Device for producing pure metal by IE rotational flow electrodeposition method

Abstract

The utility model discloses a device for producing pure metal through an IE rotational flow electrodeposition method. The device comprises an electrodeposition cell, a liquid level meter, a circulating pump, a pH detector and the like. A water inlet of the electrolyte supply pump is connected with the bottom of the electrolyte preparation tank, and a water outlet is connected with a water inlet of the shunt pipe; a water inlet of the circulating pump is connected with the bottom of the electrodeposition cell, an outlet of the electrodeposition cell is connected with a water inlet at the bottom of the ion exchange column through a pipeline, resin loaded with metal ions is arranged in the column, and an upper water outlet is sequentially connected with the pH detector and a water inlet of the shunt pipe. A shunting hole of the shunting pipe is arranged between the anode and the cathode. Meanwhile, pure water is connected with a water inlet of a circulating pump through a pipeline and a pure water valve, and through pipeline connection of the device, orderly cooperation of electrolyte preparation, ion exchange, electrodeposition and other operations is achieved, and the stability of the content of metal ions and hydrogen ions in a product in the electrodeposition process of the electrolyte is achieved.

Description

Technical Field

[0001] The utility model relates to a device for producing pure metal by IE cyclone electrowinning method, belonging to the technical field of hydrometallurgy of non-ferrous metals. Background Art

[0002] In the traditional electrowinning process, the electrolyte flows slowly, and the diffusion rate of metal ions on the cathode surface is much lower than the electro-chemical reaction rate, resulting in significant concentration polarization on the cathode, causing a small amount of impurity ions to precipitate on the cathode together with the target metal ions, reducing the quality of the cathode product. When the concentration of the target metal ions is low, the phenomenon of the reduction of the cathode product quality and the current efficiency caused by concentration polarization is more obvious. Therefore, in the traditional metal electrodeposition process, the target metal ions need to maintain a high concentration, and the impurity ions need to be maintained at a low level.

[0003] The cyclone electrowinning technology avoids the concentration polarization phenomenon caused by the slow flow of the electrolyte in the traditional electrowinning process through the relative high-speed movement of the electrolyte and the electrode, enabling the target metal to preferentially precipitate at a low concentration, realizing efficient extraction and purification.

[0004] All electrowinning technologies are based on the basic electrochemical theory, and the cyclone electrowinning technology is no exception. The traditional electrowinning technology places the anode and cathode in a slowly flowing or stagnant tank body. Under the action of an electric field, anions move directionally towards the anode, and cations move directionally towards the cathode. By controlling certain technical conditions, the metal cations to be obtained gain electrons and deposit and precipitate on the cathode, thereby obtaining electrolysis products.

[0005] The cyclone electrowinning technology is based on the difference in the theoretical precipitation potential (E¢;) of each metal ion, that is, as long as the metal to be extracted has a large potential difference from other metal ions in the solution system, the metal with a relatively positive potential is prone to precipitate preferentially on the cathode. The key is to eliminate the adverse effects on electrolysis such as concentration polarization through high-speed liquid flow.

[0006] The electrochemical principle of cyclone electrowinning is the same as that of traditional tank electrowinning, that is

[0007] Electrowinning: Me n+ + ne → Me (metal) (cathode)

[0008] n / 2H2O - ne → nH + + n / 4O2↑ (anode)

[0009] nH + + ne → n / 2H2↑ (cathode side reaction)

[0010] Since swirl electrowinning also generates hydrogen ions in the anode region, after entering the electrolyte, side reactions occur in the cathode region to produce hydrogen gas, resulting in a decrease in the production current efficiency. Moreover, pores are formed on the product surface. Excessive hydrogen ions in the electrolyte corrode the electrodes to generate impurity ions, affecting the purity of the product. The fluctuation of the target metal ion content in the electrolyte affects the purity and quality of the electrowon target metal. Especially when electrowinning metals with a more negative electrode potential than hydrogen, such as nickel, cobalt, and zinc, drawbacks such as the continuous addition of neutralizing agents or the need to open the anode solution occur.

[0011] The swirl electrowinning technology is currently widely used for the electrowinning of metals with a more positive electrode potential than hydrogen, such as gold, silver, and copper. Since the above metal ions are preferentially deposited on the cathode, it is difficult for hydrogen ions to undergo side reactions to produce hydrogen gas at the cathode. Therefore, the current efficiency of electrowinning can be maintained, and the electrowinning process can proceed continuously. For metals with a more negative electrode potential than hydrogen, such as nickel, cobalt, and zinc, since hydrogen ions preferentially produce hydrogen gas at the cathode, if the hydrogen ions cannot be removed in time, the current efficiency will rapidly decrease, making the electrowinning of the above metals unable to continue. Therefore, it is necessary to use hydroxides, oxides, or carbonates of the above metals to neutralize the hydrogen ions in the electrolyte to make the electrowinning proceed continuously.

[0012] Since the generation of hydrogen ions starts from the anode reaction, a diaphragm is used to separate the cathode and the anode, and the electrolyte in the anode region is pumped out, which can alleviate the increase in the hydrogen ion content in the cathode region. However, due to the existence of the diaphragm, the anode solution cannot be removed at a high speed, so the effect is limited, and it is still necessary to continuously supplement new electrolyte in the cathode region to maintain the continuation of electrowinning.

[0013] Chinese Patent CN115465979A discloses a swirl electrolysis-ion exchange coupling system and method for the deep removal and recovery of metal ions in water bodies. By using the method of pumping out the anode solution to desorb the metals loaded on the ion exchange, since the diaphragm cannot completely block the entry of hydrogen ions into the cathode region, the hydrogen ion content will still increase during the circulation of the electrolyte. This method cannot effectively stabilize the hydrogen ion and target metal ion contents in the electrolyte, which is not conducive to producing high-purity target metal products. Summary of the Utility Model

[0014] The hydrogen ion content and metal ion content in the electrolyte have an important impact on the purity and quality of the products of metal electrowinning. The technical problem to be solved by the present utility model is to overcome the problems of the traditional swirl electrowinning process, such as the difficulty in producing high-purity non-ferrous metals (with a purity above 5N), especially metals with a more negative electrode potential than hydrogen, such as nickel, cobalt, and zinc, due to the fluctuation of hydrogen ions and metal ions in the electrolyte during the electrowinning process; and the increase in production costs caused by the need to open the electrolyte or anode solution to control the hydrogen ion content in the electrolyte to ensure the current efficiency.

[0015] The present utility model provides conditions for the electrolyte to maintain stable electrowinning during the electrowinning process, enabling the cyclone electrowinning process to be used for producing high-purity metals, while improving the current efficiency, reducing the production cost, and enhancing the product purity and quality.

[0016] The IE method cyclone electrowinning device for producing pure metals includes a cyclone electrowinning cell, a rectifier, a first flowmeter, a first circulation pump, a stirrer, a pH meter, a liquid level gauge, an electrolyte tank, a second circulation pump, and an ion exchange column;

[0017] The inlet of the first circulation pump is connected to the bottom of the electrolyte tank through a pipeline;

[0018] The outlet of the first circulation pump is connected to the first flowmeter and the lower liquid inlet of the cyclone electrowinning cell through a pipeline, and the upper liquid outlet of the cyclone electrowinning cell is connected to the upper part of the electrolyte tank through a pipeline;

[0019] The positive pole of the rectifier is connected to the anode in the cyclone electrowinning cell, and the negative pole is connected to the cathode in the cyclone electrowinning cell;

[0020] The electrolyte tank is filled with electrolyte, and the stirrer, pH meter, and liquid level gauge extend into the electrolyte;

[0021] The inlet of the second circulation pump is connected to the bottom of the electrolyte tank through a pipeline;

[0022] The outlet of the second circulation pump is connected to the bottom water inlet of the ion exchange column through a pipeline;

[0023] The ion exchange column is filled with resin loaded with metal ions, and the metal ions loaded on the resin are the same as the metal ions in the electrolyte;

[0024] The upper water outlet of the ion exchange column is connected to the upper part of the electrolyte tank through a pipeline.

[0025] Pure water enters the electrolyte tank through a pipeline and a valve. Due to the anodic reaction during the electrowinning process and the heating of the electrolyte, the water in the electrolyte is continuously lost. When the liquid level measured by the liquid level gauge is lower than the set value, the valve is opened, and pure water enters the electrolyte tank. When the liquid level returns to the set value, the valve 18 is closed, and so on; therefore, the contents of hydrogen ions and product metal ions in the electrolyte in the electrolyte tank are always stable within the set range.

[0026] The control of this device can be divided into an automatic version and a manual version according to actual commercial needs. The automatic control system of the automatic version can be obtained through commercial procurement and is not the innovation point of this application, so it is not shown in this application.

