Electrolytic extraction process of metal gallium

Abstract

The invention relates to the field of hydrometallurgy, and particularly discloses an electrolytic extraction process of metal gallium, which comprises the following steps: preparing a 1 # electrolytic tank, a 1 # electrolytic circulating tank, a 2 # electrolytic tank, a 2 # electrolytic circulating tank, a 1 # direct-current power supply, a 2 # direct-current power supply and a temperature control system; small-current electrolysis: adjusting the current of a 1 # direct-current power supply to 29-31A, and electrolyzing the electrolytic stock solution to obtain impurity lead, impurity mercury and an electrolyte A; the concentrations of Pb < 2 + > and Hg < 2 + > are both less than or equal to 0.1 mg Carrying out large-current electrolysis, and adjusting the current of a 2 # direct-current power supply to 750-1050A to obtain metal gallium and an electrolyte C; according to the scheme, the electrolytic stock solution is electrolyzed through small current, it can be ensured that impurity lead and impurity mercury are obtained through electrolysis when the current is 29-31A, it can be ensured that the impurity lead and the impurity mercury can be formed through electrolysis, it can be ensured that metal gallium cannot be formed through electrolysis in advance, and it can be effectively reduced that after follow-up large-current electrolysis is conducted, the production cost is reduced. And the contents of impurity lead and impurity mercury in the metal gallium are effectively reduced.

Description

Technical Field

[0001] This invention relates to the field of hydrometallurgical technology, and more particularly to an electrolytic extraction process for metallic gallium. Background Technology

[0002] Electrolysis is a chemical reaction process that involves passing an electric current through an electrolyte solution, causing cations and anions to move towards the cathode and anode, respectively, where redox reactions occur. Metal ions gain electrons at the cathode and are reduced to their metallic form, while non-metal ions lose electrons at the anode and are oxidized.

[0003] When extracting gallium from gallium-containing electrolyte solutions, the electrolyte solution is typically subjected to multiple impurity removal processes. During these processes, because lead and mercury discharge before gallium, it is difficult to completely remove lead and mercury before the current for gallium deposition is reached, resulting in the presence of a small amount of Pb in the electrolyte solution. 2+ and Hg 2+ Consequently, the removal of impurities such as lead and mercury from the electrolyte is not very complete; therefore, during electrolysis, if the applied voltage (current density) gradually increases, the Pb on the cathode... 2+ Hg 2+ Will be better than Ga 3+ The gallium is preferentially reduced and precipitated. However, when gallium is finally precipitated, it is easy for it to contain impurities such as lead and mercury, which will directly affect the purity of gallium extraction. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides an electrolytic extraction process for metallic gallium, which solves the problem of Pb deposition on the cathode as the applied voltage (current density) gradually increases. 2+ Hg 2+ Will be better than Ga 3+ The preferential reduction and precipitation process leads to the presence of lead and mercury impurities in gallium.

[0005] To achieve the above objectives, the basic solution of the present invention is as follows: an electrolytic extraction process for metallic gallium, comprising the following steps:

[0006] Prepare electrolytic cell #1, electrolytic circulation cell #1, electrolytic cell #2, electrolytic circulation cell #2, DC power supply #1, DC power supply #2, and temperature control system;

[0007] Low-current electrolysis: The electrolyte is transported to the No. 1 electrolytic cell through the No. 1 electrolytic circulation tank. The electrolyte overflowing from the No. 1 electrolytic cell is returned to the No. 1 electrolytic circulation tank. The No. 1 DC power supply is located at the No. 1 electrolytic cell. The current of the No. 1 DC power supply is adjusted to 29-31A to electrolyze the electrolyte to obtain impurity lead, impurity mercury and electrolyte A.

