Cascade recovery system and method for copper-nickel waste liquid in electronic electroplating industry

Abstract

The invention provides a stepped recovery system and method for copper-nickel waste liquid in the electronic electroplating industry, and belongs to the technical field of electroplating sewage treatment. Comprising an electroplating tank for storing the copper-nickel waste liquid, a reaction kettle connected with the electroplating tank, solid-liquid separation equipment connected with the reaction kettle, an extraction assembly connected with the liquid outlet end of the solid-liquid separation equipment, and an electrolysis recovery assembly and a condensation crystallization assembly which are connected with the extraction assembly, copper ions in the copper-nickel waste liquid are replaced in the form of elementary substance copper powder through the reaction kettle, the nickel-containing waste liquid is extracted through the extraction assembly, separation and concentration of nickel are achieved, metal nickel is recycled through the electrolysis effect of the electrolysis recycling assembly, nickel sulfate crystals are recycled through the evaporation, condensation and crystallization effect of the condensation and crystallization assembly, and the recovery efficiency of the nickel sulfate crystals is improved. The waste liquid is subjected to multi-stage treatment, stepped recovery of metal ions in the copper-nickel waste liquid is achieved, heavy metal can be effectively removed, and resource reutilization of the waste liquid can be achieved on the basis of the high recovery rate.

Description

Technical Field

[0001] The invention belongs to the technical field of electroplating wastewater treatment, and specifically relates to a cascade recovery system and method for copper-nickel waste liquid in the electronic electroplating industry. Background Art

[0002] In today's electronic electroplating manufacturing industry, with the advancement of technology and the growth of market demand, large-scale production has become the norm. In the process of electronic circuit board manufacturing and electroplating parts production, copper and nickel are commonly used metal materials, and a large amount of copper-containing and nickel-containing mixed waste liquid is generated during the production process.

[0003] Traditional copper-nickel mixed waste liquid treatment is mainly based on chemical precipitation, which not only causes serious waste of copper and nickel resources, but also may cause serious secondary pollution to the environment.

[0004] In this context, it is particularly important to implement cascade recovery of copper-nickel waste liquid. The cascade recovery technology can not only effectively remove heavy metals through multi-stage treatment of waste liquid, but also realize the resource reuse of waste liquid on the basis of a higher recovery rate. Through the step-by-step recovery and extraction of metal ions, enterprises can not only reduce the overall cost of waste liquid treatment, but also improve economic benefits through resource reuse and reduce the impact on the environment. Therefore, there is an urgent need for a cascade recovery system for copper-nickel waste liquid in the electronic electroplating industry. Summary of the invention

[0005] In view of the above-mentioned problems, the present invention provides a cascade recovery system and method for copper-nickel waste liquid in the electronic electroplating industry.

[0006] The technical solution of the invention is: a cascade recovery system for copper-nickel waste liquid in the electronic electroplating industry, comprising an electroplating tank for storing copper-nickel waste liquid, a reactor connected to the electroplating tank, a solid-liquid separation device connected to the reactor, an extraction component connected to the liquid outlet of the solid-liquid separation device, an electrolytic recovery component and a condensation crystallization component connected to the extraction component;

[0007] The solid-liquid separation device is connected to a first recovery cylinder for storing copper powder, the extraction component is connected to a storage cylinder for storing polyaluminium chloride and polyaluminium sulfate solution, and a concentrator is provided at the connection between the extraction component and the storage cylinder;

[0008] The extraction component is connected with a Y-shaped connecting pipe, and the two free ends of the Y-shaped connecting pipe are respectively connected with the electrolysis recovery component and the condensation crystallization component, and the connection points are both provided with solenoid valves;

[0009] The electrolytic recovery component is connected to a second recovery cylinder for recovering metallic nickel, and the condensation crystallization component is connected to a third recovery cylinder for recovering nickel sulfate crystals;

[0010] The first recovery cylinder comprises a recovery cylinder body with an inverted V-shaped structure at the bottom end, a mounting plate connected to the bottom end of the recovery cylinder body through a rotating shaft, and a plurality of discharge seats evenly distributed on the outer wall of the recovery cylinder body along the circumferential direction, wherein the discharge seats are provided with a discharge valve, and the mounting plate is provided with a filling plate corresponding to the discharge seats one by one and located at the bottom end of the discharge valve;

[0011] The first recovery tube, the second recovery tube and the third recovery tube have the same structure.

[0012] Furthermore, the extraction component includes an extraction tower with a vertical buckle groove on the side wall, an upper buffer tank and a lower buffer tank arranged at the upper and lower ends of the extraction tower, and a guide plate assembly installed in the extraction tower through the vertical buckle groove, the upper buffer tank is connected to the liquid outlet end of the solid-liquid separation equipment, the lower buffer tank is connected to the Y-shaped connecting pipe, an aeration device is provided in the extraction tower, the upper buffer tank is connected to an exhaust valve, and the bottom end of the lower buffer tank is connected to a sewage valve.

[0013] Description: After the nickel-containing waste liquid separated by the solid-liquid separation equipment enters the extraction component, it first enters the extraction tower through the upper buffer tank, and the extractant is added to the extraction tower. The extractant and the nickel-containing waste liquid flow from top to bottom in sequence and are evenly mixed through the diversion of the guide plate component, thereby realizing the separation and concentration of nickel. The high-concentration nickel solution obtained by extraction enters the electrolytic recovery component through the lower buffer tank and realizes nickel recovery in the form of metallic nickel through electrolysis, or enters the condensation crystallization component through the lower buffer tank and realizes nickel recovery in the form of nickel sulfate crystals through evaporation, condensation and crystallization. The gas generated during the extraction process is discharged through the exhaust valve to prevent excessive pressure and potential dangers. The treated waste liquid is discharged through the drain valve, and the remaining waste liquid after extraction is further concentrated by the concentrator to form polyaluminum chloride and polyaluminum sulfate solutions. Finally, the polyaluminum chloride and polyaluminum sulfate solutions can be stored in the storage cylinder.

