Method and apparatus for using metallic copper to prepare copper oxide by means of electrolytic method

Abstract

Disclosed in the present invention are a method and apparatus for using metallic copper to prepare copper oxide by means of an electrolytic method. In the method, a copper dissolution electrolytic cell comprising a metallic copper anode, a cathode, an electrolytic power supply, a liquid sprayer, and / or a vibrator is used. An electrolyte is a solution containing sodium sulfate and / or potassium sulfate and having a chloride ion content less than or equal to 600 mg / L. The electrolytic power supply is turned on and the output voltage between positive and negative electrodes of the electrolytic power supply is caused to be greater than or equal to 0.34 V. Under this condition, an electrolytic copper dissolution operation is carried out so that metallic copper on the surface of the anode undergoes an electrochemical reaction to generate basic copper sulfate, the cathode electrically precipitates hydrogen, and as an electrolytic reaction proceeds, the basic copper sulfate is converted into copper oxide under a basic condition. During the electrolytic copper dissolution operation, the liquid sprayer is used to extract the electrolyte and spray the electrolyte to the anode, and / or the vibrator is used to oscillate the metallic copper anode and / or the electrolyte, so that the basic copper sulfate layer generated in the reaction and adhesively covering the surface of the metallic copper anode falls off under the action of an external force and the copper metal therein is exposed to continue to participate in an electrolytic copper dissolution reaction.

Description

Method and device for preparing cupric oxide by electrolysis of copper metal TECHNICAL FIELD

[0001] The present invention belongs to the technical field of oxidation reaction of metal, and particularly relates to a method for preparing cupric oxide by electrolysis of copper metal and a device thereof. BACKGROUND

[0002] The prior art has reported the preparation of cupric oxide by electrolysis, specifically: using copper metal as a soluble anode, a conductive material as a cathode, and a sodium hydroxide and / or potassium hydroxide solution as an electrolyte for electrolysis, and converting the copper metal of the anode into cupric oxide. Although the above method is feasible according to chemical principles, in actual production operation, the surface of the copper metal anode directly undergoes an electrochemical reaction during electrolytic copper dissolution and generates a compact cupric oxide film with strong binding force, so that the copper metal anode wrapped inside cannot continue to directly participate in the electrochemical reaction and dissolution. In addition, the electrochemical reaction of the electrolytic cathode mainly produces hydrogen gas, which promotes the electrolytic water reaction of the anode and cathode with the electrolyte, mainly anodic oxygen evolution and cathodic hydrogen evolution, greatly reducing the efficiency of electrolytic copper dissolution.

[0003] In addition, the copper metal anode is oxidized by electrolysis, and the volume of the copper metal anode decreases during the electrolysis reaction to form copper fines floating in the electrolyte. These copper fines also generate a cupric oxide film on the surface after oxidation, which hinders the reaction, and they are difficult to separate from the copper compounds in the electrolyte, resulting in the prepared cupric oxide product containing impurity copper powder and making it difficult to meet high quality requirements.

[0004] To solve the above problems existing in the prior art process, the existing electrolysis process needs to be improved to improve the electrolysis efficiency and the quality of the prepared cupric oxide product. SUMMARY

[0005] The first object of the present invention is to provide a method for preparing cupric oxide by electrolysis of copper metal, which effectively solves the problems of compact cupric oxide film on the surface of the copper metal anode and floating copper fines in the electrolyte in the prior art. The second object of the present invention is to provide a device for preparing cupric oxide by electrolysis of copper metal to achieve the first object.

[0006] A method for preparing cupric oxide by electrolysis of copper metal, characterized by comprising the following steps:

[0007] (1) establishing at least one copper dissolution electrolytic cell, which comprises an anode, a cathode, an electrolysis power source, and a liquid sprayer and / or a vibrator; wherein the anode is copper metal, the cathode is a conductive body, and the anode and the cathode are connected to the positive and negative electrodes of the electrolysis power source, respectively;

[0008] (2) In the copper electrolysis tank, use a solution containing sodium sulfate and / or potassium sulfate and the chloride ion content is ≤600 mg / L as the electrolyte, connect the electrolysis power supply and make the output voltage between the positive and negative electrodes of the electrolysis power supply ≥0.34 V, and under this condition, carry out the electrolytic copper dissolution operation to make the metal copper on the anode surface undergo an electrochemical reaction to generate basic copper sulfate, and hydrogen is deposited on the cathode;

[0009] (3) During the electrolytic copper dissolution operation, use a liquid sprayer to extract the electrolyte and spray it towards the anode, and / or use a vibrator to oscillate the metal copper anode and / or the electrolyte, so that the basic copper sulfate layer generated in the reaction and adhered to the surface of the metal copper anode falls off under the action of external force and exposes the copper metal inside to continue to participate in the electrolytic copper dissolution reaction; at the same time, when there are copper scraps in the electrolyte, the copper scraps are sprayed with the electrolyte towards the metal copper anode and collide with the surface to generate basic copper sulfate through discharge reaction, and the copper scraps move and float in the electric field to become secondary electrodes and undergo electrochemical reaction to generate basic copper sulfate, both of which make the copper scraps quickly transform;

[0010] (4) As the electrolysis reaction proceeds, part or all of the basic copper sulfate in the electrolyte undergoes a chemical reaction under alkaline conditions to convert into copper oxide, when the reaction conversion amount of the metal copper anode reaches the process set requirement, the metal copper anode is supplemented or replaced, or the electrolysis operation is ended.

[0011] The present application effectively solves the problems of dense copper oxide film on the surface of copper anode and floating copper powder in electrolyte in the existing electrolysis process, and avoids the problem of chlorine ion impurities in the obtained copper oxide product caused by using chlorine-containing electrolyte. First, the present application only uses sulfate electrolyte, so that the soluble copper anode surface reacts to form basic copper sulfate during the electrolysis reaction process, and avoids the formation of copper oxide film. Second, the surface of the copper anode is subjected to liquid jet and / or external force assisted by a vibrator during the electrolysis process, the copper salt layer generated by the reaction is pushed off and falls off, and the bottom copper continues to react. The copper powder is sprayed to the anode by the flow of the electrolyte, so that the collision discharge reaction generates basic copper sulfate, and the copper powder is left in the electric field to become a secondary electrode to generate basic copper sulfate by electrochemical oxidation reaction. The salt layer structure formed by basic copper sulfate is relatively loose, and can be easily removed by external force. In addition, compared with chloride ions, sulfate ions are less easily adsorbed by copper oxide powder, which improves the purity of the copper oxide product, and the copper oxide product on the market is widely used in copper sulfate electroplating process, and the sulfate ions will not affect the electroplating use of copper oxide powder. However, since tap water is usually used for production in industry, even if the chemical composition raw materials containing chloride ions are not actively used, trace amounts of chloride ion impurities will also be brought in. Therefore, the present application uses a solution containing sodium sulfate and / or potassium sulfate as the electrolyte, and controls the chloride ion content in the electrolyte to not more than 600 mg / L to ensure that the chloride ion content in the obtained copper oxide can meet the use requirements of copper oxide powder in electroplating production. Preferably, the chloride ion content in the electrolyte is controlled to not more than 300 mg / L.

[0012] In step (1), the liquid sprayer is a pump pipe structure and uses circulating pumped electrolyte as the working part of the spray liquid, which functions to remove the copper salt layer generated by flushing force, and at the same time, the electrolyte containing copper powder is sprayed to the anode to make the copper powder collide with the anode to generate basic copper sulfate by discharge reaction. The vibrator is a working part that generates periodic vibration by electromagnetic force, mechanical eccentric motion or pneumatic drive, and is divided into electric or pneumatic type according to its structure. Its function is to vibrate the copper salt layer generated by reaction and wrapped around the surface of the copper anode by external force vibration.

[0013] The electrolysis power source is a direct current electrolysis power source or a positive pulse electrolysis power source. In order to better improve the efficiency of the electrochemical reaction of the copper powder with the copper anode and the electrochemical reaction of the copper powder in the electric field as a secondary electrode, a direct current electrolysis power source is preferably used.

[0014] In step (2), the total content of sodium sulfate and / or potassium sulfate in the electrolyte is ≥0.1% by mass, wherein the concentration of sodium sulfate is ≤36% by mass, and the concentration of potassium sulfate is ≤17% by mass. The chemical reaction formula for generating basic copper sulfate in the electrolysis reaction of the present application is as follows:

[0015] or

[0016] During the reaction process of step (4), small fragments of the copper anode may fall off and float in the electrolyte or sink to the bottom of the tank as copper debris. Due to the flow of the electrolyte, the copper debris may be brought into the following three chemical reactions in the electrolyte.