[0008] Detection of Pb in electrolyte A 2+ and Hg2+ The concentration of Pb 2+ and Hg 2+ When the concentrations of all components are ≤0.1mg / L, electrolyte B is formed;

[0009] High-current electrolysis: Electrolyte B is transported to the No. 2 electrolytic circulation tank. Electrolyte B is sent to the No. 2 electrolytic tank through the No. 2 electrolytic circulation tank. The overflowing raw electrolyte in the No. 2 electrolytic tank is returned to the No. 2 electrolytic circulation tank. The No. 2 DC power supply is located at the No. 2 electrolytic tank. The current of the No. 2 DC power supply is adjusted to 750-1050A to obtain metallic gallium and electrolyte C.

[0010] Detection of Ga in electrolyte C 3+ The concentration of Ga 3+ When the concentration is ≤5g / L, the extraction of metallic gallium is stopped.

[0011] The technical principle of this invention is as follows: During implementation, this process first electrolyzes the electrolyte solution with a small current. This ensures that at a current of 29-31A, the electrolyzed electrolyte yields impurities lead and mercury, guaranteeing the electrolytic formation of these impurities while preventing premature formation of metallic gallium. Furthermore, precise detection confirms the presence of Pb in electrolyte A. 2+ and Hg 2+ The concentrations of all impurities are ≤0.1mg / L, which can effectively reduce the content of lead and mercury impurities in gallium metal after subsequent high-current electrolysis, and effectively improve the purity of gallium metal during high-current electrolysis.

[0012] In high-current electrolysis, the current of the #2 DC power supply is adjusted to 750-1050A. The high current setting allows gallium to be extracted quickly and efficiently, while ensuring the purity of the gallium. This balances the efficiency and purity of gallium extraction.

[0013] Furthermore, it also includes a No. 1 circulating pump and a No. 2 circulating pump. The No. 1 circulating pump is connected between the No. 1 electrolytic cell and the No. 1 electrolytic circulating cell, and the No. 2 circulating pump is connected between the No. 2 electrolytic cell and the No. 2 electrolytic circulating cell.

[0014] With the above setup, the No. 1 circulating pump can circulate and transport electrolyte A, allowing Pb in the final electrolyte B to be transported in a more efficient manner. 2+ and Hg 2+ The content is qualified; the No. 2 circulating pump can circulate and transport electrolyte C, improving the comprehensiveness of gallium extraction.

[0015] Furthermore, the temperature control system controls the temperature of electrolyte A to 35-45℃.

[0016] With the above settings, the temperature can be coordinated with the 29-31A current control, allowing Pb to... 2+ and Hg2+ Under suitable conditions, it is rapidly and efficiently electrolyzed, improving the impurity removal efficiency.

[0017] Furthermore, the temperature control system maintains the temperature of electrolyte C at 38-42℃.

[0018] With the above settings, this temperature can be coordinated with the 750-1050A current control, enabling Ga... 3+ Under suitable conditions, it can be rapidly and efficiently electrolyzed, improving the extraction efficiency of metallic gallium.

[0019] Furthermore, the No. 2 electrolytic cell includes:

[0020] Electrolytic cell;

[0021] Several anodes are located inside the electrolytic cell, and several anodes are connected in parallel with the positive terminal of DC power supply #2;

[0022] The cathode is located inside the electrolytic cell and is electrically connected to the negative terminal of the No. 2 DC power supply. The cathode is set vertically, and several anodes are set horizontally and arranged around the cathode. Several guide grooves are provided on the outer wall of the cathode along the cathode axis.

[0023] The gallium metal recycling component is positioned directly opposite the lower end of the flow channel.

[0024] With the above settings, the No. 2 electrolytic cell processes Ga... 3+ During electrolytic extraction, several anodes are arranged circumferentially around the cathode, which can improve the Ga... 3+ The increased electron exchange efficiency improves the extraction efficiency of gallium; simultaneously, under temperature control, the extracted gallium is in a liquid state, and under the stable guidance of the cathode surface guide groove, the gallium can be quickly collected by the gallium recovery component, thus improving the recovery efficiency of gallium.

[0025] Furthermore, the gallium metal recycling component includes:

[0026] The recovery cylinder is vertically fixed inside the bottom of the electrolytic cell, and the recovery cylinder is coaxial with and opposite to the cathode.

