Treatment method of acid-base copper-containing etching solution

Abstract

The invention relates to a treatment method of an acid-base copper-containing etching solution, which comprises the following steps: continuously adding an acidic copper-containing etching solution into an alkaline copper-containing etching solution at a constant speed until the mixed solution reaches a preset pH value, and sequentially carrying out first reaction and first solid-liquid separation to obtain a copper-containing intermediate; mixing the copper-containing intermediate with ammonia water to carry out a second reaction, and carrying out second solid-liquid separation to obtain copper hydroxide; the problem that a large amount of alkali needs to be consumed in a traditional copper extraction method of the etching liquid is solved, efficient recovery of copper resources in the acid-base copper-containing etching liquid is achieved, the purity of the obtained copper hydroxide product is preferably as high as 99.0% or above, the recovery rate of copper is preferably as high as 98.0% or above, derivation intermediate product ammonia water, a regeneration extraction agent and the like in the treatment process can be circulated and used, and the method is suitable for industrial production. And the water consumption for washing is greatly reduced, the treatment cost is reduced, the economic benefit is improved, and no secondary pollution is generated in the whole process.

Description

Technical Field

[0001] The present invention relates to the technical field of recycling and treatment of printed circuit board etching solutions, and particularly to a method for treating acid-base copper-containing etching solutions. Background Art

[0002] Copper-containing etching waste liquid mainly comes from the printed circuit board (PCB) etching industry. Due to differences in etching processes, various different systems of etching solutions have been derived. Among them, acidic copper chloride etching solutions include multiple systems such as HCl / CuCl2, NH4Cl / CuCl2, or HCl / CuCl2 / NaCl, and the common system is the HCl / CuCl2 / NaCl system; while the composition of alkaline copper chloride etching solution is relatively simple, generally consisting of NH4Cl / CuCl2 / NH3·H2O. The copper content in acidic / alkaline copper-containing etching solutions reaches nearly 10%. Most of the copper in acidic etching solutions exists in the form of CuCl4 2- and in alkaline etching solutions, it mainly exists in the form of Cu(NH3)4 2+ The etching solution has a huge space for resource conversion and utilization due to its high copper content, but other components it contains restrict the choice of disposal processes, often accompanied by a variety of secondary solids and high contents of impurities in wastewater, resulting in problems such as difficult treatment, limited resource utilization, or low reuse value.

[0003] Currently, the conventional method for treating acid and alkaline etching solutions is the neutralization method, that is, adding an alkali solution to the etching solution to convert copper ions into black copper oxide precipitate, and then the tail water is subjected to aeration to remove ammonia and distill sodium chloride. This traditional method has a certain degree of copper resource utilization, but it consumes a large amount of reagents during the treatment process, the total amount of tail water is large, and the resource utilization value of other components is also relatively low. Based on this, researchers have begun to try to synergistically utilize acid and alkaline etching solutions.

[0004] For example, CN112593233B discloses a method for treating printed circuit board etching waste liquid, in which the acidic etching waste liquid and the alkaline etching waste liquid are mixed to undergo a neutralization reaction to obtain basic copper chloride, and then acid is dissolved to synthesize copper sulfate. This method reduces the use of reagents to a certain extent, and the disposal cost can be significantly reduced. However, the basic copper chloride synthesized by this method has a very high viscosity, and a large amount of water is required to wash and remove the attached chloride ions, resulting in a large amount of secondary wastewater to be disposed of.

[0005] For example, CN105836788B discloses a method and device for preparing copper oxychloride using acidic etching solution and alkaline etching solution. This method needs to be carried out at a constant temperature, the acid and alkaline etching solutions are added simultaneously, and the pH needs to be maintained stable at all times. The operation requirements are very high, and there is still a large room for improvement and optimization in the resource utilization of acid and alkaline etching solutions.

[0006] Therefore, how to provide a method for efficiently treating acid-base copper-containing etching solution, reducing its treatment difficulty and danger, achieving full recovery and recycling of resources, and reducing treatment costs is an urgent problem to be solved in this field. Summary of the Invention

[0007] To solve the above technical problems, the present invention provides a method for treating acid-base copper-containing etching solution, which reduces the treatment difficulty and danger of the etching solution while realizing the resource-based disposal of the etching solution, and optimizes the direction of resource products; realizes the regeneration of the extractant, the circulation and utilization of ammonia water, etc., and reduces the operating cost; at the same time, obtains high-purity copper hydroxide products, and no secondary solid waste and secondary wastewater are generated during the whole process.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] The present invention provides a method for treating acid-base copper-containing etching solution, and the treatment method includes the following steps:

[0010] (1) Continuously and uniformly add the acidic copper-containing etching solution to the alkaline copper-containing etching solution until the mixed solution reaches a preset pH value, and sequentially perform a first reaction and a first solid-liquid separation to obtain a copper-containing intermediate;

[0011] (2) Mix the copper-containing intermediate obtained in step (1) with ammonia water for a second reaction, and then perform a second solid-liquid separation to obtain copper hydroxide.

[0012] When mixing the acidic copper-containing etching solution and the alkaline copper-containing etching solution, the present invention selects to continuously and uniformly add the acidic copper-containing etching solution to the alkaline copper-containing etching solution to control the morphology and looseness of the copper-containing intermediate, so that the viscosity of the obtained copper-containing intermediate is reduced and the looseness is greater, which is beneficial to the full contact with ammonia water in the subsequent process, so as to fully react and efficiently convert the copper resources in the acid-base copper-containing etching solution into copper hydroxide products.

[0013] Preferably, the acidic copper-containing etching solution in step (1) includes: 9-10 wt% Cu 2+ , 100-150 g / L Cl - , 3-4 g / L Na + and 1-2 mol / L free acid.

[0014] Among them, 9-10 wt% Cu 2+ , for example, can be 9 wt%, 9.2 wt%, 9.5 wt%, 9.8 wt% or 10 wt%, etc.; 100-150 g / L Cl - , for example, can be 100 g / L, 110 g / L, 120 g / L, 130 g / L, 140 g / L or 150 g / L, etc.; 3-4 g / L Na +, for example, it can be 3 g / L, 3.2 g / L, 3.5 g / L, 3.8 g / L, 4 g / L, etc.; 1 - 2 mol / L free acid, for example, it can be 1 mol / L, 1.2 mol / L, 1.5 mol / L, 1.8 mol / L, 2 mol / L, etc.

[0015] Preferably, the basic copper-containing etching solution in step (1) includes: 9 - 10 wt% Cu 2+ , 80 - 120 g / L Cl - , 2 - 3 g / L Na + and 150 - 200 g / L ammonia nitrogen.