[0017] The first one is the electrochemical oxidation reaction of the copper debris in the electrolyte colliding and discharging with the metal copper anode under the action of the liquid flow to generate basic copper sulfate, and the electrochemical reaction formula is as follows: 2Cu + Na2SO4 + 4H2O → Cu2(OH)2SO4 + 2NaOH + 2H2 4Cu + Na2SO4 + 8H2O → Cu4(OH)6SO4 + 2NaOH + 4H2

[0018] The second one is that the copper debris in the electrolyte forms a secondary electrode in the electric field, and the copper debris undergoes electrochemical oxidation reaction and electrochemical reduction reaction at both ends under the action of the electric field, and the electrochemical reaction formula is as follows:

[0019] Copper debris anode end: 2Cu + 2[OH] - + SO4 2- - 4e - → Cu2(OH)2SO4

[0020] Or: 4Cu + 6[OH] - + SO4 2- - 8e - → Cu4(OH)6SO4

[0021] Copper debris cathode end: 4H + + 4e - → 2H2↑

[0022] Or: 8H + + 8e - → 4H2↑

[0023] The third one is a secondary chemical reaction, and the copper debris may easily undergo oxidation reaction with oxygen in the alkaline electrolyte and / or under heating conditions, and the chemical reaction formula is as follows: 2Cu + O2 → 2CuO

[0024] The use of nitrate in the electrolyte is to reduce the cathode electrically generated nitric oxide, to avoid its gas escape to the atmosphere after the reaction with oxygen in the air to generate nitrogen dioxide pollutants.

[0025] In step (4), as the electrolytic copper is carried out, sodium hydroxide and / or potassium hydroxide are produced in the electrolyte accompanying the cathode reaction. Therefore, the use of sulfate electrolyte will become alkaline solution due to the production of sodium hydroxide and / or potassium hydroxide in the process. And the reaction product, basic copper sulfate, will further react with the hydroxyl ions brought by sodium hydroxide and / or potassium hydroxide to generate copper oxide and sulfate. Taking sodium hydroxide as an example, the chemical reaction formula is as follows. Cu2(OH)2SO4+2NaOH→Na2SO4+2CuO+2H2O

[0026] The present application can be improved as follows: the electrolyte further contains an external alkaline substance to improve the alkalinity of the electrolyte, specifically one or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate. Among them, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate will hydrolyze to generate hydroxyl ions after dissolving in the electrolyte, which has a similar effect to sodium hydroxide and potassium hydroxide. That is, before and / or during the electrolytic copper operation, the addition of alkaline substances to the electrolyte increases the hydroxyl ions in the electrolyte, accelerates the reaction of the electrolytic reactant basic copper sulfate with the hydroxyl ions brought by the alkaline substances in the electrolyte to generate copper oxide product and sulfate, which not only improves the electric efficiency but also recycles the sulfate raw material in the electrolyte. Because the hydroxyl ions in the electrolyte are improved, the reaction of basic copper sulfate to copper oxide is accelerated and the sulfate ions are quickly released, so that they can enter the next round of basic copper sulfate production as soon as possible. In this case, the addition of external alkaline substances only accelerates the reaction path of copper metal through basic copper sulfate to copper oxide, and still can well avoid the generation of dense copper oxide film.

[0027] The present application can also be improved as follows: the use of ultrasonic waves acting on the electrolyte to make it oscillate, helping to shake off the copper salt layer adhered and wrapped on the surface of the copper metal anode, exposing the inner copper metal, and promoting the electrolytic copper reaction to proceed; at the same time, the stirring effect of ultrasonic waves is used to accelerate the reaction of basic copper sulfate with sodium hydroxide and / or potassium hydroxide, and the cavitation effect of ultrasonic waves is used to directly oxidize the copper scraps in the alkaline electrolyte to generate copper oxide.

[0028] The present application can also be improved as follows: heating the electrolyte to accelerate the reaction of basic copper sulfate with sodium hydroxide and / or potassium hydroxide to generate copper oxide and sulfate.

[0029] The application can also be improved as follows: the solid matters in the electrolyte are recycled and filtered during the electrolytic copper dissolving process, that is, part of the electrolyte is extracted for solid-liquid separation, and then the filtrate is returned to continue the electrolytic copper dissolving reaction, so as to reduce the movement of solid copper salt and / or copper oxide in the electrolyte and the contact of the cathode to cause electrochemical reduction reaction to return to copper metal.

[0030] The application can also be improved as follows: a separator is additionally arranged in the copper dissolving electrolytic cell to divide the cell into an anode tank area and a cathode tank area, and the separator is one of a bipolar membrane, a reverse osmosis membrane, a filter cloth, a PE filter plate, a ceramic filter plate, an ion-selective diaphragm, and a water molecule-permeable diaphragm, or a combination of one or more of the above. The separator functions to confine the hydrogen gas generated by the cathode to the cathode tank area to escape and be discharged, and to prevent the copper salt, copper oxide and copper debris in the anode electrolyte from moving to the cathode tank area and contacting the cathode to cause electrochemical reduction reaction to become copper metal, and to use the electric field of the anode tank area to make the copper debris form a secondary electrode to generate copper salt through electrochemical reaction. In the above improvement, the anode electrolyte is a solution containing sodium sulfate and / or potassium sulfate and having a chloride ion content of ≤600 mg / L, and the cathode electrolyte is preferably a sulfate solution to avoid affecting the anode electrolyte with other impurities.

[0031] The application can also be improved as follows: when the copper dissolving electrolytic cell with a separator is used, the liquid level of the cathode electrolyte is higher than that of the anode electrolyte, so that the cathode electrolyte is pressed and infiltrated from the separator to the anode tank area to release pressure, and the thrust and lubrication of the cathode tank area infiltration liquid reduce the adhesion of copper salt and / or copper oxide solids to the separator on the side of the anode tank area, so as to dredge the micropores of the separator to improve the electrolysis efficiency.

[0032] The application can also be improved as follows: an oxidation treatment electrolytic unit is additionally arranged in the copper dissolving electrolytic cell, and / or an oxidation treatment electrolytic cell with a separator structure is additionally arranged; the oxidation treatment electrolytic unit comprises an electrolysis power source, an insoluble anode and an insoluble cathode, and the oxidation treatment electrolytic cell is provided with an insoluble anode and an insoluble cathode. The insoluble anode and the insoluble cathode of the oxidation treatment electrolytic unit are immersed in the electrolyte during electrolysis, and are connected with the positive and negative poles of the electrolysis power source of the oxidation treatment electrolytic unit, respectively. The electrolyte of the oxidation treatment electrolytic cell is a sulfate solution or a mixed electrolyte containing a sulfate, sodium hydroxide and / or potassium hydroxide, and the solid matters from the copper dissolving electrolytic cell are added to the anode tank area of the oxidation treatment electrolytic cell for chemical reaction to produce high-quality copper oxide products, and the chemical reaction is as follows:

[0033] Electrochemical reaction of anode and cathode for electrolytic water:

[0034] Anode: 4[OH] - -4e - →2H2O+O2

[0035] Cathode: 4H + + 4e - → 2H2↑

[0036] Discharge reaction of copper swarf collision with anode: 2Cu + 2[OH] - + SO4 2- - 4e - → Cu2(OH)2SO4

[0037] Or 4Cu + 6[OH] - + SO4 2- - 8e - → Cu4(OH)6SO4

[0038] Cathode: 4H + + 4e - → 2H2↑ or 8H + + 8e - → 4H2↑

[0039] Copper swarf electrochemically reacts in electrolyte as secondary electrode.

[0040] Copper swarf anode end: 2Cu + 2[OH] - + SO4 2- - 4e - → Cu2(OH)2SO4

[0041] Or: 4Cu + 6[OH] - + SO4 2- - 8e - → Cu4(OH)6SO4

[0042] Copper swarf cathode end: 2H + + 2e - → H2↑

[0043] Also copper swarf reacts in electrolyte with oxygen: 2Cu + O2 → 2CuO

[0044] Also copper salt reacts with sodium hydroxide and / or potassium hydroxide: Cu2(OH)2SO4 + 2NaOH → Na2SO4 + 2H2O + 2CuO↓

[0045] Or Cu4(OH)6SO4 + 2NaOH → Na2SO4 + 4H2O + 4CuO↓

[0046] Preferably, the filter cloth and filter plate are used as the partition to divide the oxidation treatment electrolytic cell into anode tank area and cathode tank area, and the solid filter residue obtained from the copper dissolving electrolytic cell is put into the anode tank area to produce copper oxide through chemical reaction, so as to avoid the electrochemical reduction reaction of copper oxide and cathode to generate copper, and the insoluble anode can accelerate the processing speed of the secondary electrode by increasing the pressure of the electrolytic cell.

