high-frequency electromagnetic heating, etc., so that the fluoride is melted into the molten fluoride salt system. At the moment, rare earth oxide is introduced into a fluoride molten salt system to form an electrolytic system, the mass of the introduced rare earth oxide is 2 percent of the total mass of the electrolytic system, and the electrolytic system is kept at the electrolytic temperature of 950 ℃. Introducing a preheated (preheating temperature of 320 ℃) metal supplement material, namely a metal wire into an electrolytic system, thereby forming molten metal on the liquid level of the electrolytic system, and controlling the thickness of the molten metal to be 25 mm. During electrolysis, the cathode is inserted into the molten metal to jointly form a liquid cathode, and after electrification, the liquid cathode, the melt in the electrolysis system and the anode jointly form an electrolytic cell for electrolysis. Monitoring the content of rare earth substances in the molten metal in the electrolytic process, and when the content meets the requirement, namely the content is 15 wt.%, starting a liquid pump to appropriately pump qualified molten metal from a liquid pumping pipe to form metal alloy, and sampling and monitoring the metal alloy. The PLC system arranged in the electrolysis equipment controls the whole system according to the monitored parameters in the electrolysis process, the monitored parameters comprise the temperature of a fluoride molten salt system, the temperature of a metal supplement material, the temperature of a pipeline used for extracting qualified molten metal, the voltage between a cathode and an anode of an electrolysis system, the voltage between the cathode and a liquid cathode, the voltage between an electrolytic bath and the anode, the voltage between the liquid cathode and the electrolytic bath, the voltage between the cathode and the electrolytic bath and the like, according to the monitoring of the parameters and the comparison with the standard value set according to the process requirements, the control is converted into the control of heating and heat preservation, material supplement and extraction and the like of each part of subsystem, and continuously extracting qualified molten metal under the control of the molten metal, wherein the metal wire and the rare earth oxide are continuously supplemented in the electrolysis process, and the supplement speeds of the metal wire and the rare earth oxide are respectively 85 wt.% and 19.04 wt.% of the mass of the molten metal.
Example 5
The continuous suspension electrolysis production of the rare earth intermediate alloy in the embodiment is as follows: and finishing preparation work, wherein a molten fluoride salt melting system which takes fluoride as a main component and is molten is formed in the electrolytic bath, and the fluoride is rare earth fluoride in mass ratio: barium fluoride: lithium fluoride is a mixture of 62:18:20, and the amount of fluoride added to the cell depends on the size of the cell. An anode for electrolysis is formed in the electrolytic cell. The anode may be a separate member formed inside the electrolytic cell, or may be the electrolytic cell itself. The molten fluoride salt system can be obtained by transferring energy to the fluoride in the electrolytic cell by means of external electric heating, radiant heating, high-frequency electromagnetic heating, etc., so that the fluoride is melted into the molten fluoride salt system. At the moment, rare earth oxide is introduced into a fluoride molten salt system to form an electrolytic system, the mass of the introduced rare earth oxide is 3 percent of the total mass of the electrolytic system, and the electrolytic system is kept at 900 ℃ at the electrolytic temperature. Introducing a preheated (the preheating temperature is 380 ℃) metal supplement material, namely a metal wire into an electrolytic system, thereby forming a metal liquid on the liquid surface of the electrolytic system, and controlling the thickness of the metal liquid to be 20 mm. During electrolysis, the cathode is inserted into the molten metal to jointly form a liquid cathode, and after electrification, the liquid cathode, the melt in the electrolysis system and the anode jointly form an electrolytic cell for electrolysis. Monitoring the content of rare earth substances in the molten metal in the electrolytic process, and when the content meets the requirement, namely the content is 12 wt.%, starting a liquid pump to appropriately pump qualified molten metal from a liquid pumping pipe to form metal alloy, and sampling and monitoring the metal alloy. The PLC system arranged in the electrolysis equipment controls the whole system according to the monitored parameters in the electrolysis process, the monitored parameters comprise the temperature of a fluoride molten salt system, the temperature of a metal supplement material, the temperature of a pipeline used for extracting qualified molten metal, the voltage between a cathode and an anode of an electrolysis system, the voltage between the cathode and a liquid cathode, the voltage between an electrolytic bath and the anode, the voltage between the liquid cathode and the electrolytic bath, the voltage between the cathode and the electrolytic bath and the like, according to the monitoring of the parameters and the comparison with the standard value set according to the process requirements, the control is converted into the control of heating and heat preservation, material supplement and extraction and the like of each part of subsystem, and continuously extracting qualified molten metal under the control of the molten metal, wherein the metal wire and the rare earth oxide are continuously supplemented in the electrolysis process, and the supplement speeds of the metal wire and the rare earth oxide are respectively 88 wt.% and 14.06 wt.% of the mass of the molten metal.