[0014] Furthermore, the guide plate assembly includes a vertical snap-on plate snapped to the outside of the vertical snap-on groove, a plurality of mounting circular openings arranged on the vertical snap-on plate from top to bottom, a spiral rotating rod rotatably installed in one-to-one correspondence with the mounting circular openings, a guide circular plate connected to one end of the spiral rotating rod, and an annular guide plate connected to the bottom end of the guide circular plate through a vertical annular mesh plate, and the end of the spiral rotating rod opposite to the guide circular plate extends to the outside of the mounting circular opening.

[0015] Description: When the extractant and the nickel-containing waste liquid flow from top to bottom in sequence, they first flow to the guide circular plate at the top, and are dispersed to the corresponding annular guide plate through the guide circular plate for the first time, and then further dispersed to the next guide circular plate through the vertical annular mesh plate, and the process is repeated. After the extractant and the nickel-containing waste liquid pass through each guide circular plate, annular guide plate and vertical annular mesh plate, they are dispersed and mixed many times, and the droplets are continuously refined, which improves the mass transfer efficiency between the two, is beneficial to the transfer of nickel ions from the waste liquid to the extractant, and improves the overall extraction effect. When it is necessary to clean the inner wall of the extraction tower, rotate each spiral rotating rod in turn so that the spiral rotating rod drives the corresponding guide circular plate to turn to the vertical direction. When each guide circular plate is rotated to the vertical direction, the contact area between the annular guide plate and the extraction tower is greatly reduced, which is convenient for cleaning the inner wall of the extraction tower.

[0016] Furthermore, the outer diameter of the annular guide plate is the same as the inner diameter of the extraction tower.

[0017] Note: By limiting the outer diameter of the annular guide plate to be the same as the inner diameter of the extraction tower, the purpose is to make the annular guide plate fit closely with the inner wall of the extraction tower when in a horizontal position, so as to prevent the extractant and nickel-containing waste liquid from flowing through the gap between the annular guide plate and the inner wall of the extraction tower, affecting the flow path of the extractant and the nickel-containing waste liquid, and thus reducing the extraction effect.

[0018] Furthermore, the electrolytic recovery assembly includes an electrolytic cylinder, a replacement cylinder connected to the electrolytic cylinder and provided with a control valve at the connection, a filter screen disposed in the electrolytic cylinder, and an electrolytic stirring member disposed in the electrolytic cylinder and located at the bottom of the filter screen;

[0019] The electrolytic stirring member includes a rotating mounting rod whose upper end is connected to the filter screen and whose bottom end is connected to a rotating motor, a rotating mounting sleeve which is sleeved on the outside of the rotating mounting rod and has a plurality of vertical mounting grooves on the side wall, two mounting adjustment rods which are arranged in each of the vertical mounting grooves and connected by an electric telescopic rod, and an electrolytic stirring plate connected to each mounting adjustment rod.

[0020] Description: When the high-concentration nickel solution obtained by extraction enters the electrolytic recovery component through the lower buffer tank, it first enters the electrolytic cylinder, and the solid matter and residue that are not completely reacted during the extraction process are filtered out through the filter mesh plate. At the same time, the composition of the high-concentration nickel solution entering the electrolytic area can be made more uniform. After the filtration is completed, the rotating motor is started, and the rotating mounting rod and the rotating mounting sleeve installed on the outer wall of the rotating mounting rod are driven by the rotating motor to rotate. At the same time, the high-concentration nickel solution is stirred by the electrolytic stirring plate while being electrolytically treated. Stirring can accelerate the diffusion of ions in the solution and improve the electrolytic efficiency. After the electrolytic treatment, the metal nickel is recovered. Finally, the control valve is opened to transfer the solution in the electrolytic cylinder that has been electrolytically treated to the displacement cylinder, and chemical reagents are added to the displacement cylinder for ion exchange treatment.

[0021] Furthermore, the electrolytic stirring plate includes a plurality of first electrolytic rods distributed in parallel from left to right, a stirring mesh plate arranged between two adjacent first electrolytic rods, mounting grooves are arranged on opposite sides of the first electrolytic rods located in the same vertical mounting groove and at the upper and lower ends, and a telescopic rod is arranged in each mounting groove, and the two telescopic rods located in the same vertical direction are connected by a second electrolytic rod.

[0022] Description: When the electrolytic stirring plate is in use, the distance between the two relatively distributed installation adjustment rods can be driven by the electric telescopic rod, and the first electrolytic rods and the stirring mesh plates relatively distributed in the vertical direction will move away from or close to each other. At the same time, the telescopic rod will also be extended or compressed, so as to achieve the purpose of adjusting the stirring area, which can not only avoid energy waste caused by excessive stirring, but also stir the solution more comprehensively and improve the nickel recovery rate. The uniform distribution of the first electrolytic rod and the second electrolytic rod helps to form a more uniform electric field, which can ensure that the current is more evenly distributed in the entire electrolyte volume during the electrolysis process, thereby improving the migration efficiency of nickel ions.

[0023] Furthermore, the side wall of the electrolytic tube is provided with an annular mounting opening, and the filter mesh plate includes a plurality of filter drawers circumferentially distributed in the annular mounting opening, a filter plate arranged at the bottom end of the filter drawer, and a sealing plate arranged outside the filter drawer and in contact with the outer wall of the electrolytic tube, and the inner wall of the sealing plate is connected to the outer wall of the electrolytic tube via a suction cup.

[0024] Description: By installing several filter drawers in the annular installation port, the high-concentration nickel solution can be filtered. When the filter drawers need to be cleaned, each filter drawer can be pulled out. When installation is required, the filter drawer is placed in the annular installation port so that the sealing plate of the side wall fits with the outer wall of the electrolytic cylinder and is fixed by suction through the suction cup. If a filter drawer is blocked or seriously contaminated, it can be cleaned or replaced in a targeted manner, which greatly shortens the maintenance time.

[0025] Furthermore, the condensation crystallization component includes a preheating device, an evaporator and a crystallizer which are connected in sequence, the preheating device is connected to the Y-shaped connecting pipe, and the third recovery cylinder is connected to the crystallizer.