[0027] Preferably, when there is a diaphragm between the anode and the cathode of the cyclone electrowinning cell, the specific composition method is as follows:

[0028] The inlet of the first circulation pump is connected to the bottom of the electrolyte tank through a pipeline;

[0029] The outlet of the first circulation pump is connected to the inlets of the first valve and the first flowmeter, and the inlets of the second valve and the second flowmeter respectively through pipelines.

[0030] The outlet of the first flowmeter is connected to the liquid inlet K1 of the lower cathode area of the cyclone electrowinning cell through a pipeline, and K1 is located between the cathode and the diaphragm.

[0031] The outlet of the second flowmeter is connected to the liquid inlet K3 of the lower anode area of the cyclone electrowinning cell through a pipeline, and K3 is located between the anode and the diaphragm.

[0032] The liquid outlet K2 of the upper cathode area of the cyclone electrowinning cell is connected to the upper part of the first pressure gauge and the electrolyte tank through a pipeline.

[0033] The liquid outlet K4 of the upper anode area of the cyclone electrowinning cell is connected to the upper part of the electrolyte tank through a pipeline and the second pressure gauge.

[0034] The positive electrode (+) of the rectifier is connected to the anode in the cyclone electrowinning cell, and the negative electrode (-) is connected to the cathode in the cyclone electrowinning cell.

[0035] The electrolyte tank is filled with electrolyte, and the stirrer, pH meter and liquid level gauge extend into the electrolyte.

[0036] The inlet of the second circulation pump is connected to the bottom of the electrolyte tank through a pipeline.

[0037] The outlet of the second circulation pump is connected to the bottom water inlet of the ion exchange column through a pipeline.

[0038] The ion exchange column is filled with resin loaded with metal ions, and the metal ions loaded on the resin are the same as the metal ions in the electrolyte.

[0039] The upper water outlet of the ion exchange column is connected to the upper part of the electrolyte tank through a pipeline.

[0040] Pure water enters the electrolyte tank through a pipeline and a valve.

[0041] Preferably, the resin loaded with metal ions is one of weak acidic cation exchange resin, strong acidic cation exchange resin, and chelating ion exchange resin. The weak acidic cation exchange resin includes but is not limited to carboxyl group (-COOH), phosphoric acid group (-PO2H2), and phenolic group. The chelating ion exchange resin includes but is not limited to carboxamide group, aminophosphoric acid group, thiourea group, mercapto group, and pyridyl group. The resin form is Na type or H type.

[0042] Preferably, the metal salt used for preparing the electrolyte is one of sulfate, hydrochloride, nitrate, and sulfamate; or the electrolyte is directly prepared with the regeneration solution of the resin loaded with metal ions.

[0043] Preferably, the metal salt used for preparing the electrolyte is sulfate.

[0044] Preferably, the metal salt or metal salt solution used for resin loading of metal ions is one of sulfate, hydrochloride, nitrate, and sulfamate; alternatively, a metal salt solution or an aqueous solution containing metal ions of the product in other forms can be directly used.

[0045] Preferably, the electrolyte tank is equipped with heating and temperature control devices to adapt to the process that requires temperature conditions for the electrowinning process.

[0046] A treatment method for the IE method cyclone electrowinning pure metal production device as described above: includes the following steps:

[0047] Electrolyte preparation: Add a metal salt solution or metal salt, additives, and water to the electrolyte tank to prepare the electrolyte, and stir evenly with a stirrer; the metal salt solution can also be the regeneration solution of the resin loaded with metal ions.

[0048] Preparation of the resin loaded with metal ions: Dissolve the metal salt in water to prepare an aqueous solution, and the metal ions in the aqueous solution are loaded onto the resin through ion exchange to form the resin loaded with metal ions; load the resin loaded with metal ions into the ion exchange column; alternatively, the resin can be first loaded into the ion exchange column, and then the prepared metal salt aqueous solution or other aqueous solution containing metal ions of the product is passed through to load the metal ions onto the resin to form the resin loaded with metal ions.

[0049] Start the first circulation pump. The electrolyte in the electrolyte tank enters from the lower inlet of the cyclone electrowinning cell through the first circulation pump and the first flow meter, and after passing through the cyclone electrowinning cell, it flows out from the upper inlet of the cyclone electrowinning cell and enters the electrolyte tank to form a cycle. To reduce the concentration difference of metal ions on the cathode surface and timely bring out the hydrogen ions in the electrolyte from the cyclone electrowinning cell, the hourly flow rate of the first circulation pump is 50 - 500 times the volume of the cyclone electrowinning cell.

[0050] Start the stirrer to fully mix and homogenize the electrolyte in the electrolyte tank.

[0051] For metal electrowinning that requires temperature conditions, the electrolyte temperature should always be controlled within the specified range.

[0052] Metal electrowinning: Turn on the rectifier and gradually increase the current to the set value, and the metal ions in the electrolyte start to deposit on the cathode.

[0053] Electrolyte stabilization: As metal ions continuously precipitate and are deposited onto the cathode of the cyclone electrowinning cell, the hydrogen ion content in the electrolyte in the electrolyte tank begins to rise, and the pH value drops. When the pH meter measures that the pH exceeds the set value, the second circulation pump is started. The electrolyte in the electrolyte tank passes through the second circulation pump, enters from the bottom water inlet of the ion exchange column, and after passing through the resin loaded with metal ions, flows out from the upper part of the ion exchange column and enters the electrolyte tank to form a cycle. When the hydrogen ions in the electrolyte pass through the resin loaded with metal ions, they exchange the metal ions loaded on the resin and continuously supplement them into the electrolyte to maintain the metal ion content in the electrolyte, while removing hydrogen ions. When the pH value of the electrolyte reaches the set value, the second circulation pump stops, and this process repeats. Due to the anodic reaction during the electrowinning process and the heating of the electrolyte, the water in the electrolyte continuously loses. When the liquid level gauge measures that the liquid level is lower than the set value, valve 18 is opened, and pure water enters the electrolyte tank. When the liquid level returns to the set value, valve 18 is closed, and this process repeats. Therefore, the hydrogen ion and product metal ion contents in the electrolyte in the electrolyte tank are always stable within the set range.

[0054] Regeneration of the resin loaded with metal ions: As the electrowinning continues, the product metal ions in the resin loaded with metal ions are continuously exchanged and removed from the negative charge by hydrogen ions. When the hydrogen ion content in the electrolyte begins to increase and the pH value drops, and the detection value of the pH meter exceeds the process control range, it indicates that all the metal ions in the resin have been removed from the negative charge. At this time, after the resin is loaded with metal ions again, the electrowinning process continues.

[0055] The treatment method of the above IE method cyclone electrowinning pure metal production device includes the following steps in its operation:

[0056] Electrolyte preparation: A metal salt solution or metal salt, additives, and water are added to the electrolyte tank to prepare the electrolyte, and it is stirred evenly with a stirrer. The metal salt solution can also be the regeneration solution of the resin loaded with metal ions.

[0057] Preparation of the resin loaded with metal ions: The metal salt is dissolved in water to form an aqueous solution, and the metal ions in the aqueous solution are loaded onto the resin through ion exchange to form the resin loaded with metal ions. The resin loaded with metal ions is loaded into the ion exchange column. It is also possible to first load the resin into the ion exchange column, and then pass through the prepared metal salt aqueous solution or other aqueous solutions containing product metal ions to load the metal ions onto the resin to form the resin loaded with metal ions.

[0058] Start the first circulation pump. The electrolyte in the electrolyte tank enters through the first circulation pump, valves, and the first flowmeter, valves, and flowmeter, and enters from the lower liquid inlets K1 and K3 of the vortex electrowinning cell. After passing through the vortex electrowinning cell, it flows out from the upper liquid outlets K2 and K4 of the vortex electrowinning cell and enters the electrolyte tank to form a circulation. To reduce the concentration difference of metal ions on the cathode surface and timely remove hydrogen ions in the electrolyte from the vortex electrowinning cell, the hourly flow rate of the first circulation pump is 50 - 500 times the volume of the vortex electrowinning cell. To maintain the pressure balance on both sides of the diaphragm, by adjusting the valves, the pressure values of the first pressure gauge and the second pressure gauge are kept consistent;

[0059] Start the stirrer to fully mix and homogenize the electrolyte in the electrolyte tank;

[0060] For metal electrowinning that requires temperature conditions, the electrolyte temperature should always be controlled within the specified range;

[0061] For metal electrowinning, turn on the rectifier and gradually increase the current to the set value. Metal ions in the electrolyte start to deposit on the cathode;

[0062] Electrolyte stabilization: As metal ions continuously precipitate and are deposited on the cathode of the vortex electrowinning cell, the hydrogen ion content in the electrolyte in the electrolyte tank starts to rise and the pH value drops. When the pH meter measures that the pH exceeds the set value, start the second circulation pump. The electrolyte in the electrolyte tank enters through the second circulation pump and enters from the bottom water inlet of the ion exchange column. After passing through the resin loaded with metal ions, it flows out from the upper part of the ion exchange column and enters the electrolyte tank to form a circulation; hydrogen ions in the electrolyte exchange the metal ions loaded on the resin when passing through the resin loaded with metal ions, continuously supplementing them into the electrolyte to maintain the content of metal ions in the electrolyte, and at the same time removing hydrogen ions. When the electrolyte pH reaches the set value, the second circulation pump stops, and so on; Due to the anodic reaction and electrolyte heating during the electrowinning process, water in the electrolyte is continuously lost. When the liquid level gauge measures that the liquid level is lower than the set value, open valve 18, and pure water enters the electrolyte tank. When the liquid level returns to the set value, close valve 18, and so on; Keep the hydrogen ion and product metal ion contents in the electrolyte in the electrolyte tank always stable within the set range;

[0063] Regeneration of the resin loaded with metal ions: As the electrowinning continues, the product metal ions in the resin loaded with metal ions are continuously exchanged and removed from the negative charge by hydrogen ions. When the hydrogen ion content in the electrolyte starts to increase and the pH value drops, and the pH meter detection value exceeds the process control range, it indicates that the metal ions in the resin have been completely removed from the negative charge. At this time, after the resin is loaded with metal ions again, continue the electrowinning process.

