Method and device for extracting copper and tin source materials from oxalate of copper and / or tin

Abstract

The invention discloses a method and a device for extracting copper and tin source materials from oxalate of copper and / or tin, which are characterized in that milder chemical reaction conditions are adopted for treatment, and the prepared copper source material and tin source material are used as production raw materials; the method comprises the following steps: (1) treating oxalate of copper and / or tin by adopting at least one of the following modes: mode I, carrying out chemical reaction on cupric oxalate and / or stannous oxalate and pypocholoride in an aqueous solution containing pypocholoride to generate a new copper sludge and / or tin sludge precipitate, and enabling carbon dioxide gas to escape in the reaction process; in the second mode, copper oxalate and / or stannous oxalate are / is subjected to a chemical reaction in a solution containing alkaline substances, new copper sludge and / or tin sludge precipitates are / is generated, and the alkaline substances comprise potassium-containing alkaline substances; and (2) solid-liquid separation is conducted on the solid-liquid mixture obtained after reaction in the step (1), filter residues A and filtrate B are obtained, and the filter residues A are new copper sludge and / or tin sludge.

Description

A method and device for extracting copper and tin source material from copper and / or tin oxalate Technical Field

[0001] The present invention belongs to the technical field of environmentally friendly waste treatment, recycling and reuse, and particularly relates to a method and device for extracting copper and tin source materials from copper and / or tin oxalates. Background Art

[0002] The etching process in the production of circuit boards is to remove the unnecessary copper on the copper-clad board by chemically corroding it with an etching solution, so that the required circuit pattern is formed. Commonly used etching solutions are acidic etching solutions and ammonia-alkaline etching solutions. In the micro-etching process, micro-etching solutions are used to corrode and thin the surface of the copper layer or roughen the copper surface. Both etching waste liquid and micro-etching waste liquid contain copper ions formed by the dissolution of metallic copper. When the etching solution is used to etch the circuit pattern preset on the copper-clad board, the circuit pattern is plated with a layer of tin metal as an anti-corrosion layer, and the exposed copper metal on the copper-clad board that is not protected by the tin layer reacts chemically with the etching solution and is corroded and removed. After the etching is completed, the original preset circuit pattern and the tin metal anti-corrosion layer on the through-hole need to be stripped off using a nitric acid-type tin stripping solution, which produces a nitric acid-type tin stripping waste liquid containing tin ions, which usually also contains a small amount of copper ions. The common acidic and micro-etching solutions mentioned above all come in both iron-containing and iron-free formulations. Examples include acidic copper chloride and ferric chloride etching solutions, acidic copper chloride etching solutions, sulfuric acid and hydrogen peroxide micro-etching solutions, and micro-etching solutions combining sulfuric acid with ferric sulfate and persulfate. Furthermore, the electroless tinning process also produces tin-containing wastewater. With the expansion of large-scale production, these processes result in manufacturers discharging large quantities of tin- and / or copper-containing wastewater daily.

[0003] Among existing technologies for recycling and reusing nitric acid-based tin stripping wastewater or chemical tin precipitation wastewater, one method involves using oxalic acid to recover tin metal. Alternatively, oxalic acid is used to recover copper oxalate and regenerate etching replenisher solution from circuit board acidic etching wastewater. These methods involve adding oxalic acid to the wastewater to cause precipitation of stannous oxalate and / or copper oxalate. The reactants are then subjected to solid-liquid separation to obtain a filter residue of stannous oxalate and / or copper oxalate. The filtrate obtained by the above method is mainly composed of nitric acid, which is obtained by reacting nitric acid-type tin stripping waste liquid with oxalic acid and performing solid-liquid separation. After adding concentrated nitric acid and additives for preparation, it becomes regenerated nitric acid-type tin stripping liquid and is returned to the tin stripping production line for use; and the filtrate obtained by reacting acidic etching waste liquid with oxalic acid and performing solid-liquid separation is mainly composed of hydrochloric acid. After removing the oxalic acid impurities in the filtrate, it can be returned to the acidic etching production line for recycling; after chemical precipitation tin waste liquid reacts with oxalic acid for solid-liquid separation to obtain tin salts, the filtrate is treated for environmental protection and discharged in compliance with standards. The above method of recovering metal salts using oxalic acid is simple, has low energy consumption, and has a high waste reuse rate. Therefore, more circuit board manufacturers have begun to adopt this method.

[0004] Because copper oxalate and stannous oxalate are relatively stable, few chemicals react with them under mild conditions. Furthermore, their applications are very limited, resulting in a narrow market. Therefore, copper oxalate and stannous oxalate need to be further processed to convert them into widely applicable copper and / or tin oxides and / or hydroxides, allowing them to serve as copper and tin source materials in a wider range of industrial production processes.

[0005] However, the current treatment method for the copper oxalate and / or stannous oxalate obtained from the wastewater treatment method mentioned above is mostly a high-temperature decomposition method, with a reaction temperature of at least 300°C. The chemical reaction is as follows:

[0006] A. Closed high temperature treatment equipment: SnC2O4→Sn+2CO2↑ CuC2O4→Cu+2CO2↑

[0007] B. Open high temperature treatment equipment: SnC2O4+O2→SnO2+2CO2↑ SnC2O4+O2+C→Sn+3CO2↑ 2CuC2O4+O2→2CuO+4CO2↑

[0008] Because high-temperature processes pose fire and burn hazards, and because pyrolysis consumes a lot of energy, most PCB manufacturers are reluctant to use pyrolysis to process copper and / or tin oxalates in their original production plants. Consequently, PCB manufacturers are eagerly awaiting the introduction of new processes that can process copper oxalate and / or stannous oxalate to produce copper or tin materials at room temperature and pressure. This would enable them to improve safety, reduce pollution, and achieve cost savings and increased efficiency.

[0009] Summary of the Invention

[0010] The first objective of the present invention is to provide a method for extracting copper and tin source materials from copper and / or tin oxalates, using milder chemical reaction conditions to produce copper and tin source materials for use as production raw materials. The second objective is to provide an apparatus for extracting copper and tin source materials from copper and / or tin oxalates.

[0011] The present invention achieves the above-mentioned purpose through the following technical solutions.

[0012] A method for extracting copper and tin source materials from copper and / or tin oxalates, comprising the following steps:

[0013] (1) treating copper and / or tin oxalates by at least one of the following methods:

[0014] Method 1: allowing copper oxalate and / or stannous oxalate to react chemically with hypochlorite in an aqueous solution containing hypochlorite to generate new copper sludge and / or tin sludge precipitate, with carbon dioxide gas escaping during the reaction process;

[0015] Method 2: allowing copper oxalate and / or stannous oxalate to undergo a chemical reaction in a solution containing an alkaline substance to generate new copper mud and / or tin mud precipitate, wherein the alkaline substance includes a potassium-containing alkaline substance;

[0016] (2) performing solid-liquid separation on the solid-liquid mixture after the reaction in step (1) to obtain a filter residue A and a filtrate B, wherein the filter residue A is new copper mud and / or tin mud.

[0017] The stannous oxalate described in step (1) is produced by reacting a tin-containing waste liquid with oxalic acid, or by reacting a filtrate obtained by filtering the tin-containing waste liquid to remove tin dioxide solids with oxalic acid. The copper oxalate described is produced by adding oxalic acid to a copper-containing waste liquid, mainly a circuit board acid etching waste liquid or a micro-etching waste liquid. The copper oxalate and / or stannous oxalate described above are both insoluble substances and can therefore be removed from the reaction solution by solid-liquid separation.

[0018] In the first embodiment of step (1), the hypochlorite used as the oxidant is sodium hypochlorite and / or potassium hypochlorite. In the second embodiment of step (1), the potassium-containing alkaline substance is one or more of potassium hydroxide, potassium carbonate, and potassium bicarbonate.

[0019] In step (2), the filter residue A is tin and / or copper oxides and / or hydroxides. It can be directly reused as a production raw material, or it can be selected according to the technical requirements of the recycling process to produce tin metal, tin salts, copper metal, copper oxide, cuprous oxide, and copper salts and then used as a production raw material. For example, tin salts, copper salts, and copper oxide can be reused in the electroplating production line.

[0020] In the first method of step (1), the oxalate of stannous oxalate and / or copper oxalate is oxidized by sodium hypochlorite and / or potassium hypochlorite, and the following redox reaction occurs: SnC2O4+ClO - +H2O→Cl - +Sn(OH)2↓+2CO2↑ CuC2O4+ClO - +H2O→Cl - +Cu(OH)2↓+2CO2↑

[0021] Therefore, in Method 1, the newly generated tin sludge precipitate is stannous hydroxide, which will convert to stannous oxide when the pH value of the reaction solution is high. When stannous hydroxide and stannous oxide are immersed in a reaction solution containing excessive hypochlorite for a long time, tin oxide (SnO2) will be generated. In Method 1, the newly generated copper sludge precipitate is copper hydroxide, which will convert to copper oxide when the pH value of the reaction solution is high. Therefore, when Method 1 is adopted, the main component of the filter residue A obtained in step (2) is at least one of stannous hydroxide, copper hydroxide, stannous oxide, tin oxide, and copper oxide, and the filtrate B is a solution containing chloride salts that is discharged after environmental treatment.

[0022] During the reaction process of the above-mentioned method 1, the ratio between the amount of copper hydroxide and copper oxide products generated varies with the pH value of the reaction solution, the length of reaction time, the temperature of the reaction solution and other factors in the process. The higher the pH value and temperature of the reaction solution, the more likely the new copper mud product generated by the reaction is to be copper oxide. Therefore, the appropriate reaction temperature and reaction solution pH can be determined based on practical experience by detecting the composition of the copper mud. Preferably, in method 1, in order to make the new copper mud product generated mainly copper hydroxide, the pH value of the reaction solution is controlled to be 3.5≤≤8.5 during the reaction. Preferably, in method 1, in order to make the new copper mud product generated mainly copper oxide, the pH value of the reaction solution is controlled to be ≥10 during the reaction.

[0023] The oxidant used in the chemical reaction in method 1 is preferably sodium hypochlorite solution to save costs.