[0026] Description: After the high-concentration nickel solution obtained by extraction enters the condensation crystallization component through the lower buffer tank, it first enters the preheating device, which helps to increase the temperature of the high-concentration nickel solution and make it closer to the working temperature in the evaporator. The preheated high-concentration nickel solution enters the evaporator to obtain a higher temperature and begins to evaporate. The concentrated solution coming out of the evaporator enters the crystallizer. In the crystallizer, since the high-concentration nickel solution has reached an oversaturated state, nickel sulfate will begin to crystallize and precipitate, and finally it can be recovered through the third recovery cylinder.

[0027] A method for recovering copper-nickel waste liquid in the electronic electroplating industry, based on the above-mentioned cascade recovery system for copper-nickel waste liquid in the electronic electroplating industry, comprises the following steps:

[0028] S1. The copper-nickel waste liquid generated by the electronic electroplating industry is temporarily stored in an electroplating tank. When treatment is required, the copper-nickel waste liquid is pumped into a reactor, and elemental aluminum chips are added to the reactor. The copper ions in the copper-nickel waste liquid are replaced with elemental copper powder by the elemental aluminum chips. The waste liquid after replacement is separated into solid and liquid by a solid-liquid separation device, wherein the weight ratio of the copper-nickel waste liquid to the elemental aluminum chips is 3 to 4:1;

[0029] S2. The separated single copper powder is stored in the first recovery cylinder. Since the bottom of the first recovery cylinder is an inverted V-shaped structure, the copper powder will gather at its edge and enter each discharge seat. When the recovered single copper powder needs to be loaded into a cylinder, the discharge valve at each discharge seat is opened, and a loading cylinder is placed at each filling tray, and the single copper powder will fall into each loading cylinder in batches;

[0030] S3, the separated waste liquid is pumped into the extraction component, and an extractant with a weight ratio of 20-25wt% is added to the extraction component to extract nickel ions, so as to achieve separation and concentration of nickel, and the remaining waste liquid after extraction is further concentrated by a concentrator to obtain a polyaluminum chloride solution and a polyaluminum sulfate solution, wherein the mass proportion of polyaluminum chloride in the polyaluminum chloride solution is ≥32%, and the mass proportion of polyaluminum sulfate iron in the polyaluminum sulfate solution is ≥30%, and the polyaluminum chloride and polyaluminum sulfate solutions are stored in a storage cylinder, and finally, the gas generated during the extraction process is discharged;

[0031] S4. When nickel needs to be recovered in the form of metallic nickel, the nickel solution with a concentration of 25-30 g / L obtained by extraction is passed into the electrolytic recovery component, and the metallic nickel is recovered through the electrolytic action of the electrolytic recovery component, and the nickel is temporarily stored in the second recovery cylinder. When nickel needs to be recovered in the form of nickel sulfate crystals, the high-concentration nickel solution obtained by extraction is passed into the condensation crystallization component, and the nickel sulfate crystals are recovered through the evaporation, condensation and crystallization action of the condensation crystallization component, and the nickel sulfate crystals are temporarily stored in the third recovery cylinder.

[0032] Compared with the prior art, the beneficial effects of the present invention are:

[0033] (1) When the present invention is used, a copper-nickel waste liquid cascade recovery system for the electronic electroplating industry replaces copper ions in the copper-nickel waste liquid with single copper powder by adding single aluminum chips to the reactor, extracts the nickel-containing waste liquid through the extraction component, and realizes nickel separation and concentration. When nickel needs to be recovered in the form of metallic nickel, the recovery of metallic nickel is realized through the electrolysis of the electrolytic recovery component. When nickel needs to be recovered in the form of nickel sulfate crystals, the recovery of nickel sulfate crystals is realized through the evaporation, condensation and crystallization of the condensation and crystallization component. By multi-stage treatment of the waste liquid, the cascade recovery of metal examples in the copper-nickel waste liquid is realized, which can not only effectively remove heavy metals, but also realize the resource recycling of the waste liquid on the basis of a higher recovery rate. By step-by-step recovery and extraction of metal ions, the enterprise can not only reduce the overall cost of waste liquid treatment, but also improve economic benefits through resource recycling and reduce environmental impact.

[0034] (2) The present invention stores the recovered single copper powder through the first recovery cylinder, stores the recovered metallic nickel through the second recovery cylinder, and stores the recovered nickel sulfate crystals through the third recovery cylinder. When the first recovery cylinder stores the recovered single copper powder, since the bottom end of the first recovery cylinder is an inverted V-shaped structure, the copper powder will gather at its edge, and the copper powder is more likely to be concentrated at the discharge seat. When the discharge valve is opened, the copper powder can flow out quickly and smoothly, thereby improving the discharge efficiency. When the recovered single copper powder needs to be loaded into a cylinder, the discharge valve at each discharge seat is opened, and a loading cylinder is placed at each filling tray. The single copper powder will fall into each loading cylinder in batches, which allows the single copper powder to fall into each loading cylinder in batches, thereby improving work efficiency and facilitating accurate inventory statistics and management of the recovered copper powder. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is a schematic diagram of the overall structure of the present invention;

[0036] Figure 2 is a schematic structural diagram of a first recovery drum of the present invention;

[0037] Figure 3 It is a schematic diagram of the external structure of the extraction tower when the vertical buckle plate of the present invention is not installed;

[0038] Figure 4 It is a schematic diagram of the external structure of the extraction tower when the vertical buckle plate of the present invention is installed;

[0039] Figure 5 It is a schematic diagram of the internal structure of the extraction tower of the present invention;

[0040] Figure 6 is a schematic structural diagram of the electrolytic recovery assembly of the present invention;

[0041] Figure 7 It is a schematic structural diagram of the electrolytic stirring plate of the present invention;

[0042] Figure 8 It is a top view of the filter screen plate of the present invention.