[0027] A sealing cap, which can seal the top of the recycling cylinder;

[0028] The upper end of the recovery tube passes through the bottom of the electrolytic cell and is fixedly connected to the lower end of the recovery cylinder.

[0029] A pressure relief valve installed on the recovery pipe.

[0030] With the above setup, during gallium recovery, liquid gallium can be quickly and stably guided into the recovery cylinder by the guide channel, facilitating the initial collection of gallium. When further removing gallium, the top of the recovery cylinder is sealed with the sealing cap, the pressure relief valve is opened, and the gallium can be discharged and collected through the recovery pipe. During collection, the electrolyte C is isolated by the sealing cap, ensuring that the content of electrolyte C in the collected gallium is extremely low, which can improve the purity of gallium.

[0031] Furthermore, the lower end of the cathode is conical, and the center of the lower end of the cathode is directly opposite the center of the recovery cylinder.

[0032] With the above setup, when gallium flows to the end of the cathode, it can be further guided by the tapered end of the cathode, allowing the gallium to fall accurately and stably vertically into the recovery cylinder, thus improving the accuracy of gallium recovery.

[0033] Furthermore, the gallium metal recycling component also includes:

[0034] The hydraulic telescopic rod is set horizontally. The telescopic end of the hydraulic telescopic rod passes through the side wall of the electrolytic cell and is fixedly connected to the side wall of the sealing cover. An elastic sealing layer that can abut against the end face of the recovery cylinder is fixedly provided on the lower surface of the sealing cover.

[0035] A hydraulic pump that controls the extension or retraction of a hydraulic telescopic rod.

[0036] With the above settings, the hydraulic telescopic rod can work with the hydraulic pump to control the position of the sealing cover, which makes it easier to control the sealing cover and elastic sealing layer to block or open the upper end of the recovery cylinder, and to control the timing of gallium collection.

[0037] Furthermore, the gallium metal recycling component also includes:

[0038] The scraper is annular, and the cross-sectional profile of the inner wall of the scraper is the same as that of the cathode. The inner wall of the scraper is in sliding contact with the outer wall of the cathode.

[0039] The slide rail is vertically and fixedly installed inside the electrolytic cell;

[0040] A slider that can slide along a slide rail, and the slider is fixedly connected to the side wall of the scraper;

[0041] The connecting rod is set vertically, and its lower end passes through the electrolytic cell and is connected or fixedly connected to the slider during the last rotation. The connecting rod is in sliding contact with the electrolytic cell.

[0042] With the above setup, after electrolyte C is discharged from electrolytic cell #2, the connecting rod is pushed down, which in turn pushes the slider down along the slide rail. The slider then moves the scraper down, which pushes the gallium metal remaining on the cathode, allowing it to flow quickly and completely to the lower side of the cathode. The recovery cylinder continuously collects the gallium metal. The pressure relief valve and the delivery pump are then opened again to fully extract and recover the liquid gallium metal, making electrolytic cell #2 cleaner and facilitating its reuse in the electrolytic extraction of other liquid metals.

[0043] Furthermore, there are two No. 2 electrolytic cells, and a regulating pump and an overflow output pump are installed between the two sets of No. 2 electrolytic cells;

[0044] The overflow output pump is connected to the top side of one of the No. 2 electrolytic cells, and the No. 2 DC power supply current in the No. 2 electrolytic cell is adjusted to 750-950A;

[0045] The regulating pump is equipped with a first inlet for drawing in electrolyte B, a second inlet for drawing in electrolyte C, a third inlet connected to the overflow output pump, and an output port. The output port is connected to the top side of another set of No. 2 electrolytic cells. The current of the No. 2 DC power supply in this set of No. 2 electrolytic cells is adjusted to 850-1050A.

[0046] A first switch valve is provided at the first input port, a second switch valve is provided at the second input port, and a third switch valve is provided at the third input port.