Example 6
The continuous suspension electrolysis production of the rare earth intermediate alloy in the embodiment is as follows: and finishing preparation work, wherein a molten fluoride salt melting system which takes fluoride as a main component and is molten is formed in the electrolytic bath, and the fluoride is rare earth fluoride in mass ratio: barium fluoride: lithium fluoride is a mixture of 63:25:18, and the amount of fluoride added to the cell depends on the size of the cell. An anode for electrolysis is formed in the electrolytic cell. The anode may be a separate member formed inside the electrolytic cell, or may be the electrolytic cell itself. The molten fluoride salt system can be obtained by transferring energy to the fluoride in the electrolytic cell by means of external electric heating, radiant heating, high-frequency electromagnetic heating, etc., so that the fluoride is melted into the molten fluoride salt system. At the moment, rare earth oxide is introduced into a fluoride molten salt system to form an electrolytic system, the introduced mass is 5 percent of the total mass of the electrolytic system, and the electrolytic system is kept at 940 ℃ at the electrolytic temperature. Introducing a preheated (preheating temperature of 350 ℃) metal supplement material, namely a metal wire into an electrolytic system, thereby forming molten metal on the liquid level of the electrolytic system, and controlling the thickness of the molten metal to be 22 mm. During electrolysis, the cathode is inserted into the molten metal to jointly form a liquid cathode, and after electrification, the liquid cathode, the melt in the electrolysis system and the anode jointly form an electrolytic cell for electrolysis. Monitoring the content of rare earth substances in the molten metal in the electrolytic process, and when the content meets the requirement, namely the content is 15 wt.%, starting a liquid pump to appropriately pump qualified molten metal from a liquid pumping pipe to form metal alloy, and sampling and monitoring the metal alloy. The PLC system arranged in the electrolysis equipment controls the whole system according to the monitored parameters in the electrolysis process, the monitored parameters comprise the temperature of a fluoride molten salt system, the temperature of a metal supplement material, the temperature of a pipeline used for extracting qualified molten metal, the voltage between a cathode and an anode of an electrolysis system, the voltage between the cathode and a liquid cathode, the voltage between an electrolytic bath and the anode, the voltage between the liquid cathode and the electrolytic bath, the voltage between the cathode and the electrolytic bath and the like, according to the monitoring of the parameters and the comparison with the standard value set according to the process requirements, the control is converted into the control of heating and heat preservation, material supplement and extraction and the like of each part of subsystem, and continuously extracting qualified molten metal under the control of the molten metal, wherein the metal wire and the rare earth oxide are continuously supplemented in the electrolysis process, and the supplement speeds of the metal wire and the rare earth oxide are respectively 85 wt.% and 17.58 wt.% of the mass of the molten metal.