[0043] Among them, 1-electroplating tank, 2-reactor, 3-solid-liquid separation equipment, 30-first recovery cylinder, 31-recovery cylinder body, 32-installation plate, 320-rotating shaft, 33-discharge seat, 331-discharge valve, 332-filling plate, 4-extraction component, 40-storage cylinder, 41-extraction tower, 410-vertical buckle groove, 42-concentrator, 43-Y-type connecting pipe, 44-solenoid valve, 45-upper buffer tank, 450-exhaust valve, 46-lower buffer tank, 460-drain valve, 47-guide plate assembly, 470-vertical buckle plate, 471-installation round mouth, 472-spiral rotating rod, 473-guide circular plate, 474-annular guide plate, 4740-vertical annular mesh plate, 5-electrolytic recovery component, 50-electrolysis cylinder, 51-replacement cylinder, 510-control valve, 52-filter mesh plate, 520-filter drawer, 521-filter plate, 522-sealing plate, 523-suction cup, 53-electrolysis stirring member, 530-rotating motor, 531-rotating mounting rod, 5323-rotating mounting sleeve, 5320-vertical mounting groove, 5330-electric telescopic rod, 534-mounting adjustment rod, 535-electrolysis stirring plate, 536-first electrolysis rod, 537-stirring mesh plate, 538-mounting groove, 539-telescopic rod, 54-second electrolysis rod, 55-annular mounting port, 6-condensation crystallization assembly, 60-third recovery cylinder, 61-preheating device, 62-evaporator, 63-crystallizer, 7-second recovery cylinder. DETAILED DESCRIPTION

[0044] In order to further understand the content of the present invention, the present invention is described in detail below through examples.

[0045] Example 1: Figure 1As shown, a copper-nickel waste liquid cascade recovery system for the electronic electroplating industry includes an electroplating pool 1 for storing copper-nickel waste liquid, a reactor 2 connected to the electroplating pool 1, a solid-liquid separation device 3 connected to the reactor 2, an extraction component 4 connected to the liquid outlet of the solid-liquid separation device 3, an electrolytic recovery component 5 and a condensation crystallization component 6 connected to the extraction component 4, wherein the reactor 2, the solid-liquid separation device 3, the extraction component 4, the electrolytic recovery component 5 and the condensation crystallization component 6 all adopt existing technologies, for example, the reactor 2 can adopt an existing reactor made of stainless steel such as 0Cr18Ni9 (304), 00Cr17Ni14Mo2 (316L), 1Cr18Ni9Ti (321), etc., the solid-liquid separation device 3 can adopt an LW series horizontal spiral unloading sedimentation centrifuge produced by Haishen Electromechanical General Factory (Xiangshan), the extraction component 4 can adopt an extraction device of model CHCQ-3D, and the condensation crystallization component 6 can adopt an existing forced circulation evaporation crystallizer of model HC-MVR;

[0046] The solid-liquid separation device 3 is connected to a first recovery cylinder 30 for storing copper powder, the extraction component 4 is connected to a storage cylinder 40 for storing polyaluminium chloride and polyaluminium sulfate solution, and a concentrator 42 is provided at the connection between the extraction component 4 and the storage cylinder 40, wherein the concentrator 42 adopts a concentrator of model WZⅡ1000;

[0047] The extraction component 4 is connected to a Y-shaped connecting tube 43, and the two free ends of the Y-shaped connecting tube 43 are respectively connected to the electrolytic recovery component 5 and the condensation crystallization component 6, and the connection points are provided with a solenoid valve 44, wherein the solenoid valve 44 can adopt an existing solenoid valve of model 4WE10L3X / CG24N9K4;

[0048] The electrolytic recovery component 5 is connected to a second recovery cylinder 7 for recovering metallic nickel, and the condensation crystallization component 6 is connected to a third recovery cylinder 60 for recovering nickel sulfate crystals;

[0049] like Figure 2 As shown, the first recovery cylinder 30 includes a recovery cylinder body 31 with an inverted V-shaped structure at the bottom end, a mounting plate 32 connected to the bottom end of the recovery cylinder body 31 through a rotating shaft 320, and four discharge seats 33 uniformly distributed on the outer wall of the recovery cylinder body 31 along the circumferential direction, and a discharge valve 331 is provided on the discharge seat 33, and a filling plate 332 corresponding to the discharge seat 33 and located at the bottom end of the discharge valve 331 is provided on the mounting plate 32, wherein the discharge valve 331 adopts a ball valve of model 252QMV101-16D;

[0050] The first recovery drum 30, the second recovery drum 7 and the third recovery drum 60 have the same structure.

[0051] Embodiment 2: This embodiment describes a method for recovering copper-nickel waste liquid in the electronic electroplating industry, and a cascade recovery system for copper-nickel waste liquid in the electronic electroplating industry based on Embodiment 1, comprising the following steps:

[0052] S1, temporarily storing the copper-nickel waste liquid generated by the electronic electroplating industry in the electroplating pool 1, when it needs to be processed, pumping the copper-nickel waste liquid into the reactor 2, and adding elemental aluminum chips into the reactor 2, replacing the copper ions in the copper-nickel waste liquid with elemental copper powder by the elemental aluminum chips, and performing solid-liquid separation on the waste liquid after the replacement treatment through the solid-liquid separation device 3, wherein the weight ratio of the copper-nickel waste liquid to the elemental aluminum chips is 3:1;

[0053] S2. The separated single copper powder is stored in the first recovery cylinder 30. Since the bottom end of the first recovery cylinder 30 is an inverted V-shaped structure, the copper powder will gather at its edge and enter each discharge seat 33. When the recovered single copper powder needs to be loaded into a cylinder, the discharge valve 331 at each discharge seat 33 is opened, and a loading cylinder is placed at each filling tray 332, and the single copper powder will fall into each loading cylinder in batches;

[0054] S3, the separated waste liquid is pumped into the extraction component 4, and an extractant with a weight ratio of 20wt% is added to the extraction component 4 to extract nickel ions, so as to achieve separation and concentration of nickel, and the remaining waste liquid after extraction is further concentrated by the concentrator 42 to obtain a polyaluminum chloride solution and a polyaluminum sulfate solution, wherein the mass proportion of polyaluminum chloride in the polyaluminum chloride solution is 32%, and the mass proportion of polyaluminum sulfate iron in the polyaluminum sulfate solution is 30%, and finally the polyaluminum chloride and polyaluminum sulfate solutions are stored by the storage cylinder 40, and finally, the gas generated during the extraction process is discharged;

[0055] S4. When it is necessary to recover nickel in the form of metallic nickel, the nickel solution with a concentration of 25 g / L obtained by extraction is passed into the electrolytic recovery component 5, and the metallic nickel is recovered through the electrolytic action of the electrolytic recovery component 5, and is temporarily stored in the second recovery cylinder 7. When it is necessary to recover nickel in the form of nickel sulfate crystals, the high-concentration nickel solution obtained by extraction is passed into the condensation crystallization component 6, and the nickel sulfate crystals are recovered through the evaporation, condensation and crystallization action of the condensation crystallization component 6, and is temporarily stored in the third recovery cylinder 60.