[0047] With the above setup, the two sets of No. 2 electrolytic cells can use different currents during operation, thus allowing for the staged electrolysis of two batches of electrolyte C, thereby enabling faster electrolysis of Ga. 3+ When the concentration reaches the discharge standard, the two sets of No. 2 electrolytic cells can ensure the overflow capacity of adjacent No. 2 electrolytic cells by using the time difference during extraction. They can also improve the efficiency of electrolyte C flow by adjusting the pump, and further improve the extraction efficiency of metallic gallium. Attached Figure Description

[0048] Figure 1 This is a process flow diagram of the electrolytic extraction process of metallic gallium in an embodiment of the present invention.

[0049] Figure 2 This is a schematic diagram of the structure of two sets of No. 2 electrolytic cells in the axial direction of the electrolytic extraction process of metallic gallium in an embodiment of the present invention.

[0050] Figure 3 for Figure 2 Longitudinal sectional view of electrolytic cell #2 on the left side of the middle section.

[0051] In the above-mentioned attached figures: electrolytic cell 10, anode 20, cathode 30, guide channel 301, recovery cylinder 401, sealing cover 402, elastic sealing layer 403, recovery pipe 404, pressure relief valve 405, hydraulic telescopic rod 405, hydraulic pump 406, scraper 407, slide rail 408, slider 409, connecting rod 410, regulating pump 50, first input port 501, first switching valve 502, second input port 503, second switching valve 504, third input port 505, third switching valve 506, output port 506, overflow output pump 60, and No. 2 circulation pump 70. Detailed Implementation

[0052] The technical solutions of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0053] This embodiment is basically as follows: Figure 1 , Figure 2 and Figure 3 As shown in the figure, the embodiment of the present invention proposes an electrolytic extraction process for metallic gallium, including the following steps:

[0054] Prepare an electrolytic cell #1, an electrolytic circulation tank #1, two sets of electrolytic cells #2, an electrolytic circulation tank #2, two sets of DC power supplies #1 and #2, a circulation pump #1, a circulation pump #2, and a temperature control system. The temperature control system is used to control the liquid temperature in the electrolytic cell #1, the two sets of electrolytic cells #2, and the electrolytic circulation tank #2. The circulation pump #1 is connected between the electrolytic cell #1 and the electrolytic circulation tank #1, and the circulation pump #2 is connected between the electrolytic cell #2 and the electrolytic circulation tank #2.

[0055] Among them, such as Figure 2 and Figure 3 As shown, two sets of #2 electrolytic cells and two sets of #1 DC power supplies correspond one-to-one. Each #2 electrolytic cell includes an electrolytic cell 10, 4-6 sets of anodes 20 located within the electrolytic cell 10, cathodes 30 located within the electrolytic cell 10, and a gallium metal recovery assembly. Several anodes 20 are connected in parallel with the positive terminal of the #2 DC power supply in the same set; the cathodes 30 are electrically connected to the negative terminal of the #2 DC power supply; the cathodes 30 are vertically arranged, and several anodes 20 are horizontally arranged and arranged around the cathodes 30. Several guide grooves 301 are provided on the outer wall of the cathodes 30 along the axial direction of the cathodes 30.

[0056] Among them, such as Figure 3As shown, the gallium metal recovery assembly includes a recovery cylinder 401, a sealing cap 402, a recovery pipe 404, a pressure relief valve 405 installed on the recovery pipe 404, a hydraulic telescopic rod 405, a hydraulic pump 406 for controlling the extension or retraction of the hydraulic telescopic rod 405, a scraper 407, a slide rail 408, a slider 409 that can slide along the slide rail 408, and a connecting rod 410. The recovery cylinder 401 is vertically fixedly installed in the bottom of the electrolytic cell 10, and the lower end of the cathode 30 is conical. The center of the lower end of the cathode 30 is directly opposite the center of the recovery cylinder 401; the sealing cover 402 can seal the upper end of the recovery cylinder 401, and an elastic sealing layer 403 that can abut against the end face of the recovery cylinder 401 is fixedly provided on the lower surface of the sealing cover 402; the hydraulic telescopic rod 405 is horizontally arranged, and the telescopic end of the hydraulic telescopic rod 405 passes through the side wall of the electrolytic cell 10 and is fixedly connected to the side wall of the sealing cover 402; the hydraulic pump 406 is fixedly installed outside the electrolytic cell 10 by bolts.