Example 7
The continuous suspension electrolysis production of the rare earth intermediate alloy in the embodiment is as follows: and finishing preparation work, wherein a molten fluoride salt melting system which takes fluoride as a main component and is molten is formed in the electrolytic bath, and the fluoride is rare earth fluoride in mass ratio: barium fluoride: lithium fluoride is a mixture of 68:20:14, and the amount of fluoride added to the cell depends on the size of the cell. An anode for electrolysis is formed in the electrolytic cell. The anode may be a separate member formed inside the electrolytic cell, or may be the electrolytic cell itself. The molten fluoride salt system can be obtained by transferring energy to the fluoride in the electrolytic cell by means of external electric heating, radiant heating, high-frequency electromagnetic heating, etc., so that the fluoride is melted into the molten fluoride salt system. At the moment, rare earth oxide is introduced into a fluoride molten salt system to form an electrolytic system, the mass of the introduced electrolytic system is 4.5 percent of the total mass of the electrolytic system, and the electrolytic system is kept at 980 ℃ at the electrolytic temperature. Introducing a preheated (preheating temperature of 400 ℃) metal supplement-metal wire into the electrolytic system, thereby forming molten metal on the liquid surface of the electrolytic system, and controlling the thickness of the molten metal to be 18 mm. During electrolysis, the cathode is inserted into the molten metal to jointly form a liquid cathode, and after electrification, the liquid cathode, the melt in the electrolysis system and the anode jointly form an electrolytic cell for electrolysis. Monitoring the content of rare earth substances in the molten metal in the electrolytic process, and when the content meets the requirement, namely the content is 18 wt.%, starting a liquid pump to appropriately pump qualified molten metal from a liquid pumping pipe to form metal alloy, and sampling and monitoring the metal alloy. The PLC system arranged in the electrolysis equipment controls the whole system according to the monitored parameters in the electrolysis process, the monitored parameters comprise the temperature of a fluoride molten salt system, the temperature of a metal supplement material, the temperature of a pipeline used for extracting qualified molten metal, the voltage between a cathode and an anode of an electrolysis system, the voltage between the cathode and a liquid cathode, the voltage between an electrolytic bath and the anode, the voltage between the liquid cathode and the electrolytic bath, the voltage between the cathode and the electrolytic bath and the like, according to the monitoring of the parameters and the comparison with the standard value set according to the process requirements, the control is converted into the control of heating and heat preservation, material supplement and extraction and the like of each part of subsystem, and continuously extracting qualified molten metal under the control of the molten metal, wherein the metal wire and the rare earth oxide are continuously supplemented in the electrolysis process, so that the supplement speeds of the metal wire and the rare earth oxide are 82 wt.% and 22.85 wt.% of the mass of the molten metal respectively.
Example 8
The continuous suspension electrolysis production of the rare earth intermediate alloy in the embodiment is as follows: and finishing preparation work, wherein a molten fluoride salt melting system which takes fluoride as a main component and is molten is formed in the electrolytic bath, and the fluoride is rare earth fluoride in mass ratio: barium fluoride: lithium fluoride is 65:15:16, and the amount of fluoride added to the cell depends on the size of the cell. An anode for electrolysis is formed in the electrolytic cell. The anode may be a separate member formed inside the electrolytic cell, or may be the electrolytic cell itself. The molten fluoride salt system can be obtained by transferring energy to the fluoride in the electrolytic cell by means of external electric heating, radiant heating, high-frequency electromagnetic heating, etc., so that the fluoride is melted into the molten fluoride salt system. At the moment, rare earth oxide is introduced into a fluoride molten salt system to form an electrolytic system, the mass of the introduced rare earth oxide is 5 percent of the total mass of the electrolytic system, and the electrolytic system is kept at the electrolytic temperature of 950 ℃. Introducing a preheated (preheating temperature of 300 ℃) metal supplement material, namely a metal wire into an electrolytic system, thereby forming a metal liquid on the liquid surface of the electrolytic system, and controlling the thickness of the metal liquid to be 13 mm. During electrolysis, the cathode is inserted into the molten metal to jointly form a liquid cathode, and after electrification, the liquid cathode, the melt in the electrolysis system and the anode jointly form an electrolytic cell for electrolysis. Monitoring the content of rare earth substances in the molten metal in the electrolytic process, and when the content meets the requirement, namely the content is 13 wt.%, starting a liquid pump to appropriately pump qualified molten metal from a liquid pumping pipe to form metal alloy, and sampling and monitoring the metal alloy. The PLC system arranged in the electrolysis equipment controls the whole system according to the monitored parameters in the electrolysis process, the monitored parameters comprise the temperature of a fluoride molten salt system, the temperature of a metal supplement material, the temperature of a pipeline used for extracting qualified molten metal, the voltage between a cathode and an anode of an electrolysis system, the voltage between the cathode and a liquid cathode, the voltage between an electrolytic bath and the anode, the voltage between the liquid cathode and the electrolytic bath, the voltage between the cathode and the electrolytic bath and the like, according to the monitoring of the parameters and the comparison with the standard value set according to the process requirements, the control is converted into the control of heating and heat preservation, material supplement and extraction and the like of each part of subsystem, and continuously extracting qualified molten metal under the control of the molten metal, wherein the metal wire and the rare earth oxide are continuously supplemented in the electrolysis process, so that the supplement speeds of the metal wire and the rare earth oxide are respectively 87 wt.% and 16.5 wt.% of the mass of the molten metal.