[0016] Among them, 9 - 10 wt% Cu 2+ , for example, it can be 9 wt%, 9.2 wt%, 9.5 wt%, 9.8 wt%, 10 wt%, etc.; 80 - 120 g / L Cl - , for example, it can be 80 g / L, 90 g / L, 100 g / L, 110 g / L, 120 g / L, etc.; 2 - 3 g / L Na + , for example, it can be 2 g / L, 2.2 g / L, 2.5 g / L, 2.8 g / L, 3 g / L, etc.

[0017] Preferably, the water content of the copper-containing intermediate in step (1) is 20 - 30%, for example, it can be 20%, 22%, 24%, 26%, 28%, 30%, etc.

[0018] Preferably, the porosity of the copper-containing intermediate in step (1) is 75 - 85%, for example, it can be 75%, 77%, 79%, 81%, 83%, 85%, etc.

[0019] Preferably, the water content of the copper-containing intermediate in step (1) of the present invention is 20 - 30%, the porosity is preferably 75 - 85%, and the viscosity is low, which is beneficial to the subsequent water washing process to quickly and fully remove the attached Cl - , Na + , NH4 + and a small amount of unreacted Cu 2+ rapidly and completely, which not only ensures the high purity of the subsequent copper hydroxide product, but also is beneficial to the recovery of ammonia nitrogen resources in the acid-base copper-containing etching solution, and the water consumption in the water washing process is greatly reduced, reducing the treatment cost.

[0020] Preferably, the liquid addition speed of continuously and uniformly adding the acidic etching solution to the basic copper-containing etching solution in step (1) is 80 - 120 mL / s, for example, it can be 80 mL / s, 85 mL / s, 90 mL / s, 95 mL / s, 100 mL / s, 105 mL / s, 110 mL / s, 115 mL / s, 120 mL / s, etc.

[0021] In the present invention, it is further preferred that the liquid addition rate of continuously and uniformly adding the acidic etching solution to the alkaline copper-containing etching solution in step (1) is 80-120 mL / s, and the morphology and looseness of the copper-containing intermediate are controlled to have a lower viscosity for facilitating subsequent treatment processes. If the liquid addition rate is too low, the synthesized copper-containing intermediate will turn white and be mixed with black solids, with uneven color and decreased looseness. If the liquid addition rate is too high, the viscosity of the synthesized copper-containing intermediate will increase, it is prone to agglomeration and water accumulation, and the looseness will decrease.

[0022] Preferably, the preset pH value in step (1) is 5-6, for example, it can be 5, 5.2, 5.5, 5.8 or 6, etc.

[0023] Preferably, during the process of continuously and uniformly adding the acidic etching solution to the alkaline copper-containing etching solution in step (1), first stirring is carried out.

[0024] Preferably, the rotation speed of the first stirring is 300-400 rpm, for example, it can be 300 rpm, 320 rpm, 350 rpm, 380 rpm or 400 rpm, etc.

[0025] In the present invention, it is further preferred that the rotation speed of the first stirring is 300-400 rpm, which is beneficial for the full contact reaction of materials, easy for the conversion of the copper-containing intermediate, and conducive to the stability of its morphology and looseness for facilitating subsequent treatment. If the rotation speed of the first stirring is too low, the conversion reaction will be insufficient, the overall conversion rate will be slow, and stratification or precipitation will easily occur, which may result in uneven particle size distribution of the copper-containing intermediate and difficulty in dispersion. If the rotation speed of the first stirring is too high, the instantaneously converted intermediate is easily damaged by shear force, which affects the stable generation. In addition, too high a rotation speed may cause local overheating and partial decomposition of the intermediate, and the complex composition of the intermediate may affect subsequent conversion.

[0026] Preferably, the temperature of the first reaction in step (1) is 25-35 °C, for example, it can be 25 °C, 28 °C, 30 °C, 32 °C or 35 °C, etc.

[0027] Preferably, the time of the first reaction in step (1) is 1-2 h, for example, it can be 1 h, 1.2 h, 1.5 h, 1.8 h or 2 h, etc.

[0028] Preferably, a first filtrate is also obtained after the first solid-liquid separation in step (1).

[0029] Preferably, the copper content in the first filtrate is 500-800 ppm, for example, it can be 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm or 800 ppm, etc.

[0030] Preferably, step (1) further includes mixing the first filtrate and an extraction system for extraction to obtain a copper-containing organic phase and a first raffinate aqueous phase.

[0031] Preferably, the extractant in the extraction system includes any one or a combination of at least two of P204, Mextral CLX50, or Mextral 5640H. Typical but non-limiting combinations include the combination of P204 and Mextral CLX50, the combination of Mextral CLX50 and Mextral 5640H, or the combination of P204 and Mextral 5640H, etc.

[0032] Preferably, the volume ratio of the extractant to the first filtrate is 1:(1 - 2), such as 1:1, 1:1.2, 1:1.5, 1:1.8, or 1:2, etc.

[0033] Preferably, the extraction system further includes a diluent.

[0034] Preferably, the volume ratio of the extractant to the diluent in the extraction system is 1:(1 - 1.5), such as 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, or 1:1.5, etc.

[0035] Preferably, the diluent includes sulfonated kerosene.

[0036] Preferably, the temperature of the extraction is 30 - 40°C, such as 30°C, 32°C, 35°C, 38°C, or 40°C, etc.

[0037] Preferably, the time of the extraction is 20 - 30 min, such as 20 min, 22 min, 25 min, 28 min, or 30 min, etc.

[0038] Preferably, the extraction process is accompanied by oscillation.

[0039] Preferably, the frequency of the oscillation is 80 - 120 rpm, such as 80 rpm, 90 rpm, 100 rpm, 110 rpm, or 120 rpm, etc.

[0040] Preferably, step (1) further includes stripping the copper-containing organic phase to obtain a regenerated extractant and a second raffinate aqueous phase.

[0041] Preferably, the stripping agent used for stripping includes a sulfuric acid solution.

[0042] Preferably, the mass concentration of the sulfuric acid solution is 3 - 6 wt%, such as 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, or 6 wt%, etc.

[0043] Preferably, the volume ratio of the stripping agent to the copper-containing organic phase is 1:(1-2), for example, it can be 1:1, 1:1.2, 1:1.5, 1:1.8, or 1:2, etc.

[0044] Preferably, the temperature of the stripping is 25-35°C, for example, it can be 25°C, 28°C, 30°C, 32°C, or 35°C, etc.

[0045] Preferably, the time of the stripping is 0.5-1 h, for example, it can be 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, or 1 h, etc.

[0046] Preferably, the regenerated extractant is recycled to the extraction step.

[0047] Preferably, step (1) further includes mixing the second raffinate aqueous phase and calcium hydroxide to carry out a third reaction to prepare Bordeaux mixture.