[0056] Embodiment 3: This embodiment differs from Embodiment 1 in that: Figure 3 , 4As shown in Figure 5, the extraction component 4 includes an extraction tower 41 with a vertical buckle groove 410 on the side wall, an upper buffer groove 45 and a lower buffer groove 46 arranged at the upper and lower ends of the extraction tower 41, and a guide plate assembly 47 installed in the extraction tower 41 through the vertical buckle groove 410. The upper buffer groove 45 is connected to the liquid outlet end of the solid-liquid separation device 3, and the lower buffer groove 46 is connected to the Y-shaped connecting pipe 43. An aeration device is provided in the extraction tower 41, and an exhaust valve 450 is connected to the upper buffer groove 45, and a drain valve 460 is connected to the bottom end of the lower buffer groove 46; after the nickel-containing waste liquid separated by the solid-liquid separation device 3 enters the extraction component 4, it first enters the extraction tower 41 through the upper buffer groove 45, and an extractant is added to the extraction tower 41, and the extractant and the nickel-containing waste liquid flow from top to bottom in sequence, and are evenly mixed through the diversion of the guide plate assembly 47, thereby realizing the separation and concentration of nickel, and the extraction is obtained. The obtained high-concentration nickel solution enters the electrolytic recovery component 5 through the lower buffer tank 46 and realizes nickel recovery in the form of metallic nickel through electrolysis, or enters the condensation crystallization component 6 through the lower buffer tank 46 and realizes nickel recovery in the form of nickel sulfate crystals through evaporation condensation crystallization. The gas generated during the extraction process is discharged through the exhaust valve 450 to prevent excessive pressure and potential dangers. The treated waste liquid is discharged through the drain valve 460, and the remaining waste liquid after extraction is further concentrated by the concentrator 42 to form polyaluminum chloride and polyaluminum sulfate solutions. Finally, the polyaluminum chloride and polyaluminum sulfate solutions can be stored through the storage cylinder 40, wherein the exhaust valve 450 and the drain valve 460 both adopt existing technologies, for example, the exhaust valve 450 can adopt a QSP full-pressure high-speed exhaust valve, and the drain valve 460 can adopt a (K)TP41Y valve sleeve type drain valve;

[0057] The guide plate assembly 47 includes a vertical buckling plate 470 buckled to the outside of the vertical buckling groove 410, three mounting circular openings 471 arranged on the vertical buckling plate 470 from top to bottom, a spiral rotating rod 472 rotatably mounted corresponding to the mounting circular openings 471, a guide circular plate 473 connected to one end of the spiral rotating rod 472, and an annular guide plate 474 connected to the bottom end of the guide circular plate 473 through a vertical annular mesh plate 4740, and the end of the spiral rotating rod 472 opposite to the guide circular plate 473 extends to the outside of the mounting circular opening 471; when the extractant and the nickel-containing waste liquid flow in sequence from top to bottom, they first flow to the guide circular plate 473 at the top, and are first dispersed to the corresponding annular guide plate 474 through the guide circular plate 473, and then further dispersed to the next guide circular plate through the vertical annular mesh plate 4740. Plate 473, and repeat the process. After the extractant and the nickel-containing waste liquid pass through each guide circular plate 473, the annular guide plate 474 and the vertical annular mesh plate 4740, they are dispersed and mixed for many times, and the droplets are continuously refined, which improves the mass transfer efficiency between the two, is conducive to the transfer of nickel ions from the waste liquid to the extractant, and improves the overall extraction effect. When it is necessary to clean the inner wall of the extraction tower 41, each spiral rotating rod 472 is rotated in turn, so that the spiral rotating rod 472 drives the corresponding guide circular plate 473 to turn to the vertical direction. When each guide circular plate 473 is rotated to the vertical direction, the contact area between the annular guide plate 474 and the extraction tower 41 is greatly reduced, which is convenient for cleaning the inner wall of the extraction tower 41. Among them, the extractant can adopt the existing technology such as organic phosphoric acid extractant, DY272, etc.

[0058] The outer diameter of the annular guide plate 474 is the same as the inner diameter of the extraction tower 41. The purpose of limiting the outer diameter of the annular guide plate 474 to be the same as the inner diameter of the extraction tower 41 is to enable the annular guide plate 474 to fit the inner wall of the extraction tower 41 when in a horizontal position, thereby preventing the extractant and nickel-containing waste liquid from flowing through the gap between the annular guide plate 474 and the inner wall of the extraction tower 41, affecting the flow path of the extractant and the nickel-containing waste liquid, and reducing the extraction effect.

[0059] Embodiment 4: This embodiment differs from Embodiment 2 in that:

[0060] In step S1, the weight ratio of copper-nickel waste liquid to elemental aluminum chips is 4:1;

[0061] In step S3, the separated waste liquid is pumped into the extraction component 4, and an extractant with a weight ratio of 25 wt% is added into the extraction component 4 to extract nickel ions;

[0062] In step S3, the mass proportion of the polyaluminium chloride in the obtained polyaluminium chloride solution is 50%, and the mass proportion of the polyaluminium ferric sulfate in the polyaluminium sulfate solution is 45%. Finally, the polyaluminium chloride and the polyaluminium sulfate solution are stored in the storage cylinder 40, and finally, the gas generated during the extraction process is discharged;

[0063] In step S4, when it is necessary to recover nickel in the form of metallic nickel, the nickel solution with a concentration of 30 g / L obtained by extraction is passed into the electrolytic recovery component 5, and the metallic nickel is recovered through the electrolytic action of the electrolytic recovery component 5.