Example 9
The continuous suspension electrolysis production of the rare earth intermediate alloy in the embodiment is as follows: and finishing preparation work, wherein a molten fluoride salt melting system which takes fluoride as a main component and is molten is formed in the electrolytic bath, and the fluoride is rare earth fluoride in mass ratio: barium fluoride: lithium fluoride is a mixture of 60:15:20, and the amount of fluoride added to the cell depends on the size of the cell. An anode for electrolysis is formed in the electrolytic cell. The anode may be a separate member formed inside the electrolytic cell, or may be the electrolytic cell itself. The molten fluoride salt system can be obtained by transferring energy to the fluoride in the electrolytic cell by means of external electric heating, radiant heating, high-frequency electromagnetic heating, etc., so that the fluoride is melted into the molten fluoride salt system. At the moment, rare earth oxide is introduced into a fluoride molten salt system to form an electrolytic system, the mass of the introduced rare earth oxide is 5 percent of the total mass of the electrolytic system, and the electrolytic system is kept at 820 ℃ at the electrolytic temperature. Introducing a preheated (preheating temperature of 300 ℃) metal supplement material, namely a metal wire into an electrolytic system, thereby forming a metal liquid on the liquid surface of the electrolytic system, and controlling the thickness of the metal liquid to be 13 mm. During electrolysis, the cathode is inserted into the molten metal to jointly form a liquid cathode, and after electrification, the liquid cathode, the melt in the electrolysis system and the anode jointly form an electrolytic cell for electrolysis. Monitoring the content of rare earth substances in the molten metal in the electrolytic process, and when the content meets the requirement, namely the content is 0.95 wt.%, starting a liquid pump to appropriately pump qualified molten metal from a liquid pumping pipe to form metal alloy, and sampling and monitoring the metal alloy. The PLC system arranged in the electrolysis equipment controls the whole system according to the monitored parameters in the electrolysis process, the monitored parameters comprise the temperature of a fluoride molten salt system, the temperature of a metal supplement material, the temperature of a pipeline used for extracting qualified molten metal, the voltage between a cathode and an anode of an electrolysis system, the voltage between the cathode and a liquid cathode, the voltage between an electrolytic bath and the anode, the voltage between the liquid cathode and the electrolytic bath, the voltage between the cathode and the electrolytic bath and the like, according to the monitoring of the parameters and the comparison with the standard value set according to the process requirements, the control is converted into the control of heating and heat preservation, material supplement and extraction and the like of each part of subsystem, and continuously extracting qualified molten metal under the control of the molten metal, wherein the metal wire and the rare earth oxide are continuously supplemented in the electrolysis process, so that the supplementing speeds of the metal wire and the rare earth oxide are respectively 99 wt.% and 1.1 wt.% of the mass of the molten metal.