[0057] like Figure 3 As shown, the scraper 407 is annular, and the cross-sectional profile of the inner wall of the scraper 407 is the same as that of the cathode 30. The inner wall of the scraper 407 is in sliding contact with the outer wall of the cathode 30. The slide rail 408 is vertically fixedly installed in the electrolytic cell 10, and the slider 409 is fixedly connected to the side wall of the scraper 407. The connecting rod 410 is vertically arranged, and the lower end of the connecting rod 410 passes through the electrolytic cell 10 and is rotatably or fixedly connected to the slider 409. The connecting rod 410 is in sliding contact with the electrolytic cell 10.

[0058] like Figure 3 As shown, the upper end of the recovery pipe 404 passes through the bottom of the electrolytic cell 10 and is fixedly connected to the lower end of the recovery cylinder 401. The lower end of the recovery pipe 404 can be connected to a delivery pump (not shown) for transporting metallic gallium.

[0059] At the same time, such as Figure 2 As shown, a regulating pump 50 and an overflow output pump 60 are provided between the two sets of No. 2 electrolytic cells;

[0060] Overflow output pump 60 is connected to the top side of the right side No. 2 electrolytic cell. The current of the No. 2 DC power supply in the No. 2 electrolytic cell is adjusted to 750-950A. No. 2 circulation pump 70 is connected to the No. 2 electrolytic cell.

[0061] The regulating pump 50 is equipped with a first input port 501 for drawing in electrolyte B, a second input port 503 for drawing in electrolyte C, a third input port 505 connected to the overflow output pump 60, and an output port 506. The output port 506 is connected to the top side of another set of No. 2 electrolytic cells. The current of the No. 2 DC power supply in this set of No. 2 electrolytic cells is adjusted to 850-1050A. A first switching valve 502 is provided at the first input port 501, a second switching valve 504 is provided at the second input port 503, and a third switching valve 506 is provided at the third input port 505.

[0062] like Figure 2 As shown, six sets of anodes 20 are evenly arranged on the No. 2 electrolytic cell on the left, and four sets of anodes 20 are evenly arranged on the No. 2 electrolytic cell on the right.

[0063] Low-current electrolysis: The electrolyte is transported to the No. 1 electrolytic cell through the No. 1 electrolytic circulation tank. The electrolyte overflowing from the No. 1 electrolytic cell is returned to the No. 1 electrolytic circulation tank. The No. 1 DC power supply is located at the No. 1 electrolytic cell, and the current of the No. 1 DC power supply is adjusted to 30A to electrolyze the electrolyte to obtain impurity lead, impurity mercury, and electrolyte A. During this process, the temperature control system controls the temperature of electrolyte A to 36-44℃.

[0064] Detection of Pb in electrolyte A 2+ and Hg 2+ The concentration of Pb 2+ and Hg 2+ When the concentrations of all components are ≤0.1mg / L, electrolyte B is formed;

[0065] High-current electrolysis: Electrolyte B is input into the No. 2 electrolytic circulation tank. The No. 2 circulation pump 70 pumps electrolyte B into the No. 2 electrolytic tank on the right. The current of the No. 2 DC power supply in the No. 2 electrolytic tank is adjusted to 750-950A. After energizing the anode 20 and cathode 30, the metallic gallium in electrolyte B is extracted. The extraction is carried out for 40 minutes to obtain metallic gallium and electrolyte C. The temperature control system controls the temperature of electrolyte C to 38-42℃. At this temperature, metallic gallium is in a liquid state. The metallic gallium adhering to the cathode 30 flows down to the lower end of the cone under the action of gravity. The cathode 30 guides the metallic gallium into the recovery cylinder 401. The metallic gallium reaches the bottom of the recovery cylinder 401, and then the original electrolyte in the recovery cylinder 401 slowly overflows.

