Method and device for treating copper sludge and / or tin sludge by means of efficient electro-oxidation

Abstract

A method and device for treating copper sludge and / or tin sludge by means of efficient electro-oxidation. The method comprises: (1) providing an efficient electro-oxidation device, wherein the efficient electro-oxidation device comprises at least one efficient oxidation electrolytic cell, and the efficient oxidation electrolytic cell is divided into an anode compartment and a cathode compartment; (2) adding a solid-liquid mixture (which contains: 1) a solid copper sludge and / or a solid tin sludge, and 2) chloride ions) as an anolyte of the anode compartment of the efficient oxidation electrolytic cell, and turning on an electrolysis power supply to enable a chemical reaction in the anolyte to convert the copper sludge into copper oxide, and / or convert the tin sludge into stannous hydroxide; (3) when the conversion rate of the copper sludge into copper oxide and / or the tin sludge into stannous hydroxide in the anolyte reaches a set value of the process, taking this as the end point of the electro-oxidation operation; and (4) performing solid-liquid separation on a solid-liquid mixture in the anode compartment to obtain copper oxide and / or stannous hydroxide. In the method, by using the efficient electro-oxidation device to treat the solid copper sludge and / or tin sludge, a comprehensive, energy-saving and safe electrochemical oxidation reaction is achieved, and safe, environmentally-friendly and low-energy-consumption production can be achieved by breaking and removing reducing anions and / or copper-ammonia complex ligands in the copper sludge and / or tin sludge.

Description

Method and device for treating copper sludge and / or tin sludge by high-efficiency electro-oxidation TECHNICAL FIELD

[0001] The present application belongs to the technical field of copper sludge and / or tin sludge treatment, and particularly relates to a method and device for treating copper sludge and / or tin sludge by high-efficiency electro-oxidation. BACKGROUND

[0002] In the existing printed circuit board (PCB) manufacturing process, etching is an important step. The etching solution commonly used in the production of circuit boards at present includes acidic copper chloride etching solution and alkaline copper ammonia etching solution, which are used for etching copper circuit pattern in the etching machine. In addition, there is a micro-etching process in the existing PCB manufacturing process, which is to use micro-etching solution to corrode and thin the surface of the copper layer or to roughen the copper surface. Whether it is etching solution or micro-etching solution, the waste liquid produced after use contains copper ions generated by chemical reaction and dissolution of metallic copper.

[0003] The main components of the acidic copper chloride etching solution are hydrochloric acid and copper chloride, and some process formulations also contain one or more than one of ammonium chloride, sodium chloride, ferric chloride, and other etching additives.

[0004] The alkaline copper ammonia etching solution includes alkaline copper ammonia etching solution and alkaline sulfuric acid tetraamine copper etching solution. The main components of the alkaline copper ammonia etching solution are copper ammonia complex, ammonium chloride, and ammonia water, and the main components of the alkaline sulfuric acid tetraamine copper etching solution are sulfuric acid tetraamine copper complex, ammonium sulfate, and ammonia water. The above two kinds of etching solution may also contain one or more than one of ammonium bicarbonate, ammonium carbonate, and other etching additives.

[0005] The micro-etching solution is commonly a sulfuric acid type micro-etching solution, which has main components of sulfuric acid and hydrogen peroxide, and another main component of sulfuric acid, ferric sulfate, persulfate, and / or hydrogen peroxide. Some process formulations may also contain micro-etching additives. The micro-etching waste liquid produced after the use of micro-etching solution also contains copper sulfate.

[0006] In actual etching production, with the etching reaction of etching solution and copper metal, the proportion of various components in the etching solution will continuously change, and the copper chloride in the acidic copper chloride etching solution and the divalent copper ammonia complex in the alkaline copper ammonia etching solution are both reduced to monovalent copper salt and lose etching ability. In order to ensure the stability of etching performance, new etching solution needs to be supplemented to the etching production line; the supplemented new etching solution is called etching sub-solution in the industry, and the solution overflowing outside the etching production line is called etching waste liquid.

[0007] In addition, when a circuit pattern is etched on a copper-clad plate using a basic copper-ammonia etching solution, the circuit pattern is plated with a tin metal layer as an etching resist layer, and the exposed copper metal on the copper-clad plate without protection of the tin layer is chemically reacted with the etching solution and removed by corrosion. After the etching is completed, the tin metal etching resist layer on the original preset circuit pattern and via hole needs to be stripped using a nitric acid type tin stripping solution to produce a tin ion-containing nitric acid type tin stripping waste liquid, which also contains a small amount of copper ions.

[0008] To realize extraction of copper and / or tin elements in etching waste liquid, micro-etching waste liquid and tin stripping waste liquid and recycling of the remaining treatment liquid for etching or tin stripping, the industry currently has an oxalic acid method for extracting copper mud and / or tin mud from acidic copper chloride etching waste liquid, micro-etching waste liquid and tin stripping waste liquid, and a neutralization method for extracting copper mud from basic copper-ammonia etching waste liquid.

[0009] (1) Oxalic acid method

[0010] The oxalic acid method specifically involves adding oxalic acid to acidic copper chloride etching waste liquid or micro-etching waste liquid to generate copper oxalate precipitate, and then performing solid-liquid separation to obtain copper oxalate filter residue and acidic filtrate; or adding oxalic acid to tin stripping waste liquid to generate stannous oxalate precipitate or a mixture of stannous oxalate and copper oxalate precipitate, and then performing solid-liquid separation. The chemical reactions in the above cases are as follows: CuCl2+H2C2O4→2HCl+CuC2O4↓; CuSO4+H2C2O4→H2SO4+CuC2O4↓; Cu(NO3)2+H2C2O4→2HNO3+CuC2O4↓; Sn(NO3)2+H2C2O4→2HNO3+SnC2O4↓.

[0011] The copper oxalate filter residue and / or stannous oxalate obtained after solid-liquid separation usually still contains soluble components in the filtrate, including hydrochloric acid or sulfuric acid or nitric acid, and components originally present in the etching solution or micro-etching solution or tin stripping solution.

[0012] The filtrate obtained by the above-mentioned oxalic acid method for treating acidic copper chloride etching solution is used as a regenerated etching sub-liquid after removing oxalic acid impurities and supplementing the required material components, and is used in acidic copper chloride etching operations. The filtrate obtained by the above-mentioned oxalic acid method for treating micro-etching solution is used as a regenerated micro-etching solution after removing oxalic acid impurities and supplementing the required material components, and is used in micro-etching operations. The filtrate obtained by the above-mentioned oxalic acid method for treating tin stripping solution is used as a regenerated tin stripping solution after removing oxalic acid impurities and supplementing the required material components, and is used in tin stripping operations. This scheme not only recovers copper mud and / or tin mud (i.e., copper oxalate and / or stannous oxalate), but also can recycle the remaining acidic filtrate after adjustment, and has simple recovery process and equipment, and higher economic benefits in production cost compared to the traditional electrolytic method for extracting metallic copper.

[0013] There are two methods for treating the filter residue copper oxalate in the prior art: (1) high-temperature decomposition method, i.e. using high-temperature heating decomposition method to prepare copper oxide and / or metal copper powder from the filter residue copper oxalate, and the reaction temperature is at least 300°C or above; (2) hypochlorite oxidation method, i.e. allowing the filter residue copper oxalate to react with hypochlorite to prepare copper hydroxide and / or copper oxide.

[0014] When the high-temperature decomposition method is used, the high-temperature process may cause fire, scalding and other hidden dangers, and the energy consumption of high-temperature decomposition is large, and the copper oxide dust or metal copper dust obtained by decomposition may cause the workshop to be dirty. Therefore, most circuit board production and processing enterprises are unwilling to use the high-temperature decomposition method to treat copper oxalate in the original production plant. If the filter residue copper oxalate is transferred to other places for treatment, it is necessary to handle the corresponding procedures in accordance with the policy management regulations, which increases the management and operation cost; especially, the filter residue copper oxalate extracted from the acidic copper chloride etching waste liquid contains a large amount of hydrochloric acid and chloride salt, and heating will generate hydrogen chloride acid gas with strong corrosion, which will damage the equipment, and increasing the water washing pretreatment to remove hydrochloric acid and chloride salt impurities will bring the environmental problem of increasing sewage discharge.

[0015] (i) Metal copper obtained by high-temperature decomposition method:

[0016] (ii) Copper oxide obtained by high-temperature decomposition method:

[0017] When the hypochlorite oxidation method is used, the hypochlorite solution can be directly mixed with the filter residue copper oxalate, or chlorine gas can be introduced into the alkaline solution mixed with the filter residue copper oxalate to prepare hypochlorite for oxidation reaction. However, this method requires excess hypochlorite to completely convert the copper oxalate, and the hypochlorite and chlorine gas are both prepared by electrolysis of brine in the prior art, so the power consumption is large.

[0018] (i) Industrial chlorine gas preparation method:

[0019] (ii) Industrial sodium hypochlorite preparation method: 2NaOH + Cl2→ NaClO + NaCl + H2O;

[0020] (iii) Oxidation of copper oxalate by sodium hypochlorite: CuC2O4 + NaClO→ NaCl + CuO↓ + 2CO2↑.

[0021] Stannous oxalate can be used as a raw material for reaction catalysis and solar energy fields; in the prior art, stannous oxalate is also converted into tin metal and / or tin oxide by high-temperature decomposition method, so that its application range is expanded. Like the high-temperature decomposition method for treating copper oxalate, the high-temperature heating decomposition of stannous oxalate also has the disadvantages of safety hazards, large energy consumption and much dust.

[0022] (i) High temperature decomposition method of metal tin:

[0023] (ii) High temperature decomposition method of tin dioxide:

[0024] (B) Neutralization method

[0025] The neutralization method is specifically to adjust the pH value of the alkaline copper ammonia etching waste liquid by using at least one of hydrochloric acid, carbonate, acidic copper chloride etching waste liquid, micro-etching waste liquid or a mixture thereof, so that part of the copper ions in the waste liquid are converted into copper mud and precipitate. After the solid-liquid separation of the copper mud precipitate, the obtained filter residue copper mud contains at least one of copper ammonia complex, basic copper chloride, basic copper sulfate, copper hydroxide, copper carbonate, and basic copper carbonate, and is also mixed with ammonium salt and / or ammonium hydroxide and / or soluble copper ammonia complex; when the etching waste liquid contains iron ions, the obtained filter residue copper mud also contains iron hydroxide and / or iron salt. Basic copper chloride, basic copper sulfate, copper carbonate, and basic copper carbonate can be converted into copper hydroxide in an alkaline solution, and further converted into copper oxide after heating, that is, basic copper chloride, basic copper sulfate, copper hydroxide, copper carbonate, and basic copper carbonate can all be converted into copper oxide in an alkaline solution environment. However, because the filter residue copper mud obtained by the neutralization method contains ammonia and / or ammonium, the basic copper chloride, basic copper sulfate, copper hydroxide, copper carbonate, and basic copper carbonate in the filter residue copper mud will form a dynamic equilibrium with the ammonia and / or ammonium, and thus cannot be completely converted into copper oxide by the above conventional process.

[0026] In the prior art, hypochlorite and / or chlorine gas are used to oxidize and remove ammonia and / or ammonium. When the reaction solution is alkaline, chlorine gas is converted into hypochlorite in the reaction solution and the chemical reaction of hypochlorite on copper mud occurs. When the reaction solution is acidic, chlorine gas is easy to react with ammonia and / or ammonium in the reaction solution to generate explosive nitrogen trichloride.

[0027] When hypochlorite is used to oxidize and remove ammonia and / or ammonium from the filter residue copper mud obtained by the neutralization method, at least one of the following reactions occurs: Cu(NH3)4Cl2+6NaClO+2NaOH→8NaCl+7H2O+CuO↓+2N2↑; Cu(NH3)4SO4+6NaClO+2NaOH→Na2SO4+6NaCl+7H2O+CuO↓+2N2↑; 2NH4Cl+3NaClO+2NaOH→5NaCl+5H2O+N2↑; Cu2(OH)3Cl+NaOH→NaCl+2Cu(OH)2; Cu2(OH)2SO4+2NaOH→Na2SO4+2Cu(OH)2; 2NaClO→2NaCl+O2;

[0028] But similar to the treatment of copper oxalate with hypochlorite, this method requires excess hypochlorite to complete the conversion of copper sludge from the neutralization process, resulting in high power consumption. SUMMARY

[0029] The first object of the present application is to provide a method for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation, achieving safe, environmentally friendly, and low-energy production. Specifically, by using a high-efficiency electro-oxidation device to treat solid copper sludge and / or tin sludge, a comprehensive energy-saving and safe electrochemical oxidation reaction is achieved, breaking the reducing anions and / or copper-ammonia complex ligands in the copper sludge and / or tin sludge, or further including a neutralization and dehydration reaction on basic copper salt, converting the copper sludge to copper oxide and the tin sludge to stannous hydroxide. The second object of the present application is to provide a device for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation, enabling the production process to meet the requirements of safe, efficient, and environmentally friendly automated production.

[0030] The first object of the present application is achieved by the following method steps.

[0031] A method for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation, comprising the following steps:

[0032] (1) Setting up a high-efficiency electro-oxidation device, which includes at least one high-efficiency oxidation electrolytic cell; the high-efficiency oxidation electrolytic cell is divided into an anode tank area and a cathode tank area by an electrolytic cell separator, the electrolytic anode is connected to the positive pole of the electrolytic power source and placed in the anode tank area, and the electrolytic cathode is connected to the negative pole of the electrolytic power source and placed in the cathode tank area;

[0033] (2) Adding a solid-liquid mixture containing ① solid copper sludge and / or solid tin sludge and ② chloride ions as an anode electrolyte to the anode tank area of the high-efficiency oxidation electrolytic cell, and adding a solution or solid-liquid mixture containing a soluble electrolyte as a cathode electrolyte, and connecting the electrolytic power source to make the anode electrolyte undergo a chemical reaction of converting copper sludge to copper oxide and / or a chemical reaction of converting tin sludge to stannous hydroxide;

[0034] (3) When the conversion rate of copper sludge to copper oxide and / or the conversion rate of tin sludge to stannous hydroxide in the anode electrolyte reaches the process set value, it is considered that the electrolytic oxidation operation is completed, and the solid-liquid mixture in the anode tank area meets the process treatment requirements;

[0035] (4) Performing solid-liquid separation on the solid-liquid mixture in the anode tank area that has met the process treatment requirements to obtain filter residue and filtrate, and the main component of the filter residue is copper oxide and / or stannous hydroxide.

[0036] In step (1), the electrolytic cell separator is a material that can effectively prevent bubbles from crossing, and does not limit the crossing of molecules and ions in the electrolyte under the electric field force or solution pressure; the electrolytic cell separator is specifically at least one selected from a high polymer material filter plate, a ceramic filter plate, and a filter cloth that is insoluble in the electrolyte. The electrolytic cell separator is used in a single layer or more than one layer. The method of the present application avoids using an expensive ion exchange membrane that limits the crossing of ions as the electrolytic cell separator, effectively reduces the cost of device materials, makes the device meet the economic requirements of the market, and reduces the cost of producing copper oxide products. The high polymer material filter plate is preferably a polyethylene (PE) filter plate. Preferably, the electrolytic cell separator is a filter cloth.

[0037] In step (2), the solid copper sludge and / or the solid tin sludge is insoluble or cannot be completely dissolved in the solution of the anode electrolyte. The solid copper sludge contains at least one of a reducing anion, a complex ligand, ammonia, and an ammonium ion, and specifically contains at least one of copper oxalate, a copper ammonia complex, ammonia, and an ammonium ion. The solid tin sludge contains a reducing anion, and specifically contains stannous oxalate. As a specific embodiment of the present application, the solid copper sludge is obtained by reacting a circuit board etching waste liquid and / or a micro-etching waste liquid with oxalic acid and / or by a neutralization reaction, and the solid tin sludge is obtained by reacting a tin stripping waste liquid with oxalic acid. When the solid copper sludge and / or the solid tin sludge contains chloride ions and is sufficient to make the chloride ion concentration of the anode electrolyte meet the set requirements, there is no need to add chloride ions to prepare the anode electrolyte.

[0038] In step (2), a solid-liquid mixture containing ① solid copper sludge and / or solid tin sludge and ② chloride ions is used as the cathode electrolyte, or an electrolyte solution is added to the cathode tank area of the high-efficiency oxidation electrolytic cell as the cathode electrolyte. Preferably, an electrolyte solution without solid copper sludge and / or solid tin sludge is used as the electrolyte of the cathode tank area; or a solid-liquid mixture containing solid copper sludge and / or solid tin sludge is put into the anode tank area to make the solution of the anode tank area penetrate into the cathode tank area through the electrolytic cell separator, and then the solution is used as the electrolyte of the cathode tank area; in this way, the problem of copper sludge and / or tin sludge in the cathode electrolyte blocking the electrolytic cell separator from the cathode tank area can be reduced.

[0039] In step (3), the conversion rate of the copper sludge to copper oxide and / or the conversion rate of the tin sludge to stannous hydroxide in the anode electrolyte is set according to the process treatment requirements or relevant processing standard requirements.

[0040] In step (4), the filtrate obtained by solid-liquid separation is a solution containing chloride ions, which can be processed further according to the process or used to prepare a new anode electrolyte; the filter residue, copper oxide and / or stannous hydroxide, is collected as a product.

[0041] In the electrolysis process of the method of the present application, the electrochemical oxidation reactions of oxalate and / or copper ammonia complex ligand and / or ammonia nitrogen impurities and the electrochemical oxidation reaction of chloride ions mainly occur on the electrolytic anode, and hydrogen gas is mainly electrolytically precipitated on the electrolytic cathode. The chloride ions in the anode electrolyte are oxidized to chlorine gas and dissolved in the anode electrolyte to generate hypochlorite, so the oxalate and / or copper ammonia complex ligand and / or ammonia and / or ammonium ions in the anode electrolyte collide with the electrolytic anode and are directly oxidized while also being oxidized by the newly generated chlorine gas and / or hypochlorite. The oxalate of copper oxalate is oxidized to generate copper oxide and carbon dioxide, and the oxalate of stannous oxalate is oxidized to generate stannous hydroxide and carbon dioxide; the ammonia ligand in the copper ammonia complex is oxidized to generate copper oxide and nitrogen; the ammonia nitrogen impurities in the anode electrolyte, i.e. ammonia and / or ammonium, are oxidized to generate nitrogen, and the formation of new copper ammonia complexes is reduced or even avoided, enabling the solid copper sludge to be more completely converted into copper oxide. When the electrolysis reaction occurs, copper oxide and / or stannous hydroxide are generated in the anode tank area, and nitrogen and / or carbon dioxide are precipitated; when the anode electrolyte is acidic, chlorine gas will also be precipitated. Since the copper ammonia complex, copper oxalate, and stannous oxalate can be slightly dissolved in the solution, a small amount of copper metal and / or tin metal will also be electrolytically precipitated on the electrolytic cathode when the copper ammonia complex and / or copper oxalate and / or stannous oxalate are dissolved in the cathode electrolyte. The method of the present application does not generate new pollution sources during operation, the oxidation reaction is efficient, and the processing cost is low, fully meeting the requirements of environmental protection technology indicators.

[0042] The electrolytic tank separator used in the present application can play the following four roles during electrolysis:

[0043] ① Allow the molecules and ions in the electrolyte to pass through under the action of electric field force or pressure, so that the electrolytic tank has the function of a non-separator electrolytic tank.

[0044] ② Intercept the migration of hydrogen gas bubbles in the cathode electrolyte into the anode tank area, and intercept the migration of the gas bubbles produced by the reaction in the anode tank area to the cathode tank area, avoiding the oxidation of hydrogen gas in contact with the electrolytic anode and increasing the internal energy consumption, and concentrating the hydrogen gas in the cathode tank area to facilitate the removal of the electrolytic tank.

[0045] ③ Under the movement of the liquid flow, the exchange speed of the solution between the electrolytic anode and the electrolytic cathode can be slowed down, the opportunity for the hypochlorite produced by the electrolysis reaction to directly contact the electrolytic cathode and react is reduced, the internal energy consumption is reduced, and efficient oxidation results are ensured.

[0046] ④ Block the solid in the anode electrolyte from approaching the electrolytic cathode, avoid the accumulation of electrically conductive metal copper and / or metal tin particles in the electrolytic anode and the electrolytic cathode, and structurally eliminate the problem of short circuit between the two electrodes.

[0047] The inventors have found through long-time experiments that the method of the present application can efficiently eliminate the reducing anions, complex ligands, ammonia and ammonium ions in the solid copper sludge and / or solid tin sludge. Compared with the prior art method of using sodium hypochlorite to oxidize the solid copper sludge, the present application requires much less electric energy to treat the same amount of solid copper sludge than the production of sodium hypochlorite. Under the same electric energy consumption, the treatment rate of the present application is 150% higher than that of the prior art method of using the produced sodium hypochlorite to react with the solid copper sludge. The present application can achieve the above effects because: 1) the prior art method needs an excess amount of sodium hypochlorite to realize the reaction of converting the solid copper sludge into copper oxide; 2) the present application uses the electrolytic cell separator to separate the tank area, in addition to the electrochemical oxidation reaction of the chlorine ions in the anode electrolyte to generate hypochlorite ions which can immediately react with at least one of the reducing anions, complex ligands, ammonia and ammonium ions in the solid copper sludge and / or solid tin sludge, the present application also uses the electrochemical oxidation reaction of the anode electrolyte to generate chlorine radicals (Cl·), chlorine oxygen radicals (ClO·), hydroxyl radicals (OH·) and other oxidizing radicals to participate in the oxidation reaction of the solid copper sludge and / or solid tin sludge; 3) the reducing anions, complex ligands, ammonia and ammonium ions in the solid copper sludge and / or solid tin sludge can directly undergo electrochemical oxidation reaction when they come into contact with the anode. The combination of the above reasons realizes the efficient oxidation with reduced self-consumption energy.

[0048] In step (2), the chlorine ions in the anode electrolyte are oxidized into hypochlorite and / or chlorine gas on the anode to participate in the treatment reaction of the solid copper sludge and / or solid tin sludge, and the hypochlorite exists in the form of hypochlorite salt and / or hypochlorous acid in the anode electrolyte. When the anode electrolyte is acidic (pH < 7), the chlorine ions in the anode electrolyte are oxidized into chlorine gas and easily escape, and the chlorine gas dissolved in the anode electrolyte reacts with water to generate hypochlorous acid which is also easily decomposed; when the anode electrolyte is neutral or alkaline (pH ≥ 7), the chlorine ions in the anode electrolyte are oxidized into chlorine gas which is dissolved in the anode electrolyte to become hypochlorite salt.

[0049] The present application can be improved as follows: at least one of the temperature, chlorine ion concentration, pH value and oxidation-reduction potential value (ORP value) of the anode electrolyte is controlled during the electrochemical oxidation treatment process using the high-efficiency electro-oxidation device. Preferably, the pH value and oxidation-reduction potential value (ORP value) of the anode electrolyte are controlled during the electrochemical oxidation treatment process.

[0050] Specifically, the anode electrolyte is controlled under at least one of the following conditions (1) to (4):

[0051] (1) The working temperature of the anolyte is controlled at 6-90°C to accelerate the reaction to generate copper oxide and / or stannous hydroxide, while avoiding overheating of the anolyte due to the work done by the current and the heat released by the decomposition of the oxidizing agent during electrolysis, ensuring efficient chemical reactions in a safe manner, and reducing the reading error of the pH and ORP values of the anolyte due to changes in the working temperature of the anolyte, so that the electrical control system is less affected by temperature drift. Preferably, the temperature is controlled at 30-70°C; more preferably, the temperature is controlled at 35-60°C.

[0052] (2) The concentration of chloride ions in the anolyte is controlled at ≥1 g / L to obtain the appropriate efficiency of the electrochemical oxidation reaction for normal production. The concentration of chloride ions in the anolyte is controlled in the range of 1-190 g / L, preferably in the range of 10-100 g / L, and more preferably in the range of 20-70 g / L, so that both a higher efficiency of the electrochemical oxidation reaction and the avoidance of salt crystallization saturation and precipitation in the anolyte, as well as the impact of plant effluent discharge in areas where chloride ion emissions are limited, are achieved.

[0053] (3) The pH value of the anolyte is maintained at ≥5.5 to promote the generation of copper oxide and / or stannous hydroxide and reduce the generation of explosive nitrogen trichloride. Preferably, the pH value of the anolyte is maintained at ≥7 to keep the electrolyte neutral or alkaline to avoid electrolysis in an acidic electrolyte to produce chlorine gas and even explosive nitrogen trichloride. More preferably, the pH value of the anolyte is maintained at ≥8.5. Since the hypochlorite in the anolyte is generated by dissolving chlorine gas in the anolyte through electrolysis, a higher pH value of the anolyte can increase the generation rate of hypochlorite in the anolyte, reduce the release of chlorine gas and the decomposition of hypochlorous acid, thereby effectively accelerating the generation reaction of copper oxide, and the alkaline substances in the anolyte that reach the set pH value of the process can be recycled and will not be wasted.

[0054] (4) According to the actual situation and the required reaction speed, the control range of the ORP value (Oxidation-Reduction Potential value) of the anode electrolyte is set, and / or according to the actual situation, the ORP value (Oxidation-Reduction Potential value) of the anode electrolyte is set as the reaction end value to help confirm the conversion rate of the copper sludge into copper oxide and / or the conversion rate of the tin sludge into stannous hydroxide that meets the process requirements. The change of the ORP value of the anode electrolyte can indirectly reflect the concentration of the substances to be treated in the anode electrolyte, and the ORP value will be affected by the pH value of the detected solution. Therefore, under the same electrolysis current and pH value, the ORP value of the anode electrolyte gradually rises as the concentration of the substances to be treated in the anode electrolyte decreases, and the slope of the change of the oxidation-reduction potential value or its on-site value can reflect the oxidation reaction stage of the anode electrolyte and serve as a basis for safety control. The method of the present application can achieve the required oxidation reaction speed of the anode electrolyte by adjusting the output parameters of the electrolysis power source according to the measured ORP value of the anode electrolyte. If the reaction speed is lower than the set value, the output electrolysis current of the electrolysis power source is increased, and if the reaction speed is higher than the set value, the output electrolysis current of the electrolysis power source is decreased. In addition, setting the reaction end value of the ORP value (Oxidation-Reduction Potential value) of the anode electrolyte can help confirm the conversion rate of the copper sludge into copper oxide and / or the conversion rate of the tin sludge into stannous hydroxide that meets the process requirements, and ensure that there is no excessive oxidizing agent left in the anode electrolyte after the electrolytic oxidation operation is completed, which would waste energy consumption or pose a safety hazard.

[0055] As a preferred embodiment of the present application, the filtrate obtained in step (4) is recycled for use according to the process requirements, so as to save the required chloride ions and alkaline substances in the method of the present application.

[0056] As another preferred embodiment of the present application, the hydrogen gas generated during the operation of the method of the present application is collected and reused in the process of hydrogenolysis, hydrogenation and reduction reaction of organic waste liquid in the prior art to help degrade the organic waste liquid and maximize energy utilization.

[0057] Since the cations in the anode electrolyte migrate to the cathode tank area under the action of the electric field force during the electrolysis process, and the anions in the cathode electrolyte migrate across to the anode tank area, as another preferred embodiment of the present application, if there are copper oxalate and / or stannous oxalate and / or copper ammonia complex and / or ammonia and / or ammonium from the anode electrolyte that have not been treated in the cathode electrolyte after the completion of the electrolysis operation, these cathode electrolyte is subjected to oxidation treatment again as part or all of the anode electrolyte in the subsequent electrolysis operation.

[0058] The present application can be improved as follows: an additional alkaline pH value adjusting agent is added to the anode electrolyte to control the pH value of the anode electrolyte in the electrolysis process within the range set by the process to achieve high efficiency production. The alkaline pH value adjusting agent is specifically one or more than one selected from the group consisting of alkaline cathode electrolyte after electrolysis of hydrogen, alkaline solution containing the substance to be treated, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and the substance to be treated is copper oxalate and / or stannous oxalate and / or copper ammonia complex and / or ammonia and / or ammonium. Preferably, the alkaline pH value adjusting agent comprises the cathode electrolyte after electrolysis of hydrogen, i.e. when the cathode electrolyte is alkaline in the electrolysis process, the electrolyte from the cathode tank area is added to the anode tank area after release of hydrogen as an alkaline pH value adjusting agent to supplement the anode tank area and to oxidize the copper oxalate and / or stannous oxalate and / or copper ammonia complex and / or ammonia and / or ammonium in the added cathode electrolyte.

[0059] The present application can also be improved as follows: ultrasonic waves are used to act on the anode electrolyte or on the solid-liquid mixture containing solid copper sludge and / or solid tin sludge for preparing the anode electrolyte to break the agglomerated copper sludge and / or tin sludge, to promote the reaction of the copper sludge into copper oxide and / or the reaction of the tin sludge into stannous hydroxide and to produce copper oxide and / or stannous hydroxide with smaller particles to improve product quality.

[0060] The present application can also be improved as follows: to improve the efficiency of the use of the high efficiency oxidation electrolytic tank, when the conversion rate of the copper sludge into copper oxide and / or the conversion rate of the tin sludge into stannous hydroxide in the anode electrolyte reaches the process set value to complete the oxidation operation, there is still a small amount of copper oxalate and / or stannous oxalate and / or copper ammonia complex and / or ammonia and / or ammonium in the anode electrolyte, and then the anode electrolyte after completion of the electrolytic oxidation operation is mixed with external sodium hypochlorite outside the high efficiency oxidation electrolytic tank for further oxidation reaction to further oxidize the remaining small amount of substance to be treated, and the high efficiency oxidation electrolytic tank is freed for electrolytic oxidation operation of the next batch of anode electrolyte. That is, this improvement combines the high efficiency oxidation electrolysis method of the present application with the method of the prior art, uses the high efficiency oxidation electrolytic tank to complete most of the treatment work to leave a small amount of substance to be treated in the reaction mixture, and then selects the sodium hypochlorite of the prior art to continue the remaining small amount of oxidation treatment reaction in a common chemical reaction tank.

[0061] The application can also be improved as follows: when the solid-liquid separation of the anode electrolyte subjected to electrolytic oxidation in the high-efficiency oxidation electrolytic cell is performed and the filter residue still contains solid unoxidized treated material particles, the obtained filter residue is crushed and re-prepared into anode electrolyte and then returned to the anode cell area for electrolytic oxidation operation again, so that the solid copper sludge and / or tin sludge particles in the anode electrolyte are more easily converted into copper oxide and / or stannous hydroxide.

[0062] The second inventive purpose of the application is achieved by the following scheme.

[0063] A device for efficiently electrolytic oxidation treatment of copper sludge and / or tin sludge by the above method, characterized by comprising at least one high-efficiency oxidation electrolytic cell, at least one electrolytic cell liquid flow pump pipe stirrer 11 and at least one hydrogen gas escape outlet 66.

[0064] The high-efficiency oxidation electrolytic cell comprises a cell body 1, an electrolytic cell separator 5, an electrolytic anode 2, an electrolytic cathode 3 and an electrolytic power source 44, the electrolytic cell separator 5 separates the cell body 1 into an anode cell area and a cathode cell area, the cathode cell area is a closed cell area structure and is provided with at least one feeding pipe opening and / or at least one discharging pipe opening, the electrolytic anode 2 is connected with the positive electrode of the electrolytic power source 44 and is placed in the anode cell area, and the electrolytic cathode 3 is connected with the negative electrode of the electrolytic power source 44 and is placed in the cathode cell area.

[0065] The electrolytic cell liquid flow pump pipe stirrer 11 is composed of a pump and a connecting pipe and is used to impart a circulating flow driving force to the electrolyte containing gas bubbles.

[0066] The cathode cell area of the high-efficiency oxidation electrolytic cell and the at least one electrolytic cell liquid flow pump pipe stirrer 11 are communicated to form a liquid flow circulation, and the hydrogen gas escape outlet 66 is arranged in the cathode cell area of the high-efficiency oxidation electrolytic cell and / or is arranged in the container and / or pipe section on the connecting path of the cathode cell area of the high-efficiency oxidation electrolytic cell and the electrolytic cell liquid flow pump pipe stirrer 11, so that the two form a gas-liquid separator 10.

[0067] The gas-liquid separator 10 is a pipeline gas-liquid separator or a tank gas-liquid separator, which releases the gas in the gas-containing solution by slow flow. When the pipeline gas-liquid separator is used, at least one pipe section in the connecting path between the cathode tank area of the high-efficiency oxidation electrolytic cell and the electrolytic cell liquid flow pump pipe stirrer is provided with one or more hydrogen gas release outlets 66, and the pipe section provided with the hydrogen gas release outlet has an inner diameter sufficient to leave space for gas evolution when the gas-containing solution flows through it. When the tank gas-liquid separator is used, a hydrogen gas release outlet 66 is provided in the cathode tank area of the high-efficiency oxidation electrolytic cell, and / or a hydrogen gas release transfer tank 59 is additionally provided in the connecting path between the cathode tank area of the high-efficiency oxidation electrolytic cell and the electrolytic cell liquid flow pump pipe stirrer, and a hydrogen gas release outlet 66 is provided in the hydrogen gas release transfer tank 59. Preferably, the tank gas-liquid separator provided with the hydrogen gas release transfer tank 59 is used. More preferably, the tank gas-liquid separator provided with a combination of multiple-stage hydrogen gas release transfer tanks 59 is used to more completely release hydrogen gas.

[0068] During electrolysis, the cathode electrolyte circulates between the cathode tank area of the high-efficiency oxidation electrolytic cell and the electrolytic cell liquid flow pump pipe stirrer 11 through the gas-liquid separator, to separate the hydrogen gas in the cathode electrolyte from the hydrogen gas release outlet 66, and to reintroduce the hydrogen gas-released cathode electrolyte into the cathode tank area to continue participating in the reaction.

[0069] The anode tank area of the high-efficiency oxidation electrolytic cell uses a closed tank area structure, or an open tank area structure. When the anode tank area uses a closed tank area structure, at least one inlet pipe opening and at least one outlet pipe opening are provided, and at least one gas release port is provided on the anode tank area and / or components communicating with the anode tank area. Preferably, the anode tank area uses an open tank area structure, which allows the carbon dioxide and / or nitrogen or chlorine gas produced by the reaction to escape smoothly, facilitating the conversion of copper sludge in the anode electrolyte into copper oxide and / or the conversion of tin sludge into stannous hydroxide by chemical reaction.

[0070] The electrolytic cell separator 5 is a filter plate with micro-holes that allow molecules and ions in the electrolyte to pass through, and can effectively block the passage of gas bubbles in the electrolyte, and is at least one selected from high molecular material filter plates, ceramic filter plates, and filter cloths that are insoluble in the electrolyte. The electrolytic cell separator is used as a single layer or is used in multiple layers, and is preferably a filter cloth.

[0071] Preferably, the electrolytic cell liquid flow pump pipe stirrer 11 further comprises a valve for flow adjustment.

[0072] As a preferred embodiment of the device of the present application: the high-efficiency electro-oxidation device comprises at least two electrolytic tank liquid flow pump pipe agitators 11, the cathode tank area and the anode tank area of the high-efficiency oxidation electrolytic tank are respectively communicated with different electrolytic tank liquid flow pump pipe agitators 11 to form independent liquid flow circulation systems. When the anode tank area of the high-efficiency oxidation electrolytic tank is communicated with at least one electrolytic tank liquid flow pump pipe agitator 11 to form an independent liquid flow circulation system of the anode tank area, the anode electrolyte containing bubbles can escape gas in the circulating flow. Preferably, the anode tank area of the high-efficiency oxidation electrolytic tank adopts a closed tank area structure and is communicated with at least one electrolytic tank liquid flow pump pipe agitator 11 to form a liquid flow circulation, so that the anode tank area has the function of the gas-liquid separator 10 of the anode electrolyte.

[0073] The materials used for the high-efficiency oxidation electrolytic tank body are all corrosion-resistant materials. When the working temperature of the electrolyte needs to be greater than 70℃, the tank body of the high-efficiency oxidation electrolytic tank preferably adopts polytetrafluoroethylene material. The surface material of the electrolytic anode in contact with the electrolyte is preferably at least one selected from gold, platinum, titanium-based coated insoluble anode, conductive graphite, and titanium; the surface material of the electrolytic cathode in contact with the electrolyte is preferably at least one selected from platinum, titanium, stainless steel, conductive graphite, titanium-based coated conductor, copper, and iron. The shape structure of the electrolytic anode and the electrolytic cathode can be selected from one or more of plate shape, block shape, grid shape, coiled wire shape, and strip shape. Preferably, the electrolytic anode adopts a larger specific surface area external shape structure scheme, which can make more opportunities for oxalate and / or copper ammonia complex ligand and / or ammonia and / or ammonium ion in the anode electrolyte to collide with the electrolytic anode during the reaction process, thereby promoting the discharge reaction to achieve more efficient oxidation. More preferably, the electrolytic anode adopts a coiled wire shape or a laminated structure to realize a larger specific surface area of the electrolytic anode.

[0074] In the device of the present application, the tank bodies and connecting pipelines other than the high-efficiency oxidation electrolytic tank preferably adopt high molecular material and / or titanium metal material.

[0075] The present application can be improved as follows: a solid-liquid separator 36 is added, which is connected to the high-efficiency oxidation electrolytic tank and / or at least one tank in the device of the present application through a pipeline, for solid-liquid separation of the solid-liquid mixture. The solid-liquid separator is structurally divided into filter presses, filters, centrifuges, and inclined plate filters.

[0076] The present application can also be improved as follows: an anode electrolyte transfer tank 6 is added, which is used for escaping gas or chemical reaction of the anode electrolyte. The anode electrolyte transfer tank 6 is provided with an inlet pipe opening, an outlet pipe opening, and a gas escape pipe opening, and the inlet pipe opening or the outlet pipe opening is connected to the inlet pipe opening of the anode tank area through the electrolytic tank liquid flow pump pipe agitator 11.

[0077] The present application can be improved as follows: at least one cathode box 4 is arranged in the high-efficiency oxidation electrolytic cell, and the cathode box is used to separate the anode tank area and the cathode tank area of the cell body of the high-efficiency oxidation electrolytic cell, so that the hydrogen gas generated by electrolysis is better collected. The cathode box 4 is a box-shaped structure with at least one side provided with an electric field line through hole 9; the electric field line through hole 9 is arranged on the path through which the electric field line between the electrolytic anode 2 and the electrolytic cathode 3 immersed in the electrolyte during electrolysis passes; the electrolytic tank separator 5 is tightly fixed to the electric field line through hole 9; and the electrolytic cathode 3 is arranged in the cathode box 4, and the closed area in the cathode box 4 becomes a cathode tank area. At least one discharge pipe opening and at least one inlet pipe opening are arranged on the cathode box 4, so that the reaction substances in the cathode tank area exchange with the outside through the pipelines connected by the inlet pipe opening and the discharge pipe opening in the form of liquid flow or gas flow and temperature. Preferably, the electrolytic anode 2 is mounted on the electrolytic tank separator 5 tightly fixed to the cathode box electric field line through hole 9, the electrolytic anode 2 mounted on the outside of the cathode box 4, the electrolytic cathode 3 mounted in the cathode box 4, and the electrolytic power source 44 are combined to form an independent unit of the high-efficiency oxidation electrolytic cell.

[0078] The present application can also be improved as follows: a liquid spraying pipe with its nozzle upward or upwardly inclined is mounted in the middle or lower part of the cathode tank area as a hydrogen driving liquid spraying pipe 13, and at least one overflow opening is arranged at a position higher than the nozzle of the hydrogen driving liquid spraying pipe 13 in the cathode tank area, and the hydrogen driving liquid spraying pipe 13 and the overflow opening are connected with the outlet / inlet pipe opening of the electrolytic tank liquid flow pump pipe agitator 11 in the cathode tank area to form a liquid flow circulation; and the hydrogen gas generated by electrolysis on the electrolytic cathode is moved upward along the liquid flow and discharged from the overflow opening of the cathode tank area by spraying part or all of the circulating electrolyte returned to the cathode tank area from the hydrogen driving liquid spraying pipe in the cathode tank area. Preferably, the overflow opening of the cathode tank area is connected with the hydrogen gas transfer tank 59 through a pipeline, and the cathode electrolyte after hydrogen evolution is returned to the cathode tank area through the liquid flow circulation pipeline. More preferably, the overflow opening of the cathode tank area is arranged at the top of the cathode tank area, so that the hydrogen gas generated by electrolysis can be smoothly discharged outside the cathode box.

[0079] The present application can also be improved as follows: at least one pH meter and / or ORP meter is additionally arranged in the anode tank area, the anode electrolyte transfer tank 6, or the connecting pipeline of the anode tank area and the anode electrolyte transfer tank 6. The pH value of the anode electrolyte is adjusted by adding alkaline pH value adjusting agent according to the value measured by the pH meter, so as to realize the adjustment and control of the pH value of the anode electrolyte; and the working state of the electrolytic power source is controlled according to the value measured by the ORP meter, so as to realize the control of the oxidation reaction performance and reaction safety of the anode electrolyte.

[0080] The application can be further improved by adding a cathode electrolyte feeding pipe 63, which is provided with a pump and a valve, one end of which is connected with the cathode tank area and / or the hydrogen gas transfer tank 59, and the other end is connected with the anode tank area and / or the anode electrolyte transfer tank 6 or the outlet of which is directed to the anode tank area and / or the anode electrolyte transfer tank, for feeding the cathode electrolyte after hydrogen evolution into the anode electrolyte as an alkaline pH value regulator according to the process requirements. Preferably, the valve of the cathode electrolyte feeding pipe has the functions of opening, closing and adjusting the flow size.

[0081] In the reaction process of the application, copper compound solids and / or tin compound solids and / or generated copper oxide and / or tin hydroxide may exist in the anode electrolyte, and the cathode electrolyte may also contain generated fine particles of copper and / or tin, which will settle at the bottom of the high-efficiency oxidation electrolytic tank and / or adhere to the electrolytic tank separator, hindering the electrochemical reaction.

[0082] The application can be further improved by adding a cathode liquid strong pressure pump feeding assembly 56 and / or a cathode liquid suction assembly 57 in the cathode tank area. The cathode liquid strong pressure pump feeding assembly 56 is a liquid feeding pipe provided with a pump, and the liquid outlet of which is located in the cathode tank area. The cathode liquid suction assembly 57 is a liquid suction pipe provided with a pump, and the liquid suction port of which is located in the middle or below the cathode tank area. The cathode liquid strong pressure pump feeding assembly 56 is used to treat the solids adhering to the electrolytic tank separator from the side of the anode tank area. The specific operation is to shut down the electrolytic power supply, close the gas outlet of the cathode tank area and the valve on the pipe connected with the liquid outlet pipe of the cathode tank area, and pump the cathode electrolyte into the cathode tank area by the cathode liquid strong pressure pump feeding assembly 56 to make the electrolyte in the cathode tank area pressurize the electrolytic tank separator and squeeze the solution to the anode tank area, so that the solids adhering to the electrolytic tank separator from the side of the anode tank area are squeezed off and float in the anode electrolyte. The cathode liquid suction assembly 57 is used to suck away the solids deposited at the bottom of the cathode tank area in the electrolytic oxidation process. The specific operation is to use the cathode liquid suction assembly 57 to suck the electrolyte from the bottom of the cathode tank area after shutting down the electrolytic power supply to make the solids be sucked away.

[0083] Preferably, the liquid inlet pipe of the cathode liquid strong pressure pump feeding assembly 56 and / or the liquid suction pipe of the cathode liquid suction assembly 57 are further provided with a valve.

[0084] Preferably, the cathode liquid suction assembly 57 further includes a solid-liquid separation device for filtering and removing the solid impurities in the cathode electrolyte.

[0085] Preferably, a pressure gauge is installed on the pump liquid outlet pipe of the cathode liquid strong pressure pump feeding assembly 56 for auxiliary control, making the operation safer.

[0086] Preferably, the liquid inlet pipe of the cathode liquid strong pressure pump assembly 56 and the liquid extraction pipe of the cathode liquid suction assembly 57 are the same liquid flow pipe, and the liquid flow direction is controlled by the logical relationship between the valve, the pump connection structure and the opening and closing of the valve.

[0087] The application can also be improved by adding a spouting circulating electrolyte assembly in the anode tank area of the high-efficiency oxidation electrolytic tank, which specifically includes a spouting pipe with a pump, and the liquid outlet of the spouting pipe is located at the bottom of the anode tank area. The spouting circulating electrolyte assembly is used to spout part or all of the electrolyte that needs to be returned to the anode tank area from the bottom of the anode tank area to the anode tank area when the stirring circulating liquid flow scheme is used, so as to flush the solid copper sludge deposited at the bottom and corners of the anode tank area to make it float again in the electrolyte to participate in the chemical reaction, thereby avoiding the deposition of solid matter at the bottom of the anode tank area. Preferably, the bottom of the anode tank area is funnel-shaped.

[0088] The application can also be improved by adding an automatic detection and feeding controller and at least one sensor to achieve partial automation or full automatic operation according to pre-programmed operation in the production process. The sensor is at least one selected from a liquid level meter, a specific gravity meter, a pH meter, a photoelectric colorimeter, an oxidation-reduction potential meter (ORP meter), a hydrogen gas concentration detector, a chlorine gas concentration detector, a thermometer, a pressure gauge, an ammonia gas concentration detector, and a motor current sensor. The installation position of the sensor is set according to the process design needs.

[0089] The application can also be improved by adding a liquid spouting pipe in the anode tank area of the high-efficiency oxidation electrolytic tank, the nozzle of which is close to and / or towards the electrolytic anode, and the liquid spouting pipe is connected with the electrolytic tank liquid flow pump pipe stirrer 11 in the independent liquid flow circulating system of the anode tank area, so as to spout part or all of the circulating electrolyte that needs to be returned to the anode tank area towards the electrolytic anode to participate in the reaction and improve the production efficiency.

[0090] The application can also be improved by adding an ultrasonic generator to break the agglomerated copper sludge and / or tin sludge in the anode electrolyte to promote the oxidation reaction of the copper sludge and / or tin sludge. The ultrasonic generator is directly installed on the titanium pipe or container containing or flowing through the anode electrolyte. Alternatively, the ultrasonic generator is placed in an auxiliary liquid tank containing water or solution, and the auxiliary liquid tank is fixed on the pipe or container made of high molecular resin, and the pipe or container contains or flows through the anode electrolyte. When the ultrasonic generator is placed in the auxiliary liquid tank, the ultrasonic generator is started to make the ultrasonic wave penetrate through the high molecular resin layer of the pipe or container to the anode electrolyte to exert the function of the ultrasonic wave. Preferably, the ultrasonic generator auxiliary liquid tank is made of high molecular material to better weld and connect with the pipe or container made of high molecular resin.

[0091] The application can also be improved by connecting the hydrogen outlet 66 with a high-altitude discharge pipe or hydrogenolysis hydrogenation and reduction reaction equipment. The high-altitude discharge pipe is used for safe discharge of the hydrogen gas discharged by the high-efficiency oxidation electrolytic cell, and the hydrogenolysis hydrogenation and reduction reaction equipment is used for collecting the hydrogen gas for reuse in other processes such as hydrogenolysis reaction, hydrogenation reaction, reduction reaction, etc. Preferably, the hydrogen outlet 66 is connected with a high-altitude discharge pipe and is equipped with a blower as a negative pressure hydrogen drainage equipment, which is used to fill air into the high-altitude discharge pipe to dilute the hydrogen gas in the pipe to a concentration lower than the explosion limit of hydrogen gas before assisting the discharge to high altitude. Preferably, the hydrogen outlet 66 is connected with a hydrogenolysis hydrogenation and reduction reaction equipment and is equipped with a gas pump, a bubble-type gas-liquid mixer and / or a vacuum-jet-type gas-liquid mixer as a negative pressure hydrogen drainage equipment to drain the hydrogen gas into the reactor.

[0092] The application can also be improved by adding a temporary storage tank for temporary storage of materials and chemical reaction. The temporary storage tank is connected with one or more of the high-efficiency oxidation electrolytic cell, the hydrogen gas transfer tank, the anode electrolyte transfer tank, the hydrogenolysis hydrogenation and reduction reaction equipment, and the solid-liquid separator.

[0093] The application can also be improved by adding an electrolyte discharge pipe with a valve at the bottom or near the bottom of the high-efficiency oxidation electrolytic cell to discharge the electrolyte after completing the electrolytic oxidation operation and prepare for the next step, or to discharge the electrolyte in the tank according to the process program before shutdown to reduce the corrosion of the electrolytic cathode.

[0094] The application can also be improved by adding an overflow buffer tank, which is connected to at least one tank or solid-liquid separator in the device of the application by pipeline, so that the fluid between the tanks or between the tank and the solid-liquid separator can be smoothly flowed to the target equipment by overcoming the potential energy of the fluid by power pumping.

[0095] The application can also be improved by adding a tail gas treatment tank, which is connected to at least one tank or equipment tail gas outlet in the device of the application by pipeline, and the escaped tail gas is introduced into the tail gas treatment tank by pipeline for environmental protection treatment. The tail gas treatment tank is a vacuum jet type gas-liquid mixing reaction tank and / or a spray tower type gas-liquid mixing reaction tank. When two or more tail gas treatment tanks are provided to treat tail gas from the same source, they are connected in series and / or parallel by pipeline and the tail gas is treated.

[0096] The application can also be improved by adding a chemical reaction tank for mixing reaction of the anode electrolyte treated by the high-efficiency oxidation electrolysis tank or the filtrate obtained by solid-liquid separation with hypochlorite, so as to completely treat the residual trace amounts of copper oxalate and / or stannous oxalate and / or copper ammonia complex and / or ammonia and / or ammonium, and help to improve the utilization rate of the high-efficiency electro-oxidation device. The chemical reaction tank is connected to one or more of the high-efficiency oxidation electrolysis tank, the anode electrolyte transfer tank, the temporary storage tank, and the solid-liquid separator by pipeline. Preferably, the chemical reaction tank is provided with an ORP meter, so that the mixture in the chemical reaction tank reacts under the control of the ORP meter, and the reaction liquid meets the standard requirements of the process.

[0097] The application can also be improved by adding a cold-heat temperature exchanger in at least one of the high-efficiency oxidation electrolysis tank, the anode electrolyte transfer tank, the hydrogen evolution gas transfer tank, the chemical reaction tank, and the temporary storage tank, and / or in the pipeline connected to the liquid flow of the above-mentioned at least one, to control the temperature of the liquid in the tank according to the process requirements, so as to improve the production efficiency and control the safety production process.

[0098] Compared with the prior art, the application has the following beneficial effects:

[0099] 1. The method of the application can avoid the fire and scalding hazards caused by the high-temperature decomposition method of the prior art, and can significantly reduce the reaction energy consumption and reduce the dust pollution in the copper oxide production workshop; the copper mud and / or tin mud can be treated in the production plant, avoiding the corresponding procedures and costs caused by transferring it to other places for treatment.

[0100] 2. The method of the present invention can avoid the use of the high-temperature decomposition method of the prior art. Therefore, the copper oxalate filter residue extracted from the acidic copper chloride etching waste liquid can be directly processed without worrying about the hydrochloric acid and chloride salt mixed in it generating hydrogen chloride, a highly corrosive acidic gas, damaging the equipment during the high-temperature treatment process, or the environmental problem of increased wastewater discharge caused by the addition of water washing pretreatment.

[0101] 3. The energy consumption required for copper sludge treatment by the method of the present invention is far lower than that of the existing technology using hypochlorite and / or chlorine.

[0102] 4. The method of the present invention can effectively treat ammonia and / or ammonium in filter residue copper sludge, thereby reducing or even avoiding the dynamic equilibrium that basic copper chloride, basic copper sulfate, copper hydroxide, copper carbonate, and basic copper carbonate in filter residue copper sludge will form copper ammonia complexes when they come into contact with ammonia and / or ammonium, so that the copper sludge can be more completely converted into copper oxide. Attached Figure Description

[0103] The invention will be further described below with reference to the accompanying drawings.

[0104] Figure 1 is one of the structural schematic diagrams of the electrolytic cell liquid flow pump tube stirrer of the present invention.

[0105] Figure 2 shows three structural schematic diagrams of the gas-liquid separator of the present invention.

[0106] Figure 3 is a schematic diagram of the cathode box structure of the present invention.

[0107] Figure 4 is a schematic diagram of the cathode box structure of the present invention, which is equipped with an electrolytic anode and an electrolytic cathode.

[0108] Figure 5 is a schematic diagram of the apparatus structure for the efficient electro-oxidation treatment of copper sludge and / or tin sludge in Embodiments 1, 5, and 6 of the present invention.

[0109] Figure 6 is a schematic diagram of the structure of the present invention, which uses a cathode box as the cathode tank area and forms a gas-liquid separator with it.

[0110] Figure 7 is a schematic diagram of one of the device structures of the present invention, which simultaneously includes a hydrogen evolution transfer tank and an anolyte transfer tank.

[0111] Figure 8 is a schematic diagram of a high-efficiency oxidation electrolytic cell of the present invention, which is equipped with a cathode box with an electrolytic anode.

[0112] Figure 9 is a schematic diagram of the structure of the cathode box as the cathode tank area and the cathode liquid high-pressure pump filling assembly and cathode liquid suction assembly connected thereto in this invention.

[0113] Figure 10 is a schematic diagram of the structure of the jetting circulating electrolyte assembly of the present invention.

[0114] Figure 11 is a schematic diagram of the device structure for treating copper sludge and / or tin sludge by high-efficiency electro-oxidation according to an embodiment of the present application.

[0115] Figure 12 is a schematic diagram of the device structure for treating copper sludge and / or tin sludge by high-efficiency electro-oxidation according to an embodiment of the present application. Figures 12-1 and 12-2 are enlarged views of the partial structure of Figure 12, which together form the complete device structure of the embodiment.

[0116] Figure 13 is a schematic diagram of the device structure for treating copper sludge and / or tin sludge by high-efficiency electro-oxidation according to an embodiment of the present application. Figures 13-1, 13-2 and 13-3 are enlarged views of the partial structure of Figure 13, which together form the complete device structure of the embodiment.

[0117] Figure 13 is a schematic diagram of the device structure for treating copper sludge and / or tin sludge by high-efficiency electro-oxidation according to an embodiment of the present application. Figures 13-1, 13-2 and 13-3 are enlarged views of the partial structure of Figure 13, which together form the complete device structure of the embodiment.

[0118] In the attached drawings and the following examples, the same type of substance used in multiple places in the device or the same type of component used in multiple places is indicated by "figure reference - number sequence". For example, electrolytic cell separator 5-1 means one of the electrolytic cell separators, and electrolytic cell separator 5-2 means the second electrolytic cell separator. DETAILED DESCRIPTION

[0119] The application is further illustrated by specific examples below.

[0120] In the examples, the single cathode box inner volume used is 100 liters, the electrolytic cell tank volume with three cathode boxes built-in is 1000 liters, the liquid flow pump pipe stirrer, the transfer tank, the gas-liquid separator, the hydrogenolysis hydrogenation and reduction reactor, the temporary storage tank, the overflow buffer tank, the tail gas treatment tank, the vacuum jet, and the spray tower are all products produced by Foshan Yegao Environmental Protection Equipment Manufacturing Co., Ltd. in Guangdong Province, China. The filter cloth, the solid-liquid separator, the cold and hot temperature exchanger, the electrolysis power supply, various sensors, PLC-programmed logic controller, chemical raw materials, valves, and pumps are all commercially available products. In addition to the above-mentioned products, other products with similar performance to the above-mentioned products listed in the application can also be selected by those skilled in the art according to conventional selection, and all can achieve the purpose of the application.

[0121] As shown in Figure 1, it is a structural schematic diagram of one of the electrolytic cell liquid flow pump pipe stirrers of the application. The electrolytic cell liquid flow pump pipe stirrer is composed of a pump 20, a valve 19, and a connecting pipe 43.

[0122] As shown in Figure 2, it is a schematic diagram of three structures A, B, and C of the gas-liquid separator 10 of the application. Among them, the A-type structure and the B-type structure are pipeline type gas-liquid separators 10 provided with hydrogen overflow outlets 66, specifically three-way pipelines or multi-way pipelines; the C-type structure is a tank type gas-liquid separator 10 provided with a hydrogen overflow outlet 66, which has the best gas separation effect. The cathode tank area and the tank cover of a high-efficiency oxidation electrolytic cell can also be simply combined to form a tank type gas-liquid separator.

[0123] As shown in Figure 3, it is a structural schematic diagram of one of the cathode boxes of the application. Among them, the left side of Figure 3 is the front view of the cathode box, and the right side is the side view of the cathode box. At least one side of the cathode box 4 is provided with an electric field line through hole 9, and the electrolytic cell separators 5-1 and 5-2 are respectively tightly fixed on the electric field line through holes 9 on both sides of the cathode box 4, and the electrolytic cathode 3 is placed in the cathode box 4 and makes the closed area in the cathode box become a cathode tank area. The screw rod 7-1 is buried and fastened in the cathode box, and the outer nut sleeve 8-1 is used to install and fasten the electrolytic cell separator 5-1; the fixed nut 8-2 is deeply buried and fastened in the cathode box, and the outer screw sleeve 7-2 is used to install and fasten the electrolytic cell separator 5-2.

[0124] As shown in Fig. 4, it is a schematic diagram of the structure of the cathode box with electrolytic anode installed in the application. In the figure, the left side is the front view of the cathode box with electrolytic anode installed, and the right side is the front view of the electrolytic anode of the cathode box and its A-A sectional view. At least one side of the cathode box 4 is provided with an electric field line through hole 9, and the electrolytic tank partition 5 and the electrolytic anode 2 are fixed tightly on the electric field line through hole 9 by screws and mounting nuts 8. The electrolytic anode 2 is installed outside the electrolytic tank partition 5, and the electrolytic cathode 3 is placed in the cathode box 4 to make the enclosed area in the cathode box become the cathode tank area. The cathode box 4 is provided with a discharge pipe 14 and a feed pipe 18, and a hydrogen driving liquid jet pipe 13 is arranged in the cathode box 4, with its nozzle upward and at the bottom of the cathode box. The cathode box with electrolytic anode is installed in the tank body of the high-efficiency oxidation electrolytic tank, and the area outside the cathode box in the tank body is used as the anode tank area. The electrolytic anode is installed outside the cathode box, the electrolytic cathode is installed in the cathode box, and the combination of the electrolytic power supply forms a separate unit of the high-efficiency oxidation electrolytic tank.

[0125] As shown in Fig. 6, it is a schematic diagram of the structure of the cathode box as the cathode tank area and the gas-liquid separator formed thereby in the application. At least one side of the cathode box 4 is provided with an electric field line through hole 9, and the electrolytic tank partition 5 and the electrolytic anode 2 are fixed tightly on the electric field line through hole 9 by screws and mounting nuts 8. The electrolytic anode 2 is installed outside the electrolytic tank partition 5, and the electrolytic cathode 3 is placed in the cathode box 4 to make the enclosed area in the cathode box become the cathode tank area. The cathode box 4 is provided with discharge pipes 14-1 and 14-2, feed pipes 18-1 and 18-2, and a hydrogen driving liquid jet pipe 13 is arranged at the bottom of the cathode box 4, with its nozzle upward. The overflow pipe of the cathode box, i.e. the discharge pipe 14-1, is connected with the hydrogen gas escape outlet 66 through the pipeline and the overflow pipe 12 of the cathode box, and the discharge pipe 14-2 is connected with the hydrogen gas escape outlet 66 through the pipeline and the overflow pipe 12 of the cathode box, respectively. The pipeline type gas-liquid separator is formed by the pipeline section provided with the hydrogen gas escape outlet 66. The hydrogen gas escape outlet 66 is also provided in the hydrogen gas escape transfer tank 59 to form the tank type gas-liquid separator. The hydrogen gas escape transfer tank 59 is connected with the feed pipe 18-2 of the cathode box 4 through the liquid circulation pipeline provided with the electrolytic tank liquid flow pump pipe stirrer 11. The pipeline type gas-liquid separator or the tank type gas-liquid separator can be used separately in the application, and the purpose of the application can be achieved by selecting any one or more than one gas-liquid separator connection structure in Fig. 6.

[0126] As shown in Figure 7, it is a schematic diagram of one of the device structures of the present application which is provided with both the hydrogen escape and transfer tank and the anode electrolyte transfer tank. The hydrogen escape and transfer tank 59 is a tank provided with an inlet pipe, an outlet pipe and a hydrogen escape pipe, which is used for temporarily storing the flowing cathode electrolyte and assisting the gas escape and chemical reaction; the outlet pipe is connected with the electrolyte flow pump pipe stirrer 11-2 through a pipeline, and then connected with the inlet pipe of the cathode tank area of the high-efficiency oxidation electrolytic tank through a pipeline, while the outlet pipe of the cathode tank area is connected with the inlet pipe of the hydrogen escape and transfer tank 59 through a pipeline or a pipeline provided with a hydrogen escape outlet 66, forming a gas-liquid separator of the cathode electrolyte circulation system, so that the cathode electrolyte can escape and stir in the circulation flow. The outlet pipe of the anode electrolyte transfer tank 6 is connected with the electrolyte flow pump pipe stirrer 11-1 through a pipeline, and then connected with the inlet pipe of the anode tank area of the high-efficiency oxidation electrolytic tank through a pipeline, while the outlet pipe of the anode tank area is connected with the inlet pipe of the anode electrolyte transfer tank 6 through a pipeline, forming a liquid flow circulation system of the anode electrolyte.

[0127] As shown in Figure 8, it is a schematic diagram of one of the high-efficiency oxidation electrolytic tanks of the present application which is provided with cathode boxes with electrolytic anodes. The tank body 1 of the high-efficiency oxidation electrolytic tank is placed with at least two cathode boxes 4 with electrolytic anodes 2, and the electrolytic cathode 3 is placed in the cathode box 4. The area outside the cathode box 4 in the tank body 1 is used as the anode tank area and is filled with anode electrolyte 15, while the area in the cathode box 4 is used as the cathode tank area and is filled with cathode electrolyte 16, after the electrolytic anode 2 and the electrolytic cathode 3 are respectively connected with the electrolytic power supply 44, they become two or more independent small electrolytic units combined into a parallel large electrolytic tank to improve the electrolytic efficiency. The discharge pipelines of the anode tank area are respectively provided with valve 19-1 and valve 19-2.

[0128] As shown in Figure 9, it is a schematic diagram of the structure of the cathode box as the cathode tank area and the catholyte strong pressure pump filling assembly and the catholyte suction assembly connected therewith in the present application. The difference between Figure 9 and the structure shown in Figure 6 is that the discharge pipe orifice 14-1 and 14-2 of the cathode box 4 are respectively connected with valves, the discharge pipe orifice 14-2 is connected with the hydrogen escape outlet 66 through the pipeline to form the pipeline connection with the hydrogen escape transfer tank 59, and the catholyte strong pressure pump filling assembly 56 and the catholyte suction assembly 57 are additionally connected in parallel between the cathode box 4 and the hydrogen escape transfer tank 59. In Figure 9, the original electrolytic tank liquid flow pump pipe stirrer 11 is used as the catholyte strong pressure pump filling assembly 56, specifically, the liquid inlet pipeline provided with the pump 20-1, the valve 19-3 and the sensor 39, that is, the pressure gauge is additionally provided as the sensor 39 on the basis of the original electrolytic tank liquid flow pump pipe stirrer 11; the liquid outlet of the catholyte strong pressure pump filling assembly 56 is connected with the hydrogen driving liquid spraying pipe 13, so that the liquid outlet is equivalent to the position in the cathode tank area. The catholyte suction assembly 57 is the liquid suction pipeline provided with the pump 20-2 and the valve 19-4, and the solid-liquid separator 36 is additionally provided, and the liquid suction port of the pipeline is connected with the hydrogen driving liquid spraying pipe 13, and the liquid suction port is equivalent to the position in the middle or below of the cathode tank area.

[0129] As shown in Figure 10, it is a schematic diagram of the assembly structure of the spraying circulating flow electrolyte in the present application. Specifically, the tank body 1 of the high-efficiency oxidation electrolytic tank is provided with three cathode boxes 4, the electrolytic cathode 3 is arranged in the cathode box 4, the electrolytic anode 2 is arranged outside the cathode box 4, the area outside the cathode box 4 in the tank body 1 is used as the anode tank area, and the area in the cathode box 4 is used as the cathode tank area. The anode tank area is connected with the anode electrolyte transfer tank 6, then connected with the liquid spraying pipe 53 provided in the anode tank area through the electrolytic tank liquid flow pump pipe stirrer 11-1 to form a circulating liquid flow system, and connected with the tank bottom liquid spraying pipeline 54-1 and 54-2 provided at the bottom of the anode tank area through the electrolytic tank liquid flow pump pipe stirrer 11-2 to form a spraying circulating flow electrolyte assembly. The spraying nozzle of the liquid spraying pipe 53 is close to and / or towards the electrolytic anode.

[0130] Example 1

[0131] As shown in Figure 5, it is a device for treating copper sludge and / or tin sludge by high-efficiency electro-oxidation in Example 1 of the present application. The high-efficiency electro-oxidation device is a basic type high-efficiency electro-oxidation device, which comprises a tank body 1 of a high-efficiency oxidation electrolytic tank, a ceramic filter plate partition 5 is used to divide the tank body 1 into an anode tank area and a closed cathode tank area, and further comprises an electrolytic anode 2, an electrolytic cathode 3, a hydrogen escape outlet 66, an electrolytic tank liquid flow pump pipe stirrer 11, a hydrogen driving liquid spraying pipe 13 and an electrolytic power supply 44.

[0132] The tank body 1 of the high-efficiency oxidation electrolytic tank is 100 liters, and the tank bodies of the anode tank area and the cathode tank area are 50 liters respectively.

[0133] The electrolytic anode 2 is made of titanium and conductive graphite, and the electrolytic cathode 3 is made of conductive graphite.

[0134] The two ports of the electrolytic cell liquid flow pump pipe stirrer 11 are respectively connected with the overflow pipe port 14 of the cathode tank area and the hydrogen driving liquid jet pipe 13.

[0135] The hydrogen escape port 66 is arranged at the top of the cathode tank area of the high-efficiency oxidation electrolytic cell, and the hydrogen escape port 66 and the cathode tank area form a tank-type gas-liquid separator 10.

[0136] The hydrogen driving liquid jet pipe 13 is arranged in the cathode tank area at the lower part of the electrolytic cathode, the nozzle of the hydrogen driving liquid jet pipe 13 faces upward, and the liquid inlet port of the hydrogen driving liquid jet pipe 13 is connected with the electrolytic cell liquid flow pump pipe stirrer 11.

[0137] The solid copper sludge treated in the embodiment is 5 kg of basic copper sludge containing ammonium ions, wherein 1 kg of basic copper carbonate, 3.2 kg of basic copper sulfate, and 0.3 kg of basic copper chloride are contained.

[0138] The starting cathode electrolyte is a mixed aqueous solution of 10% sodium hydroxide, 8% potassium hydroxide, 1% potassium carbonate, and 1% sodium bicarbonate, and the pH value is greater than pH 14. The starting anode electrolyte is a solid-liquid mixture obtained by mixing the cathode electrolyte with the above-mentioned 5 kg of solid copper sludge.

[0139] The method for treating copper sludge and / or tin sludge by using the high-efficiency electro-oxidation in the embodiment 1 comprises the following steps:

[0140] 1. The starting electrolyte is added to the anode tank area and the cathode tank area by using the above-mentioned high-efficiency electro-oxidation device, and the concentration of chloride ions in the anode electrolyte is 1 g / L and the pH value is greater than pH 14.

[0141] 2. The electrolytic cell liquid flow pump pipe stirrer 11 and the electrolysis power supply 44 are started to perform electrolysis under the condition that the space temperature of the test workshop is 6°C. The electrolysis current is set to 30 A, and the average tank voltage is 4.8 V. The hydrogen gas generated by cathode electrolysis is discharged through the gas-liquid separator 10, the ORP value of the anode electrolyte continuously rises, the process reaction heat is continuously released, the temperature of the electrolyte rises from 6°C to 30°C, and the concentration of chloride ions in the anode electrolyte is maintained at about 1 g / L due to circulation.

[0142] 3. The electrolytic oxidation operation is considered to be completed when the conversion rate of the copper sludge in the anode electrolyte to copper oxide reaches 100% according to the process setting. After the copper sludge is treated by electro-oxidation for 24 hours, the anode electrolyte is detected manually, the measured ORP value of the anode electrolyte is -30 mV, and the copper sludge in the solution has been completely converted into a solid-liquid mixture of copper oxide CuO and sodium copper oxide NaCuO2, and the running device is stopped.

[0143] The copper oxide and sodium cupric acid solid mixture product prepared in Example 1 is settled at the bottom of the anode tank area, and the next step is to perform solid-liquid separation treatment on the copper oxide product.

[0144] Example 2

[0145] As shown in Figure 11, the device for treating copper sludge and / or tin sludge by high-efficiency electro-oxidation in Example 2 of the present application includes a tank body 1 of a high-efficiency electrolytic tank, an electrolytic anode 2, an electrolytic cathode 3, a cathode box 4, a polyethylene (PE) microporous filter plate 5, a hydrogen gas escape outlet 66, two electrolytic tank liquid flow pump pipes 11-1 and 11-2, a cathode box liquid level raising overflow pipe 12, a hydrogen driving liquid jet pipe 13, a pH meter 39-1, an ORP meter 39-2, an electrolysis power supply 44, a liquid jet pipe 53, and a 50-liter hydrogen gas escape intermediate tank 59.

[0146] The tank body 1 of the high-efficiency oxidation electrolytic tank is 300 liters, the cathode box 4 is 100 liters, and the hydrogen gas escape intermediate tank 59 is 50 liters.

[0147] The cathode box 4 is placed in the tank body 1. The cathode box 4 has electric field line through holes 9 on both sides, and electrolytic anode mesh blocks 2 are installed on both sides of the electric field line through holes 9 after the electrolytic tank separators 5 are pasted, and the electrolytic cathode mesh blocks 3 are installed in the cathode box 4 to form a cathode tank area. The other 200-liter area space in the tank body 1 outside the cathode box serves as an anode tank area. The two electrolytic anode mesh blocks 2 are connected in parallel with the positive electrode of the electrolysis power supply 44 and are placed in the anode tank area, and the electrolytic cathode mesh blocks 3 are connected with the negative electrode of the electrolysis power supply 44 and are placed in the cathode tank area. The electrolytic tank separators 5 are PE filter plates with micropores that allow molecules and ions in the electrolyte to pass through and block the passage of bubbles. The electrolytic cathode bottom in the cathode box 4 is provided with a hydrogen driving liquid jet pipe 13 with multiple liquid jet outlets for upward liquid jet to make the hydrogen gas generated by the electrolytic cathode float upward with the liquid flow. At the same time, a discharge pipe 14 is added to the middle upper part of the cathode box 4, and a liquid level raising overflow pipe 12 is connected to raise the liquid level of the cathode box, so that the cathode electrolyte completely soaks the electrolytic cathode and reduces the empty space for hydrogen gas accumulation at the top of the cathode box.

[0148] The outlet pipe 14 of the cathode box 4, the liquid level overflow pipe 12, the hydrogen gas transfer tank 59, the electrolytic tank liquid flow pump pipe stirrer 11-1, and the inlet pipe 18 of the cathode box 4 are connected to form a pipeline for the cathode electrolyte to flow and release hydrogen gas. The outlet pipe 14 of the cathode box 4 is connected to the liquid level overflow pipe 12, one of the hydrogen gas release outlets 66 is arranged on the pipe section of the connection path between the liquid level overflow pipe 12 and the hydrogen gas transfer tank 59 to form a pipeline gas-liquid separator 10, and the other hydrogen gas release outlet 66 is arranged on the hydrogen gas transfer tank 59 to form a tank gas-liquid separator. One end of the electrolytic tank liquid flow pump pipe stirrer 11-1 is connected to the outlet pipe of the hydrogen gas transfer tank 59, and the other end is connected to the hydrogen driving liquid spray pipe 13.

[0149] The anode tank area is provided with a pH meter sensor 39-1 and an ORP meter sensor 39-2, the anode tank area liquid flow pump pipe stirrer 11-2 is connected to the liquid inlet of the liquid spray pipe 53, and the liquid spray pipe 53 is divided into two branches after entering the anode tank area to spray liquid to the two electrolytic anodes 2 on both sides of the cathode box. The surfaces of the two electrolytic anodes are gold-plated conductive bodies, the electrolytic cathode is a titanium plate, and the electrolytic tank separator 5 is a PE filter plate. The combination in FIG. 11 forms a high-efficiency electrolytic tank.

[0150] The sensor 39-1 is a pH meter, which is used to control the alkaline pH value adjusting agent solution 22 in the process reaction of the anode electrolyte to maintain the process set pH value. The ORP meter sensor 39-2 is used to manually adjust the output power of the electrolysis power supply 44 for reaction process control and reaction endpoint determination.

[0151] One end of the electrolytic tank liquid flow pump pipe stirrer 11-2 is connected to the liquid outlet pipe of the tank body 1, and the other end is connected to the liquid spray pipe 53 to extract and spray liquid to the anode tank area electrolyte.

[0152] The solid copper sludge in the treatment reactant 31 of this embodiment is copper oxalate filter residue obtained after the reaction of acidic copper chloride etching waste liquid and oxalic acid, which contains hydrochloric acid and copper chloride impurities.

[0153] The alkaline pH value adjusting agent is a mixed aqueous solution of 10% sodium hydroxide, 8% potassium hydroxide, 1% potassium carbonate, and 1% sodium bicarbonate.

[0154] The starting cathode electrolyte is an 8% sodium chloride solution.

[0155] The starting anode electrolyte 200 liters contains 5 kilograms of the above-mentioned solid copper sludge, a solid-liquid mixed aqueous solution of sodium chloride and alkaline pH value adjusting agent, and the pH value is pH 5.5.

[0156] The process features of this embodiment are that the anode electrolyte is acidic and makes self-escape gas circulation flow in the anode tank area, and the cathode electrolyte makes escape hydrogen circulation flow between the cathode box 4 and the escape hydrogen transfer tank 59. The pH value of the anode electrolyte is continuously reduced during the reaction, and a pH meter 39-1 is used to control the alkaline pH value adjusting agent to be added into the anode electrolyte to maintain the pH value of the reaction solution at 5.5. The anode electrolyte generates hypochlorous acid and / or chlorine during the reaction and chemically reacts with copper oxalate.

[0157] The method for treating copper sludge and / or tin sludge by high-efficiency electro-oxidation in this embodiment includes the following steps:

[0158] 1. The prepared starting anode electrolyte is added into the anode tank area by using the high-efficiency electro-oxidation device described above, and 8% sodium chloride solution is used as the starting cathode electrolyte and is added into the escape hydrogen transfer tank 59 and the cathode box 4. The liquid flow pump pipe stirrer 11-2 is turned on to make the solution in the anode tank area self-circulation flow, and the liquid flow pump pipe stirrer 11-1 is turned on to make the cathode electrolyte circulation flow between the cathode box 4 and the escape hydrogen transfer tank 59 and the gas-liquid separator 10. The temperature of the electrolyte is the ambient temperature of 30°C.

[0159] 2. The electrolysis power supply 44 is turned on, the electrolysis current is adjusted to 300 A, and the average value of the electrolysis tank pressure is 2.8 V. The anode electrolyte generates chlorine and hypochlorous acid during the reaction and reacts with copper oxalate. Carbon dioxide gas is escaped during the process, and the copper sludge is oxidized to generate copper oxide. The hydrogen gas generated by the cathode is taken out of the electrolysis tank by the circulation flow of the cathode electrolyte, and the pH value of the cathode electrolyte is increased. The alkaline pH value adjusting agent 22 needs to be added into the anode electrolyte during the reaction to maintain the pH value at 5.5. The temperature of the anode electrolyte is continuously increased, and the concentration of chloride ions in the anode electrolyte is maintained at 190 g / L.

[0160] 3. When the conversion rate of the copper sludge in the anode electrolyte to copper oxide reaches ≥98%, it is considered that the electro-oxidation operation is completed. The ORP value of the anode reaction solution is detected by manual observation during the electrolysis process. The ORP value gradually increases as the reaction proceeds. When the temperature of the anode electrolyte rises to 70°C and the ORP value reaches 900 mv, the anode electrolyte is sampled and checked. The result shows that the copper sludge in the anode electrolyte has been completely converted into copper oxide product, which meets the process treatment standard.

[0161] 4. The electrolysis operation is completed by turning off the electrolysis power supply and all running pumps. The anode electrolyte is subjected to solid-liquid separation to collect the copper oxide product.

[0162] Example 3

[0163] As shown in Figure 12, the device for treating copper sludge and / or tin sludge by high-efficiency electro-oxidation in Example 3 of the present application comprises a tank body 1 of high-efficiency electrolytic cell, three cathode boxes 4 with cathode and anode electrodes and separators, an anode electrolyte transfer tank 6, a hydrogen gas escape outlet 66, two electrolytic cell liquid flow pump pipes 11, three sensors 39, an electrolysis power supply 44, two tail gas treatment tanks 33, a solid-liquid separator 36, a temporary storage tank 37, two air blowers 45, a hydrogen gas high-altitude discharge pipe 46, a liquid flow pump pipe stirrer 47, two cold and hot temperature exchangers 49, two liquid injection pipes 54, a 100-liter hydrogen gas escape transfer tank 59, a chemical reaction tank 61, a cathode electrolyte feeding pipe 63, two ultrasonic generators 64, an auxiliary liquid tank 65, and multiple valves and pumps.

[0164] The tank body 1 of the high-efficiency electrolytic cell is 1000 liters, each cathode box 4 is 100 liters, and the anode electrolyte transfer tank 6 is 100 liters.

[0165] The three cathode boxes 4 are placed in the tank body 1. The cathode boxes 4 have electric field line through holes 9 on both sides, and each cathode box has electrolytic anodes 2 tightly installed on both sides of the electric field line through holes 9 after the holes are pasted with electrolytic cell separators 5 filter cloth, so that the area inside the cathode box becomes a cathode tank area, and the area inside the electrolytic cell tank body 1 outside the cathode box becomes an anode tank area. The six electrolytic anodes 2 are connected in parallel with the positive electrode of the electrolysis power supply 44 and placed in the anode tank area, and the three electrolytic cathodes 3 are connected in parallel with the negative electrode of the electrolysis power supply 44 and placed in the respective cathode tank areas. The electrolytic cathode bottom of each cathode box 4 is installed with a hydrogen driving liquid injection pipe 13, and the hydrogen driving liquid injection pipe 13 is provided with multiple upward liquid injection ports to make the hydrogen gas generated by electrolysis of the electrolytic cathode float upward with the liquid.

[0166] The top of each cathode box 4 is provided with a discharge pipe port 14 for overflow and overflow gas. The discharge pipe ports 14 of the cathode tank areas, the hydrogen gas escape transfer tank 59, the electrolytic cell liquid flow pump pipe stirrer 11-2, and the hydrogen driving liquid injection pipe 13 are connected by pipes to make the cathode electrolyte containing hydrogen bubbles in the flow system drive the electrolytic hydrogen out of the electrolytic cell. The discharge pipe ports 14 of the cathode tank areas are respectively connected to three-way pipes or four-way pipes provided with hydrogen gas escape outlets 66 to form pipe-type gas-liquid separators 10. These gas-liquid separators 10 are connected by pipes to each other and to the hydrogen gas escape transfer tank 59. The hydrogen gas escape transfer tank 59 is connected by pipes to the liquid inlets of the electrolytic cell liquid flow pump pipe stirrer 11-2 and the hydrogen driving liquid injection pipes 13 to make the cathode electrolyte in the circulating flow system drive hydrogen out of the electrolytic cell. The hydrogen gas escape transfer tank 59 is additionally provided with a hydrogen gas escape outlet 66 to form a tank-type gas-liquid separator.

[0167] The bottom of the anode electrolyte transfer tank 6 is funnel-shaped, and the bottom liquid outlet is provided with an electrolyte flow pump pipe stirrer 11-1. The electrolyte flow pump pipe stirrer 11-1 is connected with the liquid injection pipes 54-1 and 54-2 at the bottom of the tank, the overflow port of the tank body 1 and the anode electrolyte transfer tank 6 to form a liquid flow circulation pipeline, so that the anode electrolyte circulates and flows to escape and stir the solution at the bottom of the electrolytic tank. The anode tank area is provided with sensors 39-2, 39-3 and 39-4 which are pH meter, ORP meter and temperature meter respectively. The pH meter is used to control the alkaline pH value adjusting agent 22 to maintain the pH value of the anode electrolyte process setting. The ORP meter is used to detect the degree of the reaction process, and the current output of the electrolysis power supply is adjusted according to the ORP value in the process to make safety control, and the reaction endpoint is determined according to the process setting ORP value. The temperature meter is used to control the working state of the cold and hot temperature exchanger 49-1 on the tank body 1, so that the temperature of the anode electrolyte meets the process requirements. The temperature meter 39-5 and the cold and hot temperature exchanger 49-2 are installed in the hydrogen evolution transfer tank 59, so that the temperature of the cathode electrolyte meets the process requirements after heat exchange during electrolysis. The anode electrolyte transfer tank 6 is connected with the high-efficiency oxidation electrolytic tank body 1 by pipeline and is used for the anode electrolyte to escape in the circulating flow. The surfaces of the anode and the cathode of each electrolysis are plated with platinum conductors, and the separators 5 of each electrolytic tank are filter cloths. The plurality of independent electrolytic units in the tank body 1 form a parallel high-efficiency oxidation electrolytic tank.

[0168] The cathode electrolyte adding pipe 63 is composed of a valve 19-3 and a pump 20-3 and is connected with the anode electrolyte transfer tank 6 and the hydrogen evolution transfer tank 59 respectively, and is used to add the original cathode electrolyte after hydrogen evolution into the anode electrolyte transfer tank 6 to participate in the chemical reaction in the anode tank area.

[0169] The air blower 45-1 is connected with the air inlet of the hydrogen high-altitude discharge pipe 46, and is used to assist the hydrogen gas discharged from the gas-liquid separator 10 and the hydrogen evolution transfer tank 59 to flow out.

[0170] The air blower 45-2 is one of the components of the bubbling tail gas treatment tank 33-1, and is used to guide the gas produced by the anode tank area reaction into the tail gas treatment tank 33-1 for environmental protection treatment. The tank 33-1 is connected with the tank 33-2 in series by a gas pipeline, and a two-stage treatment method is used to ensure the treatment effect of the waste gas.

[0171] The sensor 39-1 is a pH meter installed in the chemical reaction tank 61, and is used to control the alkaline pH value adjusting agent 22 to adjust the starting anode electrolyte.

[0172] The solid-liquid separator is a centrifugal machine 36, which is used to separate the solid-liquid mixture after oxidation treatment and obtain the filter residue copper oxide product.

[0173] The ultrasonic generator 64-1 is installed on the titanium metal connecting pipe of the overflow tank 6 from the anode tank area to the anode electrolyte. The ultrasonic generator 64-2 is installed in the auxiliary liquid tank 65 welded on the polymeric resin tank body 1.

[0174] The two temporary storage tanks 37-1 and 37-2 are used to store the filtered residue copper oxide and the filtrate waste brine 48 respectively.

[0175] The process reactant 31 in this embodiment is the copper mud of solid copper ammonia complex, which is derived from the precipitated copper mud produced by the reaction of the alkaline copper chloride etching waste liquid and hydrochloric acid, and contains part of the basic copper chloride and ammonium salt impurities. Specifically, the starting anode electrolyte is prepared by adding water 42, sodium chloride, sodium hydroxide and solid copper mud 52 kg of copper chloride ammonia to the chemical reaction tank 61, and the starting anode electrolyte contains dissolved copper chloride ammonia copper salt, the pH value of the solution is pH 7, and the concentration of chloride ions is 70 g / L. In addition, the starting cathode electrolyte is the solution containing dissolved copper salt which is filtered from the anode tank area to the cathode tank area.

[0176] The alkaline pH value regulator 22 is sodium hydroxide solution, and the other alkaline pH value regulator is the original cathode electrolyte after hydrogen evolution in the hydrogen evolution intermediate tank 6.

[0177] The process characteristics of this embodiment are that the cathode electrolyte is circulated and flowed in the hydrogen evolution cycle between the multiple cathode boxes and the hydrogen evolution intermediate tank 59, and the anode electrolyte is circulated and flowed in the hydrogen evolution cycle between the anode tank area and the anode electrolyte intermediate tank 6. The pH meter in the anode tank area is used to control the addition of the alkaline pH value regulator 22 to the anode tank area to maintain the pH value of the anode reaction solution at 7 during the reaction of the anode electrolyte. The anode electrolyte reacts to convert the copper mud into copper oxide and release nitrogen gas during the flow, and the cathode electrolyte reacts to produce hydrogen gas and a small amount of copper powder is electrolyzed at the cathode. The temperature of the electrolyte is controlled at 70°C during the whole process, and the pipeline, tank body 1, cathode box 4, anode electrolyte intermediate tank 6 and hydrogen evolution intermediate tank 59 through which the electrolyte flows are all made of polytetrafluoroethylene material.

[0178] The method for treating copper mud and / or tin mud by high-efficiency electro-oxidation in this embodiment includes the following steps:

[0179] 1. The prepared starting anode electrolyte is added to the anode tank area and the anode electrolyte intermediate tank 6 as the starting anode electrolyte by using the high-efficiency electro-oxidation device described above, and part of the starting cathode electrolyte is added to the hydrogen evolution intermediate tank 59. The two cold and hot temperature exchangers 49, two electrolyte flow pumps 11 and three sensors 39-2, 39-3 and 39-4 are started to detect and heat the solution to 70°C during the flow.

[0180] 2. Turn on the electrolysis power supply 44, adjust the electrolysis current to 600A, the average value of the electrolytic cell voltage to 5.3V, start two ultrasonic generators 64-1 and 64-2, the anode electrolyte reacts to produce hypochlorite and reacts with ammonium salt and copper ammonia complex to produce nitrogen gas, copper mud reacts to generate copper oxide, the hydrogen gas generated by the electrolytic cathode is taken to the multiple gas-liquid separators 10 and the hydrogen gas escape transfer tank 59 for escape, wherein a small amount of copper is generated by the electrolytic cathode; During the reaction, the anode electrolyte is added with sodium hydroxide as a basic pH adjuster 22 and the original cathode electrolyte after hydrogen escape to maintain pH 7, the measured value of ORP slowly rises with the reaction, and the chloride ion concentration of the anode electrolyte is maintained at about 70g / L due to circulation.

[0181] 3. When the conversion rate of copper mud to copper oxide in the anode electrolyte reaches ≥98% according to the process setting, it is considered that the electrolytic oxidation operation is completed; After a period of electrolytic reaction, the measured value of ORP meter rises to 690mv terminal value, the anode electrolyte is sampled and detected, the ammonia nitrogen impurity concentration is 3mg / L, which reaches the process ammonia nitrogen treatment index ≤40mg / L, at the same time, all copper mud is converted to copper oxide, the electrolysis power supply, all pumps and ultrasonic generators are turned off to complete the electrolysis operation, the valve 19-2 is opened and the pump 20-2 is started to pump the solid-liquid mixture treated by oxidation to the solid-liquid separator 36 for separation treatment, after the pumping is completed, the pump 20-2 is turned off and the valve 19-2 is closed to re-input the starting anode electrolyte into the electrolytic cell.

[0182] 4. The tail gas escaped from the anode tank area in the process is introduced into the tail gas treatment tank 33-1 and 33-2 for environmental protection treatment, and the hydrogen gas generated by electrolysis is introduced into the hydrogen gas high-altitude discharge pipe by the air blower for high-altitude discharge.

[0183] 5. The solid-liquid mixture treated by oxidation is separated by using a centrifuge 36 to obtain filter residue copper oxide powder product 32 stored in temporary storage tank 37-1, and filter liquor brine 48 stored in tank 37-2.

[0184] Example 4

[0185] As shown in Fig. 13, the device for treating copper sludge and / or tin sludge by high-efficiency electro-oxidation in Example 4 of the present application comprises two high-efficiency electrolytic cells, wherein six electrolytic anodes 2, three electrolytic cathodes 3, three cathode boxes 4, six filter cloths as electrolytic cell separators 5, an anode electrolyte transfer tank 6, a hydrogen escape outlet 66, three hydrogen gas pipeline type gas-liquid separators 10 with valves, four electrolytic cell liquid flow pump pipes 11, three hydrogen driving liquid jet pipes 13, a plurality of liquid jet pipes 53, a cover plate 17 with escape holes arranged in the anode tank area; the electrolytic anodes 2 in the tank body 1-1 adopt a larger specific surface area structure of coiled wire and laminated type; the tank body 1-2 is divided into an anode tank area and a cathode tank area by two layers of filter cloths as electrolytic cell separators 5, and the anode and the cathode are connected with the positive electrode and the negative electrode of the electrolytic power supply 44-2, wherein the cathode tank area is a closed tank area, and is provided with a hydrogen driving liquid jet pipe and an electrolytic cell liquid flow pump pipe stirrer and uses a tank cover as a gas-liquid separator 10-4. The device of the example further comprises other tail gas treatment tanks 33, a vacuum jet device 34, seven solid-liquid separators 36, five temporary storage tanks 37, two overflow buffer tanks 38, fifteen sensors 39, an automatic detection and feeding controller 40, two electrolytic power supplies 44, two air blowers 45, a hydrogen high-altitude discharge pipe 46, three liquid flow pump pipe stirrers 47, two cold and hot temperature exchangers 49, tank bottom liquid jet pipes 54, organic waste liquid hydrogenolysis and hydrogenation reaction tanks 55, cathode liquid high-pressure pump filling assemblies 56, cathode liquid suction assemblies 57, two chemical reaction tanks 61-1 and 61-2, cathode electrolyte feeding pipes 63, an ultrasonic generator 64, a plurality of valves and pumps.

[0186] The tank body 1-1 and the tank body 1-2 of the high-efficiency electrolytic cell are 1000 liters respectively, and the tank body 1-2 is divided into an anode tank area of 700 liters and a cathode tank area of 300 liters by two layers of filter cloths as electrolytic cell separators. The electrolytic anodes are all titanium-based coated insoluble anode meshes, and the electrolytic cathodes are all titanium meshes, and the three cathode boxes 4 with electrolytic anodes are all placed in the tank body 1-1 of the high-efficiency electrolytic cell, the space in the tank body 1-1 after removing the volume of the three cathode boxes is used as the anode tank area, the internal space of each cathode box 4 is used as the respective cathode tank area, and after the anode and the cathode on each cathode box are respectively connected with the positive electrode and the negative electrode of the electrolytic power supply, a plurality of independent electrolytic units are combined in parallel to form one high-efficiency electrolytic cell.

[0187] Each electric field line through hole 9 of the cathode box 4 is sealed by the separator filter cloth 5, and the installation structure of the cathode box is shown in Fig. 4.

[0188] The anolyte transfer tank 6 is connected to the tank 1-1 by two liquid flow pipes, one of which is connected to the liquid spraying pipe 53 for spraying anolyte to the anode, and the other is connected to the tank bottom liquid spraying pipe 54 for stirring the solid matter accumulated at the tank bottom in the anolyte, so that the copper sludge can better participate in the reaction. The overflow pipe of the tank 1-1 is connected by a titanium pipe to the anolyte transfer tank 6 for circulating flow.

[0189] Each cathode box is provided with a discharge pipe 14, and the discharge pipe, the hydrogen evolution transfer tank 59, the electrolyte flow pump pipe stirrer provided with a pump 20-6 and a valve 19-5, and the hydrogen driving liquid spraying pipe 13 are connected by pipes, so that the catholyte containing hydrogen bubbles circulates and carries out the hydrogen evolution to leave the electrolytic tank. The discharge pipe of each cathode box is connected to a three-way pipe or a four-way pipe provided with a hydrogen outlet 66 and a valve, forming a pipe type gas-liquid separator 10, and these gas-liquid separators 10 are connected by pipes to the hydrogen evolution transfer tank 59. The hydrogen evolution transfer tank 59 is connected by pipes to the electrolyte flow pump pipe stirrer and the liquid inlet of each hydrogen driving liquid spraying pipe 13. The hydrogen evolution transfer tank 59 is additionally provided with a hydrogen outlet 66 to form a tank type gas-liquid separator.

[0190] The tank 1-2 is divided into an anode tank area and a cathode tank area by the electrolytic tank partition 5, and the cathode tank area is provided with the hydrogen outlet 66, which is combined with the cathode tank area of the tank 1-2 to form a tank type gas-liquid separator. The two ports of the electrolytic tank liquid flow pump pipe stirrer 11-4 are connected by pipes to the cathode tank area electrolyte overflow pipe of the tank 1-2 and the hydrogen driving liquid spraying pipe, and the hydrogen driving liquid spraying pipe is arranged in the cathode tank area below the electrolytic cathode.

[0191] The solid-liquid separator 36-1, 36-2, 36-3 and 36-5 are filter core type filter machines for collecting copper powder from cathode electrolyte. The solid-liquid separator 36-2 is installed on the pipeline of the cathode electrolyte feeding pipe 63. The solid-liquid separator 36-3 is installed on the pipeline of the self-circulation flow of the hydrogen gas transfer tank 59 for collecting copper powder. The solid-liquid separator 36-4 is a filter press which is connected with the anode tank area through pipeline and pump for collecting copper oxide powder from the reacted anode electrolyte. The filter press 36-4 is installed on the pipeline of the filter press and the chemical reaction tank 61 for fine filtering copper oxide powder from the filtrate of the filter press. The solid-liquid separator 36-1 is a component of the cathode electrolyte suction assembly for filtering solid substances from the cathode electrolyte. The solid-liquid separator 36-6 is installed on the pipeline of the chemical reaction tank 61-2 and the temporary storage tank 37-3 for filtering trace amount of copper oxide powder 32 from the solution of the chemical reaction tank 61-2. The solid-liquid separator 36-7 is a centrifuge for separating solid mixture of the anode tank area of the tank 1-2 to obtain high quality copper oxide powder 32-2.

[0192] The sensors 39-1, 39-2, 39-6, 39-8, 39-10 are liquid level meters, 39-4 is a pH meter, 39-3 is a temperature meter, 39-5, 39-9 and 39-15 are ORP meters. The sensors 39-5 and 39-15 automatically detect the output current of the electrolysis power sources 44-1 and 44-2 respectively through the automatic detection feeding controller 40 to control the process, so that the two electrolysis tanks can react safely according to the process requirements. The sensor 39-9 is used to feed sodium hypochlorite solution to the chemical reaction tank 61-2 to participate in the oxidation reaction with the ammonia-nitrogen-containing waste liquid 27. The sensor 39-7 is installed in the hydrogen gas transfer tank 59 for detecting the concentration of sodium hydroxide in the cathode electrolyte and adding it to the anode electrolyte transfer tank 6 through the control of the starting pump 20-4. The sensors 39-11 and 39-12 are current meters of the motor for detecting the working state of the motor. The sensor 39-16 is a pressure gauge for detecting the flow pressure of the cathode liquid high-pressure pump assembly 56 to control the rotating speed of the pump 20-6. The sensor 39-13 is a hydrogen concentration detector and the sensor 39-14 is a chlorine concentration detector, both of which are installed in the working atmosphere of the production workshop. The sensor 39-3 installed in the anode electrolyte transfer tank area is a temperature meter for controlling the working condition of the cold and hot temperature exchanger 49. The sensor 39-4 is a pH meter for controlling the pump 20-2 to feed sodium hydroxide 22 solution to the anode tank area of the tank 1-1.

[0193] The automatic detection feeding controller 40 is programmed according to the process requirements and automatically controls the operation of the device.

[0194] The hydrogen output pipeline of each valve-equipped gas-liquid separator 10 in the tank body 1-1 is connected to the hydrogen inlet pipeline of the vacuum jet 34 above the organic waste liquid hydrogenolysis and hydrogenation reaction tank 55, and hydrogen is used in the organic waste liquid hydrogenolysis and hydrogenation reaction tank 55 to carry out hydrogenolysis and hydrogenation reduction reaction on the organic waste liquid.

[0195] The hydrogen high-altitude discharge pipeline is connected to the gas outlet of the organic waste liquid hydrogenolysis and hydrogenation reaction tank 55, the hydrogen gas transfer tank 59, and the hydrogen outlet of the electrolytic tank 1-2, and the hydrogen tail gas is guided to high-altitude discharge. Two air blowers are installed on the communication pipe of the hydrogenolysis and hydrogenation reaction tank 55, the hydrogen gas transfer tank 59, and the hydrogen outlet of the electrolytic tank 1-2 and the hydrogen high-altitude discharge pipeline to assist the hydrogen tail gas to be discharged to high altitude, and the hydrogen concentration in the pipe is reduced to below the explosion limit by blowing air, and then quickly diffused to high altitude.

[0196] The tail gas treatment tank 33 is connected to the gas outlet of the anode tank area of the tank body 1-1 and 1-2, all temporary storage tanks, and chemical reaction tanks, and the tail gas G discharged from each tank is introduced into the tank 23 for environmental protection treatment.

[0197] The cold and hot temperature exchanger 49-1 is installed on the electrolytic tank 1-1, and the cold and hot temperature exchanger 49-2 is installed on the tank body of the anode tank area of the electrolytic tank 1-2, to control the temperature of the reaction liquid and make the production safe and efficient.

[0198] The chemical reaction tank 61-1 is used to prepare the starting anode electrolyte. The chemical reaction tank 61-2 is used for oxidation treatment of the ammonia-nitrogen-containing waste liquid, and the chemical reaction tank 61-2 is connected to the solid-liquid separator 36-5 and the temporary storage tank 37-3 respectively.

[0199] The liquid flow agitator 47-3 is the agitator of the anode tank area of the tank body 1-2, and the pipeline of the agitator is a titanium metal pipeline, and an ultrasonic generator 64 is installed on the titanium metal pipeline to break the copper sludge clumps flowing through the pipeline.

[0200] The temporary storage tank 37-1 is used to load the alkaline pH value adjusting agent, the temporary storage tank 37-2 is used to load the crude copper oxide 32-1, the temporary storage tank 37-3 is used to load the alkaline waste brine 48, the temporary storage tank 37-4 is used to load the sodium hypochlorite solution, and the temporary storage tank 37-5 is used to temporarily store the high-quality copper oxide product 32-2.

[0201] The hydrogen driving liquid pipe 13 of the cathode box of the groove body 1-1 in the device of the embodiment is connected with the hydrogen evolution gas transfer groove 59, and the cathode liquid strong pressure pump filling assembly 56 is installed on the hydrogen driving liquid pipe 13. The cathode liquid strong pressure pump filling assembly 56 plays the role of a cathode groove area liquid flow pump pipe stirrer. The cathode liquid suction assembly 57 is installed on the backflow pipe of the hydrogen driving liquid pipe 13. When the bottom sediment of the cathode box needs to be sucked, the automatic detection feeding controller 40 stops the electrolysis power supply 44-1 according to the design program, closes the valve 19-5 and stops the pump 20-6, opens the valve 19-4 and starts the pump 20-3 to perform the suction action. The sucked cathode electrolyte is filtered by the solid-liquid separator 36-1 and then flows into the groove 59. After the program is completed, the pump 20-3 is stopped and the valve 19-4 is closed, the valve 19-5 is opened, the pump 20-6 is restarted and the electrolysis power supply 44 is connected to restore normal operation. Because the outlet of the hydrogen evolution gas transfer groove 59 is connected to the hydrogen driving liquid pipe of each cathode box, the cathode liquid strong pressure pump filling assembly 56 is installed. When the strong pressure injection of the cathode liquid into each cathode box needs to be performed, the electrolysis power supply 44-1 should be stopped and the valves of each gas-liquid separator 10 should be closed. After the valve 19-5 is opened, the pump 20-6 is started to perform the action of pressure injection of the cathode liquid under the control of the pressure gauge 39-15, so that the copper mud outside the outermost filter cloth is squeezed out and falls back into the anode electrolyte to participate in the reaction. After the pressure injection program is completed, the valves of each gas-liquid separator 10 are opened and the pump 20-6 returns to the original speed. The electrolysis power supply 44-1 is connected again to restore normal operation.

[0202] The solid copper mud treated in the embodiment is the solid copper mud precipitated after the neutralization reaction of the alkaline copper chloride ammonia etching waste liquid of the circuit board and hydrochloric acid, and the solid copper mud obtained by the reaction of the acid copper chloride etching waste liquid and oxalic acid. That is, the treated reactants of the embodiment are a mixture of three kinds of solid copper mud of basic copper salt 28, copper oxalate 29 and copper ammonia complex 30, with a total weight of 45 kg, and also containing ammonium chloride and carbonate impurities. The main components are 10 kg of copper chloride ammonia, 1.5 kg of ammonium chloride, 3 kg of basic copper chloride and 30.5 kg of copper oxalate. The above-mentioned mixture of 45 kg of solid copper mud is put into the chemical reaction groove 61-1, and sodium chloride is further added to prepare the starting anode electrolyte of the groove body 1-1 containing 20 g / L of chloride ions. The starting cathode electrolyte of the groove body 1-1 is a 5% sodium hydroxide solution.

[0203] The starting anode electrolyte of the groove body 1-2 is an alkaline solid-liquid mixture prepared by mixing the crude copper oxide powder obtained after the oxidation treatment of the groove body 1-1, sodium chloride, sodium hydroxide and water, wherein the concentration of sodium hydroxide is 1 mol / L. The cathode electrolyte of the groove body 1-2 still uses a 5% sodium hydroxide solution.

[0204] The process of this embodiment is to separate the cathode and anode electrolyte in the tank 1-1, and to transfer part of the solution in the hydrogen gas transfer tank 59 to the anode electrolyte in the transfer tank 6 by adding the cathode electrolyte through the adding pipe 63 under process control. The anode electrolyte in the tank 1-1 is controlled to 35°C by the cold and hot temperature exchanger 49-1, and the sensor 39-4 pH meter controls the pump 20-2 to add sodium hydroxide solution 22 to the anode tank area of the tank 1-1 to maintain the pH of the anode electrolyte at 8.5.

[0205] The solid-liquid mixture in the anode tank area of the tank 1-2 is broken by a high-power ultrasonic generator during the oxidation process. The anode electrolyte is controlled to 60°C by the cold and hot temperature exchanger 49-2.

[0206] This embodiment uses a high-efficiency electro-oxidation method to treat copper sludge and / or tin sludge, which includes the following steps:

[0207] 1. Use the high-efficiency electro-oxidation device described above, and turn on the power of the device. The automatic detection and feeding controller 40 processes the data obtained by the on-site detection of the sensors, and sends instructions according to the designed process flow to make the device run according to the pre-programmed program.

[0208] 2. Add the starting anode electrolytic solid-liquid mixture in the chemical reaction tank 61-1 to the anode tank area of the tank 1-1 and the anode electrolyte transfer tank 6, and add 5% sodium hydroxide solution to the three cathode boxes and the hydrogen gas transfer tank 59.

[0209] 3. Add the prepared anode starting electrolytic solid-liquid mixture of the tank 1-2 to its anode tank area, and add 5% sodium hydroxide solution to its cathode tank area.

[0210] 4. Start the pumps according to the program control, turn on the two heat exchangers, start the two blowers, start the ultrasonic generator, and connect the two electrolysis power supplies 44-1 and 44-2 for electro-oxidation treatment. Sensor 39-4 controls pump 20-2 to add sodium hydroxide, so that sodium hypochlorite is generated in the anolyte of tank 1-1 under the condition of maintaining pH 8.5. Sodium hypochlorite reacts chemically with ammonia and copper sludge in the solution, while basic copper chloride generates copper oxide in the alkaline medium. During the operation, some copper ions in the anolyte of tank 1-1 migrate to the cathode under the action of the electric field. A trace amount of copper powder is electrolyzed in the electrolyte. The hydrogen gas electrolyzed by the cathode of tank 1-1 is carried by the circulating liquid to each gas-liquid separator 10 for separation and the hydrogen gas is guided to the organic waste liquid hydrogenolysis reaction tank 55 for reaction. The hydrogen tail gas discharged after the reaction and the hydrogen tail gas escaping from the hydrogen gas transfer tank 59 are guided by the negative pressure airflow generated by the blower to the hydrogen high-altitude emission pipe for safe high-altitude emission. During the process, the sensor 39-5 automatically adjusts the output current of the electrolysis power supply 44-1 according to the on-site detection data through the automatic detection feeding controller 40.

[0211] 5. Sensor 39-15 in the anode area of ​​tank 1-2 monitors and adjusts the working current of electrolysis power supply 44-2 to ensure normal oxidation reaction in tank 1-2.

[0212] 6. During the electrolysis reaction process, the anolyte in tank 1-1 is continuously sprayed onto each electrolytic anode through each spray pipe 53 and sprayed through the bottom spray pipe 54 to disperse the solid deposits accumulated at the bottom of the tank, creating conditions for the ammonia impurities and copper sludge in the anolyte of tank 1-1 to fully participate in the oxidation reaction. During the operation, the cathode electrolyte from the electrolytic hydrogen is sent to the hydrogen evolution gas transfer tank 59, and according to the control of sensor 39-7, part of the solution containing sodium hydroxide and ammonia in the hydrogen evolution gas transfer tank 59 is added to the anolyte transfer tank 6 through the cathode electrolyte addition pipe 63 to continue to participate in the anodic oxidation treatment. During the operation, the ORP value of the anolyte in tank 1-1 gradually increases and the temperature is controlled at 35℃, and the ORP value of the anolyte in tank 1-2 also increases with the reaction and the temperature is controlled at 60℃. The chloride ion concentration of the anolyte in both tanks will be maintained at about 20 g / L due to circulation.

[0213] 7. The process design requires that the automatic detection and feeding controller 40 issue an instruction to start the cathodic liquid high-pressure pump filling assembly 56 to inject cathodic liquid, so that the filter cloth is subjected to internal pressure and seeps liquid out of the anode tank area of ​​tank 1-1, so that the copper mud and copper oxide powder hanging on the filter cloth are squeezed out and fall into the anode electrolyte. At the same time, the process is set to perform cathodic liquid suction treatment through the cathodic liquid suction assembly 57 during operation, so as to reduce the copper powder reduced in the cathodic electrolyte from clogging the filter cloth from the inside.

[0214] 8. When the conversion rate of copper sludge to copper oxide in the anolyte reaches ≥ 94% according to the process setting, the electrolytic oxidation operation is considered complete; when the ORP value of the anolyte in tank 1-1 reaches 330mv, the anolyte is drawn for ammonia nitrogen impurity detection, and the detection result is that the anolyte still contains 74mg / L of ammonia nitrogen impurities, which does not meet the final process standard of ≤ 40mg / L. In addition, the solid copper sludge in the reaction has been basically converted into copper oxide, and the copper oxide contains only 6ppm of trace copper salt impurities.

[0215] 9. To efficiently use tank 1-1, the electrolysis power supply and the corresponding running pumps and cold-hot temperature exchanger 49-1 are turned off, valve 19-4 is closed, and valves 19-2 and 19-3 are opened. Pumps 20-7 and 20-8 are started to pump the solid-liquid mixture in the anode tank area and the anolyte in tank 6, which has been oxidized but still contains ammonia nitrogen impurities, to solid-liquid separators 36-4 and 36-5 for solid-liquid separation. The filter residue is crude copper oxide powder 32-1, and the filtrate is pumped to chemical reaction tank 61-2 and continues to be oxidized to remove ammonia by adding an appropriate amount of sodium hypochlorite solution controlled by an ORP meter.

[0216] 10. The solution in chemical reaction tank 61-2 continues to be oxidized by sodium hypochlorite solution, and a small amount of copper oxide powder is deposited at the bottom of the tank. Sampling detection shows that the solution contains 4mg / L of ammonia nitrogen impurities, meeting the process requirements. After filtration, the solution in chemical reaction tank 61-2 is pumped to temporary storage tank 37-3 for temporary storage.

[0217] 11. The automatic detection and feeding controller 40 controls the electrolysis power supply 44-2 to output an average voltage of 5.5V and an average current of 350A. After a period of electrolytic oxidation, the solid-liquid mixture in tank 1-2 is taken for detection, and the results fully meet the high-quality index requirements of copper oxide products. The detected solid-liquid mixture is centrifuged to obtain high-quality copper oxide product 32-2 as filter residue.

[0218] 12. During the electrolytic oxidation process, the waste gas emitted from the two anode tank areas and the exhaust gas G emitted from each tank is introduced into the tail gas treatment tank 33 for treatment.

[0219] 13. According to the instructions of the automatic detection and feeding controller 40, pump 20-1 is started again to add the initial solid-liquid mixture of anolyte to the anode tank areas of the two tanks, and the process re-enters the second round of electrolytic oxidation treatment.

[0220] 14. The copper oxide products 32-1 in temporary storage tanks 37-2, solid-liquid separators 36-5 and 36-6 are collected for preparation of the initial anolyte of electrolysis tank 1-2 to produce high-quality copper oxide products 32-2. Part of the solution in temporary storage tank 37-3 is pumped to chemical reaction tank 61-1 for recycling, and high-quality copper oxide products 32-2 are obtained by separating the solid-liquid mixture in solid-liquid separator 36-7.

[0221] Example 5

[0222] As shown in Fig. 5, the embodiment 5 of the present application uses the same device as that of the embodiment 1.

[0223] The solid tin sludge treated in this embodiment is 5 kg of stannous oxalate.

[0224] The starting cathode electrolyte is a mixed aqueous solution of 10% sodium hydroxide, 8% potassium hydroxide, 1% potassium carbonate and 1% sodium bicarbonate, with a pH value greater than pH 14. The starting anode electrolyte is a solid-liquid mixture of the cathode electrolyte and the above-mentioned 5 kg of solid copper sludge.

[0225] The method for treating copper sludge and / or tin sludge by high-efficiency electro-oxidation in this embodiment comprises the following steps:

[0226] 1. The high-efficiency electro-oxidation device shown in Fig. 5 is used to add the respective starting electrolytes to the anode tank area and the cathode tank area, and the concentration of chloride ions in the anode electrolyte is controlled to be 10 g / L and the pH value is greater than pH 14.

[0227] 2. The electrolyte flow pump agitator 11 and the electrolysis power supply 44 are started to perform electrolysis operation under the condition that the space temperature in the test workshop is 6°C. The electrolysis current is set to 30 A, and the average tank voltage is 4.8 V. The hydrogen gas generated by cathode electrolysis is discharged through the gas-liquid separator 10, the ORP value of the anode electrolyte continuously rises, and the process reaction heat is continuously released to raise the electrolyte temperature from 6°C to 30°C.

[0228] 3. The electrolytic oxidation operation is considered to be completed when the conversion rate of tin sludge in the anode electrolyte to stannous hydroxide reaches ≥98% according to the process setting. After 24 hours of electro-oxidation treatment, the anode electrolyte is manually detected, and the measured ORP value of the anode electrolyte is -30 mV. The stannous oxalate in the solution has been completely converted to stannous hydroxide Sn(OH)2 solid, and the running device is shut down.

[0229] 4. The stannous hydroxide solid product produced in this embodiment 5 is deposited at the bottom of the anode tank area, and the next step is to perform solid-liquid separation treatment on the stannous hydroxide product. The obtained stannous hydroxide can be used as raw material in the required industrial field, and can be further converted into other tin compounds for use.

[0230] Example 6

[0231] As shown in Fig. 5, the embodiment 6 of the present application uses the same device as that of the embodiments 1 and 5.

[0232] The solid copper sludge and solid tin sludge mixture treated in this example is a mixture of copper oxalate 0.1 kg and stannous oxalate 4.9 kg. The method steps of Example 5 are repeated, except that the starting anolyte is a solid-liquid mixture of the catholyte and the above 5 kg mixture, sodium chloride, and the non-conductive portion of the device through which the high-temperature liquid flows is made of high-temperature-resistant polytetrafluoroethylene resin material; during the electrolysis process, the anolyte chloride ion concentration is maintained at 100 g / L, and the temperature is controlled at 90°C; step 3 is considered to be completed when the conversion rate of copper sludge to copper oxide in the anolyte reaches ≥99% and the conversion rate of tin sludge to stannous hydroxide reaches ≥99%.

[0233] Comparative Example 1

[0234] The same solid copper sludge as in Example 1 is used, which is basic copper sludge containing ammonium ions 5 kg, of which there is 1 kg of basic copper carbonate, 3.2 kg of basic copper sulfate, and 0.3 kg of basic copper chloride.

[0235] The solid copper sludge is mixed with sodium hypochlorite solution for 48 hours. The amount of sodium hypochlorite used in this comparative example is 3 times the amount of sodium hypochlorite that can be produced by the amount of electricity used in Example 1. After the reaction is completed, it is measured that the conversion rate of copper sludge to copper oxide is 92%.

Claims

1. A method for treating copper sludge and / or tin sludge using efficient electro-oxidation, characterized in that, Includes the following steps: (1) A high-efficiency electro-oxidation device is provided, the high-efficiency electro-oxidation device including at least one high-efficiency oxidation electrolytic cell; the high-efficiency oxidation electrolytic cell is divided into an anode cell area and a cathode cell area by an electrolytic cell separator, the electrolytic anode is connected to the positive terminal of its electrolytic power supply and placed in the anode cell area, and the electrolytic cathode is connected to the negative terminal of its electrolytic power supply and placed in the cathode cell area. (2) A solid-liquid mixture containing ① solid copper mud and / or solid tin mud and ② chloride ions is added as the anolyte to the anode tank area of ​​the high-efficiency oxidation electrolytic cell. A solution or solid-liquid mixture containing soluble electrolyte is used as the cathode electrolyte. The electrolytic power supply is turned on to cause a chemical reaction in the anolyte to convert copper mud into copper oxide and / or a chemical reaction in the tin mud to convert tin hydroxide. (3) When the conversion rate of copper mud to copper oxide and / or the conversion rate of tin mud to stannous hydroxide in the anode electrolyte reaches the process set value, the electrolytic oxidation operation is considered to be completed, and the solid-liquid mixture in the anode tank area meets the process requirements. (4) Perform solid-liquid separation on the solid-liquid mixture in the anode tank area that has met the process requirements to obtain copper oxide and / or stannous hydroxide.

2. The method for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation according to claim 1, characterized in that, The solid copper mud contains at least one of the following: reducing anions, complexing ligands, ammonia, and ammonium ions; the solid tin mud contains reducing anions.

3. The method for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation according to claim 2, characterized in that, The electrolytic cell separator is specifically selected from at least one of polymer filter plates, ceramic filter plates, and filter cloth.

4. The method for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation according to claim 3, characterized in that, An electrolyte solution free of solid copper sludge and / or solid tin sludge is used as the electrolyte in the cathode cell; or a solid-liquid mixture containing solid copper sludge and / or solid tin sludge is introduced into the anode cell, allowing the solution in the anode cell to permeate through the electrolytic cell separator into the cathode cell, and then the solution is used as the electrolyte in the cathode cell.

5. The method for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation according to claim 4, characterized in that, During the electrochemical oxidation process using a high-efficiency electro-oxidation device, at least one of the following conditions (1) to (4) is controlled for the anolyte: (1) The working temperature of the anolyte is controlled between 6 and 90°C; (2) Control the chloride ion concentration in the anolyte to be ≥1 g / L; (3) Maintain the pH value of the anolyte ≥ 5.5; (4) Set the control range of the ORP value of the anolyte according to the actual situation and the required reaction rate, and / or set the ORP value (oxidation-reduction potential value) of the anolyte as the reaction endpoint value according to the actual situation to help confirm the conversion rate of copper sludge to copper oxide and / or the conversion rate of tin sludge to stannous hydroxide that meet the process requirements.

6. The method for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation according to claim 5, characterized in that, The working temperature of the anolyte is controlled between 30 and 70°C.

7. The method for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation according to claim 5, characterized in that, The chloride ion concentration in the anolyte is specifically controlled within the range of 1–190 g / L.

8. The method for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation according to claim 5, characterized in that, Maintain the pH value of the anolyte at ≥7.

9. The method for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation according to claim 5, characterized in that, An alkaline pH adjuster is added to the anolyte to control the pH value of the anolyte within the range set by the process during electrolysis. The alkaline pH adjuster is specifically selected from one or more of the following: alkaline cathode electrolyte after hydrogen is electrolyzed, alkaline solution containing the substance to be treated, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. The substance to be treated is copper oxalate and / or stannous oxalate and / or copper ammonia complex and / or ammonia and / or ammonium.

10. The method for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation according to claim 5, characterized in that, If the cathode electrolyte after the electrolysis operation contains untreated copper oxalate and / or stannous oxalate and / or copper ammonia complex and / or ammonia and / or ammonium dissolved from the anolyte, these cathode electrolytes shall be used as part or all of the anolyte in subsequent electrolysis operations for further oxidation treatment.

11. The method for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation according to claim 5, characterized in that, Ultrasonic waves are applied to the anolyte, or to a solid-liquid mixture containing solid copper sludge and / or solid tin sludge used to prepare the anolyte, to break up any agglomerated copper sludge and / or tin sludge.

12. The method for treating copper sludge and / or tin sludge using high-efficiency electro-oxidation according to claim 5, characterized in that, When the conversion rate of copper sludge to copper oxide and / or the conversion rate of tin sludge to stannous hydroxide in the anolyte reaches the process set value to complete the oxidation operation in step (3), there are still trace amounts of copper oxalate and / or stannous oxalate and / or copper ammonia complex and / or ammonia and / or ammonium in the anolyte. Then, the anolyte that has completed the electrolytic oxidation operation is mixed with external hypochlorite outside the high-efficiency oxidation electrolytic cell for further oxidation reaction. The remaining trace amounts of substances to be treated are further oxidized to free up the high-efficiency oxidation electrolytic cell for the next batch of anolyte to be electrolytically oxidized.

13. An apparatus for efficiently electro-oxidizing copper sludge and / or tin sludge using the method described in claim 1, characterized in that, It includes at least one high-efficiency oxidation electrolyzer, at least one electrolyzer liquid flow pump tube stirrer 11, and at least one hydrogen escape outlet 66; The high-efficiency oxidation electrolytic cell includes a cell body, an electrolytic cell separator, an electrolytic anode, an electrolytic cathode, and an electrolytic power source. The electrolytic cell separator divides the cell body into an anode cell area and a cathode cell area. The cathode cell area is a closed cell area structure and is provided with at least one inlet pipe and / or at least one outlet pipe. The electrolytic anode is connected to the positive terminal of the electrolytic power source and is placed in the anode cell area. The electrolytic cathode is connected to the negative terminal of the electrolytic power source and is placed in the cathode cell area. The electrolytic cell liquid flow pump tube agitator consists of a pump and connecting pipes, and is used to provide a circulating flow driving force for the electrolyte containing air bubbles; The cathode tank area of ​​the high-efficiency oxidation electrolyzer is connected to at least one electrolyzer liquid flow pump pipe agitator to form a liquid flow circulation; the hydrogen outlet is set in the cathode tank area of ​​the high-efficiency oxidation electrolyzer, and / or in a container and / or pipe section on the connection path between the cathode tank area of ​​the high-efficiency oxidation electrolyzer and the electrolyzer liquid flow pump pipe agitator, so that the two are combined to form a gas-liquid separator.

14. The apparatus according to claim 13, characterized in that, The gas-liquid separator is either a pipeline gas-liquid separator or a tank-type gas-liquid separator, allowing the gas-containing solution to release the gas from the solution through slow flow. When using a pipeline gas-liquid separator, at least one pipe section on the connection path between the cathode tank area of ​​the high-efficiency oxidation electrolyzer and the electrolyzer's liquid flow pump tube agitator is provided with one or more hydrogen outlets, and the inner diameter of the pipe section with the hydrogen outlet is sufficient to allow space for gas evolution when the gas-containing solution flows through it. When using a tank-type gas-liquid separator, a hydrogen outlet is provided in the cathode tank area of ​​the high-efficiency oxidation electrolyzer, and / or a hydrogen evolution transfer tank is added on the connection path between the cathode tank area of ​​the high-efficiency oxidation electrolyzer and the electrolyzer's liquid flow pump tube agitator, and a hydrogen outlet is provided therein.

15. The apparatus according to claim 14, characterized in that, The anode cell of the high-efficiency oxidation electrolyzer can be a closed cell or an open cell. If the anode cell is a closed cell, it is provided with at least one inlet and at least one outlet, and at least one vent is provided on the anode cell and / or the component connected to the anode cell.

16. The apparatus according to claim 15, characterized in that, The electrolytic cell liquid flow pump tube agitator includes valves for flow adjustment.

17. The apparatus according to claim 15, characterized in that, The high-efficiency electro-oxidation device includes at least two electrolytic cell liquid flow pump tube stirrers. The cathode cell area and anode cell area of ​​the high-efficiency oxidation electrolytic cell are respectively connected to different electrolytic cell liquid flow pump tube stirrers to form independent liquid flow circulation systems.

18. The apparatus according to claim 17, characterized in that, The anode tank area of ​​the high-efficiency oxidation electrolyzer adopts a closed tank area structure and is connected to at least one of the electrolyzer liquid flow pump pipes and agitators to form a liquid flow circulation, so that the anode tank area has the function of a gas-liquid separator for the anode electrolyte.

19. The apparatus according to claim 15, characterized in that, The materials used in the high-efficiency oxidation electrolytic cell are all corrosion-resistant materials; the surface material of the electrolytic anode in contact with the electrolyte is selected from at least one of gold, platinum, titanium-based coated insoluble anode, conductive graphite, and titanium; the surface material of the electrolytic cathode in contact with the electrolyte is selected from at least one of platinum, titanium, stainless steel, conductive graphite, titanium-based coated conductor, copper, and iron; the shape and structure of the electrolytic anode and electrolytic cathode are selected from one or more of the following: plate-shaped, block-shaped, mesh-shaped, filament-shaped, and strip-shaped.

20. The apparatus according to claim 19, characterized in that, A solid-liquid separator is added, which is connected to the high-efficiency oxidation electrolysis cell and / or at least one tank in the device via a pipeline, for solid-liquid separation of the solid-liquid mixture.

21. The apparatus according to claim 19, characterized in that, An anode electrolyte transfer tank is added for the release of gas or chemical reaction of the anode electrolyte. The anode electrolyte transfer tank is equipped with an inlet, an outlet and a gas outlet. The inlet or outlet is connected to the inlet of the anode tank area via a stirrer of the electrolytic cell liquid flow pump.

22. The apparatus according to claim 19, characterized in that, At least one cathode box is installed in a high-efficiency oxidation electrolytic cell to separate the anode and cathode areas of the cell. The cathode box is a box-shaped structure with an electric field line through-hole on at least one side. The electric field line through-hole is located on the path of the electric field lines between the electrolytic anode and the electrolytic cathode immersed in the electrolyte during electrolysis. The cell separator is fixedly attached to the electric field line through-hole. The electrolytic cathode is placed inside the cathode box, and the enclosed area inside the cathode box becomes the cathode area. The cathode box is provided with at least one discharge port and at least one inlet port.

23. The apparatus according to claim 19, characterized in that, A liquid spray pipe with its nozzle facing upward or at an angle is installed in the middle or lower part of the cathode tank area as a hydrogen-driving liquid spray pipe, and at least one overflow port is set in the cathode tank area at a position higher than the nozzle of the hydrogen-driving liquid spray pipe. The hydrogen-driving liquid spray pipe and the overflow port are respectively connected to the inlet / outlet of the electrolytic cell liquid flow pump pipe agitator in the cathode tank area to form a liquid flow circulation.

24. The apparatus according to claim 21, characterized in that, A pH meter and / or ORP meter shall be installed at least at one of the connecting pipes of the anode tank area, the anode electrolyte transfer tank, and the anode tank area and the anode electrolyte transfer tank.

25. The apparatus according to claim 24, characterized in that, An additional cathode electrolyte addition pipe is installed, which is equipped with a pump and a valve. One end of the pipe is connected to the cathode tank area and / or the hydrogen evolution transfer tank, and the other end is connected to the anode tank area and / or the anode electrolyte transfer tank, or its outlet faces the anode tank area and / or the anode electrolyte transfer tank. This pipe is used to add the cathode electrolyte after hydrogen evolution as an alkaline pH adjuster to the anode electrolyte according to process requirements.

26. The apparatus according to claim 19, characterized in that, in The cathode tank area is equipped with a high-pressure cathodic liquid filling assembly and / or a cathodic liquid suction assembly; the high-pressure cathodic liquid filling assembly is a liquid delivery pipe equipped with a pump, and its outlet is located in the cathode tank area; the cathodic liquid suction assembly is a liquid suction pipe equipped with a pump, and the suction port of the pipe is located in the middle of the cathode tank area or below.

27. The apparatus according to claim 19, characterized in that, An electrolyte jetting and circulating flow assembly is added to the anode tank area of ​​the high-efficiency oxidation electrolyzer to spray the electrolyte from the bottom of the anode tank area back into the anode tank area to prevent solids from depositing at the bottom of the anode tank area. The jetting circulating electrolyte assembly includes a jetting pipe equipped with a pump, and its outlet is located at the bottom of the anode tank area.

28. The apparatus according to claim 19, characterized in that, in The high-efficiency oxidation electrolyzer is equipped with a spray pipe in the anode tank area, with its nozzle close to and / or facing the electrolytic anode, and it is connected to the electrolytic cell liquid flow pump pipe agitator in the independent liquid flow circulation system of the anode tank area.

29. The apparatus according to claim 19, characterized in that, The hydrogen outlet is connected to a high-altitude emission pipeline or a hydrogenolysis and reduction reaction device.

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