In the above embodiments, the rare earth oxide may be lanthanum oxide or cerium oxide or praseodymium oxide or yttrium oxide, etc. The metal supplementary material is metal aluminum wire or metal magnesium wire or aluminum alloy wire or magnesium alloy wire or other metal wire rods, metal bars and the like.
In particular, the following is a partial embodiment illustrating the superiority of the present solution:
as shown in fig. 1 and 2, in the following examples:
adding yttrium fluoride, barium fluoride and lithium fluoride into an electrolytic tank according to a designed proportion, when an electrolyte is melted into an electrolytic system 5 and the temperature reaches the electrolytic temperature, forming a metal liquid 3 on the liquid surface of the electrolytic system by a metal wire preheated by a preheating pipe, inserting a cathode conductive tungsten rod 1 to enable a finger to be inserted into the liquid surface of the electrolyte by a preset depth, starting a rectifier, and adding a rare earth oxide into a feeder 6 to carry out electrolysis. In the electrolysis process, feeding and wire feeding are carried out through the wire feeder 2 and the feeder 6 under the automatic control of the PLC, the metal liquid is electrolyzed for a period of time, when the metal liquid is qualified, the liquid pump 4 is started, the alloy liquid extraction speed is calculated according to the electrolysis speed, the alloy is extracted, and the alloy is weighed and analyzed.
In example 1:
the electrolyte mass ratio is yttrium fluoride: barium fluoride: the lithium fluoride accounts for 61:20:19, and the metal supplement material and the rare earth oxide are prepared from the following raw materials in percentage by weight: yttrium oxide 95:6.35, electrolysis was carried out in a 6000A electrolytic furnace at an electrolytic current of 3800A and an electrolytic temperature of 820 ℃. 63Kg of alloy was withdrawn per hour, and the analysis results of the alloy composition were as follows.
In example 2:
the electrolyte mass ratio is yttrium fluoride: barium fluoride: the lithium fluoride is 65:18:17, and the raw material proportion of the metal supplement material and the rare earth oxide is that the metal magnesium wire: the yttrium oxide is 90:12.7, and the electrolysis is carried out in a 6000A electrolytic furnace, the electrolytic current intensity is 3800A, and the electrolytic temperature is 850 ℃. 33.2Kg of alloy was withdrawn per hour, and the analysis results of the alloy composition were as follows.
In example 3:
the electrolyte mass ratio is yttrium fluoride: barium fluoride: lithium fluoride is 70:25:15, and the ratio of the metal supplement material to the rare earth oxide is as follows: the yttrium oxide (80: 25.39) was electrolyzed in a 6000A electrolytic furnace at 3800A of electrolytic current and 980 ℃. 16.6Kg of alloy was withdrawn per hour, and the analysis results of the alloy composition were as follows.
In example 4:
the electrolyte mass ratio is yttrium fluoride: barium fluoride: the lithium fluoride accounts for 67:22:17, and the metal supplement material and the rare earth oxide are prepared from the following raw materials in percentage by weight: metal magnesium wires: yttrium oxide 42.5: 42.5:19.04, electrolyzing in an electrolytic furnace of 6000A at the current intensity of 3800A and the temperature of 950 ℃. 22.1Kg of alloy was withdrawn per hour, and the analysis results of the alloy composition were as follows.
In example 5:
the electrolyte mass ratio is lanthanum fluoride cerium: barium fluoride: the ratio of the raw materials of the metal supplement material and the rare earth oxide is metal magnesium wire: lanthanum oxide: cerium oxide 88: 7.03: 7.03, electrolyzing in a 6000A electrolytic furnace, wherein the electrolytic current intensity is 3800A and the electrolytic temperature is 900 ℃. 38Kg of alloy was withdrawn per hour, and the analysis results of the alloy composition were as follows.
In example 6:
the electrolyte mass ratio is lanthanum fluoride cerium: barium fluoride: the ratio of the metal supplement material to the rare earth oxide is metal magnesium wire: lanthanum oxide: cerium oxide 85: 8.79: 8.79, electrolyzing in an electrolytic furnace of 6000A at the current intensity of 3800A and the temperature of 940 ℃. 30.3Kg of alloy was withdrawn per hour, and the analysis results of the alloy composition were as follows.