[0024] Preferably, in Method 1, an oxidation-reduction potentiometer (ORP meter) is used to control the addition of hypochlorite during the oxidation process, or a combination of a pH meter and an ORP meter is used to control the addition of a pH adjuster and hypochlorite, respectively, so that the reaction solution maintains stable control parameters and reacts in the direction of the target product set by the process. The pH adjuster is preferably one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.

[0025] In the second embodiment of step (1), stannous oxalate and / or copper oxalate are mixed with a solution containing an alkaline substance containing potassium to react, and at least one of the following chemical reactions mainly occurs: SnC2O4+2KOH→K2C2O4+H2O+SnO↓ CuC2O4+2KOH→K2C2O4+H2O+CuO↓ SnC2O4+2K2CO3+H2O→K2C2O4+2KHCO3+SnO↓ CuC2O4+2K2CO3+H2O→K2C2O4+2KHCO3+CuO↓ SnC2O4+2KHCO3+H2O→K2C2O4+H2CO3+SnO↓ CuC2O4+2KHCO3+H2O→K2C2O4+H2CO3+CuO↓

[0026] In the second embodiment of step (1), the alkaline substance participating in the reaction is a potassium-containing alkaline substance alone, or a potassium-containing alkaline substance and a sodium-containing alkaline substance are used simultaneously. The sodium-containing alkaline substance is one or more of sodium hydroxide, sodium carbonate, and sodium bicarbonate. Preferably, the alkaline substance is potassium hydroxide, or potassium hydroxide and sodium hydroxide are used simultaneously. More preferably, the alkaline substance is potassium hydroxide.

[0027] Therefore, the main components of the filter residue A obtained in step (2) of the second method are stannous oxide and / or copper oxide, and the main components of the filtrate B are potassium oxalate or potassium oxalate and sodium oxalate, which can be reused as raw materials for other production.

[0028] When the alkaline substances involved in the reaction of the above-mentioned method 2 include sodium-containing alkaline substances, i.e., sodium hydroxide and / or sodium carbonate and / or sodium bicarbonate, sodium oxalate will be generated. Due to the low solubility of sodium oxalate, when a large amount of sodium oxalate is generated in the reaction solution, it will reach saturation in the solution and precipitate sodium oxalate solids, which will co-precipitate with stannous oxide and / or copper oxide. Although washing stannous oxide and / or copper oxide with water in the subsequent process can remove most of the sodium oxalate impurities therein, the problem of stannous oxide and / or copper oxide encapsulating sodium oxalate during the co-precipitation process not only increases the processing steps, but also increases the difficulty of purifying the copper source or tin source material. Therefore, in the method 2 of step (1), sodium-containing alkaline substances cannot be used alone to react to avoid excessive sodium oxalate generation, which will lead to a large amount of sodium oxalate co-precipitated with stannous oxide and / or copper oxide. In addition, the use of sodium-containing alkaline substances alone will also result in a low sodium oxalate concentration in the filtrate after solid-liquid separation due to the low solubility of sodium oxalate, resulting in a reduced value of the oxalic acid material in the filtrate for reuse.

[0029] In contrast, potassium oxalate has a high solubility and is not easily precipitated during the reaction. Therefore, using potassium-containing alkaline substances as part or all of the alkaline substances in the second method can have the following advantages: (1) reducing the washing work of stannous oxide and / or copper oxide, (2) effectively preventing stannous oxide and / or copper oxide from encapsulating sodium oxalate, and (3) the filtrate obtained after solid-liquid separation has a high oxalate content and therefore has a high recycling value.

[0030] Preferably, when the potassium-containing alkaline substance and the sodium-containing alkaline substance are simultaneously used for the reaction in the second method of step (1), the amount of sodium ions added to the reaction solution does not exceed 2 mol / L, more preferably does not exceed 1 mol / L.

[0031] In the second method of step (1), copper oxalate and / or stannous oxalate are subjected to a chemical reaction in a solution containing an alkaline substance. Preferably, the reaction temperature of the reaction solution is controlled within the range of 30°C to 100°C, and / or the pH value of the reaction solution is adjusted to ≥10 during the reaction. The above preferred method can accelerate the reaction of method 2.

[0032] The present invention can be improved as follows: when the oxalate reacted in step (1) is a mixture of stannous oxalate and copper oxalate, in order to separate the copper compound and the tin compound in the reaction product, filter residue A, the hydroxide precipitation points corresponding to different pH values ​​in the metal salt solution can be used to separate the copper-tin mixed compound. First, the filter residue A is dissolved in an acidic solution to obtain an acidic mixed solution containing tin salt and copper salt; an alkaline compound is added to the obtained acidic mixed solution containing tin salt and copper salt to adjust its pH value, and the low pH precipitation point of stannous hydroxide is used to control the solution to produce stannous hydroxide precipitate, and a solid-liquid separation method is used to separate the stannous hydroxide solid from the acidic copper salt solution. The acidic solution is a solution containing at least one of hydrochloric acid, sulfuric acid, and formic acid, preferably containing sulfuric acid. Preferably, the alkaline compound is at least one selected from sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, and potassium bicarbonate. The suitable pH value for separating stannous hydroxide from the acidic copper salt solution is adjusted to a range of 0.9 to 4.17, preferably a pH value of 2 to 3.2.

[0033] After removing the tin salt from the acidic solution containing the tin and copper salts, the resulting acidic copper salt solution is a mixture containing non-heavy metal salts and copper salts. To obtain a pure copper source material, an alkaline compound is added to the mixture until the pH of the solution reaches >3.5, causing copper hydroxide and / or copper oxide precipitates to form in the solution. The reaction mixture is subjected to solid-liquid separation to obtain a filter residue of copper hydroxide and / or copper oxide, and the filtrate is disposed of for environmental protection.

[0034] The present invention can be improved as follows: when the second method is adopted in step (1), the filtrate B obtained in step (2) is further mixed with a compound containing at least one of calcium, manganese, zinc, and ferrous elements to produce the desired oxalate or other products according to market demand. Preferably, the compound is selected from one or more of ferrous salts, calcium salts, and calcium hydroxide. More preferably, ferrous sulfate or calcium hydroxide is used. Taking the reaction of potassium oxalate with ferrous salt, manganese salt, calcium salt, calcium hydroxide and zinc salt as an example, the chemical reaction formulas of the above mixed reactions are as follows: K2C2O4+FeSO4→FeC2O4↓+K2SO4, K2C2O4+CaCl2→CaC2O4↓+2KCl, K2C2O4+MnSO4→MnC2O4↓+K2SO4, K2C2O4+Ca(OH)2→CaC2O4↓+2KOH, K2C2O4+CaCO3→CaC2O4↓+K2CO3, K2C2O4+Ca(HCO3)2→CaC2O4↓+2KHCO3, K2C2O4+ZnCl2→ZnC2O4↓+2KCl.

[0035] When ferrous sulfate is mixed with filtrate B for a reaction, a high-value ferrous oxalate product and potassium sulfate, a highly demanded agricultural fertilizer product, can be produced, thereby improving production economic benefits. When one or more of calcium hydroxide, calcium carbonate, and calcium bicarbonate are mixed with filtrate B for a reaction, a calcium oxalate product is produced. The regenerated alkaline substance can be reused in the next round of copper oxalate and / or stannous oxalate treatment, achieving recycling, being more environmentally friendly, and saving costs.

[0036] In step (1), when the substance to be treated contains stannous oxalate, whether using method 1 or method 2, because tin is an amphoteric metallic element, when the alkalinity of the reaction solution is high, soluble stannates will be generated, reducing the recovery rate of the new tin sludge precipitate. Preferably, the pH value of the reaction solution when treating stannous oxalate in step (1) is ≤14 to avoid the formation of soluble stannates.

[0037] The present invention can be improved as follows: the filter residue A is washed with water to obtain pure tin and / or copper hydroxide and / or oxide, thereby reducing the impurity content therein and making it more convenient for use. The waste liquid from washing the filter residue A is treated in an environmentally friendly manner and then discharged.

[0038] The present invention can also be improved as follows: the chlorine gas produced when the acidic etching waste liquid is electrolyzed is used to prepare a hypochlorite solution, and applied to the chemical reaction of method one in step (1). Specifically: the acidic etching waste liquid is electrolyzed, chlorine gas is generated at the electrolytic anode, and the produced chlorine gas is introduced into an alkaline solution to prepare hypochlorite. In the prior art, there is an electrolytic cell that electrolytically oxidizes the acidic etching waste liquid to produce chlorine gas, or at the same time, the electrolytic cathode is used to electrolyze metallic copper. This improvement saves costs and can consume excess chlorine gas electrolyzed during electrolysis. Preferably, the alkaline solution contains at least one alkaline compound selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. The chemical reaction principle for preparing hypochlorite is as follows. 2NaOH+Cl2→NaClO+NaCl+H2O 2KOH+Cl2→KClO+KCl+H2O

[0039] Preferably, copper oxalate is first added directly to the alkaline solution reaction tank for producing hypochlorite. Then, an ORP meter installed in the reaction tank is used to control the amount of chlorine gas introduced into the reaction tank. The amount of alkaline compound added is also controlled to adjust the pH value of the reaction solution to meet the process requirements, so that the reaction product is mainly CuO to produce copper oxide powder. The chemical reaction is as follows: CuC2O4+ClO - +H2O→Cl - +Cu(OH)2+2CO2↑, 2Cu(OH)2+NaClO+NaOH→2NaCuO2+HCl+2H2O, 2NaCuO2+CuC2O4+H2O→3CuO+2NaOH+2CO2↑.

[0040] The present invention can also be improved as follows: the copper oxalate precipitate obtained by the reaction of the iron-containing acidic etching solution with oxalic acid is pickled at least once with hydrochloric acid and / or sulfuric acid to remove iron. Preferably, hydrogen peroxide is added to the pickling solution of the copper oxalate for pickling to reduce the generation of ferrous oxalate. Because when copper oxalate is taken from the iron-containing acidic etching solution, the filter residue of the copper oxalate will contain iron salts after solid-liquid separation, and hydrochloric acid and / or sulfuric acid can be used to clean and remove it from the copper oxalate solid. Taking the acidic copper chloride and ferric chloride etching solution as an example, its chemical reaction is as follows. 2FeCl3+H2C2O4→2FeCl2+2HCl+2CO2↑ FeCl2+H2C2O4→2HCl+FeC2O4↓

[0041] Therefore, the cupric oxalate obtained by reacting oxalic acid with acidic cupric chloride and ferric chloride etching solution contains impurities of ferrous oxalate and ferric chloride. Similarly, when cupric oxalate is taken from a mixed micro-etching solution of sulfuric acid, ferric sulfate, copper sulfate and persulfate, the filter residue of the cupric oxalate contains impurities of ferric sulfate.