[0048] The Bordeaux mixture of the present invention is a sky-blue colloidal suspension and can be directly used as a plant fungicide.

[0049] Preferably, the mass ratio of the calcium hydroxide to the copper in the second raffinate aqueous phase is (2-3):1, for example, it can be 2:1, 2.2:1, 2.5:1, 2.8:1, or 3:1, etc.

[0050] Preferably, the temperature of the third reaction is 20-30°C, for example, it can be 20°C, 22°C, 24°C, 26°C, 28°C, or 30°C, etc.

[0051] Preferably, the time of the third reaction is 1-2 h, for example, it can be 1 h, 1.2 h, 1.5 h, 1.8 h, or 2 h, etc.

[0052] Preferably, step (1) further includes successively carrying out evaporation concentration and third solid-liquid separation on the first raffinate aqueous phase to obtain a third filtrate. Preferably, sodium chloride is also obtained after the third solid-liquid separation.

[0053] Preferably, step (1) further includes successively carrying out pH adjustment and stripping treatment on the third filtrate to obtain NH3.

[0054] Preferably, the pH adjustment is carried out using calcium hydroxide.

[0055] Preferably, the pH adjustment includes adjusting the pH of the third filtrate to 11-13, for example, it can be 11, 11.2, 11.5, 11.8, 12, 12.2, 12.5, 12.8, or 13, etc.

[0056] Preferably, step (1) further includes absorbing the NH3 to obtain ammonia water and using it in step (2).

[0057] In the present invention, the ammonia water in step (2) can directly use the ammonia water obtained by absorbing the NH3 in step (1), which greatly reduces the treatment cost of the acidic and alkaline copper-containing etching solution.

[0058] Preferably, a calcium chloride solution is also obtained after the stripping treatment.

[0059] Preferably, the purity of the calcium chloride solution is 25-40%, for example, it can be 25%, 28%, 30%, 32%, 35%, 38% or 40%, etc.

[0060] Preferably, the copper-containing intermediate in step (2) is first dispersed in water and then mixed with ammonia water for the second reaction.

[0061] Preferably, the solid-liquid ratio of the copper-containing intermediate to water during the dispersion is 1:(1.5-2), for example, it can be 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2, etc.

[0062] The present invention preferably first disperses the copper-containing intermediate in step (2) in water and then mixes it with ammonia water for the second reaction, and preferably the solid-liquid ratio of the copper-containing intermediate to water during the dispersion is 1:(1.5-2), which is beneficial to the full contact and full reaction of the copper-containing intermediate with ammonia water, improves the conversion rate of copper resources in the copper-containing intermediate to copper hydroxide while ensuring less water consumption, and realizes efficient recovery.

[0063] Preferably, the mass concentration of the ammonia water in step (2) is 15-20 wt%, for example, it can be 15 wt%, 15.5 wt%, 16 wt%, 16.5 wt%, 17 wt%, 17.5 wt%, 18 wt%, 18.5 wt%, 19 wt%, 19.5 wt% or 20 wt%, etc.

[0064] Preferably, the end point of the second reaction in step (2) is a pH of 12-13, for example, it can be 12, 12.2, 12.5, 12.8 or 13, etc.

[0065] Preferably, the copper-containing intermediate in step (2) is first washed with water for the first time and then dispersed in water.

[0066] Preferably, the solid-liquid ratio of the copper-containing intermediate to water during the first water wash is 1:(1.2-2), for example, it can be 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2, etc.

[0067] The present invention further preferably has a solid-liquid ratio of the copper-containing intermediate to water of 1:(1.2 - 2) during the first water washing, which is beneficial to the removal of impurity ions such as Cl - , Na + and NH4 + attached to the copper-containing intermediate, as well as a small amount of unreacted Cu 2+ , thereby further improving the purity of the obtained copper hydroxide product, while ensuring less water consumption and reducing the treatment cost.

[0068] Preferably, the time for the first water washing is 1 - 1.5 h, for example, it can be 1 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h or 1.5 h, etc.

[0069] Preferably, the washing water after the first water washing in step (2) is mixed into the first filtrate.

[0070] The present invention further preferably mixes the washing water after the first water washing in step (2) into the first filtrate, and the washing water contains Cl - , Na + , NH4 + attached to the copper-containing intermediate, as well as a small amount of unreacted Cu 2+ , which is beneficial to the recycling of other resources in the acidic and alkaline copper etching solution except copper.

[0071] Preferably, step (2) further includes sequentially performing a second water washing and drying on the copper hydroxide.

[0072] Preferably, the mass ratio of the copper hydroxide to water during the second water washing is 1:(10 - 15), for example, it can be 1:10, 1:11, 1:12, 1:13, 1:14 or 1:15, etc.

[0073] Preferably, the time for the second water washing is 0.5 - 1 h, for example, it can be 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h or 1 h, etc.

[0074] Preferably, a second filtrate is also obtained after the second solid-liquid separation in step (2).

[0075] Preferably, the washing water after the second water washing is mixed into the second filtrate.

[0076] Preferably, the second filtrate is recycled to step (1) and mixed with the alkaline copper-containing etching solution.

[0077] Preferably, the drying temperature is 50 - 80 °C, for example, it can be 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C or 80 °C, etc.

[0078] Preferably, the drying time is 4 to 6 h, for example, it can be 4 h, 4.5 h, 5 h, 5.5 h or 6 h, etc.

[0079] The obtained copper hydroxide product of the present invention has characteristics such as uniform particle distribution and loose porosity, which can greatly reduce the water consumption for washing and significantly reduce the energy consumption required for drying.

[0080] As a further preferred technical solution of the present invention, the treatment method includes the following steps:

[0081] (1) At a liquid addition rate of 80 to 120 mL / s, under the first stirring condition of 300 to 400 rpm, the acidic copper-containing etching solution is continuously and uniformly added to the alkaline copper-containing etching solution until the pH of the mixed solution is 5 to 6, and after the first reaction at 25 to 35 °C for 1 to 2 h, the first solid-liquid separation is carried out to obtain a copper-containing intermediate and a first filtrate; the water content of the copper-containing intermediate is 20 to 30%; the porosity of the copper-containing intermediate is 75 to 85%;

[0082] Subsequently, the first filtrate and the extraction system are mixed and extracted at 30 to 40 °C for 20 to 30 min to obtain a copper-containing organic phase and a first raffinate aqueous phase; the extractant in the extraction system includes any one or at least two combinations of P204, Mextral CLX50 or Mextral5640H; the volume ratio of the extractant to the first filtrate is 1:(1 to 2);