[0064] The present disclosure combines ion exchange technology and cyclone electrowinning technology. By utilizing the hydrogen ions generated in the electrolyte during the cyclone electrowinning process, the metal ions loaded on the resin are exchanged (depleted of negative charge) and used as a metal source to supplement the electrolyte. At the same time, the hydrogen ions in the electrolyte can be neutralized in a timely manner, ensuring that the contents of metal ions and hydrogen ions in the electrolyte remain stable throughout the process of producing metal by electrowinning, thereby enabling the production of pure metal through a new process.

[0065] The utility model can promptly remove hydrogen ions in the electrolyte, avoiding side reactions at the cathode and improving current efficiency. At the same time, there is no need to balance the hydrogen ion content by means of open-circuit electrolyte or adding neutralizing agents, thus significantly reducing production costs. When the ion exchange resin loads product metal ions, other contaminant metal ions, anionic metal, complex anions, extractants, oils, solvents, and other pollutants are removed, which is beneficial to improving the quality of electrowon metal products. During the cyclone electrowinning process of the IE method, since hydrogen ions in the electrolyte can be promptly removed, it also avoids the disadvantages of hydrogen embrittlement prone to occur in electrowon metal products in traditional electrowinning processes and the pollution of products by impurity ions brought in by electrode corrosion. At the same time, the IE method electrowinning process can keep the pH value of the electrolyte and the content of product metal ions stable throughout the electrowinning process, which is beneficial to improving product quality.

[0066] The device of the utility model can be widely used in the electrowinning production of various non-ferrous metals such as copper, nickel, cobalt, manganese, zinc, and chromium.

[0067] The IE method cyclone electrowinning is a new technology that utilizes the combined action of ion exchange and metal ion cyclone electrowinning to produce pure metal. Its process principle is as follows.

[0068] (1) Resin: R-Na (Na type) or R-H (H type)

[0069] (2) Resin loading metal ions: R-Na + Me n+ (Metal ions) → R-Me + nNa +

[0070] n is the valence state of metal ions

[0071] (3) Electrowinning: Me n+ + ne → Me (metal) (cathode)

[0072] n / 2H2O - ne → nH + + n / 4O2↑ (anode)

[0073] nH + + ne → n / 2H2↑ (cathode side reaction)

[0074] (4) Total reaction: Me n+ + n / 2H2O → Me + nH ++n / 4O2↑

[0075] (5) Desorption of metal-loaded resin: R-Me + nH + →R-H + Me n+

[0076] (6) Resin transformation: R-H + Na + →R-Na + H +

[0077] Taking the production of pure nickel by the cyclone electrowinning of nickel sulfate solution as an example:

[0078] (1) Resin: R-Na (Na type) or R-H (H type)

[0079] (2) Resin loading of nickel ions: R-Na + Ni 2+ →R-Ni + 2Na + +SO4 2-

[0080] (3) Electrowinning: Ni 2+ +2e → Ni (metallic nickel) (cathode)

[0081] H2O - 2e → 2H + +1 / 2O2 (anode)

[0082] 2H + +2e → H2↑ (cathode side reaction)

[0083] (4) Overall reaction: Ni 2+ +H2O → Me + 2H + +1 / 2O2↑

[0084] (5) Desorption of nickel-loaded resin: R-Ni + 2H + →R-H + Ni 2+

[0085] (6) Transformation of nickel-loaded resin: R-H + Na + →R-Na + H +

[0086] Further preferably, the resin loaded with metal ions is one of a weakly acidic cation exchange resin, a strongly acidic cation exchange resin, and a chelating ion exchange resin. The weakly acidic cation exchange resin includes, but is not limited to, a carboxylic acid group (-COOH), a phosphoric acid group (-PO2H2), and a phenolic group. The chelating ion exchange resin includes, but is not limited to, a carboxamide group, an aminophosphoric acid group, a thiourea group, a mercapto group, and a pyridyl group. The resin form is the Na type or the H type.

[0087] Further preferably, the metal salt used for preparing the electrolyte is one of sulfate, hydrochloride, nitrate, and sulfamate. The electrolyte can also be prepared with the regeneration solution of the resin loaded with metal ions 9;

[0088] Further preferably, the metal salt used for preparing the electrolyte is sulfate.

[0089] Further preferably, the metal salt or metal salt solution used for loading metal ions onto the resin includes but is not limited to one of sulfate, hydrochloride, nitrate, sulfamate, etc. Or the metal salt solution directly uses other forms of aqueous solutions containing product metal ions, such as leaching solutions, waste liquids, wastewaters, etc.

[0090] Further preferably, for the electrowinning process that requires temperature conditions, the electrolyte tank (7) is equipped with heating and temperature control devices.

[0091] The beneficial effects of the present utility model are as follows:

[0092] 1. The stability of the product metal ions and hydrogen ions in the electrolyte during the electrowinning process is achieved, providing an excellent cyclone electrowinning environment, which is beneficial to improving the product purity and quality;

[0093] 2. The hydrogen ions in the electrolyte are removed in a timely manner, significantly reducing the side reactions at the cathode and improving the current efficiency;

[0094] 3. There is no need to balance the hydrogen ion content by means of an open-circuit part of the electrolyte or adding a neutralizing agent, which can significantly reduce the production cost;

[0095] 4. Since the hydrogen ions in the electrolyte can be removed in a timely manner, the disadvantages of the traditional electrowinning process, such as the easy occurrence of pores in the electrowon metal products and the pollution of the products by impurity ions brought in due to the corrosion of the electrodes by the high acidity of the electrolyte, are avoided;

[0096] 5. The stability of the product metal ions in the electrolyte, as well as the reduction of the impurity ion content on the cathode surface and the avoidance of the depletion of the product metal ions by the large-flow circulation of the electrolyte, maintain the electrowinning selection advantage of the product metal ions over the impurity ions, and avoid the generation of basic metal salts due to the depletion of the product metal ions on the cathode surface, which is beneficial to improving the purity and quality of the product metal;

[0097] 6. Using ion exchange resin to load product metal ions as the metal source enables this process to use different types of metal salts as raw materials. For example, in the process of producing pure nickel by electrowinning nickel sulfate in the present utility model, nickel chloride, nickel nitrate, and other types of nickel salts can be used as the nickel source;

[0098] 7. During the process of loading product metal ions onto ion exchange resin, due to the selective adsorption of the resin and the high exchange potential formed by the fact that the content of product metal ions is much greater than that of impurity ions, the remaining sodium ions, calcium ions, and magnesium ions, extractants, oil impurities, or impurity metal ions in the product metal salt solution are not adsorbed or are displaced by product metal ions after adsorption, which improves the purity of the metal ions loaded on the resin and is conducive to producing high-quality electrowon metal products.

[0099] 8. At the same time, due to the long-term operation of the electrolyte, impurity ions and pollutants will accumulate. When they exceed the process allowable range, this electrolyte can also be used for loading product metal ions onto ion exchange resin to remove impurity ions and pollutants during the process of loading metal ions. BRIEF DESCRIPTION OF THE DRAWINGS

[0100] Figure 1 It is the device and schematic diagram of the present utility model.

[0101] Figure 2 It is another embodiment and schematic diagram of the present utility model.