[0047] Preferably, the insoluble anode in the oxidation electrolytic cell adopts the anode with large specific surface area, such as the honeycomb type with through holes, the multi-bar type, and the wire coil type, to create more opportunities for collision with copper powder to perform electrochemical reaction.

[0048] The present application can also be improved as follows: the liquid flow pump pipe agitator is used in the copper dissolving electrolytic cell and / or the oxidation treatment electrolytic cell to push the gas bubbles generated by electrolysis upward to the surface of the electrolyte, accelerate the escape of the gas bubbles, reduce the number of gas bubbles in the electrolyte, and reduce the phenomenon of blocking the electric field lines to improve the electrolysis efficiency. At the same time, the liquid flow pump pipe agitator is used to suck the electrolyte containing copper powder to form a circulating liquid flow to spray to the anode, which plays the role of liquid sprayer and helps the oxidation reaction of the copper powder in the liquid flow. The liquid flow pump pipe agitator comprises a pipeline and a pump, or further comprises a valve, the pipeline inlet is connected with the copper dissolving electrolytic cell and / or the oxidation treatment electrolytic cell and / or a pipeline or container communicated with at least one of the above tanks, and the pipeline outlet is located in the copper dissolving electrolytic cell and / or the oxidation treatment electrolytic cell. Preferably, an ultrasonic oscillator is installed on the pipeline of the liquid flow pump pipe agitator, so that the outer salt layer of the copper powder wrapped by copper salt in the flowing liquid is vibrated off.

[0049] The present application can also be improved as follows: the solid-liquid mixture in the copper dissolving electrolytic cell and / or the oxidation treatment electrolytic cell is subjected to solid-liquid separation, and the separated solid is put into a chemical reaction tank to react with a sodium hydroxide and / or potassium hydroxide solution containing an oxidizing agent, so that the separated solid material, the basic copper salt and the copper powder, can be completely reacted to produce copper oxide product. The main components of the separated solid material are one or more than one of the basic copper salt, copper oxide and copper powder. The oxidizing agent is hydrogen peroxide or sodium hypochlorite. Preferably, in order to reduce the chlorine ion impurities in the copper oxide product, the oxidizing agent is hydrogen peroxide.

[0050] The chemical reaction formula of the above improvement in the chemical reaction tank is as follows: Cu2(OH)2SO4+2NaOH→Na2SO4+2CuO+2H2O Cu+H2O2→CuO+H2O Cu+NaClO→NaCl+CuO

[0051] Preferably, the reaction liquid in the chemical reaction tank is heated, and the temperature is controlled at 30-90°C to improve the reaction speed.

[0052] The application can also be improved as follows: in order to ensure safety in production, the hydrogen gas emitted is discharged at high altitude and / or treated by a hydrogen removal machine. In the method of discharging at high altitude, an air blower is preferably used to inject air into the hydrogen gas discharge pipeline to dilute the hydrogen gas, and then the hydrogen gas is discharged at high altitude after the hydrogen gas concentration is reduced to below the explosive concentration limit of hydrogen gas.

[0053] The second object of the application is achieved by the following solution:

[0054] A device for preparing copper oxide by electrolysis using metallic copper, characterized in that it comprises at least one copper dissolving electrolytic cell, said copper dissolving electrolytic cell comprising an electrolytic cell body, a metallic copper anode, an insoluble cathode conductor, an electrolysis power source, and at least one liquid sprayer and / or vibrator, wherein:

[0055] The metallic copper anode and the insoluble cathode conductor are placed in the electrolytic cell body, the metallic copper anode is connected to the positive pole of the electrolysis power source, and the insoluble cathode conductor is connected to the negative pole of the electrolysis power source.

[0056] The liquid sprayer is a combined component comprising a pipeline and a pump, the pipeline is provided with a liquid inlet and a liquid outlet, the liquid inlet is connected to the electrolytic cell body and / or a communication pipeline or container of the electrolytic cell body, and the liquid outlet is directed towards the metallic copper anode.

[0057] The vibrator is directly fixedly connected to the metallic copper anode to form an integral whole, or is arranged in the electrolytic cell body so that it can be immersed in the electrolyte around the metallic copper anode during electrolysis.

[0058] The electrolytic cell body of the copper dissolving electrolytic cell is made of at least one of ceramic material, high polymer resin material, and metal material coated with a corrosion-resistant and electrically insulating layer.

[0059] The electrolysis power source is a direct current power source or a positive pulse power source with automatic output voltage and / or current adjustment function.

[0060] The liquid inlet of the liquid sprayer is connected to the electrolytic cell body and / or a communication pipeline or container of the electrolytic cell body, for sucking electrolyte and spraying it towards the metallic copper anode through the liquid outlet, so that the adhered and wrapped layer of basic copper salt and / or copper oxide produced on the surface of the metallic copper anode during electrolysis is washed off and exposed to the underlying copper metal, thereby accelerating the electrolytic dissolution of the metallic copper anode. Preferably, the liquid sprayer is provided with more than one liquid outlet.

[0061] The working principle of the vibrator is to generate periodic vibration by electromagnetic force, mechanical eccentric movement or pneumatic drive; and the vibrator is electric or pneumatic according to its structure. The vibrator can be directly installed in the metal copper anode or separated from the metal copper anode and immersed in the electrolyte, and the adhered and wrapped layer of basic copper salt or copper oxide on the surface of the metal copper anode is shaken off and separated from the surface of the anode by the vibration.

[0062] The application can be further improved by installing a separator on the copper dissolving electrolytic cell to divide the electrolytic cell into an anode cell area and a cathode cell area, which can better collect the hydrogen gas electro-deposited by the cathode and avoid the chemical reaction of the copper salt and / or copper oxide powder touching the cathode to be reduced, and limit the copper powder in the anode electrolyte to the periphery of the metal copper anode and form a secondary electrode in the electric field of the electrolytic cell to generate basic copper salt by reaction. The separator is one or more of a bipolar membrane, a reverse osmosis membrane, an ion-selective diaphragm, a filter cloth, a PE filter plate and a ceramic filter plate, or a combination of one or more of them; and the filter cloth is preferably used.

[0063] The application can be further improved by additionally providing an electrolytic cell gas drainage groove cover on the top of the electrolytic cell body, and providing an exhaust port or an exhaust port and a feeding port in the groove cover to drain and collect the gas escaping from the electrolyte. The drainage groove cover of the cathode cell area is connected to a hydrogen gas high-altitude discharge pipe or a gas-liquid mixer through a pipeline, and the drainage groove cover of the anode cell area is connected to other pipelines for collection and treatment.

[0064] The application can be further improved by additionally providing a solid-liquid separator to separate the solid-liquid mixture in the electrolyte, so as to reduce the solid matter of the basic copper salt and / or copper oxide in the electrolyte to improve the electrolysis efficiency. The solid-liquid separator is a filter press, a centrifuge or a filter, which is connected to the copper dissolving electrolytic cell through a liquid circulation pipeline, or a temporary storage tank is additionally provided to connect the solid-liquid separator to the copper dissolving electrolytic cell and the temporary storage tank through a pumping pipeline.

[0065] The application can be further improved by additionally providing a chemical reaction tank for chemical reaction of the basic copper salt and / or copper powder to completely produce copper oxide products. The chemical reaction tank is connected to the solid-liquid separator through a pipeline, and the produced copper oxide powder is separated after reaction.

[0066] The application can be further improved by additionally providing a cold-hot temperature exchanger to heat the electrolyte to improve the electrolysis efficiency and the reaction yield of the copper oxide products. The cold-hot temperature exchanger is installed on the electrolytic cell body of the copper dissolving electrolytic cell, and / or the pipeline of the liquid sprayer, and / or the chemical reaction tank.

[0067] The application can also be improved by adding an ultrasonic generator to use ultrasonic waves to shake off the copper salt and / or copper oxide adhering to the surface of the copper anode and / or to stir the copper salt and / or copper powder and / or copper oxide in the electrolyte as a solid-liquid mixture to accelerate the reaction towards the production of copper oxide. The ultrasonic generator is installed on the electrolytic tank and / or the chemical reaction tank and / or the liquid flow pipeline of the electrolyte.