In example 7:
the electrolyte mass ratio is yttrium fluoride: barium fluoride: the lithium fluoride accounts for 68:20:14, and the metal supplement material and the rare earth oxide are prepared from the following raw materials in percentage by weight: metal magnesium wires: yttrium oxide 60: 22:22.85, electrolyzing in a 6000A electrolytic furnace, wherein the electrolytic current intensity is 3800A and the electrolytic temperature is 980 ℃. 18.4Kg of alloy was withdrawn per hour, and the analysis results of the alloy composition were as follows.
In example 8:
the electrolyte mass ratio is yttrium fluoride: barium fluoride: the lithium fluoride accounts for 65:15:16, and the metal supplement material and the rare earth oxide are prepared from the following raw materials in percentage by weight: metal magnesium wires: yttrium oxide 62: 25:16.5, electrolyzing in a 6000A electrolytic furnace, wherein the electrolytic current intensity is 3800A and the electrolytic temperature is 950 ℃. 25.5Kg of alloy was withdrawn per hour, and the analysis results of the alloy composition were as follows.
In example 9:
the electrolyte mass ratio is lanthanum fluoride cerium: barium fluoride: the ratio of the metal supplement material to the rare earth oxide is as follows: lanthanum oxide: cerium oxide 99: 0.55: 0.55, electrolysis was carried out in a 2000A electrolytic furnace at an electrolysis current intensity of 800A and an electrolysis temperature of 820 ℃. 54.6Kg of alloy was withdrawn per hour, and the analysis results of the alloy composition were as follows.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and the technical scheme also comprises the technical scheme formed by any combination of the technical characteristics. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.
Claims (9)
1. A method for producing rare earth master alloy by continuous suspension electrolysis comprises the following steps:
A. forming a fluoride molten salt system in an electrolytic cell with an anode to form a uniform electrolytic system;
B. adding a metal supplement material into an electrolytic system to form a molten metal in the electrolytic system, wherein the molten metal and a cathode together form a liquid cathode;
C. the control system obtains real-time electrolysis process parameters in the process flow, and controls any one of the supplement speed at least comprising metal supplement materials, the supplement speed of rare earth oxides or the extraction speed of qualified molten metal prepared by electrolysis according to the real-time electrolysis process parameters: at least in the electrolysis process after the electrification, the control system also monitors the monitoring amount in the liquid cathode, and qualified molten metal can be extracted to be continuously electrolyzed after the preset standard is met.
2. The method for producing rare earth master alloy through continuous suspension electrolysis as claimed in claim 1, wherein the control system monitors the content of rare earth elements in the liquid cathode in real time during electrolysis after power-on, and the predetermined standard met when qualified molten metal is extracted is 1-20 wt.% of the total content of rare earth elements in the molten metal of the liquid electrode.
3. The method for producing rare earth master alloy through continuous suspension electrolysis according to claim 1, wherein the step C, the control system obtaining real-time electrolysis process parameters in the process flow, at least comprises any one of the following steps: the temperature of a fluoride molten salt system, the temperature of a metal supplement material, the temperature of a pipeline used for extracting qualified molten metal, the voltage between a cathode and an anode of an electrolytic system, the voltage between the cathode and a liquid cathode, the voltage between an electrolytic bath and an anode, the voltage between the liquid cathode and the electrolytic bath, and the voltage between the cathode and the electrolytic bath.
4. The method for producing a rare earth intermediate alloy by continuous suspension electrolysis as claimed in claim 1, wherein the thickness of the molten metal in step B is 10-25 mm.
5. A method for continuous suspension electrolysis production of rare earth master alloys according to claim 1, wherein the rare earth oxide is replenished at a rate of 1.1 wt.% to 25.39 wt.% of the quality of the ready-to-draw metal bath.