[0102] In the figure: 1. Cyclone electrowinning cell; 2. Rectifier; 3. First flowmeter; 4. First circulation pump; 5. Agitator; 6. pH meter; 7. Electrolyte tank; 8. Second circulation pump; 9. Ion exchange column; 10. Resin loaded with metal ions; 11. Diaphragm; 12. Second flowmeter; 13. First valve; 14. Second valve; 15. First pressure gauge; 16. Second pressure gauge; 17. Liquid level gauge; 18. Valve. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0103] The IE method cyclone electrowinning device and process principle for producing pure metal (see Figure 1 ), including a cyclone electrowinning cell 1, a rectifier 2, a flowmeter 3, a circulation pump 4, an agitator 5, a pH meter 6, an electrolyte tank 7, a circulation pump 8, an ion exchange column 9, and a resin loaded with metal ions 10; the specific composition method is as follows:

[0104] (1) The water inlet of the circulation pump 4 is connected to the bottom of the electrolyte tank 7 through a pipeline;

[0105] (2) The water inlet of the first circulation pump 4 is connected to the bottom of the electrolyte tank 7 through a pipeline;

[0106] (3) The water outlet of the first circulation pump 4 is connected to the flowmeter 3 and the lower liquid inlet of the cyclone electrowinning cell 1 through a pipeline, and the upper liquid outlet of the cyclone electrolysis cell 1 is connected to the upper part of the electrolyte tank 7 through a pipeline;

[0107] (4) The positive pole of the rectifier 2 is connected to the anode in the cyclone electrowinning cell 1, and the negative pole is connected to the cathode in the cyclone electrowinning cell 1;

[0108] (5) The electrolyte tank 7 is equipped with a stirrer 5, a pH meter 6 and a liquid level meter 17. For metal electrowinning with temperature requirements, the electrolyte tank 7 is equipped with a heating and temperature control device (not shown in the figure);

[0109] (6) The water inlet of the second circulation pump 8 is connected to the bottom of the electrolyte tank 7 through a pipeline;

[0110] (7) The outlet of the second circulation pump 8 is connected to the bottom water inlet of the ion exchange column 9 through a pipeline;

[0111] (8) The resin 10 loaded with metal ions is loaded into the ion exchange column 9;

[0112] (9) The water outlet at the top of the ion exchange column 9 is connected to the top of the electrolyte tank 7 through a pipeline.

[0113] (10) Pure water enters the electrolyte tank (7) through the pipeline and valve 18.

[0114] Its operation includes the following steps:

[0115] (1) Preparation of electrolyte: Add metal salt solution or metal salt, additive and water into electrolyte tank 7 to prepare electrolyte, and stir evenly with stirrer 5; wherein the metal salt solution may also be the regeneration liquid of resin 10 loaded with metal ions;

[0116] (2) Preparation of metal ion-loaded resin 10: dissolving metal salt in water to prepare aqueous solution, and loading metal ions in the aqueous solution onto resin through ion exchange to form metal ion-loaded resin 10; loading metal ion-loaded resin 10 into ion exchange column 9; or loading resin into ion exchange column 9 first, and then introducing prepared metal salt aqueous solution or other aqueous solution containing product metal ions to load metal ions onto resin to form metal ion-loaded resin 10;

[0117] (3) Start the first circulation pump 4. The electrolyte in the electrolyte tank 7 enters from the lower inlet of the cyclone electrowinning tank 1 through the first circulation pump 4 and the flowmeter 3. After passing through the cyclone electrowinning tank 1, it flows out from the upper inlet of the cyclone electrowinning tank 1 and enters the electrolyte tank 7 to form a cycle. In order to reduce the concentration difference of metal ions on the cathode surface and to bring hydrogen ions in the electrolyte out of the cyclone electrowinning tank 1 in time, the hourly flow rate of the first circulation pump 4 is 50-500 times the volume of the cyclone electrowinning tank 1.

[0118] (4) starting the stirrer 5 to fully mix the electrolyte in the electrolyte tank 7;

[0119] (5) For metal electrowinning that requires temperature conditions, start the heating and temperature control devices of the electrolyte tank to control the electrolyte temperature within the specified range;

[0120] (6) Metal electrowinning: Turn on the rectifier 2 and gradually increase the current to the set value. Metal ions in the electrolyte start to deposit on the cathode.

[0121] (7) Electrolyte stabilization: As metal ions continuously precipitate and deposit on the cathode of the electrocyclic deposition tank 1, the hydrogen ion content in the electrolyte in the electrolyte tank 7 starts to rise and the pH value drops. When the pH meter 6 measures that the pH exceeds the set value, start the second circulation pump 8. The electrolyte in the electrolyte tank 7 enters through the bottom water inlet of the ion exchange column 9 via the second circulation pump 8, and after passing through the resin 10 loaded with metal ions, flows out from the upper part of the ion exchange column 9 and enters the electrolyte tank 7 to form a cycle. Hydrogen ions in the electrolyte exchange the metal ions loaded on the resin when passing through the resin 10 loaded with metal ions, continuously supplementing them into the electrolyte to maintain the content of metal ions in the electrolyte and removing hydrogen ions at the same time. When the pH value of the electrolyte reaches the set value, the second circulation pump 8 stops, and so on. Due to the anodic reaction and electrolyte heating during the electrowinning process, water in the electrolyte is continuously lost. When the liquid level gauge measures that the liquid level is lower than the set value, open the valve 18, and pure water enters the electrolyte tank. When the liquid level returns to the set value, close the valve 18, and so on. Keep the hydrogen ion and product metal ion contents in the electrolyte in the electrolyte tank 7 always stable within the set range.

[0122] (8) Regeneration of the resin 10 loaded with metal ions: As the electrowinning continues, the product metal ions in the resin 10 loaded with metal ions are continuously exchanged and removed from the negative charge by hydrogen ions. When the hydrogen ion content in the electrolyte starts to increase and the pH value drops, and the detection value of the pH meter 6 exceeds the process control range, it indicates that the metal ions in the resin have been completely removed from the negative charge. At this time, the resin 10 is loaded with metal ions again and the electrowinning process continues.

[0123] Another embodiment of the present utility model: When a diaphragm 11 is used between the cathode and anode of the hydrocyclone electrodeposition tank 1, the specific composition method is (see Figure 2 ):

[0124] (1) The water inlet of the first circulation pump 4 is connected to the bottom of the electrolyte tank 7 through a pipeline;

[0125] (2) The water outlet of the first circulation pump 4 is connected to the water inlets of the first valve 13 and the first flowmeter 3, and the water inlets of the second valve 14 and the second flowmeter 12 through pipelines;

[0126] (3) The water outlet of the first flowmeter 3 is connected to the liquid inlet K1 in the lower cathode area of the hydrocyclone electrodeposition tank 1 through a pipeline. K1 is located between the cathode and the diaphragm;

[0127] (4) The water outlet of the second flowmeter 12 is connected to the liquid inlet K3 in the lower anode area of the hydrocyclone electrodeposition tank 1 through a pipeline. K3 is located between the anode and the diaphragm;

[0128] (5) The liquid outlet K2 at the upper cathode area of the cyclone electrolytic cell 1 is connected to the upper part of the electrolyte tank 7 through a pipeline and a first pressure gauge 15;

[0129] (6) The liquid outlet K4 at the upper anode area of the cyclone electrolytic cell 1 is connected to the upper part of the electrolyte tank 7 through a pipeline and a second pressure gauge 16;

[0130] (7) The positive electrode (+) of the rectifier 2 is connected to the anode in the cyclone electrowinning cell 1, and the negative electrode (-) is connected to the cathode in the cyclone electrowinning cell 1;

[0131] (8) A stirrer 5, a pH meter 6 and a liquid level gauge 17 are installed on the electrolyte tank 7. For metal electrowinning with temperature requirements, the electrolyte tank 7 is equipped with heating and temperature control devices (not shown in the figure);

[0132] (9) The water inlet of the second circulation pump 8 is connected to the bottom of the electrolyte tank 7 through a pipeline;

[0133] (10) The outlet of the second circulation pump 8 is connected to the bottom water inlet of the ion exchange column 9 through a pipeline;

[0134] (11) The ion exchange column 9 is filled with a resin 10 loaded with metal ions;

[0135] (12) The upper water outlet of the ion exchange column 9 is connected to the upper part of the electrolyte tank 7 through a pipeline;

[0136] (13) Pure water enters the electrolyte tank (7) through a pipeline and a valve 18.