[0083] After that, the copper-containing organic phase is back-extracted with a sulfuric acid solution with a mass concentration of 3 to 6 wt% at 25 to 35 °C for 0.5 to 1 h to obtain a regenerated extractant and a second raffinate aqueous phase; the volume ratio of the back-extraction agent to the copper-containing organic phase is 1:(1 to 2); then the second raffinate aqueous phase and calcium hydroxide are mixed to carry out a third reaction to prepare Bordeaux mixture; the mass ratio of calcium hydroxide to copper in the second raffinate aqueous phase is (2 to 3):1; and the first raffinate aqueous phase is successively subjected to evaporation concentration and third solid-liquid separation to obtain a third filtrate; then the pH of the third filtrate is adjusted to 11 to 13, and then stripping treatment is carried out to obtain NH3, and the NH3 is absorbed to obtain ammonia water and used in step (2);

[0084] (2) The copper-containing intermediate described in step (1) is first washed with water for 1 to 1.5 h, and the copper-containing intermediate after the first water washing is first dispersed in water, and then mixed with ammonia water with a mass concentration of 15 to 20 wt% for a second reaction, and then the second solid-liquid separation is carried out to obtain a copper hydroxide product; the solid-liquid ratio of the copper-containing intermediate to water during the first water washing is 1:(1.2 to 2); the solid-liquid ratio of the copper-containing intermediate to water during the dispersion is 1:(1.5 to 2); the end point of the second reaction is a pH of 12 to 13.

[0085] Compared with the prior art, the present invention has at least the following beneficial effects:

[0086] (1) The treatment method of the acid-base copper-containing etching solution provided by the present invention controls the morphology and looseness of the copper-containing intermediate through a continuous and uniform liquid addition method, reduces its viscosity and increases its porosity, which is beneficial to the subsequent water washing process and ammonia conversion process, and then improves the purity of the obtained copper hydroxide, up to more than 81.9%, and increases the recovery rate of copper in the acid-base copper-containing etching solution, up to more than 83.7%, realizing the efficient recovery of copper resources in the acid-base copper-containing etching solution, and greatly reducing the water consumption for washing. No secondary solid waste and secondary wastewater are generated during the whole process.

[0087] (2) The treatment method of the acid-base copper-containing etching solution provided by the present invention further improves the purity of the obtained copper hydroxide, preferably up to more than 99.0%, and further increases the recovery rate of copper in the acid-base copper-containing etching solution, preferably up to more than 98.0% by controlling process parameters such as the liquid addition speed of continuous and uniform liquid addition, the rotation speed of the first stirring during the process, and the solid-liquid ratio of the first water washing and dispersion before the subsequent ammonia water reaction; reduces the treatment difficulty and danger of the etching solution, realizes the full recovery and utilization of copper resources and ammonia nitrogen and other resources. At the same time, it greatly reduces the water consumption for washing, and a large number of derivative intermediate products such as regenerated extractant and ammonia water are fully circulated and utilized in the treatment method, greatly reducing the treatment cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0088] Figure 1 is the process flow chart of the treatment method of the acid-base copper-containing etching solution provided in Example 1 of the present invention;

[0089] Figure 2 is the sample diagram of the copper-containing intermediate obtained by the treatment method of the acid-base copper-containing etching solution provided in Example 1 of the present invention;

[0090] Figure 3 is the SEM diagram of the copper-containing intermediate obtained by the treatment method of the acid-base copper-containing etching solution provided in Example 1 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0091] The technical solutions of the present invention will be further described below with reference to the drawings and through specific embodiments. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the patent protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0092] As a specific embodiment of the present invention, a treatment method of an acid-base copper-containing etching solution is provided, and the treatment method includes the following steps:

[0093] (1) At a liquid addition rate of 80 - 120 mL / s, under the first stirring condition of 300 - 400 rpm, continuously and uniformly add the acidic copper-containing etching solution to the alkaline copper-containing etching solution until the pH of the mixed solution is 5 - 6, and carry out the first reaction at 25 - 35 °C for 1 - 2 h, then perform the first solid-liquid separation to obtain a copper-containing intermediate and a first filtrate; the water content of the copper-containing intermediate is 20 - 30%; the porosity of the copper-containing intermediate is 75 - 85%; the copper content in the first filtrate is 500 - 800 ppm;

[0094] Subsequently, mix the first filtrate and the extraction system and carry out extraction for 20 - 30 min at 30 - 40 °C and an oscillation frequency of 80 - 120 rpm to obtain a copper-containing organic phase and a first raffinate aqueous phase; the extractant in the extraction system includes any one or at least two combinations of P204, MextralCLX50, or Mextral 5640H; the volume ratio of the extractant to the first filtrate is 1:(1 - 2); the extraction system further includes a diluent; the diluent includes sulfonated kerosene; the volume ratio of the extractant to the diluent is 1:(1 - 1.5);

[0095] Afterwards, use a sulfuric acid solution with a mass concentration of 3 - 6 wt% to carry out back-extraction on the copper-containing organic phase at 25 - 35 °C for 0.5 - 1 h to obtain a regenerated extractant and a second raffinate aqueous phase; the volume ratio of the back-extraction agent to the copper-containing organic phase is 1:(1 - 2); the regenerated extractant is recycled to the extraction step; then mix the second raffinate aqueous phase and calcium hydroxide, and under the second stirring condition of 20 - 30 °C and 250 - 350 rpm, carry out the third reaction for 1 - 2 h to prepare Bordeaux mixture; the mass ratio of calcium hydroxide to copper in the second raffinate aqueous phase is (2 - 3):1; and perform evaporation concentration and the third solid-liquid separation on the first raffinate aqueous phase in sequence to obtain a third filtrate and sodium chloride; and mix the distilled water obtained into the third filtrate; then adjust the pH of the third filtrate to 11 - 13, and carry out stripping treatment to obtain NH3 and a calcium chloride solution with a purity of 25 - 40%, and the NH3 is absorbed to obtain ammonia water with a mass concentration of 15 - 20 wt% and used in step (2);

[0096] (2) First, wash the copper-containing intermediate obtained in step (1) with water for 1 - 1.5 h, disperse the first water-washed copper-containing intermediate in water first, then mix it with the ammonia water in step (1) for the second reaction, and then perform the second solid-liquid separation to obtain a copper hydroxide product and a second filtrate; the solid-liquid ratio of the copper-containing intermediate to water during the first water washing is 1:(1.2 - 2); the solid-liquid ratio of the copper-containing intermediate to water during the dispersion is 1:(1.5 - 2); the end point of the second reaction is pH 12 - 13; the washing water after the first water washing is mixed into the first filtrate; the second filtrate is recycled and used as the alkaline copper-containing etching solution for recycling;

[0097] Subsequently, the copper hydroxide is first subjected to a second water wash for 0.5 - 1 h, and then dried at 50 - 80 °C for 4 - 6 h; during the second water wash, the mass ratio of the copper hydroxide to water is 1:(10 - 15); the wash water after the second water wash is mixed into the second filtrate.