[0066] After the #2 electrolytic cell on the right side is powered on for 40-60 minutes, the regulating pump 50 is turned on, the second switch valve 504 is opened, and the first switch valve 502 and the third switch valve 506 are closed. The electrolyte C enters the #2 electrolytic cell on the left side through the second input port 503, the second switch valve 504 and the output port 506 in sequence. The current of the #2 DC power supply in the #2 electrolytic cell is adjusted to 850-1050A. Gallium metal is extracted for 35-55 minutes. The temperature control system controls the temperature of the electrolyte C to 38-42℃.

[0067] Alternatively, when the No. 2 electrolytic circulation tank on the right is initially put into use and the No. 2 electrolytic circulation tank on the left is empty, the regulating pump 50 is turned on, and the first switch valve 502, the second switch valve 504 or the third switch valve 506 are opened. Electrolyte C enters the No. 2 electrolytic tank on the left through the first input port 501, the first switch valve 502 and the output port 506 in sequence. The current of the No. 2 DC power supply in the No. 2 electrolytic tank is adjusted to 900-1050A, and gallium metal is extracted for 35-55 minutes. The temperature control system controls the temperature of electrolyte C to 38-42℃.

[0068] Alternatively, when there is too much electrolyte C in the No. 2 electrolytic circulation tank on the right, the overflow output pump 60, the regulating pump 50 and the third switch valve 506 are opened, and the first switch valve 502 and the second switch valve 504 are closed, pumping the excess electrolyte C into the No. 2 electrolytic tank on the left. The current of the No. 2 DC power supply in the No. 2 electrolytic tank is adjusted to 950-1050A for high-current rapid extraction of gallium metal. Gallium metal is extracted for 35-50 minutes, and the temperature control system controls the temperature of electrolyte C to 38-42℃.

[0069] Detecting Ga in electrolyte C in electrolytic cell #2 on the left 3+ The concentration of Ga 3+ When the concentration is ≤5g / L, stop the extraction of metallic gallium; drain the electrolyte C from the left side of electrolytic cell #2.

[0070] When the recovery cylinder 401 is full of metallic gallium, the hydraulic pump 406 controls the hydraulic telescopic rod 405 to extend, and the hydraulic telescopic rod 405 pushes the sealing cover 402 to the left. The elastic sealing layer 403 on the sealing cover 402 abuts against the top of the recovery cylinder 401 to seal the recovery cylinder 401. Then, the pressure relief valve 405 and the delivery pump are opened to draw and recover the liquid metallic gallium. The drawing and recovery takes 10-20 seconds. Then, the hydraulic pump 406 controls the hydraulic telescopic rod 405 to shorten, and the top of the recovery cylinder 401 is exposed to continue collecting metallic gallium.

[0071] After the electrolyte C is discharged from the No. 2 electrolytic cell on the left, the connecting rod 410 is pushed down. The connecting rod 410 pushes the slider 409 down along the slide rail 408. The slider 409 drives the scraper 407 down. The scraper 407 pushes the metallic gallium remaining on the cathode 30, so that the metallic gallium flows quickly and completely to the lower side of the cathode 30. The recovery cylinder 401 continues to collect the metallic gallium. The pressure relief valve 405 and the transfer pump are opened again to fully pump and recover the liquid metallic gallium.

[0072] The electrolytic extraction process for gallium in this embodiment allows for the initial electrolysis of the electrolyte stock solution using a small current. Maintaining the temperature of electrolyte A at 36-44°C ensures that at a current of 30A, the electrolysis yields impurities lead and mercury. This process ensures the electrolytic formation of impurities lead and mercury while preventing premature formation of gallium. Furthermore, it minimizes the amount of Pb in the final electrolyte A. 2+ and Hg 2+ When the concentrations of all impurities are ≤0.1mg / L, the content of lead and mercury impurities in gallium metal can be effectively reduced after subsequent high-current electrolysis, thus effectively improving the purity of gallium metal during high-current electrolysis.