[0137] Its operation includes the following steps:

[0138] (1) Preparation of the electrolyte. A metal salt solution or a metal salt, an auxiliary agent and water are added to the electrolyte tank 7 to prepare the electrolyte, and it is stirred evenly with the stirrer 5; the metal salt solution can also be the regeneration solution of the resin 10 loaded with metal ions;

[0139] (2) Preparation of the resin 10 loaded with metal ions. A metal salt is dissolved in water to prepare an aqueous solution, and the metal ions in the aqueous solution are loaded onto the resin through ion exchange to form the resin 10 loaded with metal ions; the resin 10 loaded with metal ions is loaded into the ion exchange column 9; it is also possible to first load the resin into the ion exchange column 9, and then pass through the prepared metal salt aqueous solution or other aqueous solutions containing the product metal ions, and load the metal ions onto the resin to form the resin 10 loaded with metal ions;

[0140] (3) Start the first circulation pump 4. The electrolyte in the electrolyte tank 7 enters through the first circulation pump 4, valve 13 and flowmeter 3, valve 14 and flowmeter 12, and enters from the lower liquid inlets K1 and K3 of the cyclone electrowinning cell 1. After passing through the cyclone electrowinning cell 1, it flows out from the upper liquid outlets K2 and K4 of the cyclone electrowinning cell 1 and enters the electrolyte tank 7 to form a cycle. In order to reduce the concentration difference of metal ions on the cathode surface and timely remove hydrogen ions in the electrolyte from the cyclone electrowinning cell 1, the hourly flow rate of the circulation pump 4 is 50 - 500 times the volume of the electro-cyclone cell 1. In order to maintain the pressure balance on both sides of the diaphragm, by adjusting valve 13 and valve 14, the pressure values of the first pressure gauge 15 and the second pressure gauge 16 are kept consistent;

[0141] (4) Start the stirrer 5 to fully mix and homogenize the electrolyte in the electrolyte tank 7;

[0142] (5) For the electrowinning of metals that require temperature conditions, start the heating and temperature control device in the electrolyte tank 7 to control the electrolyte temperature within the specified range;

[0143] (6) For metal electrowinning, turn on the rectifier 2 and gradually increase the current to the set value. The metal ions in the electrolyte start to deposit on the cathode;

[0144] (7) Electrolyte stabilization: As metal ions continuously precipitate and deposit on the cathode of the electro-cyclone cell 1, the hydrogen ion content in the electrolyte in the electrolyte tank 7 starts to rise and the pH value drops. When the pH meter 6 measures that the pH exceeds the set value, start the second circulation pump 8. The electrolyte in the electrolyte tank 7 enters through the second circulation pump 8 from the bottom water inlet of the ion exchange column 9, and after passing through the resin 10 loaded with metal ions, it flows out from the upper part of the ion exchange column 9 and enters the electrolyte tank 7 to form a cycle; the hydrogen ions in the electrolyte exchange the metal ions loaded on the resin when passing through the resin 10 loaded with metal ions, continuously supplementing them into the electrolyte to maintain the content of metal ions in the electrolyte, and at the same time removing hydrogen ions. When the electrolyte pH reaches the set value, the second circulation pump 8 stops, and so on; due to the anodic reaction during the electrowinning process and the heating of the electrolyte, the water in the electrolyte is continuously lost. When the liquid level gauge measures that the liquid level is lower than the set value, open valve 18, and pure water enters the electrolyte tank. When the liquid level returns to the set value, close valve 18, and so on; so that the hydrogen ion and product metal ion contents in the electrolyte in the electrolyte tank 7 are always stable within the set range;

[0145] (8)Regeneration of the resin 10 loaded with metal ions. As the electrowinning continues, the product metal ions in the resin 10 loaded with metal ions are continuously de-negatively exchanged by hydrogen ions. When the hydrogen ion content in the electrolyte starts to increase, the pH value drops, and the detected value of the pH meter 6 exceeds the process control range, it indicates that all the metal ions in the resin have been de-negatively charged. At this time, after the resin 10 is loaded with metal ions again, the electrowinning process continues.

[0146] Example 1: IE cyclone electrowinning to produce pure nickel 1

[0147] The device consists of a cyclone electrowinning cell, a rectifier, a flow meter, a circulation pump, a stirrer, a pH meter, a liquid level meter, an electrolyte tank, an ion exchange column, valves, and a resin loaded with metal ions;

[0148] The specific composition is as follows:

[0149] (1) The water inlet of the circulation pump 4 is connected to the bottom of the electrolyte tank 7 through a pipeline;

[0150] (2) The water outlet of the circulation pump 4 is connected to the flow meter 3 and the lower liquid inlet of the cyclone electrowinning cell 1 through a pipeline. The upper liquid outlet of the cyclone electrolysis cell 1 is connected to the upper part of the electrolyte tank 7 through a pipeline;

[0151] (3) Specifications of the cyclone electrowinning cell 1 (cathode size): Φ50*1*245mm, electrode material: the cathode is pure titanium, and the anode is iridium-coated titanium;

[0152] (4) The positive pole of the rectifier 2 is connected to the anode in the cyclone electrowinning cell 1, and the negative pole is connected to the cathode;

[0153] (5) The electrolyte tank 7 is a 3000L glass beaker, equipped with a stirrer 5, a pH meter 6, and a liquid level meter 18 on it, and is placed in a heating water bath with a temperature control device;

[0154] (6) The water inlet of the circulation pump 8 is connected to the bottom of the electrolyte tank 7 through a pipeline;

[0155] (7) The outlet of the circulation pump 8 is connected to the bottom water inlet of the ion exchange column 9 through a pipeline;

[0156] (8) The ion exchange column 9 is filled with a resin 10 loaded with nickel ions, and the resin 10 uses Lewatit CNP80;

[0157] (9) The upper water outlet of the ion exchange column 9 is connected to the upper liquid inlet of the electrolyte tank 7 through a pipeline.

[0158] (10) Pure water enters the electrolyte tank (7) through a pipeline and a valve 18.

[0159] Its operation includes the following steps:

[0160] (1) Add the nickel sulfate solution purified by microfiltration membrane filtration into the electrolyte tank 7, then add boric acid and pure water to prepare the electrolyte, and stir evenly with the stirrer 5; the control components of the electrolyte are:

[0161] Ni 30 - 35 g / L, Cu ≤ 0.0005 g / L, Zn ≤ 0.0005 g / L, Cd ≤ 0.0001 g / L, Fe ≤ 0.001 g / L, Mn ≤ 0.001 g / L, Cd ≤ 0.0001 g / L, Cr ≤ 0.001 g / L,

[0162] H3BO3 6 - 8 g / L, Cl - ≤ 0.01 g / L;

[0163] (2) Dissolve the nickel sulfate solution in step 1 with water to prepare an aqueous solution containing 12 - 15 g / L of nickel, and pre-load the nickel ions in the aqueous solution onto the resin 10 through ion exchange; load the resin 10 loaded with nickel ions into the ion exchange column 9;

[0164] (3) Start the first circulation pump 4, and the electrolyte in the electrolyte tank 7 enters from the lower inlet of the vortex electrowinning cell 1 through the first circulation pump 4 and the flowmeter 3. After passing through the vortex electrowinning cell 1, it flows out from the upper inlet of the vortex electrowinning cell 1 and enters the electrolyte tank 7 to form a cycle. The flow rate of the first circulation pump 4 is 150 L / h;

[0165] (4) Start the stirrer 5 to fully mix the electrolyte in the electrolyte tank 7 evenly;

[0166] (5) Start the water bath heating and temperature control device, and control the electrolyte temperature at 65 - 70 °C;

[0167] (6) Nickel electrowinning, turn on the rectifier 2, adjust the voltage to 2 - 4 V, and gradually increase the current to 5 - 6 A. The nickel ions in the electrolyte start to deposit on the cathode;

[0168] (7) Electrolyte stabilization: As nickel ions are continuously precipitated and deposited onto the cathode of the electro - cyclone deposition tank 1, the hydrogen ion content in the electrolyte in the electrolyte tank 7 starts to rise, and the pH value drops. When the pH meter 6 measures that pH ≤ 3.5, the second circulation pump 8 is started. The electrolyte in the electrolyte tank 7 passes through the second circulation pump 8, enters from the bottom water inlet of the ion exchange column 9, and after passing through the resin 10 loaded with nickel ions, flows out from the upper part of the ion exchange column 9 and enters the electrolyte tank 7 to form a cycle. When the hydrogen ions in the electrolyte pass through the resin 10 loaded with nickel ions, the nickel ions loaded on the resin are exchanged and continuously replenished into the electrolyte to maintain the nickel ion content in the electrolyte, while removing hydrogen ions. When the electrolyte pH value ≥ 4, the second circulation pump 8 stops, and this process repeats. As the anodic reaction during the electrodeposition process continuously decomposes water, and the heating of the electrolyte causes continuous loss of water in the electrolyte, when the liquid level gauge measures that the liquid level has decreased by 1 - 5%, the valve 18 is opened, and pure water enters the electrolyte tank. When the liquid level is restored, the valve 18 is closed, and this process repeats. The pH value of the electrolyte in the electrolyte tank 7 is controlled within 3 - 4, and the nickel ion content is maintained at 30 - 35 g / L.

[0169] (8) Regeneration of the resin 10 loaded with nickel ions: As the electrodeposition continues, the nickel ions in the resin 10 loaded with nickel ions are continuously exchanged and removed from the negative charge by hydrogen ions. When the hydrogen ion content in the electrolyte starts to increase and the pH value drops, and the detection value of the pH meter 6 ≤ 3, it indicates that all the nickel ions in the resin have been removed from the negative charge. At this time, the resin 10 is loaded with nickel ions again, and the electrodeposition process continues.