[0064] Embodiment 5: This embodiment differs from Embodiment 4 in that:

[0065] In step S3, after the nickel-containing waste liquid separated by the solid-liquid separation device 3 enters the extraction component 4, it first enters the extraction tower 41 through the upper buffer tank 45, and the extraction agent is added to the extraction tower 41. The extraction agent and the nickel-containing waste liquid flow from top to bottom in sequence and are evenly mixed by the guide of the guide plate assembly 47, thereby achieving separation and concentration of nickel;

[0066] When the extractant and the nickel-containing waste liquid flow from top to bottom in sequence, they first flow to the guide circular plate 473 at the top, and are dispersed to the corresponding annular guide plate 474 through the guide circular plate 473 for the first time, and then are further dispersed to the next guide circular plate 473 through the vertical annular mesh plate 4740, and the process is repeated. After the extractant and the nickel-containing waste liquid pass through each guide circular plate 473, the annular guide plate 474 and the vertical annular mesh plate 4740, they are dispersed and mixed for multiple times;

[0067] When the inner wall of the extraction tower 41 needs to be cleaned, each spiral rotating rod 472 is rotated in sequence so that the spiral rotating rod 472 drives the corresponding guide circular plate 473 to rotate to the vertical direction. When each guide circular plate 473 is rotated to the vertical direction, cleaning can be performed.

[0068] Embodiment 6: This embodiment differs from Embodiment 3 in that: Figure 6 , 7 As shown in FIG. 8 , the electrolytic recovery assembly 5 includes an electrolytic cartridge 50, a replacement cartridge 51 connected to the electrolytic cartridge 50 and provided with a control valve 510 at the connection, a filter screen 52 disposed in the electrolytic cartridge 50, and an electrolytic stirring member 53 disposed in the electrolytic cartridge 50 and located at the bottom end of the filter screen 52;

[0069] The electrolytic stirring member 53 comprises a rotating mounting rod 531 whose upper end is connected to the filter screen 52 and whose lower end is connected to a rotating motor 530, a rotating mounting sleeve 532 which is sleeved on the outside of the rotating mounting rod 531 and has two vertical mounting grooves 5320 on the side wall, two mounting adjustment rods 534 which are arranged in each vertical mounting groove 5320 and connected by an electric telescopic rod 5330, and an electrolytic stirring plate 535 connected to each mounting adjustment rod 534; when the high-concentration nickel solution obtained by extraction enters the electrolytic recovery component 5 through the lower buffer tank 46, it first enters the electrolytic cylinder 50, and the solid matter and residue that are not completely reacted during the extraction process are filtered out by the filter screen 52. At the same time, the composition of the high-concentration nickel solution entering the electrolytic area can be made more uniform. After the filtration is completed, the rotating motor 530 is started, and the rotating motor 5 30 drives the rotating mounting rod 531 and the rotating mounting sleeve 532 mounted on the outer wall of the rotating mounting rod 531 to rotate. At the same time, the electrolytic stirring plate 535 stirs the high-concentration nickel solution while performing electrolytic treatment. Stirring can accelerate the diffusion of ions in the solution and improve the electrolytic efficiency. After the electrolytic treatment, the metal nickel is recovered. Finally, the control valve 510 is opened to transfer the electrolytically treated solution in the electrolytic cylinder 50 to the replacement cylinder 51, and chemical reagents are added to the replacement cylinder 51 for ion exchange treatment. Among them, the rotating motor 530 and the electric telescopic rod 5330 both adopt existing technologies. For example, the rotating motor 530 can adopt a rotary servo motor with a model of SGMGV-13ADC61, and the electric telescopic rod 5330 can adopt an electric telescopic rod with a model of YNT-03.

[0070] The electrolytic stirring plate 535 includes three first electrolytic rods 536 distributed in parallel from left to right, a stirring mesh plate 537 arranged between two adjacent first electrolytic rods 536, and mounting grooves 538 are arranged on the opposite sides of the first electrolytic rods 536 located at the upper and lower ends in the same vertical mounting groove 5320, and a telescopic rod 539 is arranged in each mounting groove 538, and the two telescopic rods 539 located in the same vertical direction are connected by the second electrolytic rod 54; when the electrolytic stirring plate 535 is used, the distance between the two relatively distributed mounting adjustment rods 534 can be driven by the electric telescopic rod 5330, and the first electrolytic rods 536 and the stirring mesh plates 537 relatively distributed in the vertical direction are moved away from or close to each other, and at the same time , the telescopic rod 539 will also be extended or compressed, so as to achieve the purpose of adjusting the stirring area, which can avoid energy waste caused by excessive stirring, and can stir the solution more comprehensively to improve the recovery rate of nickel. The uniform distribution of the first electrolytic rod 536 and the second electrolytic rod 54 helps to form a more uniform electric field, which can ensure that the current is more evenly distributed in the entire electrolyte volume during the electrolysis process, and improve the migration efficiency of nickel ions. Among them, the first electrolytic rod 536, the telescopic rod 539 and the second electrolytic rod 54 all adopt existing technologies. For example, the first electrolytic rod 536 and the second electrolytic rod 54 can adopt the electrolytic rod of model EPH-300-SC, and the telescopic rod 539 can adopt the telescopic rod of model TTL-120;

[0071] The side wall of the electrolytic cylinder 50 is provided with an annular mounting opening 55, and the filter screen 52 includes four filter drawers 520 distributed in the annular mounting opening 55 along the circumferential direction, a filter plate 521 arranged at the bottom of the filter drawer 520, and a plugging plate 522 arranged outside the filter drawer 520 and in contact with the outer wall of the electrolytic cylinder 50. The inner wall of the plugging plate 522 is connected to the outer wall of the electrolytic cylinder 50 through a suction cup 523. By installing several filter drawers 520 in the annular mounting opening 55, the high-concentration nickel solution is filtered. When the filter drawers 520 need to be cleaned, the filter drawers 520 can be cleaned. When cleaning, each filter drawer 520 can be pulled out. When installation is required, the filter drawer 520 is placed in the annular installation opening 55, so that the sealing plate 522 of the side wall fits with the outer wall of the electrolytic cylinder 50, and is adsorbed and fixed by the suction cup 523. If a filter drawer 520 is blocked or seriously polluted, it can be cleaned or replaced in a targeted manner, which greatly shortens the maintenance time. Among them, the suction cup 523 adopts the existing technology, for example, a suction cup with model FGB-R-52X25-SI-50 can be used.

[0072] Embodiment 7: This embodiment differs from Embodiment 6 in that:

[0073] In step S4, after the high-concentration nickel solution obtained by extraction enters the electrolytic recovery component 5 through the lower buffer tank 46, it first enters the electrolytic cylinder 50, and the solid matter and residue that are not completely reacted during the extraction process are filtered out by the filter mesh plate 52. After the filtering is completed, the rotating motor 530 is started, and the rotating mounting rod 531 and the rotating mounting sleeve 532 installed on the outer wall of the rotating mounting rod 531 are driven by the rotating motor 530 to rotate. At the same time, the high-concentration nickel solution is stirred by the electrolytic stirring plate 535 while being electrolytically treated. After the electrolytic treatment, the metal nickel is recovered. Finally, the control valve 510 is opened to transfer the electrolytically treated solution in the electrolytic cylinder 50 to the replacement cylinder 51, and chemical reagents are added to the replacement cylinder 51 for ion exchange treatment;

[0074] When the electrolytic stirring plate 535 is in use, the distance between the two relatively distributed installation adjustment rods 534 can be driven by the electric telescopic rod 5330, and the first electrolytic rods 536 and the stirring mesh plate 537 relatively distributed in the vertical direction move away from or close to each other. At the same time, the telescopic rod 539 will also be extended or compressed, thereby achieving the purpose of adjusting the stirring area.

[0075] Embodiment 8: This embodiment differs from Embodiment 6 in that: Figure 1 As shown, the condensation crystallization component 6 includes a preheating device 61, an evaporator 62 and a crystallizer 63 which are connected in sequence. The preheating device 61 is connected to the Y-type connecting pipe 43, and the third recovery cylinder 60 is connected to the crystallizer 63. After the high-concentration nickel solution obtained by extraction enters the condensation crystallization component 6 through the lower buffer tank 46, it first enters the preheating device 61, which helps to increase the temperature of the high-concentration nickel solution and make it closer to the working temperature in the evaporator 62. The preheated high-concentration nickel solution enters the evaporator 62 to obtain a higher temperature and begins to evaporate. The concentrated solution coming out of the evaporator 62 enters the crystallizer 63. In the crystallizer 63, since the high-concentration nickel solution has reached an oversaturated state, nickel sulfate will begin to crystallize and precipitate, and finally it can be recovered through the third recovery cylinder 60. Among them, the preheating device 61, the evaporator 62 and the crystallizer 63 all adopt existing technologies. For example, the preheating device 61 can adopt a model of HR-3000, the evaporator 62 can adopt a model of EV-500, and the crystallizer 63 can adopt a model of CR-250.

[0076] Embodiment 9: This embodiment differs from Embodiment 7 in that:

[0077] In step S4, the high-concentration nickel solution obtained by extraction enters the condensation crystallization component 6 through the lower buffer tank 46, and first enters the preheating device 61 for preheating. The preheated high-concentration nickel solution enters the evaporator 62 to obtain a higher temperature and begins to evaporate. The concentrated solution coming out of the evaporator 62 enters the crystallizer 63. In the crystallizer 63, since the high-concentration nickel solution has reached an oversaturated state, nickel sulfate will begin to crystallize and precipitate, and finally be recovered through the third recovery cylinder 60.

Claims

1. A cascade recovery system for copper-nickel waste liquid in the electronic electroplating industry, characterized in that: The invention comprises an electroplating pool (1) for storing copper-nickel waste liquid, a reaction kettle (2) connected to the electroplating pool (1), a solid-liquid separation device (3) connected to the reaction kettle (2), an extraction component (4) connected to the liquid outlet of the solid-liquid separation device (3), an electrolytic recovery component (5) connected to the extraction component (4), and a condensation crystallization component (6); The solid-liquid separation device (3) is connected to a first recovery cylinder (30) for storing copper powder, the extraction component (4) is connected to a storage cylinder (40) for storing polyaluminium chloride and polyaluminium sulfate solution, and a concentrator (42) is provided at the connection between the extraction component (4) and the storage cylinder (40); The extraction component (4) is connected to a Y-shaped connecting tube (43), and two free ends of the Y-shaped connecting tube (43) are respectively connected to the electrolytic recovery component (5) and the condensation crystallization component (6), and electromagnetic valves (44) are provided at the connection points; The electrolytic recovery component (5) is connected to a second recovery cylinder (7) for recovering metallic nickel, and the condensation crystallization component (6) is connected to a third recovery cylinder (60) for recovering nickel sulfate crystals; The first recovery cylinder (30) comprises a recovery cylinder body (31) with an inverted V-shaped structure at the bottom end, a mounting plate (32) connected to the bottom end of the recovery cylinder body (31) via a rotating shaft (320), and a plurality of discharge seats (33) uniformly distributed on the outer wall of the recovery cylinder body (31) along the circumferential direction, wherein the discharge seats (33) are provided with discharge valves (331), and the mounting plate (32) is provided with a filling plate (332) corresponding to the discharge seats (33) one by one and located at the bottom end of the discharge valve (331); The first recovery tube (30), the second recovery tube (7) and the third recovery tube (60) have the same structure.

2. The cascade recovery system for copper-nickel waste liquid in the electronic electroplating industry according to claim 1 is characterized in that: The extraction assembly (4) comprises an extraction tower (41) having a side wall provided with a vertical buckle groove (410), an upper buffer groove (45) and a lower buffer groove (46) provided at the upper and lower ends of the extraction tower (41), and a guide plate assembly (47) installed in the extraction tower (41) through the vertical buckle groove (410), the upper buffer groove (45) being connected to the liquid outlet end of the solid-liquid separation device (3), the lower buffer groove (46) being connected to the Y-shaped connecting pipe (43), an aeration device being provided in the extraction tower (41), an exhaust valve (450) being connected to the upper buffer groove (45), and a sewage discharge valve (460) being connected to the bottom end of the lower buffer groove (46).

3. A cascade recovery system for copper-nickel waste liquid in the electronic electroplating industry according to claim 2, characterized in that: The guide plate assembly (47) includes a vertical buckling plate (470) buckled to the outside of the vertical buckling groove (410), a plurality of mounting circular openings (471) arranged on the vertical buckling plate (470) from top to bottom, a spiral rotating rod (472) rotatably mounted in a one-to-one correspondence with the mounting circular openings (471), a guide circular plate (473) connected to one end of the spiral rotating rod (472), and an annular guide plate (474) connected to the bottom end of the guide circular plate (473) through a vertical annular mesh plate (4740), and the end of the spiral rotating rod (472) opposite to the guide circular plate (473) extends to the outside of the mounting circular opening (471).

4. The cascade recovery system for copper-nickel waste liquid in the electronic electroplating industry according to claim 3 is characterized in that: The outer diameter of the annular guide plate (474) is the same as the inner diameter of the extraction tower (41).

5. The cascade recovery system for copper-nickel waste liquid in the electronic electroplating industry according to claim 1 is characterized in that: The electrolytic recovery assembly (5) comprises an electrolytic cylinder (50), a replacement cylinder (51) connected to the electrolytic cylinder (50) and provided with a control valve (510) at the connection, a filter screen (52) arranged in the electrolytic cylinder (50), and an electrolytic stirring member (53) arranged in the electrolytic cylinder (50) and located at the bottom end of the filter screen (52); The electrolytic stirring member (53) comprises a rotating mounting rod (531) whose upper end is connected to the filter screen (52) and whose lower end is connected to a rotating motor (530), a rotating mounting sleeve (532) which is sleeved on the outside of the rotating mounting rod (531) and whose side wall is provided with a plurality of vertical mounting grooves (5320), two mounting adjustment rods (534) which are arranged in each of the vertical mounting grooves (5320) and connected via an electric telescopic rod (5330), and an electrolytic stirring plate (535) which is connected to each mounting adjustment rod (534).

6. A cascade recovery system for copper-nickel waste liquid in the electronic electroplating industry according to claim 5, characterized in that: The electrolysis stirring plate (535) comprises a plurality of first electrolysis rods (536) distributed in parallel from left to right, a stirring mesh plate (537) arranged between two adjacent first electrolysis rods (536), mounting grooves (538) are arranged on opposite sides of the first electrolysis rods (536) located in the same vertical mounting groove (5320) and located at the upper and lower ends, and a telescopic rod (539) is arranged in each mounting groove (538), and the two telescopic rods (539) located in the same vertical direction are connected by a second electrolysis rod (54).

7. The cascade recovery system for copper-nickel waste liquid in the electronic electroplating industry according to claim 5 is characterized in that: The side wall of the electrolytic cylinder (50) is provided with an annular mounting opening (55), and the filter mesh plate (52) comprises a plurality of filter drawers (520) distributed circumferentially in the annular mounting opening (55), a filter plate (521) arranged at the bottom end of the filter drawer (520), and a sealing plate (522) arranged outside the filter drawer (520) and in contact with the outer wall of the electrolytic cylinder (50), wherein the inner wall of the sealing plate (522) is connected to the outer wall of the electrolytic cylinder (50) via a suction cup (523).

8. The cascade recovery system for copper-nickel waste liquid in the electronic electroplating industry according to claim 1 is characterized in that: The condensation crystallization component (6) includes a preheating device (61), an evaporator (62) and a crystallizer (63) connected in sequence, the preheating device (61) is connected to the Y-shaped connecting pipe (43), and the third recovery cylinder (60) is connected to the crystallizer (63).

9. A method for recycling copper-nickel waste liquid in the electronic electroplating industry, based on a cascade recycling system for copper-nickel waste liquid in the electronic electroplating industry described in any one of embodiments 1-8, characterized in that: The following steps are involved: S1. temporarily storing the copper-nickel waste liquid generated by the electronic electroplating industry in an electroplating tank (1); when treatment is required, pumping the copper-nickel waste liquid into a reaction kettle (2); adding elemental aluminum chips into the reaction kettle (2); replacing copper ions in the copper-nickel waste liquid with elemental copper powder by the elemental aluminum chips; and subjecting the waste liquid after the replacement treatment to solid-liquid separation through a solid-liquid separation device (3); wherein the weight ratio of the copper-nickel waste liquid to the elemental aluminum chips is 3 to 4:1; S2. The separated single copper powder is stored in the first recovery cylinder (30). Since the bottom end of the first recovery cylinder (30) is an inverted V-shaped structure, the copper powder will gather at its edge and enter each discharge seat (33). When the recovered single copper powder needs to be loaded into a cylinder, the discharge valve (331) at each discharge seat (33) is opened, and a loading cylinder is placed at each filling plate (332), and the single copper powder will fall into each loading cylinder in batches; S3, the separated waste liquid is pumped into the extraction component (4), and an extractant with a weight ratio of 20-25wt% is added to the extraction component (4) to extract nickel ions, thereby achieving separation and concentration of nickel. The remaining waste liquid after extraction is further concentrated by a concentrator (42) to obtain a polyaluminum chloride solution and a polyaluminum sulfate solution, wherein the mass proportion of polyaluminum chloride in the polyaluminum chloride solution is ≥32%, and the mass proportion of polyaluminum sulfate iron in the polyaluminum sulfate solution is ≥30%. The polyaluminum chloride and polyaluminum sulfate solutions are stored in a storage cylinder (40), and finally, the gas generated during the extraction process is discharged; S4. When it is necessary to recover nickel in the form of metallic nickel, the nickel solution with a concentration of 25-30 g / L obtained by extraction is passed into the electrolytic recovery component (5), and the metallic nickel is recovered through the electrolytic action of the electrolytic recovery component (5), and is temporarily stored in the second recovery cylinder (7). When it is necessary to recover nickel in the form of nickel sulfate crystals, the high-concentration nickel solution obtained by extraction is passed into the condensation crystallization component (6), and the nickel sulfate crystals are recovered through the evaporation condensation crystallization action of the condensation crystallization component (6), and is temporarily stored in the third recovery cylinder (60).

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