[0073] In the high-current electrolysis step, the No. 2 electrolytic circulation tank works in conjunction with the No. 2 circulation pump 70 to achieve the circulation and delivery of electrolyte B. During electrolysis, the No. 2 electrolytic tanks on the left and right work together. The No. 2 electrolytic tank on the right prioritizes the rapid extraction of gallium from electrolyte B using a lower current and shorter time, before the electrolyte enters the No. 2 electrolytic tank on the left for further rapid extraction of gallium using a higher current and shorter time. The synergistic effect of the two sets of No. 2 electrolytic tanks allows for the simultaneous extraction of two batches of electrolyte B while also enabling the stratified extraction of Ga at different concentrations. 3+ Extraction using electrolyte can effectively shorten the time required for a single batch of electrolyte B to extract metallic gallium, thereby effectively improving the extraction efficiency of metallic gallium.

[0074] Meanwhile, because the No. 2 electrolytic cell on the left uses a higher current and a shorter electrolysis time, it can accelerate the electrolysis of Ga. 3+ When the concentration reaches the discharge standard, the left-side No. 2 electrolytic cell can serve as the overflow containment space for the right-side No. 2 electrolytic cell through the time difference of its extraction cycle, which improves the efficiency of electrolyte C flow and can also further improve the extraction efficiency of metallic gallium.

[0075] In the extraction and recovery of liquid gallium, several anodes 20 are arranged circumferentially around the cathode 30, which can improve the efficiency of Ga extraction. 3+ The increased electron exchange efficiency improves the extraction efficiency of gallium metal. Simultaneously, the liquid gallium metal can be rapidly and stably guided into the recovery cylinder 401 by the guide channel 301 and the end of the cathode 30, facilitating the initial collection of gallium metal through this process. Furthermore, by sealing the top of the recovery cylinder 401 with the sealing cap 402 and the elastic sealing layer 403, and by opening the delivery pump and pressure relief valve 405, the gallium metal in the recovery cylinder 401 can be quickly drawn in, ensuring that the residual electrolyte C content in the gallium metal after drawing is extremely low, further improving the purity of the gallium metal.

[0076] In both sets of No. 2 electrolytic cells, the above method can be used for efficient and rapid recovery of gallium metal. Throughout the process, the extraction of gallium metal will not be interrupted, which can further improve the extraction efficiency of gallium metal.

[0077] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. An electrolytic extraction process for metallic gallium, characterized in that, Includes the following steps: Prepare electrolytic cell #1, electrolytic circulation cell #1, electrolytic cell #2, electrolytic circulation cell #2, DC power supply #1, DC power supply #2, and temperature control system; Low-current electrolysis: The electrolyte is transported to the No. 1 electrolytic cell through the No. 1 electrolytic circulation tank. The electrolyte overflowing from the No. 1 electrolytic cell is returned to the No. 1 electrolytic circulation tank. The No. 1 DC power supply is located at the No. 1 electrolytic cell. The current of the No. 1 DC power supply is adjusted to 29-31A to electrolyze the electrolyte to obtain impurity lead, impurity mercury and electrolyte A. Detection of Pb in electrolyte A 2+ and Hg 2+ The concentration of Pb 2+ and Hg 2+ When the concentrations of all components are ≤0.1mg / L, electrolyte B is formed; High-current electrolysis: Electrolyte B is transported to the No. 2 electrolytic circulation tank. Electrolyte B is sent to the No. 2 electrolytic tank through the No. 2 electrolytic circulation tank. The overflowing raw electrolyte in the No. 2 electrolytic tank is returned to the No. 2 electrolytic circulation tank. The No. 2 DC power supply is located at the No. 2 electrolytic tank. The current of the No. 2 DC power supply is adjusted to 750-1050A to obtain metallic gallium and electrolyte C. Detection of Ga in electrolyte C 3+ The concentration of Ga 3+ When the concentration is ≤5g / L, the extraction of metallic gallium is stopped.