[0170] (9) When the electrodeposition time reaches 72 hours, the nickel sheet on the cathode is taken out. The thickness is ≥ 2 mm. After washing, the nickel purity is detected to be ≥ 99.9995%.

[0171] The principle is as follows.

[0172] (1) Resin: R - Na (Na type) or R - H (H type)

[0173] (2) Resin loading of nickel ions: R - Na (resin) + Ni 2+ (nickel ions) → R - Ni + 2Na +

[0174] (3) Electrodeposition: Ni 2+ + 2e → Ni (metallic nickel) (cathode)

[0175] H2O - 2e → 2H + + 1 / 2O2 (anode)

[0176] 2H + + 2e → H2↑ (cathode side reaction)

[0177] (4) Resin desorption: R - Ni + 2H+ → R-H + Ni 2+

[0178] (5) Resin transformation: R-H + 2Na + → R-Na + 2H +

[0179] Example 2: IE swirl electrowinning produces pure nickel 2

[0180] The specific composition is as follows (see Figure 2 ):

[0181] (1) The water inlet of the first circulation pump 4 is connected to the bottom of the electrolyte tank 7 through a pipeline;

[0182] (2) The water outlet of the first circulation pump 4 is connected to the water inlets of the first valve 13 and the first flowmeter 3, and the water inlets of the second valve 14 and the second flowmeter 12 through pipelines;

[0183] (3) Specifications of the swirl electrowinning cell 1 (cathode size): Φ219 * 3 * 1550 mm, the diaphragm is a composite diaphragm with a pore size of 2 - 3 μm, and the electrode material: the cathode is pure titanium, and the anode is iridium-coated titanium;

[0184] (4) The water outlet of the first flowmeter 3 is connected to the liquid inlet K1 in the lower cathode area of the swirl electrowinning cell 1 through a pipeline, and K1 is located between the cathode and the diaphragm;

[0185] (4) The water outlet of the second flowmeter 12 is connected to the liquid inlet K3 in the lower anode area of the swirl electrowinning cell 1 through a pipeline, and K3 is located between the anode and the diaphragm;

[0186] (5) The liquid outlet K2 in the upper cathode area of the swirl electrolysis cell 1 is connected to the upper part of the electrolyte tank 7 through a pipeline and the first pressure gauge 15;

[0187] (6) The liquid outlet K4 in the upper anode area of the swirl electrolysis cell 1 is connected to the upper part of the electrolyte tank 7 through a pipeline and the second pressure gauge 16;

[0188] (7) The positive electrode (+) of the rectifier 2 is connected to the anode in the swirl electrowinning cell 1, and the negative electrode (-) is connected to the cathode in the swirl electrowinning cell 1;

[0189] (8) The electrolyte tank 7 is an enamel reaction kettle with an effective volume of 2 m 3 equipped with a stirrer 5, a pH meter 6 and a level gauge 17;

[0190] (9) The water inlet of the second circulation pump 8 is connected to the bottom of the electrolyte tank 7 through a pipeline;

[0191] (10) The outlet of the second circulation pump 8 is connected to the bottom water inlet of the ion exchange column 9 through a pipeline;

[0192] (11) The ion exchange column 9 is filled with a resin 10 loaded with nickel ions. The resin 10 is a macroporous polyacrylic acid resin - D113 sodium form resin;

[0193] (12) The upper water outlet of the ion exchange column 9 is connected to the upper part of the electrolyte tank 7 through a pipeline;

[0194] (13) Pure water enters the electrolyte tank (7) through a pipeline and a valve 18.

[0195] Its operation includes the following steps:

[0196] (1) Add the nickel sulfate solution purified by microfiltration membrane into the electrolytic cell 7, then add boric acid and pure water to prepare the electrolyte, and stir evenly with a stirrer 5; The controlled components of the electrolyte are:

[0197] Ni 50 - 55 g / L, Cu ≤ 0.0005 g / L, Zn ≤ 0.0005 g / L, Cd ≤ 0.0001 g / L, Fe ≤ 0.0005 g / L, Mg ≤ 0.005 g / L, Pb ≤ 0.0001 g / L, Mn ≤ 0.0005 g / L, Cr ≤ 0.0005 g / L, H3BO3 5 - 6 g / L, Cl - ≤ 0.01 g / L;

[0198] (2) Dissolve the purified nickel chloride solution in water to prepare an aqueous solution containing 10 - 20 g / L of nickel. Pre - load the nickel ions in the aqueous solution onto the resin 10 through ion exchange; Load the resin 10 loaded with nickel ions into the ion exchange column 9;

[0199] (3) Start the first circulation pump 4. The electrolyte in the electrolyte tank 7 enters through the first circulation pump 4, valve 13 and flowmeter 3, valve 14 and flowmeter 12, and enters from the lower liquid inlets K1 and K3 of the vortex electrowinning cell 1. After passing through the vortex electrowinning cell 1, it flows out from the upper liquid outlets K2 and K4 of the vortex electrowinning cell 1 and enters the electrolyte tank 7 to form a cycle. The flow rate of the circulation pump 4 is 20 m 3 / h. Adjust valves 13 and 14 to keep the pressure values of the first pressure gauge 15 and the second pressure gauge 16 consistent;

[0200] (4) Start the stirrer 5 to fully mix the electrolyte in the electrolyte tank 7 evenly;

[0201] (5) Start the heating and temperature control device in the electrolyte tank 7 to control the electrolyte temperature at 60 - 65 °C;

[0202] (6) Nickel electrowinning, turn on the rectifier 2, adjust the voltage to 2 - 4 v, and gradually increase the current to 200 A. The nickel ions in the electrolyte start to deposit on the cathode;

[0203] (7) Electrolyte stabilization: As nickel ions are continuously precipitated and deposited onto the cathode of the electro - cyclone deposition tank 1, the hydrogen ion content in the electrolyte in the electrolyte tank 7 starts to rise, and the pH value drops. When the pH meter 6 measures that pH ≤ 3, the second circulation pump 8 is started. The electrolyte in the electrolyte tank 7 passes through the second circulation pump 8, enters from the bottom water inlet of the ion exchange column 9, and after passing through the resin 10 loaded with nickel ions, flows out from the upper part of the ion exchange column 9 and enters the electrolyte tank 7 to form a cycle. When the hydrogen ions in the electrolyte pass through the resin 10 loaded with nickel ions, the nickel ions loaded on the resin are exchanged and continuously replenished into the electrolyte, maintaining the nickel ion content in the electrolyte and removing hydrogen ions at the same time. When the pH meter 6 measures that pH ≥ 3.5, the second circulation pump 8 stops, and this process repeats. As the anode reaction during the electrowinning process continuously decomposes water and the heating of the electrolyte causes continuous loss of water in the electrolyte, when the liquid level gauge measures that the liquid level has decreased by 1 - 5%, the valve 18 is opened, and pure water enters the electrolyte tank. When the liquid level is restored, the valve 18 is closed, and this process repeats. The pH value of the electrolyte in the electrolyte tank 7 is controlled at 3 - 3.5, and the nickel ion content is maintained at 50 - 55 g / L.

[0204] (8) Regeneration of the resin 10 loaded with nickel ions: As the electrowinning continues, the nickel ions in the resin 10 loaded with nickel ions are continuously exchanged and removed from the negative charge by hydrogen ions. When the hydrogen ion content in the electrolyte starts to increase and the pH value drops, when the pH meter 6 measures ≤ 2.8, it indicates that all the nickel ions in the resin have been removed from the negative charge. At this time, the resin 10 is loaded with nickel ions again, and the electrowinning process continues.

[0205] (9) When the electrowinning time reaches 120 hours, the nickel sheet on the cathode is taken out. The thickness is ≥ 3 mm. After washing, the nickel purity is detected to be ≥ 99.999%.

[0206] Example 3: IE cyclone electrowinning to produce pure zinc

[0207] The specific composition of the IE device is the same as that in Example 2

[0208] Its operation includes the following steps:

[0209] (1) Add the solution made of electroplating - grade zinc sulfate, which has been filtered and purified by a micro - filtration membrane, into the electrolyte tank 7, and then add additives and pure water to prepare the electrolyte. Stir it evenly with the stirrer 7. The composition of the electrolyte is (g / L): Zn 30 - 40, Cu ≤ 0.0005, Cd ≤ 0.0002, Pb ≤ 0.0001 g / L, Fe ≤ 0.0005, Co ≤ 0.0005, Ni ≤ 0.0005, As ≤ 0.0001, Sb ≤ 0.0005, Ge ≤ 0.00005, Mn ≤ 0.001, Cl ≤ 0.005, thiourea 0.005 - 0.01;

[0210] (2) Load the resin 10 into the ion exchange column 9. Dissolve the zinc sulfate solution in step (1) in water to prepare an aqueous solution containing 10 - 15 g / L of zinc, and then pass this solution into the ion exchange column 9. Through ion exchange, the zinc ions in the solution are loaded onto the resin 10.