[0068] The application can also be improved by adding an oxidation treatment electrolytic unit in the copper dissolution electrolytic tank and / or adding an oxidation treatment electrolytic tank in the device for chemical reaction of the basic copper salt and / or copper powder to produce higher grade copper oxide products. The oxidation treatment electrolytic unit includes an electrolytic power source, an insoluble anode and an insoluble cathode, and the insoluble anode and the insoluble cathode of the oxidation treatment electrolytic unit are connected to the positive and negative electrodes of the electrolytic power source of the oxidation treatment electrolytic unit. The oxidation treatment electrolytic tank has a partition structure with an insoluble anode and an insoluble cathode. Preferably, the insoluble anode structure adopts a honeycomb-like, multi-bar-like, or wire coil-like anode with a large specific surface area. Preferably, filter cloth and / or filter plate are used as the partition of the anode and cathode tank area of the oxidation treatment electrolytic tank, and the treated basic copper salt and / or copper powder is put into the anode tank area for chemical reaction to reduce the electrochemical reduction reaction of copper oxide and basic copper salt touching the cathode.

[0069] The application can also be improved by adding a cathode liquid spraying pipe to spray liquid from the bottom of the cathode to the cathode to assist the hydrogen gas generated by the cathode to float upwards along the liquid flow and escape from the electrolyte for collection and processing, thereby reducing the production safety hazards and stirring the electrolyte in a liquid flow mode.

[0070] The application can also be improved by adding a sensor and an automatic detection and feeding controller to enable the device to operate automatically according to a pre-programmed program. The sensor is at least one selected from a pH meter, a liquid level meter, a thermometer, a redox potential meter, a weighing meter, and a hydrogen gas concentration detector. The weighing meter is used for real-time weighing of the anode, and copper metal material is added according to the detection value. The sensor is installed at least one of the copper dissolution electrolytic tank, the chemical reaction tank, various tanks, the liquid flow pipeline, and the work space.

[0071] The application can also be improved by adding a liquid flow agitator composed of a pump, a valve, and a pipeline installed on at least one of the electrolytic tank, the chemical reaction tank, and the temporary storage tank.

[0072] The application can also be improved by adding a hydrogen gas high-altitude discharge pipe and / or a hydrogen gas removal machine to safely process the hydrogen gas generated by the cathode of the copper dissolution electrolytic tank and / or the oxidation treatment electrolytic tank. The gas-liquid mixer on the hydrogen gas high-altitude discharge pipe and / or the hydrogen gas removal machine is connected to the hydrogen gas drainage tank cover of the electrolytic tank through a gas flow pipeline.

[0073] The application can also be improved by additionally adding a blower to assist the hydrogen high-altitude discharge pipe in diluting the hydrogen concentration when discharging hydrogen, so that the discharged hydrogen concentration is discharged at the lower limit of the hydrogen explosion concentration to eliminate safety hazards.

[0074] The application can also be improved by additionally adding a titanium basket in the copper dissolving electrolytic cell for loading metal copper anodes, reducing the floating of metal copper particles in the electrolyte, and using the titanium basket bottom to continue the reaction with the fallen copper particles to generate copper salt. Preferably, the titanium basket bottom is not provided with through holes to facilitate the shielding contact of the fallen copper particles for continued electrolytic dissolution reaction to generate basic copper salt.

[0075] The application can also be improved by adopting a funnel type structure for the bottom of the electrolytic cell body of the copper dissolving electrolytic cell, connecting the liquid sprayer and / or solid-liquid separator at the funnel outlet, to better collect solid precipitates and spray the copper particles in the middle of the solid precipitates to the metal copper anode through the liquid sprayer for collision contact reaction, so as to improve the quality of copper oxide; and the solid precipitates in the copper dissolving electrolytic cell are collected through the solid-liquid separator, so as to reduce the floating of solid materials in the electrolyte and improve the electric efficiency.

[0076] Compared with the prior art, the application has the following beneficial effects:

[0077] 1. The process of the application uses sulfate electrolyte, which generates an easy-to-fall basic copper salt layer on the surface of the metal copper anode during electrolytic copper dissolution, avoiding the formation of a dense copper oxide film on the surface of the metal copper anode and affecting the electrolysis. Compared with the prior art, the process of the application limits the chlorine ions in the electrolyte to produce copper oxide products with less or even no chlorine ion impurities, thereby achieving higher product quality requirements. The application solves the quality problem of copper oxide products containing copper particles by using the collision of copper particles with the anode and the electrochemical oxidation reaction of the secondary electrode in the electric field.

[0078] 2. The process of the application has simple device and low equipment investment, and is energy-saving, environmentally friendly and high in economic benefit.

[0079] 3. The process of the application does not produce new pollution sources, and meets the requirements of environmental protection process indicators.

[0080] 4. When the separator is provided in the process of the application, the hydrogen generated by cathode electrolysis can be effectively limited in the cathode tank area and discharged outside, thereby improving production efficiency and reducing safety hazards of hydrogen. BRIEF DESCRIPTION OF DRAWINGS

[0081] Figure 1 is a schematic diagram of the device structure for preparing copper oxide by electrolysis using metal copper in Example 1.

[0082] Figure 2 is a schematic diagram of the device structure for preparing copper oxide by electrolysis using metal copper in Example 2.

[0083] Figure 3 is a schematic diagram of the device structure for preparing copper oxide by electrolysis using copper metal in Example 3.

[0084] Figure 4 is a schematic diagram of the device structure for preparing copper oxide by electrolysis using copper metal in Example 4; Figures 4-1 and 4-2 are partial enlarged views of Figure 4, which together constitute a schematic diagram of the device structure of Example 4.

[0085] Reference signs: 1 - electrolytic cell body, 2 - separator, 3 - copper metal anode, 4 - insoluble cathode conductor, 5 - electrolysis power supply, 6 - vibrator, 7 - liquid sprayer, 8 - copper oxide, 9 - basic copper salt, 10 - electrolytic cell gas collection cover, 11 - cold-hot temperature exchanger, 12 - ultrasonic generator, 13 - sensor, 14 - automatic detection and feeding controller, 15 - solid-liquid separator, 16 - temporary storage tank, 17 - overflow buffer tank, 18 - liquid flow pump pipe stirrer, 19 - hydrogen removal machine, 20 - hydrogen gas high-altitude discharge pipe, 21 - air blower, 22 - gas-liquid mixer, 23 - valve, 24 - pump, 25 - electrolyte, 26 - sulfate solution, 27 - hydrogen peroxide, 28 - sodium hydroxide and / or potassium hydroxide solution, 29 - chemical reaction tank, 30 - copper ball or copper sheet, 31 - titanium basket, 32 - cathode liquid spraying pipe, 33 - hydrogen peroxide, 34 - oxidation treatment electrolytic cell, 35 - residue filter, 36 - copper powder, 37 - gas bubble, 38 - oxidation treatment electrolytic unit.

[0086] In the accompanying drawings and the following examples, the same type of components in the device are indicated by "reference sign - number sequence". For example, ultrasonic generator 12-1 means one of the ultrasonic generators 12, and ultrasonic generator 12-2 means the second one of the ultrasonic generators 12. DETAILED DESCRIPTION

[0087] The process technical solutions of the present application will be described in detail below in conjunction with specific examples, so that those skilled in the art can better understand and implement them.

[0088] In the following examples, the 500-liter copper dissolution electrolytic cell body, electrodes, titanium baskets, liquid flow stirrers, liquid sprayers, chemical reaction tanks, hydrogen gas high-altitude discharge pipes, hydrogen removal machines, and gas-liquid mixers used are products of Guangdong Foshan Yigao Environmental Protection Equipment Manufacturing Co., Ltd. The electrolysis power supply, automatic detection and feeding controller, sensor, solid-liquid separator, vibrator, ultrasonic generator, air blower, cold-hot temperature exchanger, valve, pump, and chemical raw materials are all commercially available products. In addition to the above-mentioned products, those skilled in the art can also choose other products with similar properties to the above-mentioned products according to conventional selection, which can also achieve the purpose of the present application.

[0089] Example 1

[0090] As shown in Fig. 1, the device for preparing copper oxide by electrolysis using copper metal in Example 1 of the present application comprises a copper dissolving electrolytic cell, which comprises an electrolytic cell body 1, a copper metal anode 3, an insoluble cathode conductor 4, an electrolysis power source 5, a liquid sprayer 7, valves and pumps.