[0098] I. Example

[0099] Example 1

[0100] This example provides a method for treating an acid-base copper-containing etching solution, which is carried out according to the process flow as Figure 1 shown, and the treatment method includes the following steps:

[0101] (1) At a liquid addition rate of 100 mL / s, under the first stirring condition of 350 rpm, the acidic copper-containing etching solution is continuously and uniformly added to the alkaline copper-containing etching solution until the pH of the mixed solution is 5.6, and after the first reaction at 30 °C for 1.5 h, filtration is carried out to obtain a copper-containing intermediate and a first filtrate; the water content of the copper-containing intermediate is 25%; the porosity of the copper-containing intermediate is 80%; the copper content in the first filtrate is 600 ppm;

[0102] Subsequently, the first filtrate and the extraction system are mixed and subjected to extraction at 35 °C and an oscillation frequency of 90 rpm for 25 min to obtain a copper-containing organic phase and a first raffinate aqueous phase; the extraction system is a Mextral 5640H extractant and sulfonated kerosene with a volume ratio of 1:1.2; the volume ratio of the extractant to the first filtrate is 1:1.5;

[0103] After that, the copper-containing organic phase is back-extracted with a sulfuric acid solution with a mass concentration of 5 wt% at 30 °C for 0.7 h to obtain a regenerated extractant and a second raffinate aqueous phase; the volume ratio of the sulfuric acid solution to the copper-containing organic phase is 1:1.5; the regenerated extractant is recycled to the extraction step; then the second raffinate aqueous phase (dilute copper sulfate solution) and calcium hydroxide are mixed, and under the second stirring condition of 25 °C and 300 rpm, after the third reaction for 1.5 h to prepare Bordeaux mixture; the mass ratio of calcium hydroxide to copper in the second raffinate aqueous phase is 2.8:1; and the first raffinate aqueous phase is successively subjected to evaporation concentration and filtration to obtain a third filtrate and sodium chloride; and the distilled water obtained is mixed into the third filtrate; then the pH of the third filtrate is adjusted to 12, and stripping treatment is carried out to obtain NH3 and a calcium chloride solution with a purity of 29.4%, and the NH3 is absorbed to obtain ammonia water with a mass concentration of 18 wt% and used in step (2);

[0104] (2) The copper-containing intermediate described in step (1) is first washed with water for 1.4 h. The copper-containing intermediate after the first water wash is first dispersed in water, and then mixed with the ammonia water described in step (1) for a second reaction, and then filtered to obtain a copper hydroxide product and a second filtrate; the solid-liquid ratio of the copper-containing intermediate to water during the first water wash is 1:1.5; the solid-liquid ratio of the copper-containing intermediate to water during the dispersion is 1:1.8; the end point of the second reaction is a pH of 12.5; the wash water after the first water wash is mixed into the first filtrate; the second filtrate is recycled to step (1) and recycled as an alkaline copper-containing etching solution;

[0105] Subsequently, the copper hydroxide is first washed with water for 0.8 h, and then dried at 60 °C for 5 h; the mass ratio of the copper hydroxide to water during the second water wash is 1:12; the wash water after the second water wash is mixed into the second filtrate.

[0106] As Figure 2 and Figure 3 shown, from the sample diagram and SEM diagram of the copper-containing intermediate obtained in step (1) of this example, it can be seen that the copper-containing intermediate is a green solid powder, and the color and particle size distribution are uniform, and the copper-containing intermediate is cubic particles, with good dispersibility, uniform shape and smooth surface.

[0107] The component compositions and their corresponding contents of the acidic copper-containing etching solution and the alkaline copper-containing etching solution in this example are shown in Table 1;

[0108] Table 1

[0109]

[0110]

[0111] Note: "-" in Table 1 indicates no relevant data.

[0112] Example 2

[0113] This example provides a method for treating an acid-base copper-containing etching solution, and the treatment method includes the following steps:

[0114] (1) At a liquid addition speed of 80 mL / s, under the first stirring condition of 300 rpm, the acidic copper-containing etching solution is continuously and uniformly added to the alkaline copper-containing etching solution until the pH of the mixed solution is 5, and after the first reaction at 25 °C for 1 h, it is then filtered by suction to obtain a copper-containing intermediate and a first filtrate; the water content of the copper-containing intermediate is 20%; the porosity of the copper-containing intermediate is 75%; the copper content in the first filtrate is 500 ppm;

[0115] Subsequently, the first filtrate and the extraction system are mixed and subjected to extraction for 20 min at 30°C and an oscillation frequency of 80 rpm to obtain a copper-containing organic phase and a first raffinate aqueous phase; the extraction system is a Mextral CLX50 extractant and sulfonated kerosene with a volume ratio of 1:1; the volume ratio of the extractant to the first filtrate is 1:1;

[0116] After that, the copper-containing organic phase is subjected to stripping with a sulfuric acid solution with a mass concentration of 3 wt% at 25°C for 0.5 h to obtain a regenerated extractant and a second raffinate aqueous phase; the volume ratio of the sulfuric acid solution to the copper-containing organic phase is 1:1; the regenerated extractant is recycled to the extraction step; then the second raffinate aqueous phase (dilute copper sulfate solution) and calcium hydroxide are mixed, and under the second stirring condition of 20°C and 250 rpm, a third reaction is carried out for 1 h to prepare Bordeaux mixture; the mass ratio of calcium hydroxide to copper in the second raffinate aqueous phase is 2:1; and the first raffinate aqueous phase is sequentially subjected to evaporation concentration and filtration to obtain a third filtrate and sodium chloride; and the distilled water obtained is mixed into the third filtrate; then the pH of the third filtrate is adjusted to 11, and stripping treatment is carried out to obtain NH3 and a calcium chloride solution with a purity of 32.6%; the NH3 is absorbed to obtain ammonia water with a mass concentration of 15 wt% and used in step (2);

[0117] (2) The copper-containing intermediate in step (1) is first washed with water for 1 h, and the copper-containing intermediate after the first water wash is first dispersed in water, and then mixed with the ammonia water in step (1) for a second reaction, and then filtered to obtain a copper hydroxide product and a second filtrate; the solid-liquid ratio of the copper-containing intermediate to water during the first water wash is 1:1.2; the solid-liquid ratio of the copper-containing intermediate to water during the dispersion is 1:1.5; the end point of the second reaction is pH 12; the wash water after the first water wash is mixed into the first filtrate; the second filtrate is recycled to step (1) and recycled as an alkaline copper-containing etching solution;

[0118] Subsequently, the copper hydroxide is first washed with water for 0.5 h and then dried at 50°C for 6 h; the mass ratio of the copper hydroxide to water during the second water wash is 1:10; the wash water after the second water wash is mixed into the second filtrate.