2. The electrolytic extraction process for metallic gallium as described in claim 1, characterized in that, It also includes a No. 1 circulating pump and a No. 2 circulating pump. The No. 1 circulating pump is connected between the No. 1 electrolytic cell and the No. 1 electrolytic circulating cell, and the No. 2 circulating pump is connected between the No. 2 electrolytic cell and the No. 2 electrolytic circulating cell.

3. The electrolytic extraction process for metallic gallium as described in claim 2, characterized in that, The temperature control system controls the temperature of electrolyte A to be 35-45℃.

4. The electrolytic extraction process for metallic gallium as described in claim 3, characterized in that, The temperature control system controls the temperature of electrolyte C to be 38-42℃.

5. The electrolytic extraction process for metallic gallium as described in claim 4, characterized in that, The No. 2 electrolytic cell includes: Electrolytic cell; Several anodes are located in the electrolytic cell, and several of the anodes are connected in parallel with the positive terminal of DC power supply #2; The cathode is located inside the electrolytic cell and is electrically connected to the negative terminal of the No. 2 DC power supply. The cathode is vertically arranged, and several anodes are horizontally arranged and arranged around the cathode. Several guide grooves are provided on the outer wall of the cathode along the cathode axis. A gallium metal recycling component, wherein the lower end of the gallium metal recycling component is directly opposite the flow channel.

6. The electrolytic extraction process for metallic gallium as described in claim 5, characterized in that, The gallium recovery assembly includes: The recovery cylinder is vertically fixed inside the bottom of the electrolytic cell, and the recovery cylinder is coaxial with and opposite to the cathode. A sealing cap, which can seal the upper end of the recycling cylinder; A recovery tube, the upper end of which passes through the bottom of the electrolytic cell and is fixedly connected to the lower end of the recovery cylinder; A pressure relief valve installed on the recovery pipe.

7. The electrolytic extraction process for metallic gallium as described in claim 6, characterized in that, The lower end of the cathode is conical, and the center of the lower end of the cathode is directly opposite the center of the recovery cylinder.

8. The electrolytic extraction process for metallic gallium as described in claim 7, characterized in that, The gallium recovery assembly also includes: A hydraulic telescopic rod is provided, which is set horizontally. The telescopic end of the hydraulic telescopic rod passes through the side wall of the electrolytic cell and is fixedly connected to the side wall of the sealing cover. An elastic sealing layer that can abut against the end face of the recovery cylinder is fixedly provided on the lower surface of the sealing cover. A hydraulic pump that controls the extension or retraction of a hydraulic telescopic rod.

9. The electrolytic extraction process for metallic gallium as described in claim 8, characterized in that, The gallium recovery assembly also includes: The scraper is annular, and the cross-sectional profile of the inner wall of the scraper is the same as that of the cathode, and the inner wall of the scraper is in sliding contact with the outer wall of the cathode. A slide rail, which is vertically and fixedly installed inside the electrolytic cell; A slider that can slide along a slide rail, the slider being fixedly connected to the side wall of the scraper; A connecting rod is provided, which is set vertically. The lower end of the connecting rod passes through the electrolytic cell and is connected to or fixedly connected to the slider during the previous rotation. The connecting rod is in sliding contact with the electrolytic cell.

10. The electrolytic extraction process for metallic gallium as described in claim 9, characterized in that, There are two No. 2 electrolytic cells, and a regulating pump and an overflow output pump are provided between the two sets of No. 2 electrolytic cells; The overflow output pump is connected to the top side of one of the No. 2 electrolytic cells, and the current of the No. 2 DC power supply in the No. 2 electrolytic cell is adjusted to 750-950A. The regulating pump is equipped with a first input port for drawing in electrolyte B, a second input port for drawing in electrolyte C, a third input port connected to the overflow output pump, and an output port. The output port is connected to the top side of another set of No. 2 electrolytic cells. The current of the No. 2 DC power supply in this set of No. 2 electrolytic cells is adjusted to 850-1050A. A first switching valve is provided at the first input port, a second switching valve is provided at the second input port, and a third switching valve is provided at the third input port.

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