[0211] (3) Start the first circulation pump 4. The electrolyte in the electrolyte tank 7 passes through the first circulation pump 4, valve 13 and flowmeter 3, valve 14 and flowmeter 12, and enters from the lower liquid inlet K1 and K3 of the cyclone electrowinning cell 1. After passing through the cyclone electrowinning cell 1, it flows out from the upper liquid outlet K2 and K4 of the cyclone electrowinning cell 1 and enters the electrolyte tank 7 to form a cycle. The flow rate of the circulation pump 4 is 25 m 3 / h. Adjust valves 13 and 14 to keep the pressure values of the first pressure gauge 15 and the second pressure gauge 16 consistent.

[0212] (4) Start the stirrer 5 to fully mix and homogenize the electrolyte in the electrolyte tank 7.

[0213] (5) Start the heating and temperature control device in the electrolyte tank 7 to control the electrolyte temperature at 35 - 45 °C.

[0214] (6) Zinc electrowinning. Turn on the rectifier 2, adjust the voltage to 2 - 4 V, and gradually increase the current to 500 A. The zinc ions in the electrolyte start to deposit on the cathode.

[0215] (7) Electrolyte stabilization. As nickel ions are continuously precipitated and deposited on the cathode of the cyclone electrowinning cell 1, the hydrogen ion content in the electrolyte in the electrolyte tank 7 starts to rise and the pH value drops. When the pH meter 6 measures that pH ≤ 3, start the second circulation pump 8. The electrolyte in the electrolyte tank 7 passes through the second circulation pump 8 and enters from the bottom water inlet of the ion exchange column 9. After passing through the resin 10 loaded with metal ions, it flows out from the upper part of the ion exchange column 9 and enters the electrolyte tank 7 to form a cycle. The hydrogen ions in the electrolyte exchange the zinc ions loaded on the resin when passing through the resin 10 loaded with zinc ions, continuously supplementing the zinc ions in the electrolyte to maintain the content of zinc ions in the electrolyte, and at the same time removing hydrogen ions. When the pH meter 6 measures that pH ≥ 3.5, the second circulation pump 8 stops, and so on. As the anode reaction in the electrowinning process continuously decomposes water, and the heating of the electrolyte causes continuous loss of water in the electrolyte, when the liquid level gauge measures that the liquid level has decreased by 1 - 5%, open valve 18, and pure water enters the electrolyte tank. When the liquid level is restored, close valve 18, and so on. Control the pH value of the electrolyte in the electrolyte tank 7 at 3 - 3.5, and keep the zinc ion content at 30 - 40 g / L.

[0216] (8)Regeneration of the resin 10 loaded with metal ions. As the electrowinning progresses, the zinc ions in the resin 10 loaded with zinc ions are continuously de-negatively exchanged by hydrogen ions. When the hydrogen ion content in the electrolyte starts to increase and the pH value drops, and when the pH meter 6 measures ≤ 2.8, it indicates that all the zinc ions in the resin have been de-negatived. At this time, after the resin 10 is loaded with zinc ions again, the electrowinning process continues.

[0217] (9)When the electrowinning time reaches 120 hours, the zinc sheet on the cathode is taken out, with a thickness ≥ 3 mm. After washing, the nickel purity is detected to be ≥ 99.999%.

[0218] The principle is as follows.

[0219] (1)Resin: R-Na (Na type) or R-H (H type)

[0220] (2)Resin loading with nickel ions: R-Na (resin) + Zn 2+ (zinc ions) → R-Zn + 2Na +

[0221] (3)Electrowinning: Zn 2+ + 2e → Zn (metallic zinc) (cathode)

[0222] H2O - 2e → 2H + + 1 / 2O2 (anode)

[0223] 2H + + 2e → H2↑ (cathode side reaction)

[0224] (4)Resin desorption: R-Zn + 2H + → R-H + Zn 2+

[0225] (5)Resin transformation: R-H + 2Na + → R-Na + 2H +

[0226] Example 4: IE swirl electrowinning to produce pure copper

[0227] The ion exchange resin loaded with copper ions used in the IE swirl electrowinning device is a carboxamido chelating type ion exchange resin, and other composition methods are the same as those in Example 1.

[0228] Its operation includes the following steps:

[0229] (1)In the electrolyte tank 7, electroplating grade copper sulfate, additives and pure water are added to prepare an electrolyte containing 35 - 40 g / L of copper. It is stirred evenly with a stirrer 11, and then electronic grade sulfuric acid is added under stirring conditions to make the pH value of the electrolyte 2 - 2.5;

[0230] (2) Dissolve copper nitrate in water to prepare an aqueous solution containing 5-10 g / L of copper. Pre-load the copper ions in the aqueous solution onto the resin 10 through ion exchange; load the resin 10 loaded with copper ions into the ion exchange column 9; (3) Start the first circulation pump 4. The electrolyte in the electrolyte tank 7 passes through the first circulation pump 4 and the flow meter 3, and enters from the lower inlet of the cyclone electrowinning cell 1. After passing through the cyclone electrowinning cell 1, it flows out from the upper inlet of the cyclone electrowinning cell 1 and enters the electrolyte tank 7 to form a cycle. The flow rate of the first circulation pump 4 is 150 L / h;

[0231] (4) Start the stirrer 5 to fully mix the electrolyte in the electrolyte tank 7 evenly;

[0232] (5) Start the water bath heating and temperature control device to control the electrolyte temperature at 35-40 °C;

[0233] (6) Copper electrowinning. Turn on the rectifier 2, adjust the voltage to 2-4 V, and gradually increase the current to 4-5 A. The copper ions in the electrolyte start to deposit on the cathode;

[0234] (7) Electrolyte stabilization. As the copper ions are continuously precipitated and deposited on the cathode of the cyclone electrowinning cell 1, the hydrogen ion content in the electrolyte in the electrolyte tank 7 starts to rise and the pH value drops. When the pH meter 6 measures that pH ≤ 2, start the second circulation pump 8. The electrolyte in the electrolyte tank 7 passes through the second circulation pump 8, enters from the bottom water inlet of the ion exchange column 9, and after passing through the resin 10 loaded with copper ions, flows out from the upper part of the ion exchange column 9 and enters the electrolyte tank 7 to form a cycle; the hydrogen ions in the electrolyte exchange the copper ions loaded on the resin when passing through the resin 10 loaded with copper ions, continuously supplementing them into the electrolyte to maintain the copper ion content in the electrolyte and removing hydrogen ions at the same time. When the electrolyte pH value ≥ 2.5, the second circulation pump 8 stops, and so on; as the anode reaction in the electrowinning process continuously decomposes water, and the electrolyte heating causes continuous loss of water in the electrolyte, when the liquid level meter measures that the liquid level has decreased by 1-5%, open the valve 18, and pure water enters the electrolyte tank. When the liquid level is restored, close the valve 18, and so on; control the pH value of the electrolyte in the electrolyte tank 7 at 2-2.5, and keep the copper ion content at 35-40 g / L;

[0235] (8) Regeneration of the resin 10 loaded with copper ions. As the electrowinning continues, the copper ions in the resin 10 loaded with copper ions are continuously exchanged and removed by hydrogen ions. When the hydrogen ion content in the electrolyte starts to increase and the pH value drops, and the detection value of the pH meter 6 ≤ 1.8, it indicates that all the copper ions in the resin have been de-loaded. At this time, the resin 10 is loaded with copper ions again, and the electrowinning process continues.

[0236] (9) When the electrowinning time reaches 72 hours, take out the copper sheet on the cathode with a thickness of ≥ 3 mm. After washing, detect that the copper purity is ≥ 99.9999%.

[0237] The principle is as follows.

[0238] (1) Resin: R-Na (Na type)

[0239] (2) Resin loaded with nickel ions: R-Na (resin) + Ni 2+ (Nickel ions) → R-Ni + 2Na +

[0240] (3) Electrowinning: Cu 2+ + 2e → Cu (metallic copper) (cathode)

[0241] H2O - 2e → 2H + + 1 / 2O2 (anode)

[0242] (4) Resin desorption: R-Cu + 2H + → R-H + Cu 2+

[0243] (5) Resin transformation: R-H + 2Na + → R-Na + 2H +

[0244] Example 5: IE cyclone electrowinning to produce pure cobalt

[0245] The composition of the IE cyclone electrowinning cobalt device is the same as that in Example 1.

[0246] Its operation includes the following steps:

[0247] (1) Add the cobalt sulfate solution purified by microfiltration membrane into the electrolytic cell 7, then add boric acid and pure water to prepare the electrolyte, and stir evenly with the stirrer 5; the control components of the electrolyte are:

[0248] Co 70 - 80 g / L, Cu ≤ 0.0005 g / L, Ni ≤ 0.0005 g / L, Zn ≤ 0.0005 g / L, Cd ≤ 0.0001 g / L, Fe ≤ 0.0005 g / L, Mg ≤ 0.005 g / L, Pb ≤ 0.0003 g / L, Mn ≤ 0.0005 g / L, Cr ≤ 0.0005 g / L, H3BO3 6 - 8 g / L, Cl - ≤ 0.01 g / L.

[0249] (2) Dissolve cobalt chloride in water to prepare an aqueous solution containing 5 - 10 g / L of cobalt. Pre-load the cobalt ions in the aqueous solution onto the resin 10 through ion exchange in advance; load the resin 10 loaded with cobalt ions into the ion exchange column 9. (3) Start the first circulation pump 4. The electrolyte in the electrolyte tank 7 passes through the first circulation pump 4 and the flow meter 3, and enters from the lower inlet of the cyclone electrowinning cell 1. After passing through the cyclone electrowinning cell 1, it flows out from the upper inlet of the cyclone electrowinning cell 1 and enters the electrolyte tank 7 to form a cycle. The flow rate of the first circulation pump 4 is 150 L / h.

[0250] (4) Start the stirrer 5 to fully mix the electrolyte in the electrolyte tank 7 evenly.

[0251] (5) Start the water bath heating and temperature control device to control the electrolyte temperature at 50 - 60 °C.

[0252] (6) Cobalt electrowinning. Turn on the rectifier 2, adjust the voltage to 3 - 4 V, and gradually increase the current to 7 - 8 A. The cobalt ions in the electrolyte start to deposit on the cathode.

[0253] (7) Electrolyte stabilization. As the cobalt ions are continuously precipitated and deposited on the cathode of the cyclone electrowinning cell 1, the hydrogen ion content in the electrolyte in the electrolyte tank 7 starts to rise and the pH value drops. When the pH meter 6 measures that pH ≤ 3, start the second circulation pump 8. The electrolyte in the electrolyte tank 7 passes through the second circulation pump 8, enters from the bottom water inlet of the ion exchange column 9, and after passing through the resin 10 loaded with cobalt ions, flows out from the upper part of the ion exchange column 9 and enters the electrolyte tank 7 to form a cycle; the hydrogen ions in the electrolyte exchange the cobalt ions loaded on the resin when passing through the resin 10 loaded with cobalt ions, continuously supplementing them into the electrolyte to maintain the content of cobalt ions in the electrolyte, and at the same time removing hydrogen ions. When the pH value of the electrolyte ≥ 4, the second circulation pump 8 stops, and so on; as the anode reaction in the electrowinning process continuously decomposes water and the electrolyte heating causes continuous loss of water in the electrolyte, when the liquid level gauge measures that the liquid level has decreased by 1 - 5%, open the valve 18, and pure water enters the electrolyte tank. When the liquid level is restored, close the valve 18, and so on; control the pH value of the electrolyte in the electrolyte tank 7 at 3 - 4, and keep the cobalt ion content at 70 - 80 g / L.

[0254] (8) Regeneration of the resin 10 loaded with cobalt ions. As the electrowinning continues, the cobalt ions in the resin 10 loaded with cobalt ions are continuously exchanged and removed by hydrogen ions. When the hydrogen ion content in the electrolyte starts to increase and the pH value drops, and the detection value of the pH meter 6 ≤ 2.5, it indicates that all the cobalt ions in the resin have been de-loaded. At this time, after re-loading the cobalt ions onto the resin 10, continue the electrowinning process.

[0255] (9) When the electrowinning time reaches 72 hours, take out the cobalt sheet on the cathode with a thickness ≥ 2 mm. After washing, detect that the cobalt purity ≥ 99.999%.

[0256] The principle is as follows:

[0257] (1) Resin: R-Na (Na type)

[0258] (2) Resin-loaded nickel ions: R-Na (resin) + Ni 2+ (nickel ions) → R-Ni + 2Na +

[0259] (3) Electrowinning: Co 2+ + 2e → Co (metallic cobalt) (cathode)

[0260] H2O - 2e → 2H + + 1 / 2O2 (anode)

[0261] (4) Resin desorption: R-Co + 2H + → R-H + Co 2+

[0262] (5) Resin transformation: R-H + 2Na + → R-Na + 2H + .

Claims

1. Device for producing pure metal by IE swirl electrowinning method, characterized in that: It includes a cyclone electrowinning cell (1), a rectifier (2), a first flowmeter (3), a first circulation pump (4), a stirrer (5), a pH meter (6), an electrolyte tank (7), a second circulation pump (8), an ion exchange column (9), an on-line liquid level gauge (17), and a valve (18); The water inlet of the first circulation pump (4) is connected to the bottom of the electrolyte tank (7) through a pipeline; The water outlet of the first circulation pump (4) is connected to the first flowmeter (3) and the lower liquid inlet of the cyclone electrowinning cell (1) through a pipeline. The upper liquid outlet of the cyclone electrowinning cell (1) is connected to the upper part of the electrolyte tank (7) through a pipeline; The positive pole of the rectifier (2) is connected to the anode in the cyclone electrowinning cell (1), and the negative pole of the rectifier (2) is connected to the cathode in the cyclone electrowinning cell (1); The electrolyte tank (7) is filled with electrolyte, and the stirrer (5), pH meter (6), and liquid level gauge (17) extend into the electrolyte; The water inlet of the second circulation pump (8) is connected to the bottom of the electrolyte tank (7) through a pipeline; The outlet of the second circulation pump (8) is connected to the bottom water inlet of the ion exchange column (9) through a pipeline; The ion exchange column (9) is filled with a resin (10) loaded with metal ions, and the metal ions loaded on the resin (10) are the same as the metal ions in the electrolyte; The upper water outlet of the ion exchange column (9) is connected to the upper part of the electrolyte tank (7) through a pipeline; Pure water enters the electrolyte tank (7) through a pipeline and a valve (18).

2. The device for producing pure metal by the IE cyclone electrowinning method according to claim 1, characterized in that: When there is a diaphragm (11) between the anode and cathode of the cyclone electrowinning cell (1), the specific composition method is as follows: The water outlet of the first circulation pump (4) is connected to the water inlets of the first valve (13) and the first flowmeter (3), and the water inlets of the second valve (14) and the second flowmeter (12) through pipelines; The water outlet of the first flowmeter (3) is connected to the lower cathode area liquid inlet K1 of the cyclone electrowinning cell (1) through a pipeline, and K1 is located between the cathode and the diaphragm (11); The water outlet of the second flowmeter (12) is connected to the lower anode area liquid inlet K3 of the cyclone electrowinning cell (1) through a pipeline, and K3 is located between the anode and the diaphragm (11); The upper cathode area liquid outlet K2 of the cyclone electrowinning cell (1) is connected to the first pressure gauge (15) and the upper part of the electrolyte tank (7) through a pipeline; The upper anode area liquid outlet K4 of the cyclone electrowinning cell (1) is connected to the second pressure gauge (16) and the upper part of the electrolyte tank (7) through a pipeline; The positive pole of the rectifier (2) is connected to the anode in the cyclone electrowinning cell (1), and the negative pole is connected to the cathode in the cyclone electrowinning cell (1).

3. The device for producing pure metal by the IE cyclone electrowinning method according to claim 1 or 2, characterized in that: The resin (10) is one of a weakly acidic cation exchange resin, a strongly acidic cation exchange resin, and a chelating ion exchange resin. The weakly acidic cation exchange resin includes, but is not limited to, carboxyl group -COOH, phosphoric acid group -PO2H2, and phenolic group. The chelating ion exchange resin includes, but is not limited to, carboxamide group, aminophosphoric acid group, thiourea group, mercapto group, and pyridyl group. The resin form is Na type or H type.

4. The device for producing pure metal by the IE swirl electrowinning method according to claim 1 or 2, characterized in that: The metal salt used for preparing the electrolyte is one of sulfate, hydrochloride, nitrate, and sulfamate; or the electrolyte is directly prepared by using the regeneration liquid of the resin (10) loaded with metal ions.

5. The device for producing pure metal by the IE swirl electrowinning method according to claim 4, characterized in that: The metal salt used for preparing the electrolyte is sulfate.

6. The device for producing pure metal by IE cyclone electrowinning method according to claim 1 or 2, characterized in that: The metal salt or metal salt solution used for resin loading of metal ions is one of sulfate, hydrochloride, nitrate, and sulfamate; or a metal salt solution or an aqueous solution directly containing product metal ions is used.

7. The device for producing pure metal by IE cyclone electrowinning method according to claim 1 or 2, characterized in that: The electrolyte tank (7) is equipped with heating and temperature control devices for adapting to the process that requires temperature conditions for the electrowinning process.

Images