[0119] In this example, the component compositions and their corresponding contents of the acidic copper-containing etching solution and the alkaline copper-containing etching solution are shown in Table 2;

[0120] Table 2

[0121] Item <![CDATA[Cu 2+ / wt%]]> <![CDATA[Cl - / g / L]]> <![CDATA[Sodium + / g / L]]> Free acid / mol / L Ammonia nitrogen / g / L Acidic copper-containing etching solution 9.8 110 3.8 1.2 - Alkaline copper-containing etching solution 9.5 110 2.2 - 160

[0122] Note: "-" in Table 2 indicates no relevant data.

[0123] Example 3

[0124] This embodiment provides a method for treating an acid-base copper-containing etching solution, and the treatment method includes the following steps:

[0125] (1) At a liquid addition rate of 120 mL / s and under the first stirring condition of 400 rpm, continuously and uniformly add the acidic copper-containing etching solution to the alkaline copper-containing etching solution until the pH of the mixed solution is 6, and carry out the first reaction at 35 °C for 2 h, and then obtain a copper-containing intermediate and a first filtrate through suction filtration; the water content of the copper-containing intermediate is 30%; the porosity of the copper-containing intermediate is 85%; the copper content in the first filtrate is 800 ppm;

[0126] Subsequently, mix the first filtrate and the extraction system and carry out extraction for 30 min at 40 °C and an oscillation frequency of 120 rpm to obtain a copper-containing organic phase and a first raffinate aqueous phase; the extraction system is a Mextral CLX50 extractant and sulfonated kerosene with a volume ratio of 1:1.5; the volume ratio of the extractant to the first filtrate is 1:2;

[0127] Then, carry out back-extraction of the copper-containing organic phase with a sulfuric acid solution with a mass concentration of 6 wt% at 35 °C for 1 h to obtain a regenerated extractant and a second raffinate aqueous phase; the volume ratio of the sulfuric acid solution to the copper-containing organic phase is 1:2; the regenerated extractant is recycled to the extraction step; mix the second raffinate aqueous phase (dilute copper sulfate solution) and calcium hydroxide, and under the second stirring condition of 30 °C and 350 rpm, carry out the third reaction for 2 h to prepare Bordeaux mixture; the mass ratio of calcium hydroxide to copper in the second raffinate aqueous phase is 3:1; and carry out evaporation concentration and filtration on the first raffinate aqueous phase in sequence to obtain a third filtrate and sodium chloride; and the distilled water obtained is mixed into the third filtrate; then adjust the pH of the third filtrate to 13, and carry out stripping treatment to obtain NH3 and a calcium chloride solution with a purity of 28.7%, and the NH3 is absorbed to obtain ammonia water with a mass concentration of 20 wt% and used in step (2);

[0128] (2) First wash the copper-containing intermediate obtained in step (1) for 1.5 h, disperse the first washed copper-containing intermediate in water first, then mix it with the ammonia water in step (1) for a second reaction, and then obtain a copper hydroxide product and a second filtrate through filtration; the solid-liquid ratio of the copper-containing intermediate to water during the first washing is 1:2; the solid-liquid ratio of the copper-containing intermediate to water during the dispersion is 1:2; the end point of the second reaction is pH 13; the washing water after the first washing is mixed into the first filtrate; the second filtrate is recycled to step (1) for recycling as the alkaline copper-containing etching solution;

[0129] Subsequently, the copper hydroxide is first subjected to a second water wash for 1 h and then dried at 80 °C for 4 h; during the second water wash, the mass ratio of the copper hydroxide to water is 1:15; the wash water after the second water wash is mixed into the second filtrate.

[0130] In this example, the component compositions and their corresponding contents of the acidic copper-containing etching solution and the alkaline copper-containing etching solution are shown in Table 3;

[0131] Table 3

[0132] Item <![CDATA[Cu 2+ / wt%]]> <![CDATA[Cl - / g / L]]> <![CDATA[Sodium + / g / L]]> Free acid / mol / L Ammonia nitrogen / g / L Acidic copper-containing etching solution 10 140 3.2 2 - Alkaline copper-containing etching solution 9.8 120 2.8 - 200

[0133] Note: "-" in Table 3 indicates no relevant data.

[0134] Example 4

[0135] This example provides a method for treating an acid-base copper-containing etching solution. Except that the liquid addition rate in step (1) is 70 mL / s, the rest are the same as in Example 1.

[0136] The water content of the copper-containing intermediate in step (1) of this example is 42.6%, and the porosity is 37%.

[0137] Example 5

[0138] This example provides a method for treating an acid-base copper-containing etching solution. Except that the liquid addition rate in step (1) is 130 mL / s, the rest are the same as in Example 1.

[0139] The water content of the copper-containing intermediate in step (1) of this example is 56%, and the porosity is 24%.

[0140] Example 6

[0141] This example provides a method for treating an acid-base copper-containing etching solution. Except that the rotation speed of the first stirring in step (1) is 200 rpm, the rest are the same as in Example 1.

[0142] The water content of the copper-containing intermediate in step (1) of this example is 46.5%, and the porosity is 38%.

[0143] Example 7

[0144] This example provides a method for treating an acid-base copper-containing etching solution. Except that the rotation speed of the first stirring in step (1) is 500 rpm, the rest are the same as in Example 1.

[0145] The water content of the copper-containing intermediate in step (1) of this example is 53.7%, and the porosity is 42%.

[0146] Example 8

[0147] This embodiment provides a method for treating an acid-base copper-containing etching solution. Except that the solid-liquid ratio of the copper-containing intermediate to water is 1:1 during the first water washing in step (2), the rest are the same as those in Embodiment 1.

[0148] Embodiment 9

[0149] This embodiment provides a method for treating an acid-base copper-containing etching solution. Except that the solid-liquid ratio of the copper-containing intermediate to water is 1:2.2 during the first water washing in step (2), the rest are the same as those in Embodiment 1.

[0150] Embodiment 10

[0151] This embodiment provides a method for treating an acid-base copper-containing etching solution. Except that the solid-liquid ratio of the copper-containing intermediate to water is 1:1.2 during the dispersion in step (2), the rest are the same as those in Embodiment 1.

[0152] Embodiment 11

[0153] This embodiment provides a method for treating an acid-base copper-containing etching solution. Except that the solid-liquid ratio of the copper-containing intermediate to water is 1:2.2 during the dispersion in step (2), the rest are the same as those in Embodiment 1.