6. The method for producing rare earth master alloy through continuous suspension electrolysis as claimed in claim 1, wherein the replenishing speed of the metal supplement material is 80 wt.% to 99 wt.% of the quality of the instantly extracted qualified molten metal.
7. The method for producing the rare earth intermediate alloy by continuous suspension electrolysis according to claim 1, wherein the fluoride molten salt electrolysis system is obtained by mixing and melting fluorides.
8. The method for producing rare earth master alloy by continuous suspension electrolysis according to claim 1, wherein the fluoride has a composition of, by mass: rare earth fluoride: barium fluoride: lithium fluoride (60-70): (15-25): 10-20).
9. The method for producing rare earth intermediate alloy by continuous suspension electrolysis is applied to aluminum alloy, magnesium alloy, aluminum-zirconium alloy, aluminum-beryllium alloy, magnesium-zirconium alloy and magnesium-beryllium alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911158186.2A CN110904469B (en) | 2019-11-22 | 2019-11-22 | Method for producing rare earth intermediate alloy by continuous suspension electrolysis and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911158186.2A CN110904469B (en) | 2019-11-22 | 2019-11-22 | Method for producing rare earth intermediate alloy by continuous suspension electrolysis and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110904469A true CN110904469A (en) | 2020-03-24 |
| CN110904469B CN110904469B (en) | 2021-08-03 |
Family
ID=69819107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911158186.2A Active CN110904469B (en) | 2019-11-22 | 2019-11-22 | Method for producing rare earth intermediate alloy by continuous suspension electrolysis and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110904469B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613864A (en) * | 2009-07-29 | 2009-12-30 | 中国科学院青海盐湖研究所 | The method of preparing magnesium-rare earth alloy by fused salt electrolysis process |
| CN101724769A (en) * | 2008-10-13 | 2010-06-09 | 北京有色金属研究总院 | Rare earth aluminum alloy, and method and device for preparing same |
| KR101192290B1 (en) * | 2012-06-27 | 2012-10-17 | 한국지질자원연구원 | Continuous electrolytic apparatus for molten salt |
| CN103590073A (en) * | 2013-11-14 | 2014-02-19 | 扬州宏福铝业有限公司 | Method for preparing mixed intermediate alloy of magnesium and light rare earth with double-cathode method |
| CN104775137A (en) * | 2014-01-13 | 2015-07-15 | 赣州飞腾轻合金有限公司 | Method for preparing aluminum-samarium interalloy through liquid-state cathode salt fusion electrolysis method |
| CN109295478A (en) * | 2018-11-30 | 2019-02-01 | 包头铝业有限公司 | A kind of preparation method of alumal |
| CN109487302A (en) * | 2017-10-18 | 2019-03-19 | 虔东稀土集团股份有限公司 | A method of producing rare earth metal and alloy |
| CN109487301A (en) * | 2017-10-18 | 2019-03-19 | 虔东稀土集团股份有限公司 | A kind of industrialized preparing process of rare earth metal or alloy |
| CN110195243A (en) * | 2019-06-28 | 2019-09-03 | 东华理工大学 | A kind of liquid cathode molten-salt electrolysis Extraction of rare earth and the method for preparing plumbum rare earth alloy |
-
2019
- 2019-11-22 CN CN201911158186.2A patent/CN110904469B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724769A (en) * | 2008-10-13 | 2010-06-09 | 北京有色金属研究总院 | Rare earth aluminum alloy, and method and device for preparing same |
| CN101613864A (en) * | 2009-07-29 | 2009-12-30 | 中国科学院青海盐湖研究所 | The method of preparing magnesium-rare earth alloy by fused salt electrolysis process |
| KR101192290B1 (en) * | 2012-06-27 | 2012-10-17 | 한국지질자원연구원 | Continuous electrolytic apparatus for molten salt |
| CN103590073A (en) * | 2013-11-14 | 2014-02-19 | 扬州宏福铝业有限公司 | Method for preparing mixed intermediate alloy of magnesium and light rare earth with double-cathode method |