[0091] The electrolytic cell body 1 is made of a metal material coated with an anticorrosion and electrically insulating layer, and the copper metal anode 3, the cathode 4 and the liquid sprayer 7 are installed in the electrolytic cell body 1. The liquid sprayer 7 is composed of a valve 23, a pipeline and a pump 24, the liquid inlet of which is installed on the cell wall of the electrolytic cell body 1, and the liquid outlet thereof faces the copper metal anode 3, which is used to extract the solution in the electrolytic cell and spray it towards the copper metal anode 3, so as to flush and remove the copper salt generated on the surface of the copper metal anode 3 during the electrolysis process.

[0092] The copper metal anode 3 is connected with the positive pole of the electrolysis power source 5, and the insoluble cathode conductor 4 is connected with the negative pole of the electrolysis power source. The electrolysis power source 5 is a direct current electrolysis power source.

[0093] The electrolyte used in the copper dissolving electrolytic cell is a mixed aqueous solution of 0.05% sodium sulfate and 0.05% potassium sulfate, and the pH value thereof is pH 7.

[0094] The method for preparing copper oxide product by using the above device comprises the following steps:

[0095] 1. The electrolyte is poured into the electrolytic cell body 1, so that the copper metal anode 3, the insoluble cathode conductor 4 and the liquid inlet of the liquid sprayer 7 are all immersed in the electrolyte.

[0096] 2. The electrolysis power source 5 is turned on, and the output voltage thereof is 24 V and the current is 0.6 A, so that the copper metal anode generates an electrochemical reaction to generate basic copper salt, and the cathode generates hydrogen gas and a small amount of copper metal.

[0097] 3. The pump 24 is started to flush and remove the copper salt generated on the surface of the copper metal anode, and with the electrolysis, the pH value of the salt-containing electrolyte is increased to pH 7.6. The sodium hydroxide and potassium hydroxide in the solution react with the basic copper sulfate to generate part of the copper oxide product.

[0098] In this example, the content of chloride ions in the obtained copper oxide reaches the use requirement of copper oxide powder in electroplating production.

[0099] Example 2

[0100] As shown in Fig. 2, the device for preparing copper oxide by electrolysis using copper metal in Example 2 of the present application comprises a copper dissolving electrolytic cell, which comprises an electrolytic cell body 1, a copper metal anode 3, an insoluble cathode conductor 4, an electrolysis power source 5, a vibrator 6, an oxidation treatment electrolysis unit 38, valves and pumps.

[0101] The electrolytic cell body 1 is made of ceramic material, and a metal copper anode 3, a cathode 4 and a vibrator 6 are installed in the ceramic material. The vibrator 6 is directly embedded on the metal copper anode 3, and the copper salt generated on the surface of the metal copper anode 3 is vibrated to make the copper salt layer fall off during the electrolysis process.

[0102] The metal copper anode 3 is connected with the positive pole of an electrolysis power source 5, and the insoluble cathode conductor 4 is connected with the negative pole of the electrolysis power source 5. The electrolysis power source 5 is a direct current electrolysis power source.

[0103] The oxidation treatment electrolysis unit 38 comprises an electrolysis power source, an insoluble anode and an insoluble cathode. The insoluble anode is in the form of a through-hole honeycomb.

[0104] The electrolyte used in the copper dissolving electrolytic cell is a 17% potassium sulfate aqueous solution, and the pH value is pH 7.

[0105] The method for preparing copper oxide product by using the above device comprises the following steps:

[0106] 1. The electrolyte is poured into the electrolytic cell body 1 so that the metal copper anode 3, the insoluble cathode conductor 4, the insoluble anode and the insoluble cathode of the oxidation treatment electrolysis unit 38 are all immersed in the electrolyte.

[0107] 2. The electrolysis power source 5 is turned on, and the output voltage is 3V and the current is 6.5A. The metal copper anode generates an electrochemical reaction to generate basic copper salt, and the cathode generates hydrogen gas and a small amount of metal copper by electrolysis. At the same time, the electrolysis power source of the oxidation treatment electrolysis unit 38 is started.

[0108] 3. The vibrator 6 is started to make the copper salt generated on the surface of the metal copper anode fall off. With the electrolysis, the pH value of the salt-containing electrolyte is increased to pH 10.5. The potassium hydroxide in the solution reacts with the basic copper sulfate to generate copper oxide product.

[0109] In the embodiment, the content of chloride ions in the obtained copper oxide reaches the use requirement of copper oxide powder in electroplating production.

[0110] Embodiment 3

[0111] As shown in FIG. 3, the device for preparing copper oxide by electrolysis using metal copper in the embodiment 3 of the application comprises a copper dissolving electrolytic cell, a cold and hot temperature exchanger 11, three ultrasonic generators 12, four sensors 13, three solid-liquid separators 15, two temporary storage tanks 16, two overflow buffer tanks 17, a liquid flow agitator 18, a chemical reaction tank 29, multiple valves and pumps. The copper dissolving electrolytic cell comprises an electrolytic cell body 1, a metal copper anode 3, an insoluble cathode conductor 4, an electrolysis power source 5, a titanium basket 31, a vibrator 6, a liquid sprayer 7 and a cathode liquid spraying pipe 32.

[0112] The electrolytic cell body 1 is made of polymer resin material, and the bottom near the anode is designed as a funnel structure to better collect solid objects; it is installed with a titanium basket 31, a cathode 4 and a temperature sensor 13-2, wherein the titanium basket 31 is hung with a weighing sensor 13-1 and the inside is installed with a metal copper anode 3 composed of a metal copper ball or copper sheet 30. A cold and hot temperature exchanger 11-1 and an ultrasonic generator 12-1 are installed on the electrolytic cell body. The electrolytic power supply 5 is a positive pulse electrolytic power supply, the positive electrode is connected with the titanium basket, and the negative electrode is connected with the cathode.

[0113] The liquid sprayer 7 is a multi-spray structure, and the spray outlets are arranged in the electrolyte liquid surface and the electrolyte liquid towards the metal copper ball or copper sheet 30 inside the titanium basket; the spray outlets, pipes, valves 23-1 and pumps 24-1 constitute the liquid sprayer 7, and the liquid inlet of the liquid sprayer 7 is located below the funnel structure of the electrolytic cell body 1.

[0114] The vibrator 6 is directly welded on the titanium basket 31. The cathode liquid spraying pipe 32 is located at the bottom of the cathode, and the liquid inlet is connected with the electrolytic cell body 1.

[0115] The solid-liquid separator 15-1 is a centrifugal machine for separating the solid-liquid mixture 35 in the copper dissolving electrolytic cell. The solid-liquid separator 15-2 is a filter press for separating the solid-liquid mixture 8 in the chemical reaction tank 29. The solid-liquid separator 15-3 is a precision filter for collecting the fine copper oxide powder in the filtrate from the solid-liquid separator 15-2. The solid-liquid separator 15-1 is connected with the copper dissolving electrolytic cell, overflow buffer tank 17-1 and temporary storage tank 16-2 through pipes respectively; the solid-liquid separator 15-2 is connected with the chemical reaction tank, overflow buffer tank 17-2, solid-liquid separator 15-3 and temporary storage tank 16-4 through pipes respectively.

[0116] The ultrasonic generator 12-1 is installed in the copper dissolving electrolytic cell, the ultrasonic generator 12-2 is installed on the chemical reaction tank 29, and the ultrasonic generator 12-3 is installed on the liquid flow pipeline of the liquid flow agitator 18 of the chemical reaction tank.

[0117] The chemical reaction tank 29 is used for reacting the basic copper salt with sodium hydroxide and / or potassium hydroxide solution to produce copper oxide. The chemical reaction tank 29 is installed with a cold and hot temperature exchanger 11-2 for heating the reaction liquid, and an ultrasonic generator for oscillating and stirring the reaction liquid; and is installed with sensors 13-3 and 13-4 in the tank, which are a thermometer and a liquid level meter respectively. The chemical reaction tank 29 is connected with the solid-liquid separator 15-2 and the temporary storage tank 16-4 through pipes respectively.

[0118] The temporary storage tank 16-1 stores the filter residue collected at the bottom of the solid-liquid separator 15-1, and the temporary storage tank 16-3 stores the filter residue copper oxide product collected at the bottom of the solid-liquid separator 15-2.

[0119] The electrolyte used in the copper dissolving electrolytic cell is 36% sodium sulfate solution as the starting electrolyte, which contains 300 mg / L of chloride ions.

[0120] The main components of the reaction liquid in the chemical reaction tank are a mixture of 5% sodium hydroxide, 2% potassium hydroxide, and 1% hydrogen peroxide.

[0121] The method for producing copper oxide products using the above device has the following steps:

[0122] 1. Put the metal copper into the titanium basket 31, so that the weight of the copper metal reaches the set value of 60 kg of the weighing sensor 13-1, and add the electrolyte 25 to the copper dissolving electrolytic cell.

[0123] 2. Start the pump 24-1 and turn on the electrolysis power supply, so that the output voltage of the electrolysis power supply is 0.35 V and the output current is 0.91 A, for electrolytic copper dissolving. The copper salt generated by the anode reaction of the copper metal in the titanium basket is washed off by the sprayer 7 and falls off by the vibrator 6. Hydrogen gas is electrolyzed on the cathode, and a small amount of metal copper is electrolyzed.

[0124] 3. The ultrasonic generator 12-1 continuously vibrates to help the copper salt on the surface of the metal copper anode fall off. The cold and hot temperature sensor 11-1 controls the electrolyte temperature at 50°C, which improves the electrolysis efficiency. During the process, copper debris falls and floats in the electrolyte.

[0125] 4. According to the process, the pump 24-2 is started in an intermittent control mode, and the solid-liquid separator 15-1 is started to separate the solid from the electrolyte, obtaining the filter residue 35 of basic copper salt, copper oxide, and copper debris, which is collected in the temporary storage tank 16-1. The filtrate is pumped to the temporary storage tank 16-2 through the overflow buffer tank 17-1, and is sent back to the copper dissolving electrolytic cell by the pump 24-4 for recycling.

[0126] 5. The filter residue 35 in the temporary storage tank 16-1 is put into the chemical reaction tank 29 to react with the mixture of sodium hydroxide, potassium hydroxide, and hydrogen peroxide to produce copper oxide. The reaction liquid temperature is controlled at 70°C, and the ultrasonic generator 12-2 and the liquid flow stirrer 18 with the ultrasonic generator 12-3 continuously oxidize and stir the reaction liquid.

[0127] 6. The copper oxide generated by the reaction in the chemical reaction tank 29 is separated by the solid-liquid separator 15-2 and the solid-liquid separator 15-3, and the obtained copper oxide powder 8 is temporarily placed in the temporary storage tank 16-3. The filtrate is pumped to tank 16-4 for temporary storage, and is pumped back to the chemical reaction tank 29 by the pump 24-7 for recycling according to the process requirements.

[0128] 7. During the production process, metal copper 30 is continuously added to the titanium basket for continuous production. The produced copper oxide products are temporarily stored in tank 16-3 for further processing.

[0129] In this embodiment, the content of chloride ions in the obtained copper oxide reaches the use requirements of copper oxide powder in electroplating production.

[0130] Example 4

[0131] As shown in Figure 4, the device for preparing copper oxide by electrolysis in Example 4 of the present application comprises a copper dissolving electrolytic cell, a cold-hot temperature exchanger 11, an ultrasonic generator 12, five sensors 13, an automatic detection and feeding controller 14, two solid-liquid separators 15, three temporary storage tanks 16, two overflow buffer tanks 17, three liquid flow agitators 18, a hydrogen removal machine 19, a hydrogen gas high-altitude discharge pipe 20, a blower 21, a gas-liquid mixer 22, an oxidation treatment electrolytic cell 34, and multiple valves and pumps. The copper dissolving electrolytic cell comprises a copper dissolving electrolytic cell body 1, a cell separator 2-1, a metal copper anode 3, an insoluble cathode conductor 4, an electrolysis power supply 5, a vibrator 6, a liquid sprayer 7, a titanium basket 31, a cathode liquid spraying pipe 32, and a cell gas collection cover 10.

[0132] The electrolytic cell body 1 is made of polytetrafluoroethylene material. The electrolytic cell body 1 is provided with a separator 2-1 filter cloth, which is divided into an anode tank area and a cathode tank area, and the cathode tank area is provided with a cell gas collection cover 10-1. The anode tank area is provided with a titanium basket 31, sensors 13-1 and 13-2, a cold-hot temperature exchanger 11, and two ultrasonic generators 12-1 and 12-2; the titanium basket 31 is provided with metal copper balls or copper sheets 30 and a vibrator 6, and the sensors 13-1 and 13-2 are a thermometer and a liquid level meter, respectively. The cathode tank area is provided with an insoluble cathode conductor 4, a sensor 13-3, and a cathode liquid spraying pipe 32; the sensor 13-3 is a liquid level meter, and the liquid spraying pipe 32 has a spraying port at the bottom of the cathode and a liquid inlet connected to the cathode tank area, forming a liquid flow agitator 18-1. The positive electrode of the direct current electrolysis power supply is connected to the titanium basket, and the negative electrode of the direct current electrolysis power supply is connected to the cathode. The separator structure of the copper dissolving electrolytic cell can effectively concentrate the hydrogen gas generated by cathodic deposition, and reduce the reduction reaction of the cathode caused by the collision and contact between copper salt and copper oxide.

[0133] The liquid sprayer is arranged in two in the copper dissolving electrolytic cell, and the combined components of the liquid sprayer 7-1, i.e., a valve and a pump 24-2 and a spraying pipe, are arranged above the titanium basket; the other liquid sprayer 7-2, which is composed of a valve and a pump 24-3, is arranged at the bottom of the titanium basket and sprays towards the metal copper anode.

[0134] The solid-liquid separator 15-1 is a filter press, which is used for solid-liquid separation of the solid-liquid mixture in the anode tank area of the copper dissolution electrolytic cell. The solid-liquid separator 15-1 is connected with the electrolytic cell body 1, the overflow buffer tank 17 and the temporary storage tank 16-2 by pipelines, respectively. The filter residue 35 is obtained in the filtration and temporarily stored in the temporary storage tank 16-1. The solid-liquid separator 15-2 is a filter press, which is used for solid-liquid separation of the mixture in the anode tank area of the oxidation treatment electrolytic cell.

[0135] The sensor 13-1 is a thermometer, 13-2 is a liquid level meter, 13-3 is a liquid level meter, 13-4 is a hydrogen concentration detector, 13-5 is a redox potential meter, and 13-6 is a liquid level meter.

[0136] The sensors 13-3 and 13-6 are both liquid level meters, which are used for controlling the liquid level of the cathode electrolyte to be higher than the liquid level of the anode electrolyte, so that the mesh of the filter cloth in the electrolytic cell body 1 can seep the solution in the cathode tank area, and the basic copper salt, copper oxide and copper powder on the filter cloth in the anode tank area can be pushed away by the seepage and fall into the anode electrolyte. The sensor 13-4 is a hydrogen concentration detector, which is used for safety detection of the hydrogen concentration in the air of the working space. When the hydrogen concentration exceeds the set value, an alarm is given.

[0137] The temporary storage tank 16-1 stores the filter residue 35 of the solid-liquid separator 15-1, and the temporary storage tank 16-2 temporarily stores the filtrate of the solid-liquid separator 15-1. The temporary storage tank 16-2 is connected with the anode tank area of the copper dissolution electrolytic cell by a pipeline, and the solution in the temporary storage tank 16-2 is sent back to the copper dissolution electrolytic cell for recycling according to the process control of the automatic detection feeding controller 14. The temporary storage tank 16-3 is used for temporarily storing the crude copper oxide separated from the solid-liquid separator 15-2.

[0138] The hydrogen elimination machine 19 is provided with a sensor 13-5, i.e. a redox potential meter, which is used for controlling the reaction of hydrogen and hydrogen peroxide. The hydrogen elimination machine is also provided with a vacuum jet type gas-liquid mixer 22, which is used for guiding the hydrogen gas escaping from the copper dissolution electrolytic cell to participate in the elimination reaction in the hydrogen elimination machine, so as to solve the safety problem caused by the large amount of hydrogen produced due to the large power output of the power supply.

[0139] The oxidation treatment electrolytic cell 34 is a structure with a partition, in which an insoluble anode and an insoluble cathode are arranged; the insoluble anode is made of platinum metal block and platinum wire, the insoluble cathode is made of stainless steel, and the partition is filter cloth. In the working process of the oxidation treatment electrolytic cell 34, the liquid level of the cathode electrolyte is higher than that of the anode electrolyte, so that the filter cloth of the partition leaks high-pH electrolyte, which not only balances the pH values of the anode and cathode electrolytes, but also overcomes the problem of adhesion of solid substances on the filter cloth on the side of the anode tank area. The main function of the oxidation treatment electrolytic cell is to make the copper powder in the filter residue 35 collide with the anode to generate copper salt through discharge reaction, and then make the copper salt react with sodium hydroxide to generate copper oxide product. The anode and cathode tank areas of the oxidation treatment electrolytic cell 34 are respectively provided with liquid flow agitators 18-2 and 18-3.

[0140] The gas inlet pipe of the hydrogen high-altitude discharge pipe 20 is connected with the gas outlet of the air blower and the hydrogen removal machine and the gas outlet of the cathode tank area of the oxidation treatment electrolytic cell through pipelines, so as to guide the residual hydrogen in the hydrogen removal machine and the hydrogen generated by the oxidation treatment electrolytic cell to high-altitude discharge.

[0141] The electrolyte of the copper dissolving electrolytic cell is a mixed solution of 20% sodium sulfate, 4% potassium sulfate and 4% sodium hydroxide as the starting electrolyte 25-1, which contains 600 mg / L of chloride ions.

[0142] The electrolyte 25-2 of the oxidation treatment electrolytic cell is a 7% sodium hydroxide solution.

[0143] The method for preparing copper oxide product by using the above device is as follows:

[0144] 1. Put the metal copper into the titanium basket 31, add the electrolyte 25-1 to the anode tank area and the cathode tank area of the copper dissolving electrolytic cell respectively, add an appropriate amount of electrolyte 25-1 to the temporary storage tank 16-2, and add the sodium hydroxide electrolyte 25-2 to the oxidation treatment electrolytic cell.

[0145] 2. Turn on the power supply of the device to make the automatic detection and feeding controller 14 process the on-site data of each sensor and automatically operate according to the pre-programmed program.

[0146] 3. The automatic detection and feeding controller 14 starts the pumps 24-2, 24-3 and the liquid flow agitator 18-1, turns on the electrolysis power supply 5 of the copper dissolving electrolytic cell to make the power supply output 5.8 V and the current 12 A for electrolytic copper dissolution, the copper salt is generated on the surface of the copper metal anode in the titanium basket, the copper powder is washed out of the titanium basket, and hydrogen is generated by cathodic deposition.

[0147] 4. The two ultrasonic generators in the process are constantly vibrating to help the copper salt on the surface of the copper anode to fall off. The cold and hot temperature sensor 11 controls the temperature of the electrolyte at 75°C. The flow constantly stirs the solid matter in the electrolyte, causing the basic copper salt in the electrolyte to react with sodium hydroxide to produce copper oxide and sodium sulfate, and causing the copper powder to collide with the titanium basket and copper ball to produce a discharge reaction to generate copper salt.

[0148] 5. The difference between the values of sensors 13-2 and 13-3 (liquid level meter) controls the opening of pump 24-1, while pump 24-6 is started to supplement the liquid.

[0149] 6. The automatic detection and feeding controller 14 turns off the electrolysis power supply 5, pumps 24-1, 24-2 and 24-3, and the flow agitator 18-1 according to the operating time, and turns on pump 24-4 to pump the solid-liquid mixture in the anode tank area of the copper dissolution electrolytic cell into the solid-liquid separator 15-1 for solid-liquid separation. The filter residue 35 is temporarily stored in the temporary storage tank 16-1, and the filtrate is introduced into the temporary storage tank 16-2 for recycling.

[0150] 7. After the solid-liquid mixture in the anode tank area of the copper dissolution electrolytic cell is pumped out, the solution in the temporary storage tank 16-2 is pumped back into the anode tank area, and metal copper is added to the titanium basket in preparation for the next process. The automatic detection and feeding controller 14 continues to electrolyze copper dissolution under its instructions.

[0151] 8. The filter residue 35 is put into the anode tank area of the oxidation treatment electrolytic cell, and the automatic detection and feeding controller 14 controls the closing of its electrolysis power supply to make its output voltage 4.2V and current 4A, and starts the flow agitator 18-2. The copper powder in the filter residue collides with the anode to produce a discharge reaction, and forms a secondary electrode under the action of the electric field to produce an electrochemical reaction to generate basic copper sulfate.

[0152] 9. When the oxidation treatment electrolytic cell reaches the set reaction completion time, the controller 14 turns off the power supply, the flow agitators 18-2 and 18-3, and starts the pump 24-8 to separate the electrolyte in the anode tank area through the solid-liquid separator 15-2 to obtain the filtrate which is temporarily stored in the temporary storage tank 16-4, and the crude copper oxide 8 is temporarily stored in the tank 16-3.

[0153] 10. In the production process, the hydrogen gas emitted from the cathode tank area of the copper dissolution electrolytic cell is introduced into the hydrogen elimination machine through the gas-liquid mixer 22 to react with hydrogen peroxide for elimination, and the remaining hydrogen gas tail gas and the hydrogen gas emitted from the oxidation treatment electrolytic cell are discharged to high altitude safely by using a hydrogen gas high altitude discharge pipe and starting a blower.

[0154] In this embodiment, the content of chloride ions in the obtained copper oxide reaches the requirements for the use of copper oxide powder in electroplating production.

[0155] Comparative Example 1

[0156] The method for preparing copper oxide was the same as that of Example 1 using the apparatus of Figure 1, except that the electrolyte was a mixed solution of 5% sodium hydroxide and 5% potassium hydroxide.

[0157] A black compact copper oxide film was soon formed on the surface of the copper metal anode 3, which hindered the dissolution of copper, and the main reaction of the electrolytic anode became electrolysis of water and evolution of oxygen.

[0158] Comparative Example 2

[0159] The method for preparing copper oxide was the same as that of Example 1 using the apparatus of Figure 1, except that the electrolyte was a mixed aqueous solution of 0.05% sodium sulfate and 0.05% potassium sulfate, and 1000 mg / L of chloride ions were contained therein.

[0160] The chloride ion content of the obtained copper oxide was still too high after washing and purification, and the use requirement of copper oxide powder in electroplating production could not be met.

[0161] Comparative Example 3

[0162] The method for preparing copper oxide was the same as that of Example 1 using the apparatus of Figure 1, except that the electrolyte was a mixed aqueous solution of 0.01% sodium sulfate and 0.01% potassium sulfate.

[0163] The electrolytic current was low under the same electrolytic voltage, the dissolution of the copper metal anode 3 was slow, and the surface thereof gradually became dark.

Claims

1. A method for producing copper oxide by electrolysis using metallic copper, characterized in that, The method comprises the following steps: (1) establishing at least one copper dissolving electrolytic cell, which comprises an anode, a cathode, an electrolysis power supply, a liquid sprayer and / or a vibrator; wherein the anode is copper and the cathode is an electric conductor, and the anode and the cathode are connected to the positive and negative poles of the electrolysis power supply, respectively; (2) using a solution containing sodium sulfate and / or potassium sulfate and having a chloride ion content of ≤600 mg / L as the electrolyte in the copper dissolving electrolytic cell, connecting the electrolysis power supply and making the output voltage between the positive and negative poles of the electrolysis power supply ≥0.34 V, and performing electrolytic copper dissolving operation under the above conditions to make the copper on the surface of the anode undergo electrochemical reaction to generate basic copper sulfate and hydrogen is deposited on the cathode; (3) during the electrolytic copper dissolving operation, the liquid sprayer is used to extract the electrolyte and spray it towards the anode, and / or the vibrator is used to vibrate the copper anode and / or the electrolyte, so that the basic copper sulfate layer generated in the reaction and adhered to the surface of the copper anode is detached under the action of external force and exposes the copper inside to continue participating in the electrolytic copper dissolving reaction; at the same time, when there are copper scraps in the electrolyte, the copper scraps are sprayed with the electrolyte towards the copper anode and collide with the surface of the copper anode to generate basic copper sulfate through discharge reaction, the copper scraps move and float in the electric field to become secondary electrodes and generate basic copper sulfate through electrochemical reaction, and the combination of the two makes the copper scraps rapidly transform; (4) as the electrolytic reaction proceeds, part or all of the basic copper sulfate in the electrolyte undergoes chemical reaction under alkaline conditions to be converted into copper oxide, the copper anode is replaced or the electrolytic operation is ended when the reaction conversion amount of the copper anode reaches the process set requirement.

2. The method of claim 1, wherein the copper oxide is produced by electrolysis of metallic copper. In step (2), the total content of sodium sulfate and / or potassium sulfate in the electrolyte is ≥0.1% by mass percentage, and the concentration of sodium sulfate is ≤36% by mass percentage and the concentration of potassium sulfate is ≤17% by mass percentage.

3. The method of claim 2, wherein the copper oxide is produced by electrolysis of metallic copper. The electrolyte contains an external alkaline substance to increase the alkalinity of the electrolyte, and the alkaline substance is one or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.

4. The method of claim 2, wherein the copper oxide is produced by electrolysis of the metal copper. Ultrasonic waves are used on the electrolyte; and / or the electrolyte is heated.

5. The method of claim 2, wherein the copper oxide is produced by electrolysis of the metal copper. The solid matter in the electrolyte is subjected to cyclic filtration separation during the electrolytic copper dissolving process, that is, part of the electrolyte is extracted for solid-liquid separation and then the filtrate is returned to continue participating in the electrolytic copper dissolving reaction.

6. The method of claim 2, wherein the copper oxide is produced by electrolysis of the metal copper. A separator is additionally arranged in the copper dissolving electrolytic cell to divide it into an anode tank area and a cathode tank area, and the separator is one or more of a bipolar membrane, a reverse osmosis membrane, a filter cloth, a PE filter plate, a ceramic filter plate, an ion-selective diaphragm and a water molecule-permeable diaphragm used in a stacked combination; wherein the anode electrolyte is a solution containing sodium sulfate and / or potassium sulfate and having a chloride ion content of ≤600 mg / L, and the cathode electrolyte is a sulfate solution.

7. The method of claim 6, wherein the copper oxide is prepared by electrolysis of metallic copper. When the copper dissolving electrolytic cell with a separator is used, the liquid level of the cathode electrolyte is higher than that of the anode electrolyte.

8. The method of claim 2, wherein the copper oxide is produced by electrolysis of the metal copper. An oxidation treatment electrolytic unit is additionally arranged in the copper dissolving electrolytic cell, and / or an oxidation treatment electrolytic cell with a separator structure is additionally arranged; The oxidation treatment electrolytic unit comprises an electrolysis power supply, an insoluble anode and an insoluble cathode. The oxidation treatment electrolytic cell is provided with insoluble anode and insoluble cathode, electrolyte is sulfate solution or mixed electrolyte containing sulfate, sodium hydroxide and / or potassium hydroxide, solid matter from copper dissolving electrolytic cell is added to anode tank area of oxidation treatment electrolytic cell for chemical reaction, filter cloth and filter plate are used as partition to separate oxidation treatment electrolytic cell into anode tank area and cathode tank area, solid filter residue obtained by filtering from copper dissolving electrolytic cell is put into anode tank area for chemical reaction to produce copper oxide, insoluble anode of oxidation electrolytic cell adopts through-hole honeycomb type, multi-strip type and coil wire type structure.

9. The method of claim 8, wherein the copper oxide is produced by electrolysis of the metal copper. In copper dissolving electrolytic cell and / or oxidation treatment electrolytic cell, liquid flow pump pipe agitator is used to push gas bubble produced by electrolysis upward to electrolyte surface, and liquid flow pump pipe agitator is used to suck electrolyte containing copper powder for circulating liquid flow injection to anode, which plays the role of liquid sprayer and helps copper powder in liquid flow to be oxidized; the liquid flow pump pipe agitator comprises pipe and pump, or further comprises valve, pipe inlet is connected with copper dissolving electrolytic cell and / or oxidation treatment electrolytic cell and / or pipe or container communicated with at least one of the cells, and pipe outlet is located in copper dissolving electrolytic cell and / or oxidation treatment electrolytic cell.

10. The method of claim 9, wherein the copper oxide is produced by electrolysis of the metal copper. Ultrasonic oscillator is installed on pipe of liquid flow pump pipe agitator.

11. The method of claim 10, wherein the copper oxide is produced by electrolysis of the metal copper. Solid-liquid mixture in copper dissolving electrolytic cell and / or oxidation treatment electrolytic cell is subjected to solid-liquid separation, solid matter obtained by separation is put into chemical reaction tank to react with sodium hydroxide and / or potassium hydroxide solution containing oxidant, and alkaline copper salt and copper powder obtained by separation can be completely reacted to produce copper oxide product, reaction liquid in chemical reaction tank is heated, and temperature is controlled at 30-90℃ to improve reaction speed.

12. An apparatus for preparing copper oxide using the method of claim 1, characterized in that, The copper dissolving electrolytic cell comprises an electrolytic cell body, a metal copper anode, an insoluble cathode conductor, an electrolysis power supply, and at least one liquid sprayer and / or vibrator. The metal copper anode and the insoluble cathode conductor are arranged in the electrolytic cell body, the metal copper anode is connected with the positive pole of the electrolysis power supply, and the insoluble cathode conductor is connected with the negative pole of the electrolysis power supply. The liquid sprayer is a combined component comprising a pipe and a pump, the pipe is provided with a liquid inlet and a liquid outlet, the liquid inlet is connected with the electrolytic cell body and / or a pipe or container communicated with the electrolytic cell body, and the liquid outlet is directed to the metal copper anode. The vibrator is directly fixedly connected with the metal copper anode to form an integral whole, or is arranged in the electrolytic cell body so as to be immersed in electrolyte around the metal copper anode during electrolysis.

13. The apparatus of claim 12, wherein, The liquid inlet of the liquid sprayer is connected with the electrolytic cell body and / or a pipe or container communicated with the electrolytic cell body, is used to suck electrolyte and spray the electrolyte to the metal copper anode through the liquid outlet, and the surface of the metal copper anode is impacted by circulating liquid flow to separate and fall off the adhered and wrapped layer of alkaline copper salt and / or copper oxide produced during electrolysis and expose the inner copper metal, so as to accelerate electrolytic dissolution of the metal copper anode. The vibrator is directly installed with the metal copper anode inlay or is apart from the metal copper anode and is soaked in the electrolyte, and the adhered and wrapped layer of basic copper salt or copper oxide on the surface of the metal copper anode is shaken off and separated from the surface of the anode by the vibration.

14. The apparatus of claim 13, wherein, A partition is installed on the copper dissolving electrolytic cell to separate the electrolytic cell into an anode cell area and a cathode cell area; the partition is one of a bipolar membrane, a reverse osmosis membrane, an ion-selective diaphragm, a filter cloth, a PE filter plate and a ceramic filter plate or is one or more stacked combinations.

15. The apparatus of claim 13, wherein, A solid-liquid separator is additionally provided; the solid-liquid separator is a filter press, a centrifuge or a filter, and is connected with the copper dissolving electrolytic cell through a liquid circulation pipeline or is connected with the copper dissolving electrolytic cell and a temporary storage tank through a pump pipeline. A chemical reaction tank is additionally provided for chemical reaction of the basic copper salt and / or copper powder to completely produce copper oxide products; the chemical reaction tank is connected with the solid-liquid separator through a pipeline, and the produced copper oxide powder is separated.

16. The apparatus of claim 15, wherein, A cold-heat temperature exchanger and an ultrasonic generator are additionally provided; the cold-heat temperature exchanger is installed on the electrolytic cell body of the copper dissolving electrolytic cell and / or on the pipeline of the liquid sprayer and / or on the chemical reaction tank; the ultrasonic generator is installed on the electrolytic cell body and / or on the chemical reaction tank and / or on the liquid pipeline of the electrolyte.

17. The apparatus of claim 15, wherein, An oxidation treatment electrolytic unit is additionally provided in the copper dissolving electrolytic cell, and / or an oxidation treatment electrolytic cell is additionally provided in the device for chemical reaction of the basic copper salt and / or copper powder to produce higher grade copper oxide products. The oxidation treatment electrolytic unit comprises an electrolysis power source, an insoluble anode and an insoluble cathode, and the insoluble anode and the insoluble cathode of the oxidation treatment electrolytic unit are connected with the positive pole and the negative pole of the electrolysis power source of the oxidation treatment electrolytic unit, respectively. The oxidation treatment electrolytic cell has a partition structure, and the insoluble anode and the insoluble cathode are arranged in the oxidation treatment electrolytic cell; the filter cloth and / or the filter plate are used as the partition of the anode cell area and the cathode cell area of the oxidation treatment electrolytic cell.

18. The apparatus of claim 13, wherein, A cathode liquid spraying pipeline is additionally provided, and the sprayed liquid flows from the bottom of the cathode to the cathode to assist the hydrogen gas generated by the cathode to float upward along the liquid flow and escape from the electrolyte for collection and treatment. A titanium basket is additionally provided in the copper dissolving electrolytic cell for loading the metal copper anode to reduce the floating of the copper powder in the electrolyte, and the titanium basket bottom continues to react with the fallen copper powder to generate copper salt.

Images