[0154] II. Comparative Examples

[0155] Comparative Example 1

[0156] This comparative example provides a method for treating an acid-base copper-containing etching solution. Except that when adding the acidic copper-containing etching solution to the alkaline copper-containing etching solution in step (1), the addition is not continuous but at a uniform speed in each addition stage. First, add half of the amount of the copper-containing etching solution at a liquid addition speed of 100 mL / s, then stop adding the liquid for 10 minutes, and then continue to add the remaining acidic copper-containing etching solution to the alkaline copper-containing etching solution at a liquid addition speed of 100 mL / s, the rest are the same as those in Embodiment 1.

[0157] In this comparative example, due to the non-continuous but uniform liquid addition, local concentration in the reaction system is too high or too low, which may trigger various side reactions, resulting in diverse intermediate compositions. The unevenness of the products is extremely likely to cause an increase in the viscosity of the intermediate and make it difficult to separate. The water content of the copper-containing intermediate obtained in step (1) is 61.2%, and the porosity is 28%.

[0158] Comparative Example 2

[0159] This comparative example provides a method for treating an acid-base copper-containing etching solution. Except that in step (1), when adding the acidic copper-containing etching solution to the alkaline copper-containing etching solution, the addition is continuous but not uniform. First, add 1 / 3 of the amount of the copper-containing etching solution at a liquid addition rate of 80 mL / s, then add 1 / 3 of the amount of the copper-containing etching solution at a liquid addition rate of 100 mL / s, and finally add 1 / 3 of the amount of the copper-containing etching solution at a liquid addition rate of 120 mL / s. The rest is the same as in Example 1.

[0160] In this comparative example, due to the continuous but non-uniform addition of the liquid, the concentration distribution of the reaction system materials is uneven, the conversion efficiency is affected, and it is also extremely easy to promote the generation of various by-products, resulting in complex components of the product and difficult dispersion of agglomerates. As a result, the water content of the copper-containing intermediate obtained in step (1) is 54.7%, and the porosity is 35%.

[0161] III. Tests and Results

[0162] The purity of the copper hydroxide obtained in the method for treating the acid-base copper-containing etching solution provided in the above examples and comparative examples and the recovery rate of copper in the treatment method (excluding the copper content in Bordeaux mixture) were tested and calculated. The results are shown in Table 4;

[0163] Table 4

[0164] Item Purity of copper hydroxide / % Recovery rate of copper / % Example 1 99.4 98.5 Example 2 99.6 98.6 Example 3 99.2 98.3 Example 4 87.5 89.4 Example 5 81.9 83.7 Example 6 88.4 89.1 Example 7 82.6 84.3 Example 8 89.2 88.6 Example 9 98.9 96.3 Example 10 88.6 88.2 Example 11 98.8 96.0 Comparative Example 1 81.4 82.6 Comparative Example 2 80.6 81.8

[0165] It can be seen from the data in Table 4 that:

[0166] (1) From Examples 1 to 3, it can be seen that: for the method for treating the acid-base copper-containing etching solution provided by the present invention, by controlling the morphology and looseness of the copper-containing intermediate, the purity of the obtained copper hydroxide product and the recovery rate of copper are improved. The purity of copper hydroxide is as high as over 99.0%; the recovery rate of copper in the acid-base copper-containing etching solution is as high as over 98.0% (excluding the copper content in Bordeaux mixture), realizing the efficient recovery and utilization of copper in the acid-base copper-containing etching solution.

[0167] (2) From the comprehensive implementation of Example 1 and Examples 4 to 7, it can be seen that whether the liquid addition speed in step (1) of Example 4 is too slow or the liquid addition speed in step (1) of Example 5 is too fast, or the rotation speed of the first stirring in step (1) of Example 5 is too slow or too fast, it will result in a decrease in the purity of copper hydroxide and a decrease in the recovery rate of copper. This indicates that the present invention further preferably sets the liquid addition speed of continuously and uniformly adding the acidic etching solution to the alkaline copper-containing etching solution in step (1) to be 80 - 120 mL / s, and further preferably sets the rotation speed of the first stirring to be 300 - 400 rpm, which further improves the looseness of the copper-containing intermediate, reduces its viscosity, enables the attached impurity ions to be efficiently removed with less water, and can fully react with the subsequent ammonia water, thereby improving the purity of the copper hydroxide product and the recovery rate of copper.

[0168] (3) From the comprehensive implementation of Example 1 and Examples 8 to 11, it can be seen that in Example 8, the solid-liquid ratio of the copper-containing intermediate to water during the first water washing is too large, that is, the amount of water used is too small, resulting in the inability to fully remove the impurity ions attached to the copper-containing intermediate, and the purity of the copper hydroxide product is reduced to 89.2%. In Example 9, the solid-liquid ratio of the copper-containing intermediate to water during the first water washing is too small, that is, the amount of water used is too large, but it does not significantly improve the purity of the obtained copper hydroxide product, but instead increases the treatment cost. In Example 10, the solid-liquid ratio of the copper-containing intermediate to water during the dispersion is too large, that is, the amount of water used is too small, resulting in the inability of the copper-containing intermediate to fully react with ammonia water, and the recovery rate of copper is reduced to 88.6%. In Example 11, the solid-liquid ratio of the copper-containing intermediate to water during the dispersion is too small, that is, the amount of water used is too large, but it does not significantly improve the recovery rate of copper, but instead causes an increase in cost. This indicates that the present invention further preferably sets the solid-liquid ratio of the copper-containing intermediate to water during the first water washing in step (2) to be 1:(1.2 - 2), and further preferably sets the solid-liquid ratio of the copper-containing intermediate to water during the dispersion in step (2) to be 1:(1.5 - 2), which further improves the purity of the obtained copper hydroxide and the recovery rate of copper while ensuring low cost.

[0169] (4) From the comprehensive implementation of Example 1 and Comparative Example 1 and Comparative Example 2, it can be seen that when adding the acidic copper-containing etching solution to the alkaline copper-containing etching solution, in Comparative Example 1, the liquid is not added continuously and uniformly but discontinuously but uniformly, and in Comparative Example 2, the liquid is not added continuously and uniformly but continuously but non-uniformly, both of which result in an increase in the water content and viscosity of the obtained copper-containing intermediate and a decrease in the porosity, thereby making it difficult to remove the impurity ions attached to the copper-containing intermediate during the subsequent first water washing, and the reaction is insufficient due to insufficient contact during the subsequent reaction with ammonia water, ultimately resulting in a decrease in the purity of the obtained copper hydroxide product and the recovery rate of copper.

[0170] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by any person skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A method for treating an acid-base copper-containing etching solution, characterized in that, The described treatment method includes the following steps: (1) Continuously and uniformly add the acidic copper-containing etching solution to the alkaline copper-containing etching solution until the mixed solution reaches a preset pH value, and sequentially carry out a first reaction and a first solid-liquid separation to obtain a copper-containing intermediate; (2) Mix the copper-containing intermediate described in step (1) with ammonia water for a second reaction, and then carry out a second solid-liquid separation to obtain copper hydroxide.

2. The processing method according to claim 1, wherein The acidic copper-containing etching solution in step (1) includes: 9-10 wt% Cu 2+ , 100-150 g / L Cl - , 3-4 g / L Na + and 1-2 mol / L free acid; Preferably, the alkaline copper-containing etchant in step (1) comprises: 9-10 wt% Cu 2+ , 80-120 g / L Cl - , 2-3 g / L Na + and 150-200 g / L ammonia nitrogen.

3. The processing method according to claim 1 or 2, characterized in that, The water content of the copper-containing intermediate described in step (1) is 20-30%; Preferably, the porosity of the copper-containing intermediate described in step (1) is 75-85%.

4. The processing method according to any one of claims 1 to 3, characterized in that The liquid addition rate of continuously and uniformly adding the acidic etching solution to the alkaline copper-containing etching solution in step (1) is 80-120 mL / s; Preferably, the preset pH value in step (1) is 5-6; Preferably, a first stirring is accompanied during the process of continuously and uniformly adding the acidic etching solution to the alkaline copper-containing etching solution in step (1); Preferably, the rotation speed of the first stirring is 300-400 rpm; Preferably, the temperature of the first reaction in step (1) is 25-35 °C; Preferably, the time of the first reaction in step (1) is 1-2 h.

5. The processing method according to any one of claims 1 to 4, characterized in that A first filtrate is also obtained after the first solid-liquid separation in step (1); Preferably, step (1) further includes mixing the first filtrate and an extraction system for extraction to obtain a copper-containing organic phase and a first raffinate aqueous phase; Preferably, the extractant in the extraction system includes any one or a combination of at least two of P204, Mextral CLX50, or Mextral 5640H; Preferably, the volume ratio of the extractant to the first filtrate is 1:(1-2); Preferably, the temperature of the extraction is 30-40 °C; Preferably, the time of the extraction is 20-30 min.

6. The processing method according to claim 5, characterized in that Step (1) further includes stripping the copper-containing organic phase to obtain a regenerated extractant and a second raffinate aqueous phase; Preferably, the stripping agent used for stripping includes a sulfuric acid solution; Preferably, the mass concentration of the sulfuric acid solution is 3-6 wt%; Preferably, the volume ratio of the stripping agent to the copper-containing organic phase is 1:(1-2); Preferably, the temperature of the stripping is 25-35 °C; Preferably, the time of the stripping is 0.5-1 h; Preferably, step (1) further includes mixing the second raffinate aqueous phase and calcium hydroxide for a third reaction to prepare Bordeaux mixture; Preferably, the mass ratio of calcium hydroxide to copper in the second raffinate aqueous phase is (2-3):

1.

7. The processing method according to claim 5 or 6, characterized in that, Step (1) further includes sequentially carrying out evaporation and concentration and a third solid-liquid separation on the first raffinate aqueous phase to obtain a third filtrate; Preferably, step (1) further includes sequentially carrying out pH adjustment and stripping treatment on the third filtrate to obtain NH3; Preferably, the pH adjustment includes adjusting the pH of the third filtrate to 11-13; Preferably, step (1) further includes absorbing the NH3 to obtain ammonia water and using it in step (2).

8. The processing method according to any one of claims 1 to 7, characterized in that The copper-containing intermediate in step (2) is first dispersed in water and then mixed with ammonia water for a second reaction; Preferably, the solid-liquid ratio of the copper-containing intermediate to water during dispersion is 1:(1.5-2); Preferably, the mass concentration of the ammonia water in step (2) is 15-20 wt%. Preferably, the end point of the second reaction in step (2) is a pH of 12-13.

9. The processing method according to any one of claims 1 to 8, characterized in that The copper-containing intermediate in step (2) is first washed with water for the first time and then dispersed in water. Preferably, the solid-liquid ratio of the copper-containing intermediate to water during the first water washing is 1:(1.2-2). Preferably, the time for the first water washing is 1-1.5 h.

10. The processing method according to any one of claims 1 to 9, characterized in that, The treatment method comprises the following steps: (1) At a liquid addition rate of 80-120 mL / s, under the first stirring condition of 300-400 rpm, the acidic copper-containing etching solution is continuously and uniformly added to the alkaline copper-containing etching solution until the pH of the mixed solution is 5-6, and after the first reaction at 25-35 °C for 1-2 h, the first solid-liquid separation is carried out to obtain a copper-containing intermediate and a first filtrate; the water content of the copper-containing intermediate is 20-30%; the porosity of the copper-containing intermediate is 75-85%; Subsequently, the first filtrate and the extraction system are mixed and extracted at 30-40 °C for 20-30 min to obtain a copper-containing organic phase and a first raffinate aqueous phase; the extractant in the extraction system includes any one or at least two combinations of P204, Mextral CLX50 or Mextral 5640H; the volume ratio of the extractant to the first filtrate is 1:(1-2); After that, the copper-containing organic phase is back-extracted with a sulfuric acid solution with a mass concentration of 3-6 wt% at 25-35 °C for 0.5-1 h to obtain a regenerated extractant and a second raffinate aqueous phase; the volume ratio of the back-extraction agent to the copper-containing organic phase is 1:(1-2); then the second raffinate aqueous phase and calcium hydroxide are mixed for the third reaction to prepare Bordeaux mixture; the mass ratio of calcium hydroxide to copper in the second raffinate aqueous phase is (2-3):1; and the first raffinate aqueous phase is sequentially subjected to evaporation concentration and the third solid-liquid separation to obtain a third filtrate; then the pH of the third filtrate is adjusted to 11-13, and then stripping treatment is carried out to obtain NH3, and the NH3 is absorbed to obtain ammonia water and used in step (2); (2) The copper-containing intermediate in step (1) is first washed with water for the first time for 1-1.5 h, the copper-containing intermediate after the first water washing is first dispersed in water, and then mixed with ammonia water with a mass concentration of 15-20 wt% for the second reaction, and then the second solid-liquid separation is carried out to obtain a copper hydroxide product; the solid-liquid ratio of the copper-containing intermediate to water during the first water washing is 1:(1.2-2); the solid-liquid ratio of the copper-containing intermediate to water during the dispersion is 1:(1.5-2); the end point of the second reaction is a pH of 12-13.

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