| CN104775137A (en) * | 2014-01-13 | 2015-07-15 | 赣州飞腾轻合金有限公司 | Method for preparing aluminum-samarium interalloy through liquid-state cathode salt fusion electrolysis method |
| CN109487302A (en) * | 2017-10-18 | 2019-03-19 | 虔东稀土集团股份有限公司 | A method of producing rare earth metal and alloy |
| CN109487301A (en) * | 2017-10-18 | 2019-03-19 | 虔东稀土集团股份有限公司 | A kind of industrialized preparing process of rare earth metal or alloy |
| CN109295478A (en) * | 2018-11-30 | 2019-02-01 | 包头铝业有限公司 | A kind of preparation method of alumal |
| CN110195243A (en) * | 2019-06-28 | 2019-09-03 | 东华理工大学 | A kind of liquid cathode molten-salt electrolysis Extraction of rare earth and the method for preparing plumbum rare earth alloy |
Non-Patent Citations (4)
| Title |
|---|
| RUI GUO等: ""Preparation of Al-Sc Alloy by LiF-ScF3-ScCl3 Molten Salt Electrolysis"", 《MATERIALS SCIENCE FORUM》 * |
| 孙强超: ""氟化物体系电解制备Ni-Yb中间合金基础研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 王健 等: ""熔盐电解法制备稀土镁合金的研究进展"", 《稀土》 * |
| 纪德彬: ""La、Pr、Sm在Mg、Al阴极上沉积机理研究"", 《中国博士学位论文全文库》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110904469B (en) | 2021-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101724769B (en) | Rare earth aluminum alloy, and method and device for preparing same | |
| CN107858707B (en) | A kind of mold roasting method of aluminium frame anode | |
| CN103924266B (en) | A kind of method that co-electrodeposition method prepares rare earth gadpolinium alloy | |
| CN100562608C (en) | A kind of preparation method of high rare-earth content magnesium master alloy | |
| CN104805471B (en) | The method and apparatus that lower catholyte and ingot casting in situ synchronously prepare rare earth metal | |
| CN104928720B (en) | A kind of electrolytic method of titanium soluble anode | |
| CN102140656A (en) | Method for preparing Dy-Fe alloy through oxide molten salt electrolysis | |
| CN112813463A (en) | Method for preparing rare earth metal or rare earth alloy | |
| CN109136995B (en) | Method for producing rare earth metal and alloy | |
| CN104131317B (en) | The method of thin lead powder is prepared in a kind of electro-deposition | |
| CN110904469B (en) | Method for producing rare earth intermediate alloy by continuous suspension electrolysis and application thereof | |
| US11981979B2 (en) | Device and method for preparing low-impurity regenerated brass alloy through step-by-step insertion of electrode | |
| CN104746106B (en) | Molten salt electrolysis method for preparing aluminum-scandium intermediate alloy | |
| CN104264003B (en) | A kind of energy-saving aluminium alloy wire of stretch-proof and preparation method thereof | |
| CN105603461A (en) | Method of preparing praseodymium-neodymium-dysprosium-terbium quaternary alloy by molten salt electrolysis | |
| CN105908031B (en) | Aluminum alloy materials of high conductivity and preparation method thereof | |
| CN111945023A (en) | Vacuum induction melting method of titanium and titanium alloy ingots | |
| CN106835196A (en) | Produce the mixing electrolysis system of tough cathode | |
| CN109055995B (en) | Method for preparing carbon oxide anode for electrolytic extraction of titanium | |
| CN116237667A (en) | Electrified repair welding agent for aluminum bus | |
| CN110106532A (en) | A kind of method that molten-salt electrolysis prepares terbium ferroalloy | |
| CN100443640C (en) | Apparatus and method for adding element during metal smelting process | |
| CN104831093A (en) | Zr-2.5Nb alloy casting ingot preparation method | |
| CN110526714B (en) | Silicon carbide ramming paste for aluminum electrolysis cell cathode and preparation method thereof | |
| CN202415701U (en) | Electrolytic cell for electrolyzing rare-earth metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |