CN107513730A - The continuous device and method for preparing tungsten powder and cobalt powder - Google Patents

Abstract

The present invention relates to electrochemical technology field, there is provided a kind of continuous device and method for preparing tungsten powder and cobalt powder, the device include storage compartment, reative cell, reaction member, dosage unit, driver element, the first power supply and second source；The both ends of reaction member are respectively equipped with the first graphite cuvette and the second graphite cuvette；Suspension has first anode basket and second plate basket respectively in first graphite cuvette and the second graphite cuvette, the both ends of the bottom of first graphite cuvette offer the first collection pit and the second collection pit respectively, and the both ends of the bottom of the second graphite cuvette offer the 3rd collection pit and the 4th collection pit respectively；First power supply and second source are respectively arranged on the both sides of reative cell；Driver element is used to drive reaction member to rotate by the center of circle of its center.Application way of the present invention not only can continuously obtain cobalt in the first collection pit and the 4th collection pit, tungsten is obtained in the second collection pit and the 3rd collection pit, but also significantly improve the rate of recovery and separative efficiency, avoid electrode conversion.

Description

Device and method for continuously preparing tungsten powder and cobalt powder

technical field

The invention relates to the field of electrochemical technology, in particular to a device and method for continuously preparing tungsten powder and cobalt powder.

Background technique

Refractory metal tungsten and rare metal cobalt are recognized as extremely important strategic elements in the world, and have a very important impact on improving national economic and military competitiveness. The tungsten resources with mining value are very limited in the world, but the use of tungsten resources is increasing year by year, which further leads to the shortage of tungsten resources. In addition, my country's cobalt resources are also extremely short, and a large amount of imports are required to maintain the demand every year. These have greatly threatened the sustainable development of the cemented carbide industry. Cemented carbide is a material with high hardness and high bending strength made of refractory metal tungsten carbide and bonding metal by powder metallurgy. It is widely used in machinery manufacturing, mining, transportation, energy exploration, and architectural decoration. and other fields have been widely used. At present, more than 50% of the world's tungsten resources are used to manufacture cemented carbide, and the tungsten content in waste cemented carbide has reached 74% to 91%. Therefore, recycling waste cemented carbide is a very effective way to recover tungsten and cobalt.

Existing methods for recycling waste cemented carbide mainly include mechanical crushing, zinc melting, electrochemical, oxidation-reduction, and acid leaching. However, the recovery efficiency of the mechanical crushing method and the zinc dissolution method is low, and some impurity elements are easily brought in; the electrochemical method and the redox method cannot be recovered continuously, and the recovery efficiency is also low; the acid leaching method will generate some waste gas such as SO ₂ , NO ₂ .

Contents of the invention

What the invention aims to solve is the technical problem that the recovery rate of tungsten and cobalt in the prior art is low and cannot be recovered continuously.

In order to solve the above problems, the invention provides a device for continuously preparing tungsten powder and cobalt powder, which device comprises:

A material storage room, the material storage room is provided with a first vacuum port and a material inlet and a material outlet that can be opened and closed;

A reaction chamber, the reaction chamber is arranged below the storage chamber, and the reaction chamber is provided with a second vacuum port, an air inlet, an air outlet and a heater;

A reaction unit, the reaction unit is located in the reaction chamber, the two ends of the reaction unit are respectively provided with a first graphite groove and a second graphite groove; the first graphite groove and the second graphite groove are respectively suspended A first anode basket and a second anode basket are placed, and the upper parts of the first anode basket and the second anode basket are connected with anode conductive columns; the two ends of the bottom of the first graphite tank are respectively provided with first A collection pit and a second collection pit, the two ends of the bottom of the second graphite tank are respectively provided with a third collection pit and a fourth collection pit, the first collection pit, the second collection pit, the third collection pit The bottoms of the collection pit and the fourth collection pit are inserted with cathode conductive columns; the first anode basket and the second anode basket, the first collection pit and the fourth collection pit, and the first anode basket Both the second collection pit and the third collection pit are symmetrical about the center of the reaction unit;

A feeding unit, the inlet of the feeding unit is set below the discharge port, and the outlet is set above the circumference of the first anode basket and the second anode basket;

The first power supply and the second power supply, the first power supply and the second power supply are respectively arranged on both sides of the reaction chamber, and the positive poles of the first power supply and the second power supply are connected to the first power supply through wires. metal sheet, the first metal sheet is arranged on the circumference where the top of the anode conductive column is; The metal sheet is arranged on the circumference where the bottom end of the cathode conductive column is located; and

a driving unit, the driving unit is used to drive the reaction unit to rotate around its center, so that each of the first metal sheet and the second metal sheet is connected to the corresponding anode conductive column and the corresponding The cathode conductive post is electrically connected.

Wherein, the upper cover of the first graphite tank is provided with a first corundum plate for suspending the first anode basket, and the upper cover of the second graphite tank is provided with a second corundum plate for suspending the second anode basket plate.

Wherein, a first siphon opening is opened on the first corundum plate and the second corundum plate, and a second siphon opening adjacent to the first siphon opening is opened on the reaction chamber.

Wherein, the reaction unit includes an upper tank body embedded with the first corundum plate and the second corundum plate, and a lower tank body provided with the first graphite tank and the second graphite tank.

Wherein, corundum is filled between the lower tank body and the first graphite tank and the second graphite tank.

Wherein, the inlet of the feeding unit is funnel-shaped, and the size of the inlet is larger than the size of the outlet.

Wherein, the first collection pit, the second collection pit, the third collection pit and the fourth collection pit are respectively pluggably connected to corresponding cathode conductive posts.

Wherein, the cathode conductive column includes a nickel rod and a corundum sleeve sheathed on the nickel rod.

Wherein, the driving unit includes a transmission rod inserted in the center of the bottom of the reaction unit and a motor electrically connected to the transmission rod.

In order to solve the above problems, the present invention also provides a method for continuously preparing tungsten powder and cobalt powder, the method comprising the following steps:

S1. Add materials into the storage chamber through the feed port, and jump to step S2; wherein, the materials include zinc particles, waste cemented carbide and NaF-KF molten salt;

S2. Close the feed port, and evacuate the storage chamber through the first vacuum port until the pressure in the storage chamber reaches the first specified pressure, and skip to step S3;

S3. Open the discharge port to add materials to the first anode basket. After the first specified time, close the discharge port and jump to step S4;

S4, drive the reaction unit to rotate 180°, and jump to step S5;

S5. Open the discharge port to add materials to the second anode basket. After the first specified time, close the discharge port and skip to step S6;

S6. Vacuumize the reaction chamber through the second vacuum port until the pressure in the reaction chamber reaches the second designated pressure, and at the same time start the heater until the temperature in the reaction chamber reaches the first designated temperature, and skip to step S7;

S7. Pass inert gas into the reaction chamber through the air inlet until the pressure in the reaction chamber reaches the third designated pressure, open the gas outlet, and start the heater until the temperature in the reaction chamber reaches the second designated temperature, and jump to execution Step S8;

S8. Start the first power supply to apply a 0.6V voltage to the first anode basket and the first collection pit, and simultaneously start the second power supply to apply a 2V voltage to the second anode basket and the third collection pit, and skip to step S9;

S9, after the second specified time, drive the reaction unit to rotate 180°, so that the first power supply applies a 0.6V voltage to the second anode basket and the fourth collection pit, and the second power supply applies a voltage to the first anode basket and the second collection pit 2V voltage, and jump to step S10;

S10. After the second designated time elapses, drive the reaction unit to rotate by 180°, and skip to step S8.

The present invention utilizes the characteristics that the first anode basket and the second anode basket, the first collection pit and the fourth collection pit, and the second collection pit and the third collection pit are all symmetrical about the center of the reaction unit, and drives the reaction unit to rotate through the driving unit, so that When the reaction unit rotates to the specified position, the first power supply applies a voltage of 0.6V, and the second power supply applies a voltage of 2V, so that the first power supply, the first anode basket and the first collection pit together form an electrolysis circuit, and at the same time make the second power supply, The second anode basket and the third collection pit jointly form another electrolytic circuit; when the reaction unit continues to rotate 180°, a power supply, the second anode basket and the fourth collection pit can jointly form an electrolytic circuit, and at the same time the second The power supply, the first anode basket and the second collection pit jointly constitute another electrolytic circuit, so that the cobalt can be obtained continuously in the first collection pit and the fourth collection pit, and in the second collection pit by utilizing the different precipitation coefficients of tungsten and cobalt. Tungsten is obtained from the third collection pit, which not only significantly improves the recovery rate and separation efficiency, but also avoids electrode switching and prolongs the service life of the device.

Description of drawings

Fig. 1 is a schematic structural view of a device for continuously preparing tungsten powder and cobalt powder in Example 1 of the present invention;

Fig. 2 is the structural representation of reaction unit in the embodiment 1 of the present invention;

3 is a schematic structural view of the cathode conductive column in Example 1 of the present invention;

Fig. 4 is a schematic structural view of the lower tank body in Embodiment 1 of the present invention;

Fig. 5 is a schematic structural view of the upper tank body in Embodiment 1 of the present invention;

Fig. 6 is the XRD pattern of the cobalt powder and tungsten powder prepared in the embodiment 2 of the present invention, wherein, Fig. 6 (a) is the XRD pattern of cobalt powder; 6 (b) is the XRD pattern of tungsten powder;

7 is an SEM image of cobalt powder and tungsten powder prepared in Example 2 of the present invention, wherein, FIG. 7(a) is an SEM image of cobalt powder; 7(b) is an SEM image of tungsten powder.

Reference signs:

1. Storage chamber; 1-1. First vacuum port; 2. Reaction chamber; 2-1. Air inlet;

2-2, air outlet; 2-3, second vacuum port; 2-4, second siphon port;

3. Feeding unit; 4. Reaction unit; 4-1. Upper tank body; 4-11. First corundum plate;

4-12, the second corundum plate; 4-13, the first siphon port; 4-2, the lower tank body;

4-21, the first graphite tank; 4-211, the first collection pit; 4-212, the second collection pit;

4-22, the second graphite tank; 4-221, the third collection pit; 4-222, the fourth collection pit;

4-23, corundum; 4-3, the first anode basket; 4-4, the second anode basket;

4-5, anode conductive column; 4-6, cathode installation hole; 4-71, nickel rod;

4-72, corundum sleeve; 5, the first metal sheet; 6, the second metal sheet; 7, transmission rod.

detailed description

In order to make the purpose, technical solutions and advantages of the invention clearer, the technical solutions in the invention will be clearly described below in conjunction with the accompanying drawings in the invention. Obviously, the described embodiments are part of the embodiments of the invention, not all of them. Example. Based on the embodiments of the invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the invention.

In the description of the present invention, unless otherwise specified, the orientation or positional relationship indicated by the terms "upper", "lower", "top", "bottom" etc. is based on the orientation or positional relationship shown in the drawings, and is only for the purpose of It is convenient to describe the present invention and simplify the description, but does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operate in a specific orientation, and thus should not be construed as limiting the present invention.

It should be noted that, unless otherwise clearly stipulated and limited, the term "connection" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be directly connected or through Intermediaries are indirectly connected. Those of ordinary skill in the art can understand the specific meanings of the above terms in the invention in specific situations.

Example 1

1 to 5, the present invention provides a device for continuously preparing tungsten powder and cobalt powder, the device comprising:

A material storage chamber 1, the side wall of the material storage chamber 1 is provided with a first vacuum port 1-1, and the top and bottom are respectively provided with a feed port and a discharge port that can be opened and closed;

Reaction chamber 2, reaction chamber 2 is located at the below of material storage chamber 1, and reaction chamber 2 is provided with the second vacuumizing port 2-3, air inlet 2-1, air outlet 2-2 and heater; Wherein, air inlet The port 2-1 and the gas outlet 2-2 are respectively arranged on both sides of the reaction chamber 2, and the air inlet 2-1 is positioned above the gas outlet 2-2; the heater is preferably a heating wire wound on the outer wall of the reaction chamber 2 .

Reaction unit 4, reaction unit 4 is located in reaction chamber 2, and the two ends of reaction unit 4 are respectively provided with first graphite groove 4-21 and second graphite groove 4-22; First graphite groove 4-21 and second graphite groove A first anode basket 4-3 and a second anode basket 4-4 are respectively suspended in the groove 4-22, and the upper parts of the first anode basket 4-3 and the second anode basket 4-4 are connected with an anode conductive column 4- 5; The first collection pit 4-211 and the second collection pit 4-212 are respectively provided at both ends of the bottom of the first graphite tank 4-21, and the third collection pit 4-212 is respectively provided at both ends of the bottom of the second graphite tank 4-22. The bottoms of the collection pit 4-221 and the fourth collection pit 4-222, the first collection pit 4-211, the second collection pit 4-212, the third collection pit 4-221 and the fourth collection pit 4-222 are inserted There are cathode conductive columns; the first anode basket 4-3 and the second anode basket 4-4, the first collection pit 4-211 and the fourth collection pit 4-222, and the second collection pit 4-212 and the third collection pit 4 -221 are all symmetrical about the reaction unit 4 center;

The feeding unit 3, the inlet of the feeding unit 3 is located below the discharge port, and the outlet is located above the circumference of the first anode basket 4-3 and the second anode basket 4-4;

The first power supply and the second power supply, the first power supply and the second power supply are respectively arranged on both sides of the reaction chamber 2, and the positive poles of the first power supply and the second power supply are all connected with the first metal sheet 5 by wires, and the first metal sheet 5 Be located on the circumference where the top of the anode conductive column 4-5 is; the negative poles of the first power supply and the second power supply are connected with the second metal sheet 6 by wires, and the second metal sheet 6 is located at the bottom of the cathode conductive column. on the circumference; and

The drive unit is used to drive the reaction unit 4 to rotate around its center, so that each first metal sheet 5 and second metal sheet 6 are electrically connected to the corresponding anode conductive column 4-5 and cathode conductive column, respectively, That is to say, when the reaction unit 4 rotates to the specified position, the first metal piece 5 connected to the positive pole of the first power supply contacts with the anode conductive column 4-5 on the first anode basket 4-3, and contacts with the anode conductive column 4-5 of the first power supply. The second metal sheet 6 connected to the negative electrode is in contact with the cathode conductive column inserted on the first collection pit 4-211, that is, the first power supply, the first anode basket 4-3 and the first collection pit 4-211 together form an electrolytic Loop; at the same time, the first metal sheet 5 connected to the positive pole of the second power supply is in contact with the anode conductive column 4-5 on the second anode basket 4-4, and the second metal sheet 6 connected to the negative pole of the second power supply In contact with the cathode conductive column inserted on the third collection pit 4-221, that is, the second power supply, the second anode basket 4-4 and the third collection pit 4-221 jointly constitute another electrolytic circuit. And when the reaction unit 4 continues to rotate 180, the first metal sheet 5 connected with the positive pole of the first power supply contacts the anode conductive post 4-5 on the second anode basket 4-4, and the first metal sheet connected with the negative pole of the first power supply The two metal sheets 6 are in contact with the cathode conductive column inserted on the fourth collection pit 4-222, that is, the first power supply, the second anode basket 4-4 and the fourth collection pit 4-222 together form an electrolytic circuit; Simultaneously, the first metal sheet 5 connected with the positive pole of the second power supply is in contact with the anode conductive column 4-5 on the first anode basket 4-3, and the second metal sheet 6 connected with the negative pole of the second power supply is inserted into the The cathode conductive column on the second collection pit 4-212 is in contact, that is, the second power supply, the first anode basket 4-3 and the second collection pit 4-212 together constitute another electrolytic circuit.

Specifically, when using:

First, put materials in the storage chamber 1, namely zinc particles, waste cemented carbide and NaF-KF molten salt;

Secondly, after the storage chamber 1 is evacuated through the first vacuum port 1-1, the material outlet is opened, and the material can directly fall into the first anode basket 4-3 through the feeding unit 3;

Then, start the driving unit, so that the reaction unit 4 rotates 180 °, and now the outlet of the charging unit 3 is just above the second anode basket 4-4, so that after opening the discharge port again, the material can pass through the charging unit 3 directly. Fall into the second anode basket 4-4;

Then, the reaction chamber 2 is evacuated through the second vacuum port 2-3, and the heater is started at the same time until the temperature in the reaction chamber 2 reaches 300°C, and argon is filled into the reaction chamber 2 through the air inlet 2-1 , when the pressure in the reaction chamber 2 reaches 10 ⁵ Pa, open the gas outlet 2-2, and at the same time start the heater again until the temperature in the reaction chamber 2 reaches 750°C. At this time, the first anode basket 4-3 And the NaF-KF molten salt in the second anode basket 4-4 and the zinc particle melt completely, and the NaF-KF molten salt just flows in the first graphite groove 4-21 and the second graphite groove 4-22, because the density of zinc is higher Large, so liquid zinc will be deposited in the first collection pit 4-211, the second collection pit 4-212, the third collection pit 4-221 and the fourth collection pit 4-222;

Next, a voltage of 0.6V was applied through the first power supply, while a voltage of 2V was applied through the second power supply. At this time, the first metal piece 5 connected to the positive pole of the first power supply is just in contact with the anode conductive column 4-5 on the first anode basket 4-3, and the second metal piece 6 connected to the negative pole of the first power supply is in contact with the plug. The cathode conductive column that is located on the first collection pit 4-211 is in contact with, that is, the first power supply, the first anode basket 4-3 and the first collection pit 4-211 together constitute an electrolytic circuit; and are connected to the positive pole of the second power supply The first metal sheet 5 is in contact with the anode conductive column 4-5 on the second anode basket 4-4, and the second metal sheet 6 connected to the negative pole of the second power supply is connected to the third collection pit 4-221. The cathode conductive column contacts, that is, the second power supply, the second anode basket 4-4 and the third collection pit 4-221 jointly constitute another electrolysis circuit. Because the precipitation potentials of tungsten and cobalt are different, that is, when the applied voltage is less than 0.8V, cobalt is easy to precipitate, and when the applied voltage is greater than 0.8V, tungsten is easy to precipitate. Therefore, after the waste cemented carbide in the first anode basket 4-3 is gradually ionized in the NaF-KF molten salt, the cobalt ions will be reduced to simple substances and deposited in the first collection pit 4-211, while the second After the waste cemented carbide in the anode basket 4-4 is gradually ionized in the NaF-KF molten salt, the tungsten ions will be reduced to simple substances and deposited in the third collection pit 4-221;

Finally, after 1 hour, the drive unit was activated to rotate the reaction unit 4 by 180°. Since the first collection pit 4-211 and the fourth collection pit 4-222 and the second collection pit 4-212 and the third collection pit 4-221 are all symmetrical about the center of the reaction unit 4, after the reaction unit 4 rotates 180°, The first metal sheet 5 connected to the positive pole of the first power supply is in contact with the anode conductive column 4-5 on the second anode basket 4-4, the second metal sheet 6 connected to the negative pole of the first power supply is inserted into the fourth The cathode conductive column on the collection pit 4-222 contacts, that is, the first power supply, the second anode basket 4-4 and the fourth collection pit 4-222 together form an electrolytic circuit; and the first metal connected to the positive pole of the second power supply The sheet 5 is in contact with the anode conductive column 4-5 on the first anode basket 4-3, and the second metal sheet 6 connected to the negative pole of the second power supply is in contact with the cathode conductive column inserted in the second collection pit 4-212 , That is, the second power supply, the first anode basket 4-3 and the second collection pit 4-212 jointly constitute another electrolysis circuit. Thus, after the waste cemented carbide in the second anode basket 4-4 is gradually ionized in the NaF-KF molten salt, the cobalt ions will be reduced to simple substances and deposited in the fourth collection pit 4-222, while the first anode After the waste cemented carbide in the basket 4-3 is gradually ionized in the NaF-KF molten salt, the tungsten ions will be reduced to simple substances and deposited in the second collection pit 4-212.

Thus, every 1 hour, the reaction unit 4 is rotated once, and cobalt will be continuously deposited in the first collection pit 4-211 and the fourth collection pit 4-222. Meanwhile, tungsten will be continuously deposited in the second collection pit 4. -212 and the third collection pit 4-221 were deposited. Since the density of zinc is different from that of tungsten and cobalt, after the preparation is completed, the liquid zinc can be sucked out directly, and then pure tungsten and pure cobalt can be obtained.

Preferably, the upper cover of the first graphite tank 4-21 is provided with the first corundum plate 4-11 for suspending the first anode basket 4-3, and the upper cover of the second graphite tank 4-22 is provided with the upper cover for suspending the second anode basket. The second corundum plate 4-12 of the basket 4-4, specifically, the middle part of the first corundum plate 4-11 is provided with a first installation hole, the top of the first anode basket 4-3 is clamped with the first installation hole, and the second The two ends extend into the first graphite groove 4-21; the middle part of the second corundum plate 4-12 is provided with a second installation hole, the top of the second anode basket 4-4 is clamped with the second installation hole, and the second end extends Enter the second graphite tank 4-22.

Further, the first corundum plate 4-11 and the second corundum plate 4-12 are provided with a first siphon port 4-13, and the reaction chamber 2 is provided with a second siphon port 2 adjacent to the first siphon port 4-13. -4. Thus, when the preparation is completed, the first collection pit 4-211, the second collection pit 4-212, the second collection pit 4-212, and the The liquid zinc in the third collection pit 4-221 or the fourth collection pit 4-222 is sucked out, and then pure tungsten and pure cobalt can be obtained.

Preferably, the reaction unit 4 includes an upper tank body 4-1 embedded with a first corundum plate 4-11 and a second corundum plate 4-12, and a first graphite tank 4-21 and a second graphite tank 4-22 The lower tank body 4-2. More preferably, the upper tank body 4-1 is detachably connected to the lower tank body 4-2, for example, the upper tank body 4-1 and the lower tank body 4-2 are connected by pins.

Further, corundum 4-23 is filled between the lower tank body 4-2 and the first graphite tank 4-21 and the second graphite tank 4-22.

Preferably, the inlet of the feeding unit 3 is funnel-shaped, and the size of the inlet is larger than that of the outlet, so as to ensure that all materials falling from the outlet enter the feeding unit 3 .

In addition, since the cathode conductive column is extremely easy to corrode, in order to facilitate later update and replacement, the first collection pit 4-211, the second collection pit 4-212, the third collection pit 4-221 and the fourth collection pit 4-222 are respectively corresponding to The cathode conductive post of the pluggable connection. Specifically, the centers of the bottoms of the first collection pit 4-211, the second collection pit 4-212, the third collection pit 4-221, and the fourth collection pit 4-222 are provided with cathode installations for inserting cathode conductive posts. Holes 4-6. Wherein, the cathode conductive column includes a nickel rod 4-71 and a set of corundum 4-23 sleeved on the nickel rod 4-71.

Wherein, the drive unit includes a transmission rod 7 inserted in the center of the bottom of the reaction unit 4 and a motor electrically connected to the transmission rod 7, that is, one end of the transmission rod 7 is inserted in the center of the bottom of the reaction unit 4, and the other end is connected to the motor. Thus, when the motor drives the transmission rod 7 to rotate, the reaction unit 4 will be driven by the transmission rod 7 to rotate together.

Preferably, both the first anode basket 4-3 and the second anode basket 4-4 are braided by platinum wire.

Example 2

Based on the above-mentioned device for continuously preparing tungsten powder and cobalt powder, the present invention also provides a method for continuously preparing tungsten powder and cobalt powder, the method comprising the following steps:

S1, add materials into the storage chamber 1 through the feed port, and jump to step S2; wherein, the materials include zinc particles, waste cemented carbide and NaF-KF molten salt; wherein, the molar ratio of NaF-KF is preferably 4:6.

S2. Close the feeding port, and evacuate the storage chamber 1 through the first vacuum port 1-1 until the pressure in the storage chamber 1 reaches the first specified pressure, and skip to step S3;

S3, open the discharge port, because the outlet of the feeding unit 3 is just above the first anode basket 4-3 at this time, after opening the discharge port, the material can directly fall into the first anode basket 4-3 through the feeding unit 3 In step 3, after the first designated time passes, add a designated amount of material into the first anode basket 4-3, close the discharge port, and jump to step S4;

S4, drive the reaction unit 4 to rotate 180°, and jump to step S5;

S5, open the discharge port, since the first anode basket 4-3 and the second anode basket 4-4 are symmetrical about the center of the reaction unit 4, after the reaction unit 4 rotates 180°, the outlet of the feeding unit 3 is just located in the second anode basket 4-4, so that after the discharge port is opened again, the material can directly fall into the second anode basket 4-4 through the feeding unit 3, and it will be added to the second anode basket 4-4 after the first specified time After the specified amount of material is supplied, close the discharge port and skip to step S6;

S6. Vacuumize the reaction chamber 2 through the second vacuum port 2-3 until the pressure in the reaction chamber 2 reaches the second specified pressure, and start the heater at the same time until the temperature in the reaction chamber 2 reaches the first specified temperature, and jump Proceed to step S7; wherein, the first specified temperature is preferably 300°C.

S7. Pass the inert gas into the reaction chamber 2 through the air inlet 2-1 until the pressure in the reaction chamber 2 reaches the third specified pressure, open the gas outlet 2-2, and start the heater until the pressure in the reaction chamber 2 When the temperature reaches the second specified temperature, skip to step S8; wherein, the inert gas is preferably argon, the third specified pressure is preferably 10 ⁵ Pa, and the second specified temperature is preferably 750°C.

S8. Start the first power supply to apply 0.6V voltage to the first anode basket 4-3 and the first collection pit 4-211, and simultaneously start the second power supply to apply 2V to the second anode basket 4-4 and the third collection pit 4-221 voltage, and jump to step S9; because, at this time, the first metal sheet 5 connected to the positive pole of the first power supply is just in contact with the anode conductive column 4-5 on the first anode basket 4-3, and is in contact with the positive pole of the first power supply. The second metal sheet 6 connected to the negative electrode is in contact with the cathode conductive column inserted on the first collection pit 4-211, that is, the first power supply, the first anode basket 4-3 and the first collection pit 4-211 together form an electrolytic loop; and the first metal sheet 5 connected with the positive pole of the second power supply is in contact with the anode conductive column 4-5 on the second anode basket 4-4, and the second metal sheet 6 connected with the negative pole of the second power supply is connected with the inserted The cathode conductive post contact on the third collection pit 4-221, that is, the second power supply, the second anode basket 4-4 and the third collection pit 4-221 together constitute another electrolytic circuit; therefore, the first anode basket 4-221 After the waste cemented carbide in 3 is gradually ionized in the NaF-KF molten salt, the cobalt ions will be reduced to simple substances and deposited in the first collection pit 4-211, while the waste cemented carbide in the second anode basket 4-4 After the tungsten alloy is gradually ionized in the NaF-KF molten salt, the tungsten ions will be reduced to simple substances and deposited in the third collection pit 4-221;

S9, after the second specified time, drive the reaction unit 4 to rotate 180°, so that the first power supply applies a 0.6V voltage to the second anode basket 4-4 and the fourth collection pit 4-222, and the second power supply applies a voltage of 0.6V to the first anode Apply a voltage of 2V to the basket 4-3 and the second collection pit 4-212, and skip to step S10; wherein, the second specified time is preferably 1 hour. Because the first collection pit 4-211 and the fourth collection pit 4-222 and the second collection pit 4-212 and the third collection pit 4-221 are all symmetrical about the center of the reaction unit 4, therefore, after the reaction unit 4 rotates 180° The first metal sheet 5 connected to the positive pole of the first power supply is in contact with the anode conductive column 4-5 on the second anode basket 4-4, and the second metal sheet 6 connected to the negative pole of the first power supply is inserted into the second anode basket 4-4. The cathode conductive columns on the four collection pits 4-222 are in contact, that is, the first power supply, the second anode basket 4-4 and the fourth collection pit 4-222 jointly form an electrolytic circuit; and the first positive electrode connected with the second power supply The metal sheet 5 is in contact with the anode conductive column 4-5 on the first anode basket 4-3, the second metal sheet 6 connected to the negative pole of the second power supply and the cathode conductive column inserted on the second collection pit 4-212 The contacts, ie the second power supply, the first anode basket 4-3 and the second collection pit 4-212 together constitute another electrolytic circuit. Thus, after the waste cemented carbide in the second anode basket 4-4 is gradually ionized in the NaF-KF molten salt, the cobalt ions will be reduced to simple substances and deposited in the fourth collection pit 4-222, while the first anode After the waste cemented carbide in the basket 4-3 is gradually ionized in the NaF-KF molten salt, the tungsten ions will be reduced to simple substances and deposited in the second collection pit 4-212.

S10. After the second designated time elapses, drive the reaction unit 4 to rotate by 180°, and skip to step S8.

Thus, every 1 hour, the reaction unit 4 is rotated once, and cobalt will be continuously deposited in the first collection pit 4-211 and the fourth collection pit 4-222. Meanwhile, tungsten will be continuously deposited in the second collection pit 4. -212 and the third collection pit 4-221 were deposited. Since the density of zinc is different from that of tungsten and cobalt, after the preparation is completed, the first collection pit 4-211, the second collection pit 4-211, the second The liquid zinc in the collection pit 4-212, the third collection pit 4-221 or the fourth collection pit 4-222 is sucked out, and then pure tungsten and pure cobalt can be obtained. As shown in Figure 6 and Figure 7, the finally prepared tungsten powder and cobalt powder have uniform particles and a single composition.

It should be noted that the voltage applied by the first power supply is not limited to 0.6V, and the voltage applied by the second power supply is not limited to 2V, as long as the voltage applied by the first power supply is less than 0.8V and the voltage applied by the second power supply is greater than 0.8V.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical scheme of the invention, rather than limiting it; although the invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: it still can The technical solutions described in the foregoing embodiments are modified, or some of the technical features are replaced equivalently; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the invention.

Claims (10)

1. A device for continuously preparing tungsten powder and cobalt powder, characterized in that, comprising: A material storage room, the material storage room is provided with a first vacuum port and a material inlet and a material outlet that can be opened and closed; A reaction chamber, the reaction chamber is arranged below the storage chamber, and the reaction chamber is provided with a second vacuum port, an air inlet, an air outlet and a heater; A reaction unit, the reaction unit is located in the reaction chamber, the two ends of the reaction unit are respectively provided with a first graphite groove and a second graphite groove; the first graphite groove and the second graphite groove are respectively suspended A first anode basket and a second anode basket are placed, and the upper parts of the first anode basket and the second anode basket are connected with anode conductive columns; the two ends of the bottom of the first graphite tank are respectively provided with first A collection pit and a second collection pit, the two ends of the bottom of the second graphite tank are respectively provided with a third collection pit and a fourth collection pit, the first collection pit, the second collection pit, the third collection pit The bottoms of the collection pit and the fourth collection pit are inserted with cathode conductive columns; the first anode basket and the second anode basket, the first collection pit and the fourth collection pit, and the first anode basket Both the second collection pit and the third collection pit are symmetrical about the center of the reaction unit; A feeding unit, the inlet of the feeding unit is set below the discharge port, and the outlet is set above the circumference of the first anode basket and the second anode basket; The first power supply and the second power supply, the first power supply and the second power supply are respectively arranged on both sides of the reaction chamber, and the positive poles of the first power supply and the second power supply are connected to the first power supply through wires. metal sheet, the first metal sheet is arranged on the circumference where the top of the anode conductive column is; The metal sheet is arranged on the circumference where the bottom end of the cathode conductive column is located; and a driving unit, the driving unit is used to drive the reaction unit to rotate around its center, so that each of the first metal sheet and the second metal sheet is connected to the corresponding anode conductive column and the corresponding The cathode conductive post is electrically connected. 2. The device for continuously preparing tungsten powder and cobalt powder according to claim 1, wherein the first graphite tank loam cake is provided with a first corundum plate for suspending the first anode basket, the The upper cover of the second graphite tank is provided with a second corundum plate for suspending the second anode basket. 3. The device for continuously preparing tungsten powder and cobalt powder according to claim 2, wherein a first siphon port is provided on the first corundum plate and the second corundum plate, A second siphon opening adjacent to the first siphon opening is opened. 4. The device for continuously preparing tungsten powder and cobalt powder according to claim 2, wherein the reaction unit includes an upper tank body embedded with the first corundum plate and the second corundum plate and a device There is a lower tank body of the first graphite tank and the second graphite tank. 5. The device for continuously preparing tungsten powder and cobalt powder according to claim 4, characterized in that corundum is filled between the lower tank body and the first graphite tank and the second graphite tank. 6. The device for continuously preparing tungsten powder and cobalt powder according to claim 1, wherein the inlet of the feeding unit is funnel-shaped, and the size of the inlet is larger than the size of the outlet. 7. The device for continuously preparing tungsten powder and cobalt powder according to claim 1, characterized in that, the first collection pit, the second collection pit, the third collection pit and the fourth collection pit are respectively pluggably connected to the corresponding cathode conductive columns. 8. The device for continuously preparing tungsten powder and cobalt powder according to claim 7, characterized in that, the cathode conductive column comprises a nickel rod and a corundum sleeve sheathed on the nickel rod. 9. The device for continuously preparing tungsten powder and cobalt powder according to any one of claims 1 to 8, characterized in that, the drive unit includes a drive rod inserted in the center of the bottom of the reaction unit and connected to the drive unit. The rod is electrically connected to the motor. 10. A method for continuously preparing tungsten powder and cobalt powder, characterized in that, comprising the following steps: S1. Add materials into the storage chamber through the feed port, and jump to step S2; wherein, the materials include zinc particles, waste cemented carbide and NaF-KF molten salt; S2. Close the feed port, and evacuate the storage chamber through the first vacuum port until the pressure in the storage chamber reaches the first specified pressure, and skip to step S3; S3. Open the discharge port to add materials to the first anode basket. After the first specified time, close the discharge port and jump to step S4; S4, drive the reaction unit to rotate 180°, and jump to step S5; S5. Open the discharge port to add materials to the second anode basket. After the first specified time, close the discharge port and skip to step S6; S6. Vacuumize the reaction chamber through the second vacuum port until the pressure in the reaction chamber reaches the second designated pressure, and at the same time start the heater until the temperature in the reaction chamber reaches the first designated temperature, and skip to step S7; S7. Pass inert gas into the reaction chamber through the air inlet until the pressure in the reaction chamber reaches the third designated pressure, open the gas outlet, and start the heater until the temperature in the reaction chamber reaches the second designated temperature, and jump to execution Step S8; S8. Start the first power supply to apply a 0.6V voltage to the first anode basket and the first collection pit, and simultaneously start the second power supply to apply a 2V voltage to the second anode basket and the third collection pit, and skip to step S9; S9, after the second specified time, drive the reaction unit to rotate 180°, so that the first power supply applies a 0.6V voltage to the second anode basket and the fourth collection pit, and the second power supply applies a voltage to the first anode basket and the second collection pit 2V voltage, and jump to step S10; S10. After the second designated time elapses, turn off the first power supply and the second power supply, drive the reaction unit to rotate by 180°, and jump to step S8.