[0042] The present invention also provides a device for extracting copper and tin source materials from copper and / or tin oxalates, which mainly includes: at least one hypochlorite reaction tank and / or at least one alkali solution reaction tank, and at least one solid-liquid separator.

[0043] The hypochlorite reaction tank is used for reacting copper oxalate and / or stannous oxalate with hypochlorite in the above step (1) to mainly produce stannous hydroxide and / or copper hydroxide and / or copper oxide. The alkali solution reaction tank is used for reacting copper oxalate and / or stannous oxalate with a solution containing potassium-containing alkaline substances in step (1) to mainly produce stannous oxide and / or copper oxide.

[0044] The solid-liquid separator is used to separate the solid-liquid mixture during the process reaction. The solid-liquid separator is selected from at least one of a filter press, a centrifuge and a filter.

[0045] The present invention can be improved as follows: the alkali solution reaction tank is provided with a hot and cold temperature exchanger, specifically a heater, to become an alkali solution reaction tank with a heater, so that copper oxalate and / or tin oxalate react with a solution containing a potassium-containing alkaline substance under heating conditions to quickly produce stannous oxide and / or copper oxide.

[0046] The present invention can also be improved as follows: a pH meter and / or an ORP meter can be added to the hypochlorite reaction tank to control the reaction process toward the process target reactant.

[0047] The present invention can also be improved as follows: a cleaning tank is added to clean the iron-containing copper oxalate and / or the copper and / or tin compound filter residue obtained by the reaction to obtain clean copper oxalate or pure stannous hydroxide, copper hydroxide, stannous oxide, and copper oxide products.

[0048] The present invention can also be improved as follows: a temporary storage tank is added to temporarily store materials.

[0049] The present invention can also be improved as follows: a common chemical reaction tank is added for preparing the solution.

[0050] The present invention can also be improved as follows: an agitator is added to the hypochlorite reaction tank and / or the alkali solution reaction tank and / or the ordinary chemical reaction tank to uniformly stir the solution. The agitator is structurally divided into an impeller agitator and a liquid flow pump tube agitator.

[0051] The present invention can also be improved as follows: a hot and cold temperature exchanger is added to the hypochlorite reaction tank and / or the ordinary chemical reaction tank to control the temperature of the reaction liquid according to the process requirements.

[0052] The present invention can also be improved as follows: an exhaust gas processor is added to perform environmentally friendly treatment on the exhaust gas discharged from each tank.

[0053] The present invention can also be improved by adding detection sensors and an automatic detection and feeding controller to enable automated program control during the production process through data collection and processing. The sensor signal input of the automatic detection and feeding controller is connected to the sensor signal output of the detection sensor, and the control signal output of the automatic detection and feeding controller is connected to the control signal inputs of the heater, hot and cold temperature exchanger, agitator, valve, and pump within the device. The detection sensors include a thermometer, a liquid level gauge, an acidity meter, a pH meter, a hydrometer, a redox potentiometer, and a chlorine concentration meter.

[0054] The present invention can also be improved as follows: an electric furnace is added to dry the product powder obtained after solid-liquid separation.

[0055] The present invention can also be improved as follows: an overflow buffer tank is added to solve the problem of liquid flow between the tanks in the device.

[0056] The present invention can also be improved by adding an electrolytic cell, in which the chlorine produced by electrolysis using the acidic etching waste liquid as the electrolyte is used to prepare the hypochlorite solution. The electrolytic cell is provided with a separator, which is divided into an anode cell area and a cathode cell area. The separator serves to facilitate the collection and utilization of the chlorine produced by the electrolysis anode.

[0057] Compared with the prior art, the present invention has the following beneficial effects:

[0058] 1. The process of the present invention abandons the prior art method of treating copper oxalate and / or tin oxalate by high-temperature decomposition, and adopts milder chemical reaction conditions. This makes it more likely that companies will use stannous oxalate and / or copper oxalate obtained from waste liquid to produce tin or copper source materials on-site, and even reuse the obtained tin and copper source materials in their own production processes, thereby significantly reducing production costs. Compared with the existing high-temperature decomposition method, it can greatly improve production safety and reduce energy consumption.

[0059] 2. The present invention can combine the electrolysis process to produce hypochlorite solution by electrolyzing chlorine gas in the process of electrolytic copper extraction from acidic etching waste liquid, thereby reducing the processing cost of extracting tin source materials or copper source materials.

[0060] 3. The process of the present invention does not add any new pollution sources during the treatment process, and meets the requirements of environmentally friendly production processes.

[0061] 4. The process of the present invention is safe, reliable and easy to operate, with low equipment investment and operation and management costs.

[0062] 5. The present invention can utilize oxalate ions in stannous oxalate or copper oxalate to produce other oxalate products, thereby maximizing material utilization, reducing environmental pollution and saving energy. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] FIG1 is a device and process flow chart for extracting copper and tin source materials from copper and / or tin oxalates according to Example 1 of the present invention.

[0064] FIG2 is a flow chart of an apparatus and process for extracting copper and tin source materials from copper and / or tin oxalates according to Example 2 of the present invention.

[0065] Figures 3 and 4 constitute an apparatus and process flow chart for extracting copper and tin source materials from copper and / or tin oxalates according to Example 3 of the present invention, wherein Figure 4 is the left part of the apparatus and Figure 5 is the right part of the apparatus diagram.

[0066] 5 , 6 and 7 constitute a device and process flow chart for extracting copper and tin source materials from copper and / or tin oxalate according to Example 4 of the present invention.

[0067] 8 and 9 constitute an apparatus and a process flow chart for extracting copper and tin source materials from copper and / or tin oxalates according to Example 5 of the present invention, wherein FIG8 is the left portion of the apparatus and FIG9 is the right portion of the apparatus diagram.

[0068] 10 and 11 constitute a device and a process flow chart for extracting copper and tin source materials from copper and / or tin oxalate according to Example 6 of the present invention.

[0069] FIG12 is a flow chart of an apparatus and process for extracting copper and tin source materials from copper and / or tin oxalates according to Example 7 of the present invention.

[0070] FIG13 is a flow chart of an apparatus and process for extracting copper and tin source materials from copper and / or tin oxalates according to Example 8 of the present invention.

[0071] FIG14 is a flow chart of an apparatus and process for extracting copper and tin source materials from copper and / or tin oxalates according to Example 9 of the present invention.

[0072] Figure Symbols: 1-hypochlorite reaction tank, 2-alkali solution reaction tank, 3-general chemical reaction tank, 4-cleaning tank, 5-solid-liquid separator, 6-temporary storage tank, 7-impeller agitator, 8-liquid flow pump tube agitator, 9-cold and hot temperature exchanger, 10-exhaust gas processor, 11-detection sensor, 12-automatic detection and feeding controller, 13-tin-containing and / or copper-containing waste liquid, 14-solid mixture of copper oxalate and stannous oxalate, 15-copper oxalate, 16-stannous oxalate, 17-oxalic acid, 18-solution mainly containing soluble oxalate, 19-crude stannous hydroxide, 20-crude copper hydroxide, 21-crude stannous oxide, 22-crude copper oxide, 23-pure stannous hydroxide, 24-pure stannous oxide, 25-pure copper hydroxide, 26-pure copper oxide, 27-acidic solution, 28-alkaline solution, 29-immersion tin plating solution, 30-chemical tin plating solution, 31-acid electroplating tin plating solution, 32-chemical tin production line, 33-water, 34-pure hydrochloric acid, 35-pure sulfuric acid, 36-stannous chloride solution, 37-stannous sulfate solution, 38-metal tin block, 39-tinned parts, 40-prepared tin Other raw materials for tin plating solution, 41-Other raw materials for preparing chemical tin plating solution, 42-Other raw materials for preparing acid electroplating tin plating solution, 43-Salt waste liquid, 44-Hypochlorite solution, 45-Valve, 46-Pump, 47-Electric furnace, 48-Carbon dioxide gas, 49-Sealing tank cover, 50-Spray tower, 51-Vacuum ejector, 52-Overflow buffer tank, 53-Filter residue C, a mixture of tin and copper compounds with less impurities, 54-Acid copper chloride etching line, 55-Acid electroplating Tin plating production line, 56-electrolytic cell, 57-electrolytic cell separator, 58-electrolytic anode, 59-electrolytic cathode, 60-electrolytic power supply, 61-acidic copper chloride etching waste liquid, 62-sodium percolate, 63-copper metal, 64-evaporator, 65-solid potassium oxalate, 66-calcium hydroxide, 67-ferrous sulfate, 68-calcium oxalate, 69-ferrous oxalate, 70-potassium sulfate, 71-copper oxalate containing iron impurities, 72-hydrogen peroxide, 73-solid sodium oxalate, 74-solid alkaline substance. DETAILED DESCRIPTION

[0073] The present invention will be further described below through specific embodiments.

[0074] The present invention uses an 800-liter hypochlorite reaction tank, an 800-liter alkali liquor reaction tank, an 800-liter conventional chemical reaction tank, and a 1000-liter cleaning tank in the embodiments. The above tanks and the tail gas processor are all products of Yegao Environmental Protection Equipment Manufacturing Co., Ltd. in Foshan City, Guangdong Province, China. The solid-liquid separator, 2000-liter temporary storage tank, chemical tin precipitation production line, electrotin plating production line, acid copper chloride etching line, agitator, sensor, automatic program controller, hot and cold temperature exchanger, electric furnace, valve, pump, and chemical raw materials are all commercially available products. The stannous oxalate and cupric oxalate processed are obtained by adding oxalic acid to tin-containing and / or copper-containing waste liquid. In addition to the above enumeration, those skilled in the art can also select other products with similar performance to the above-mentioned products enumerated in the present invention according to routine selection, all of which can achieve the purpose of the present invention.

[0075] Example 1

[0076] As shown in FIG1 , the apparatus for extracting copper and tin source materials from copper and / or tin oxalate according to Example 1 includes a hypochlorite reaction tank 1 , a solid-liquid separator 5 , a temporary storage tank 6 , an impeller stirrer 7 , valves, and a pump.

[0077] The hypochlorite reaction tank 1 is connected to a solid-liquid separator 5 , which is a filter and is further connected to a temporary storage tank 6 .

[0078] In this embodiment, stannous oxalate 16 is to be treated, and the hypochlorite solution 44 used is a mixture of sodium hypochlorite and potassium hypochlorite, wherein the hypochlorite concentration is 9%, the pH value is 14, and the specific gravity is 1.069 g / ml.

[0079] The method of extracting copper and tin source materials from copper and / or tin oxalates in this embodiment includes the following steps.

[0080] 1. A fixed amount of water and 20 kg of stannous oxalate 16 are added to a hypochlorite reaction tank 1. Then, a hypochlorite solution 44 is slowly added to react with the stannous oxalate. The amount of hypochlorite added is 1.1 times the reaction equivalent of stannous oxalate. An impeller stirrer 7 in the hypochlorite reaction tank 1 is started, and a chemical reaction is carried out for 1 hour to obtain a new tin sludge precipitate.

[0081] 2. Start pump 46 to separate the reactants from hypochlorite reaction tank 1 through solid-liquid separator 5 to obtain filter residue A and filtrate B. Filter residue A is mainly crude stannous hydroxide 19, which is retained in the filter. Filtrate B is saline waste liquid 43. After the reaction is complete, remove the stannous hydroxide product.

[0082] 3. During the filtration process, the salty waste liquid 43 is drained into the temporary storage tank 6 for temporary storage.

[0083] After the above steps, stannous oxalate is subjected to the chemical reaction of the first embodiment of the present invention to obtain a stannous hydroxide product.

[0084] Example 2

[0085] As shown in FIG2 , an apparatus for extracting copper and tin source materials from copper and / or tin oxalates according to Example 2 of the present invention is shown, which includes an alkali solution reaction tank 2, a cleaning tank 4, two solid-liquid separators 5, two temporary storage tanks 6, two impeller stirrers 7, valves, and pumps.

[0086] The alkali liquid reaction tank 2 is connected to the solid-liquid separator 5-1, and the cleaning tank 4 is connected to the solid-liquid separator 5-2. The two solid-liquid separators are also connected to their corresponding temporary storage tanks. A sealing tank cover 49 is provided on the top of the alkali liquid reaction tank 2.

[0087] The solid-liquid separator 5-1 is a centrifuge, and 5-2 is a filter press.

[0088] The impeller stirrer 7 - 1 is disposed in the alkali solution reaction tank 2 , and the impeller stirrer 7 - 2 is disposed in the cleaning tank 4 .

[0089] In this embodiment, the substance to be treated is copper oxalate 15, and the alkaline solution 28 used is a mixture of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate, with a solution specific gravity of 1.3 g / ml.

[0090] The method of extracting copper and tin source materials from copper and / or tin oxalates in this embodiment includes the following steps.

[0091] 1. Add a fixed amount of water and a fixed amount of 20 kg of copper oxalate 15 to an alkali solution reaction tank 2, then add an alkaline solution 28 until the weight of the alkaline substance is greater than twice the equivalent number of the reaction with the copper oxalate and the amount of sodium ions in the reaction solution is 1 mol / L. A chemical reaction is carried out, and the impeller stirrer 7-1 is started and the chemical reaction is carried out at room temperature for 24 hours to produce a new precipitate, which is mainly a mixture of unwashed crude copper oxide 22 and sodium oxalate.

[0092] 2. Start pump 46-1 to separate the reactants in alkali liquor reaction tank 2 into solid-liquid form through solid-liquid separator 5-1, obtaining filter residue A and filtrate B. Filter residue A is crude copper oxide 22 and solid sodium oxalate, and filtrate B is a solution 18 mainly containing soluble oxalate. Filtrate B is drained into temporary storage tank 6-1 for temporary storage.

[0093] 3. The solid sodium oxalate impurities in the unwashed crude copper oxide product 22 are washed with water in a washing tank 4, and the pure copper oxide product 26 and the salt-containing waste liquid 43 are obtained after solid-liquid separation in a solid-liquid separator 5-2.

[0094] After the above steps, copper oxalate is subjected to the chemical reaction of the second embodiment of the present invention to obtain copper oxide product. The main component of the solution in the temporary storage tank 6-1 is a mixture of alkaline substances and oxalate.

[0095] Example 3

[0096] As shown in Figures 3 and 4, the apparatus for extracting copper and tin source materials from copper and / or tin oxalate according to Example 3 includes a sodium hypochlorite reaction tank 1, two ordinary chemical reaction tanks 3, three cleaning tanks 4, seven solid-liquid separators 5, three temporary storage tanks 6, two impeller stirrers 7, four liquid flow stirrers 8, a hot and cold temperature exchanger 9, two exhaust gas processors 10, seven detection sensors 11, an electric furnace 47, and multiple valves and pumps.

[0097] Sodium hypochlorite reaction tank 1 is sequentially connected to solid-liquid separators 5-1 and 5-2. Solid-liquid separator 5-2 is further connected to temporary storage tank 6-2 via a liquid pipeline. Temporary storage tank 6-1 is used to store the filter residue separated by solid-liquid separator 5-1. Temporary storage tank 6-2 is connected to cleaning tank 4-1, and is circulated through solid-liquid separator 5-3 and overflow buffer tank 52-1. Temporary storage tank 6-3 is used to store the filter residue separated by solid-liquid separator 5-3.

[0098] The common chemical reaction tank 3-1 is connected to the common chemical reaction tank 3-2 via the solid-liquid separator 5-4, and the common chemical reaction tank 3-2 is connected to the temporary storage tank 6-2 via the solid-liquid separator 5-5.

[0099] The cleaning tanks 4-2 and 4-3 are respectively connected to the solid-liquid separator, and then connected to the temporary storage tank 6-2.

[0100] The top of each reaction tank in the device is provided with a sealing tank cover.

[0101] The sodium hypochlorite reaction tank 1 is equipped with an impeller stirrer and a heat exchanger.

[0102] The solid-liquid separators 5-1 and 5-3 are filter presses, and 5-2, 5-4, 5-5, 5-6, and 5-7 are filters.

[0103] The device of this embodiment is further provided with an electric furnace 47, and exhaust gas processors 10-1 and 10-2.

[0104] The electric furnace 47 is used to heat and dry the copper hydroxide to remove moisture.

[0105] The exhaust gas processor 10-1 is specifically used to treat the oxidizing exhaust gas emitted from the sodium hypochlorite reaction tank 1, and the exhaust gas processor 10-2 is used to treat the exhaust gas emitted from the three ordinary chemical reaction tanks 3 in the device.

[0106] The detection sensor 11-1 is an ORP meter, 11-2 is a pH meter, and 11-3 is a thermometer, which are arranged in the sodium hypochlorite reaction tank 1; the detection sensor 11-4 is a liquid level meter, which is arranged in the cleaning tank 4-1; the detection sensor 11-5 is a liquid level meter, and 11-6 is a pH meter, which are arranged in the ordinary chemical reaction tank 3-1; the detection sensor 11-7 is a pH meter, which is arranged in the ordinary chemical reaction tank 3-2.

[0107] The hypochlorite solution 44 used in this embodiment is a sodium hypochlorite solution having a concentration of 9% and a pH of 14. The acidic substance 27 is a mixture of sulfuric acid, hydrochloric acid, and formic acid. The alkaline solution 28, also the pH adjuster, is a sodium hydroxide solution.

[0108] In this embodiment, what needs to be processed is a mixture 14 of stannous oxalate and copper oxalate solids.

[0109] The method of extracting copper and tin source materials from copper and / or tin oxalates in this embodiment includes the following steps.

[0110] 1. To a hypochlorite reaction tank 1, 20 kg of a solid mixture of stannous oxalate and copper oxalate 14 and water 33 were quantitatively added. The temperature of the reaction solution was controlled at 30° C. using a thermometer. Sodium hypochlorite solution was added using an ORP meter at an ORP value of 700 mV, and an alkaline substance 28 was added using a pH meter at a pH value of 8 to maintain the solution at pH 8. The reaction was carried out for 3 hours to produce precipitates of new copper mud and new tin mud.

[0111] 2. Start pump 46-2 to perform solid-liquid separation on the mixture in hypochlorite reaction tank 1 through solid-liquid separator 5-1 and solid-liquid separator 5-2, obtaining filter residue A which is a mixture of crude stannous hydroxide 19 and crude copper hydroxide 20. The filtrate is a salt-containing waste liquid which is temporarily stored in temporary storage tank 6-2.

[0112] 3. The filter residue A in the temporary storage tank 6-1 and the solid-liquid separator 5-2 is placed in the cleaning tank 4-1 and washed with clean water 33. After washing, the solid-liquid separator 5-3 is used for solid-liquid separation to obtain a filter residue C containing a mixed compound of tin and copper with less impurities and a washed salt-containing waste liquid. The filter residue C is stored in the temporary storage tank 6-3, and the washed salt-containing waste liquid is drained through the overflow buffer tank 52-1 to the temporary storage tank 6-2 for temporary storage.

[0113] 4. The filter residue C was placed in a conventional chemical reaction tank 3-1 and, under the control of a pH meter, an acidic solution 27 was added to adjust the pH of the reaction solution to 0.2. The reaction was allowed to proceed for 10 minutes. Subsequently, an alkaline solution 28 was added to maintain the pH of the solution at pH 3 for 0.5 hours. Stannous hydroxide precipitate appeared in the solution.

[0114] 5. The mixture in the conventional chemical reaction tank 3-1 is subjected to solid-liquid separation using a solid-liquid separator 5-4 to obtain a crude stannous hydroxide product 19 and an acidic copper salt solution. The acidic copper salt solution is drained into the conventional chemical reaction tank 3-2 to continue the alkali addition reaction, so that the pH value of the reaction solution is controlled to pH 7 and copper hydroxide precipitate appears.

[0115] 6. Use a solid-liquid separator 5-5 to perform solid-liquid separation on the mixture in the ordinary chemical reaction tank 3-2 to obtain a crude copper hydroxide product 20 and a salt-containing waste liquid after the reaction, wherein the salt-containing waste liquid after the reaction is drained into a temporary storage tank 6-2 for treatment.

[0116] 7. Take the crude stannous hydroxide 19 and the crude copper hydroxide 20 and put them into the cleaning tank 4-2 and the cleaning tank 4-3 respectively for washing with water. After washing, use solid-liquid separators 5-6 and 5-7 for solid-liquid separation to obtain pure stannous hydroxide 23 and pure copper hydroxide 25 respectively. The salt-containing waste liquid after washing is led to the temporary storage tank 6-2 for centralized treatment.

[0117] 8. Take pure copper hydroxide 25 and put it into electric furnace 47 for heating and drying to remove moisture.

[0118] After the above steps, the mixture of copper oxalate and stannous oxalate is chemically reacted to produce copper oxide and stannous hydroxide products respectively.

[0119] Example 4

[0120] As shown in Figures 5, 6 and 7, the device for extracting copper and tin source materials from copper and / or tin oxalate according to Example 4 includes an alkali solution reaction tank 2, a hot and cold temperature exchanger 9, four ordinary chemical reaction tanks 3, two cleaning tanks 4, eight solid-liquid separators 5, five temporary storage tanks 6, seven impeller agitators 7, two liquid flow pump tube agitators 8, an exhaust gas processor 10, fourteen detection sensors 11, an automatic detection and feeding controller 12, a chemical precipitation tin production line 32, a sulfate electroplating tin production line 55, a metal tin plate 38, a surface tin plating treatment part 39, and multiple valves and pumps.

[0121] The alkali solution reaction tank 2 is connected to the solid-liquid separator 5-1, and the solid-liquid separator 5-1 is connected to the temporary storage tank 6-1; the temporary storage tank 6-1 is used to load the filter residue separated by the solid-liquid separator 5-1.

[0122] The ordinary chemical reaction tank 3-1 is connected to the ordinary chemical reaction tank 3-2 through the solid-liquid separator 5-2, and the ordinary chemical reaction tank 3-2 is connected to the temporary storage tank 6-4 through the solid-liquid separator 5-3; the temporary storage tank 6-1 is used to load the filter residues separated by the solid-liquid separators 5-2 and 5-3 respectively.

[0123] The cleaning tank 4-1 is connected to the solid-liquid separator 5-4 and then to the temporary storage tank 6-6. The cleaning tank 4-2 is connected to the solid-liquid separator 5-5 and then to the temporary storage tank 6-6.

[0124] The common chemical reaction tank 3-3 is connected to the chemical tin production line 32 for circulating liquid flow through the solid-liquid separator 5-6. The acid electroplating tin production line 55 is connected to the common chemical reaction tank 3-4.

[0125] The alkali solution reaction tank 2 is equipped with an impeller stirrer 7-1 and a plurality of detection sensors, wherein the detection sensor 11-1 in the tank is a pH meter and the detection sensor 11-2 is a thermometer.

[0126] The conventional chemical reaction tank 3-1 is equipped with an impeller agitator 7-2 and multiple detection sensors, including a liquid level gauge 11-3, a hydrometer 11-4, and a pH meter 11-5. The liquid level gauge controls the amount of water added and the liquid level of the reaction solution. The hydrometer controls the amount of the mixture of crude stannous hydroxide 19 and crude copper hydroxide 20 added. The pH meter controls the amount of acid or alkaline substance added to dissolve the stannous oxide and copper oxide and react to precipitate stannous hydroxide in the reaction solution. The conventional chemical reaction tank 3-2 is used to react and precipitate copper hydroxide 20. The conventional chemical reaction tank 3-3 is used to prepare a conventional, commonly used chemical immersion tin plating solution 29. The conventional chemical reaction tank 3-4 is used to prepare a conventional, commonly used acidic electrotin plating solution 31.

[0127] The cleaning tank 4-1 is used to clean the stannous hydroxide 19, and the cleaning tank 4-2 is used to clean the stannous hydroxide twice.

[0128] The solid-liquid separators 5-1, 5-2 and 5-3 are filter presses, the solid-liquid separator 5-4 is a centrifuge with a scraper, and the solid-liquid separators 5-5, 5-6, 5-7, 5-8 and 5-9 are filters.

[0129] The chemical immersion tin production line 32 is a conventional chemical immersion tin line, which is equipped with a hot and cold temperature exchanger 9-2, a hydrometer 11-11, and a liquid level meter 11-12.

[0130] The acid electroplating tinning production line 55 is a sulfate electroplating tinning production line, whose electrolytic anode is an insoluble anode, and is equipped with a hydrometer 11-13 and a liquid level meter 11-14; the tinned part 39-1 is a tin-immersion part on the chemical immersion tin production line 32, and the tinned part 39-2 is a cathode tin-plated part on the acid electroplating production line 55, specifically a metal tin block 38.

[0131] The exhaust gas processor 10 is used to absorb and treat the polluted waste gas escaping from each tank, and its exhaust gas treatment spray liquid is sodium hydroxide solution.

[0132] The twelve detection sensors transmit the process parameters detected by on-site sampling to the automatic detection and feeding controller 12 for processing. The automatic detection and feeding controller 12 outputs a control signal to execute a pre-programmed working program to enable the device to operate automatically.

[0133] The conventional chemical reaction tanks 3-3 and 3-4 are respectively equipped with detection sensors 11-9 and 11-10, both of which are hydrometers for controlling the addition of stannous hydroxide 23-2 when preparing the plating solution.

[0134] This embodiment requires a solid mixture 14 of copper oxalate and stannous oxalate; the alkaline solution 28-1 is a potassium hydroxide solution, and the alkaline solution 28-2 is a sodium hydroxide solution; the acidic solution 27 is sulfuric acid; and the other raw materials 40 for preparing the chemical tin plating solution are thiourea and other auxiliary raw materials used in the prior art. Other raw materials 42 for preparing the acidic electroplating tin plating solution are sulfuric acid and auxiliary raw materials used in the prior art.

[0135] The method of extracting copper and tin source materials from copper and / or tin oxalates in this embodiment includes the following steps:

[0136] 1. Turn on the power of the device to put the automatic detection and feeding controller 12 into operation.

[0137] 2. A solid mixture 14 of copper oxalate and stannous oxalate is added in a fixed quantity of 20 kg into an alkali solution reaction tank 2 filled with water. Field data obtained by detection by a pH meter and a thermometer is transmitted to an automatic detection and feeding controller 12 for processing. Alkaline solution 28-1 is added to the alkali solution reaction tank 2 under control of the pH meter to control the pH value of the reaction solution at pH 13.5. At the same time, the thermometer is set to 75° C., causing the hot and cold temperature exchanger 9-1 to heat the reaction solution to maintain the temperature of the reaction solution at 75° C. The reaction is carried out for 3 hours to ensure that the copper oxalate and stannous oxalate in the reaction solution react thoroughly to form stannous oxide and copper oxide precipitates.

[0138] 3. After shutting down the heating device 9-1 and the impeller agitator 7-1 on the alkali liquor reaction tank 2, the pump 46-1 is turned on to perform solid-liquid separation on the mixture in the alkali liquor reaction tank 2 to obtain a filter residue A and a filtrate B. The filter residue A is a solid mixture of the crude stannous oxide 21 and the crude copper oxide 22, and the filtrate B is a salt-containing waste liquid 18.

[0139] 4. Add the filter residue A to a conventional chemical reaction tank 3-1 containing an acidic solution 27 to completely dissolve the filter residue A. During the process, the amount of filter residue A added is controlled by a hydrometer in the tank so that the reaction solution reaches a set specific gravity. Then, a pH meter is used to control the addition of alkaline solution 28-1. A liquid level meter is used to control the addition of water, acid, and alkaline solutions. When the liquid level meter is within the control volume range and the pH meter is adjusted to a pH value of 3.0, the precipitation of stannous hydroxide precipitate in the reaction solution is considered to be the end point.

[0140] 5. Start pump 46-2 to separate the solid and liquid of the mixture in the common chemical reaction tank 3-1, to obtain a filter residue of crude stannous hydroxide 19 and an acidic copper-containing filtrate, and drain the filtrate to the common chemical reaction tank 3-2.

[0141] 6. Add alkaline solution 28-1 to the common chemical reaction tank 3-2, adjust the pH value of the reaction solution to pH 7, and precipitate copper hydroxide 20 in the reaction solution.

[0142] 7. Start pump 46-3 to perform solid-liquid separation on the mixture in the common chemical reaction tank 3-2 to obtain a crude copper hydroxide product 20 and a salt-containing waste liquid 43-2. ​​The crude copper hydroxide product 20 is stored in tank 6-4.

[0143] 8. The crude stannous hydroxide product 19 is placed in a cleaning tank 4-1 and washed with water 33 to remove soluble impurities. The addition of fresh water is controlled by a level gauge in the tank. After the water washing is completed, pump 46-4 is started to place the mixture in the cleaning tank 4-1 into a solid-liquid separator 5-4 for solid-liquid separation, thereby obtaining pure stannous hydroxide 23-1 and a cleaning waste liquid, i.e., a salt-containing waste liquid 43-3.

[0144] 9. Put the pure stannous hydroxide 23-1 into the cleaning tank 4-2 and wash it twice with water. After filtering, the pure stannous hydroxide 23-2 is obtained.

[0145] 10. Take stannous hydroxide 23-2 and put it into the common chemical reaction tank 3-3 according to the control of the hydrometer in the tank, and react with the reflux liquid of the chemical immersion tin production line 32 to supplement the tin source. The hydrometer in the chemical immersion tin production line 32 controls the pump 46-6 to supplement the tin source to the chemical immersion tin production line 32 to ensure normal production. During the process, other raw materials 40 for preparing the immersion tin plating solution are added for plating solution maintenance.

[0146] 11. Take stannous hydroxide 23-2 and put it into the common chemical reaction tank 3-4 to react with the acidic electroplating solution refluxed from the acidic electrotin plating production line 55 to supplement the tin source. The tin content concentration in the acidic electroplating solution is controlled by a hydrometer, and the production is normalized by adding tin by pump 46-7.

[0147] 12. The polluted tail gas and cleaning waste liquid produced during the process shall be treated in an environmentally friendly manner.

[0148] 13. During operation, the device uses the automatic detection and feeding controller 12 to operate according to the designed pre-programmed operation.

[0149] Through the above steps and the use of the apparatus shown in FIG4 , a method can be achieved to obtain a mixture of stannous oxalate and cupric oxalate from a mixed waste liquid containing tin and copper, and then recycle the tin source material therein. In this embodiment, a coarse tin bar 38 is electroplated on the cathode of a sulfate electroplating tin production line. The coarse tin bar can be heated and melted to produce tin blocks or tin balls of appropriate size for use as soluble anode metal tin.

[0150] Example 5

[0151] As shown in Figures 8 and 9, the apparatus for extracting copper and tin source materials from copper and / or tin oxalate according to Example 5 includes a hypochlorite reaction tank 1, a conventional chemical reaction tank 3, four solid-liquid separators 5, seven temporary storage tanks 6, a hot and cold temperature exchanger 9, an exhaust gas processor 10, eight detection sensors 11, an automatic detection and feeding controller 12, a spray tower 50, a vacuum ejector 51, an electrolytic cell 56, a separator 57, an electrolytic anode 58, an electrolytic cathode 59, and an electrolytic power supply 60.

[0152] The electrolytic cell 56 is a separator-equipped electrolytic cell, divided into an anode and cathode compartments. The electrolytic anode 59 is a titanium-coated anode, the electrolytic cathode 59 is a copper plate, and the electrolytic separator is a cation exchange membrane. The anode and cathode compartments are each connected to the temporary storage tank 6-3 via an overflow buffer tank. The anode compartment is also connected to the vacuum ejector 51 located in the hypochlorite reaction tank 1 via a gas pipeline.

[0153] The temporary storage tank 6 - 1 is used for temporarily storing acidic copper chloride etching waste liquid and is connected to the common chemical reaction tank 3 and the anode tank area and cathode tank area of ​​the electrolytic tank 56 respectively.

[0154] The common chemical reaction tank 3 is connected to the temporary storage tank 6-3 through the solid-liquid separator 5-1, the overflow buffer tank 52-1, and the solid-liquid separator 5-2; the temporary storage tank 6-2 is used for the filter residue separated by the solid-liquid separator 5-1.

[0155] The hypochlorite reaction tank 1 is configured to react chlorine gas with a sodium hydroxide solution to produce sodium hypochlorite. This oxidant, while being produced, reacts chemically with copper oxalate 15. The hypochlorite reaction tank 1 is connected to a temporary storage tank 6-5 via a solid-liquid separator 5-3, an overflow buffer tank 52-4, and a solid-liquid separator 5-4.

[0156] The solid-liquid separators 5-1 and 5-3 are filter presses, and 5-2 and 5-4 are filters.

[0157] The detection sensor 11-1 is a liquid level gauge used to control the liquid level of the reaction solution in the conventional chemical reaction tank 3; the detection sensor 11-2 is a hydrometer installed in the cathode tank area to control the addition of waste liquid 61 to the cathode tank area; the detection sensor 11-3 is a hydrometer installed in the anode tank area to control the addition of waste liquid 61 to the anode tank area; the detection sensor 11-4 is an ORP meter installed in the anode tank area to provide a safety interlock for the electrolysis power supply 60; the detection sensor 11-5 is a liquid level gauge, 11-6 is a pH meter, 11-7 is an ORP meter, and 11-8 is a thermometer, all of which are installed in the hypochlorite reaction tank 1; the detection sensor 11-9 is a spatial chlorine concentration detector for the work site. The pH meter 11-6 is used to control the addition of potassium hydroxide solution, the ORP meter 11-7 controls the operating current of the electrolysis power supply or shuts it down, and the thermometer 11-8 controls the operating temperature of the reaction solution.

[0158] The detection sensor transmits the process parameters detected by on-site sampling to the automatic detection and feeding controller 12 for processing. The automatic detection and feeding controller 12 outputs a control signal to execute a pre-programmed working program to enable the device to operate automatically.

[0159] The alkaline solution 28 used in this embodiment is also a pH regulator, which is a potassium hydroxide solution; the copper oxalate 15 to be treated is prepared by reacting the acidic copper chloride etching waste liquid 61 with oxalic acid 17.

[0160] The tail gas treatment tank 10 uses potassium hydroxide solution 28 as the tail gas absorption reaction liquid.

[0161] The electrolytes for both the cathode and anode in the electrolytic cell 56 are acidic copper chloride etching waste liquid 61 , wherein the main components of the acidic copper chloride etching waste liquid are a mixture of hydrochloric acid, copper chloride and chloride salt, and the copper ion concentration in the waste liquid is 130 g / L.

[0162] The method of extracting copper and tin source materials from copper and / or tin oxalates in this embodiment includes the following steps.

[0163] 1. Turn on the power of the device to put the automatic detection and feeding controller 12 into operation.

[0164] 2. Start pumps 46-1, 46-2 and 46-3 to add acidic copper chloride etching waste liquid 61 to the common chemical reaction tank 3 and the cathode and anode areas of the electrolytic tank, respectively, and add potassium hydroxide solution to the hypochlorite reaction tank 1.

[0165] 3. Start the impeller stirrer 7 and add a fixed amount of oxalic acid 17 to the constant volume of etching waste liquid in the common chemical reaction tank 3 to react and produce copper oxalate 15.

[0166] 4. The solid-liquid mixture in the ordinary chemical reaction tank 3 is separated into solid and liquid by solid-liquid separators 5-1 and 5-2. The collected copper oxalate 15 is temporarily stored in the temporary storage tank 6-2, and the filtrate 43-1 containing hydrochloric acid is drained to the tank 6-3 for temporary storage.

[0167] 5. Automatic detection and feeding controller 12 starts the electrolytic cell, causing chlorine to be electrolytically deposited at the anode and copper to be electrolytically deposited at the cathode. The electrolytic chlorine is introduced into hypochlorite reaction tank 1 to participate in the reaction. During the reaction, hot and cold temperature exchanger 9 in the cell is opened to control the reaction solution at 60° C. Potassium hydroxide solution is controlled by a pH meter to maintain the pH value of the reaction solution at pH 14. The redox potential of the reaction solution is controlled at 100 mV by an ORP meter. A fixed amount of 20 kg of copper oxalate is added to the hypochlorite reaction tank 1 in small amounts several times. The reaction time is 9 hours, and the copper oxalate 15 is oxidized to copper oxide and a trace amount of sodium percuprate.

[0168] 6. The solid-liquid mixture after the reaction in the hypochlorite reaction tank 1 is separated into solid and liquid by a filter press 5-3 and a filter 5-4 to obtain a mixture of copper oxide and a trace amount of sodium percuprate as a filter residue, which is temporarily stored in a temporary storage tank 6-4. The filtrate of the salt-containing waste liquid 43-2 is drained to a temporary storage tank 6-5 for further treatment.

[0169] 7. The operation process of the device is executed by the automatic detection and feeding controller 12 according to the pre-programmed operation, wherein the chlorine concentration detector 11-9 is used to monitor the chlorine concentration in the production workshop space.

[0170] After the seven steps above, copper oxalate is chemically reacted to produce copper oxide and sodium percolate. This process is optimized by combining the electrolysis of acidic copper chloride etching wastewater to extract copper, resulting in greater energy savings and emission reductions.

[0171] During the above production process, the hydrochloric acid waste liquid 43-1 can be used as a raw material to prepare a regenerated etching solution based on the requirements for the preparation of an acidic copper chloride etching solution and then recycled back into the etching production line. Furthermore, the resulting copper oxide product contains trace amounts of sodium percolate, which can be removed by heating with water to decompose it or by adding a reducing agent.

[0172] Example 6

[0173] As shown in Figures 10 and 11, the apparatus for extracting copper and tin source materials from copper and / or tin oxalate according to Example 6 includes an alkali solution reaction tank 2, a common chemical reaction tank 3, two cleaning tanks 4, five solid-liquid separators 5, four temporary storage tanks 6, three impeller stirrers 7, a hot and cold temperature exchanger 9, multiple sensors 11, three overflow buffer tanks 52, an evaporator 64, and multiple valves and pumps.

[0174] The cleaning tanks 4-1 and 4-2 are used for pickling the copper oxalate 71-1 containing iron impurities, and the clean copper oxalate 15 is obtained by removing the iron impurities through cleaning.

[0175] The alkali reaction tank 2 is connected to the solid-liquid separator 5-3 and then to the overflow buffer tank 52-3 via a liquid pipeline. The temporary storage tank 6-4 is used to store the filter residue separated by the solid-liquid separator 5-3. The overflow buffer tank 52-3 is connected to the conventional chemical reaction tank 3 through the solid-liquid separator 5-4, and then to the evaporator 64. The temporary storage tank 6-5 is used to store the solid product obtained from the evaporator 64.

[0176] The alkali solution reaction tank 2 is equipped with an impeller stirrer 7-3, a hot and cold temperature exchanger 9 and multiple detection sensors. The detection sensor 11-1 in the tank is a liquid level meter, 11-2 is a thermometer, and 11-3 is a pH meter. The hot and cold temperature exchanger 9 is used to heat the reaction liquid in the alkali solution reaction tank 2.

[0177] The solid-liquid separators 5-1, 5-2 and 5-3 are filter presses, and 5-4 is a filter.

[0178] The evaporator 64 is used to evaporate and concentrate the potassium oxalate solution to produce a solid potassium oxalate product.

[0179] The detection sensor 11 - 4 is a pH meter, which is arranged in a common chemical reaction tank 3 .

[0180] In this embodiment, the copper oxalate 71 containing iron impurities needs to be treated. The alkaline solution 28 used is a potassium hydroxide solution with a concentration of 30%.

[0181] The method of extracting copper and tin source materials from copper and / or tin oxalates in this embodiment includes the following steps.

[0182] 1. Copper oxalate 71-1 containing iron impurities, hydrochloric acid 34, and hydrogen peroxide 72 are put into a cleaning tank 4-1 for pickling. After solid-liquid separation in a filter press 5-1, filter residue 71-2 and salt-containing waste liquid 43 are obtained.

[0183] 2. The copper oxalate 71-2 containing iron impurities and sulfuric acid are put into the cleaning tank 4-2 for further cleaning, and then filtered to obtain the copper oxalate 15 and salt-containing waste liquid 43, wherein the waste liquid 43 is drained to the tank 6-3 for temporary storage.

[0184] 3. Add a fixed amount of water and a fixed amount of 20 kg of copper oxalate 15 to the alkaline solution reaction tank 2. Use a pH meter for intermittent sampling. After cooling, test the solution and, based on the test results, control the addition of alkaline solution 28 to adjust the pH of the reaction solution to > pH 14. Use a hot / cold temperature exchanger 9 to control the operating temperature of the reaction solution to 100° C. Start the impeller agitator 7 to conduct a chemical reaction for 1 hour to produce new copper sludge precipitate and copper oxide powder.

[0185] 4. After the reaction is completed, the hot and cold temperature exchanger 9 in the alkali solution reaction tank 2 is started for cooling, and then the pump 46-1 is started to separate the reactants in the alkali solution reaction tank 2 into solid-liquid form via the solid-liquid separators 5-1 and 5-2, thereby obtaining a filter residue A and a filtrate B. The filtrate A is the crude copper oxide 22, and the filtrate B is a mixed solution of soluble potassium oxalate and potassium hydroxide. The filtrate B is then drained into the conventional chemical reaction tank 3.

[0186] 5. According to the process setting value of the pH meter in the ordinary chemical reaction tank 3, oxalic acid 17 is added to the ordinary chemical reaction tank 3 to neutralize the potassium hydroxide in the mixed solution therein. When the pH meter drops to the set value, the addition of oxalic acid is stopped.

[0187] 6. The potassium oxalate solution prepared in the common chemical reaction tank 3 is put into the evaporator 64 for evaporation and concentration to produce solid potassium oxalate, and the obtained potassium oxalate product is temporarily stored in the tank 6-2.

[0188] After the above steps, the copper oxalate 71 containing iron impurities is acid-washed and then subjected to the chemical reaction of the second embodiment of the present invention to produce copper oxide 22 and solid potassium oxalate product 65.

[0189] Example 7

[0190] As shown in FIG12 , Example 7 of the method and apparatus for extracting copper-tin source materials from copper and / or tin oxalate according to the present invention is shown. The apparatus includes an alkaline solution reaction tank 2, a common chemical reaction tank 3, three solid-liquid separators 5, three temporary storage tanks 6, two impeller agitators, valves, and a pump.

[0191] The alkali liquor reaction tank 2 is sequentially connected to the solid-liquid separator 5-1 and the temporary storage tank 6-1. The cleaning tank 4 is sequentially connected to the solid-liquid separators 5-2 and 5-3. The temporary storage tank 6-2 is used to receive the filter residue from the solid-liquid separator 5-2, and the temporary storage tank 6-3 is connected to the solid-liquid separator 5-3 to receive the filtrate. The temporary storage tank 6-3 is also connected to the alkali liquor reaction tank 2.

[0192] The solid-liquid separator 5-1 is a centrifuge, 5-2 is a filter press, and 5-3 is a filter.

[0193] The substance to be treated is copper oxalate.

[0194] The alkaline solution 28 used in this embodiment is a potassium hydroxide solution.

[0195] The method of extracting copper and tin source materials from copper and / or tin oxalates in this embodiment includes the following steps.

[0196] 1. Add a fixed amount of water and a fixed amount of 20 kg of copper oxalate 15 to the alkali solution reaction tank 2, and then add an alkaline solution 28 until the weight of the alkaline substance is greater than 1.5 times the equivalent number of the alkaline substance that reacts with the copper oxalate. A chemical reaction is carried out. The impeller stirrer 7-1 is started and the chemical reaction is carried out at room temperature for 24 hours to produce a new copper mud precipitate, i.e., a crude copper oxide product 22.

[0197] 2. Start pump 46-1 to separate the reactants in alkali liquor reaction tank 2 into solid-liquid form through solid-liquid separator 5-1, obtaining filter residue A and filtrate B. Filter residue A is crude copper hydroxide 20, and filtrate B is a solution 18 mainly containing soluble oxalate. Filtrate B is drained into tank 6-1 for temporary storage.

[0198] 3. Calcium hydroxide is reacted with solution 18 in a conventional chemical reaction tank 3 to obtain a solid-liquid mixture of calcium oxalate and potassium hydroxide. After solid-liquid separation in solid-liquid separators 5-2 and 5-3, calcium oxalate 68 and alkaline solution 28 are obtained.

[0199] 4. The prepared potassium hydroxide solution 28 is used for the next round of copper oxalate treatment.

[0200] After the above steps, copper oxalate is subjected to the chemical reaction of method 2 of the present invention to produce a copper oxide product. Calcium hydroxide is reacted with solution 18, which primarily contains potassium oxalate, to produce a calcium oxalate precipitate and a potassium hydroxide solution. After solid-liquid separation, the potassium hydroxide solution 28 is recycled.

[0201] Example 8

[0202] As shown in Figure 13, the device of this embodiment includes an alkali solution reaction tank 2, a general chemical reaction tank 3, three solid-liquid separators 5, three temporary storage tanks 6, and two impeller agitators. It is similar to the device in Figure 7, except that the temporary storage tank 6-3 is not connected to the alkali solution reaction tank 2.

[0203] This embodiment adopts the same operation steps as embodiment 7, except that:

[0204] The alkaline solution 28-1 added to the alkali solution reaction tank 2 is a mixed solution of potassium hydroxide and sodium hydroxide; the alkaline solution 28-2 in the temporary storage tank 6-2 is a mixed solution of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, and potassium bicarbonate.

[0205] The solid alkaline substance 74 is calcium carbonate or calcium bicarbonate.

[0206] In step 1, an alkaline solution 28 is added, the weight of the alkaline substance added is greater than 1 times the equivalent number of the reaction with copper oxalate, and the amount of sodium ions in the reaction solution is 2 mol / L. During the reaction, the copper oxalate is completely reacted to form a new co-precipitate of copper oxide and sodium oxalate.

[0207] In step 2, solid-liquid separation is performed to obtain a mixture of copper oxalate and sodium oxalate as a filter residue, and the filtrate 18 is a mixture of potassium oxalate, sodium oxalate, potassium hydroxide, and sodium hydroxide. The mixture of copper oxalate and sodium oxalate as a filter residue is washed with water to remove sodium oxalate.

[0208] In step 3, the filtrate 18 is reacted with a mixture of calcium hydroxide, calcium carbonate, and calcium bicarbonate in a common chemical reaction tank 3. After solid-liquid separation, a calcium oxalate precipitate and a mixed solution 28-2 containing potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, and sodium bicarbonate are obtained and temporarily stored in a temporary storage tank 6-2.

[0209] Example 9

[0210] As shown in FIG14 , the apparatus for extracting copper and tin source materials from copper and / or tin oxalate according to the present invention includes an alkaline solution reaction tank 2 with a heater, two ordinary chemical reaction tanks 3, four solid-liquid separators 5, four temporary storage tanks 6, two impeller stirrers 7, an evaporator 64, and multiple valves and pumps.

[0211] In the device of this embodiment, the alkali liquid reaction tank 2, the solid-liquid separator 5-1, the solid-liquid separator 5-2, the ordinary chemical reaction tank 3-1, the solid-liquid separator 5-3, the solid-liquid separator 5-4, the temporary storage tank 6-3, the ordinary chemical reaction tank 3-2, and the evaporator 64 are connected in sequence; the temporary storage tanks 6-1 and 6-2 are used to receive the filter residues of the solid-liquid separators 5-1 and 5-3 respectively, and the temporary storage tank 6-4 is used to load the solid product obtained from the evaporator 64.

[0212] The solid-liquid separators 5-1 and 5-3 are filter presses, and 5-2 and 5-4 are filters.

[0213] The substance to be treated is copper oxalate 15.

[0214] The acidic solution 27 is sulfuric acid.

[0215] The alkaline substance 28 used in this embodiment is potassium hydroxide solution.

[0216] The detection sensor 11-1 is a thermometer, which is arranged in the alkali solution reaction tank 2; the detection sensor 11-2 is a pH meter, which is arranged in the ordinary chemical reaction tank 3-1; the detection sensor 11-3 is a liquid level meter, and 11-4 is a pH meter, which is arranged in the ordinary chemical reaction tank 3-2.

[0217] The ferrous sulfate raw material 67 is used to produce potassium sulfate and ferrous oxalate products during the operation. The evaporator 64 is used to evaporate the potassium sulfate solution.

[0218] The method of extracting copper and tin source materials from copper and / or tin oxalates in this embodiment includes the following steps.

[0219] 1. Add a fixed amount of water and a fixed amount of 20 kg of copper oxalate 15 to the alkali solution reaction tank 2, and then add an alkaline solution 28. The weight of the alkaline substance added is greater than 1.1 times the reaction equivalent number of the copper oxalate. Start the impeller stirrer 7-1 and control the temperature to 70°C to allow the chemical reaction to proceed for 6 hours to produce a new copper mud precipitate, i.e., crude copper oxide 22.

[0220] 2. Start pump 46-1 to separate the reactants in alkali liquor reaction tank 2 into solid-liquid form through solid-liquid separators 5-1 and 5-2, producing filter residue A and filtrate B. Filter residue A is crude copper oxide 22, and filtrate B is a solution 18 primarily containing soluble oxalate. Filtrate B is then drained into tank 3-1 for the next chemical reaction. The resulting copper oxide is temporarily stored in tank 6-1.

[0221] 3. Under the control of a pH meter, ferrous sulfate is added to the common chemical reaction tank 3-1 to react with a mixed solution of potassium oxalate and potassium hydroxide to obtain a solid-liquid mixture of ferrous oxalate, potassium sulfate and potassium hydroxide.

[0222] 4. The solid-liquid mixture after the reaction in the ordinary chemical reaction tank 3-1 is separated into solid and liquid by solid-liquid separators 5-3 and 5-4 to obtain a filter residue of ferrous oxalate and a filtrate of a mixture of potassium sulfate and potassium hydroxide.

[0223] 5. Temporarily store the ferrous oxalate in tank 6-2, and drain the filtrate from the solid-liquid separator 5-4 into the temporary storage tank 6-3.

[0224] 6. Under the control of the liquid level meter, extract the solution in the temporary storage tank 6-3 and add it into the common chemical reaction tank 3-2. Under the control of the pH meter in the tank, add sulfuric acid for neutralization reaction to produce pure potassium sulfate solution.

[0225] 7. Add the potassium sulfate solution in the ordinary chemical reaction tank 3-2 to the evaporator 64, evaporate and crystallize to obtain the potassium sulfate solid product 70, which is temporarily stored in the tank 6-4.

[0226] After the above steps, copper oxalate 15 is subjected to the chemical reaction of method 2 of the present invention to obtain a copper oxide product. Ferrous sulfate and potassium oxalate solution are reacted to obtain ferrous oxalate and potassium sulfate products.

Claims

1. A method for extracting copper and tin source materials from copper and / or tin oxalates, characterized in that: The following steps are involved: (1) treating copper and / or tin oxalate by at least one of the following methods: Method 1: allowing copper oxalate and / or stannous oxalate to react chemically with hypochlorite in an aqueous solution containing hypochlorite to generate new copper mud and / or tin mud precipitate, and the reaction process is accompanied by the release of carbon dioxide gas; Method 2: allowing copper oxalate and / or stannous oxalate to undergo a chemical reaction in a solution containing an alkaline substance to generate new copper mud and / or tin mud precipitate, wherein the alkaline substance includes a potassium-containing alkaline substance; (2) subjecting the solid-liquid mixture after the reaction in step (1) to solid-liquid separation to obtain a filter residue A and a filtrate B, wherein the filter residue A is new copper mud and / or tin mud.

2. The method for extracting copper-tin source materials from copper and / or tin oxalates according to claim 1, characterized in that: The hypochlorite is sodium hypochlorite and / or potassium hypochlorite; the potassium-containing alkaline substance is one or more of potassium hydroxide, potassium carbonate and potassium bicarbonate.

3. The method for extracting copper-tin source materials from copper and / or tin oxalates according to claim 2, characterized in that: The stannous oxalate is prepared by reacting tin-containing waste liquid with oxalic acid, or by reacting the filtrate obtained by filtering the tin-containing waste liquid to remove tin dioxide solids with oxalic acid; the copper oxalate is prepared by adding oxalic acid to the copper-containing waste liquid for reaction.

4. The method for extracting copper and tin source materials from copper and / or tin oxalates according to claim 3, characterized in that: In the first method, if the new copper mud product is mainly copper hydroxide, the pH value of the reaction solution is controlled to be 3.5≤≤8.5 during the reaction; if the new copper mud product is mainly copper oxide, the pH value of the reaction solution is controlled to be ≥10 during the reaction.

5. The method for extracting copper and tin source materials from copper and / or tin oxalates according to claim 4, characterized in that: - Using a redox potentiometer to control the addition of hypochlorite, or using a combination of a pH meter and a redox potentiometer to control the addition of a pH adjuster and hypochlorite respectively, so that the reaction solution maintains stable control parameters and performs a chemical reaction in the direction of the reaction of the target product set by the process; the pH adjuster is preferably one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.

6. The method for extracting copper and tin source materials from copper and / or tin oxalates according to claim 5, characterized in that: In the second method of step (1), the alkaline substance participating in the reaction is a potassium-containing alkaline substance alone, or a potassium-containing alkaline substance and a sodium-containing alkaline substance are used simultaneously.

7. The method for extracting copper and tin source materials from copper and / or tin oxalates according to claim 6, characterized in that: When the potassium-containing alkaline substance and the sodium-containing alkaline substance are used simultaneously for the reaction in the method 2 of step (1), the amount of sodium ions added to the reaction solution does not exceed 2 mol / L.

8. The method for extracting copper and tin source materials from copper and / or tin oxalates according to claim 7, characterized in that: The alkaline substance is potassium hydroxide.

9. The method for extracting copper and tin source materials from copper and / or tin oxalates according to claim 8, characterized in that: The reaction temperature of the reaction solution in the second method is controlled within the range of 30° C. to 100° C., and / or the pH value of the reaction solution is adjusted to ≥10 during the reaction.

10. The method for extracting copper and tin source materials from copper and / or tin oxalates according to claim 9, characterized in that: When the oxalate involved in the reaction in step (1) is a mixture of stannous oxalate and cupric oxalate, in order to separate the copper compound and the tin compound in the reaction product filter residue A, the filter residue A is first dissolved in an acidic solution to obtain an acidic mixed solution containing tin salt and copper salt; an alkaline compound is added to the obtained acidic mixed solution containing tin salt and copper salt to adjust the pH value thereof, the precipitation point of stannous hydroxide at a low pH value is used to control the solution to produce stannous hydroxide precipitate, and the stannous hydroxide solid is separated from the acidic copper salt solution by a solid-liquid separation method; the alkaline compound is continuously added to the acidic copper salt solution to generate copper hydroxide and / or copper oxide precipitates in the solution, and the filter residue copper hydroxide and / or copper oxide is collected by solid-liquid separation; The acidic solution is a solution containing at least one of hydrochloric acid, sulfuric acid and formic acid; the alkaline compound is at least one selected from sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate and potassium bicarbonate.

11. The method for extracting copper and tin source materials from copper and / or tin oxalates according to claim 10, characterized in that: When the second method is adopted in step (1), the filtrate B obtained in step (2) is mixed with a compound containing at least one of calcium, manganese, zinc and ferrous elements to produce the desired oxalate product.

12. The method for extracting copper and tin source materials from copper and / or tin oxalates according to claim 11, characterized in that: The pH value of the reaction solution during the treatment of stannous oxalate in step (1) is ≤14 to avoid the formation of soluble stannate.

13. The method for extracting copper and tin source materials from copper and / or tin oxalates according to claim 12, characterized in that: The chlorine gas produced by electrolyzing the acidic etching waste liquid is introduced into an alkaline solution to prepare a hypochlorite solution, which is applied to the chemical reaction of method 1 in step (1).

14. The method for extracting copper and tin source materials from copper and / or tin oxalates according to claim 13, characterized in that: First, copper oxalate is directly added to the alkaline solution reaction tank for preparing hypochlorite, and then the amount of chlorine gas introduced into the reaction tank is controlled by the redox potentiometer installed in the reaction tank, and the amount of alkaline compound added is controlled to make the pH value of the reaction solution meet the process, so that the reaction product is mainly copper oxide to prepare copper oxide powder product.

15. The method for extracting copper and tin source materials from copper and / or tin oxalates according to claim 14, characterized in that: The copper oxalate precipitate obtained by the reaction of the iron-containing acidic etching solution with oxalic acid is subjected to at least one pickling process to remove iron by using hydrochloric acid and / or sulfuric acid.

16. A device for extracting copper and tin source materials from copper and / or tin oxalate using the method of claim 1, characterized in that: Mainly include: At least one hypochlorite reaction tank and / or at least one alkali solution reaction tank, at least one solid-liquid separator; The hypochlorite reaction tank is used for reacting copper oxalate and / or stannous oxalate with hypochlorite in step (1). Stannous hydroxide and / or copper hydroxide and / or copper oxide are obtained; the alkaline solution reaction tank is used for reacting copper oxalate and / or tin oxalate with a solution containing potassium-containing alkaline substances in step (1) to obtain stannous oxide and / or copper oxide; the solid-liquid separator is used for solid-liquid separation of the solid-liquid mixture during the process reaction.

17. The device for extracting copper and tin source materials from copper and / or tin oxalate according to claim 16, characterized in that: The alkaline solution reaction tank is provided with a hot and cold temperature exchanger, so that the copper oxalate and / or tin oxalate react with the solution containing potassium alkaline substances under heating conditions to quickly produce stannous oxide and / or copper oxide.

18. The device for extracting copper and tin source materials from copper and / or tin oxalate according to claim 17, characterized in that: A pH meter and / or a redox potentiometer is added to the hypochlorite reaction tank to allow the reaction process to proceed toward the process target reactant under control.

19. The device for extracting copper and tin source materials from copper and / or tin oxalate according to claim 18, characterized in that: A cleaning tank is added to clean the copper oxalate containing iron and / or the compound residue containing copper and / or tin obtained by the reaction; Add temporary storage tanks to temporarily store materials; Add a common chemical reaction tank for preparing solutions; Add overflow buffer tank to solve the problem of liquid flow between tanks in the device; An electric furnace is added to dry the product powder obtained after solid-liquid separation.

20. The device for extracting copper and tin source materials from copper and / or tin oxalate according to claim 19, characterized in that: A stirrer is added to the hypochlorite reaction tank and / or the alkali solution reaction tank and / or the common chemical reaction tank to uniformly stir the solution; A hot and cold temperature exchanger is added to the hypochlorite reaction tank and / or the ordinary chemical reaction tank to control the temperature of the reaction liquid according to the process requirements.

21. The device for extracting copper and tin source materials from copper and / or tin oxalate according to claim 20, characterized in that: Add an exhaust gas processor to treat the exhaust gas discharged from each tank in an environmentally friendly manner; Detection sensors and automatic detection and feeding controllers are added to realize automatic program control through data collection and processing during the production process; wherein the sensor signal input end of the automatic detection and feeding controller is connected to the sensor signal output end of the detection sensor, and the control signal output end of the automatic detection and feeding controller is connected to the control signal input end of the heater, hot and cold temperature exchanger, agitator, valve and pump in the device; the detection sensors include thermometers, liquid level meters, acidity meters, pH meters, densitometers, redox potentiometers, and chlorine gas detection concentration meters.

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